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ii. 913 General and Physical Chemistry Solutions. I. Relations between Density and Refractive Index in Binary Mixtures. F. SCHWERS (Bull. Eoc. chirn. 1910 [iv] 7 875-882).-Pulfrich’s formula (D - D,)/D = a(N- &)IN ex- pressing the relationship between change of volume and change in refractive index from the calculated values for any binary mixture of liquids does not admit of an absolute comparison between the two changes since in devising the formula Pulfrich introduced the density value in arriving at the refractive index contraction Nv. The author suggests instead the relation C = AC where Cr. = 100(n - n,)/n n being the observed refractive index of the m.ixture and n the calculated value and C = l O O ( 0 - B,)D D being the observed specific gravity and D the calculated value.The value of A has been deter- mined for mixtures of water with alcohol acids aldehydes ketones glycols hydroxy-acids esters ethers amines cyclic compounds etc. and from the results obtained the following conclusions are drawn. The value of A for a mixture of two given liquids is independent of (1) the concentration of either constituent (2) the wave-length of the light used and (3) to a certain extent of the temperature of observ- ation. It is specific for each mixture and its magnitude is dependent on the molecular volume and structure of each constituent. These observations lend no support to the ‘‘ hydrate” theory of solution since if “hydrates ” mere formed it is inconceivable that A would be independent of the concentration of each constituent in a given binary mixture.When a substance undergoes change in volume (by coffipression polymerisation or fusion) the change in refractive index exhibits a relation to the change in volume which is peculiar to each substance and depends on its constitution. T. A. H Flusrescenoe and Band Spectra of Oxygen. WALTER STEUBING (Ann. Physik 1910 [iv) 33 563-584).-Tt has been found that oxygen exhibits three banded emission spectra one of which lies in the region extending from the red to the greenish-yellow rays whilst the others are in the ultra-violet. Detailed observations relating to the three spectra are recorded. The first ultra-violet spectrum which has usually been attributed to water-vapour by previous observers is shown to be characteristic of oxygen. The bands of this spectrum in the neighbourhood of 185pp were repeatedly obtained under conditions which seemed to ensui’e the absence of water vapour.These conditions were such that the strongest hydrogen lines are not visible and the author concludes that the first ultra-violet spectrum exhibited by tubes containing oxygen cannot be due to water vapour. The experimental data are discussed from the point of view of Stark’s electron theory. H. M. D VOL. XCVIZI. ii. 62ii. 914 ABSTRACTS OF CHEMICAL PAPElC3. Dispersion of Light by Potassium Vapour. P. V. BEVAN (PTOC. Roy Soc. 1910 84 8,209-225).-1n continuation of previous experiments (compare Abstr. 1909 ii 783; this vol. ii 87) on the dispersion produced by potassium vapour quantitative measurements have now been made for different wave-lengths.The observed devia- tions extend over the whole of the visible spectrum and for a consider- able distance in the ultra-violet. Strong absorption takes place at the lines of the principal series and anomalous dispersion is found in the neighbourhood of these lines. This phenomenon has been investigated for seven of the pairs forming the principal series lines. As the pairs in this series get closer together with diminishing wave- length the dispersion effects can only be seen outbide the lines forming a pair and a lack of symmetry in the dispersion curves is found which corresponds with the different intensities of the lines forming the pair. The quantitative data are discussed in reference to Sellmeier’s theory. I n regard to the natural periods which correspond with the series lines it is suggested that these are not due to the atom itself but t o differentiated forms of the atom exhibiting real differences in physical properties.H. 11 D. [v of Series Spectrum of Mercury. S. R. MILNER (Plid. Mag. 1910 i] 20 636-642).-1t has been found that the photographic records the spectrum of the mercury arc in a vacuum show no trace of the continuous back-ground even when the time of exposure is more than fifty times as loog as the normal exposure suitable for registration in the case of the mercury arc in air. These records show a large number of lines which have not been observed previously. The wave-lengths of the lines of the principal series down to na= 16 in Rydberg’s formula and of the diffke a i d sharp series down to m = 16 and n ~ .= 14 respectively have been measured. The data are utilised to show the accuracy of Rydberg’s empirical law according to which the difference of the frequency of the convergence limit of the principal series and that of the common limit of the sharp and diffuse series is equal to the frequency of the first line of the sharp series. The agreement is such as to’indicate the absolute accuracy of this law. H. M. D. Influence of Pressure on the Absorption of Ultra-red Radia- tion by Gases. EVA VON BAHR (Ann. Physik 1910 [iv] 33 585-597).-1n continuation of previous measurements (Abstr. 1909 ii 630) of the dependence of the ultra-red absorption on t h e pressure experiments have been made with sulphur dioxide hydrogen chloride nitrogen peroxide ozone benzene and methyl alcohol.As in the case of tbe gases examined previously the absorption of t h e first four substances increases as the total pressure on the gas is raised and tends towards a constant maximum value. For benzene and methyl alcohol on the other hand the absorption is independent of the pressure between 5 and 760 mm. The collected data indicate that in general the pressure a t which maximum absorption is reached diminishes as the size of the molecules of the gas increases.GENEkAL AND PQYSICAL CIIEMlfSTRY ii. 916 Experiments with nitrous oxide show that a change of pressure not only influences the quantity of the absorbed radiation but also brings about a change in the character of the absorbed rays. This variation in the nature of the absorbed radiation is inconsiderable except at lower pressures.H. M. D. A New Radiant Emission from the Spark. ROBERT W. WOOD (Phil. Mug. 1910 [vi] 20 707-712).-When a condenser spark passes between aluminium electrodes screened by a metal strip although nothing is visible to the eye a photograph taken with a quartz lens shows that the air round the spark is glowing with ultra- violet light for a very short distance. This was shown not to be due to fluorescence of the air caused by the absorption of Schumann waves or to scattering of the light OF the spark by air or dust. The light given out by the emission is embraced between the wave-lengths of 300 to 310 aad its spectrum consists of two broad bands one very strong the other weaker identical with the ‘‘ water bands ” of the oxghydrogen fl3me. I n addition are three lines at 3576 3537 and 3369 identical with those attributed by Eder and Valenta to nitrogen in the spectrogram of the spark between wet carbon poles.No differ- ence was observed whether the spark took place in dry or moist air but in oxygen there was practically no emission whilst in nitrogen it was much brighter and extended a greater distance. No substame has been found transparent to the emission itself. A jet of oxygen killed the emission but in a jet of nitrogen the emission shot out much further and mas of greater intensity The emission appears to be shot out with very high velocity for it is not affected by air currents The new emission appears of great importance in connexion with the origin of the so-called “water-bands,” and it is possible it may be identical with the ‘‘ Entladungsstrahlen.” P.s. Rotatory Power of Tartaric and Malic Acids in Presence of Ammonium Molybdate and Sodium Phosphate. G. MADERNA (Atti R. Accud. Lirzcei 1910 [v] 19 ii 130-138).-Seeking an explana- tion of the phenomena observed in connexion with the precipitation of ammonium phosphomolybdate in the presence of organic acids (this vol. ii 804) the author has repeated and extended the work of Gernez (Abstr. 1889 859 1147) more especially in order to obtain indications as to whether the phosphate radicle enters into the organic complex He confirms the results of Gernez as regards the rotatory power of tartaric acid in the presence of ammonium molybdate. Rise of temperature affects the rotatory power differently at different con- centrations.The concentrations at which a decrease is observed are those at which a precipitation of phosphomolybdate can be effected. Sodium phosphate does not affect the rotatory power of tartaric acid t o any marked,extent its influence being in fact no greater than that of sodium or ammonium chlorides. The action of sodium phosphate and ammonium molybdate together is similar to that of the latter substance alone so that it is probable that the complex substances in solution involve only the acid and the molybdate. The recults obtained with rntlic acid were simiiar. The author fiuds reLtson to doubt tho s t a t e 62-2ii. 916 ABSTRACTS OF CHEMICAL PAPERS. ments of previous workers as to the composition of the complex compounds present in these solutions. R.V. S. Action of Quinones and their Sulphonic Derivatives on Photographic Images from Silver Salts. AUGUSTE LUMI~RE Lours LUNI~RE and ALPHONSE SEYEWETZ (Compt. rend. 1910 151 61 6-61 8).-pBenzoquinone and its sulphonic derivative act as ‘‘ reducing ” agents in acid solution towards the negative photographic image A solution containing 2% of p-benzoquinone and 0.5% of sulphuric acid is recommended for use in photography. This bleaches the opaque portions of the image more rapidly than the half tones. The reaction is explained by the equation C6H,02 + H2S04 + 2Ag = C,H,(OH) + Ac2S04. I n the presence of an alkali chloride or bromide however p-benzo- quinone produces strong intensification The effect is less marked in the case of the sulphonic derivative.The solution recommended contains 0.5% of p-benzoquinone and 2.5% of potassium bromide. The reaction is represented as 2C6H,02 + 2KBr 4 2Ag + H20 = C6H4(OE() + C6H4(OH)2 + Ag,0Br2. w. 0. w. Temperature-coefficient of the Bleaching of Colouring Mattem in the Visible Spectrum. B. SCHWEZOFF (Zeitsoh. Photo- chern. 1910 9 65-70).-The influence of temperature on the rate of bleaching of cyanine pinachrom pinaverdol and pinacyanol when exposed to light of known wavelength has been investigated. For a rise of 10’ the increase in the rate of bleaching was found to vary from 1.036 t o 1.054. These temperature-coeficients are the smallest which have yet been observed in connexion with photochemicai changes.H. M. D. Acceleration of t b e Bleaching of Colouring Matters by Aromatic Compounds. GOTTFRIED KUMMELL (Zeitsch. Photochem. 191 0 9 54-60).-The increased sensitiveness of colouring matters towards light in presence of certain aromatic compounds has been measured by means of Vogel’s actinometer using specially prepared chromate paper as a comparison standard. Observations mere made on cyanine methylene-blue and erythrosin the substances added being anethole eugenol isoeugenol safrole isosafrole propenylphenol and vinylanisole. To obtain comparable results these were added in such quantity that the molar concentration of the sensitiser in the exposed collodion or gelatin film mas in all cases twenty-five times as large as that of the colouring matter. From the tabulated results it is found tbat safrole and isosafrole lower the light sensitiveness of all three colouring matters.The other five aubstancv accelerate in general the rate of bleaching and the sensitising influence of the members of the group increases as the molecular weight decreases. Experiments are described in support of the view that the bleaching is due to an oxidation process and that the active substances accelerate the bleaching by acting as oxygen carriers. H. M. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 917 The Probability Variations in the Distribution of a-Particles. ERNEST RUTHERFORD and HANS GEIaER [with a note by H. BATEMAN] (Phil. Mag. 1910 [vi] 20 698-707).-The object of the experi- ments was to see whether the rate of emission of a-particles was governed by the laws of probability or whether the expulsion of one a-particle might not precipitate the disintegration of a neighbouring atom.The scintillations from the a-particles of a polonium source were observed by eye and recorded on a chronograph tape by closing an electric circuit by hand a t the instant of each scintillation. Two thousand scintillations a day mere counted for five days and the chronograph records examined. The differences between the number of scintillations observed in successive one-eighth one-quarter and one minute intervals respectivelg,and the true average number (total number divided by total number of intervals) were compared with the expression deduced by Bateman from the theory of probability. I f x be the true average number of particles observed in any interval the probability Z7E that n a-particles are observed in the same interval is L P.The agree- n! ment between theory and experiment was found to be practically perfect especially for the one-eighth minute intervals and there is no evidence of greater variations than would be expected from a random distribution F. S. Rate of Emission of a-Particles from Uranium and its Products. J. N. BROWN (Proc. Roy. Soc. 1910 A 84 151-154).- The number of a-particles emitted from pitchblende films of known weight per unit area has been determined by the scintillations pro- duced in zinc sulphide. For thin enough films the number was proportional to the thickness so that the total number emitted per gram per second could be calculated.The percentage of uranium in the pitchblende was determined. Per gram of uranium in the pitch- blende the number emitted per second was 7.36 x lo4 in fair agree- ment with the number 9.25 x lo4 calculated from Rutherford’s value for radium. F. S. The Number of a-Particles Emitted by Uranium and Thorium and by Uranium Minerals. HANS GEIGER and ERNEST RUTHERFORD (Phil. Mug. 1910 [vi] 20 691-G98).-The number of a-particles emitted per second from one gram of uranium calculated from the number emitted by radium and the ratio between uranium and radium in minerals is 11,600 if each uranium atom emits one a-particle On Boltwood’s view (Abstr. 1908 ii 454) that two a-particles per atom are emitted by uranium and one from each of the subsequent a-ray products the calculated number of a-particles emitted per second from an old mineral containing 1 gram of uranium is 96,700.The number has been experimentally determined by counting the scintillations produced on a zinc sulphide screen from very thin films of material. The scintillations from uranium are much fainter and more difficult to count than from the uranium minerals and from thorium. Films of pure uranoso-uranic oxide selected Joachimsthal uraninite and thorium oxide five weeks old from thorite prepared by Boltwood were employed The number of a-particles per second perii. 918 ABSTRACTS OF CHEMICAL PAPERS. gram of uranium or thorium were for these three preparations 23,700 96,000 and 27,000 respectively. These represent the mean values corrected for defects of the screen escape of emanation from the uraninite and decay of radio-thorium in the thorium oxide.These experiments confirm the view that uranium alone gives two a-particles all its products giving only one per atom disintegrating. The agree- ment between the calculated and experimental numbers is closer than could be expected. It was observed that the scintillations from ionium were as bright as if not brighter than those irom uranium showing that the range of the a-particle from the latter is not greater than that of ionium (2,s cm. of air) which is the lowest hitherto measured. A preliminary measurement of the rauge of the uranium a-particle gave 2.7 cm. The Scattering of Homogeneous ,!3 -Rays and the Number of Electrons in an Atom. J. ARNOLD CROWTHER (Proc. Roy. Xoc.1910 A 84 226-247).-The fact t h a t @-rays are scattered in a thickness or” material far too small to effect the velocity of the rays renders experiments on scattering more simple theoretically than those on absorption. The results are interpreted of the theory of J. J. Tbomson (Camb. Phil. SOC. Yroc. 1910 15 v) which is borne out in all points. Homogeneons @rays from a radium source produced in the manner previously described (compare this vol. ii 672) are scattered by screens of various materials and thickness and by means of stops of various sizes the scattered rays are confined to a known angle and pass into an ionisation chamber so shaped that the paths of all rays through it are similar. The following results deduced from the theory mere experimentally established (1) for rays of given velocity and cone of given angle the intensity of the radiation I varies with the thickness t of material traversed according t o the formula I/Io= 1 - e-k/t where k is a constant ; (2) +/ Jx= constant where t is the thickness necessary t4 cut down to one-half the radiation tbrough a stop of angle + ; (3) mu21 J<=constant where mv2 twice the kinetic energy of the rays is obtained from the magnetic deflexion.I n addition the results lend themselves t o a calculation of the number of electrons in an atom which is found to be three times the atomic weight for all atoms examined on the assumption that the positive electricity within the atom is not in an electronic condition but uniformly distributed. An important experi- ment showed that homogeneous @-rays when passed through only 0.001 cm.of platinum are completely scattered and are then absorbed by aluminium exponentially whereas the absorption in aluminium alone is quite different the curve having two inflexions in opposite directions making the middle part nearly linear as Wilqon found. The view is taken that Completely scattered homogeneous P-radiation is exponentially absorbed. F S. Influence of the Temperature on the Change of Radioactive Substances. 11. H-EINRICH W. SCHMIDT and PAUL CERMACK (Piqsikal. Zeitsch. 1910 11 793-800. Compare Abstr. 1909 ii 9). -The changes in P-rays from a quartz tube containing radium during F. S.GENERAL AND PEYSICAL CHEMISTRY. ii. 919 and after heating in a platinum-foil furnace a t 1200’ to 1300O have been exhaustively examined and amid much irregular variation certain generalities have transpired.The y-rays throughout in all the experiments show absolutely no definite change in intensity. while the P-rays on heating the tube suddenly increase to a maximum remain constant during the heating (usually one-half to one hour) then on cooling very rapidly and steadily decrease to the value before heating then increase in three hours to the value during heating and finally after many days return to the value before heating. These results are attributed to (1) the gasification of the products radium- A -B and -C by the heating whereby theabsorption of @-rays which takes place in the radiumitself when these products are formed within it no longer occurs; (2) the sudden adsorption into the mass of the radium again of these products on cooling ; (3) the formation in three hours of a new set of products on the walls of the tube and not within the radium due to the complete expulsion of emanation from the radium during heating ; (4) the decay of this emanation with the four- day half-period and the re-growth of fresh emanation and products within the radium as initially.All the quartz tubes after repeated heatings became porous and allowed emanation to escape but some tubes lasted far better than others. The /3-rays of uranium-X were also examined similarly t o those of radium but apart from initial changes due to the heat altering the distribiition OF the substance no definite changes occurred The conclusion is arrived at that none of the experiments prove any direct influence of temperature on the rate of transformation of a radioact’ive substance.F. S. The Consequences of the Corpuscular Hypothesis of the y-and X-Rays and the Range of P-Rays. WILLIAX H. BRAGG (Phil. Mag. 1910 [vi] 20 385-41 7).-The paper reviews exhaustively the present state of knowledge of the ionisation penetration reflexion scattering transformation etc. of cathode- X - a- p- and y-rays from the point of view of the (‘corpuscular ” or ‘‘ entity ” hypothesis which recognises that each type of radiation consists of icdividual entities to be followed each by itself from its origin through all its changes of direction and sometimes changes of form (conversion of cathode- into X-rays of y- into p-rays) until its gradually diminishing energy becomes too small to be detected.A method is described OF deter- mining the average range of P-ritys in various substances defined as the average weight of substance crossed by the P-ray when its zig-zag path is straightened out before i t disappears. It is deduced theoretically that the relative ionisations inside similar vessels of different materials thick enough in the walls to prevent P-rays pene- trating them exposed to a constant stream of y-rays gives the relative average ranges of the P-rays in the metals. Results so obtained by H. L. Porter show the greatest range in lead and the least in card. The greater apparent absorption in lead than in other substances is due to the more zig-zag character of the path of the P-ray iu lead the total length of path (in weight units) being actually the greatest in lead.The view is strongly upheld that y - and X-rays do not ionise gases directly at all but only through first being transformed intoii. 920 ABSTRACTS OF CHEMICAL PAPERS. p- or cat hode-radiation. The chief evidence against the corpuscular theory is from the work of Barkla on polarisation of X-rays which however is considered a much more simple phenomenon than the polarisation of light and one not necessarily calling for a wave-motion explanation. The attempt is made to explain the homogeneous secondary X-radiation of Barkla by a double transformation first of primary X-rays into cathode-rays and secondly the reconversion of the latter into ‘‘ secondary ” X-rays the existence of a oritical speed being assumed which it is necessary for a cathode-ray falling on an atom to possess in order to produce an X-ray.F. S. Typical Cases of Ionisation by X-Rays. CHARLES G. BARKLA (Phil. Mug. 1910 [vi] 20 370-379).-The relative ionisations in air carbon dioxide and ethyl bromide produced by the homogeneous secondary X-rays from twelve elements with atomic weights lying between iron and antimony have been studied. The iron radiation was seventy times more easily absorbed than that from antimony and throughout the whole range of penetrating. power the ionisation in carbon dioxide was proportional to that in air being about 1.4 times greater. Similar results hold for other gases less dense than carbon dioxide For ethyl bromide and air the proportionality held for radiations not more penetrating than the bromine radiation.For more penetrating secondary X-rays the relative ionisation of ethyl bromide rises suddenly to over three times its previous value and then more slowly with increasing penetrating power t o between five and six times. These results are similar t o those previously found for the absorption of the radiations. Similar variations occur in the ionisations in vapours of methyl iodide stannous chloride and selenium chloride a t the particular penetrating power characteristic of iodine tin and selenium while carbon hydrogen and chlorine give no characteristic secondary X-radiation. No anomalous cases of X-ray ionisation have been observed. The penetrating power of the characteristic secondary X-radiation emitted by the constituent elements of the gas determine the way i n which the ionisation depends on the penetrating power of the ionising radiation.F. S. The Accumulation of Helium in Geological Time. IV. ROBERT J. STRUTT (Proc. Roy. Soc. 1910 A 84,194-196. Compare this vol. ii 175).-Several examples of Archean rocks show a higher ratio of helium to radioactive matter than thorianite. The minimum age indicated by the helium ratio for sphenes from Archean rocks is about 700 million years. A sphene from the recent volcanic rocks of the Laacher Sea showed a helium ratio at least two thousand times less. An explanation for the anomalous case of beryl which contains helium out of all proportion to its radioactive content due to Bolfmood is that in the crystallisation of the beryl one of the longer-lived products of disintegration as radium ionium etc.has separated also of which after a few thousands of years nothing would be recognisable but the helium to which it had given rise. F. 8.GENERAL AND PHYSICAL CHEMISTRY ii. 921 The Absorption of Radium Emanation by Cocoanut Charcoal. JOHN SATTERLEY (Phil. Hag. 1910 [vi] 20 778-788). -The first point tested was whether the same fraction of radium emanation whatever the amount may be is absorbed by charcoal when the experimental conditions are the same. For solutions of strengths 3 x and 6 x 10-9 gram of radium but not for stronger solutions proportionality between the emanation retained and the amount of radium present held good justifying the method previously employed (Abstr.1908 ii 918). With a steady source of emanation the fraction absorbed decreases with the length of the experiment as though the charcoal became saturated. The humidity of the air stream made no difference. A constant air stream was sent through two charcoal tubes in series. The ratio of the amount of ernanation absorbed in the second to that in the first rose with the time of experiment. With tubes 8 sq. cm. in cross section containing 30 cm. length of coarsely powdered cocoanut charcoal and an air stream 0.5 litre per minute continued twenty-one hours 62 per cent. of the total emanation is absorbed. For air streams 0.11 0.25 and 0.80 litre per minute the fractions absorbed were respectively 0.86 0.73 and 0.23. F. S The Relation between Uranium and Radium.V. FREDERICK SODDY (Phil. Mug. 1910 [vi] 20 340-342),-The rate of growth of radium in the three uranium solutions which previously had proceeded according to the square of the time (compare this vol. ii lo) has since not been maintained and it has been found that the constant of the electroscope employed has changed the instrument now being about 10% more sensitive than a t first. Previous estimates of the period of the parent of radinm (ionium) are therefore in error the data still only affording the means of calculating the minimum period of the long-lived intermediate substance assuming there is but one and not as proving the production of radium from the uranium The minimum period from present results is 35,000 years and the true period may be much greater.A method of obtaining an upper limit for the period from a study of the intensely active ionium preparations separated from thirty tons of pitchblende by the Austrian Government is given. F. S. The Rays and Products of Uranium-X. 11. FREDERICK SODDY (Phil. Mag. 1910 [vi] 20 342-345).-The preparations of uranium-X previously described (this vol. ii 10) have now been under observation for periods of a year to eighteen months and in none has there been any increase of the initial a-radiation present which is ascribed to an impurity present from the start in the uranium. This is in agreement with the revised estimate for the minimum period of ioniurn (compare preceding abstract) for if this is greater than 35,000 years the detection of the ionium produced from the uranium-X by means of its a-rays would not be possible with the arrangements employed.The proportion of P-rays in the radiation of uranium possessing an apparent value for Hp above 8640 is given as 1/750th Tests to see whether sctiniuru is producad from the uranium-X pre-ii. 922 ABSTRACTS OF CHEMICAL PAPERS. parations have so far given negative results. Actinium is present in all the preparations but it is ascribed to initial impurities in the uranium. F. 5. The Ratio between Uranium and Radium in Minerals F~EDERICK SODDY and RUTH PIRRET (Phil. Nag. 1910 [vi] 20 345-349).-Determinations are given of the ratio of radium to uranium in autunite and thorianite (compare Mlle. Gleditsch Abstr. 1909 ii 714). The ratio for thorianite was found t o be only 3% higher than for Joachimsthal pitchblende while for autunite (of Portuguese origin) it was very low being only 44.5% of that of pitch- blende.The natiiral explanation is that autunite is of such recent formation that the uranium-radium series is not yet in equilibrium. The specific a-activities of the oxides of uranium separated from autuuite pitchblende and thoiianite were practically the same which excludes the possible explanation t h a t the variations in the uranium- radium ratio are due to two successive slow a-changes in uranium itself. F. S. Selective Photo-electric Effect of Potassium Mercury Alloys. ROBERT POHL and P. PRINGSHEIN (Ber. Beut. physikd. Gee. 1910 12 697-710. Compare this vol. ii 379-472).-The photo-electric Fensitiveness of potassium amalgams of varying composition has been investigated.Amalgams containing 2.5 to 17.3 atoms % of potassium do not exhibit the selective effect at X=436 pp which is characteristic of potassium. This selective action is indeed no longer found in the case of either liquid or solid alloys containing as little as 21 atoms % of mercury. For alloys containing from 17 to 70 atoms % of potassium a Selective effect has been found in the neighbourhood of A- 386 pu and for alloys which contain from 5 to 10 atoms % of potassium it is probable that there is a further characteristic photo-electric effect at about A = 31 3 pp. The selective effect at X 386 pp is supposed to be due at any rate in the case of the solid alloy to the compound KHg. H. M. D. The Ionisation Produced by the Splashing of Mercury. J.J. LONSDALE (Phil. Mug. 1910 [vi] 20 464-474).-The ions produced by splashing have been usually examined for volatile liquids and have been found to move with very small velocity. Hence mercury was tried to see if this was due to condensation of vapour on the ions. The results were found to be independent of electrification of the mercury and of its purity but depended on the nature of the splash- plate. Cleaning the plate did not much affect the positive ionisation but reduced the nega- tive. Platinum gave smaller positive and negligible negative mercury negligible positive but larger negative ionisation. The minimum mobility of the ions with iron splash-plate was 0,013 (cm. per volt-cm.) for the positive and 0.004 for the negative.But in the former case the saturation curve showed a second maximum due either to ions of With iron the positive ions were in great excess.GENERAL AND PHYSICAL CHEMISTRY. ii. 923 smaller mobility or to neutral doublets broken up by the action of the field. The latter explanation was favoured by further experiments negative ions in some cases being initially absent but produced in the gas by the application of a field. The negative ions appear to arise altogether from the breaking up oE the doublets. By varying the height of fall of the mercury it was foucd that no slow positive ions and no negative (therefore no doublets) are produced when the height ie below 21.5 cm. The saturation curves when heated aluminium phosphate or lime was used as the source of the ionisation showed similar peculiarities for the positive ions.F. S. Specific Change of the Ions Emitted by Hot Substances. 11. OWEN W. RICHARDSON and E. R. HULBIRT (Phil. icfag. 1910 [vi] 20 545-559. Compare Abstr. 1908 ii 1009).-The ratio of the charge to the mass for the positive ions emitted by heated metals has been determined for platinum palladium gold silver copper nickel iron osmium tantalum tungsten brass “ nichrome,” and steel. From this the mass of the ion in terms of the hydrogen atom as unity is deduced on the assumption that unit charge is carried. A correction reducing the values to 0.62 of the experimental is made because the value for the negative ion from platinum found by the same apparatus and method was wrong to this extent. The general result is to show t h a t the mass of the positive ion From all substances is of the same order the mean value being 23.3.Some of the substances proved difficult on account of irregularities in the ionisation and because the initial value was different from the values after some heating. The suggestion is made that the positive ionisation is due to sodium as a common impurity in all the metals F. S. Positive Electrification due to Eeating AlumiDium Phos- phate. A. E. GARRETT (Phil. Mag. 1910 [iv] 20 573-591).-When aluminium phosphate is heated a t about 1200° large numbers of positive ions are emitted and this phenomenon has been investigated by measuring the conductivity imparted to the surrounding gaseous atmosphere. The emission effect decays with time and the activity of the substance at any moment can be represented by an expression of the form A(e-*it - e - W ) + B(l - e-hst).During the first portion of the period of decay the nature of the surrounding gas and the traces of water present in the active substance have a marked influence on the form of the decay curve. This is no longer evident when the steady state has been reached. For a given temperature the current due to the positive ions has a maximum value for a particular pressure ; this pressure diminishes as the temperature is raised. A t constant pressure the relationsbip between the current and the absolute temperature can be expressed satisfactorily by means of Richardson’s formula. Measurements of the value of elm show that the smallest positive ions which are emitted at the lowest pressures are comparable in size with the hydrogen atom.In consequence OF the high velocity of the ions at low pressure even in the absence of an external field a tubeii. 924 ABSTRACTS OF CHEMICAL PAPERS. containing strongly heated aluminium phosphate can be used as a rectifier for alternating currents Observations are also recorded which seem t o show that aeutral doublets as well as ions are emitted by the heated substance. He M. D. The Electrical Conductivity of Liquid Alloys. KARL BORNEMANN and PAUL 'MULLER (Metallurgis 19 10 '7 396-402).- Very few data exist as to the electrical conductivity of liquid alloys. The experiments described have been made in glass or quartz tubes heated in an oil-bath or an electric furnace according to the tempera- ture required.Iron platinum or carbon electrodes are used auxiliary electrodes being introduced in quartz tubes a t different points for the measurement of the fall of potential. The liquid alloys of sodium and potassium give a conductivity- concentration curve which exactly resembles that typical of a continuous series of solid solutions such as gold and silver. The conductivity of each liquid metal is lowered by the addition of the other and the curve has a well-marked minimum. There is no indication of the compound Na,K the existence of which is shown on the freezing-point curve as a change of direction and it therefore appears that this compound is much dissociated in the molten alloys. On the other hand liquid alloys of lead and tin exhibit a conductivity which varies with the concentration in an almost perfectly linear manner.The curves of temperature-coefficients of the conductivity follow a similar course t o the conductivity curves. Sodium amalgams exhibit a depression of conductivity at both ends of the series rising to an intermediate maximum a t a point corre- sponding with the compound NaHg which probably exists i n the liquid in a largely undissociated condition as evidenced by the very high freezing point of the compound in comparison with those of its components. A similar but less marked maximum is caused in the amalgams of potassium by the compound KHg,. A new criterion for the existence of compounds in solution is thus obtained. Observations on dilute amalgams shorn that the conductivity of mercury is lowered by the addition of either of the alkali metals but the older observations that the conductivity is raised by the addition of other metals are confirmed.The abnormally low temperature- coefficient of mercury (0.001) was attributed by Liebenow to the presence in the liquid of two or more different kinds of molecules giving it the properties of an alloy. I n accordance with this view the addition of the alkali metals which form compounds with mercury and thus increase the number of complex molecules lowers its conductivity whilst the indifferent metals which dissolve in the monatomic form raise it. It is shown that lead which has an even lower temperature-coeEcien t than mercury has its conductivity raised by the addition of metals which do not combine with it such as zinc cadmium antimony and bismuth although the conductivity of bismuth is loss than that of lead.Potassium and sodium have a normal temperature-coefficient (0.004) and their conductivity isGENERAL ANb PHYSICAL CHEMISTRY ii. 925 lowered by the addition of other metals whether fhey form stable compounds or not. Heterogeneous mixtures of liquid metals such as lead and zinc have a conductivity strictly proportional to the concentration whether the liquids are emulsified or in distinct layers The temperature at which the separation of a homogeneous liquid alloy into two layers takes place may be determined more accurately by the conductivity than by the thermal method being indicated by an abrupt change of direction in the conductivity-temperature curve.C. H. D. The Electrical Conductivity and Hardnese of Alloys of Silver and Copper. NIKOLAI S. KURNAKOFP NIKOLAI A. PUSHIN and N. SENKOWSKY (Zeitsch. unorg. C'hem. 1910 68 123-140; J. Rugs. Phys. Chem. soc. 1910 42 733-751).-The electrical conductivity and hardness of the alloys of silver and copper have been re-determined with special precautions. The conductivity falls from that of pure copper until 4 atomic % Ag is reached after which it remains nearly constant until 91 atomic % Ag is reached and then rises rapidly to that of pure silver. The curve for hard-drawn wires closely resembles that for the annealed metals but the conductivity is throughout lower. The curves representing the temperature- coefficient of the conductivity have exactly the same form. The determinations of hardness are best made by means of Brinell's ball test on specimens anneaIed at 650-'700'.The curve obtained is the converse of the conductivity curve and indicates the same limits of concentration of the solid solutions namely 0-4 and 91-100 atomic % Ag. The alloys thus represent the simplest type of a series composed of two solid solutions separated by a gap. C. H. D. Conduction of Electricity Through Solid Silver Chloride. 11. MAX LE BLANC and FRITZ KERSCHBAUM (Zeitsch. Ekktrochem. 1910 16 680-681).-The conductivity of solid silver chloride produced by prolonged treatment with contiiiuous current (this vol. ii 382) is shown t o be due to excessively thin threads of metallic silver. T E. Potential of Iron Calculated from Equilibrium Measure- ments. ARTHUR B.LAMB (J. Amer. Chem. Soc. 191O,El2,1214-1220). -Richards and Behr (Abstr. 1907 ii 222) have found that the true potential of iron is 0.18 volt for the porous form and 0.15 volt for the massive form the calomel electrode being taken as - 0.56 volt whilst other authors have obtained values about 0.1 volt lower. A calculation from existing data has now been made which shows that the poteritial of iron against a molecular normal solution of ferrous ions is 0.192 volt the calomel electrode being taken as -0.564 volt. E. G. Evolution of atas and Capacity of the Lead Accumulator FRANZ STREINTZ (Zcitsch. Elektrochem. 1910 16 747-754).-The quantities of oxygen and hydrogen evolved during the charge of sii. 926 ASSTRACTS OF CBEMICAL PAPERS' small accumulator are compared with those given o@ frbm platinbm electrodes through which the same current passes The differences give the capacities of the plates and these are compared with the capacity of the accumulator when discharged.About 94% of the charge is obtained from the lead plate and about 87% from the lead peroxide plate. It is also shown that the fullycharged platea continue t o absorb a little hydrogen or oxygen if the charging current is con- tinued I n the case of the lead plate this is due to occllusion of hydrogen ; in that of the lead peroxide plate it is due to slow oxidation of the lead framework supporting the peroxide. Chemical Action of the Silent Electrical Discharge. A. MOSER and N ISGARISCREFF (Zeitsch. Elektrocliem.1910,16,6 13-620). -Various gases are submitted to the action of the silent discharge in ordinary ozone-tubes The current and the voltage are measured and also the temperature and premure of the gas in the tube When pure carbon dioxide or a mixture of carbon monoxide and oxygen (2 vols. 1 vol.) is used an equilibrium is attained which depends on the voltage used the temperature and the distance apart of the electrodes. Only traces of ozone are formed and the same equilibrium is attained in presence of chlorine but much more slowly. If excess of carbon monoxide or oxygen is used either the brown solid formed from carbon monoxide alone orozoae is produced. With about 6000 volts at 20' and the electrodes 1-7 mm. apart about 14% of the carbon dioxide is dissociated when equilibrium is attained.This increases with increased voltage and diminishes at higher temperatures and with increased distance apart of the electrodes. The quantity dissociated is from thirty to one hundred times more than would be calculated from Faraday's law but the free energy of the carbon monoxide and oxygen produced is only from 1 *2 to 6*37& of the electrical energy expended in producing t be decomposition The decomposition of hydrogen chloride is very small (about 1% with 14,000 volts). Sulphur dioxide and oxygen combine quantitativeiy to form the trioxide. The yield of sulphur trioxide per kilowatt hour varies from 3.5 to 14.3 grams. A mixture of hydrQgen chloride and oxygen is converted largely (95%) into chlorine and water 10 to 13 grams of chlorine per kilowatt hour being formed T.E. T. E. The Oxygen Electrode. Electromotive Behaviour of the Oxides of Platinum. G. GRUBE (Zeitsch. EZektrochem. 1910 16 621 -632).-The measurements of the potentials of platinum oxide electrodes made by Lorenz (Abstr. 1909 ii 463 640 857) may be too low owing to the lack of conductivity of the oxides and to the fact that in one set of measurements the electrodes were yielding a small current. l h e author has made measurements on electrodes containing several grams of the oxide mixed with graphite and com- pressed in a perforated platinum foil case. The results referred to the hydrogen electrode for ZNesulphuric acid at IS0 are Pt02,4H,0 1-06 volts; Pt0,,2H20 1.04 volts; PtO about 1.5 volts; PtO,GENERAL AND PHYSICAL CHEMISTRY.ii. 92'7 indefinite about 0.9 volt. An electrode containing the trioxide evolves oxygen continuously and its potential falls slowly. An electrode of the dioxide when polarised anodically behaves in the same way as one made of the trioxide. A monoxide electrode when anodically polarised possesses at first a higher potential than the dioxide which falls off steadily. The potential of a platinised platinum electrode after anodic polarisation was followed for two hundred and sixty-two days. It fell quite steadily from 1.5 volts to 1.05 a t which point it remained for eight days then falling to 1.02 volts where it remained without further change. It appeara therefore that potentials from 1.5 volts downwards are due to solid solutions of PtO i u PtO or of PtO in PtO.Since platinum electrodes can be polarieed up to potentials of 2 volts i t appears probable that an unknown tetroxide of platinum may exist. T. E. Anodic Behaviour of Molybdenum Manganese Chromium and Tantalum. HANS KUESSNEB (Zeitsch. Elektrochem. 1910 16 754-772).-A molybdenum anode dissolves quantitatively with the valency 6 i n N-potassium hydroxide. The metal used contained a little iron and traces of carbon and oxide but two different pieces of it behaved differently One of them became passive when the current density exceeded about 0.05 ampere per sq. cm. whereas the other showed no signs of passivity with very much larger current densities. With a manganese anode in neutral solutions (of potassium chloride or sulphate). the metal dissolves and both hydrogen and oxygen are evolved the whole of the metal fiually present in the solution being bivalent.Manganese itself dissolves with evolution of hydrogen but the rate is too slow to account for the quantities of hydrogen observed ; it is therefore thought probable that univalent manganese ions are formed mliich react with the hydrogen ions in the solution thus 2Mn' + 2H' = 2Mn" + H,. From S-lO% of the manganese dissolves in this way. The oxygen is evolved when the potential of the manganese anode is more than 0.3 volt more negative than the normal hydrogen electrode whilst hydroxyl ions could only be discharged directly if it were 1.62 volts more positive ; the oxygen is therefore a secondary product. The potential measurements show further that the dis- solution of manganese accompanied by evolution of oxygen at the anode and of hydrogen at the cathode is a process which takes place of its own accoid; hence the gain of free energy due to the conversion of metallic manganese into ions cannot be less than the loss due to the decomposition of water.Following this out quantitatively it appears that the manganese must dissolve primarily in the form of tervalent ions which then react with hydroxyl ions thus 2Mn'** + 20H' = 2Mn" + H,O + $0,. Increasing the alkalinity of the electrolyte leads to the formation of A chromium anode in solutions of potassium chloride dissolves with At low temperhtures and small manganese ions of higher valency in increasing quantity. diffeient valencies between 2 and 6.ii. 928 ABSTRACTS OF CHEMICAL PAPERS.current densities the valency approaches 6 ; at higher temperatures it falls but the author could not find any set of conditions in which only one kind of ion is formed. This was equally the case in alcoholic solutions of zinc chloride. I n 16N-solutions of potassium hydroxide a tantalum anode is con- verted into the pentoxide the electro-chemical valency being 5. The pent- oxide forms a layer on the anode which permits a small current to pass. Increasing the applied voltage does not increase this current beyond 0-02 to 0.03 ampere per sq. cm. T. E. Migration of Ions in t h e Water Voltameter. PRANZ STREINTZ (Zeitsch. Elektrochern. 19 10,16 744-747).-1n Hofmann’s voltameter in the form commonly used for demonstrating the electrolytic decom- position of water the sulphuric acid in the cathode tube rises whilst that in the anode tube falls.The effect is measurable after one hour’s electrolysis with 1 ampere or more. The author has compared the rise and fall (due t o changes in the density of the acid) in a special apparatus with narrow tubes with those calculated from Hittorf’s measurements of the migration of sulphuric acid and has found a fairly close agreement. The changes of level are however larger than those calculated instead of being smaller owing to partial equalisation of the densities by diffusion. T. E. Electrolysis of the Iodides of the Alkaline Earths Dissolved in Pyridine. GEORG YON HEVESY (Zeitsch. EZektrochem. 1910 16 672-673).-A saturated solution of barium iodide in pyridine con- tains 20.358 grams per litre at 25’.The conductivity per equivalent at 25’ is v= 9.606 A = 8.855 ; v = 18.01 A = 10.723 ; v = 38.59 A = 13.045 ; V = 81.06 A = 15.961. When these solutions were electrolysed with platinum electrodes separated by a porous partition a firmly adherent non-conducting deposit was very soon formed on the cathode. This consisted of barium hydroxide and carbonate and was due to traces of moisture in the solutions. The pyridine was then dried completely by prolonged electrolysis with 11 0 volts but the barium produced by the electro- lysis of the dry solutions reacted with the pyridine itself giving a reddish-brown slime; this was the case even at - 40”. A barium amalgam containing up to 30% of barium may be prepared by electrolysing the dry pyridine solutions with a mercury cathode the current efficiency being about 80%.T. E. Sparking at the Electrodes in the Electrolysis of Molten Salts. AXTON KAILAN (Zeitsch. unorg. Chern. 1910 68 141-159).- When molten chlorides are electrolysed with a carbon anode and an iron cathode the operation is sometimes interrupted by the separation of the mass from the anode the cessation of the evolution of chlorine and a rapid fall of the current strength. It is shown by measurements of the fall of potential when chlorides are electrolysed that the effect is not due to the formation of a subchloride or to the separation of a layer of silica derived from the crucible. The effect is completely inhibited by increase ofGENERAL AND PHYSICAL CHEMISTRY. ii.929 temperature a critical temperature being observed a t 500' in a mixture of equal weights of potassium and lithium chlorides and at about 590° in pure lithium chloride. The addition of lithium bromide hinders the effect. The effect of temperature appears to be connected with the change of viscosity a conclusion which is confirmed by experiments with dilute sulphuric acid to which glycerol has been added. The effect occurs with a platinum anode as well as with carbon. When the effect is present the apparent resistance of the cell falls with increasing potential difference. Experiments with an oscillograph show that the variations in the current are very small provided that the anode dips suEciently far into the electrolyte. There are about 2000 oscillations in a second.A purely mechanical explanation of the phenomenon is suggested. C. H. D. Properties of Salt Solutions in Relation t o the Ionic Theory. I. Mol-numbers Derived from the Freezing-point Lowering. ARTHUR A. NOYES and K. Q. FALK (J. Amer. Chem.d'oc. 1910 32 101 1-1030).-This paper is devoted to a consideration of the lowering of freezing point caused by wids bases and salts and includes a large number of numerical data collated from the best published observations. The symbol i has been employed to represent the factor by which the number of formula weights N associated with 1000 grams of water must be multiplied if the osmotic pressure is to be correctly calculated by the laws of a perfect solution. This has been calculated for several substances in dilute aqueous solution from the simplified equation iN= At/l*858.( 1 + 0-0055At) deduced from Washburn's expression (Tech.Quart. 1908 21 273); At is the lowering of freezing point. The principal table contains the values of the ratio At/N (called the formal freezing-point lowering) for forty- two substances also the weighted mean of several determinations the best value for the ratio and finally the mol-number i in each case for concentrations between 0.005 and 0.5 equivalent per 1000 grams of water. The author utilises the results in the discussion of the relation of the mol-number to the type of salt and its variation with concentration. w 0. w. Elevation of' Boiling Point under Reduced Pressure. KARL DRUCHER (Zeitsch. physikal. Chem. 19 10 74 6 1 2-6 18).-An apparatus for measuring the elevation of the boiling point under reduced pressure similar to that used by Rose-Innes (Trans.1902 81 682) is described and figured. As in Beckmann's most recent form of apparatus electrical heating is used. The apparatus has been tested with benzene chloroform and alcohol as solvents and camphor as solute with satisfactory results. The observed values of the elevation and those calculated by the van't Hoff formula are in excellent agreement for benzene and for alcohol but not for chloroform. The experimental value for the latter at 61' is 39.1 in agreement with recent measurements of Beckmann and of Turner (Trans. 1910 97 1184) whilst the calculated value at the same temperature is 38.3 G. 5. VOL. XCVIII. ii. 63ii. 930 ABSTRACTS OF CHEMICAL PAPERS.Vaporieation in Vacuum. JARCWLAV HLAD~K (Biochem. Zeitsch. 1910 28 29-33).-An apparatus is described for the rapid evapota- tion of solutions under reduced pressure. The vapour is condensed on the inner surface of a cooled bell-shaped vessel which forms the upper part of the vaporising chamber. The condensed liquid collects in a circular trough which communicates with a collecting bottle out side through which communication is made with a pump for exhausting the apparatus. R. AX. D. Binary Solution Equilibria of the Three Isoheric Nitro- anilines. ROBERT KREMANN (with J. GEBA and E. Noss) (MonuteJt. 1910 31 855-859).-The melting-point curve for mixtures of 0- and m-nitroanilines falls from the melting point of each component to a eutectic point at 47" the eutectic composition being 66% of o-nitro- aniline.m- and p-Nitroanilines give a similar curve the eutectic temperature being 86O and eutectic composition 66% of m-nitroaniline. Similar results are obtained with mixtures of 0- and p-nitroanilines the eutectic temperature and composition being 52' and 78% o-nitro- aniline respectively. The irregular curves obtained by Tingle and Rolker for these substances (Abstr. 1908 i 408 974) are due to the fact that small quantities' were used and the melthg points determined by the ordinary method employed in organic chemical practice T. S. P. A Simple Distillation Apparatus. F. VOLLRATH (Chem. Zeit. 1910 .34 1068).-A simple substitute for a condenser is described consisting of a bottle with double-bored cork through one hole of which the tube from the distilling flask enters whilst the other is fitted with a funnel in which a flask filled with cold water rests.C. H. D. Adiabatic Determination of Heats of Solution of Metals in Acids. 11. Heat of Dilution of the Acid Solutions. THEODORE W. RICHARDS ALLEN W. ROWE and LAURIE L. BURGESS (J. Amer. Chem. Soc. 1910 32 1176-1186).-1n an earlier paper (this vol. ii 391) an account was given of a series of determinations of the heat of solution of zinc aluminium magnesium cadmium and iron in an excess of hydrochloric acid a t 20'. I n the course of this work i t was found that the heats of dilution both of the acids and of the residual solutions after the completion of the reactions affect the results to a considerable extent. I n order t o reduce t o the same standard it was therefore necessary to carry out experiments on the heats of dilution and a n account of this work is now presented. The heats of dilution at 2 5 O of the acids HC1,20H20 and HC1,8.808H20 to HC1,200H20 were determined and found t o be 0.556 and 1.330 Cal.(or 2-32 and 5.56 kilojoures) respectively The heats of dilution of the products obtained by dissolving zinc aluminium cadmium and iron in excess of concentrated acid were determined. The substitution of salt for acid was found to affect seriously the heat of dilution especially in the cases of zinc and cadmium. From there data the heats of solution of a gram-atom of the five metals in exactlyGENERAL AND PHYSICAL CHEMISTRY. ii. 931 the theoretical q!iantity of HC1,300H,O have been calculated and are given in 18' Cals.and also in kilojoules zinc 36.6 Cal. or 153.1 kilojoules ; aluminium 127.0 Cal. or 531.0 kilojoules ; magnesium 110.2 Gal. or 460.6 kilojoules; cadmium 17.2 Gal. or 71.9 kilojoules; and iron 20.8 Cal. or 87.0 kilojoules. E. G. Effect of the Glass S u r f a c e in Vapour Density Determina- tions. KARL DRUCKER and Q. ULLMAN (Zeitsch. physikutl. Chem. 1910 '74 567-611).-The densities of the vapours of a number of organic compounds a t varying temperatures and pressures have been in- vestigated by a modification of the Hofmann method under such con- ditions that the influence of the glacs surface could be determined. The glass surface was varied by using different quantities of glass wool in the interior of the density bulb.The method of measurement adopted is described in detail. The corresponding measurements of Ramsay and Steele (Abstr. 1903 ii 635) are affected by a consider- able error owing to inaccurate determination of the temperature of the mercury column in the measuring tube. From the results the percentage values of pv as compared with that for an ideal gas are calculated anda p1o:ted as ordinates against the corresponding pressures as abscisste. The vapours of benzene ethyl ether chloroform and ethyl alcohol are adsorbed to a small extent on the glass surface but the adsorption can be neglected for ordinary measurements. Acetic acid on the other hand is condensed very considerably ; this adsorption is not satisfactorily represented by the ordinary adsorption formula with coefficient less than unity.From the results the complex constant k = [ bimolecular acid] / [unimolecular acid12 has been obtained. A t l l O o 85*L0 and 80.2' the values of k are 0.11 0-25 and 0.60 x 103 respectively. The alteration with temperature is much smaller than that observed by Ramsay and Steele. Ramsay and Young state that the saturated vapour of acetic acid shows a minimum in the density with change of temperature but t h e authors point out that the extrapolation of Ramsay and Young leads to inaccurate values owing to the influence of adsorption and t h a t there is no real abnormality of the nature indicated. The thickness of the layer of acetic acid on the surface of the measuring tube is 0.16-0*60p that of chloroform 0*10-0.20p and t h a t of alcohol only 0*004-0*01 lp.G. S. van Laar's Theory of the Contraction in Water-Alcohol Solutions. A. G. DOROSCHEWSKY and M. S. ROSCHDESTVENSKY ( J . Buss. Phys. Chem. Soc. 1910 42 442-452. Compare van Lsar Abstr. 1900 ii 189).-A theoretical discussion of van Laar's theory of the association of liquid molecules in which the authors conclude that van Laar has given no proof of the fundamental principles under- lying his theory. Using van Laar's formula for mixtures of water with propyl and isopropyl alcohols the contraction of volume of the water which according to van Laar should equal 8-44 at 15 56' is only 4.67 for the former and 4-79 for the latter; on the other hand the contraction with ethyl alcohol at 20' is 8-31 Z. K. 63-2ii. 932 ABSTRACTS OF CHEMICAL PAPERS.Molecular Volumes of Solids H. H. STEPHENSON (C'hem. News 1910 102 178-180 187-189).-Regularity may be traced in the molecular volumes of solids without departing from the atomic volumes of the free elements. Molecular condensation is defined and shown to be equal for anhydrous salts in each group or sub-group of the Periodic Table for each class of compound but tovary with the groups and with the acid radicle. The density aud moleculir volume of any solid compound may therefore be calculatsd if the group condensation is known. The atomic volumes of elements may also be obtained from the density of any of their compounds ; for instance ytterbium has an unknown atomic volume but its oxide Yb,O has a molecular volume of 43 and the condensation of the sesquioxides of its group is 48 which gives Yb= 19.8 showing a density of 8.7.Hydrated salts double salts acid and basic salts are generally additive in molecular volume the value for each molecule of water averaging 14. Formuls are given connecting the densities of hydrated and anhydrous salts. It is also shown that the apparent equality of volume of some series of similar and isomorphous salts is due to the fact that they have undergone equal condensation from approximately equal theoretical volumes. w. P. 8. The Equation of Continuity of the Liquid and Gaseous States of Matter. RICHARD D. KLEEMAN (Phil. Mag. 1910 [vi] 20 665-689) .-A mathematical paper in which the expression deduced previously for the attraction between two molecules is made the starting point for the deduction of equations relating t o the con- tinuity of the liquid and gaseous states of aggregation.Certain of these relationships are examined by reference to experimental data for various organic compounds. H. M. D. Surface Energy and Surface Tension. JAMES E. MILLS and DUNCAN MACRAE (J. Arnes.. Chem. Xoc. 1910 32 1162-11'76).- Whittaker (Abstr. 1908 ii 817) has stated that the surface energy of a liquid in contact with its own rapour at any temperature is proportional to the product of the internal latent heat and the absolute temperature. This relation has now been investigated and found t o be only approximately true. It is shown t h a t the relation suggests a division of the so-called surface energy of a liquid into two parts one due to the liquid surface and the other to the surface of the Tapour over the liquid and this point will be further investigated.E. G. Measurement of Surface Tension by the Method of Maximum Pressure of Small Bubbles. R. MAQINI ( A t t i R. Accad. Lincei 1910 [v] 19 ii 184-l89).-By the adoption of certain improvements in the experimental arrangements the author has succeeded in obtaining by this method (compare Cantor Ann. Php. Chem. 1892 [ii] 47 399 422 ; Feustel Ann. Physik 1905 [iv] 16 61) measurements of the surface tension of benzene nitrobenzene,GENERAL AND PHYSICAL CHEMISTRY. ii. 933 liquid air and water with a degree of exactness comparable with that okkained by Rayleigh's wave method (compare Abstr.; 1907 ii 334). R. V. S. Surface Tension of Aqueous Solutions and Laplace's Constant.WILLIAM C. McC. LEWIS (Zeitsch. physikal. Chem. 1910 '74 619-640).-It has already been shown that whilst inorganic salts increase the surface-tension liquid/vapour they diminish the surface- tension liquid/iiquid. I n this connexion the surface-tension liquid/vapour has been measured by the dropping method for rosaniline hydrochloride Congo-red met hyl-orange methyl-violet sodium glycocholate carb- amide malonic acid and copper sulphate a t 14O 43O 61° and 78". The action of the dissolved substances diminishes gradually as the temper- ature rises but in no case has an inversion been observed. The different effect of inorganic salts in the two cases is discussed and accounted for on the basis of Laplace's theory of internal pressure. Employing instead of the surface-tension G Laplace's capillary factor H where cr= H0p2//2 p being the density it is shown that Ho for water is diminished by the addition of all dissolved substances both at the surface liquidjliquid and a t the surface liquidlvapour.With reference to the specific internal pressure go (where K=Kop2) it is shown that with the exception of those liquids which are completely miscible with water the addition of any dissolved substance to water diminishes the value of KO whereas according to Tammann in the same circumstances K always increases. Conhidering only the surface liquid-vapour it is shown that the changes of the internal pre-sure X and the surface tension Q are always in the same direction This rule does not apply when the solute is volatile or for certain colloidal solutions The considerable diminution of the surface tension produced by certain solutes can be accounted for on the basis of Laplace's theory.G . S. The Physico-chemical Theory of Soap Emulsions. Emulsifl- cation of Hydrocarbon Oils by Aqueous Solutions of Salts of the Fatty Acids. FREDERICK G. DONNAN and H. E. POTTS (Zeitsch. Chem. Ind. Kolloide 1910 '7 208-214).-The influence of the sodium salts of eleven normal fatty acids on the surface tension at the contact surface between wafer and a nearly acid-free hydrocarbon oil has been investigated. The fatty acids used formed a continuous series from acetic to decoic and in addition lauric and myristic acids were examined. All these salts diminish the surface tension and the extent of the diminution increases in general with increasing molecular weight of the acid.The action begins to be considerable in the case of sodium octoate and from this point onwards the influence increases more and more rapidly as the molecular weight increases. In harmony with these observations it is found that the sodium salts of lauric and myristic acids are the only members of the series which give rise to emulsification effects. In these two cases the emulsification capacity increases rapidly with the concentration of the dissolved salt and then decreases rapidly at higher coucentrations. The existence of thisii. 934 ABSTRACTS OF CHEMICAL PAPERS. maximum effect is attributed to the salting-out action of the sodium ions. It is supposed that the changes in surface tension which are obviously connected with the emulsifying power of certain solutions are accompanied by changes in the potential differences at the contact surface.H. M. D. Autosorption (Auto-adsorp tioa). WILLIAM C. McC. LEWIS (Zeitsch. Chem. Ind. Kolloide 19 10 7 197-205).-The views ex- pressed in this paper relating to the nature of the liquid vapour contact surface have been for the most part published previously (compare this vol. ii €329). The term autosorption is introduced in reference to the greater density of the surface layer of a liquid as compared with its bulk density. Whereas autosorption has been found for a nnmber of liquid organic compounds which have been examined there appears to be little difference in the surface and bulk densities in the case of the elements mercury bromine and iodine.For these substances the autosorption is therefore of very small magnitude and this appears to be the case for zinc and cadmium. The surface and bulk densities of water are employed to calculate the difference between the quantity of water actually present in the surface layer of water and that which would be present if capillary forces were eliminated. The value thus obtained is of the order 10-6-10-7 gram per sq. cm. REGINALD 0. HERZOG and GEORG ROSENBERG (Zeitsch. Chem. Ind. Kolloide 1910 7 222-227). -In continuation of previous experiments (Abstr. 1908 ii 262) on the adsorption of substances from aqueous solution by lightly chromed bide powder the authors have made similar measurements with non- chromed powder.Aqueous solutions of sodium picrate silver nitrate crystal-violet- patent-blue new-magenta and phenol were examined. The removal of sodium picrate from aqueous solution takes place in accordance with the simple law of distribution the value of the exponent in the adsorption formula being equal to unity. With chromed hide powder the proportion of adsorbed substance increases somewhat with the concentration of the solution. I n the case of silver nitrate the data agree with the formula K=Bm/C in which C is the quantity of the adsorbed substance and B is the concentration of the residual solution if sn is made equal to 0.5. The adsorption of the three colouring matters is also in accord with the exponential equation but the data for phenol show considerable divergence and this is considered to indicate that the removal of phenol by the hide powder is not due to a simple adsorption process.An empirical formula is given by means of which the data for phenol can be satisfactorily reproduced. In general there is no essential difference in the behaviour of chromed and non-chromed hide powder in regard to their adsorptive proper ties. H. M. D. ZDENKO H. SKRAUP E. KRAUSE and A . VON BIEHLER (Monatsh. 1910 31 753-776).-111 the case of d l organic acids the regularities which have been previously observed H. Bl. D. Changes in Tanning [Processes]. The Capillary Rise of Acids.GENERAL AND PEYSICAL CIIEMISTRY. ii. 935 are confirmed (compare Abstr. 1909 ii 868; this vol. ii 191). The stronger the acid is the more it is absorbed by the filter paper and the less is the capillary rise; the weaker it is tha less is the absorption. ‘Che large capillary rise with acetic acid is much diminished when i t is transformed into trichloroacetic acid ; the same result is true for the pairs of acids succinic and dibromosuccinic ; benzoic and nitrobenzoic.Phosphoric acid has a very small capillary rise and the suggestion has been made that this is due to its polybasicity. I n order to test the validity of this suggestion measurements have been made with benzene-mono- di- and tri-sulphonic acids with different carboxy-acids of benzene including mellitic acid and with oxalic malonic succinic glutaric and tricarballylic acids. It is found that a decrease in the capillary rise does not t-tke place with increase in the basicity of the benzenesulphouic acids; i t doea take place with tho carboxy-acids of benzene but the decrease stops when the value of the capillary rise becomes the same as that for strong acids.In the case of tricarballylic acid the capillary rise is greater than that for malonic succinic or glutaric acids. Arsenic acid is similar t o phosphoric acid in that it has an abnormally low capillary rise. Pyrophosphoric acid in contra- distinction to orthophosphoric acid shows an abnormally high rise whereas metaphosphoric and phosphorous acids give much lower rises the rise with the latter acid approximating to that for relatively strong acids. Hydrofluoric acid gives practically the same result as bydrochloric acid although it is much less dissociated.Using a modification of Holmgren’s circle method the absorptions of sulphurous and hydrocyanic acids and solution of hydrogen sulphide have been investigated Hydrocyanic acid has a higher capillary rise than hydrochloric acid whereds with the other two acids the rises are practically the same as for hydrochloric acid. The present investigation shows that there are undoubted regularities in the case of organic acids but with inorganic acids the number of irregularities has been increased. T. S. P. Osmotic Equilibrium between Two Fluid Phases. L. GAY (Compt. rend. 19 10 151 612-616).-A purely mathematical treat- Relation of Osmotic Pressure to the Intrinsic Presaure of Liquids. M. M. GARTER (J. Physical Chem. 1910 14 651-664. Compare this vol.ii 398).-The intrinsic or internal pressure of a gas in which the molecules exercise no attraction for one another is numerically equal to the extrinsic pressure exercised by the gas on the containing vessel. The intrinsic pressure of a liquid is equal to the extrinsic pressure plus the effect of molecular attractions and has a different value in the surface film where molecular attractions are not wholly balanced. The author assumes that the average molecular energy of trans- lation is the Fame in the gaseous and liquid phases if the molecular ment of the subject. w. 0. w.ii. 936 ABSTRACTS OF CHEMICAL PAPERS. weight (m) is the same since the mean square of the molecular velocity (v) i n either phase represents the absolute temperature. If pi and P are the intrinsic pressures of gas and liquid respectively P = Q(n2rnv2)/2 = $(nimw2)/2 x n2!nl =pi x n,ln where n and n1 are the numbers of molecules per unit volume in liquid and vapour phase respectively.The intrinsic pressure of a liquid is very simply obtained by multiplying the vapour pressure by the ratio of densities of liquid t o vapour. Further it is deduced t h a t PP=pv=BT that is the gas lams hold for liquids if P is interpreted as intrinsic pressure. If P and P be the intrinsic pressures of a solvent and solution respectively P - P2 = pRT/,log,p,/p = the osmotic pressure where p and p 2 are the vapour pressures of solvent and solution respectively. Osmotic pressure is thus defined as the reduction in intrinsic pressure or normal activity of the solvent due t o the introduction of the solute.This reduction is brought about by the reduction of the number of molecules of solvent from N t o ( N - n ) n being the solute molecules. The volume concerned i n osmotic calculations is the volume of the solvent multiplied by N/n whilst the pressure is diminished in the ratio m / N . The intrinsic pressure of water at 0' is 1235 atm. A weight- normal solution contains 1 molecule of solute to 55.6 of solvent and its osmotic pressure is therefore 1235/55 6 = 22.2 atm. If the membrane is not wetted by the liquid a surface film exists which with its unbalanced molecular attractions prevents free circula- tion of the solvent so that no osmosis occurs. The principal part in osmotic phenomena is played by the solvent and some form of association hypothesis is necessary.R. J. C. Methods of Diffusion Experiments. RAPHAEL E. LIESEGANU (Zeitsch. C l ~ m . Ind. Xolloide 1910 7 219-222).-The nature of the precipitation membranes which are- formed when gelatin solutions of silver nitrate and the halogen salts of the alkali metals are juxtaposed is shown to depend on the circumstances in which the diffusion processes take place. H. M. D. Inconstancy of the S o l u b i l i t y P r o d u c t . ARTHUR E. HILL (J. Amer Chem. Xoc. 1910 32 1186-1 193).-Cameron (Abstr.? 1902 ii 75) has found that the solubility of gypsum is increased by addition of sodium chloride up to a certain concentration and t h a t beyond this point the solubility diminishes. Hill and Simmons (Abstr. 1909 ii 647) have observed a similar behaviour when silver sulphate is treated with nitric acid solutions.It is shown that this decrease in total solubility can only be accounted for by assuming that the concentrations of the ions of the solute have diminished and t h a t the value of the Solubility product has accordingly been reduced. The work now described was carried out with the object of gaining further evidence on this point. The solubility of thallous chloride in acetic acid of concentrations between zero and 16N and t h a t of tetramethylammonium iodide in potassium hydroxide of concentrations bet ween zero and 8*3N has been determined at 25'. Measurements of the conductivity of aGENERAL AND PHYSICAL CHEMISTRY. ii. 937 saturated solution of tetramethylammonium iodide and of solutions varying from iV/S to N/1024 have also been made for use in the calculations.The results show that the solubility of thallous chloride and tetramethylammonium iodide is so diminished in presence of the other electrolytes as to prove conclusively that the solubility product is not a constant but that it decreases with increase in the total concentrat'ion of electrolytes present. E. G. Ionisation Relations of Sulphuric Acid. ARTHUR A. NOYES and M. A. STEWART (J. Amsr. Chern. Soc. 1910 32 1133-1162).- Sulphuric acid is usually assumed t o undergo ionisation in aqueous solution according to the equations H,SO = H' + HSO; and HSO,' = H' + SO," but the only investigation yielding valuable evidence as to the proportion of the HS0,- ion present is that of Noyes and Eastman Carnegie h a t .Publications 1907 63 239). The present work was therefore undertaken with the view of obtaining more definite information with regard to the ionisation of this acid. The hydrogen-ion concentration CH can be calculated from the value of the mol. number i as determined from the depression of the f. p. by means of the relation CHIC = i - 1. The values of C=/C at Oo have been thus derived from the recorded f. p. data. It is shown that by combining conductivity and transference data there can be derived maximum and minimum values of the hydrogen- ion concentration in sulphuric acid corresponding with the two limiting cases in which the only negative ion present is SO,- or HS0,- and in this way limiting values of CH~C at 25" and 0" have been calculated.Incidentally it has been found from a study of existing conductivity data a t 0' that the best values for the equivalent conductivity a t 0" of certain ions are AK = 40.3 Acl= 41.1 As0 = 42.8 and A ~ = 2 2 4 . The value of AH SO^ a t 2 5 O and 0" can be approximately calculated from the transference and conductivity data if it is true that the HS0,- ion is present in the sulphuric acid solution in considerable quantity so that its conductivity may enter as a factor. The values obtained are 35-40 a t 25' which are nearly half of that of Aso4 namely 79 at 25". The values of CHIC have also been calculated from a consideration of the relative effects of sulphuric and hydrochloric acids on the hydrolysis of sucrose a t 25" as determined by Ostwald (Abstr.1885 882) and on that of ethyl acetate as determined by Kay (Proc. Roy. Soc. Edin. 1898 22 493). A new isohydric method of determining the hydrogen-ion concen- tration is described which consists in determining the relative concentrations of hydrochloric and sulphuric acids which drive back the ionisation of picric acid to the same extent. The values of CHIC a t various concentrations a t 0' and 25' obtained by these different methods are tabulated. I n order to derive the concentrations of the HSO,' and SO," ions from the values of the hydrogen-ion concentration Noyes and Eastman (Zoc. cit.) assumed that under corresponding conditions the first hydrogen of sulphuric acid is dissociated to an equal extent to that of hydrochloric acid andii. 038 ABSTRACTS OF CHEMICAL PAPERS.hence estimated the concentration of t h e non-ionised sulphuric acid. From this concentration and that of the hydrogen ion the concentra- tions of the SO and HYO io'ns were obtained by subtraction. Similnr cdculations have noq been made and the results shorn that both the SO and HSO ions are present in large proportions at medium concentrations that the latter is present in much larger quantity at 0.05 formal and the former at 0.005 forma1,and that at 0-05 formal the ratio CHSO$CSO increases greatly between Oo and 25". The hydrogen-ion concentration decreases markedly within the same range of temperature. Experiments have been made on the distribution of sulphuric acid between water and amyl alcohol. The ratio of the concentration of the acid in the alcohol to that in the water was found to increase as the proportion of non-ionised su!phuric acid in the aqueous solution increased.The rate of this increase is somewhat smaller even than in the case of hydrochloric acid indicating that the non-ionised sulphuric acid is formed from two ions H' and HSO,' instead of from three ions H' H' and SO,". Determinations have been made of the transference of Na H and SO during the electrolysis of sodium hydrogen sulphate a t 25'. The conductivity of this salt has also been measured at various concentm- tions at 254 By combining these data the concentrations of Na and H ions in a 0.1 formal solution have been calculated and the values Cxa/C = 0.68 and CHIC = 0.44 obtained. From the results obtained by Kay (Zoc.cit.) on the catalysis of ethyl acetate by 0.1 formal sodium hydrogen sulphate the value of CHIC has been derived and found to be 0.416. By means of the values of CHIC and CH/CN~ derived from the transference and conductivity data the concentrations of the other ions in a 0.1 formal solution of sodium hydrogen sulphate have been computed and found to be C~soJC=0*44 and CSO,/C=O*~~ respect ivel J . From these data and also from the corresponding data for 0.05 formal sulphuric acid the values of the product CHCSO~/CHSO~ the ionisation constant of the second hydrogen of the acid have been found to be 0.034 and 0 031 respectively. E. G . Hydrolysis of Cyanogen. R. NAUMANN (Zeitech. Elektrochem. 19 10 16 772-778).-The conductivity of potassium cyanate solutions is measured ; the mobility of the cyanate ion at 18" is 56.5.When cyanngen is passed into aqueous solutions of potassium hydroxide the conductivity diminishes to a constant value. The observed conductivity agrees well with that calculated on the assumption that cyanide and cyanate are the only products. The conductivity of solutions of cyaoic acid tit 0' is measured and the dissociation constant found to be about 120 x When cyanogen is passed through water a t O" the conductivity increases to a constant value owing to the formation of cyanic acid (the hydrocyanic acid is practically a non-conductor) ; the saturated solution contains 0.22 1 gram-molecule of cyanogen and 0*00005 gram-molecule of cyanic acid per litre so that 0.023% of the cyanogen is hydrolysed. At the ordinary temperature the conductivityGENERAL AND PHYSICAL CHEMISTRY ii. 939 OE water through which cyanogen is passing depends very much on the rate of the current of gas and it diminishes rapidly when the gas is stopped.This is due to the decomposition of the cyanic acid into ammonia and carbon dioxide. Cganogen has therefore no definite solubility in water at 1 8 O the quantity absorbed increasing continuously with the time of contact. I n the calculation of the dissociation constant o€ hydrocyanic acid (this vol. ii 386) a serious error was made the correct value is log,,K= - 29.13 instead of - 10.14. This new value is not in harmony with the view that the E.M.F. of the hydrogen-cyanogen element is due t o the formation of hydrncyanic acid. Electrochemis try of Proteins.11. Dissociation of Basic Caseinogenates of the Alkaline Earths. T. BRAILSFORD ROBERTSON (J. PhysicaZ Chem. 1910 14 601-611. Compare this vol. ii 679).-It is probable Eince the neutral and basic caseinogenates of the alkalis obey Ostwald's dilution law that a molecule of caseinogenate gives only two ions. The cation is eupposod to be a complex ion containing the metal in a non-dissociable form. 06 this hypothesis basic calcium strontium and barium caseinogenates instead of disso- ciation into three ions one of which mould be the metal should give only two complex ions and the dissociation should obey Ostwald's law. gram -equivalents of calcium strontium and barium hydroxido ; they were practically neutral to phenolphthalein. The conductivity-dilution curve is in accord with Ostwald's law for a binary electrolyte.If vl. and v2 are the ionic velocities and p the number of molecules of caseinogenate formed from one molecule of base the values of p(wl + v2) are about twice as great for the caseinogenates of the alkalis as for the alkaline earths As all the ions concerned are supposed to be complex protWu ions,:(v,+v,) must be much the Bame in all the salts. Hence p may be taken as two for the alkalis and one f o r the alkaline earths The simplest formula of sodium caseinogenate is [NaX" + X(OH)A] and of calcium caseinogenate each ion having twice as many cbarges as there are molecules of base per molecule of caseinogen. The values of (q + w2) are about 40 x 10-6 at 30'. This is approxi- mately the value calculated by Bredig as the minimum which ionic mobility approaches when the ions become very large. The caseino- genates of the alkalis are nearly completely dissociated whilst calcium caseinogenate is only 57% dissociated.The freezing-point determinations of .Robertson and Burnet t (Abstr. 1909 i 447) are explainable on the hypothesis that caseinogenate ions are quadrivalent so that the sodium salt is written T. E. The solutions examined contained 1 gram of caseinogen to 80 x [ca(x.),+(X(OH):},] [Na,X"" +X(OH)t']. This formula suggests that two C0,H groups of the caseinogen molecule are active in the neutralisation of bases. Influence of the Degree of Dispersity of a Solid Crystal on its Melting Point. P. P. VON WEIMARN (Zeitsch. Chern. Ind. KoUoide 1910 7 205-208).-A theoretical paper in which the author analyses R.J. C.ii. 940 ABSTRACTS OF CHEMICAL PAPERS. the relationships involved in the transition from the liquid to the amorphous and crystalline solid states of aggregation. H. M. D. A General Theory for Obtaining Disperse Systems by the Dispersion Method. P. P. VON WEIMARN (J. Russ. Phys. Chem. Xoc. 1910 42 453-474. Compare Abstr 1909 ii 132 221 306 606 646).-A more detailed theoretical discussion of matter already published and n classification of the methods of peptisation. A11 the dispersion methods of obtaining disperse systems can be explained according to one general theory the fundamental general principle of which can be formulated thus If for some reason or other the intensity of the forces of solution a t the surface of disperse particles increases to an extent not greater than that a t which the velocity of recrystallisation becomes considerable then the disperse particles are peptisised by the dispersion medium.For an explanation of the theory the paper itself must be consulted. Z. K. Colloidal Chemistry. A General Introduction. P. P. VON WEIMARN (J. Russ. Phys. Chem. Xoc. 1’310 42 476-480).-A short historical and theoretical introduction to the two following papers. A good general method of obtaining any solid substance in the state of an amorphous solid solution of any degree of dispersion has been devised and is based on the rapid cooling of a dilute liquid solution of a substance in a dispersion medium which in the pure state itself solidifies to a glass when rapidly cooled.The best method of obtaining liquid colloidal solutions is based on the rapid condensation of the molecules of the dissolved siib&ance when the solvent is replaced by a dispersion medium which dissolves the solvent but practically does not dis*olve the dissolved substance. If a concentrated solution is added to such a dihpersion medium fine disperse precipitates are obtained but not colloidal iolutione. z. K. A Simple General Method for Obtaining Solid Colloidal Solutions of any Degree of Dispersion. P. P. YON WEIMARN and J. 13. KAGAN (J. Russ. Phys. Chern. Soc. 1910 42 480-484. Com- pare preceding abstract).-When a transparent solid solution is heated gradually the viscobity of the dispersion medium decreases whilst the velocity of the molecules and molecular aggregates and the coefficient of diffusion increases ; consequently at first when L in the formula JV=K.(Q-L)/L (J.Russ. Phys. Chem. Soc. 1910 42 214-228) has not yet increased appreciably the condensation process occurs and a bluish-violet opalescence appears which becomes more and more marked until the solution becomes turbid. When L has increased sufficiently the dispersion process commences which is indicated by a diminution in the turbidity of the solution and by a gradual re- appearance of the bluish-violet opalescence which then gradually disappears. When a 0.04% solution of sulphur in alcohol is immersed in liquid air a solid strongly opalescent but partially transparent suspended solution is obtained which when heated and well shaken only sbowsGENERAL AND PHYSICAL CHEMISTRY. ii.941 the second the dispersion process described above. With a 0.02% solution of sulphur a wholly transparent solid solution is obtained which behaves entirely in accordance with the above theoretical scheme. The solution can be fixed o r arrested at any stage of opges- cence or a t any degree of dispersion by rapidly immersing .the tube containing the solution at the given stage in liquid air. By employing very dilute solution of sulphur molecular disperse solid solutions are obtained in which when heated the condensation process is so rapidly followed by the dispersion process that opalescence can sometimes scarcely. be observed. Exactly similar results were obtained with phosphorus sodium bromide and sodium and potassium chlorides.A 0.25% solution of phosphorus in alcohol gives a turbid glass; 0.05 -0.04% solution yields a partly trawparent suspeuded solid solution whilst 0.025% gives a wholly transparent suspended solid so!u tion. Z . K. A Simple Method of Obtaining Sulphur Selenium Tellurium and Phosphorus in a Colloidal State. P. P. VON M’ETTUIARN and B. V. MALJISHEFF (J. Kuss. Phys. Chem. Soc. 1910,42 484-487. Compare two preceding abstracts).-Five t o twenty-five C.C. of a solution of the metal saturated at the ordinary temperature or at the boiling point of the solvent (alcohol for sulphur and phosphorus carbon disulphide for selenium) are rapidiy added to 1000 C.C. of the dispersion medium and stirred vigorously. The dispersion medium for sulphur and phosphorus was cold water ; €or selenium cold ether.The concentrations of these suspended solutions varied within the limits of several l/lO,OOO’s t o several 1/1OO’h% the solutions in the latter case being very turbid and rapidly coagulating. The solid solutions are coloured opalescent and fairly stable the stability of the plrosphorus and selenium solutions depending on the peptisation processes. This method of obtaining colloidal solutions is recommended for lecture experiments The probable solubility of selenium in carbon disulphide is 0*02-0.015 gram in 100 of solvent. Colloidal tellurium is obtained by adding 0.1 of the element to 5 C.C. of a boiling solution of pstassiurn hydroxide saturated a t the ordinary temperature and adding the solution of the metal thus formed to 1000 C.C.of cold water the mixture being stirred vigorously. The stability of the colloidal tellurium solution depends directly on the peptieation processes and can be greatly increased. The solution can also be made more stable by the addition of gelatin or similar substances. Z. K. Phenomena of the Colloidal State. PAUL ROHLAND (Biochem. Zeitsch. 1910 28 53-55).-0bservations relating to the behaviour of adsorbed substances are referred to as showing that substances in the colloidal condition are frequently much less reactive than they are in the crystalloidal form. The viscosity of colloidal substances is very often increased or decreased by special types of ions. H M. D.ii. 942 ABSTRACTS OF CHEMICAL PAPERS. The Purification of Colloids by Dialysis.RICHARD ZSIGBIONDY and R. HEYER (Zeitwh. alzorg. Chern. 1910 68 169-187).-A com- parison of parchment collodion and fish-bladder membranes in the didpsis of colloidal silica shows t h a t the last-named acts most rapidly. Collodion membranes which are perfectly impervious to colloidal silver allow silica to pass with considerable ease. Continuous renewal of the water in the outer vessel has no advantage over a renewal every two bours. With a suitable membrane the chlorine is reduced t o the limit of recognition by means of silver nitrate in about twenty hours. An improved dialyser is described in which a membrane is stretched over a vulcanite ring placed on a vulcanite tray with edges only 4 mm. high and provided with radial ribs. The water enters at the centre of this tray and travels radially in a thin sheet escaping at the cir- cumference. In order t o estimate chlorine in colloidal solutions of silica the free hydrochloric acid is first estimated by titration with X/lOO-sodium hydroxide. Another quantity is then exactly neutralised with sodium hydroxide a drop of 5% potassium chromate solution is added and the chlorine is titrated with N/lOO-silver nitrate.A standard solution may be used for comparison. Under these conditions 0.01 C.C. of N/lOO-silver nitrate run in from a graduated capillary pipette pro- duces a distinct change of colour and it is possible t o detect 0.004 mg. of chlorine in 1 C.C. of the dialyaed liquid. The dialysis however proceeds beyond this limit. and i t is necessary t o employ Jordis’ method (this vol.ii 416) of distillation with sulphuric acid. The residue ob- tained after neutralising 100 C.C. and evaporating to dryness is trans- ferred to a small distilling flask 0.5 to 1 C.C. of concentrated sulpburic acid is added after closing the apparatus and the distillation is con- tinued until nearly all the sulphuric acid has passed over. The chlorine in the absorbing liquid is estimated by Richards’ nephelo- metric method (Abstr. 1904 ii 287) by means of silver nitrate. The precipitation of silver chloride is not hindered by the presence of colloidal silica unless the latter is in very large excess. If some sulphuric acid is present the precipitation is in all cases normal. Sodium sulphate is much less readily removed from silica by dialysis than chlorides.Alumina and iron derived from the sodium silicate used are not eliminated. Minute quantities of hydrochloric acid increase the stability of the colloid sodium hydroxide at first diminishes it but subsequent additions increase the stability. This appliance allows of rapid dialysis. C. H. D. The Binary System Pyridine-Potassium Thiocyanate. KARL L. WAGNER and ERKST ZERNER (Xonatsh. 1910 31 833-841).-The course of the fusion and solubility curves of two substances between the meking and eutectic points has been thoroughly studied only for the case that the mutual solubilities of the two substances decrease with falling temperature. The temperature-concentration diagram for fusions containing the two substances is then the ordinary curve with two branches neither of which shows a minimum and one eutectic point.When the solubility of one substance in the other passes throughGENERAL AND PHYSICAL CHEMISTRY ii. 943 a minimum there are four cases which are theoretically possible and for which the authors give the curves. One of these is where t h e two branches of the fusion curve intersect below the minimum in an eutectic point. The system pyridine-potassium thiocyanate partly conforms t o this type differing from i t in that between the eutectic point and the melting point of the potassium thiocyanate there is a four-phase invariant system namely liquid pyridine-liquid potassium thiocyana te-solid potassium thiocyanate-vapour. The mutual s o h bil i t y of the two liquid phases increases as the temperature falls.The various points on the curves were obtained by heating together weighed quantities of pyridine and potassium thiocyanate in sealed tubes and observing the temperature at which the crystals disappear or are deposited. The eutectic temperature is approximately - 43.3' the mixture containing 3.1% of potassium thiocyanate. The four-phase system is formed at 188.5'. Potassium thiocyanate has m. p. 173.8'. Influence of Substitution in the Components on the Equilibrium in Binary Solutions. IV. Phenol and the Methylcarbamides. ROBERT KREMANN [with J. DAIMER F. GUQL and H. LIEB] (Molzatsh. 1910 31 843-853. Compare Abstr. 1907 i 912).-The melting-point curve for mixtures of phenol and as-dimethylcarbamide falls from the melting point of the dimethylcarbamide to a break a t 25-25*5O and then to a eutectic point at go representing mixtures containing 63% and 84% of phenol respectively. The break a t 25' is due to the separation of the compound formed from one molecule of each of the components the composition of the compound being determined by measuring the times OF arrest for mixtures varying in composition from 0-63% phenol.l'he eutectic is a mixture of this compound with phenol The curve obtained for mixtures of phenol and mooomethyl- carbamide is similar in character the break occurring at 8' and the eutectic at - 7" representing mixtures containing 60% and 77% of phenol respectively. The break at 8' is again due to the separation of a compound containing one molecule of each of the components. The curve for mixtures of phenol and s-dimethylcarbamide is the ordinary one for a two-component system giving one compound and two eutectics.The compound is formed from two molecules of phenol and one molecule of dimethylcarbamide and has m. p. 14'. The eutectic temperatures are + 5' and - 3 O representing mixtures containing 81% and 47% of phenol respectively. The above results support the statement that asymmetric substitu- tution diminishes the power to form compounds whereas symmetrical substitution does not have this effect (compare Abstr. 1906 ii 268). T. 5. P. T. S. P. Equilibrium between Solid Cuprous Iodide and Aqueous Solutions Containing Cupric Salt and Iodine. WILLIAM 0. BRAY and G. M. J. NACKAY (J. Amer. Cl~rn. Soc. 191 0,32 1207-1214).- The results described in this paper are the outcome of a study of t h e law of the mass-action in dilute aqueous solutions.ii.944 ABSTRACTS OF CHEMICAL PAPERS. Cuprous iodide is only slightly solu'ble ir water but in the presence of iodine a considerable amount dissolves owing to the formation of cupric iodide and tri-iodide. The following equilibria are involved CuI(so1id) + 41,- Cu" + 21' and I,'= I + 1'. Values have been determined a t 25' under widely different conditions for the former equilibrium. The ionic concentrations in the various mixtures were calculated by means of the relations derived from conductivity measurements. The values obtained for the equilibrium function K' = ( Cu")(1')2/124 shorn that this equilibrium conforms with the law of mass-action only as far as the influence of iodine is concerned and deviates from it when cupric salt iodide or other salt is added.In all cases however the deviations are of such a nature that K' inereases with increasing concentration. This result is an illustration of the rule that when the concentration of an ion is based on conductivity mehsurements the ratio of its '' activity " (Lewk Abstr. 1908 ii 16) t o its concentration decreases somewhat with increasing ion concentration. From this rule it follows that the solubility product of a salt will not be constant but will increase with increasing ion concentration. Values have also been calculated for the equilibrium function R= (1')(I2)/(&'). The results confirm the conclusion (this vol. ii 820) that K decreases with increasing concentration of iodide but that other aalts do not produce a similar effect. Conductivity determinations made with several of the equilibrium solutions have shown that cupric iodide and tri-iodide are ionised to the same extent as magnesium chloride and that cupric nitrate is ionised to a somewhat smaller extent.E. G. Equilibria in the Precipitation of Metals by Hydrogen Sulphide. LUDWIK BRUNER and J. ZAWADSKI (Bull. Acad. Sci. Cracow 1909 267-31 2).-The precipitation of thallium sulphide by hydrogen sulphide is a reversible reaction. Measurements in solutions of different acid and hydrogen sulphide concentrations show that at 2 5 O K= [Tl']2[H,S]/[H*]2 = 0.63'7. The equilibrium has also been approached from the other side by adding thallium sulphide t o sulphuric acid and passing hydrogen sulphide.Measurements a t 0' and 40" lead to values for the equilibrium constant from which a value for the heat of precipitation of thallium sulphide is obtained by van't Hoff's equation in agreement with that derived from thermochemical data. The values of K obtained for the precipitation of ferrous sulphide vary owing t o experimental difficulties but lie betweeu 2.7 x lo3 and 9.1 x 103. Calculations are made of the solubility products of iron cadiuium and lead and the results of previous observers for these and other sulphides are discussed and criticised. It is shown that the publiahed values for the solubility of sulphides in pure water calculated from the electrical conductivity are not in accordance with the analytical behaviour of the metals.The results from thallium sulphide are employed to calculate the electrolytic potential of sulphur. The experiments with lead sulphide lead to a result in close agreement with this. From the potential thneGENERAL AND PHYSICAL CHEMISTRY. ii. 945 obtained the solubility products of the sulphides are calculated by means of Bodlander’s formula and values are obtained in good agree- ment with the experimental results with a few exceptions. The observed solubilities are then used to calculate the heat of formation of the sulphides in good agreement with Thomsen’s results. C. H. D. Equilibria in the Preaipitation of Metals by Hydrogenl Sulphlde. LUDWIK BBUNER and J. ZAWADSKI (Zeitcrch. anorg. Chem. 1910 6’7 454-455).-0wing to differences in the methods of expressing concentrations in the data from different sources there are certain numerical errors in the authors’ calculations (see preceding abstract).The corrected value for the potential of sulphur against the hydrogen electrode is Eh= +0*545. Employing this value to calculate the solubility constants and adopting more recent values for the electrolytic potentials of iron and silver the agreement between the calculated and observed values is improved. The imperfect agree- ment in the case of zinc is attributed to the known transformation of PZnS into the less soluble aZnS. C. H. D Equilibria in the Action of Potassium Hydroxide on Mercuric Bromide a n d Chloride. WALTER HERZ (Zeitsch. anorg. Chem. 1910 68 165-168).-In the reaction HgBr + 2EOH ~2 HgO + 2KBr c H,O the constant [HgBr2][KOH)2/[KBr]2 is found to have the average value 10.1 x 10-4.Basic salts are however also formed. The reaction of potassium bromide with an excess of mercuric oxide (Bersch Abstr. 1891 1413; Bugarszky Abstr. 1893 ii 450 566) gives a constant 15 x The precipitation of mercuric chloride by an excess of potassium hydroxide has also been measured in two concentrations. C. H. D. Kinetics of the Formation of Ethyl Ether from Alcohol and Ethyl Hydrogen Sulphate. ROBERT KREMANN (Mowtsh. 19 10 31 671-685).-The rate at which the reaction between ethyl alcohol and ethyl hydrogen sulphate proceeds at loo’ 125O and 135’ has been deter- mined by measuring the increase in acidity during the course of the reaction. The increase in acidity is not a direct measure of the extent to which the reaction has taken place since the sulphuric acid formed enters into reaction with the alcohol to re-form ethyl hydrogen sulphate according to the equilibrium reaction EtOH + H2S045EtS0,H + H,O.At the temperature of experiment this equilibrium adjusts itself prac- tically instantaneously and since the equilibrium constant has been previously determined (this vol. ii 700) the correction to be applied to the observed increase in acidity in order to obtain a correct measure of the velocity of reaction can be determined. The alcohol was always in large excess and the reaction is assumed to be bimolecular a number of simplifications having to be made in order to reduce the differential equation to a form in which it can be readily integrated.The values obtained for the velocity constant are not even approximately constant but decrease very considerably during the XCVIII. VOL. ii 64ii. 946 ABSTRACTS OF CHEMlCAL PAPERH. course of the reaction the rate of decrease being the greater the greater the initial concentration of the ethyl hydrogen sulphate. This is probably due to the retarding effect of the water formed by the action of the alcohol on the sulphuric acid. A comparison of the times necessary for the reaction to proceed to the same extent at different temperatures gives a temperature quotient of 2.5 for 10'. The ordinary method for making etber is discussed in the light of the results obtained. T. S. P. The Mechanical Vibration of Atoms. WILLIAM SUTHERLAND (Phil. Mug.1910 [vi] 20 657-660).-0n the assumption that the atoms of an element may be replaced by cubes of uniform density having the same mass as the atoms and just large euough to circumscribe them the author calculates the wave-lengths corresponding with the fundamental mechanical vibrations of the atoms of the alkali metals and the halogens. It is shown that the wave-lengths corresponding with the vibration of the molecules of the alkali halogen salts are probably represented by the sums of the wave-lengths of the constituent elements. When the computed wave-lengths for sodium chloride potassium chloride bromide and iodide are compared with the lengths of the longest infra-red waves examined by Rubens and Hollnagel in the case of these four substances it is found that a nearly constant ratio of eight is obtained.According to this the calcu- lated mechanical period of vibration is only three octaves below the lowest period experimentally investigated in each of these four cases. H. M. D. New Proof of the Existence of Molecules. THE SVEDBEHG and NILS PIHLBLAD (Zeitsch. physikal. Chem. 19 10 '74,5 1 3-536. Compare Abstr. 1909 ii 277 561 723).-The relationship between the absorp- tion in a colloidal solution and the size of the particles has been further investigated. Some of the measurements were made with a Vierord t spectrophotometer and a light source giving a continuous spectrum but the later and more accurate measurements were made with a Eonig-Martens spectrophotometer with liomogeneous light. The results are expressed in terms of k =- 1 log 1 0 - or kTn= k/mol.cllog 1 per litre where I and I represent the inte.nsities of the light before and after traversing the absorbing layer and d is the thickness of the absorbing layer in cm. A series of solutions of colloidal gold containing particles of different magnitude have been prepared and it is shown that the wave-length for maximum absorption diminishes progressively as the size of the particles diminishes whilst the maximum value of km increases a t first attains a maximum and finally diminishes with progreesive diminu- tion in the size OF the particles. When a solution of phosphorus in ether is added to a solution of chlorauric acid HAuCl (the absorption maximum of which is in the ultra-violet) the absorption spectrum is at first displaced a little towards the ultra-violet and then a slow continuous displacement towards the visible spectrum occurs. TheCfBNERhL AND PHYSICAL CHEMISTRY. ii. 947 chaiige from gold solutions n4t.h a known degree of dispersion (size of particle) and absorption in the visible region to chlorauric acid (with molecular dispersion and maximuni absorption in the ultra-violet) is continuous. Examination of solutions of colloidal and dissolved selenium confirms the above results ; in this case the maximum absorption of the molecular solution (in carbon disulphide) lies in the visible region. Some observations with indigotin solutions are also described. A relationship has been found between the absorption exerted by each particle and the degree of dispersion. G. S. Berzelius’ Error as to the Discoverer of the Law of MAX SPETER (J. pr. Chem. 1910 [ii] 397-408). Neutralisation. -Historical. c. s. A Simplified and Improved Form of Toepler’s Mercury Air- Pump. ANDREAS VON ANTROPOFF (Chem. Zed. 1910 34 979).-The throwing up of mercury in the Toepier pump is avoided in this form by placing the cylindrical vessel in an inclined position. The vessel need not have a capacity of more than 100 C.C. It is drawn out into a conical form a t its upper end at the junction with the capillary. The pump may be worked rapidly without injury and is very simple in construction C. H. D. New Modiflcation of the Hipp Gas Generator. F. ALEX. MCDERMOTT (J. Ind. and Eng. Chem. 1909 1 811-812).-The paper contains a sketch and description of a modification of the Kipp gas generator in which the base is made cylindrical with a dome-shaped top and in two portions which fit together with a ground joint; an indentation encircles t h e inside of the cylinder at a convenient distance from the bottom and carries a perforated porcelain or lead tray to carry the active material ; it has a hole in the centre through which the &ern of the acid reservoir passes in the usual manner. The advantages claimed for this apparatus are (1) accessibility of all parts for cleaning and recharging; (2) stability as it is not so tall as the usual forms ; (3) an even distribution of the active material over a relatively large area. F. 11. G. M. Weighing. OTTO KUHN (Chem. Zeit. 1910 34 1097-1098 1108-1 109).-Neglect to reduce the weighings of crucibles and other chemical apparatus to the weight in a vacuum may cause a n error of several tenths of a milligram if the atmospheric conditions vary between two weighings. The correction should therefore be made in analytical work. Double weighing should be employed in order to eliminate errors due to unequal expansion of the arms of t h e balance. C. H. D. 64-2

ISSN:0368-1769    

DOI:10.1039/CA9109805913

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ii. 948 ABSTRACTS 08’ CEEMICAL PAPERS Inorganic Chemistry. The Molecular Weight of Water in Different Solvents. GIUSEPPE BRUNI and M. AMADORI (Gaxxetta 1910 40 ii 1-8).- Water is not sufficiently soluble in any bydrocarbon to permit of cryoscopic measurements but a number of other solvents which might be expected to cause association have been examined. In each case the degree of association increases with the concentration being very near to 1 in dilute solutions in brornoform ethylene bromide dimethyl- aniline p-toluidine methyl oxalate methyl succinate and veratrole. Alcohol phenol and acetic acid are associated in the same solventP ethylene bromide having the greatest effect and methyl succinate the least. Alcohol and phenol like water form single molecules in dilute solution but acetic acid is associated even in very dilute solution in ethylene bromide.C. H. D. Direct Synthesis of Volatile Hydrogen Compounds. ALEX- phosphorus arsenic antimony and sulphur be transformed into their hydrides by heating with sodium formate but also other elements especially those which are volatile and various compounds The less volatile a substance is the more difficult it is to reduce it. If a compound is made up of two volatile components both are reduced giving the two hydrides; this is the case with the sulphides of phosphorus arsenic and antimony and the phosphides of arkenic and antimony. If only one component is volatile that alone is hydro- genised ; for example the phosphides sulphidee arsenides antimon- ides selenides and tellurides of the metals.A large number of chloro- bromo- iodo- and A uoro-derivatives especially those of the heavy metals give the corresponding halogen hydrides. Nitrides of the metals give ammonia. Silicides borides and carbides are not reducible. Selenium and tellurium form the hydrides when heated with sodium formate t o 400’; the yield is limited owing to the reverse reaction (decomposition) which takes place. Hydrogen silicide is formed to a slight extent when an equimolecular mixture of amorphous silicon and sodium formate is heated at 1300O. The reaction takes place more readily when the silicon is dissolved in aluminium (3 parts of silicon t o 60 of aluminium) and the temperature kept at 750’. Hydrogen boride is formed when the silicon is ieplaced by amorphous boron (1 part of boron to 25 parts of aluminium); it also results when a mixture of boron with sodium forinate is heated in the electric arc.ANDER CH. VOURNASOS (Bel.. 1910 43 2672-22’74).-Not Only C a l l T. S. P. Some Analogiea between Derivatives of Oxygen and Axam0 ANGELI (Atti R. Accad. Limei 1910 Lv] 19 Compare this vol. ii 814).-The author amplifies and Nitrogen. ii 94-101.INORGANIC CHEMISTRY ii 949 extwds the views put forward in the former paper as t o the analogy displayed in many of their reactions between hydrogen peroxide hydroxylamine hydrazine et c. R. V. S. Decomposition of Ozone by Ultra-violet Light EVA VON BAHR (Ann. Physik 1910 [iv] 33 598-606).-When ultra-violet light from a quartz-mercury lamp is allowed to fall on ozonised oxygen the ozone is decomposed. The rate of decomposition increases rapidly as the pressure on the gas is reduced. For a given intensity of the incident ultra-violet radiation the ozone disappears at a rate which agrees with the requirements of the equation for a unimolecular change if the pressure is kept constant.The velocity constant is nearly independent of the pressure when this exceeds 200 mm. of mercury but for lower pressures the constant increases rapidly as the pressure falls. I n consequence of the decomposing action of ultra-violet light the measurement of the absorption of ultra-violet radiation cannot be applied to the estimation of ozone at low temperatures. H. M. D. Ozone. V. The Development of Heat in the Decomposition of Ozone. ANTON KAILAN and STEPHAN JAHN (Zeitsch.anorg. Chem. 1910 68 243-250. Compare Abstr. 1909 ii 37).-The oxygen containing 10% of ozone is led through a decomposition tube contain- ing soda-lime enclosed in a vacuum vessel as calorimeter containing water. A manganio spiral is also provided for heating the apparatus electrically in order to calibrate it. With this apparatus a rise of temperature of 0*Zo in ten to fifteen minutes may be measured t o O.O0lo. The corrected value for the development of heat in the decomposition of ozone a t constant volume is 34,500 cal. per gram- molecule. Experiments with other catalytic agents show that platinum-black gives high values and rapidly loses its activity. With a heated platinum wire which is easily calibrated the concordant value 34,000 cal. per gram-molecule is obtained C.H. D. New Hydrogen Sulphide Apparatue. STEFAN URBASCH (Chsrn. Zeit. 1910 34 1040-1041).-The apparatus may be used in the laboratory room close t o a fume chamber without causing any in- convenience whatever and owing to the high pressure several solutions may be treated simultaneously with hydrogen sulphide. A holds 5 litres B altogether 6 litres C altogether 4 litres B also 4 litres. When used for the first time B is filled with water and a glass tube reaching t o the bottom is introduced. C contains iron sulphide D dilute hydrochloric acid (2 1). Hydrogen sulphide is now passed until the water in B is quite saturated and the apparatus is then fitted up as shown in the figure. If the gas is wanted first stopcockfand then stopcock g are opened causing the acid to flow from D to C.The gas evolved enters by the tube a into B passes through the water and by means of the tube b c and stopcock y then passes through the solution to be tested. The gascurrent is easily regulated and the spent acid is drawn off from the bottom of C If saturatedii. 950 ABSTRACTS OF CHEMICAL PAPERS. hydrogen sulphide water is required i t is allowed t o drain from the burette and the volunie may thus be measured. Owing to the difference in level fresh water flows from A into B until the former height has been again reached and this water becomes again saturated with hydrogen sulphide. Not until 5 litres of hydrogen sulphide water have been used is there any need for replenishing the contents of A . During the passing of tho gas the siphon is closed as otherwise a little of the solution might find its way into A .When no gas but only the solutiou is required I no fresh water is introduced into B ; the contents last a long time and cannot deteriorate. I n order t o empty the burette when the siphon is closed it is necessary t o open the pinchcockf for a momont. B is made of dark glass so as t o prevent any decomposition by light L. DE x. The Constitution of Weber's Acid. KONRAD W JURISCH (Chent. Zeit. 1910 34,1065-1066).-0bjections are brought forward against the validity of the ordinary structural formule for sulphuric acid and nitrosylaulphonic acid. The former is regarded as a n additive compound of sulphur trioxide and water and the latter as H,O,.SO,,SO,,N,O,. Thermochemical reasons are given for supposing that the group SO is present in both compounds and t h a t hydroxjl groups are absent.C. H. D. Action of Crushed Quartz on Nitrate Solutions. HARRISON 8. PATTEN (J. Physical Chem. 1910 14 612-619),-A filter bed was mde with fine q u u t z flour of 740 sq cm. aren per gram which was1NORQANIC CHEMISTRY. G. 951 washed with hydrochloric acid and distilled water. On percolating through i t an 0.01N-solution of silver nitrate sterilised with chloroform some silver remained on the quartz in a n insoluble condition and the filtrate contained upwards of 1% of nitrite calculated as silver nitrite. The silver remaining on the quartz which was perhaps i n the form of silver oxide or silver silicate was soluble in ammonia but the percolated silver nitrate was not tested for acidity.The reduction of nitrate decreases as the adsorptive capacity of the quartz surface becomes satisfied. Sodium nitrate under sterile conditions is not reduced in contact with quartz to give any substance oxidisable with permanganate. The looser combination and the greater hydrolysis of the heavy metal nitrates may facilitate their reduction by quartz. R. J. C. The Hydration of Metaphosphoric Acid. D. BALAREFF (Zeitsch. unorg. Chem. 1910 68 266-268. Compare this vol. ii 607).-Although it is not found possible,. on account of the volatility of metaphosphoric acid to reach the temperature a t which ortho- phosphoric acid would pass directly into the meta-acid it is found that metaphosphoric acid in aqueous solution becomes directly hydrated to form the ortho-acid without any intermediate formation of pyro- phosphoric acid.C. H. D. S y n t h e s i s of Hydrogen Arsenide from its Elements ALEXANDER CH. VOURNASOS (Ber. 1910 43 2264-2272).-Dry nascent hydrogen as prepared by heating sodium formate readily combines with certain of the metalloids to form the hydrides of these elements (compare this vol. ii 286). Hydrogen arsenide may be obtained by passing the vapoucs of arsenic heated t o 460' over sodium formate contained in a tube heated to a temperature just below the decomposition point of the formate. The heat of the arsenic vapour completes the decomposition and a mixture of hydrogen and hydrogen arsenide is obtained. The reaction is carried out much more con- veniently by heating a mixture of three parts of powdered arsenic with eight parts of dry sodium formate rapidly to 400' in a round-bottomed flask.Yields of 12-17 volume % of hydrogen arsenide have been obtained. Instead of using sodium formate alone it is better t o use an equi- molecular mixture of sodium formate and sodium hydroxide or lime to prepare the nascent hydrogen as this prevents the formation of sodium oxalate and hence of carbon monoxide when the temperature is raised too high. Moreover arsenious oxide sodium arsenite or arsenic acid may be used in place oE arsenic. When a mixture of equal weights of sodium formate and normal sodium ortho-arsenite is heated to temperatures not exceeding 400° a gaseous mixture of hydrogen arsenide ahd hydrogen is obtained containing not more than 2-3% of the latter gas.One great advantage of this reaction is that sulphur compounds and other inorganic and organic compounds of arsenic for example solid hydrogen arsenide Schweinfurt green arsenic trisulphide arsenic- containing magenta etc. all give arsenic trihydride when heated withii. 952 ABSTRACTS OF CHEMICAL PAPERS. sodium formate or with a mixture of sodium formate and sodium hydroxide Marsh's test may thus be carried out without it being necessary t o transform the arsenic compound into one of its oxygen derivatives Organic compounds are best destroyed by oxidation with nitric and sulphuric acids and the dry residue which may still contain carbon heated directly with t h e formate mixture. I n some cases it is an advantage to transform the arfienic acid produced by the oxidation into arsenic sulphide before further treatment.This is best done by means of pure hydrogen sulphide prepared by heating ten parts of the formate-hydroxide mixture with three parts of flowers of sulphur to 400'. Urine which is t o be tested for arsenic is made strongly alkaline and evaporated to dryness the residue then being treated a8 above. Acids are first neutralised and then evaporated etc. Aniline dyes and textiles dyed with colours containing arsenic can be treated directly with the formate-hydroxide mixture since organic matter does not affect the reaction but it is better first to isolate the arsenic as chloride by distillation and then transform it into the sulphide or else to destroy the organic matter by fusion with sodium nitrate.By the above methods i t is possible to detect 0*001 mg. of arsenic. A mixture of antimony oxide and sodium formate gives no trace of hydrogen antimonide when heated to 400° metallic antimony alone being formed. When however sodium antimonite is used instead of antimony oxide and the mixture rapidly heated to 800° small quantities of the hydride of antimony are formed. This compound is also produced to a slight extent when metallic antimony is used and the mixture heated to a bright red heat. Antimony tri- and penta- sulphides simply give rise to metallic antimony and hydrogen sulphide at 400'. Thus arsenic may be separated from antimony in their compounds by heating with the formate-hydroxide mixture to 400° the antimony remaining behind in the metallic form At 800° however some antimony also volatilises as the hydride.T. S. P. Percarbonates. ERNST H. RIESENFELD (Ber. 1910 43 A reply to Tanatar (compare this vol. 2594-2595).-Polemical. ii 33 203 290 774). T. S. P. Silicon Monosulphide. LIVIO CAMBL ( A tti R. Accad. Lincei 1910 [v] 19 ii 294-300).-When silicon (in the form of ferro- silicon) and sulphur are heated together in an electric arc furnace a vigorous reaction takes place and a grey mass results from which by sublimation in an electric furnace silicon monosulphide may be obtained. The compound sublimes at 940-980' at 20-30 mm. and it occurs in two forms namely a black solid which may assume a vitreous character and a yellow powder. On resublimation of either form both are produced the yellow one being deposited in the colder parts of the tube employed.Analysis of either product leads to the formula SiS and the substance does not appear to be a mixture. The black modification has Di6 1.853. With alkalis the compound reacts according to the equation SiS + 2KOH = SiO + K,S + H,. The black sulphide dissolves in water with evolution of hydrogen sulphide andINORGANIC CHEMISTRY. ii. 953 formation of soluble silica and of a finely-divided orange subRtance which appears to be related t o the oxygenated silicon hydrides of Wohler (Annalen 1863,127 257). It decomposes slowly in water more rapidly in alkalis with evolution of hydrogen and formation of silica. It disolves in hydrofluoric acid hydrogen being evolved but it is insoluble in other acids.The yellow sulphide is also hydrolysed with evolution of hydrogen sulphide but instead of soluble silica and the compound just described a white insoluble substance is formed which yields hydrogen when treated with alkalis. R. V. S. The Equilibrium Diagram of the Silver-Cadmium Alloys. GIUSEPPE BRUNI and E. QUERCIGH (Zeitsch. anorg. Chern. 1910 68 198-206).-Silver and cadmium are melted together in an atmosphere of nitrogen. The diagram obtained is simpler than that of Rose (Abstr. 1905 ii 86) although agreeing with it in the form of the liquidus. From 0 to 80 atomic % of cadmium the alloys form a continuous series of solid solutions. The crystallisation intervals increase from 0 to 40 atomic % Cd diminish to zero a t SO% increase to 60% and again reach zero a t 80% Cd.This indicates the existence of two compounds AgCd and AgCd both of which form solid solutions This part of the curve resembles that of the magnesium- cadmium alloys (Grube Abstr. 1906 ii 355). The compound AgCd undergoes a transformation at 433'. From 80 atomic % Cd to 97% crystals of AgCd separate and from this point onwards solid solutions are formed There is no eutectic point the freezing point of cadmium being raised by the addition of silver even in minute proportion. C. H. D Peptisation of Silver Bromide. RAPHAEL E LIESEGANG (Zeit8cA. Photochem. 1910 9 60-64).-A theoretical paper i n which the author discusses the nature of the changes involved in the granulation and peptisation of the silver haloids. H. M. D. Silver Nitrate Formed by the Action of Nitric Acid on Silver Sulphide HIPPOLYTE GRUENER (J.Arner. Chern. Soc. 1910 32 1030-1032).-Boiling nitric acid of concentration above 5% dissolves silver sulphide rapidly forming silver sulphate and nitrate. Acid Fitronger than 94% however forms only the sulphate. The maximum amount of nitrate (95%) is obtained by the use of 15-20% acid greater dilution than this resulting in a smaller percentage. The production of the nitrate is diminished by boiling the acid or prolonging its time of action. w. 0. w. Action of Potassium Hydroxide on Normal Calcium Phosphate. WILLIAM OECHSNER DE CONINCK (Bull. Acad. roy. Belg. 1910 662-664).-Normel calcium phosphate is not acted on when heated with a 1qrge ezcess of potassium hydroxide at 96-97O for fifty hours.T. S. P,ii. 954 ABSTRACTS OF CHEMICAL PAPERS. The Binary Systems of Calcium Metasilicate with Calcium Chloride and Calcium Fluoride. B. KABAND~EFF (Zeitsch. anorg. Chem. 1910 68 188-197).-Mixtures of calcium carbonate silica and calcium fluoride are melted in a carbon tube and subjected to thermal analysis the porcelain tube of the thermo-couple being pro- tected with a layer of t a r and graphite. Calcium metasilicate and calcium fluoride form a simple eutectiferous series with a eutectic point at 48 molecular % CaF and 1130O. The conversion of pscudo- wollastonite into wollastonite on cooling may be followed micro- scopically but does not produce any thermal effect. The eutectic point in mixtures of calcium metasilicate and calcium chloride lies close to the calcium chloride point and So below it.Solid solutions may be formed up to 10 molecular % CaCI2. There is no evidence of the formatiou of additive compounds. C. H. D. Metallic Strontium. BEN L. GLASCOCK (J. Amer. Chem,. Soc. 1910 32 1222-1230).-A study has been made of the conditions necessary for the preparation of strontium by the electrolysis of its fused chloride. A quantity of the metal was prepared in the following manner. A hemispherical cast-iron vessel of 25 cm. diameter was used as a container and a carbon anode 8 cm. x 8 cm. was emplojed. With pure strontium chloride as electrolyte and a current of 125 amperes and 40 volts for seven hours 76 grams of strontium were obtained giving a current efficiency of 5.3%. The metal thus obtained had a purity of 97-98.5% D 2.55 and specific heat 0.0742.Strontium is a very light soft metal which has a silvery lustre when freshly cut but rapidly becomes yellow and afterwards coated with a white layer of oxide. It reacts with water methyl and ethyl alcohols ethyl acetoacetate and malonate and aniline with evolution of hydrogen and also reacts siowly with boiling ethyl iodide. The metal is without action on silicon tetrachloride. It dissolves readily in liquid ammonia forming a deep blue solution from which a dark blue precipitate separates. It burns in an atmosphere of carbon dioxide and illuminating gas as energetically as in air but not so violently as calcium does under similar conditions. When hydrogen and nitrogen are passed over the heated metal the hydride and nitride are formed.An alloy of strontium and iron has been prepared and is described E. G. The Ternary Alloys of Magnesium Zinc and Cadmium. I. GIUSEPPE BRUNT G. SANDONNINI and E. QUERCIGH (Zeitsch. anovy. Chem. 1910 68 73-90).-BIngnesium and zinc form a single com- pound MgZn and no solid solutions. On the other hand zinc and cadmium form a simple eutectifcrous series whilst magnesium and cadmium form a compound MgCd which forms a continuous series OF solid solutions with both components. It is found that the system MgZn,-Cd behaves like a binary system and the present investigation includes the alloys of the ternary group MgZn,-Cd-Zn leaving the remainder for a second part. I n the zinc-cadmium series t h e eutectic point is a t 2 6 2 O and 73.5 atomic % Cd and cadmium holds about '3 atomic % Zn in solidIN0 ROA NIC CHEMISTRY.ii. 955 solution. The eutectic point between Zn and MgZn lies at 363' and 7 5 atomic % Mg. The eutectic point Cd-MgZo lies at 280' and 80.05 atomic % Cd. The ternary series examined is therefore of a simple type having three binary eutectic lines and a ternary eutectic point the last lying at 250' and 73 atomic % Cd 25% Zu and 2% Mg. The total number of alloys examined in this section of the system is 109. C. H. D. Chemical Analyses of Minoan Metals from the Excavations of Crete. ANGELO Mosso (Atti R. Accad. Lincei 1910 [v] 19 ii 225-228).-0f six samples of lead OF Minoan origin only one con- tained tin (1.460%). It is suggested that the absence of tin objects in the Minoan remains is to be ascribed to the action of the " tin pest." A piece of gold was found to be alloyed with 20% of silver this alloy being the so-called electron.A piece of silver was found to contain 20% of copper. The two pieces of electron and the piece of silver analysed belong to the third Middle Minoan Period (Evans' classifica- tion). A sphere of mineral examined was found to be a n emery of the composition A1,03. Fe,O,. CaO. MgO. SiO,. Total. 55'40 38.60 1-50 0.54 3-iO 99-74 R. V. S. Antique Glass Mirror. ERANZ W. DAFERT and R. MIKLAUZ (Monatsh. 1910 31 781-784).-Chemical investigation of an antique glass mirror found in a large Roman grave-yard in the Wiener Strasse in Laibach shows that it was made by pressing lead foil on to the glass some kind of balsam being used as an adhesive.I n the course oE centuries the balsam has resinified and entered into combination with the lead the lead thereby being converted for the most part into red lead. The lead forming the frame and hinder part of the mirror wits changed on the surface into the basic carbonate. The Influence of Light on White Lead Blackened by Hydrogen Sulphide. ERNST TAUBER (Chenz. Zeit. 1910 34 1126). -Contrary to the results of Sacher (this vol. ii 712) the author finds that lead sulphide in white lead paints is bleached by the action of light even in the absence of oxygen. The action is attributed to the peroxides of the drying oils in the paints. A blackened surEace of white lead coated in places with poppy-seed oil is bleached by light only in the parts coated with oil.Freshly painted surfaces are even bleached in the absence of light although more slowly. Crystallisation of Fused Lead Silicates. SIEGFBIED HILPERT and RICHARD NACKEN (Ber. 1910 43 2565-2573. Compare Abbtr. 1909 ii 890).-The authors describe various apparatus by means of which they have taken the cooling curves of fused mixtures of lead oxide and silica the fused mass being vigorously stirred during the cooling and have measured the velocity of crystallieation and the crystallisation power .(number of nuclei farmed) of such fusions at T. S. P. C. H. D.ii. 956 ABSTRACTS OF CHEMICAL PAPERS different temperatures. The results obtained are combined in a freezing-point diagram for mixtures varying in composition from lead monoxide to lead metasilicate. A t first sight the curve seems to com- prise two eutectics and one maximum the latter corresponding with lead orthosilicate m.p. 749 O. The eutectics however correspond with the compositions 3Pb0,2Si02 and 3PbO,SiO and further careful experiments (cooling curves measurements of velocity of crystallisa- tion and microscopic examination of thin sections) with mixtures of these compositions show that the first supposed eutectic really consists of two eutectics close together with a small maximum i n between corresponding with the compound 3Pb0,2Si02 m. p. about 690'. The evidence for the second compound 3Pb0,Si02! is not so satisfactory but the examination of thin sections points to its existence. T. S. P. Ternary Alloys of Copper Antimony and Bismuth. NICOLA PARRAVANO and E.VIVIAN (Atti R. Accad. Limel 1910 [v] 19 ii 197-201 243-247. Compare this vol. ii 779 852).-The first paper contains the experimental results obtained for the ternary systems Cu,Sb-Sb-Bi and the diagram of the system constructed with their aid. Microscopic examination of the alloys has confirmed the results obtained by thermal methods and photomicrographs of some of the typical appearances observed are reproduced in this paper. I n the second this diagram is discussed R.. V. 5. Compounds of Nitric Oxide with Cupric Salts. WILHELM MANCHOT (AnnaZen 1910 375 308-315. Compare Kohlschiitter Abstr. 1904 ii 734; Manchot this vol. ii 137). It has long been known that a solution of copper sulphate in concentrated sulphuric acid develops a violet or bluish-violet coloration with nitric oxide.The author shows that the coloration is due to the formation of an easily dis- sociable compound of 1 mol. each of copper sulphate and of nitric oxide. Its formation is influenced by the concentration of the water and of the copper salt present. No coloration or absorption of nitric oxide can be detected when sulphuric acid containing less than 70.8% of H,SO is used whatever the concentration of the copper sulphate. A t 0' and 752 mm. solutions containing 0.0053 to 0,0265 mol. of CuSO per litre of 97.6% sulphuric acid absorb exactly 1 mol. of nitric oxide per 1 atom of copper; with greater concentrations of copper sulphate the amount of nitric oxide absorbed is less. A solution containing about 0-0175 mol. of CuSO absorbs only 1 mol. of nitric oxide per 1 atom of copper when the pressure of the nitric oxide is increased from 322 mm.to 1303 mm. Similar results are recorded for alcoholic solutions of hydrated cupric chloride The dark violet compound is even more sensitive than the preceding to the decomposing action of water for even in absolute alcohol solutions containing 0.005 to 0.1352 mol. of CuCI per litre absorb oulg 17 to 18 litres of nitric oTide (at 0" and 750-753 mm.) per 1 atom of copper,INORGANIC CHEMISTRY. ii. 957 When dry hydrogen chloride is led into liquid nitric oxide cooled by liquid air or when nitric oxide is passed into liquid hydrogen chloride a dark red liquid is formed which rapidly solidifies to a dark red crystalline mass ; the substance decomposes however even at the temperature of a mixture of solid carbon dioxide and acetone c.s. Atomic W e i g h t of Mercury. 11. C. W. EASLEY (J. Amer. Chsm. h’oc. 1910,32 1117-1126).-In an earlier paper (Abstr. 1909 ii 1013) the atomic weight of mercury was determined by a study of the ratio HgCI ZAgC1. I n order to confirm the value thus obtained estimations were made of the mercury in mercuric chloride by precipi- tating mercuric oxide with sodium hydroxide and reducing i t by means of hydrogen peroxide. Although the results of these experiments agreed closely with those obtained by the former method the difficulty of collecting the mercury completely rendered the process untrust- worthy. Determinations have now been made of the ratio HgC1 Hg by the electrolysis of a solution of mercuric chloride.A special method waa devised in which the metal was deposited in globular form by means of a mercury cathode and without being removed was washed by decantation freed from water by means of acetone and afterwards weighed. The results of five preliminary experiments and of six final experiments each gave a mean value for the atomic weight of mercury 200.63 (C1= 35*46) whilst the value obtained in the earlier paper (Zoo. cit.) from the ratio HgCl 2AgC1 was 200.62. E. G. Ultra-microscopic Oblservations of the Hydrolysis of Mercuric Chloride. HERMANN W. FISCHER and E. BRJEGER (Zeilsch. Chena. Ind. Kolloide 1910 7 196-197).-An aqueous solution of meicuric chloride has been found to contain a number of ultra- microscopic particles. These are attributed -to the formation of a colloidal substance as a result of hydrolytic decomposition. The colloidal product ages with time and becomes lees soluble; this leads t o further hydrolytic decomposition and to an increase in the number of ultra-microscopic particles.Rise of temperature has the same effect and this observation supports the view that the presence of sub- microns is due to hydrolysis. The protective influence of sodium chloride on a solution of mercuric chloride eis attributed to the diminution of the hydrolysis in consequence of the formation of the complex salt Na,HgCl,. H.M. D. Lutetium and Neoytterbium or Cassiopeium and Alde- baraniurn. GEOEGES URBAIN (Zeitsch. anorg. Chem. 19 10 68 236-342).-Claim for priority against Welsbnch (Abstr. 1908 ii 591 ; compare Abstr.1908 ii 283 849). C. H. D The Preparation of Mangsnio Fluoridea and the Titration of Manganese by Volhard’s Method in Presence of Fluor- ides. ERICH M~~LLEB and PAUL KOPPE (Zeitsch. anorg. Chem. 1910 68 160-164).-3Ianganic fluoride has been prepared previously fromii 958 ABSTRACTS OF CHEMICAL PAPER& mangano-matlganic oxide and hgdrofluorio acid. A fluopide of tervalent manganese is readily obtained by the action of permanganates on a manganous salt in presence of hydrofluoric acid the reaction being MnO,' + 4Mn" + 811' = 6Mn"' + 4H,O The difference be- tween the reactions in presence of hydrofluoric and sulphuric acids is due to the conversion of Mn'" into a complex fluoride ion in the former case. By mixing in the order given a solution of 8.9 grams of manganous sulphste in 30 C.C.of water 8 C.C. of 40% hydrofluoric acid a solu- tion of 1.58 grams of potassium permanganate in 25 C.C. of water and one of 5.8 grams of potassium fluoride in 20 c.c. in a platinum basin a salt is obtained which after washing with hydrofluoric acid and alcohol and drying in a desiccator has the composition 2KF,Mn F,,H,O. Manganese dioxide which is insoluble in hydrofluoric acid dissolves if a manganous salt is also present. Blanganic fluoride free from potassium may be obtained by electrolysing a neutral solution of tt msnganous salt and dissolving the oxide precipitated at the anode in hydrofluoric acid. The di6culty of observing the end-point in presence of the pink manganic salt makes it impossible to obtain accurate results on titrating manganese with permanganate in presence of hydrofluoric acid.The reaction appears however to be nearly complete in a warm solution. The presence of fluorides causes a large error in the titration of manganese by Volhard's method but not in the titration of ferrous salts. C. H. D. Electrolytic Conversion of Manganates into Perman- ganates. KYRT BRAND and J. E. RAMSBOTTOM (J. p. Chem. 1910 [ii] 82 336-396).-The authors have been forestalled by Askenasg and Klonowsky (this vol. ii 413) in the publication of their results. The manganate melt for the electrolytic production of potassium per- menganate is made by heating manganese dioxide potassium hydr- oxide and a little water a t a dark red heat oxygen being supplied by the atmosphere and not by potassium nitrate or chlorate since t h e addition of the latter results in the formation of potassium nitrite or chloride the presence of either of which during the electrolysis is disadvantageous.The apparatus consists of a slender glass vessel containing an earthenware vessel in which are the anode of nickel gauze and the anodic liquor consisting of a solution containing 4% of potassium manganate and 14% of potassium hydroxide ; the cathode is also made of nickel and the surrounding solution is 2.2% potassium hydroxide. The results of the experiments show that the yield of potassium permanganate is appreciably increased by stirring thoroughly the anodic solution and decreases with increase of the current density at the anode the highest practicable value being 0.0125 ampere per sq. cm.with a nickel anode and 0.005 with an iron anode. The solubility of potassium permanganate in aqueous potassium hydroxide of varying strength has been determined and it is shownINORQAh’IC CHEMISTRY ii. 959 that the potassium permanganate remaining dissolved in the anodic liquor can be isolated either by evaporating the solution carefully protected from dust particles etc. or by continually adding the solid manganate melt to the anodic solution during the electrolysis whereby the concentration of the potassium hydroxide becomes ultimately so great that the potassium permanganate is almost entirely precipitated. c. s. The System Iron-Nickel. RUDOLF RUER and EMIL SCE~Z (LMetaZZurgie 1910 7 415-420).-The freezing-point curve of t h e system iron-nickel determined from quantities of 150 grams is con- tinuous with a shallow minimum and the liquidus and solidus curves practically coincide throughout.Determinations of the temperatures of magnetic transformation yield results in general agreement with those cf Guillaume and Osmond but the boundary between the reversible and irreversible alloys is now placed at 29% of nickel. The maximum of the reversible transformation curve at 618” and the minimum of the freezing-point curve at 1435’ both lie near to 70% of nickel pointing to the existence of a compound FeNi,. The electrical conductivity OF rods cast in narrow magnesia cplin- ders and annealed by heating to 900” and cooling slowly shows a minimum a t 35% Ni and the compound FeNi is not indicated on the curve.C. K. D. Goldschmidt’s Ferroboron and Manganese-Boron and the Residue Obtained on Heating Ferroboron in Hydrogen Bulphide. JOSEF HOFFMANN (Chem. Zeit. 1910 34 1045-1046. Compare this vol. ii 508).-Goldschmidt’s borides behave towards reagents as heterogeneous substances and this view is confirmed by microscopical examination which shows distinct crystallites in a homogeneous grounci mass. Detailed descriptions of some of the crystals are given. The residue obtained when hydrogen sulphide acts on ferroboron contains borides which are resistant to acids and also boron sulphide and a sulphur compound which is not ferrous sulphide but probably a ferrous thioboride. C. H. D. Complex Compounds of Cobalt with Chloric and Per- chloric Acids. ROBERTO SALVADORI (Gaxzetta 19 10 40 ii 9-18).-A number of cobaltiammine chlorates and perchlorates have been examined. They are all explosive the cblorates by percussion or on ignition the perchlorates by percussion or detonation. The per- chlorates are very stable at the ordinary temperature whilst the chlorates decompose slowly the luteo-derivatives being more stable than the roseo- or purpureo-compounds. For the analysis the chlorates are reduced by means of ferrous sulphate in ammoniacal solution and the perchlorates by fusion with sodium carbonate in a platinum crucible placed in an outer crucible also containing sodium carbonate. Ammonia is estimated by distil- lation with sodium hydroxide and cobalt by electrolytic reduction in presence OF ammonium oxalate.The metallic deposit contains carbon,ii. 960 ABSTRACTS OF CHEMICAL PAPERS. and it is necessary to dissolve i t in sulphuric acid t o filter and to re- deposit the cobalt electrolytically Luteo-cobalticcmrnine chlorate Co(NH,),(C10,),,H20 qrepared by passing oxygen through a 5% solution of cobalt chlorate in an excess of ammonia a t 50° adding chloric acid and evaporating forms yellow crystals and explodes a t 120' if rapidly heated. It may be obtained in an anhydrous form from luteo-cobaltiammine chloride and silver chlorate by cooling the filtrate in a freezing mixture. I t then forms yellow needle$ soluble in water to the extent of 7.87% a t 18' much more at higher temperatures. Cobulthydraxine pemhlorute Co(N2H,),!C10,) obtained by adding hydrazine hydrate to luteo-cobaltiammine chloride forms yellow crystals which are highly explosive.If carbon dioxide is passed into the solution containing hydrazine hydrate cobalthydrazine carbonate and hydrazine hydrochloride are formed and nitrogen is evolved the reaction probably proceeding as follows Co(N2H,),(C10,) + N2H,C0 = C'o(N,H,),CO + 2HCl+ 6 0 ; 2HCl i- 6 0 + 5N2H = 6H20 + 3N2 + 2N,H5C1. Roseo-cobaZticcmmine chlomte obtained from the mother liquor of the luteo-salt or from silver chlorate and roseo-cobaltiammine chloride is a pink very soluble powder the solubility in water a t 1 8 O being 105 -8%. The purpureo-saltp also obtained by double decomposition forms large garnet-red tetrahedra. CobuZt pewddorute CO(C~O,)~,~H,O prepared from cobalt carbonate and perchloric acid and crystallised slowly forms prisms 4 cm.long loses water at 100' to form a violet hygroscopic powder and explodes by percussion. When rapidly heated it deflagrates without exploding When ammonia and ammonium perchlorate are added to its solution a red powder having the composition Co(C104),,6NH is precipitated ammonia directly replacing water. Boiling water decomposes it according t o the equation ~CO(CIO,),,GNH + 2H20 = Co(OH) + Co(ClO,) + NH4C10 + 4NH3. Other metallic perchlorates behave in a similar manner. Luteo-cobaltiammine perchlorate Co(NH,),(C104)3,H20 is soluble in water to the extent of 0.967% at 18' (compare Alvisi Abstr. 1902 ii 24). Roseo-cobaltiammi?ze percldorccte and thepurpureo-sa,lt dissolve in water at 18" to tahe extent of 7.4% and 11% respectively.Co(NH3),,H20,( c104)3 H2°? C. H. D. Compounds of Chromium. VIII. Triamminechromium Salts. ALFRED WERNER (Bey. 1910 43 2286-2295).-The starting point in the preparation of triamminechromium salts is triammine- chromium tetroxide for which a new method of preparation is given. To a strongly cooled solution of 30 grams of chromic acid in 300 C.C. of water are added 300 C.C. of pyridine. After remaining for half a n hour in a freezing mixture 750 C.C. of 3% hydrogen peroxide are added. The precipitated pyridine perchromate is collected washed and added t o 90 C.C. of well-cooled 25% ammonia. The precipitated triamminechromium tetroxide is collected after ten minutes and washed with water alcohol and ether,INORGANIC CHEMIS'l'RY. ii. 961 TT ichlorotr hmminec hromium (N H3 ),Cr C1 9 results when t r iam mine- chromium tetroxide is added to cold Concentrated hydrochloric acid.A grey to bluish-grey precipitate is formed and the filtrate from this deposits the tricblorotriamminechromi~im on keeping for two days. The crystals are dark blue with a greenish tinge. It is almost insoluble in water in which properties it resembles trichlorotriamminecobalt. It dissolves in hot water giving a blue solution from which the dichloroaquotriamminechromium salts (A bstr. 1906 ii 760) are pre- cipitated by appropriate reagents. The grey to bluish-grey precipitate mentioned above is probably a mixture of dichloroaquotriammine- chromium chloride and trichlorotriamminechromium. ~~iaquotrictmminech~orrLium chloride YCl where Y = Cr(NH3)3 is obtained as follows A mixture of 1 gram of dichloroayuo- triamminechromium chloride with 8 C.C.of water is covered with 5 C.C. of pyridine. The resulting solution is filtered and the hydroxoiodide precipitated by the addition of solid potassium iodide. The chloride is then obtained by triturating the hydroxoiodide with concentrated hydrochloric acid. After purification by solution in water and pre- cipitation with hydrogen chloride i t forms brownish-red hygroscopic crystals. It was also prepared by dissolving triamminechromium tetroxide in dilute hydrochloric acid (1 4) and saturating the cooled solution with hydrogen chloride. The chboride-nitrate YCI,NO is precipitated when concentrated nitric acid is added to a cold con- centrated solution of the chloride.When nitric acid is replaced by perchloric acid pale red plates of the perchlorate Y(ClO,) are obtained. 1 Pul c (NH,) 1 ' Dibromoaquotriamminechromi-salts YX where Y = Br,CroH2 To prepare the bromide Y Br triamminechromium tetroxide is dissolved in cooled hydrobromic acid (D 1 *49) whereby bromine is evolved and concentrated sulphuric acid added to the well-cooled solution. Intense green crystals are obtained soluble io water to a green solution which rapidly turns bluish-red. The iodide YI thiocyanate YSCN nitrate YNO and sukhate Y2s0 all form green crystals and are prepared from a fresh solution of the bromide by precipitation with potassium iodide potassium thiocyanate nitric and sulphuric acids respectively. The green colour of these salts corre- sponds with that of the dichloro- and dibromo-diethylenediamine- chromium salts.The dichloroaquotriamminechromium salts are however blue. This difference in colour is not due to a difference in constitution since when the green dibromo-bromide is converted into triaquotriamminechrornium nitrate Cr(OH2)3 (NO,) by means of silver nitrate and the dichloronquotriamminechromium nitrate prepared from this by means of hydrogen chloride the usual blue salt is obtained Both the green and the blue salts are therefore prasessal ts. Bromodiaquots.&ammi~chromi-salts Y& where Y = [BrCr( OH,),] Five grams of triamminechromium tetroxide are dissolved in 50 grams vor,. XCVIII. ii 65 [ PHJ3I (NHi3)3 'ii. 962 ABSTRACTS OF CHEMICAL PAPERS. of well-cooled hydrobromic acid (D 1.49).The solution is then boiled until bromine ceases to be evolved cooled and 30 C.C. of con- centrated sulphuric atid added whereby a brownish-red crystalline deposit forms. If this is dissolved i n water the solution rapidly filtered and the filtrate treated with concentrated hydrobromic acid reddish-violet crystals of the bi*ornide YBr are obtained. With con- centrated hydrochloric acid the solution of the bromide gives reddish- violet crystals of t'he chloyide YCI from which salt tjhe sulphate YSO may be obtained as violet crystals. The transformation of the chloride into the sulphate proves that the bromine is in the complex. Hit'herto it has not been possible to isolate the tribromotriammine- chromium only the following three hydrates of the bromo-series being known namely [..[;:;$] Br,.T. S. P. The Behaviour of Iron towards Solutions of Stannous Salts. ALFRED THIEL and K. KELLER (Zeitsch. rcnoi-g. Chern. 1910 68 220-235).-The fact that when iron is added to a solution of the chlorides of tin and antimony only antimony is precipitated is in contradiction t o the positions of iron and tin in the electrochemical mries. It is now shown that tin is actually precipitated but only in very minute quantity forming a very thin protecting layer of a tin- iron alloy on the surface of the iron. Iron dissolves much less rapidly in an acid if a tin salt is present. Measurements of electrolytic potential show that i n pure acid t i n is always less noble than iron the difference being greater in stronger acids.I n acid corjtaining a stannous salt the potential of iron varies and finally assumes a value equal or near to that of tin according to the conditions. The deposition of t i n on iron is recognisable by analysis if iron having a relatively large surface such as turnings is taken for the experiment. If iron is introduced into a vessel containing a concentrated electro- lyte containing t i n in the lower part and a more dilute electrolyte free from tin i n the upper part the iron becomes covered with crystals of tin where it dips into the concentrated electrolyte but remains free from t i n if immersed completely in either the concentrated or the dilute solution. C. H. D. Atomic Weight of Tantalum. CLARENCE W. BALKE (J. Amer. Chern. Xoc. 1910,32 1127-1 133).-Owing to the uncertainty existing with regard to the value of the atomic weight of tantalum deter- minations have been made of t8he ratio 2TaCI,:Ta205 the chloride being converted into the oxide by methods similar to those used in the determination of the atomic weight of columbium by Balke and Smith (Abstr.1908 ii 1043). Tantalumchloride was prepared by heating the oxide in a current of chlorine and vapour of sulphur chloride. The chloride was converted into the oxide in quartz bulbs. The bulbs containing the chlorideMINERALOGICAL CHEMISTRY. ii. 963 were placed in a vacuum desiccator with water and the air was pumped out. The chloride gradually underwent hydrolysis ; small quantities of water andconcentratednitric acidwere thenintroduced into the bulb,and the mass was evaporated to dryness. The addition of water and nitric acid and the subsequent evaporation were twice repeated and the dry mass was finally ignited until no further loss of weight occurred. The mean of eight experiments with three samples of the chloride gave a value for the atomic weight 18152 (Cl=35*46) whilst the value given in the international table of atomic weights is 181.0. Tantalum chloride has D 3.68 at 27". SDecimens of the oxide prepared from the chloride had -D varying froA 7.91 to 8.62. E. G. Easy Method for Preparing Colloidal Gold. WILLIAM OECHSNER DE CONINCK (Bull. Acad. roy. Belg. 1910 664-665).- A dilute solution of gold chloride containing a little starch is heated for a short time and then filtered. The filtrate is at first colourless but gradually becomes deep violet in colour. The starch remaining on the filter paper is coloured violet and after a few days presents a metallic reflecting surface. On exposing the violet filtrate to diffused light for some days the gold is slowly deposi$ed. If the original solution of gold chloride and starch is gently heated for some minutes the filtrate which is opalescent will reduce Fehling's solution. T. 8. P.

ISSN:0368-1769    

DOI:10.1039/CA9109805948

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY. Mine ra l o g i c a1 C h e mi s t ry. ii. 963 A Method for Isolating Native Iron from Basalt without Destroying its Form. MAX SEEBACH (Centv. Min. 1910,641-643). -Native iron occurs in the basalt of Buhl near Weimar in the form of a fine network. The basalt may be removed without destroying the form of the iron by heating with Plattner’s flux (10 parts sodium carbonate 13 parts potassium carbonate 5 parts borax glass and 5 parts dry starch) in a graphite crucible. I n order to prevent the formation of a thin layer of oxide on the iron charcoal may be mixed with the flux and the whole covered with a layer of sodium chloride. A piece of basalt 1 C.C. in size is destroyed in one and a-half hours. The last traces of rock enclosed in the meshes of the iron are removed by fusion with boron trioxide.When it is only required to isolate the iron without preserving its form it is best to crush the basalt and fuse with boron trioxide. C. H. D. Diffusion of Crude Petroleum through Fuller’s Earth. J ELLIOTT GILPIN and OSCAR E. BRANSKY (Amer. Chem. J. 1910,44 251-.303).-Uilpin and Cram (Abstr. 1909 i 1) have shown that when petroleum is allowed to diffuse upwards through tubes packed 65-2ii. 964 ABSTRACTS OF CHEMICAL PAPERS. with fuller’s earth fractionation takes place and the fractions rising t o the top of the tubes are of lower sp. gr. than those a t the bottom. The paraffin hydrocarbons collect in the upper parts of the tubes and the unsaturated hydrocarbons in the lower parts. A study has now been made of the behaviour of crude Illinois petroleum when treated in this way.Gilpin and Cram’s results have been confirmed and it has been found that the amount of the sulphur Compounds like that of the unsiturated hydrocarbons increases gradually from the lightest oil at the top to the heavier oils at the bottom of the tube. When a solution of benzene in petroleum is allowed to diffuse through fuller’s earth the benzene like the olefines and sulphur compounds tends to accumulate i n the lower part of the tube. When fuller’s earth wbich has been used for such diffusion experi- ments and afterwards treated with water in order to remove as much oil as possible is dried and extracted with ether oils of high specific gravity and viscosity are obtained containing considerable quantities of unsaturated hydrocarbons and sulphur compounds.It is therefore evident that fuller’s earth exercises a selective action on the petroleum. A discussion is given of the causes of the differences between the various oils of the United States. Pennsylvania petroleum differs horn those of Ohio Texas and California in containing a much larger proportion of paraffin hydrocarbons and a much smaller proportion of benzene unsaturated hydrocarbons and compounds of sulphur and of nitrogen. I n view of the results of the present investigation it is suggested that this difference may be explained by assuming that the Pennsylvania petroleum has diffused upwards through porous media such as shales limestones and sandstones and thus undergone fractionation resulting in the removal of the unsaturated and aromatic hydrocarbons and the sulphur compounds.It is probable that the nitrogen compounds also behave like the unsaturated hydrocarbons and sulphur compounds and this que3tion is beiug studied. E. G. Grahamite a Solid Native Bitumen. CL~FFORD RICHARDSON (J. Amer. Chem. Xoc. 1910 32 1032-1049).-There is a regular gradation in properties and composition between paraffins asphalts inanjaks and grahamitey corresponding probably with different stages of metamorphosis. The author discusses the relations between these ininerais and suggests that the term “ grahamite ” should be confined to that type of solid native bitumen characterised by a schistose or hackly fracture by its sparing solubility in naphtha and by a high percentage of residual coke.A list of occurrences of grahamite in America is given in tabular form with the physical properties percentage of bitumen and ultimate composition of the bitumen The bitumen from a typical grahamite from West Virginia gave C 86.56 H 8.68 and S 1.79%. The ash of . grahamites contains vanadium that of a specimen from the Impson Valley containing 11-15%of V,O (compare Hewett this vol. ii 719). Trinidad bitumen should be classed as a grahamite rather than as 8 man jak. w. 0. w.MINERALOGICAL CHEMISTRY. ii. 96.5 Mosesite a New Mercury Mineral from Terlingua Texas. FREDERICK A. CANFIELD WILLIAM F. HILLEBRAND and WALDEHA~ T. SCHALLER (Amer. J. Xci. 1910 [iv] 30 202-20S).-The mineral occurs as minute simple octahedra or spipel-twins on calcite and is canary-yellow with an adamantine lustre.It is a mercury-ammonium compound with chlorine (about 5%) and sulphate (about 3.5% SO,) being thus similar t o kleinite (Abstr. 1907 ii 788) but probably with mercurous rather than mercuric sulphate and chloride. I n hydro- chloric acid it is very slowly changed to calomel whilst kleinite is completely although very slowly dissolved Heated gradually in a bulb-tube mosesite first changes colour to black then to white and at a higher temperature volatilises giving sublimates of calomel and mercury. The crystals are optically birefringent but they become isotropic at 186O ; on cooling they revert very slowly to the birefringent modification Kleinite shows the same change from the optically birefringent to the isotropic state a t a slightly higher temperature. L.J. S. The Synthetic Sapphires of Verneuil. ALFRED J. MOSES (Amer. J. Xci. 19 10 [iv] 30 271-274).-The crystallised coruudum of a fine sapphire-blue colour prepared artificially by A. Verneuil (this vol. ii 212) gave on analyses by M. A. Lamme Al,O 99.83-99*85% ; TiO 0.11-0*13% ; Fe,O trace ; SiO nil ; D 3.977-4 01. Refractive indices (sodium-light) w = 1.7680 c = 1,7594. The optical interference-figure varies from uniaxial to slightly biaxial in character and the optic axis is inclined at about 40’ to the axis of the conical mass. The pleochoism is distinct (w indigo-blue E pale blue). L. J. S. Lanthanite. GUSTAF LINDSTROM (Jahrb. Bin. 1910 ii Ref. 15 ; from Geol. For. Po&. Stockholm 1910 32 206-214).-Lanthanite of D 2-69-2.74 collected from cerite specimens from Bastnas Sweden gave on analysis (La Di),O,.Ce,O,. Y,O,. GO,. H,O. Insoluble. Total. 28-34 25-52 0.79 21-95 23-40 0 -13 100.13 This like the analyses of American lanthanice agrees with the formula R,O 3C0,,8H20. Hisinger’s analysis of ‘‘ hydrofluocerite ” from Bastnas has come to be wrongly quoted in the text-books under lanthanite owing to the incorrect translation of the Swedish “ flusspatssyra ” as “ carbonic acid ” in an early abstract in Edin. J Sci. 1826. L. J. S. New Occurrence of Hydrogiobertite. ROGER C. WELLS (Amer. J. Xci. 1910 [iv] 30 189-190).-The material occurs in conbiderable amount as a white encrustation on shale in Chiles Valley Napa Co. California and has been deposited from t2he water of springs; the serpentine-rocks occurring in the neighbourhood probably supplied th0 magnesium.The structuie is spherulitic and the spherules often contain a nucleus of shale ; D 2.152. Analyses of material containingii. 966 ABSTRACTS OF CHEMICAL PAPERS. admixed &ale gave the following results agreeing with the hydro- giobertite formula 2Mg0,C0,,3H20. Insoluble. (A1,Fe),03. CaO. MgO. co,. H,O. Total. 25.33 1-90 2-60 31.81 18-06 20.06 99-76 14-93 1-06 1'84 36'40 2 3 5 1 20'81 98-75 L. J. 8. Analyses of Minerals from Croatia. Fa. TU~AN (Jahrb. Min. 1910 ii Ref. 39-41 ; from Glusnik [Berichte] kroat. naturw. Ges. Agram 1907 19).-I. Dolomite from the Fruika mountains ; pale green coarsely granular from serpentine-rocks. 11. Magnesite from the Buknica stream near Trgove ; milk-white compact with conchoidal fracture from serpentine-rocks 111.Magnesite from the BeoEinski potok stream in the Frugka mountains ; similar t o the last. IT-TTI. Strontianocalcite from Kndoboj ; fibrous aggregates associated with fitrontisnite. VII. Hydrozincite from Ivanec in the Ivanhica moun- tains ; milk-white reniform aggregates associated with smithsonite. VIII-X. Muscovite from the pegmatites at various localities in the Krndi ja mountains. h1,0,. FeO. MnO. CaO. SrO. MgO. CO,. Insol. Total. I.* 0-21 1'53 1'30 30'78 trace 19.47 46-80 0.10 100-19 TI. 0'62 1'80 trace 0'37 - 41.98 47.29 8.61 100.67 1II.f 0.57 4'39 trace 0.23 - 30'94 36.84 27.01 99.98 IV. - trace trace 54.11 2-26 - 43.51 0.10 99-98 v. - trace trace 40.59 19-32 - 40.05 - 99-96 v11.2 - 1.25 - 0.20 - - 14.30 - 100.27 TI.- trace traco 53-07 3.66 - 43'26 - 99-99 * N O trace. t Na,O,K,O,Li,O trace. $ ZnO 73-75 ; H20 10.77. SiOz. A l 2 0 ~ FezOS FeO. MnO. CaO. MgO. K2O. NazO. LizO. HzO. Total. VIII. 47.72 28'70 7.24 0'58 trace 0'54 - 7 3 1 1.9% trace 6'34 100.35 IX. 46'93 34'32 3'1s - trace 0.63 0.21 b*S9 242 trace 5-83 99.41 X. 46.66 37-40 2'32 0.18 trace 0'53 trace 6 09 2'41 trace 4'98 100'57 L. J. S. Chalybite from Croatia. FR. T U ~ A N (Juhrb. Min. 1910 ii Ref. 12 ; from Nastumi vjesnik Afonatsber. kroat. Miltelschulver. Agrum 1908 17).-Fourtecn analyses are given of chalybite from various localities in Croatia. L. J. S. New Occurrence of Plumbojarosite. WILLIAM F. HILLEBRAND and FRED. E. WRIGHT (Amer. J. Sci. 1910 [iv) 30 191-192. Com- pare Abstr.1902 ii 667).-The mineral was found at American Fork Utah as friable lumps consisting of minute brownish-red glistening crystals with pyromorphite and calcite. The crystals are rhombo- hedra] with the basal pinacoid largely developed and a rhombohedron (CP = 53O40' about) ; they are optically uniaxial and negative and strongly dichroic. Analysis gave Fe,08. PbO. K20. Na,O. SO,. H,O. CuO. CaO. Insol. Total. 42*87* 18.46 0.15 0.52 27.67 10.14 0.10 0.06 0'40 100.37 * Includingpery little P,Oa and probably some Al,O,. L. J. S.MINERALOGICAL CHEMIS I'ltY. ii. 967 Oxalite from Cape d'Arco (Island of Elba). ERNESTO MAKASSE (Atti. R. Accad. Lincei 1910 [v] 19 ii 138-145).-The mineral was found in a vein of oxide and hydroxide of iron and manganese which also contains pyrites and galena.It forms small transparent prisms or tablets of an amber-yellow colour hardness about 2 D 2.28. Analysis leads to the formula FeC20,,2H,O FeO. MgO. C,O,. H20 (by difference). 40'72 trace 40.18 19-10 An oxalate of similar composition but only microcrystalline was prepared. from ferrous ammonium sulphate or ferrous chloride with oxalic acid. The crystallographic examination of the mineral gave [a b c = 0.77297 1 1.103921. The crystals are birefractive to an unusual degree. R. V. S. Mizzonite from Cape d'Arco (Island of Elba). ERNESTO MANASSE ( A t t i R. Accccd. Lincei 1910 [v] 19 ii 211-215).-The mineral was found in association with quartz in small veins of mangsn- ese oxide and hydroxide in a mine which yields iron and manganese.I n close proximity occur crystalline schists and calcite of presilurian origin. It has hardness 5-6 and D 2.60. The crystals are prismatic have a nacreous lusbre and are birefractive. SiO,. AI20,. Fe,O,. CaO. MgO. Na.,O. K,O. C1. redheat Total. 54-40 24'44 trace 10.19 trace 7-59 1'69 1.53 1-43 101.27 which is in agreement with those required by the amorphous mixture The values observed for the indices of refraction and the birehaction are also in accord with this structure. Analysis gave Loss at i Na,IlAlClI AI2ISi,O,J&,ICa,C A101 ~ 1 * [ S ~ 2 ~ 1 0 1 ~ 2' R. V. S. Minerals from Ruwenzori. LUIGI COLOMBA (Jcdrb. Jf in. 19 10 ii Ref. 41-42; from 66L? Iiuwenxori" by the Duca degli Ab?*ztxxi Milccno 1909 2 281-286).-'l!he minerals collected from the amphi- bolite granite and pegmatite are described and analysis given of the following I-IV Epidote as small striated needles (I greyish- green ; 11 prtle green ; 111 bromnish-green ; IV colourless from Lake of Garda in northern Italy).SiO R,O (RO,R,O) = 10 5 9 whilst in the others it is 2 1 2. V Albite,as small crystal drusea in crevices ; TI Microcline massive ; VII Garoet (pyrope) as bright red distorted crystals associated with microcline ; VITI Ilmenite in- distinct crystals associated with albite SO,. A1,0,. Fe,O,. FeO. CaO. MgO. K,O. Na,O. H,O. Total. I. 38.21 30.84 - 7 25 20.43 0'38 - - 2-71 99'82 11. 37.63 31.41 - 4.38 23-70 - - - 2'19 99'31 111. 38.31 23'47 12'29 - 23-52 - - - 2'42 100*01 7'83 20'34 0.93 - - 2.64 100.07 V. 67'43 20'15 - - 1.43 - - 10.2i" - 99.28 VI.64-30 19.69 - - I - 15.33 0.71 0.40 100'43 VI1.f 41.43 24.71 1-37 10.31 5.33 16'51 - - - 99.66 In analysis 111 the ratio of IV. 37-95 30.38 - * M'ith a little K,O. t MnO trace. TiO,. FeO. Fe,O,. MgO. Total. VIII. 52.i3 45 83 nil. 1'25 99'81 L. J. S.ii. 968 ABSTRACTS OF CHEMICAL PAPERS. A Garnet containing Iron and Chromium from Praborna (St. Marcel). LUIGI COLOMBA (86ti R. Accad. fimei 1910 [v] 19 ii 146-150).-The mineral occurs in association with hsmatite quartz albite and tihnite whilst native gold and kammererite are also to be found in the same situation. Analysis yielded the following figures SiO,. A1,03. Fe,O Cr,O,. CaO. MgO. MnO. FeO. Total. 35.57 0.62 22'22 7.81 27-13 trace 3.94 2'51 99-80 which correspond when the small amount of aluminium is neglected with the typical garnet composition R:(Ri)V1Si304' From a com- parison of the analytical data with those found for various specimens of uvarowite.the author considers it mobable that this mineral also belongs to that group. It has D 3-81 aAd isvery strongly birefractive. R. V. S. Gageite a New Mineral from Franklin New Jersey. ALEX- ANDER H. PHILLIPS (Amer. J. Xci. 1910 [iv] 30 283-284).-This is found in very small amount as delicate acicular and hair-like colourless crystals arranged in radiating bundles and is associated with zincite willemite calcite and leucophcenicite. When heated the clear crystals lose wafer and assume a deep bronze colour. Analysis by R. B. Gage gave SiO,. MnO. ZnO. MgO. H,O. Total. 24'71. 50-19 8 *76 11.91 [4.43] 100.00.Formula 8R0,3Si0,,2H20. The mineral appears to be closely related t o leucophcenicite (Penfield and Warren Abstr. 1900 ii 89) and it is perhaps one of the undescribed species mentioned by Penfield and Warren. The Chemical Composition of the Stassfurt Salt Clays. E. MARCUS and WILHELM BILTZ (Zeitsch. anorg. Chem. 1910 68 91-lOl).-The portion soluble in water is estimated by boiling with water and washing until no more chlorine passes through. The main analysis is made by Hillebrand's method. Water is estimated by heating with dried sodium carbonate or lead oxide in 3 current of air. The methods employed are described in detail. In the following arialyces arranged in order of depth I is a hard salt clay I1 a shaly salt clay 111 a soft loamy clay and I V a hard clay immediately in contact with the anhydrite Xoluble in Water L J.S. NaCl. KCl. MgCl,. K,SO,. CaSO,. MgSO,. I. 0-36 - - 16.94 36.11 12.06 11. 0.61 0.31 0'73 - 35-14 0.94 111. 1-09 0.40 5'41 0.33 1.19 - IV. 0'23 0.16 1 *44 - Insoluble CaSO,. CaO. MgCO,. MgO. R,O. Na,O. Al,O,. I. 22'72 0.53 - 1-56 0.11 0'26 0.78 11. 27'06 0'88 - 3.88 0.61 0.005 4-51 IT. 0.70 - 75-43 0.54 0.29 0.09 2.16 111. 0.87 - - 10.41 2.53 0'38 17-04 0 *92 0.74 Fe,O,. FeO. Mn,O ZnO. SiO,. 0'40 0.05 - trace 2.98 0.50 0'49 0.14 19.46 2.00 1.56 0.27 0.11 37.80 0.37 1'51 0.10 11.17 + +PHYSIOLOGICAL CHEMISTRY. ii. 969 Total Bitu- TiO,. P,O,. H20. C. COP S. Vd,O,. (corrected). men. I. 0.05 trace 4-51 0.07 0.69 trace - 100'22 0 '11 11. 0-24 0.01 3'99 0'15 0.53 trace ~0'02 100 21 0.15 I11 0-64 0'13 16'39 0.16 0.75 0.03 0'02 99-52 0.12 IV.0.13 0.08 3 94 0.22 - 0'03 <0-01 100.25 0'11 All contain traces of lithium and chromium and all but (I) also contain small quantities of boric acid and bromine. The minute quantities of ammonia nitrates and copper have been recorded previously (Abstr. 1909 ii 571 1011). C. H. D. The Amount of Thorium in Sedimentary Rocks. 11. Arenaceous and Argillaceous Rocks. JOHN JOLY (Phil. Mug. 1910 [vi] 20 353-357).-Whereas the calcareous rocks show a small almost negligible quantity of thorium (compare this vol ii 723) the detrital sediments in almost every case contain easily measured amounts the argillaceous group having almost double the amount in the arenaceous group. For the former 1.3 and for the latter 0.6 ( x 10-5 gram per gram) may be taken as average values. Twelve specimens of arenaceous and conglomeritic rocks mainly sand- stones were examined and eighteen specimens of argillites mainly slates. A specimen designated as '' Graumacke Wipperfurth Rben- Prussia Middle Devonian" gave the highest result (2.4). The higher thorium content of the slates and shales is attributed to the sorting out by gravity of the large particles of quartz or felspar which are poor in radioactive constituents. F. 5.

ISSN:0368-1769    

DOI:10.1039/CA9109805963

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. ii. 969 Influence of a Rise of Body Temperature on the Blood Gases. WILHELM CAS!ARI and ADOLF LOEWY (Blochem. Zeitsch. 1910 27 405-417).-At great altitudes (Monte Rosa) a rise of body temperature is very frequent and symptoms of acidosis occur. The fall in the oxygen tension is compensated for by increased respiration so that the oxygen in the tissues is but little affected ; the elevation of body temperature and the acidosis are favourable factors for the dissociation of oxyhaemoglobin in the tissues. The body is thus able to compensate for the alterations in pressure. The heart is not affected. W. D. H. The Gases of Gat’s Blood. GEORGE A. BUCKMASTER and JOHN A. GARDNER (J. Physiol. 1910 41 60-63).-Data of the gases in cat’s blood are scanty ; the authors used their new form of gas pump.The following are the mean figures of niimerous analyses. In the third line the analyses were made with a Topler-Barcroft pump; here the nitrogen values mere between 1-5 and 4%; these have been adjusted to 1-00 to make the figures comparable to those in the firstii. 970 ABSTRACTS OF CHEMICAL PAPERS. line. anasthetised with urethane The cats used were killed either by a blow on the head or were Total gas. cop Oxygen. Nitrogen. Arterial blood ......... 39 $8 25'07 13-60 1 -00 Venous blood ............ 51 -53 40.83 9'93 0.77 Arterial blood.. .......... 33'29 17.69 14-61 1 -00 W. D. H. Cryoscopy of Blood. W. R. G. ATKINS (Bio.-Chem. J. 1910 5 225-216).-A few observations on the_value of A for the blood of various animals; some amount of variation is noted and in some cases this may have been pathological.W. D. H. The Inorganic Constituents of the Blood in Vertebrates and Invertebrates and Its Origin. ARCHIBALD B. MACALLUM (Proc. Roy. Xoc. 1910 B 82 602-624. Compare Abstr. 1904 ii 495).-Analyses of the ash of the blood in various animals are given and compared with the saline contents of the ocean at various geological periods. The arguments advanced are speculative but the facts so far as a t present collected support the author's previous conclusion that the saline composition' of the sea determines that of the blood of marine organisms and that the inorganic cornposition of vertebrate blood-plasma is an heirloom of life in the primeval ocean. The date of the origin of the vertebrate kidney is placed between the second eighth and the second sixth of the whole geological period W.D. H. Haemolysis. Is there a Cocaine Haemolysis? GEORG FISCHER (P$iiger's Archiv 1910 134 45-58).-Cocaine solutions have no specific haemolytic power but such hsemolysis as occurs is due to dissociation and liberation of hydrogen ions or to decomposition of the cocaine molecule and liberation of hydrogen ions and alcohol. W. D. 13. Origin and Destiny of Cholesterol in the Animal Organism. VII. The Quantity of Cholesterol and Cholesterol Esters in the Blood of Rabbits Fed on Diets containing Varying Amounts of Cholesterol. MARY T FRASER and JOHN A. GARDNER (Proc. Roy. SOC. 1910 B 82 559-568).-When chol6sterol is given with the food some is absorbed and the free cholesterol and the cholesterol esters in the blood are increased. If phytosterol is given this substance is partly absorbed and the free cholesterol of the blood rises.The digitonin method for estimating cholesterol is very accurate. Phytosterol does not appear in the blood as such. W. D. H. Action of Acids a n d Alkalis on the Artiflcial Anti-serum of the Ox which is Hzemolytic to Rabbits. GIOVANNI MoRuzzr (Biochem. Zeitsch. l910,!2'7,498-515).-Hydrochloric acid completely inhibits the haemolysis when present to the extent of 0.015N; it doesPHYSlOLOGICAL CHEMISTRY. ii. 971 not destroy the hsemolytic power for this again becomes evident on neutralisation. There is no destruction either of the amboceptor or the complement. Dilution with normal saline solution does not revive the process.Similar experiments with sodium hydroxide show many analogies to the action of hydrochloric acid. There is no increase in viscosity in either case W. D. H. The Relationship between the Anti-trypsin of the Blood and that of the Urine. GOICHI HIRATA (Biocl~m. Zeitsch. 1910 27 397-404).-1n artificial nephritis in rabbits there is a great rise in the anti-trypsin of the urine and of the blood. In nephritis produced by uranium salts the rise is first seen in the urine ; in t h a t produced by chromic acid first in the blood; in spontaneous albuminuria and in that produced by mercuric chloride the rise in both fluids is simultaneous. W. D. H. Inhibition of Precipitation by Precipitoids. WILHELM SPAT (Biochem.Zeitscl’. 1910 28 7-15).-The experiments described show that the inhibition of precipitation produced by inactivated immune serum or normal serum is not brought about by a union between the inactive serum (precipitoid) and extracts of bacteria employed. W. D. H. Estimation of Adrenaline in Normal Blood and after its Injection by means of Physiological Methods. PAUL TRENDELENBUHG (Arch. exp. Path. Pharm. 1910 68 161-176) -The physiological test adopted was in principle that of Laewen (ibid. 1904 51 415) namely the measurement of the vaso-constrictor effect on the frog’s hind limbs by the rate of outflow when perfused with the sub- stance dissolved in Ringer’s solution. The quantity of adrenaline in the blood stream of cats after an injection runs parallel to its pressor effect.As the blood pressure falls the amount OE adrenaline in the circulation sinks. Adrenaline thus resembles muscarine in its rapid dieappearance. W. D. B. Speciflc Adaptation of Digestive Juices. I. Specificity of Gastric and Pancreatic Juice. E. S. LONDON and W. N. LUKIN. 11. Specificity of Duodenal Mixed Juices. E. S. LONDON and R. S. KRYM. 111. E. S. LONDON and N. DOBROWOLSKP-JA (Zeitsch. physiol. Chem. 1910 68 366-370 371-373 374-377).-T. From experiments on fistulous dogs varying kinds of food placed in the intestine lead to specific variations in the quantity of bile and pancreatic juice secreted but not to variations in the amounts of the pancreatic enzymes. When fat is introduced there is no increase (five cases out of seven) in the lipase secreted in the ‘‘ small stomach.” I T .The same is true for the mixture of juices in the duodenum when the food is introduced into the lower jejunum and ileum. 111. There is similarly no adaptation of the enzymes of the intestinal juice. Oleic acid and amino-acids are specially powerful stimulants in regard to the amount of juice secreted W. D. H.ii. 972 ABSTRACTS OF CHEMICAL PAPERS The Laws of Digestion and Absorption. VI. The Distance Law of Solution by Duodenal Juice. E. 8. LONDON and C. SCHWARZ. VII. The Neutralisation Laws of Digestive Juices. E. S. LONDON and 0. J. GOLMBERC. VIII. The Action of Various External Factors on the Secretion of Duodenal Juices. IX. Digestion of Carbohydrates. E. S. LONDON and A. P. KORCHOW (Zeitsch. physiol. Chem. 1910 68 346-351 352-357,358-362,363-365.Compare this vol. ii 422).-.VI. By experiments on dogs with fistulse it was found that the effect of an acid peptone solution in calling forth the secretion of the pancreas and liver is not limited to the duodenum but extends as far as tho upper ileum a distance of about 2 metres ; this action in stimulating secretion diminishes analwards with the square root of the distance from the point of stimulation. VII. The quantity of pancreatic juice is directly proportional to the square root of the concentration of the gastric juice and its alkalinity inversely proportional The total amount of alkali in the duodenal juices is inversely proportional to the square root of the gastric juice concent ration. VIII. Further laws are laid down in regard to the duodenal juices (bile pancreatic juice intestinal juice) in all of which the square root figures largely.IX. Three hours after a meal of flesh and starch in a dog the stomach contents contain the same amount of starch although the amount given varies from 40 to 100 grams. W. D. H. The Chemistry of Digestion and Absorption in the Animal Body. XL. The Study of Gastric Digestion on a Mixed Protein Diet. E. S. LONDON and C. SCHWARZ (Zeitsch. physiol. Chem. 1910 68 378-380. Compare this vol. ii 422).-Gastric digestion is epecially furthered by those proteins (such as meat compared with egg- white) which stay longest in the stomach W. D. H. Digestion of Fat in the Stomach and Small Intestine and the Effect of Lecithin on it. USUKI (Arch. exp. Path.Pharm. 1910 63 270-293).-1f lecithin or egg-yolk is mixed with milk the rate of fat digestion is increased and the contents leave the stomach sooner. The addition of lecithin lessens the amount of soaps in the intestine and increases it (after egg-yolk) in the faxes ; this is explained by absorption processes in the large intestine. The splitting of lecithin in the stomach occurs more quickly than that of neutral fats. Lecithin favours the saponification and digestion of neutral fats. I n spite of its small percentage of lecithin fat digestion is more favoured by egg-yolk than by lecithin itself; this is probably due to the fineness of the emulsion as well as the chemical nature of the fat in yolk. No lecithin was found in the intestine; it must therefore be split up either in the stomach or soon after its entrance into the duodenum.The observations were made on dogs and children. W. D. H. Phosphorus Metabolism in the Animal Organism. FELIX ROGOZINSKI (Bull. Acad. Sci. Cracow 1910 B 260-312).-SodiumPHYSIOLOGICAL CHEMISTRY. ii. 973 phosphate phytin and lecithin added to the diet of a grown dog produce no marked change in nitrogenous metabolism. Sodium phosphate is excreted quantitatively in the urine. Lecithin when given is not found in the fzeces; its phospharic acid appears quantita- tively as inorganic phosphate in the urine ; the phosphorus of phytin appears to the extent of 30% as phosphoric acid in the urine; the remainder is Found as phytin in the faeces. I n opposition to the work of others phytin in man causes no change in the excretion of nitrogen or phosphorus; a small part of the phosphorus is retained; the remainder appears as inorganic phosphate in the faeces. I n contrast with the dog human faeces contain abundant lecithin corppounds. No inositol is found in human urine after feeding on phytin.The bacteria of human faxes are able in vitro to decompose phytin and produce inorganic phosphates from it W. D. H. Physiological Protoplasmic Metabolism and Purine Forma- tion. F. MAREB (P’tiger’a A~chiv 19 10,134 59-102).-The various theories of the origin of purine substances especially uric acid (for instance the muscular theory the leucocyte theory etc.) are discussed a t length Purely chemical views are discountenanced for the source of purine is to be sought in the physiological activity of the living cell.The constancy of uric acid excretion in individuals is true only for fasting periods and c6nsiderable stress is laid on the importance of the work of the digestive organs as a means of increasing uric acid forma- tion. The nucleus of the cell is the main part concerned and the same is true for other active cell masses for instance malignant growths The importance of the digestive glands is shown by the fact that pilocarpin raises the uric acid output W. D. H. The Metabolism of Some Purine Compounds in the Rabbit Dog Pig and Man. LAFAYETTE B. MENDEL and JOHN F. LYMAN (J. Biol. Chem. 1910 8 115-144).-The examination of tissue extracts has shown that in different animals the purine enzymes are differently distributed ; the present experiments in which purines were given either parenterally (in animals) or by the mouth (in man) support the view that the metabolic history of the purines varies in different animals The difficulty man has in oxidising uric acid as shown by its reappearance in the urine after parentsral administration fits in with the examination of tissue extracts in which no uricolytic enzyme is found in human tissues.On the other hand a large proportion of the uric acid introduced into the rabbit does not reappear as such. After injection of adenine in dogs and rabbits there is a relatively large output of unaltered adenine and but little uric acid or allantoin. If guanine is given there is a larger output of allantoin xanthine and uric acid. Guanase is more widespread in rabbit and dog tissues than adenase.I n the pig uric acid is not the chief end-product of purine metabolism. I n man the protocols given ernphasise the fact that all the ordinary purines lead to an increase of exogenous uric acid with but little influence on the elimination of purine bases in the urine. W. D. H.ii. 974 ABSTRACTS OF CHEMICAL PAPERS. Cleavage of HiRtidine in the Organism of the Dog. ENIL ABDERHALDEN HANS NINBECK and JULIUS SCEMID (Zcitsch. physiol. Chem. 1910 68 395-399. Compare Abytr. 1909 ii 906).- Intravenous administration of histidine in a dog does not lead to increase in tho excretion of allantoin in the urine. If given by the mouth the increase of allantoin is very slight and sometimes absent. Very little of the histidine given (0.4 out of 20 grams) is recoverable as such in the urine.Nucleic acid raises the allantoin excreted. W. D. H. Influence of the Removal of Fragments of the Gaetro- intestinal Tract on the Character of Nitrogen Metabolism. 111. The Excision of the Stomach. A. CARREL GUSTAVE M. MEYER and PH~BUS A. LEVENE (Arner. J. PJ~ysioZ. 1910 26 369-380. Compare this vol. ii 323).-Two dogs were operated on and in one of them the extirpation of the stomach mas quite complete. Before the tenth week there is high nitrogen retention probably because the pancreatic and intestinal secretions are interfered with but after this date no nitrogen retention occurs Parenterally introduced protein was completely retained in the organism. W. D. H. Imbibition of the Intestinal Mucous Membrane with Sodium Chloride and Sulphate Solutions of Different Concentrations.G. QUAGLIARIELLO (Biochem. Zeitsch. 19 10 27 5 16-529).-The present experiments deal with sodium sulphate ; they support Loepei’s conclusions and show that the salt has an inhibitory influence on imbibition but this is regarded as a secondary effect ; the opinion is held that it is the ions working on t h e intestinal muscle which explains the purgative action of the salt. W. D. H. The Influence of Sugar on the Permeability of the Intestinal Membrane. ERNST MAYERHOFER and ERNST STEIN (Biochem. Zeitsch. 1910 2’7 376-384).-The permeability of the intestinal mucous membrane of rabbits removed after deatb is increased t o wards normal ammonium chloride solution by placing the membrane in a 5% solution of dextrose.Supposing the same to be true in vivo cases of dyspepsia due to excess of sugar are explicable. W. D. H. The Fate of Sucrose after Parenteral Introduction in Animals. LAFAYETTE B. MENDEL and ISRAEL 8. KLEINER (Amer. J. Phyezol. 19 10 26 396-406).-When sucrose is introduced intra- peritoneally or subcutaneously into dogs and cats in doses of 1-2 grams per kilo. of body-weight about 65% is recovered in the urine and a reducing laevorotatory substance is also sometimes present. The excretion begins within a few minutes and is usually completed in thirty-six hours. The actual figure however varies with different conditions (fasting pregnancy etc.). Sucrase was not found in the blood; nevertheless as Abderhdlden and Brahm showed there i 3 a possibility of sucrose digestion in the blood which may account for the disappearance of part of the sugar.W. D. H.PHYSlOLOGICAL CHEMISTRY. ii. 975 The Value of Beer-extract a n d Beer in the Human and Animal Organism. WILHELM VOLTZ RUDOLF ~ORSTER and AUGUST BAUDREXEL (P’iiger’s Archiv 1910 134 133-258).-The dry residue of beer extract elevates the absorption of non-nitrogenous material especially fat. Approximately 40% of the nitrogenous substance is absorbed. Observations both on men and dogs are given and deductions as to its nutritive value coincide i n the main with those of Atwater and Benedict. Observations with toxic doses are also given. The general trend of the article is a defence of the use of alcohol in moderation especially in the form of beer.W. D. H. Digestibility of Bleached Flour. ELBERT W. ROCKWOOD (J. Biol. Chem. 1910 8 327-340).-Experiments on the artificial digestion of unbleached flour as compared with specimens of the same flour bleached with nitrogen peroxide show no loss of digestibility and in some cases the bleached specimens digested more rapidly than the unbleached. W. D. H. The Value of the Cleavage Products of Protein in the Animal Organism. XVI. EMIL ABDERHALDEN and AKIKAZU SUWA (Zeitsch. physiot. Chenz. 1910 68 416-420. Compare this vol. ii 877).-A dog mas fed exclusively on the cleavage products of flesh without admixture of fat or carbohydrate. The preparation used was ‘‘ ereptone,” made from meat by the successive action of gastric pancreatic and intestinal juices. Vomiting and diarrhea were to some extent overcome by giving the food carefully in small doses through a gastric fistula.The animal gained in weight and put on flesh. The conclusions drown by Voit and Zisterer (this vol. ii 425) from somewhat similar experiments are criticised. W. D. H. The Temperature-coefficient of Cytolysis in the Unfertilised Egg of the Sea-Urchin. A. R. NOORE (Quurt. J. exper. Pl~ysiol. 1910 3 257-260).-The temperature-coefficient for the process of cytolysis of sea-urchin eggs in sea-water was found to be about 200 for a difference in temperature of 10”. The same figure was calculated from Gros’s data for h~molysis. Differentiation of Proteins of Closely Related Species by the Precipitin Reaction. D. A. WELSH and H. G. CHAPMAN (J. Hygiene 1910 10 177-184).-1t is possible to distinguish hetero- logous proteins of closely related species by preciyitin interactions arranged with regard to the fact that in the conditions of experiment the weight of precipitates is proportional to the weight of the anti-serum employed.This is illuztrated by experiments with the albumin prepared from different birds’ eggs. The experiments support the authors’ previously expressed view that the anti-serum is the main source of the precipitate in the precipitin reaction. Chemico-Physical Investigations on the Crystalline Lens. FILIPPO BOTTAZZI and Noh SCALINC~ (Atti K . Accad. Lincei 1910 [v] 19 ii 162-169. Compare this vol. ii 143).-The authors have W. D. H. W. D. H.ii. 976 ABSTRACTS OF CHEMICAL PAPERS. investigated the influence of various chlorides (those of sodium potw4um.calcium and magnesium) and of varioua sodiiim salts (chloride nitrate acetate sulphate and tartrate) on the imbibition of water by the crystalline fens. Solutions of the following concentrations were employed iV/3 N/50 N/lOO A*/lEO N/200. In all cases the imbibition was less than that which occurs when the lens is immersed in pure water and the decrease was greater in the case of the N/5- solutions than with the weaker ones. As regards the specific actions of the different ions (For the elucidation of which the results with the strongest solutions are the most trustworthy) it appears that the bivalent cations (magnesium and calcium) diminish the imbibition more than the univalent cations (sodium and potassium) although there are considerable irregularities which are still more pronounced in the case of the different anions K.v. s. Heart Metabolism. I. Metabolic Investigations of the Surviving Warm-blooded Heart. ERWIN KOHDE (Zeitsch. physiol. Chem. 1910 68 181-235).-Previous work on the isolated mammalian heart such as that by Locke and Rosenheim on its capacity to utilise sugar or of Barcroft and Dixon on its gaseous metabolism is on the whole confirmed ; the special feature of the apparatus here used is that simultaneously means are adopted for measuring the work of the heart. The metabolic changes run parallel to the amount of work done. I n the presence of sugar not only is sugar burnt but often constituents in the heart itself (reserve material) are burnt also and thus leads to the production of carbon dioxide When sugar or other nutritive material is absent these reserve materials are alone utilisable; these probably originate from fat and protein and the hypothesis is put forward that the heart forms a sort of internal secretion in which glycolysis occurs W.D. H. The I n j u r y t o the Heart’B Activity Produced by Glyoxylic Acid. R. H. KAHN and EMIL STARHENSTEIN (Pjiiger’s Archiu 1910 133 579-597).-The bulk of this paper has but little chemical interest. Cardiac activity was studied by the cardio-electro- gram and the causes of pulsus alternans are discussed. I n glyoxglic acid poisoning this symptom is pronounced. W. D. H. Union Relationships of Heart Muscle and Digitalis. B. SCHLIOMENSUN (Arch. exp. J’ccth. f’harm.1910 63 294-302).-From the hearts of men and animals a group of substances can be isolated namely the alcohol-soluble phosphatides which appear to have a special capacity to combine with the active material in digitalis. The corre- sponding fractions from the skeletal muscles and liver do not possess this property. It is not possible a t present to say what are the definite chemical substance or substances that participate in this specific reaction. W. D. H. The Formation in the Animal Body of I-P-Hydroxybutyric Acid by the Reduction of Acetoacetic Acid. HENRY D. DAKIN (J. Biol. Chem. 1910 8 97-104).-The liver contains not only anPHYSIOLOGlCAL CElEhlISZ'RY. ii. 97'9 oxydase which converts /I-hydroxybutyric acid into acetoacetic acid but also a reductase which produces the reverse change. The view taken of E-P-hydroxybutyric acid acidosis is that its main underlying cause is defective catabolism of acetoacetic acid.The conclusions are supported by experiments. The question is discussed whether the phenomena are due to the reversible action of one enzyme or to the antagonistic action of two enzymes. The latter hypothesis fits in best with the facts. The Degradation of Carboxylio Acids in the Animal Body. XII. A New Method of Formation of P-Hydroxybutyric Acid in the Animal Body. ERNST FRIEDMANN and C. MAASE (Biochem. Zeitsch. 1910,27 474-490. Compare this vol.,ii 794 795). -In experi- ments on perfusion of the dog's liver with ox-blood a fair amount of I-P-hydroxybutyric acid is formed in most cases without the addition to tbe perfusing liquid of any substance which yields acetoacetic acid.If sodium acetoacetate is added to the perfusing blood a large amount disappears and from 42 t o 62% of this is accounted for by the I-P-hydroxybutyric acid formed. If sodium butyrate or especially iso- valerate is added there is a large formation of both acetoacetic and /?-hydroxybutyric acids. Similar results were obtained in experiments with pounded liver substance. The agent which converts acetoacetic acid into I-/3-hydroxybutyric acid is termed ksto-reductase. W. D. H. W. D. H. The Decomposition of Acetoacetic Acid by Enzymes of the Liver. 11. ALFRED J. WAKEMAN and HENRY D. DAEIN (J. Baol. Chem. 1910 8 105-108).-Further facts are given in relation to the liver reductase; the primary product of its action on acetoacetic acid is not acetic acid but I-/?-hydroxybutyric acid.H. ACKROYD (Bio.-Chem. J. 1910 6 217-224).-The liver of dogs when perfused with normal saline solution produces a small quantity of allantoin. When sodium urate is added to the perfusion fluid a part of it is destroyed; part only of this is recovered as allantoin; no urea could be isolated. The dog's liver has not the power to destroy allantoin. The Formation of Uramido-aoids in the Organism. I. FRITZ LIPPICH (Zeitsch. physiol. Chem. 1910 68 277-292).-The formation of uramido-acids in the body is important from the stand- point of urea formation and former work on the question is quoted a t length. The present experiments on the action of the dog's liver in the formation of such acids gave negative results.W. D. H. Uric Acid Metabolism in Dogs. W. D. H. W. D. H Liver Pigments of Invertebrates. RAFFAELE PALADINO (Biochem Zeitsch. 19 lo,% 56-59).-From the liver of invertebrates (molluscs being mainly used) two pigments were obtained one soluble in water the other in chloroform or alcohol. The former is rich in iron and gives a continuous spectrum the latter poor in or free from iron gives absorption bands. The same pigments are stated to be also obtainable from the vertebrate liver. W. D. H VOL. XCVIII ii. 66ii. 978 ABSTRACTS UP CHEMICAL PAPERS. Study of Autolysis by Physico-chemical Methods. If. ROBERT L. BENSON and H. GIDEON WELLS (J. Biol. Chem. 1910 8 61-67 Compare ibid. 1907 3 35).-Autolysis is usually measured by the change in the amount of nitrogen contained in forms coagulable and not coagulable by heat but it is shown by experiment3 with dog’s liver blood-serum and blood that autolysis can be followed much more satisfactorily by freezing-point determinations supplemented by electrical conductivity measurements. Toluene was found to be the most satisfactory antiseptic in these experiments. I n agreement with Eaer and Loeb (Abstr.1905 ii 734) the authors find that the inhibiting effect of serum on autolysis (the effect of dog serum on the autolysis of dog liver was observed) is scarcely affected by heating the serum at 8 5 O or 95’ for thirty minutes. In other cases the inhibiting effect of serum appears to be diminished by heating but there seems t o be some discrepancy in the results obtained when the autolytic changes are measured by physical or chemical means and when they are measured by the histological changes taking place in the cells.G. 8. The Occurrence of Free Guanosine in the Pancreas. PH~EBUS A. LEVENE and WALTER A. JACOBS (Biochem. Zeitsch. 1910 28 127-1 30).-The separation of guanylic acid from the pancreas was found to be difficult owing t o the presence of guanosine which is regarded as being in the free state. I n fact it is sometimes more abundant than the acid. W. D. H. Ethyl Acetate Extracts of Organs and their Behaviour in Autolysis. KENHO KONDO (Biochem. Zeitsch. 19 10 2’7 427-435 436-441. Compare this vol. ii 791).-The present experiments with kidney spleen sud blood were carried out in the same way as in previous work on the liver.The results with kidney and spleen (to some extent) were very similar and there appears to be present in these organs substances other than cholesterol containing hydroxjl groups the quantity of which increases in the warm. I n the case of the blood there was no evidence of any enzyme either in the corpuscles or plasma capable of splitting cholesterol esters. The acetpl number remains unchanged after autolysis. This is not due t o the presence of an inhibiting agent for the increase occurs when liver extract is added. IV. and V. W. D. H. Formation of Oxalic Acid in the Organiem. HERMANN JASTROWITZ (Eiochem. Zeitsch. 1910 28 34-47).-Oxalic acid can arise from uric acid aminodicarboxy lic acids and carbohydrates. In intermediate metabolism it is formed especially in the spleen and probably also in the liver and muscles (in dogs).I n anomalies of nuclein metabolism (gout leucEmia) increased oxalic acid formation occurs very seldom but it may occur in diabetes. W. D. H. Metabolic Disturbances after the Extirpation of both Supra- renal Glands. OSWALD SCHWARZ (PJltigev’s Archiv 1910 134 259-288).-Tlie animals used were rats j when both the suprareDakPIIYSIOLOG~CAL CHEMIS~~RV. ii. 979 arb i-enioved the hepatic glycogen is much reduced or disappears entirely ; this is regarded not as due to general marasmus but as a specific effect of the operation; when then fed on bread glycosuria is produced; with feeding on pure dextrose the glycogen returns in some measure to the liver. The administration of laevulose leads neither t o glycogen form-ztion nor to laevulosuria ; it is apparently completely utilised in the body ; feeding on sucrose leads to glycogen formation in virtue of its dextrose component ; after feeding on starch alanine or aspartic acid the liver is free from glycogen.Phloridzin is highly toxic to these animals; it produces glycosuria; they are also sensitive to adrenaline injections. A sugar mobilising function is assigned to adrenaline. W. D. H. Toxic Action of Compoundson Isolated Muscle Regarded as a Chemical Change. VICTOR H. VELEY (Quart. J. Exper. Physiol. 19 10 3 233-240).-Prom the experiments previously recorded by the author (mainly in conjunction with Waller this vol. ii 55 228 331 524) the conclusion is drawn that living muscular tissue behaves as if it contained not only proteins as such but even their products of decomposition or hydrolysis or in other words the living muscle behaves like a lifeless chemical reagent ; the results obtained are not greatly inferior in accuracy to those obtained in reactions between highly refined chemical compounds under rigid physical conditions.W. D H. The Quantitative Relations of Diastase in Different Organs of Different Animals. GOICHI HIRATA (Biochem. Zeitsch. 19 10 !27 385-396).-1n estimating the diastase Wohlgemuth’s method and notation are employed. The paccreas spleen liver blood kiduey and other organs of various mammals birds fishes and amphibians were investigated. The pancreas in all ca5es contains most diastase; the blood and liver generally come next; in rats on a starch diet the diastase value of the pancreas rises from 300 to 400-fold. L ~ O N GRIMBERT and E.TURPAUD (J. Phccrm. Chim. 1910 [vii] 2,289-292). -The presence of reducing substances in aqueous extracts of beef has long been known and the action has been variously ascribed to dextrose maltose isomaltose pentoses or glycuronic acid. The author finds that bouillon defaecated by mercuric nitrate solution or boiled with hydrochloric acid yieldR with phenylhydrazine a mixt.ure of phenylglucosazone arid phenylglycurosazone (Grimbert and Cernier this vol. ii 163). Glycuronic derivatives can also be detected by Tollens’ reagent in bouillon defaecated by mercuric acetate and from which the dextrose has been eliminated by the action of Bacterium coli.T. A. H. HAROLD C. BBADLEY (J. Biol. Cbem. 1910 8 237-250. Compare Abstr. 1907 ii 567).-Analyses of the amount- o€ manganese in the different parts of varions mussels are given. It is not regarded as merely adven- titious; it is con8:antly preseut asd in spite of the small amount W. D. H. Presence of Glycuronic Derivatives in Beef Bouillon. Manganese of t h e Tissues of Lower Animals. 66-2ii. 980 ABSTRACTS OF CHEMICAL PAPERS present in the muscular tissue (which has a low order of activity in theseanimals) probably plays a r81e in respiration. I n lakes poor in manganese (and poor also in the Crenothrix and diatoms which contain large amounts of manganese and form the food of the mussels) mussels cannot live. W. D. H. Alcohol-Oxydase in Animal Tissues.FR. BATTELLI and (Mlle.) IJNA STERN (Biochem. Zeitsch. 1910 28 145-1 68).-AZcohoZ-oxydase (alcoholase) is an enzyme which acts chiefly on ethyl alcoho1,and converts it into acetic acid byabsorptionof molecultw oxygen ; aldehyde is an inter- mediate product ; i t also oxidises aldehyde directly The enzyme does not decrease in amount in the tissues one or two days after death It is most abundant in the liver especially of the horse; the amount in human liver is relatively small ; the kidneys also contain it but the amount in other organs is very small It acts neitber in acid nor in strongly alkaline media; it acts best in faintly alkaline media Addition of spleen to the liver increases the effect. Hydrogen peroxide has no effect. W. D. H. Further Investigations on the Use of Silk Peptone for the Detection of Peptolytic Enzymes.Enm ABDERHALDEN and EUGEN STEINECR (Zeitsch. physiol. Chem. 19 10 68 3 12-3 16).-Details are given in regard t o the best methods for obtaining silk peptone. Slices of organs (for instance kidneys) placed in the peptone solution become i f :L peptolytic enzyme is present covered with cyrosine crystals. Whether healthy and pathological organs vary in this direction is to be further investigated. I n the developing chick peptolytic enzymes appear in the tissues at seventh t o eighth day of incubation ; in the pig embryo in nearly all the tissues after the thirty-seventh day of development. W. D. H. Enzymatic Acceleration of Cannizzaro’s Aldehyde Trans- formation by Tissue Extracts. 1. JAKOB PARNAS (Biochent.Zeitsch. 19 10 28 274-294).-Animal tissues usually contain both fatty acid and the corresponding alcohol and i t is suggested that these are both derived from aldehyde by the Cannizzaro transforma- tion. The liver but not the lungs contains a soluble ferment which accelerates this transformation so that it takes place with aldehydes which otherwise tend to undergo aldol condensation. Qiian titative production of the corresponding acid and alcohol was obtained from n- and isovaleraldehydes isobutaldehyde and propaldehyde also from heptaldehyde after three hours’ action of pig or ox liver. Cenz- aldehyde yielded a small quantity of alcohol ; salicylaldehyde was not attacked. The name aldehydemutase is proposed for the enzyme E. F. A. Enterolipase. B. C. P.JANSEN (Zeitsch. physiol. Chem. 1910 68 400-415),-As Lombroso showed a mixture of bile and oleic acid stimulates the secretion in the intestine of a juice rich in lipase. Oleic acid alone has no such effect. Bile alone has not so great an effect as [fie mixture. These experiments were made with intestinalPHYSIOLOGICAL CHEMISTRY. ii. 081 loops. 1% witro the addition of bile increases the lipolytic action of the juice. Soap solution causes the secretion of a feebly lipolytic juice ; in vitro soap inhibits lipolytic action but a small addition of alkali increases it. The addition of bile acids to bile increases its power of stimulating the secretion of lipase and the effect of the mixture of bile and oleic acid is probably due to the bile acids. The group in the bile acid molecule to which this is due is to be the subject of renewed investigation.W. D. H. Occurrence of Serine in Human Perspiration. GUSTAV ENBDEN and HERMANN TACHAG (Biochenz. Zeitsch. 1910 28 230-236). -Hitherto only two nitrogenous substances carbamide and ammonia have bsen isolated from perspiration. From fresh perspiration fairly large quantities of serine are now isolated by means of ,&naphthalene- sulphonic acid. This method is advantageous in separating serine from the mixture of protein decomposition products obtained by acid hydrolysis. E. F. A. The Production of Glycosuria in Relation to the Activity of the Pancreas. IVOR L. TUCKETT (J. Physiol. 1910,41,88-144). -Glycosuria due to anssthesia and operation is probably n o t influenced by the pancreatic factor ; neither is there evidence that the carbohydrate in the diet stimulates the pancreas to an increase in its internal secretion. Glycosuriafollowing fistula orligature of the thoracic duct is probably due to the anssthetic employed and to disturbance of nerves but as the internal seeretion of the pancreas finds its way into the circulation by this duct that may possibly be a subsidiary factor.The glycosuria associated with morphine and ether narcosis is the result of the rapid production of sugar from hepatic glycogen other carbohydrates in the body and also from fat. The sugar in the blood of cats exhibiting experimental glycosuris has a reducing power equal to that of dextrose W. D. H. Nature of Bence-Jones Protein. OWEN T. WILLIAMS (Bio.-Chem. J.1910 5 225-229).-The protein was obtained in the urine of a case of myeloma; it is shown that it varies in composition from time t o time even in the same case and probably the true explanation lies in the fact than in the disintegration of bones and tendons chondro-mucins are liberated which are more or less broken up and thus excreted differently according to the stage of the disease. The protein in the present case gave the typical reactions of the Bence-Jones protein It resembles mucoid in that it contains a carbo- hydrate radicle and a high percentage of sulphur. The latter however varies and when it sinks the amount of ethereal sulphato in the urine rises. W. D. H. Diastase in the Blood and Urine of Rabbits. GOICHI EIRATA (Biochenz. Zeitsch. 19 10 28 23-28).-1n experimental nephritis in rabbits the diastase in the urine sinks; this is regarded as due to lessened functional activity of the kidney cells and the decrease is greatest in cases where the injury is greatest.The rise of diastase i 4ii. 982 ABSTRACTS OF CHEMICAL PAPERS. the blood which accompanies this is regarded as due to defective elimination by the kidneys. W. D. H. Metabolism in Addison's Disease H. BEUTTENM~LLER and FELICITAS STOLTZENBERG (Biochem Ztitsch. 1910 28 138-1 44).- I n the case of Addison's disease investigated there was no important departure from the normal in nitrogen metabolism; on an abundant diet the patient retained nitrogen ; the administration of adrenal tablets had no effect. W. D. H. The Excretion of Creatine in Diabetes.R. A. KRAUSE (Quart. J. Exper. Physiol. 1910 3 289-296).-A full account of experi- ments already published as a preliminary communication (see Krause and Cramer this vol. ii 793). W. D. I€. Prophylaxis in Malaria. Action of Small Continuous Doses of Quinine on the Development of the Animal Organism and its Application in Intectious Disease. ALBERT GRAZIANC (Arch. Hygiene 19 10 73 39-80).-1njection of quinine hydrochloride for o m hundred days in doses of 0.005 gram per kilo. of body-weight in young rabbits and guinea-pigs delays growth and in adult animals lessens their weight. There is no change in the corpuscles or hzmoglobin of the blood; the bactericidal power of the lungs or of the serum is unaltered; so also are the opsonic index and the agglutinating action of t h e blood in reference to typhoid bacilli ; in fact in most cases the immunising power of the blood is diminished The animals which had received quinine are much less resistant towards infection (t-yphoid anthrax cholera pneumonia) than the control animals.Obscrvat>ions on the blood of nian show the same results and the conclusion is drawn that the same loss of resistance occurs in man also. w. 1). €3. Atoxyl. IV. FERDINAND BLUMENTHAL (Biochem. Zeitsch. 19 10 28 91-96. Compare Abstr. 1909 ii 255).-The use of rttoxyl preparations and of its various iodine and bromine derivatives in byphilis is suggested. The present experiments are mainly on animals t o discover the relative toxicity of these compounds; the silver salts are less poisonous than those of mercury.Absorption of Hydrogen Chloride by Animals. KARL B. LEHMANN and ARTHUR BURCK (Arch. Ifygiene 1910 72 343-357).- I n tracheotomised rabbits the amount of hydrogen chloride absorbed in the first hour varied between 58 and SO% of the amount inspired ; higher figures were obtained when the gas was given through the noee. The absorption increanes with the depth of respiration. I n the second hour there was no marked falling off in the rate of absorption ; experi- ments lasting more than two hours were not made. W. D. H. W. D. H. Absorption of Chloroform Carbon Tetrachloride and Tetrachloroethane in Animals and Man KARL B. LEHMANN and HASEGAWA (Arch. Hygiene 1910 72 327-342),-The experi-PHYSIOLOGICAL CHEMISTRY ii. 983 ments on two men mere carried out by estimating the chloroform in the inspired and expired air the difference giving the amount absorbed. I n periods of five to ten minutes from 53 to 73% of the cbloroform given was absorbed.I n experiments for longer periods the amount absorbed was greatest in the first five minutes and then gradually declined. I n rabbits the same falling off was noticed but the total absorption was less than in man. Administration was either made by the nose or by the tracheal tube but the method made no difference. Similar figures (in rabbits) were obtained with carbon tetrachloride and tet rac hloroethane. Influence of Gases on the Organism. XV. Hydrogan Arsenide. L. 0 DUBITZKI (Arch. Elygiene 19 10 '73 1-38).-This gas was estimated in the air volumetrically either by calcium chloride silver nitrate or potassium iodate.I n cats 0*0050/ is fatal in sixty to niuety minutes 0.004% in three hours. A prominent symptom is hzmolysis leading to haemoglobinuria. The absolute fatal dose varies from 8.7 to 13.7 milligrams. Action of Radium Emanations on the Development of Animal Eggs. 11. OSCAR HERTWIG (Sitxungsber. K Akad. Viss. Berlkn 1910 39 751-771).-Experiments on various eggs confirm the author's previous conclusions. The main interest of the paper relates to the action of the radium emanations on the sperm of the frog. After exposures varying from five minutes to twelve hours the spermatozoa becomes more or lees altered but the nucleus is the most affected. These spermatozoa are still capable of fertilisine; the eggs although development is slow in cases of long exposure and abnormal embryos are formed.This is regarded a s an additional proof that the nuclear substance is the most important part of the male cell in fertilieation. W. D. H. Action of Radium Bromide on the Skin of the Rabbit's Ear. J. 0. WAKELIN BARRATT (Quart. J. exper. Physiol. 1910 3 261-270). -A disk of radium bromide placed on the ear of the rabbit pro- duced a ring of pigmentation corresponding with the edge of the d~sk. Within the ring more or less depigmentation occurred. The deposit of pigment took place chiefly i n the epidermis. I n albino rabbits and with human skin no such effects were observed. W. D. H. W. D. H. W. D. H. The Pharmacological Action of Uranium. D. E. JACKSON (Amer. J. Physiol. 1'310 26 381-395).-The action of uranium is generally believed to resemble that of cyanides but there are many points of difference.Intravenously administered as the sodium uranium tartrate there is no increase in the flow of lymph from the thoracic duct even in lethal doses. The rise of arterial pressure is much more pronounced than that produced by CyanideQ and the stimulating action on respiration is less marked. Blood coagulation is prevented probably by union of the metal with one or more of the protein factors in the process. Further there is no change in the baeemoglobin. Cyanides binder the guaiacum reaction with oxtract of potato peelings ; uranium does not. W. D. H,ii. 984 ABSTRACTS OF CHEMICAL PAPERS. Behaviour of Iodoso- Iodoxy- and Iodonium Compounds in the Animal Organism 11.Behaviour of Iodoxybenzene. RICCARDO LUZZATTO and G. SATTA (Arch. Pawn sper. Sci. 1910 9 241-253. Compare this vol ii 433).-Even in quantities five times greater than the toxic dose of iodosobenzene iodoxybenzene does not cause death in dogs rabbits or frogs. The effects it produces are similar in kind t o those of the former substance but its action is much weaker and slower. It is converted in the organism into iodo- benzene for iodophenylmercapturic acid can be isolated from the urine and its lower toxicit,y is probably due to the fact that this reduction occurs more easily than in the case of iodosobenzene. Iodoxybenzene does not exhibit any curare-like action on from. R. V. S. - The Behaviour of P-p-Hydroxyphenyl-a-lactic Acid and p-Hydroxyphenylpyruvic Acid in the Surviving Liwer.ERNST SCHMITZ (Biochem. Zeitsch. 19 10,28,117-120).-Neubauer and Falta have shown that those aromatic substances the ring of which is e a d y burnt in the body are excreted in alcaptonuria as homogentisic acid whereas those which are not or only with difficulty broken up have no such influence on the excretion of homogentisic acid. Embden Saloruon and Schmidt have shown that the former group leads in the isolated liver t o formation of acetoacetic acid whereas the latter does not. I n the present experiments on liver peifusion this is confirmed ; /3-p-hpdroxyphenyl-a-lactic acid does not yield homogentisic acid and leads to a negligible formation of acetone substances in the liver; p-hydi oxyphenylpyruvic acid leads to homogentisic acid formation in alcaptonurics and t o an abundant formation of acetone substances in the surviving liver.W. D. H. Chemical and Physiological Properties of Triphenglstibine Sulphide. Behaviour of this Substance in the Animal Body. LUDWIG KAUFMANN (Biochonz. Zeitsch. 19 10 28 67-86 86-90. Compare Abstr. 1908 i 1031).-Triphenylstibine sulphide has the power to produce the evolution of oxygen from hydrogen peroxide and other peroxides ; the sulphur is split off and oxidised to sulphuric acid wbilst the residue is oxidised to antimony oxide or hydroxide and precipitated as sull 'hate by the sulphuric acid. The reaction runs quantitatively a t a temperatnre of 36-37'. The sulphite is -one hundred times more active than ordinary sulphur. The therapeutic use of the sulphide in cases (for instance of skin disease) where sulphur is usually employed appears from a few preliminary observations and experiments to be justifiable.W. D. H. Chemical Structure and Sympathomimetic Action of Amines. GEORGE BARGER and HENRY H. DALE (J; Physiol. 1910 41 19-59). -The action of adrenaline on the sympathetic is termed sympatt:omimetic arid is also shown by ii litrge series of amines the siniplest being primary fatty amines. The action incrrases with approximation to adrendline structure. The amines active in this wayPHYSIOLOGICAL CHEMISTRY. ii. 985 are primary or secondary ; the quaternary amines corresponding with the aromatic members of the series have an action like that of nicotine. The optimum carbon skeleton for sympathomimetic activity consists of a benzene ring with a side-chain of two carbon atoms the terminal one bearing the amino-group.Another optimum condition is the presence of two phenolic hydroxyls in the 3 4 position relative to the side- chain ; when these are present an alcoholic hydroxyl still further intensifies the activity. A phenolic hydroxyl in the 1 position does not increase the activity. Catechol has no such activity. The methyl- amino-group including adrenaline reproduces inhibitory sympathetic effects more readily than motor effects; the opposite is true for the primary amines of the same series. Instability and activity show no parallelism in the series. W. D. H. The Pate of p-Hydroxyphenylethylamine in the Organism. ARTHUR J. EWINS and PATRICK P. LAIDLAW (J.I-’hpi~Z. 1910 41 78-87).-This amine is converted in part in the body into p-hydroxy- phenylacetic acid; the surviving liver can effect this change so also can the plain muscle of the uterus but not that of the lung vessels. The isolated heart causes complete destruction oE the amine. The amine is less readily converted into hydroxyphenylacetic acid than the primary amine and hordenine the tertiary base still less readily than the secondary base. The Behaviour of Veronal (Sodium Veronal) in the Animal Body after One Administration and in the Chronic Con- dition. C. BACHEM (Arch. exp. Path. Phc~rrn. 1910 63 228-241).- After the subcutaneous injection of small doses of veronal about 90% appears in the urine; in larger doses this sinks to 45-50% whether the drug is given in one or successive doses.The faeces contain only a small quantity so about half is destroyed in the body how or why is unknown. Small doses do not influence the well-being of the animals used. After three days only small amounts are still found in the urine and organs. Its affinity for brain tissue is doubtless related to its narcotic properties. Even after large doses a small fraction only is found in the stomach some hours later. I n acute poisoning the stomach must therefore be washed out early if it is to be of any avail. W. D. H. The Prophylactic Action of Atropine in Immediate Anaphylaxis of Guinea Pigs. 111. JOHN AUER (Amer. J. Physiol. 1910 26 439-452).-Guii~ea pigs seribitised by the subcutaneous injection of 1 to 2 C.C. of horse-serum reach their maximum sensitive- ness about the ninth week and this is then maintained for a t least twenty-three weeks (the longest interval tested).Atropine was used as a prophylactic as the symptoms of anaphylaxis are mainly due to contraction of bronchial muscles. Experimentally atropine was found to be of distinct therapeutic utility. Without atropine the death rate was 75% with it only 28%. The Clinical Application of Ergotarnine (Tyramine). ALFRED CLARK (Bio,-Chem J. 1910 5 236-242).-Tyrdrnine given by ths W. D. H. W. D. H.ii. 986 ABSTRACTS OF CHEMLCAL PAPERS. mouth to a healthy subject in doses o€ 30 to 100 mg. causes a slight rise of blood-pressure which lasts some hours. When injected hypo- dermically (20 to 50 ma.) the rise is rapid and well marked lasting about twenty minutes.When similarly given in cases of ‘‘ shock,” the blood-pressure rises slightly. W. D. H. Action of Curarine and Allied Substances. RUDOLF BOEIJM (Arch. exp. Path. Pharm. 1910 63 177-227).-The direct excit- ability of skeletal muscle (frog) to induction shocks remains unaltered even by large doses of curarine but the excitability varies in different parts. Towards condenser discharges the effects are variable as also they are in normal muscles. Muscles can easily be poisoned with curarine by immersing them in a solution of the drug. The great toxicity of the drug comes out when it is compared with other ammonium derivatives ; the fol!owing relative figures are given Choline 0.35 ; tetraethylammonium 0.1 25; trimethylethylammonium 0.015 ; neurine 0.012 ; tetramethylammonium 0.005 ; muscarine 0.0025 ; trimethylvalerylammonium (valearine) 0.001 ; curarine 0~00001.W. D. H. Elementary Action of Digitalis Substances. RUDOLF MAGNUS and (Miss) S. C. M. SOWTON (Arch. exp. Path. Pharm. 1910 63 255-262).-Obserrations by the authors confirm Straub’s views on the action of the digitalis group. The increased activity of the heart can be shown not only in the intact animal but also on the isolated heart. Illustrative experiments on the effect of strophanthin are given in full. W. D. H. The Concentration of Ammonia in the Blood of Cats and Dogs necessary to Produce Ammonia Tetany. CLARA JACOB- SON (Amer. J . Physiol. 1910 26 407-412).-Ammonium carbonate was injected intravenously and the concentration in the blood found necessary to produce tetany is identical with the concentration of ammonia in the blood when tetany occurs as a result of removal of the parathyroids.In the latter condition the liver is depressed in its power to destroy ammonia. W. D. H. Antimony Poisoning in Compositors. P. SCHRUMPF and H. ZABEL (Arch. exp. Path. Pharm. 1910 63 242-254).-Various symptoms presented by compositors could not be attributed t o lead poisoning but are due to antimony ; the blood conditions underlying this are a slight leucocytosis but a great excess of eosinophile cells. Similar conditions can be produced artificially by antimony in rabbits. No drug treatment is suggested ; mere cessation of work in the men; or cessation of antimony dosage in animals leads rapidly t o a return to normal conditions. W. D. H. The Comparative Toxicity of Theobromine and Caffeine as Measured by their Direct Effect upon the Contractility of Isolated Muscle. VICTOR H. VELEY and AUGUSTUS D. WALLER (PTOC. Roy. Soc. 1910 82 B 56S-574).-Caffeine produces con-VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 987 tracture and finally abolition of contraction i n muscle. With caffeo- tannic acid the admixture with tannic acid retards the change. Theobromine cause8 a similar effect its toxic value compared with that of caffeine being 1.7 1 for equal molecules or 1.8 1 for equal weights. The introduction of the methyl group into theobromine to form caffeine lowers the toxicity a result converse to that found in certain other organic compounds. Experiments are also recorded with extracts of tea and coffee; “caffeine-free’’ coffee has but little action. The Relationship of Surface-tension to t h e Union of Toxin and Anti-toxin. AMTLCARE BERTOLINI (Biochem. Zeitscla. 19 10 28 60-66).-Traube sbated that hoxins in opposition to anti-toxins lower the surface-tension and that the union of toxin and anti-toxin has a still greater effect than the toxin. The present investigations made with diphtheria and tetanus toxin and anti-toxin do not confirm this view. The union has no effect on surface-tension as tested by Traube’s stalagmometer. W D. H W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9109805969

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 987 Chemistry of Vegetable Physiology and Agriculture. Apparatus for Collecting and Measuring the Gases Evolved During Fermentation. ARTHUR HARDEN J. THOMPSON and WILLIAM J. YOUNG (Bio.-CI~em. J. 19 10 5 230-235).-1n measuring the t o t d quantity and rate of evolution of gases evolved during fermentation it is essential to keep the pressure in the flask as nearly constant as possible throughout the experiments. Two forms of apparatus devised and used by the authors for this purpose are fully described with diagrams. Influence of the Mineral Constituents of Nutritive Solutions on t h e Development of Azotobacter. (TYlme.) H. KRZEMIENIEWSEA (Bul. Acad. Xci. Cracow 1910 B 376-413).- Potassium calcium magnesium phosphorus and sulphur are all essential t o the development of Axotobucter.Under the conditions of the experiments the minimum amounts required for the normal consumption of 1 gram of dextrose were as follows K 0.38 ; Ca 0.36 ; Rfg 0.35; P 2.46 ; and S more than 0.49 mg. Deficiency of any essential mineral constituent of the nutritive solution results in the less economical utilisation of the dextrose and consequently less nitrogen is fixed per gram of dextrose. The organisms leaves off increasing whilst the respiration of the existing cells goes on. The addition of potassium sodium and magnesium compounds above certain limits acts injuriously on Azotobacter. The injurious effect is diminished or prevented by addition of calcium salts. Addition of magnesium salts lessens the injurious action of excessive amounts of potassium and sodium W.D. H. N H. J. M.ii 988 ABSTRACTS OF CHEMICAL PAPERS. Assimilation of Nitrogen by Certain Nitrogen-fixing Bacteria in the Soil. W. B. BOTTOMLEY (Proc. Roy. Soc. 1910 U 82 627-629. Compare ibid. 81 287)-Culture solutions inoculated respectively with pure cultures of Axotobacter from garden soil and Pseudorrionas from bean and clover nodules and with both organisms together showed that whilst Azotobacter alone fixed 2.19 mg. and Pseudomonns alone 2.30 mg. of nitrogen per unit of carbohydrate the two organisms together fixed 4.51 mg. per unit of carbohydrate. Further experiments are described in which garden soil (5 oz.) both without and with lime was inoculated from an extract of soil which had been sterilised and then inoculated with Axotobacter and Pseudo- rnonas so as to accustom the organisms to soil conditions.I n ten days the mixed culture in limed soil gave an increase of 35 mg. of nitrogen and in the unlimed soil an increase of 25 mg. The amount of nitrogen introduced by the culture itself was 6 mg. N. H. J. M. Some Factors Concerned in the Fixation of Nitrogen by Azotobacter. CONRAD HOFFMANN and B. W. HAMMER (Centr. Bakt. Pas*. 1910 ii 28 127-139).-Experirnents with a number of different soils showed that their nitrogen-fixing power varied from 0.15 t o 14.47 mg. of nitrogen per gram of mannitol consumed. Mannitol and lactose proved to be the best sugars for maximum fixation in impure cultures whilst very little fixation was obtained with maltose and sucrose.With pure cultures mannitol and dextrin gave the best results and good results werealso obtained with sucrose but not with lactose. As regards mineral nutrients di- and tri-calcium phosphates give better results (in impure cultures) than the monocalcium salts. The period of incubation for impure cultures should be from twenty- one to twenty-eight days. If too prolonged losses of nitrogen may occur. Calcium carbonate need only be present in very small amounts. The amount of protein in the cell8 of Axotobacter was found to range from 8-31 to lS*13% whilst the phosphorus (as P,O,) varied from 2.51 t o 2.9'1%. N. H. J. 3!L The Products Resulting from the Putrefaction of Fibrin by Clostridium carnofoetidus and the Rauschbrand Bacillus. FRANCIS H. MCCRUDDEN (J.Biol. Chein. 1910 8 109-114).-The two micro-organisms mentioned are selected as widely different types of aua6robes. The products of putrefaction of fibrin show distinct differences Rauschbrand leading for instance to the formation of about one-fifteenth of the gases produced by Clostridiurn. The question is t o be followed up in the hope that such differences may be of diagnostic value. W. D. H. Action of Dysentery Bacilli on Nitrites and Nitrates. W. J . LOGIE (J. Hygiene 1910 10 143-154).-A11 the dyPentery strains examined wit'h one exception (B. N~~SBRT Ac.) reduced nitrates to nitrites; none which fail to ferment mannitol destroyed nitrites. B. dysen- teriae Jurgens although closely related t o B dys. Flexnet- differs fromVEGETABLE PHYsIoLoaY AND AGRICULTURE ii.989 ft in its action on litmus whey and in failing to destroy nitrite. B. dys. Jiirgens is the only strain found to form indole and therefore to give the cholera-red reaction. The addition of dextrose enables Shiga strains to destroy nitrites. With an abundant supply of oxygen all the strains fail to destroy nitrites and nitrates but in media which contain dextrose the inhibitory effect of oxygen is less marked. Under anaei obic conditions Shiga strains and B. dys. Jiirgens still fail to destroy nitrites. W H .D. The Enzymes in Different Bacteria. EMIL ABDERHALDEN LUDWIG; PINCUSSOHN and ADOLF R. WALTHER (Zeitsch. physiol. Chem. 1910 68,471-476).-The culture fluids of a paratyphoid-like bacillus and of Streptococcus pleuyo-pneumoniae have no peptolytic action on various kinds of peptone.Puratyphws B. slightly decomposes casein peptone. Various bacilli were grown in different media with and without peptone and the change in the rotatory power noted. It is hoped that this method of which a few preliminary examples are given may be utilised in the differentiation of micro-organisms. W. D. H. Amount of Phosphorus in Yeast and in Some Yeast Preparations. EDUARD BUCHNER and HUGO HAEHN (Biochenz. Zeit. 1910 2’7 418-426).-Yeast which had been subjected to a pressure of 70 atmospheres was found to contain about two-thirds of the total phosphorus originally present. Yeast prepared with acetone contains more phosphorus than when acetone and ether are employed. No connexion seems to exist between the fermenting power of yeast and the percentage of phosphorus.N. J. H. M. Action of Sodium Selenite on the Production of Carbon Dioxide from Living and Dead Yeast. MARIE KORSAKOFF (Belo. deut. bot. Ges. 1910 28 334-338).-Whilst a 1% sodium selenite solution completely checks the production of carbon dioxide from zymin living yeast produces considerable amounts even in 30% solutions. Small amounts of sodium selenite (0*1-0*5%) even increase the activity of living yeast. N. H. J. M. Fermentation of Galactose by Yeast and Yeast Juice. ARTHUR HARDEN and ROLAND V. NORRIS (Proc. Roy. SOC. 1910 B,82 645-649).-The results of other investigators showing that some yeasts when cultivated in a medium containing galactose acquire the property of fermenting galactose are confirmed. Yeast trained in this manner yields a juice capable of fermenting galactose. A fermenting mixture of yeast juice and galactose reacts with phosphate in a manner similar to yeast juice and dextrose.The rate is accelerated; an extra amount of carbon dioxide is evolved equivalent to the phosphate added after which the rate again becomes normal. An organic phosphorus compound is produced which is not precipitated by magnesium citrate mixture. Small amounts of sodium arsenate also accelerate the fermentat ion of galactose. N. H. J. M.Disinfection by Chemical Agencies and l%€ water HARRIETTE CHICK (J. Hygiene 1910 10 237-286).-Further experi- ments are adduced to sham that disinfection is an orderly time process analogous to a chemical reaction between the bacterium and the disinfectant The destruction OF bacteria by water between 4 5 O and 55' is also a consistent time process and runs parallel to the heat coagulation of proteins; both proceed in accordance with the mass- law and in agreement with the lam of Arrhenius in relation to temperature changes.The temperature-coeacient is very high. Disinfection by drying and by sunlight go fap as can be judged by the scanty data at present available fall into line also. A large number of dift'erent micro-organisms were subjected to experiment W. D. H. The Influence of Cell Lipoids on t h e Autolysis of Wheat Seedlings. MARIE KORSAKOFF (Biochem. Zeitsch. 19 10 28 12 1-1 26) -Powdered wheat seedlings mere allowed to autolyse and the amount of proteolysis was estimated; previous extraction of the powder with solvents of lipoids (light petroleum ether alcohol etc.) leesens the amount of sutolysis from which the conclusion is drawn that they have an important influence on the process W.D. H. R81e of Reduction Processes in the Respiration of Plants W. ZALESKI (BeT. deut. hot. Ges. 1910 28 319-32Y).-The reducing power of various seeds as indicated by methylene-blue was found to be greatest in peas and least in cereals and oil seeds whilst wheat and lupins occupy hn intermediate position. There is a certain parallelism between the anaerobiose and the reducing power of seeds since the anaerobiose is highest in leguminous seeds and lowest in cereal and oil seeds (Godlewski and Polzeniusz Abstr. 1893 ii 400 ; 1901 ii 618). Acid salts such as dihydrogen potassium (or sodium) phosphate depress the reducing power of pea seeds.Neutral salts and sodium selenite and ammonium vanadate act still more unfavourably. Alkalis and especially dibasic phosphates stimulate the reduction process. N. H. J. 31. Action of Salts on the Respiration of Plants and on the Respiration Enzymes. W. ZALESKI and A. REINHARD (Biochem. Zeitsch. 1910 27 450-473).-All the salts contained in Knop's nutritive solution depress the energy of respiration. An acid reaction is especially injurious and alkalis also cause a decrease. Dibasic phosphates considerably increase the production of carbon dioxide in ground living seeds of Yisum satiuum Zea Mais and Lupinus angustifolius and in the seeds frozen and killed with acetone In the case of T n t i c u m the energy of respiration was diminished.Acid phosphates diminish tbe production ot carbon dioxide. Only basic phospnntes have a stimulating effect. Phosphates stimulate not only the zymase but also the oxydases catalases and reductaes. As regards the relative amounts or the relative activity of the reductase and catalase of different seeds it was found that the activityVEGErABLE PHYSIOLOGY AND AGRICULTURE. ii. 991 of the redrxctase increased in the following order Zea (0) Triticum (l) Lupinus (lo) and Pisum (480) whilst in the case of catalases the order is reversed Pisum (lo) Lupinus (12) Triticum (30) and Zea (50). N. H. J. M. Importance of Mucilages in the Germination of Seeds. CIRO RAVENNA and M. ZAMORANI (Atti R. Accad. Lincei 1910 [v] 19 ii 247-252).-Linseed which has been deprived of its mucilage by repented treatment with water yields fewer seedlings than the untreated seed and their weight and ash are less than that of normal seedlings.When however the sand in which germination is effected is treated with a solution containing sugar and the inorganic con- stituents foilnd in the mucilage extracted the weight and ash of the seedlings obtained approximate to those of normal seedlings. This tends to ahom that the mucilage functions as a reserve food material during germination. R. V. S. Lecithin and Lecithides in Germinating Seeds. LUICII BERNARDINI and G. CHIARULLI (Bled. Zentr. 1910 39 594-596 ; from Xtux. sper. agrar. ital. 1909 42 97).-Seeds of cereals contain both free and combined lecithin in the proportion of about 1 2.During normal germination both forms of lecithin increase at about the same rate until the period of chlorophyll production after which it decreases. In absence of light germination is accompanied by a loss of lecithin chiefly of the combined portion N. H. J. M. Occurrence and Detection of Chlorogenic Acid in Plants. Extraction and Yield of caffeic Acid from Plants. CHABLEB CHARAUX (J. Pharm. Chim. 1910 [vii] 2 292-298).-Prom Gorter's results (Abstr. 1908 i 186 345) it appears that caffeic acid in plants results from chlorogenic acid and the author has therefore devised a quantitative method of extracting caffeic acid from plants and from the results so obtained he proposes to deduce the quantity of chloro- genic acid present on the assumption that the latter is equivalent to about half its weight of caffeic acid.The residue left on distilling the solvent from an alcoholic extract of the finely-ground plant is taken up with warm water and this shaken out twice with ether to remove impurities. The filtered aqueous extract is treated with excess of a solution of basic lead acetate the precipitate collected washed and decomposed with cold dilute aulphuric acid in slight excess giving a solution of impure chlorogenic acid. This is rendered slightly alkaline boiled for thirty minutes and excess of dilute sulphuric acid added. The liberated caffeic acid is extracted with ether purified by re-crystallisation from boiling water and weighed. I n some cases it requires further treatment for the removal of impurities.A number of colour reactions for the detection of chlorogenic acid are given and a list of plants in which this acid has been found and estimated as caffeicacid by the process outlined above. The quantity of caffeic acid found varied from 0.6 to 10% for different plants T. A. H.ii. 992 ARSTRACTS OF CHEMICAL PAPERS R61e of Catalase in Plants. ANNA ROSENBERQ (Ber. deut. bot. Ges 1910 28 280-288).-Results of experiments with a variety of seeds in which equal weights of the powdered substance were dige.sted for an hour with water and treated with hydrogen peroxide indicated that no direct connexion exists between the anaerobiose and the catalase since the leguminous seeds acted the least on hydrogen peroxide whilst the cereal seeds although little suited t o anaerobiose proved to be very rich in oatalase.Acids even 0.25% citric acid are very injurious to catalase and the acid phosphates of sodium and potassium decrease its activity. Alkali salts such as sodium carbonate and dibasic phosphates are favourable the latter acting most in the case of seeds which only contain small amounts of catalase. Addition of dibasic phosphates protects the catalase from decomposition ; the amount however gradually diminishes when the temperature is raised. Whilst the amount of catalase increases during germination addition of potassium nitrate magnesium sulpbate potassium dihydrogen phosphate and calcium nitrate respectively (0.5%) was found to retard the production of catalase. The catalase of lupins is rapidly destroyed by autolyais.N. H J. M. Alkaloidal Content of Cinchona Leaves. P. VAN LEERSUM (Proc. K. Akad. Fetensch. Amsterdam 1910 13 210-227).-The researches of Junghuhn de Vrij (Abstr. 1897 i 383) Broughton Howard and Moens have shown on the whole that cinchona leaves contain alkaloids although they leave some doubt as to the existence of other than amorphous alkaloids in these plant organa. Lotsy’s physiological experiments with cinchona leaves (Ann. Jard. Bot. Ruit. 1899 12 36) indicated that alkaloids are formed in the leaves whence they are transported to the stem where the final formation of crystal- line alkaloids occurs a r d hence are to be regarded as assimilation products. The present paper disproves Lotsy’s contention and shows that the alkaloids which include quinine and cinchonine occurring in the leaves are products of metabolism.The method of estimating the total alkaloids consisted in mixing the ground leaves o r bark with slaked lime sodium hydroxide and ammonia and extracting with ether the alkaloids being recovered from the latter in the usual manner dissolved in N/lO-acid and the excess of acid titrated. The results obtained show (1) that exposure of living leaves to light or dark has no effect on their alkaloidal content; (2) that no evidence could be obtained of the transport of alkaloid through the branches to the stem and (3) that both the mesophyll and veins of the leaves of C. Ledgerirzna and C. succirubra contain the crystalline alkaloids quinine and cinchonine. These results are on the whole in harmony with those found for Datura Xtramonium by Feldhaus (Abstr. 1905 ii 648) and for tea by Du Pasquier (Inawg.Diss. Zurich 19OS) and by Weevers (Ann. Jard. Bot. Buit. 1904 21 ii Part l) with the exception that Weevers found no caffeine in fallen tea leaves whilbt in the present investi-VEGETABLE PHYsioLow AND AGRICULTURE. ii. 993 gation fallen cinchona leaves proved to be as rich in alkaloids as the living leaves. ‘r. A. H. The Alkaloid of Pituri Obtained from Duboisia hopwoodii. A. C. H. ROTHERA (Bio.-Chem. J. 1910 5 193-206).-The alkaloid of pituri is nicotine; no evidence was found of the presence of any other a1 kaloid. W. D. H. Action of Ultra-violet Rays on Plants Yielding Coumarin and on Plants in which the Odour is due to Decomposable Glucosides. JEAN POUGNET (Compt.rend. 1910 151 566-569. Compare Heckel this vol. ii 63).-An odour of coumarin is rapidly developed when the leaves of plante such as Melilotus ojicinalis or Aspemla odorata are exposed for a short time to the light from a quartz-mercury lamp. The leaves become blackened owing to the death of the protoplasm; the enzymes survive however and effect scission of the glucosides. The action of ultra-violet light in this respect is identical with that of cold and masthetics (Grignard Abstr. 1909 ii 813 ; Mirande ibid. ii 824). Similar results have been obtained in experiments on the leaves of the cherry laurel and other plants which develop their characteristic odour on exposure to the rays. w. 0. w. Effect of Poisonous Solutions Containing Alkaloids on Soils and Plants.RICHARD OTTO and W. D. KOOPER (Landw. Jahrb. 1910 39 397-407. Compare ibid. 1896 25 1007).-Nicotine solutions (0.306) are very favourable t,o the growth of Nicotiana tabaeum and favourable t o Solccnum tuberosum. I n the case of Nicotiana the amount of alkaloid was increased and similar results were obtained with other nitrogenous substances such as sodium nitrate. The alkaloid had no appreciable effect on the other constituents. It partly decomposes in the soil with production of ammonia and a part is lost by volatilisation. Eu’icotine is absorbed physically by humus and sandy soils. N. H. J. M. Origin and Physiological Function of Pentosans in Plants. 11. CIRO RAVENNA and 0. MONTANARI (Atti R. Accad. Lincei 1910 [v] 19 ii 202-207. Compare Ravenna and Cereser Abstr.1909 ii 1046). -The results previously described have been confirmed in most respects by further experiments on the leaves of Picia faba minor. The quantity of pentosans present in the leaves showed a tendency to increase during the day and decrease during the night. A considerable increase occurs when the leaves are supplied with carbohydrate food (dextrose fructose sucrose) whilst prevention of the function of the chlorophyll i n the leaves and the absence of carbohydrate nutriment cause the amount of pentosans to decrease. R. V. S. Chemico-physiological Investigations on the Tubercles of Vicia faba. UIOVANNI SANA (Atti R. Accad. Lincei 1910 [v] 19 ii 207-211).-1n the fresh plant the bacteroidal tissue of the tubercles was found to contain 0.965% of nitrogen the cortical layer VOL.XCVIII. ii. 67ii. 994 ABSTRACTS OF CHEMICAL PAPERS. only traces. In the roots 002987% of nitrogen was found in the stems 0.1635-0.065% and in the leaves 0*707-0*7995%. The non- protein nitrogen in the tubercles amounted to 0.033%. Boiling water extracts various amino-acids from the tubercles ; among them Z-asparagine and glycine were identified. R. V. S. Metabolism of Moulds. Aspergillus fumigatus. I. GIRO RAVENNA and G. PIGHINI (Atti R. Accad. Lincei 1910 [v] 19 ii 312-31 6)-From alcoholic extracts of three cultures of A. fumigatus the authors isolated the following three substances respectively ( I ) a highly toxic substance forming colourless prismatic crystals m. p. about 300'; (2) mannitol; (3) trehalose. Behaviour of Moulds Towards the Stereoisomerides of Unsaturated Dibasic Acids.ARTHUR W. Dox (J. BioZ. Chern 19 10 8 265-267).-Buchner found that Pecnicillium glaucum and Aspergi~hus niger will grow in media contaking ammonium salts of fumaric acid. But they were not able similarly to utilise maleic acid as a source of carbon. The latter is not found in nature; never- theless the distinction is surprising because of the readiness with which the two acids are convertible one into the other. The present experiments made with a large number of moulds confirm Buchner's statement. Mesaconic and citraconic acids also resemble maleic acid. Itaconic acid gave a slight growth in a few cases but no normal colony. W. 1). H. Amylase of Ungerminated Cereals and Malt. T. CHRZASZCZ (Bied.Zentr. 1910 39 641-642 ; from Zeitsch. Spiritusind. 1909 32)-Malt amylase acts most favourably when 1% potato starch is employed with a temperature between 5b0 and 55'. The amylase of ungerminated cereals shows the same optimal temperatures for sacchari6cation but is less active than the amylase of malt. The diastatic power o€ wheat and rye is greater than that of barley and still greater than that of oats. Theassumption that malt has a special amylase different from the amylase of restiDg grain would therefore seem to be incorrect. It is probable t h a t in cereals the action of the amylase is retarded by some unknown factor (amylum-coagulase). It is suggested that cereal seeds contain an amylase which does not possess the full enzymatic power a pro-enzyme which changes to active enzyme during germination. Composition of Barbados Rain. R. RADCLYFFE HALL and J. R. BOVELL (Rep. Agric. Work Barbados ; Imp. Dept. Agric. West Indies Jor 1907-1309 3. Compare Brunnich this vol. ii 647). -Analyses of fortnightly samples of rain-water from December 1907 to May 1909. The average amounts of nitrogen as ammonia and as nitrates in the rain of 1908 and the total amouuttj per acre were as follows Nitrogen per million Per cent. of Total N. -6 - inches. Arcmonia. Nitrates. Ammonia. Nitrates. Total. Ammonia. Nitrates. 40'28 0'032 0.384 0295 3.498 3.793 7 '8 92.2 R. V. S. N. H. J. M. Nitrogen per acre (lb.) A Rainfall as as as as as asAN ALPTICAL CBEM ISTRY ii. 995 The chlorine in the rain-water amounted to 8.38 per million N. H. J. M. corresponding with 76.39 lb. per acre.

ISSN:0368-1769    

DOI:10.1039/CA9109805987

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ANALP'I'ICAI CBEMISTRY. An alg tical Chemistry . ii. 995 A New Indicator for Alkalimetry and Acidimetry. 6-Sulpho-P-naphthol-1 -azo-m-hydroxybenzoic Acid. R. MELLET (Chem. Zeit 1910 34 1073-1074) -When 4-amino-3-hydroxy- benzoic acid is diazotised and combined with P-naphthol-6-sulphonic acid a soluble dye is obtained which may be used as an indicator. The sodium salt forms dark violet crystals dissolving readily in water to a violet solution. The acid is also soluble and forms deep red solutions. Alkalis change the colour to violet but an excess of alkali causes a change to cherry-red; the indicator is therefore unsuitable for use on test-papers. The indicator is prepared by adding N/lO-hydrochloric acid to a 1% solution of the sodium salt until the colour is distinctly red.Such a solution is three times as strongly coloured as one of litmus of equal concentration. In N/lOO-solutions of acids or alkalis the sensitiveness is equal to that of phenol- phthalein C. H. D. Chart Presentation of Recent Work on Indicators. GEORGE S. WALPOLE (Bio.-Chem. J. 1910 5 207-214. Compare this vol. ii 54 I ).-The apparatus previously described is explained more fully the new method of notation of hydrogen-ion concentration explained and a diagram is given of how Sorensen's results can be conveniently displayed on a chart A few examples illustrate how the chart may be used. W. D. H. Apparatus for Measuring Known Quantities of Liquids. J. HUDIG and M. J. VAN'T K a u ~ s (Chem. Weekblad 1910 '7 879-882).-Six vertical tubes closed by stopcocks at the lower end are sealed at their upper ends into a tube slightly inclined to the horizontal connected at one end through a stopcock to a water pump and a t the other (lower) through a long vertical tube t o the vessel containing the liquid to be measured.A short glass tube sealed into the main tube and closed with rubber tube and a pinchcock serves to admit air to the apparatus at will. The liquid is drawn up into the horizontal tube by the water pump and flows into the vertical stopcock tubes. Definite volumes are marked on these tubes aud can be measured off. The apparatus is specially adapted t o the measurement of given volumes of strong acids. A. J. 147. Quantitative Spectral Analysis. WALTHER HEMPEL and RALPH L. VON KLEYPERER (Zeitsch. angew. Chem. 1910 23 1756-1759).-An arrangement is described by means of which certain metals can be quantitatively estimated by spectroscopic observations.The spectroscope is focussed on a oxyhydrogen flame VOL. XCVIII. ii. 68ii. 996 ABSTRACTS OF CBEMICAL PAPERS. supplied with hydrogen and oxygen at constant pressure and the metals are introduced into the flame by allowing the gases evolved from an acidified solution of the metal by an electric current of constant strength to mix with the entering hydrogen. The concentra- tion of the solution under examination is diminished until the characteristic lines of the particular metal j u s t cease to be recognisable in the spectroscope. From comparative observations under exactly similar circumstances with a standard solution the concentration of tho metal in a solution of unknown atrength can be obtained.The method can be applied to the estimation of potassium lithium calcium and thallium and is recommended for the estimation of the two former in samples of soil. It is shown that the presence of small quantities of other flarne- colouring metals is without much influence on the results obtained. Larger quantities lead to an apparent diminution in the quantity of tho metal under examination. H. M. D. Volumetric Method of Estimating Iodide in Presence of Chloride Bromide or Free Iodine. WILLIAM C. BRAY and G. M. J. MACKAY (J. An7ev. Chem. Soc. 1910 32 1193-1204)- A method of estimating iodides in aqueous solution is described which is based on that suggested by Sammet (Abstr. 1906 ii 153) and depends on the oxidation of the iodide by potassium permanganate the removal of the liberated iodine with carbon tetrachloride and its subsequent titration with standard sodium thiosulphate.Experiments have been made with potassium iodide solutions of known Strength which show that the results obtained by this method are accurate within 0.1% and are independent of the presence of chlorides bromides or copper sulphate. When free iodine is present in the solution to be analysed it is estimated by direct titration with sodium thiosulphate ; the amount of iodine present as iodide is then ascertained by subtracting this quantity from the total iodine. The estimation may be carried out by titrating the solution directly with potassium permanganate in presence of carbon tetrachloride since as the concentration of the potassium iodide is decreased a larger pro- portion of the iodine is dissolved by the carbon tetrachloride until finally the aqueous liquid becomes colourless.It has been found how- ever t h a t this method is not entirely satisfactory since the reduction of the permanganate to the manganous salt is not quite complete and an error amounting to about 0*4-0*5% of the permanganate solution is thus introduced. E. G. Estimation of Fluorine in Aromatic Fluorine Derivativee. HANS MEYER and ALFRED RUB (Monatsh. 1910 31 933-938).-See this vol. i 735. An Ozonometer. STEPHAN JAHN (Bey. 1910,43 2319-2321).- The ozonometer consists essentially of a U-tube fitted with stop- cocks one of these being a three-way one and connecting with a mano- meter containing paraffin oil.The U-tube is 2 cm. in diameter and has an internal volume of about 70 C.C. ; sealed into it and runningANALYTICAL CHEMISTRY ii. 997 through its length is a thin platinum wire which can be heated by an electric current,. To use the instrument 150-200 C.C. of the gaseous mixture con- taining ozone are passed through the U-tube which is then closed at the inlet. The three-way tap is turned to connect with the manometer and the liquid in the latter adjusted to a zero mark. The platinum wire is then heated to a dull red heat for five to ten seconds this time being suficient to destroy the ozone. When the original temperature has been attained the manometer is again adjusted to zero and the increase of pressure determined from which the percentage of ozone can be calculated.A correction has to be applied f o r the amount of ozone decomposed while the gas is in contact with the cold platinum wire before the latter is heated. This is determined by a blank experiment. The method is more exact and quicker than the determination of ozone with potassium iodide. T. S. P. The Quantitative Analysis of Some Inorganic Sulphur Acids. ANGELO CASOLARI (Gaxzetta 19 10 40 ii 22-27).-A polythionate containing m atoms of sulphur in the molecule yields m - 1 molecules of sulphuric acid when treated with hydrogen peroxide and sodium or potassium hydroxide (Abstr. 1908 ii 222). The solution to be titrated is therefore rendered perfectly neutral and treated with a pure neutralised solution of hydrogen peroxide and a known volume of N/lO-alkali hydroxide.After heating on the water- bath,the excess of alkali is titrated with acid Na2S,0 + (3m - 5)H,O + (m - 1)H,O = Na,SO + (m - 1)H2S0 + (3m - 5)H,O. The same reaction may be used for thiosulphates Na,S20 + 4H,O + H,O = Na,S04 + H,SO + 4H20. Under the same conditions thiocyanates are decom- posed into a sulphate and a cyanate KSCN+4H,02+2KOH= K2S0 + KCNO + 5H,O. A volume of N/lO-sulphuric acid equal to that of the alkali taken is then added and after boiling for a few minutes the acidity of the solution is determined. If ammonium thiocyanate is present the ammonia must be expelled by boiling with alkali before oxidising. When a thiosulphate acd a thiocyanate are both present in tho solution the sum of the two may be estimated as abore and the thiosulphate estimated separately by means of iodine.C. H. D. H. RUSSELL ELLIS (Chew. iVews 1910 102 187).-The test described by Castellsna (Abstr. 1305 ii 201) is untrustworthy owing to the fact that cyanide is formed when powdered magnesium and sodium or potassium carbonate are heated together in a limited supply of air the nitrogen necessary to the formation of cyanide being obtained from the atmosphere. When however the reaction is allowed to proceed rapidly in a copious supply of air cyanide is not formed. Similar reactions take place when mixtures consisting of magnesium and either calcium carbonate barium carbonate or strontium carbonate are heated-in contact with a small amount of air ; in these cases cyanide Detection of Nitrogen in Organic Substances.cyanamide nitride and carbide are formed. w. P. 53. 68-2ii. 998 ABSTRACTS OF CHEMICAL PAPERS. Estimation of Ammonia Nitrogen in Water in Presence of Hydrogen Sulphide. EDWARD BARTOW and B. H. HARRISON (J. Amer. Chem. Xoc. 1910 32 1256-1259).-The presence of hydrogen sulphide in a water interferes with the Nessler test. When a large amount of ammonia is present the hydrogen sulphide may be removed by precipitation with a salt of zinc or lead and the ammonia can then be estimated directly by the Nessler reagent. If however the quantity of ammonia is small and it is desirable t o distil and test the distillates the results obtained are inaccurate. It has been found that accurate results can be obtained by the following method.To 500 C.C. of the water a measured quantity of N-sulphuric acid is added and 100 C.C. are distilled ; by this means the hydrogen sulphide is completely removed. A volume of N-sodium hydroxide equal t o that of the sulphuric acid used is now added the water is again distilled until 200 C.C. have collected and the Nessler test is applied to the distillate. E. G. Estimation of Small Q u a n t i t i e s of Nitrogen by Pelouze's Reaction. A. T. DAVENPORT (J. Amer. Chenz. Xoc. 1910 32 1237-1 241).-A method is described for estimating small quantities of nitrogen occurring in the form of nitrates by Pelouze's reaction which consists in the oxidation of ferrous chloride in presence of hydrochloric acid. The most important features of this method are the measurement of the volume of gas over sodium hydroxide solution in a jacketed burette graduated to 1/20 c.c.as in the Schultze-Tiemann method and the correction of the volume by comparison with a standard volume contained. in another burette under exactly the same conditions. The process is simple and easily manipulated permits of an estimation being carried out in ten minutes and gives accurate results. A diagram of the apparatus is given. E. G. Easy Detection of Arsenic; Rapid Separation of Arsenic and Some Other Metals from Liquids C. E. CAPLSON (Zeitsch. plrysiol. Chem. 1910 68 243-362).-On adding hydrogen sulphide t o an acid solution of arsenious acid or thioacetic acid to a solution of arsenic acid arsenious sulphide is precipitated but iE the amount is only a fraction of a mg.the separation takes a long time. If however ether is added or preferably a mixture of ether and chloroform and the whole well shaken the ethereal layer contains all the arsenious sul phide in suspension or in pseudo-solution. Addition of alcohol promotes the separation. On being evaporated on the water-bath arsenious sulphide is left which may then be further identified by the mirror test. When testing urine (or other organic liquid) this is evaporated to dryness and the residue is distilled with hydrochloric acid and some ferric chloride ; the distillate is diluted with solution of hydrogen sulphide and shaken with ether. The quantitative process is briefly as follows The ethereal residue is heated with 1 C.C. of 30% sulphuric acid and 2 C.C.of 5% potassium per- manganate for ten to fifteen minutes. The arsenic acid formed is reduced to the arsenious state by heating for half an hour a t 50-70" with addition of 10 C.C. of strong solution of sulphur dioxide and theANALYTICAL CHEMISTKY. ii. 999 solution is finally evaporated nearly to dryness. Another 5 C.C. of sulphur dioxide are added and the evaporation is repeated. The residue is now dissolved in 15 C.C. of water 2 grams of sodium hydrogen carbonate are added and the arsenic is titrated with N/lOO- iodine with starch as indicator. Other sulphides such as those of lead and mercury are also taken up Estimation of Potassium by the Cobaltinitrite Method L. T. BOWSER (J. Ind. and Eng. Chem. 1909 1 791-798).-8 detailed account of the methods employed and the results obtained by previous workers those of Drushel and of Adie and Wood being fully discussed and stated to be unsatisfactory in several ways when repeated by the author who suggests the following modifications.The potash is brought into solution any excess of acid driven off and the residue boiled with sodium carbonate to remove any interfering metals the filtrate concentrated acidified with acetic acid and the potassium precipitated with excess of the reagent according to the equation Na,Co,(NO,),,,H,O + 2K,SO = 2K2NaCo(N0,) + H,O + 2Na,SO,. This precipitate can be boiled with sodium hydroxide the precipitated cobalt hydroxide Co(OH) separated and the filtrate and washings titrated with potassium permanganate the reaction being 10EN0 + 20NaN0 + 6K,Mn,08 + 33H,S04 = 11K,S04+ 10Na2S0,+ 13MnSO,+ 30HNO,+ 18H,O; or the precipitate can be treated directly with potassium permanganate when a more complicated reaction occurs owing to tervalent cobalt being reduced to bivalent and thereby releasing one atom of oxygen which oxidises some of the precipitate 10[K,NaCo(N0,),,H20] + 1 lK,Mn,O + 58H,SO = readily by ether.L. DE K. 21E,S04 + 5Na2S0 + lUCoS0 + 22MnS0 + 60HN0 + 38H,O. Likewise the di-potassium-sodium-cobaltinitrite may be collected on asbestos oxidised by hot standard potassium permanganate which is decolorised by an excess of standard oxalic acid and then titrated back with permanganate. The influences exerted on the reaction by (1) varying the con- centrations of the solutions; (2) the presence of other salts and (3) the acid with which the potassium is combined are also investigrtted and the results tabulated. Rapid Estimation of Copper Silver Cadmium and Bismuth by means of the Mercury Cathode and Stationary Anode.RAYMOND C. BENNER (J. Arner. Chem. Xoc. 1910 32 1231-1237),- Stoddard (Abstr. 1909 ii 347) has described a method of electro- analysis by means of a mercury cathode and a stationary platinum gauze anode in which the evolution of the gas by the current causes sufficient agitation of the liquid to enable the metals to be deposited in an adherent form. This method has now been applied to the estima- tion of copper silver cadmium and bismuth. The apparatus is as simple as any other form of electrolytic apparatus employed for the purpose the metal is deposited nearly as rapidly as by the rotating anode and mercury cathode and the results are as accurate as those obtained by other methods in which mercury is used as the cathode.F. M. G. M.ii. 1000 ABSTRACTS OF CHEMICAL PAPERS. The precipitation is complete in twenty minutes with copper ten minutes with silver and cadmium and twenty-five minutes with bismuth. E. G. Volumetric Estimation of Mercury by means of Ammonia. G. BRESSANIN (Boll. chim. farm. 1910 49 589-591 *).-Archetti’s method based on tho estimation of the acid liberated according to the equation HgCI + NH = NH,HgCl+ HC1 only gives quantitative results when four times the moleciilar quantity of ammonia is taken for the reaction the excess being afterwards estimated by titration with litmus.R. V. S. Estimation of Indium with the Use of a Mercury Cathode. LILY G. KOLLOCK and EDGAR F. SNITH (J. Amer. Chem. Xoc. 1910 32 1248-1250).-1t has been found that the indium in a solution of indium sulphate containing a little free acid can be satisfactorily estimated electrolytically with the use of a rotating mercury cathode. When 10 C.C. of the solution containing about 0.10 gram of metal were used with a current of 2-4 amperes an E.M.3’. of 6.5-7-5 volts and an anode rotating 750 times per minute the precipitation was complete in fifteen minutes. Estimations were also made by using a platinum cathode and a rotating platinum spiral anode; i n presence of 0.1 C.C. of concentrated sulphuric acid and a few drops of gelatin an adherent deposit of indium was obtained in twenty-five minutes.A potassium cyanide electrolyte and one containing Rochelle salt also proved satisfactory. E. G. Volumetric Method for the Estimation of Manganese. FLOYD J. METZGER and ROBERT F. MCCRACKAN (J. Arne?.. Chem. Soc. 1910 32 1250-1251).-Metzger and Heidelberger (this vol. ii 656) have stated that when a solution of manganese in sulphuric acid is treated with sodium bismuthate it is oxidised to the quadrivalent state. A method has now been devised for estimating manganese by means of this reaction. Fifty C.C. of a standard manganese solution are treated with 10-15 C.C. of concentrated sulphuric acid 1-2 grams of finely- powdered sodium bismuthate are added to the cooled liquid and tho mixture is heated in a water-bath until the basic bismuth compound subsides in a granular form The flask is cooled a known excess of ferrous sulphate solution is added the liquid is diluted to about 200 c.c.and titrated back with standard potassium permanganate. The value of the permanganate in terms of iron multiplied by 0.4918 gives the value in terms of manganese. It is being applied to the analysis of spiegel and manganese ores. J. RODENBURG (Chern. Weekblad 1910 ’7 877-879).-As the tint of the solution of peimanganate obtained in the estimation of manganese in potable water by the persulphate method usually differs from that of the colorimetric standard made from potassium permanganate the author employs as standard one or more C.C. OF a solution of manganese The method is rapid and the end-point is sharp and distinct Estimation of Manganese in Potable Water.E. G. * and Ann. Chim. anal. 1910 15 413-419.ANALYTICAL CHEMISTRY. ii. 1001 ammonium sulphate containing 0.0025 gram Mn,O per litre this solution being oxidised with persulphate in the same way as the sample under investigation. This difference of tint being due to chlorides in the sample they must be eliminated. The author's procedure is as follows 50 C.C. of the sample are boiled for several minutes with 5 C.C. of 50% nitric acid a slight excess of silver nitrate solution added and then 10 C.C. of a 10% solution of ammonium persulphate. The solution is brought to the boiling point cooled and compared with the standard tint. The method will shorn the presence of 0.025 mg. of Mn,04. A. J. W. Detection of Small Quantities of Manganese in Foods.DUMITRESCOU and E. NICOLAU (Ann. Fa7s$ 1910 3 370-372).- The material is incinerated the ash is treated with nitric acid evaporated to drynesa the residue is dissolved in water and the solution is filtered. A portion of the filtrate. is then mixed with an equal volume of a 40% ammonium persulphate solution 1 drop of a 2% cobalt nitrate solution is added and the mixture is heated to boiling. Should maljganese be present a pink coloration develops due to the formation of permanganate. The authors have detected the presence of manganese in such substances as flesh brain bile pea beans lentils cereals plums eggs milk wine etc by means of thw test m. P. s. Error in Permanganate Titrations. WILLIAM C. BRAY (J. Amer. Chem. Soc. 1910 32 1204-1207).-It has been shown by Bray and MacKay (this vol ii 996) that when an iodide is titrated directly with potassium permanganate the latter is not completely reduced t o the mangnnous state and an error results amounting to about 0.10 C.C.of a O.12N-permanganste solution. It is evident therefore that the reduction of the permanganate takes place in stages and it is probable that a similar error may occur in other cases'of titration with this salt. Skrabal (Abstr. 1908 ii 17) has shown that the reduction from the manganic to t h e manganous btate by oxalic acid is a slow reaction and that a stable complex is formed between the manganic salt and the oxalic acid. Experiments have therefore been made to ascertain the conditions in which the error due to incomplete reduction of permanganate is appreciable in oxalic acid titrations and it has been found that the error varies from 0.01 to 0.14 C.C.of a O.12N-permanganate solution and is negligible if the acid is present in only small amount and the final temperature is 70-80'. An investigation is being carried out with the object of determining whether there is an appreciable error in the titration of ferrous sulphate solutions with permanganate. The Determination of Iron and Aluminium in Inorganic Plant Constituents. R. F. HARE (J. Ind. and Eng. Chem. 1910 2 27-28).-The estimation of iron and aluminium in the presence of manganese calcium magnesium and phosphoric acid is a difficult one and no sativfactory process has been suggested previously. E. G.ii. 1002 ABSTRACTS OF CHEMICAL PAPERS. A solution of and representing one gram of the ash is treated with more than sufficient pure ferric chloride to combine with all the phosphoric acid; sodium carbonate is added until a permanent precipitate is just formed which is then redissolved with 1 C.C.of SO% acetic acid and the solution boiled for three or four minutes and rapidly filtered ; the precipitate is dissolved in hydrochloric acid and the iron and aluminium reprecipitated with ammonium hydroxide dried ignited and weighed ; this weight minus the phosphoric acid and ferric oxide (found by other methods) and the ferric oxide added will give the weight of aluminium oxide in the ash. A great deal depends on the proper adjustment of the amounts of sodium carbonate and of acetic acid added an excess of either causing serious error.The addition of ferric chloride gives a more easily filtered and washed precipitate and ensures compiete precipitation of. phosphoric acid The iron is determined in a fresh solution of the ash by the Zimmermann-Reinhardt method the ferric iron being instantly reduced with stannous chloride and titrated with potassium permanganate in the presence of hydrochloric acid after the addition of a “titrating solution ” of manganese sulphate phosphoric and sulphuric acids. This method is claimed to be more accurate and rapid than when zinc is employed for the reduction of the ferric salt. F. M. G. M. Estimation of Ferrous Oxide in Silicates. MAX DITTRICH and A. LEONHARD (Ber. Vers. Oberrheinisch. Geol. Ver. 1910 ii 92-93).- The process usually employed is that recommended by Pebel-Do1 ter consisting in heating the silicate with a mixture of sulphuric and hydrofluoric acid in an atmosphere of carbon dioxide. The solution is then titrated with permanganate as usual.The authors however state that if the silicate contains manganese also the titration proceeds in an irregular manner and the results become untrustworthy. This may be prevented by adding to the acid mixture 1-2 grams of potassium sulphate; the titration will then proceed normally. L. DE K. Ammonium Perchlorate as a Reagent. Metalammine Perchlorates. ROBERTO SALVADORI (Gaszetta 19 10 40 ii 19-21). -Perchlorates of the metallic ammines are obtained by adding a 20% solution of ammonium perchlorate in ammonia D 0.90 to ammoniacal solutions of metallic salts. Precipitation is complete in the case of cobalt nickel manganese and cadmium even in dilute solutions.Zinc is incompletely precipitated and copper only slowly from very con- centrated solutions. The mercury precipitate is soluble in an excess of the reagent. The method may be used for the separation of cadmium from the sulphides of the second group. The sulphides are dissolved in nitric acid excess of ammonia is added and the bismuth is removed by filtration. The ammoniacal solution of ammonium per- chlorate is added to the filtrate and the cadmium is immediately precipitated carrying with it a small quantity of copper. The reagent may also be used to separate a cobalt salt from a cobalt- amrnine salt. I n presence of an excess of ammonium perchlorate and out of con tact with air cobalt is completely precipitated as the compoundANALYTICAL CHEMISTRY.ii. 1003 Co(C1O4),,6NH the cobaltammine remaining in solution (compare this vol. 11 959). The cadmium and zinc compounds form white crystals c d ( c 1 0 ) 4 ~ ~ and Zn(C10,),,4NR3 stable at looo melting a t about 220° and decomposing rapidly at 250'. They explode by percussion or if heated rapidly. C. H. D. Detection of Small Quantities of Nickel. ALBEETO BIANCHI and ETTORE DI NOLA (BoZZ. chim. farm 1910 49 517-520).- Nickel-plating may be recognised without damage to the object by moistening it with a drop of wid which is then absorbed by blotting paper or allowed to fall on to a porcelain surface rendered alkaline with ammonia acidified with acetic acid and tested with dimethyl- glyoxime.In the presence of a.cetic acid there is no possibility that the red coloration will be masked by other coloured substances (cupric hydroxide ferric hydroxide). R. V. S. Estimation of Tin in Presence of Antimony. JEAN A. SANCHEZ (Bull. Xoc. chim. 1910 [iv] 7 890-894).-The process depends on the fact that whilst ferric chloride is reduced quantitatively by stannous chloride it is unaffected by antimonous chloride. I n the case of a simple mixture of the two chlorides the solution is titrated with a standard ferric chloride solution in presence of hydro- chloric acid the formation of a permanent greenish-yellow coloration being taken as the end-point. Where both substances must be estimated they are converted into their sulphides in the usual manner and the mixture of sulphides treated with hydrochloric acid and potassium chlorate.To this solution aluminium is added and when the reduction is completed the antimony is filtered off and the filtrate and washings diluted to a known volume with diluted hydrochloric acid (50%) and titrated with a ferric chloride solution which has been stnndardised against a solution of stannous chloride containing the equivalent of 1% of tin. The precipitated antimony is dissolved by means of hydro- chloric acid and iodine solution and estimated as the sulphide. 0.1 Gram of tin in presence of 1-1 gram of antimony can be estimated accurately by this method. Analysis of Tin-Antimony Alloys. LEROY W. MCCAY (J. Amer. Chem. Xoc. 1910 32 1241-1248).-It has been shown in an earlier paper (Abstr.1909 ii 351) that the separation of tin and antimony cant be effected by taking advantage of the fact that when a dilute solution of hydrofluoric acid containing tin in the stannic condition and anti- mony in the antimonious state is treated with hydrogen sulphide only the antimony is precipitated. The following method is reoommended for the analysis of alloys of tin and antimony. From 0.5 to 1 gram of the alloy in the form of filings or fine borings is heated rapidly with concentrated sulphuric acid in a quartz or porcelain dish until fumes of sulphuric anhydride begin to escape and the heating is then continued for half an hour. If the liquid is now clear and the residue consisting Qf laad sulphate is T.A. H.ii. 1004 ABSTRACTS OF CHEMICAL PAPERS. quite white the dish is cooled and its contents are transferred to a 250 C.C. platinum dish containing 5 C.C. of hydrofluoric acid (48%) and 20 C.C. of water. The solution is heated until it boils and is then diluted to 150 c.c. and 50 c.c of 95% alcohol are added. When the lead sulphate has subsided it is collected washed with water containing one-fourth of its volume of alcohol and a little sulphuric acid and is dried ignited and weighed. The filtrate is collected in a large platinum dish diluted to about 450 c.c. and treated with a rapid current of hydrogen sulphide for an hour. The precipitate is collected washed with a saturated solution of hFdrogen sulphide containing acetic acid and afterwards digested repeatedly with colourless sodium sulphide solution.The eupric sulphide which is left after this treatffient is dissolved in nitric acid and the copper estimated electrolytically. The sodium sulphide solution is acidified with sulyhuric acid and the antimony precipitate is converted into the black anhydrous sulphide. The tin in the filtrate from the copper and antimony sulphides may be estimated by evaporating the liquid and subsequently heating it until sulphuric anhydride fumes are evolved and precipitating the tin as stannic acid by pouring the sulphuric acid solution into an excess of water. E. G. Separation of Bismuth from Alloys containing also Lead and Tin. CHARLES E. SWETT (J. I n d . and Eng. Chem 191 0,2 28)- The following expedient is suggested as a means of overcoming the difficulties usually experienced in this estimation.The nitric acid filtrate from the stanuic oxide is treated with a moderate excess of potassium or sodium hydroxide which precipitates bismuth and cadmium if iresent and redissolves the lead hydroxide. The hydroxides are collected washed and redissolved in hydrochloric acid the bismuth being then separated as oxychloride by pouring into a large quantity of water. F. M. G. &I. ARISTIDE D A I ~ (Chem. Zeit. 1910 34 1057-1058).-1n order to ascertain whether R water is suitable for drinking the author recommends that the follow- ing estimations be made The calcium and magnesium present may be estimated volumetrically the former by the titration of its oxalate after this has been precipitated and separated in the usual way and the latter by precipitating it as ammonium magnesium phosphate and titrating this salt with a uranium solution.Sulphatea are titrated with barium chloride solution and the total carbon dioxide is titrated with barium hydroxide-sucrose solution allowance being made for the alkalinity of the water. Nitrites are estimated colorimetrically by means of the indole reaction and the proportion of organic matters is estimated by heating the water with permanganate solution in the presence of sodium carbonate. The organic matters may also be esti- mated by titration according to Deniges’ cyanide-silver nitrate method. Should further information be required as to the quality of the water the ammonia chlorides nitrates etc. may be estimated the usual methods being employed for the purpose.In addition tests may be applied for the detection of Bacterium coli. Rapid Methods for the Analysis of Water. w P. 8.ANALYTICAL CHEMISTRY. ii. 1005 Acid Content of Moor Water. KURD ENDELL (J. pr. Chem. 1910 [ii] 82 414-422).-The acidity of moor water has been determined by direct titration with N/ 1 00-potassium hydroxide. The method of adding standard barium hydroxide and titrating the excess does not give trustworthy results the titre decreasing with time probably owing to the action of the alkali on humus substances present as sols. Before titration it is necessary to dialyse the water in order to get rid of humus substances. The moor water of the red and of the black moors of the Rhone are 0.007 normal.The water of the Paulsborner moor is 0.0063 normal the acidity being due entirely to carbonic acid c. s. Estimation of Butyl and Amy1 Alcohols in Alcoholic Liquids. A. LASSERRE (Ann. China. nnal. 1910 15 338-341).- Instead of estimating the total quantity of higher alcohols in alcoholic liquids as is done in the Allen-Marquardt process the method described by the author limits the estimation to that of butyl and amyl alcohols ; propyl alcohol is eliminated by treating the alcoholic liquid with carbon disulphide which extracts the butyl and amyl alcohols. After oxidation the butyric and vnleric acids are extracted from the solution by means of benzene and their quantity estimated by titration. The details of the process are as follows 100 C.C. of the alcoholic liquid 70 C.C.of carbon disulphide and 450 C.C. of saturated sodium chloride solution are placed in a separating funnel and after the addition of a quantity of water sufficient to redissolve the precipated sodium chloride the mixture is shaken for five minutes. The carbon disulphide is then separated and the extraction is twice repeated the united carbon disulphide extracts being next shaken three successive times with moderately concentrated sulphuric acid. The sulphuric acid extract is now heated to 60' in order t o remove any traces of carbon disulphide then diluted with 20 C.C. of hot water and 5 grams of potassium dichromate and 1 cc. of concentrated sulphuric acid are added. The whole mixture is then heated in a closed flask for one hour at 50° cooled and diluted to a volume of 100 C.C.Twenty-five C.C. of this solution are shaken for three minutes with 30 C.C. of benzene the latter is separated filtered mixed with an equal volume of alcohol and the solution is titrated with N/QO-alcoholic potassium hydroxide solution using phenolphthalein as indicator. The quantity of alkali used in the titration may be calculated into amyl alcohol but the result obtained must be multiplied by 2.082 this being the ratio of the total amount of the acids present to that portion which is obtained by one extraction with benzene. A method has been described previously (Abstr. 1907 ii 991) for the separate estimation of butyric and valeric acids. w. P. s. Physico-chemical Estimation of t h e Ash of Wine. HENRI PELLET (Ann. Chirn.anal. 1910 15 385).-1t is pointed out that the conductivity process described by Dutoit and Duboux (this vol. ii 552) has already been applied t o the estimation of mineral matters in various substances ; twenty years ago Reichert employed the method for the estimation of ash in sugars etc. but the resultsii. 1006 ABSTRACTS OF CHEMICAL PAPERS. obtained were unsatisfactory. More recently Main in a paper submitted to the Seventh International Congress of Applied Chemistry London 1909 gave the details of procedure necessary for the correct Polarimetric Estimation of Sucrose in Presence of Reducing Sugars. P. LEMELAND (J. Pharm. Chiva. 1910 [vii] 2,298-302 *).- The method is based on the observation made by Cross Bevm and Smith (Trans. 1898 '73 463) that hydrogen peroxide destroys the optical activity of reducing sugars forming products eventually identified by Morrell and Crofts as osones (ibid. 1899,'75 786).The author finds that lactose and dextrose are attacked by hydrogen peroxide in presence of manganese dioxide forming optically inactive products whilst sucrose remains unaffected If therefore the optical activity of a solution containing one of these sugars and sucrose is known the amount of sucrose can be estimated by a determination of the optical activity after the effect of the reducing sugar has been eliminated. Where a small quantity of sucrose occurs with much dextrose the latter may be almost completely separated by treat- ment with alcohol of 91' (Lindet Abstr. 1894 ii 64) and the part soluble inalcohol may then be recovered and treated as described above.This method is not applicable where sucrose occurs with maltose. Details of the method of working are given in the original. estimation of ash in sugar syrups by this process. w. P. 8. T. A. H. Detection of Inositol as a means of Identifying Wine Vinegar. P. FLEURY (J. Pharrn. Chim. 1910 [vii] 2 264-266).- A number of samples of genuine wine vinegar examined by the author all contained distinct quantities of inositol ; the detection of inositol is therefore considered to be of use in determining the genuineness of a sample of mine vinegar. If inositol is not present the sample is probably prepared from alcohol and not from wine. The method described previously by Meillere and Fleury (this vol. ii 553) may be w.P. s. employed for detecting the inositol. Estimation of Formaldehyde. WALTER BRAUTIGAM (Phccrm. Zentv.-h. 1910 51 915-916).-The process described depends on the decomposition of formaldehyde by calcium hypochlorite ; calcium carbonate is formed and its quantity is a measure of the amount of form- aldehyde present. The reaction proceeds according t o the equations CH20 + CaOCI = HC0,H + CaC1 ; HC0,H + CaOCl = CO + H,O + CaCl ; and 2CaOC1 + CO + H20 = CaC0 + CaCI + 2HC10. One molecule of formaldehyde therefore yields one molecule of calcium carbonate. I n carrying out the estimation a definite volume of the formaldehyde solution is mixed in a flask with an excess of freshly prepared calcium hypochlorite solution and the mixture is placed aside for some hours at the ordinary temperature.The clear super- natant liquid is then passed through a weighed filter and the filtrate is heated almost to boiling in order to ascertain whether all the * and Anst. Chzm. anal. 1910 15 415-419.ANALYTICAL CHEMISTRY. ii. 1007 formaldehyde has been decomposed ; should such be the case the solution remains clear but i f a-further quantity OE calcium carbonate forms it must be collected on the filter together with the main bulk of the precipitate. The precipitate and filter are washed until free from chlorides dried a t looo and weighed. w. P. s. Estimation of Formic Acid in the Presence of Acetic Acid. H. DELEHAYE (Ann. Falsif. 19 10,3,386-388).-The method proposed depends on the reduction of mercuric sulphate to insoluble mercurous sul phate. A quantity of the solution under examination containing not more than 0.2 gram of formic acid is mixed with 50 C.C.of mercuric sulphate solution (prepared as describpd below) and boiled under a reflux apparatus for forty-five minutes. The mixture is then cooled rapidly the liquid is decanted through a weighed filter and the volume of the filtrate is measured; the precipitate is then rinsed on to the filter with the aid of a saturated mercurous sulphate solution washed with 50% alcohol dried at 110" and weighed. To the weight found isadded a quantity in the proportion of 0.20 gram for every 100 C.C. of the filtrate ; the weight thus corrected is then multiplied by 0.0927 to obtain the amount of the formic acid. The mercuric sulphate solution employed is prepared by mixing 10 grams of mercuric oxide with 20 C.C.of hot water adding sulphuric acid until the oxide has dissolved and diluting the mixture to a volume of ?50 C.C. The filtrate obtained in the estimation Phould measure not less than 100 c.c. and the filtration must be carried out immediately the mixture has been cooled in order to prevent contamination of the mercurous sulphate with mercuric sulphate which is liable t g cry stallise out subsequently. w. P. s. The Separation and Estimation of Aspartic and Glutamic Acids THOMAS B. OSBOHNE and LEONARD 1\1. LIDDLE (Amer. J. Physiol. 1910 26 420-425).-Aspartic and glutamic acids react acid to litmus but their acid sodium salts do not. By Fischer's method of protein analysis glutamic hydrochloride is usually con- taminated with leucine hydrochloride and the two cannot be separated by direct crystallisation. When however the solution is made neutral to litmus leucine crystallises out readily and horn the mother liquor it is possible to separate out a further large amount of glutamic hydrochloride It was found possible to effect a fairly satisfactory separation of leucine and aspartic acid by taking out a small fraction of the esters after most of the leucine had distilled over and before the aspartic ester begins to distil freely and then treating this separately by a method described with detail in the text.Methods for the Detection and Volumetric and Gravimetric Estimation of Salicylic Acid in Wines and its Detection in Gases of Poiaoning. GUISEPPE CATTINI (Boll.chim. farm. 19 10 49 641-649).-For the detection of salicylic acid in wine urine and other coloured organic products acidification and subsequent extraction with toluene are recommended this solvent being preferable to ether because it does not remove colouriag matter from the aqueous liquid. W. D. H.ii. 1008 ABSTRACTS OF CEfBMICAL PAPERS. Various methods which have been proposed for the estimation of salicylic acid are shown t o be inaccurate. G. DIESSELHORST (PJiiger's ArcAiu 1910 134 496-500).-The fat extracted from flesh or tissue by Dormeyer's process (digestion with pepsin extraction of the digest with ether and weighing the ethereal extract) is very impure and consequently the results yielded by the method are untrustworthy. It is shown that if the dry powder is first extracted with ether in a mill as described by Lehmann and Viiltz (Ahstr.1903 ii '702) the fat obtained has the chemical and physical properties of beef fat. When the extracted residue of flesh is subjected to further treatment by Dormeyer's process an additional small quantity of " fat ' I is obtained which is largely contaminated with substances other than beef fat. w. P. s. R. V. S. Estimation of Fat in Flesh. Estimation of Cocoanut Oil in Admixture with Butter Fat. NOEL C. CASSAL and B. HENRY GERRANS (Chem. A7ews 1910 102 190-191).-In the process described the fatty acids obtained from the fat are subjected to a somewhat prolonged distillation with steam a t a high temperature in order t o increase the difference between the titration number of the insoluble volatile fatty acids from cocoanut oil and the tijxation number of the insoluble volatile fatty acids from butter fat.The process is as follows 3 grams of the fat are saponified by heating with 10 C.C. of alcohol and 2 C.C. of 50% sodium hydroxide solution ; after the alcohol has been removed by evaporation the residual soap is dissolved in 50 C.C. of boiling water 10 C.C. of con- centrated hydrochloric acid are added and then 50 grams of anhydrous calcium chloride. The flask is now connected with a condenser and heated by means of a calcium chloride bath b. p. 141-146' and when the contents of the flask begin to boil sheam is admitted and the distillation is continued until 500 C.C. of distillate have been collected. The distillate is filtered as it distils over and the filtrate is collected in a 500 C.C.flask. At the end of the distillation the condenser tube and the fatty acids on the filter are washed with cold water t o remove hydrochloric acid and soluble fatty acids the insoluble fatty acids are then dissolved from the condenser tube and the filter by means of hot alcohol and the solution is titrated with N/lO-barium hydroxide solution. I n the case of cocoanut oil the insoluble volatile fatty acids require 66 C.C. of N/lO-alkali for neutsalisation whilst those from butter fat require 16 C.C. w. P. 8. Alkylamines as Products of the Kjeldahl Digestion. C. C. ERDYANN (J. Biol. Chern. 8 41-55).-Compounds containing the groups =NMe -NHMe or NMe can yield mono- di- or tri-methyl- amine on digestion with sulphuric acid and a catalyst.The separation of organic base from ammonia in the Kjeldahl distillate is effected by adding t o the neutralised solution 5-10 C.C. of an alkaline mixture containing 20% of sodium hydroxide and 30% of sodium carbonate and 0.1 gram of yellow mercuric oxide for every C.C. of A',/lO-base present. After shaking for one hour in the dark and keeping till the mercuryANALYTICAL CHEMISTRY. ii. 1009 has settled an aliquot part of the supernatant liquid is distilled. The ammonia is retained by the mercuric oxide and the organic base which distils is titrated. The ammonia is then estimated by difference. The author suggests that the method can be used as a general qualitative method for determining in nitrogenous substances the presence of alkplamine groups and can probably also be used for approximately quantitative determinations as well.Vor tmann’s Nitroprusside Reaction for Hydrogen Cyanide. H. J. VAN GIFFEN (Pharrn. Weekbkud 1910 47 1043).-A modifica- tion of Vortmann’s process for the detection of hydrogen cyanide. Although not quite so delicate as the original method it has the advantage of not being interfered with by the presence of alcohol. To a portion of the distillate are added a few pieces of sodium nitrite and then 2 or 3 drops of officinal ferric chloride solution. To the brownish-yellow liquid is then added dilute sulphuric acid drop by drop when effervescence takes place and the liquid turns bright yellow. After heating to boiling tho iron is precipitated by adding excess of ammonia and the filtrate is evaporated to dryness on the water-bath. The residue is dissolved in a little water and the solution cooled i n ice. On adding a drop of dilute ammonium sulphide a violet colour is formed whicb according to the amount of cyanide present more or less rapidly passes into blue green and Estimation of Nitrogen Existing as Cyanamide and as Dicyanodiamide in Calcium Cyanamide.ALBERT STUTZER and J. SOLL (Zeitsch. nngew. Chem. 1910 23 1873-1874).-An extract of calcium cyanamide is first prepared by shaking the sub; c tance (10 grams) with 400-450 C.C. of water for two and a-half hours in R rotary apparatus The flask is theu filled to the mark (500 c.c.) and the contents filtered. The nitrogen in the form of cyanamide is estimated in 25 C.C. (= 0.5 gram of substance) by adding 10 C.C.of silver acetate solution (pre- pared by adding 400 C.C. of 10% ammonia to 100 grams of silver acetate and diluting to 1 litre). The precipitate is collected on a nitrogen-free filter and after all the solution has run through and the beaker below the filter has been changed is washed with water and the nitrogen determined by the Kjeldahl method The nitrogen as dicyanodiamide is estimated in the undiluted filtrate from silver cyanamide (25 C.C. =0*357 gram of original substance) by adding 10 C.C. of 10% potassium hydroxide solution and estimating the nitrogen in the precipitated silver dicyanodiamide. I n directly estimating the dicyanodiamide an alcoholic extract is made by shaking the substance (10 grams) for an hour with 250 C.C.of 94% alcohol. A portion of the filtered extract (100 c.c.) ie evapor- ated to dryness dissolved in hot water treated with 10 C.C. of the silver acetate solution filtered and the precipitate washed. The filtrate is then mixed with 10 C.C. of 10% potassium hydroxide G. 5. W. yellow. L. DE K. at once filtered and then estimated by Kjeldahl’s method. - N. H. J. N.ii. 1010 ABSTRACTS OF CHEMICAL PAPERS. Calcium Cyanamide ; its Analysis and the Changes in Composition it Undergoes when Exposed to the Atmosphere. CH. BRIOUX (Ann. C’him. anal. 1910 15 341-346).-Calcium cyanamide gradually undergoes decomposition when e3posed to moist air the calcium being converted into calcium hydroxide and carbonate and cyanamide is liberated ; the latter polymerises to form a double molecule dicyanodiamide.All these changes proceed more rapidly when the air contains carbon dioxide and is saturated with moisture ; under these conditions as much as 80% of the soluble nitrogenous compounds present in calcium cyanamide may be converted into dicyanodiamide in the coui-se of a few months. As dicyanodiamide has toxic properties and is injurious to vegetation it is of some importance to know to what extent the decomposition has proceeded in any sample of calcium cyanamide which has been stored in sacks or bags. This may be ascertained by estimating the cyanamide and dicyanodiamide present in a solution of the calcium cyanamide and the process recommended for the purpose depends on the fact that cyanamide yields a precipitate with silver nitrate which is insoluble in excess of ammonia whilst the analogous precipitate obtained in the case of dicyanodiamide is soluble in ammonia ; fut ther both substances are precipitated by silver nitrate in the presence of potassium hydr- oxide One gram of the calcium cyanamide is shaken with 250 C.C.of water for three hours and the solution is then filtered; 100 C.C. of the filtrate are now treated with 20 C.C. of 5% silver nitrate solution and an excess of ammonia is added. The precipitate is collected on a filter mashed first with dilute ammonia then with water and is next dissolved in warm dilute nitric acid (a &mall quantity of black residue sometimes remains insoluble) and the amount of silver thus obtained in solution is titrated with N/lO-ammonium thiocyanate solution ; each C.C.of the latter solution is equivalent to 0.0014 gram of nitrogen. A second quantity of 100 c c. of the filtrate is then treated with silver nitrate solution in the presence of an excess of potassium hydroxide; the precipitate formed is collected and the nitrogen in it is estimated by Kjelddhl’a method The difference between the amounts of nitrogen found in the two estimations gives the nitrogen present in the form of dicyanodiamide. w. P. s. Estimation of Digitoxin in Foxglove Leaves and their Preparations. JAMES BURMANN (Bull. SOC. chim. 1910 [iv] 7 973-982).-1t is now known that the three chief glucosides of fox- glove leaves are digitoxin digitalin and digitonin of which the first is of primary physiological importance and is the one usually estimated for medical purposes.Keller’s method of estimation (Abstr. 1898 ii 267 657) is that generally used and a comparison has therefore been made between the amorphous digitoxin ($-digitoxin) isolated by this method of estimation and ( a ) crystalline digitoxin and ( b ) Cloetta’s soluble digitoxin (digalene of commerce). The results show that $-digitoxin and Cloetta’s soluble digitoxin are both amorphous and are practically identical in melting point solubility and physiological activity and that both are less active than crystalline digitoxin and show quite different physical constants.AKALYTICAL CHEMISTRY. ii. 1011 Keller’s process can only be regarded as useful in estimating the medicinal value of the drug and its preparations if it is admitted that in the product weighed there is a constant relation between the digitoxin and the other glucosides present.T. A. H. Estimation of Adrenaline in Normal Blood and a f t e r its Injection by means of Physiological Methods. PAUL TRENDELENBURG (Arch. expt. Path. Phrni. 1910 63 171-176).-See this vol. ii 971 Estimation of Caffeine in Roasted Coffee. C. VIRCHOW ( C h . Zeit. 1910 34 1037-1038).-Twenty grams of ground coffee are moistened with about 10 C.C. of prater and the mass is introduced into a shaking cylinder furnished with a stopcock and ground stopper. One hundred C.C. of chloroform are added and the whole is well shaken for a minute. The chloroform is drawn off and the extraction is repeated twice. To the united filtrate is added 1 gram of paraffin and the chloroform is recovered by distillation.To the residue in the flask are then added 25 C.C. OF hot water tho liquid is poured into a beaker and the flask rinsed twice with 25 C.C. of hot water. The mixture is well stirred then allowed to cool and filtered; no caffeine is retained by the paraffin. On evaporating the aqueous solution crude caffeine is left which may be weighed. It is then purified by re- dissolving it in water and again evaporating to dryness with addition of a little magnesium oxide and extracting the mass thrice with chloroform; on evaporating this almost pure caffeine is left but it is advisable by way of a check to ascertain its nitrogen content by Toxicological Detection of Golchicine. HERMANN FUHNW (Arch. exp. Path. Pharrn.1910 63 357-373).-Colchicine can in forensic cases be detected with certainty by a combination of chemical and biological tests. A slight modification is proposed in Zeisel’s test. 0.1 mg. kills a white mouse. In frogs the toxicity of colchicine is increased 500-fold by warming them to 30-32’ and immunity can be produced in the usual way. In frogs if the drug is inbroduced under the skin i t in part re-appears in the urine. W. R. BLOOR (2 Biot. Chem. 1910 8 227-232).-Methods previously proposed for the estimation of ‘‘ saccharin ” in the urine after its administration are not sufficiently exact when dealing with small quantities. The new method proposed is colorimetric and gives good results; the colour is due to the transformation of “saccharin” into what is probably phenolsulphonephthalein (sulphurein) by treatment with a phenol- sulphuric acid mixture and is a bright yellow in weakly acid solutions and purple-red in alkali.The purple fades after a time but the yellow remains unchanged for a month or more. The test is performed with a benzene extract of the urine. W. D. H. ALFRED J. WAKEMAN (J. Biol. C&rn. 1910 8 233-236).-The method is means of a Kjeldahl estimation. L. DE K. W. D. H. Estimation of ‘‘ Saccharin ” in Urine. Estimation of ‘‘ Saccharin ” in Urine and FEeces.ii. 1012 ABSTRACTS OF CHEMICAL PAPERS. practically the same as Bloor’s (see preceding abstract) but differs in the apparatus used in the employment of ethyl acetate instead of benzene as solvent and in one or two other minor points. Amylases.I. Examination of Methods for Determination of Diastatic Power. HENRY C. SHERMAN E. C. KENDALL and E. D. CLARK ( J . Amer. Chern. Soc. 1910 32,1073-1086).-A critical study of some of the methods in use for measuring diastatic power carried out mainly on taka-diastase and pancreatin. The Lintner method is said to be insufficiently accurate for preparations of high diastatic power A modified form of the iodine method is described by means of which satisfactory results were obtained with taka-diastase but not with pancreatin. Methods depending on the action of the latter enzyme on pure starch in pure water were found to be useless because such a medium is too poor in electrolytes for the diastase to function normally. The optimum conditions necessary for the amylase to behave normally have been worked out and incorporated in a new gravimetric copper-reduction method which is described in detail.With commercial pancreatin this process gave results twenty times as w. 0. w. Reaction Distinguishing between the Organic Derivatives of Arsenious Acid and Those of Arsenic Acid. ERCOLE COVELLI (Boll. chim. farm. 1910 49 50-51. Compare Abstr. 1909 ii 830). -The difference in stability towards reducing agents in a1 kaline solu- tion which is shown by the above acids is shared by their organic derivatives. Atoxyl is reduced by nascent hydrogen in acid solution giving a yellow precipitate whilst in alkaline solution it is not attacked. The corresponding arsenious derivative NH,*C,H4;As0,2H,0 m. p. goo is prepared by treating atoxyl with sulphur dioxide in the cold and precipitating with sodium carbonate. It is reduced by nascent hydrogen in alkaline solution (aluminium and potassium hydroxide) giving a yellowish-white precipitate and also in acid solution with formation of a sulphur-yellow precipitate. Methylarsinic acid which is reducible in acid but not in alkaline solution yields when treated with sulphur dioxide a liquid which when reducad with potassium hydroxide and aluminium gives a yellow precipitate and blackens a test-paper impregnated with nmmoniacal silver nitrate. W. D. H. high as when no electrolyte had been added. R. V. S. Characteristic Reactions of Atoxyl. QUINTO FIORI (Boll. chirn. farm. 1910 49 98-99).-Atoxyl yields an orange-red colora- tion with a solution of bleaching powder in the cold. Sodium methyl- arsinate and sodium cacodylate do not give this reaction whilst an tifebrin gives an olive-green coloration only when warmed. Mercuric chloride produces in solutions of atoxyl a white precipitate which is soluble in dilute hydrochloric acid and in ammonia. Sodium methyl- areinate gives with the same reagent a brick-red precipitate which is also soluble in hydrochloric acid or ammonia whilst acetaldehyde and the cacodylate yield no precipitate. The presence of arsenic in atoxyl can be shown readily after a preliminary fusion with sodium hydroxide. R. V. S.

ISSN:0368-1769    

DOI:10.1039/CA9109805995

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ii. 1013 General and Physical Chemistry Influence of Temperature on the Refractive Index af White of Egg. AMEDEO HERLITZKA (Zeitsch. Chem. Ind. Ilottoide 1910 ’7 251-256).-Previous observations relating to the influence of salts on the refractive index of egg-albumin are referred to. Contrary t o the conclusions drawn by Frei (this vol. ii 365) the author’s data indicate that dissolved salts have no influence on the refractive index of colloids. New measurements of the refractive indices of a series of solutions of egg-albumin have been made a t temperatures between 7’ and 4 7 O . Whereas Frei’s data led him to conclude that the refractive index of colloids varies with the temperature according to a linear equation the author finds that a quadratic equation of the form Nt= N ( l - K1t - K2t2) is necessary for the representation of the temperature i u fluence.H. M. D. Anomalous Dispersion of Light in an Aqueous Solution of Neodymium Nitrate. L. ISAKOFF (J. Russ. Phys. Chem. Soc. 1910 42 236-243 [Physical Part]).-Some preliminary experiments on the dispersion of neodymium nitrate by the interference method A figure of the apparatus and a table and curves of the results obtained are given. The experimental results agree well with those calculated from the dispersion formula deduced. Z. K. Distribution of Chemical Elements in the Earth’s Crust. WLADIMIR J. VERNADSKY (Bull. Acad. Sci. St. Petersburg 1910 [vi] 11 29-1 148).-The spectra of a large number of minerals have been investigated in the oxygen gas flame and the results are given in a series of tables showing which elements are present numerous notes being added regarding the origin nature and so forth of the minerals and elements dealt with.Indium thallium rubidium caesium gallium and boron have been found for the first time in several minerals. I n some natural glasses bismuth copper and lead have been identified. When the spectrum of indium is obtained by sparking a solution of a salt or a mineral containing the metal the platinum wire continues t o give the indium spectrum even after being repeatedly washed; the same phenomenon occurs with lithium ; in the laster case it sometimes happens that a platinum wire which has ceased giving the lithium spectrum when dipped in pure water or acid suddenly re-commences to give the specbrum; t h i s may possibly be due to the formation of some compound of lithium and platinum.Various methods of determining the spectra of elements are discussed. 2. K VOL xcvIn. i. 69ii. 1014 ABSTRACTS OF CHEMlCAL PAPERS. Ultra-red Line Spectra. 111. Accurate Measurement of Wave-lengths greater than 27,000 A.-U. FRIEDRICH PASCHEN (Ann. Phyaik 1910 [iv] 33 717-738. Compare Abstr. 190% ii 630).-The experimental arrangemeut is described by means of which measurements of the wave-lengths of lines in the ultra-red spectra of lithium sodium potassium rubidium czsium and thallium have been made. Observations relating to the ultra-red spectra of cadmium aluminium silver helium and mercury are also recorded. A special form of iron-constantan thermo-element suitable for use in such measurements is described.Ultra-red Line Spectra. (Spectra of Silver Copper C=siuni Rubidium Strontium Barium.) IT. M. RANDALL (Arm. Yhysik 1910 [iv] 33 739-746. Compare preceding abstract).-Wave- length measurements in the ultra-red spectra between 8000 and 30,000 i . - U . are recorded. The grating spectro-bolometer designed by Paschen was employed. Relative Duration of Spectral Rays Emitted by Magnesium Vapour in the Electric Spark. GUSTAVE A. HEMSALECR (Compt. rend. 1910 151 668-671 ).-Kayser and Runpe’s triplets in the magnesium spectrum a s well as Rpdberg’s series of nebular liues have been studied by the method previously described (Comnpt. rend. 1905 141 1327; 1910 150 1743). The ielative intensity of the lines is given in tabular form together with their relative duration a t two capacitiep.The lines of the nebular series are the more sensitive to changes in capacity. The presence of impurities in the magnesium electrodes was rendered evident by the abnormal duration of the foreign lines. The method may be of value in detecting unknown Spectra of Anode Rays. OTTO REICHENHEIM (Ann. Physik 1910 [iv] 33 747-762).-Spectral observations have been made of the anode rays which are emitted by salts of the alkali and alkaline-earth metals. I n the case of the alkali metals the spectra show lines of the principal and first subsidiary series but no lines belonging t o the second subsidiary series could be detected even on the plates which were obtained with the longest possible exposure. I n general the anode ray spectra resemble the arc spectra so far as the relative intensity of the individual lines is concerned.The anode ray spectra of the alkaline-earth elements are much simpler than the corresponding arc spectra. The spectra of all three metals are of the same type and consist of a series of pairs of lines having the same difference in frequency and further of a single line which bears no obvious relationship to the other lines. The isolated lines i n the case of calcium and strontium are the flame spectrum lines X = 4227 and A = 4608 respectively. On the other hand the isolated line found in the case of barium is X = 6142 whereas the flame spectrum line is X = 5536. The lines in the anode ray spectra mere found to exhibit the Doppler effect and the magnitude of this was measured in several CBS&S. The various observations are discussed with reference to the H.M. D. H. M. D. impurities in analysis. w. 0. w.GENERAL AND PHYSICAL CHEMISTRY. 5. 1015 question of what are the carriers of the negative electrons which are responsible for the line spectra. The author considers that the carriers in the case of both the principal and subsidiary series of lines are positively charged ions in accordance with Stark's theory. H. M. D. Absorption and Inversion Phenomena in Luminous Hydrogen. AL. PFL~GER (Ber. Deut. physikal. Ges. 1910 12 719-724).-Polemical against Ladenburg (this vol. ii 81 1). The results. of the author's previous work are summarised. Absorption Spectra of Sulphur Vapour at Different Tem- peratures and Pressures and their Relation to the Molecular Complexity of this Element.J. IVON GRAHAM (Proc. Roy. Soc. 1910 A 84 31 1-324).-The absorption spectra of sulphur vapour have been photographed at temperatures varying from 530" to 900° and at pressures ranging from atmospheric down to 10 mm. of mercury. The records obtained at constant pressure over the above interval of temperature show that two distinct absorption spectra are present and these are attributed to the molecular complexes S8 and S,. The various photographs obtained at constant temperature and different pressures indicate that above 580' the S molecules dissociate directly into the diatomic molecules whereas at or below 520" dissociation takes plcae with the formation of molecules which are intermediate in complexity.The wave-lengths and frequencies of the bands which are due to the S and S molecules are tabulated. The conclusions thus arrived a t on the basis of spectroscopic evidence are in agreement with the views expressed by Preuner in explanation of the course of dissociation of sulphur vapour at 448'. Absorption Spectra and Constitution of Benzene Deriv- atives. I. NICOLAI A. WALIASCHKO (J. Russ. Yhys. Chem. Soc. 1910 42 751-805).-Curves and tables are given of measurements made of the absorption spectra of o- p- and m-hydroxy- methoxy- and -acetoxy-benzaldehydes phenol and benzaldehyde in aqueous and alcoholic solutions of various concentrations and with and without the addition of hydrochloric acid ; also for the sodium bisulphite derivatives of benzaldehyde for anisole acetoxyphenol resorcinol monomethyl ether guaiacol in alcoholic or aqueous solution mix- tures of benzaldehyde and some of its derivatives with chloroform and for various mixtures of benzaldehyde and guaiacol in alcoholic solution.The results are discussed in detail. All the ortho- and meta-derivatives give absorption spectra curves of the same type as benzaldehyde the only difference between the various spectra being that some of the bands in some compounds are more developed than in others. &The met%-spectra are intermediate between those of benzaldehyde and the corresponding ortho- compound and are more readily changed by the addition of hydro- chloric acid to the alcoholic solution the effect being to make the fipectra approach nearer to that of phenol.The reason for this is the formation of the unstable compound OH*C,H4*CHC1*OH which becomes hydrolysed on greater dilution. In water this compound is IT. RI. D. H. M. D. e9-2ii. 1016 ABSTRACTS OF CFIEMICAL PAPERS. completely hydrolysed consequently the addition of b ydrochloric acid to an aqueous solution of the compounds has no effect. On the other hand the ortho-benzaldehyde derivatives in aqueous solution are similarly affected by the addition of sodium hydrogen sulphite and the greater the concentration of the latter the more do their spectra approach that of phenol. The p-hydroxy- and -methoxy-derivatives in acid and neutral alcoholic or aqueous and in chlorofoym solution give curves of the same type as phenol but the spectra of the p-acetoxy-derivative is more like that of o-hydroxybenzaldehyde.The introduction of the benzaldehyde group into the benzene ring in- duces a definite new state of the latter and this effect is strengthened by the introduction in the ortho- or meta-position of an acetoxy- methoxy- or hydroxy-group ; these groups are therefore regarded as auxo- or batho-chromes the influence of which on the spectra is to move the absorption bands from the violet towards the red end of the spectrum. A similar effect is produced by the acetylation of benzsldehyde in the para-position the effect being the same as the acetylation of phenol which greatly decreases the influence of the hydroxyl group on the benzene ring but the hydroxy- or methoxy-group in the para-position decreases greatly the influence of the aldehyde group on the benzene ring but has no influence on the hydroxyl group in phenol+ conse- quently the spectra differs little from that of the latter.The absorption spectrum of a mixture of benzaldebyde and phenol in equimolecular proportions is very much like that of p-acetoxybenz- aldehyde. A study of the complex curves obtained by mixtures of substances leads the author to reject Baly and Collie's explanation (Trans. 1905 87 1332) of the benzaldehyde spectrum. On the contrary it is maintained that Eenzaldehyde has a greater selective absorption than phenol and that the entrance of the aldehyde group does not retard the internal motion of the benzene but induces a new form of vibration. The general results and conclusions drawn from the study of complex absorption spectra agree with -those of Hartley (Trans.1909 95 52). Progressive Phosphorescence at a Low Temperature JOSEPH DE KOWALSKI (Cornjot. rend. 1910 151 810-812).-The fluorescence of some aromatic compounds in alcoholic solution has been examined a t different temperatures between - 100' and - 190'. A t about - 135' the solutions were viscous the fluorescence extended towards the red and was apparent even when not visible a t the ordinary temperature. I n the case of phenanthrene anthracene and others the fluorescence terminated in the ultra-red. Fluorescence was observed below - 135" when the solutions solidified whilst at - 150' to - 165O phosphorescence also appeared the duration of the latter increasing as the temperature mas lowered.A progressive phosphorescence was also observed having an emission spectrum characteristic for the substance in solution but independent of the temperature. The bands of which it was composed mere more intense and persistent than the broad bands due to ordinary phosphorescence which disappears as soon as the light exciting it is removed. Z. K.GENERAL AND PHYSICAL CHEMISTRY. ii. 1017 For each substance there was a definite temperature above which progressive phosphorescence did not appear. This temperature limit appears to be independent of the freezing point or electrical con- ductivity of the solution. Phenanthrene does not show the phenomenon above - 158". w. 0. m. Rotation Dispersion. 11. HERMANN GROSSMANN and BERNHARD LANDAU (Zeitsch. physikd Chent.19 10 75 129-218. Compare Abstr. 1909 ii 713; this vol. ii 563).-The optical rotation of methyl Z-malate in over ninety solvents in different dilutions has been measured a t 20Q for red yellow green light blue dark blue and violet light by the method already described (Zoc. cit.) and a number of measurements have also been made with ethyl d-tartrate. Methyl malate is specially advantageous for such measurements owing to the fact that the dispersion curve of the pure liquid is normal as the following figures show Light. Red. Yellow. Green. Light blue. Dark blue. Violet. [a]2o" - 5.62 -6'42 -7'57 -8.96 -9'49 -9'86 The dispersion curve of methyl tartrate is abnormal. For full details as to the magnitude and sign of the rotation in the different solvents in varying dilutions the original paper must be consulted.The more important general conclusions with reference to the action on methyl malate are as follows. I n organic solvents containing halogens (over thirty such solvents were used) there is a tendency to reverse the direction of the rotation. This tendency attains its maximum when there are four chlorine atoms in the molecule; it is less when five chlorine atoms are present. BromaI chloral and acetyl chloride have an effect different from that of the other halogen com- pounds which is accounted for by the fact that the solutions show mutarotation. Further in most cases the rotation attains a maximum in these solvents and then diminishes somewhat and the final value is attained only after four or five days. Somewhat similar results are obtained with ethyl tartrate Heat is developed when the esters are dissolved in the above three solvents so that the mutarotation is doubtless connected with chemical combination but this does not account for the maxima.The effect of solvents containing a hydroxyl (including carboxyl) or nitro-group is similar to those containing halogens but solvents con- taining a free aminu-group or a nitrogen in the ring of a heterocyclic compound markedly increase the lsevorotation of the ester. That the effect just described is due to these groups is supported by the observa- tion that when the hydroxyl or amino-group is modified by putting in alkyl or other groups the influence on the rotation is lessened or non- existent. The methyl group as shown by observations with hydro- carbons and fatty acids also has a tendency to reverse the sign OF the rotation.Solutions in formic acid showed mutarotation and detailed observations on this phenomenon were made. In contrast t o other groups the aldehyde group in aliphatic compounds markedly increases the laevorotation of the ester. The same group in aromatic compounds has a similar but less pronounced influence,ii. 1018 ABSTRACTS OF CHEMICAL PAPERS. As regards isomeric compounds examples are given where a group in the meta-position has a greater influence on the rotation than when in the ortho-position. The difference in the effect of a group when in the nucleus and side-chain was analogous i n all cases ; the effect is greater i n the latter position. As inorganic solvents water sulphuric acid arsenic trichloride phosphorus trichloride and phosphoryl chloride were used and measure- ments with both active esters were made.Water has very little effect on the specific rotation of methyl malate. The two halogen compounds of phosphorus cause rotation t o the left with both esters. Methyl malate shows mutarotation in phosphoryl chloride but ethyl tartrate does not. Of all the solvents examined arsenic trichloride has the greatest effect in reversing the rotation. I n the violet the specific rotation of ethyl tartrate is -39.64 of methyl malate +29*68. I n sulphuric acid the natural rotation of the esters is considerably increased. The observations show that anomalous rotation dispersion is by no means a rare phenomenon ; it occurs in each case where the solvent has a tendency to reverse the direction of rotation of the solute.The influence of concentration on rotation is also discussed. G. S. Measurement of the Rotation Dispersion of Optically Active Compounds by means of the Nernst Light. HERMANN GROSSMANN and BERNHARD LANDAU (Zeitsch. Ver. deut. Zuckarind 19 10 1109-1117).-The use of a Nernst lamp in combination with suitable light filters is recommended for the measurement of rotation dispersion. The rotation produced by a 1-millirnetre quartz plate has been deter- mined for the approximately monochromatic light which is obtained by use of the coloured solutions suggested as filters by Landolt and by Winther. The specific rotations of dimethyl I-malate and diethyl d-tartrate for the various coloured rays are recorded and diagrams are given showing the influence of the solvent on the rotation dispersionof these substances in solution (see preceding abstract).H. M. D. Liquids with Conical Focal Lines. GEORGES FRIEDEL and F. GRANDJEAN (Compt. rend. 1910 151 762-765. Compare this vol. ii 809).-A geometrical description and discussion of the appearances presented by anisotropic liquids of the type of ethyl azoxybenzoate when these are viewed between crossed nicols under the microscope. w. 0. w. Triboluminescence. WLADIMIR I. VERNADSKY (Bull. Acud. Xci Xt. Petersburg 1910 [vi] 1037-1041).-'l'he property of tribo- luminescence of substances is closely associated with their electric properties; thus where triboluminescence occurs in substances having a centre of symmetry pyroelectric and other electric properties also occur.Triboluminescence is a surface phenomenon and temporary triboluminescence is due to the ckiange in the physical propertiec; of the surface of the crystal. Z. K.GENERAL AND PHYSICAL CHEMISTRY. ii. 1019 The Nature of Triboluminescence. IWAN VON OSTROMISSLENSKY (J. Russ. Phys. Chern. Soc. 1910,42 591-606. Compare preceding abstract).-A large number of substances chiefly organic compounds investigated by the author and others are tabulated with respect to their triboluminescence and the following conclusions are drawn. If one member of a group of chemical compounds which form solid solutions with one another or with some common substance is permanently triboluminescent then all the other members will be permanently triboluminescent.An apparent exception occurs in a group of substances forming solid solutions with dibenzyl but the latter is shown to occur in two modifications of which the /3-modification and the substances forming solutions with it are not luminescent. A permanently tribolu- minescent crystal does not give solid solutions with non-luminescent sub-tances and if one component of a solid solution is triboluminescent then the solution is likewise triboluminescent. The triboluminescence of a substance depends only on the syskem and structure of its crystals; it depends on its chemical constitution only so far as the latter influences crystalline form. kacemic mixtures of triboluminescent substances are always non-luminescent ; apparent exceptions are probably not racemates but only physical mixtures of the two compounds or they may be cases of temporary luminescence ; on the other hand optically inactive compounds of such type as mesotartaric acid may be triboluminescent. Only substances the crystals of which have no centre of symmetry can possess the property of permanent triboluminescence.Exceptions to this rule observed by Vernadsky and others are either cases of temporary luminescence (for in some cases the decay of this property may take a very long time) or the crystalline form of the substance in question has not yet been accurately determined. Thus at 130° potassium nitrate which a t that temperature exists as hexagonal crystals of the rhombohedra1 class is permanently triboluminescent but a t the ordinary temperature when the crystals belong to the rhombic system of the holohedral class they are only triboluminescent when freshly prepared. There is also reason to think that the intensity of triboluminescence depends on the system and class to which the crystals of a substance belong.Z. E. Triboluminescence of Racemic Compounds. IWAN YON OSTROMISSLENSKY (J. Russ. Phys. Chern. Soc. 1910 42 607-609. Compare preceding abstract).-The fact that racemic compounds are never triboluminescent can be used as a very rapid simple method of distinguishing between the racemate and the mere mixture of two optically active compounds and also to ascertain the exact point at which a racemate is resolved into its constituents and vice versa. This method may also be employed to determine exactly when one non- triboluminescent modification of a substance passes into a new crystal- line triboluminescent modification.Z. K. Triboluminescence of Minerals. B. A. LINDENER (Bull. Acnd. Sci. St. Petursburg 1910 [vi] 999-1022).-A historical resume ofii. 1020 ABSTRACTS OF CHEMICAL PAPERS. the previous work done on the subject. The triboluminescence of various natural minerals has been examined and the minerals are classified with respect to this property and their chemical con- stitution. The folloming conclusions are drawn (1) Tribolnminescence i n organic substances is of frequent occurrence. (2) Whereas the triboluminescence of artificial crystals is sometimes only temporary that of the natural crystals is constant and does not depend on the time.(3) Minerals belonging to the most varied chemical classes and groups can show the property but with few exceptions either all or none of the members of an isomorphous series are tribolumineecent. (4) The hardness of a mineral exercises no influence but the more brittle and the more marked the cleavage the more intense is the luminescence. (5) All triboluminescent minerals are non-conductors of electricity and all those that have pyroelectric properties are also tribo- luminescent. The character of the luminescent sparks is the same for all minerals. (6) The triboluminescence does not depend on the character and temperature of the medium surrounding the mineral. After reviewing the various theories advanced to explain tribo- luminescence the author draws the conclusion that the most applicable is Vernadsky’s (Bull.Acctd. Sci. St. Petersburg 1906 49) namely that the triboluminescence of chemical compounds is closely dependent on their crystalline form. So far as is at present known the crystal- line form of nearly all triboluminescent substances belongs t o tbe class in which there is no centre of symmetry Oxidation of Hydrogen Iodide under the Influence of Light. B. S. SCHWEZOFF (J. Buss. Phys. Chenz. Soc. 1910 42 219 [Physical Part]).-The purpose of the Pesearch was the construction of a chemical photometer. The oxidising action of sulphuric hydrochloric and nitric acid on potassium iodide in diffused sunlight was investigated in a special apparatus of which a figure is given.A constant current of air passing through the mixture kept the concentration of oxygen in it constant. Nitric acid reacts rapidly even in the dark; sulphuric and hydrochloric acid react much more slowly and with about the same velocity. The order of reaction calculated by the formula (Q and Q2 =concentration of the separated iodine ; C and C the concen- tration of potassium iodide) is 2 for dilute solution and 2.25 for concen- trated solutions (compare Plotkinoff Ahstr. 1907 ii 212 ; 1908 ii 790). Equivalent quantities of sodium potassium and cadmium iodide under similar conditions evolve equal quantities of iodine. Chemical Changes Produced by Different Kinds of Rays. IV. Catalytic Action of Sunlight in the Presence of In- organic Substances. CARL NEUBERG (Biochem.Zeitsch. 19 10 29 279-293. Compare Abstr. 1908 ii 915).-The author summarises the chemical changes already investigated when various substances are exposed to sunlight in the presence of uranium salts. He now shows that various other inorganic substances exert a similar action and gives the qualitative results of the exposure of solutions of forty-five different substances in the presence of ferric sulphate. Most of these substances show changes of degradation Certain reactions were also Z. K. n = (lop& - logQ2)/(logC - IOgC,) Z. K.GENERAL AND PHYSICAL CHEMISTRY. ii. 1021 quantitatively investigated. I n the case of alcohols the amount of aldehyde formed was estimated ; in that of a-amino-acids and peptones the amount of ammonia evolved in deamidisation ; in that of p-amino- acids the amount of amino-aldehyde formed.I n the case of I-glucose the diminution of fermentable sugar was estimated and in those of the disaccharides the amount of inversion. The amount of uric acid destroyed was also estimated and also the amount of phosphoric acid set free from nucleic acids aud the amount of salicylic acid formed from benzoic acid. s. B. s. Photo-electric Experiments with Anthracene. WALTER STEUBING (Berr. Deut. physikal. Ges. 1910 12 867-868).-A reply to criticism on the part of Byk and Bmck (this vol. ii 814) of previous experiments by Stark and Steubing (Abstr. 1908 ii 746) on the photo-electric sensitiveness of anthracene. The experimental arrange- ment employed is described and reasons are advanced in support of the validity of the conclusion that anthracene is photo-electrically active.H. M. D. Nature of the Ionisation Produced by a-Rays. FRANK E. WHEELOCK (Amerr. J. sci. 19 10 [iv] 30 233-255) -Experiments have been made to test whether columnar ionisation affords a complete explanation of the lack of saturation obtained in a-ray ionisation when moderate fields are employed or whether " initial re-combina- tion" also plays any part. With a perpendicular field the lack of saturation is less than with a parallel field as Moulin found (Abstr. 1908 ii 921). The ratio of two currents obtained with a constant field and two sources of a-rays differing in intensity does not depend on the field when it is parallel to the path of the rays but does when it is perpendicular as though with strong currents the ions in different columns interspersed with one another.A theoretical expression based on the hypothesis of columnar ionisation gave a saturation curve different from the experimental saturation being approached as the field increases more slowly than the expression required. On this and other data the conclusion is drawn that possibly bohh the hypotheses of columnar ionisation and of initial re-combination may be necessary to explain all the peculiarities of a-ray ionisation. F. S. Absorption and Reflexion of the P-Particles by Matter. ALOIS F. KOVARIK (Phil. Mag. 1910 [vi] 20 849-866).-The radio- active substances employed radium-D and -E actinium-C radium-& thorium-A -B -C and -D were deposited on very thin aluminium leaf the absorption and scattering of which is negligible.Such preparations covered directly with thin aluminium foil and placed some distance below the electroscope give an absorption curve showing an increase in the ionibation for the first 0.05 to 0.01 mm. of aluminium or equivalent thickness of tin which is ascribed to scattering. When the distance of the absorbing foils from the preparation was increased the maximum decreased in magnitude until finally the reverse effect studied by Crowther showed itself. In a hemispherical ionisation chamber arranged so that the path of all rays mas the same it mas shown thatii. 1022 ABSTRACTS OF CHEMICAL PAPERS. the rays reflected from the support beneath the preparation were always less penetrating than the direct rays the less so tbe greater the atomic weight of the reflector.Measurements of the absorption coefficients of the various rays were taken with as much aluminium below as above the preparation to compensate for reflexion. The curves obtained mere very nearly exponential. r“or different P-rays the percentage of the radiation reflected increases with increase in the velocity of the rays and with the atomic weight of the reflector. For very penetrating P-rays [A(crn.)-l above 201 however the percentage reflected again decreases. By multiple reflection from the sides of the ionisation chamber the ionisation may be increased three and a-half times. F. S. The Reflexion of Homogeneous P-Particles of Different Velocities. ALOIS F. KOVARIK and W. WJL~ON (Phil. Mag. 1910 [vil 20 866-870).-The P-rays of radium C from a sealed bulb of radium emanation mere sorted out into homogeneous rays by a mag- netic field and entered a flat ionisation chamber made of thin aluminium leaves which could be inclined a t different angles to the rays and could be covered with reflecting substances.It was found that the power of substances to reflect the rays increased with the velocity of the rays from H = 1000 to H =about 3000 and then slightly decreased again but the ratio of the reflective powers of lead and copper was the same whatever the velocity of the rays. F. s. The Heterogeneity of P-Rays from a Thick Layer of Radium-E. J. A. GRAY and W. WILSON (Phil. Mag. 1910 [vi] 20 870-8’75).-Using a thick layer of radium-l) and -E it was found that although the whole radiation was absorbed exponentially [A(cm.)-l= 431 by aluminium different bundles of rays of widely different penetrating power [X(cm.)-l from 13 to 62-51 could be sorted out by a magnetic field.When the rays had first to pass through aluminium it was proved by magnetic deflexion measure- mcnts that the average velocity of the rays surviving was increased. F. S. The Deflexion by an Electrostatic Field of Radium-B on Recoil from Radium-A. SIDNEY Buss and WALTER MAKOWER (Phil. Mag.. 1910 [vi] 20 S75-882).-Some at least of the atoms of radium-B recoiling from radium-A are positively charged although in the disintegration of radium-A positively charged a-rays are also expelled. The ‘‘ recoil atoms ” from a wire made active by a deposit of radium-A were passed between oppositely charged plates in a vacuum and fall upon a metal cross-piece.The distribution of the activity on the latter was determined by moving it under a narrow slit in the base of an a-ray electroscope. The point of maximum distribution was shifted by the application of a field to the plates and from the magni- tude of the shift the charge carried by the ‘‘recoil atoms” was deduced on the assumption that the velocity of the atoms was 3.27 x lo7 cm. per second which is that calculated from the principle of equality of momentum of the two parts of a disintegrating atom.GENERAL AND PHYSICAL CHEMISTRY. ii. 102.3 The values obtained indicated that the recoil atom carries unit positive charge and that its mass is 214 in agreement with what is to be anticipated from the disintegration theory.The Deflexion by a Magnetic Field of Radium-B on Recoil from Radium-A. WALTER MAKOWER and E. J. EVASS (Phil. Mag. 19 10 [vi] 20 882-S86).-SimiIar experiments to those described in the preceding abstract were carried out the “recoil atoms” being deviated in a magnetic instead of an electrostatic field. The distribu- tion of the activity on the cross-piece was determined by laying it on a photographic plate and then measuring the photograph obtained by projecting it on to a screen by means of a lantern. The value for Zfp of the deflected “recoil atoms” was 6-52 x lo5. This is twice that obtained by Rutherford for the a-particle of radium-A and since Hp=m/ue and the value of m v must be the same in both cases on the principle of equality of momentum it follows that the cbarge carried is the unit charge instead of twice the unit charge as in the case of the a-particle.By combining the results of the electrostatic and magnetic deflection measurements it follows that the velocity of the ‘‘ recoil atom ” is 3.23 x 107 and its mass is 194 (H = l) which is as close to the theoretical value 214 as can be expected. Measurements of t h e Rate at which Helium is Produced in Thorianite and Pitchblende with a Minimum Estimate of of their Antiquity. (Hon.) ROBERT J. STRCTT (Proc. Roy. Soc. 1910 A 84 379-388).-A description is given of the methods employed to measure the rate of production of helium from solutioiis of thorianite (two varieties one specially rich in uranium from the Galle district of Ceylon) in nitric acid and of pitchblende. The latter mas dissolved in nitric acid and the insoluble sulphntes con- verted into carbonates and dissolved to form a separate solution.The solutions were contained in large flasks closed by barometer tubes dipping beneath mercury and the gaseous contents were removed periodically with steam by boiling the liquids. The volume of helium was estimated in the expelled gas after subjection t o cooled charcoal in a narrow capillary tube. The rate of production of helium per gram of mineral per annum was found to be 3.7 ( x lo-* c.c.) for Galle thorianite containing 24.5% of U,O and 65.44% of Tho,; 2-79 for ordinary thorianite containing 13.10% of U,O and 72.65% of Tho ; and 3.16 for pitchblende containing 37.6% of U,O,.‘l’hese results are in good agreement with those calculated earlier on certain assumptions. The minimum ages of the t w o thorianites are 2.50 and 2.80 ( x 10-5 years) respectively as calculated from the period required to produce the contained helium no allowance being made for the helium that escapes The minimum ages of 4 minerals previously worked with are in millions of years (1) sphaerosidenite (Oligocene) 8.4 ( 3 ) hzlematite (Eocene) 31 (3) haernatite (Carboniferous limestone) 150 (4) sphene (Archean) 710. Disengagement of Emanation from Radium Salts. 111. L ~ O N KOLOWRAT (Le Radium 1910 7 266-269. Compare this vol. ii 9 1).- Wit4 barium chloride containing only minute proportions F. S. F. S. F. S.ii. 1024 ABSTRACTS OF CEEMlCAL PAPERS.of radium chloride the disengagement of emanation from the salt a t a temperature 8 after a period of accumulation t from the moment of complete removal of emanation by fusing the salt is the same whether the temperature is maintained a t 6 throughout or for only a short time at the end of the period of accumulation and is represented by c(l - ~--ht)/X where h is the constant of the emanation and c a co- efficient between 0 and 1 which is a function of 8 but independent of t ; c may be considered as the fraction of the emanation generated retained by the solid salt at 8" and may be determined with con- sistency in different experiments at the one temperature for different times for the same preparation but varies greatly with different preparations otherwise apparently similar.Impure preparations seem t o have lower values of c than those only containing barium and radium chloride. The idea that part of the radium chloride is in the form of a solid solution in the barium chloride and gives up its emanation more readily than the rest supposed to be present with the barium chloride in the form of mixed crystals (Kolowrat this vol. ii 767) does not account for the differences as there is no regular relation between the value of c and the proportion of radium present. Using a few thousandths of a milligram of pure radium chloride i t was found that heating to the fusion temperature no longer effected complete release of the accumulated emanation the material being changed by high temperature into an insoluble and probably infusible product.This agrees with Mme. Curie's observation that heating reduces the escape of emanation from radium chloride and was con- firmed by observations on the minimum @radiation attained by the preparations after heating. The 1% barium-radium chlorides are less easily changed by heat and give up the whole of their contained emanation by fusion. F. S. Action of Radium Emanation on Colloids. WILLEM P. JORISBEN and H. W. WOUDSTRA (Chem. Weekbkud 1910 '7 941-948. Compare Henri and Mnyer Abstr. 1904 ii 184).-The authors con- firm the results obtained by Henri and Mayer in their work on the action of radium emanation on colloids. They find that the sensitive- ness of a colloid towards an electrolyte is increased by this ernanation. A. J. W. The Diffusion of Gaseous Ions.EDOUARD SALLES (Compt. rend. 1910 151 712-714).-The coefficients of diffusion of ions in care- fully dried air carbon dioxide nitrogen and oxygen produced by the a-rays of polonium have been measured by a method the principle of which is due to Townsend. The values are in accord with those given by Townsend for ions produced in other ways the positive ion for oxygen (k= 0.030) being the only one in disagreement. Experiments under pressure p (mm. of mercury) showed for p x k constant values of about 22 for the positive and 32 for the negative ions in air and nitrogen. F. S. Attempts to Prepare Metallic Radium. ERICH EBLER (Ber. 1910 43 2613-2618).-From 0.02 gram of barium bromide con-GENERAL ANb PHYSICAL CHEMISTRY. ii. 1025 taining 25% of radium bromide about 1 mg.containing 9% was prepared by crystallisation converted into carbonate and dissolved in aqueous hydrazoic acid. On evaporation a white crystalline mass of radium azoimide Ra(N,) containing barium azoimide was left. Pre- vious experiments with barium azoimide had shown that it is not decom posed by the action of radium rays. The preparationwas brought into a narrow '' melting-point tube," supported inside a perfectly exhausted glass tube and heated in a special sand-bath very slowly to lS0-2509 After some hours a shining metallic mirror was formed which was sealed off from the preparation and found to contain 73% of the radium employed by electroscopic measurements. The radium mirror was dissolved out of the tube and converted into chloride. I n spite of the impurity of the preparation the experiment proves that elementary radium is chemically and physically analogous to elementary barium.It appears to form nitride with moist air even more readily than barium. F. S. The Radium Content of Waters of the Cam Cambridge Tap Water and Some Varieties of Charcoal JOHN SATTERLEY (Proc. Camb. Phil. Xoc. 1910 15 540-544).-The emanation generated per litre of Cambridge tap water and of Cam river water respectively is that in equilibrium with 130 and 5 ( x gram of radium) while the amount of radium is 1.6 and 3.2 ( x 10-l2 gram). The Cambridge waters are therefore richer in radium than those of Montreal which accounts for the higher values found for the quantity of emanation in the air of Cambridge than in that of Montreal.I n four varieties of charcoal the radium contents per gram were (1) cocoanut 0.4 (2) cocoanut 0.3 (3) Brazil-nut 1.3 (4) wood 0.3 ( x 10-12 gram). Investigations on the Radium Content of Rocks. I. ERNST H. BUCHNER (Proc. R. Akad. Wetenuch. Amsterdam 1910 13 359-36b).-'l'he investigation includes ten rocks from the West Coast of Sumatra comprising quartz porphyrite granite basalt andesite augite-andesite,. granitite diorite and diabase. These rocks showed a content of radium of the order of gram per gram similar in magnitude to those which have been examined by other investigators. The highest was a basalt from the volcano of Asar (13.0) and the lowest were the diorite and diabase (0.3 x gram of radium per gram). (Hon.) ROBERT J. STRUTT (Proc. Roy. Xoc.1910 A 84 377-379).-The discrepancy between the author's results and those of Joly on the radium content of igneous rocks is greatest in the case of basalts the value found by the latter being about eight times that found by the former. New measurements with special precautions have therefore been made on a new set of three basalts which give results even lower than the previous set (from 0.16 to 0.35 x 10-12 gram radium per gram) whilst in one sample previously employed a new determination gives the same result as before (0.57). It is possible that Joly has met with exceptional specimens. F. 8 F. S. F. S. The Radium Content of Basalt.ii. 1026 ABSTRACTS Ol C€IEMIOAL PAPERS. The Presence of Radioactive Elements in Some hcrustzt- tions from the Fumaroles of Vesuvius.GIUSEPPE I.ERNOT (Rend. Accad. Sci. Pis. Mat. Napoli 1910 [iiia] 16 48-50. Compare Abstr. 1907 ii 365).-Incrustations from recent fumaroles dissolved in hydrochloric acid and precipitated with hydrogen sulphide yield a mixture of sulphides from which after removing arsenic by ammonium sulphide boiling with dilute hydrochloric acid and dissolving in nitric acid lead is removed as sulphate and a greyish-white precipitate is then obtained by the addition OF ammonia. This precipitate is markedly radioactive. C. H. D. The Radioactivity of the Products of the Recent Eruption of Etna. ARNALDO PIUTTI and GENNARO MaaLI (Rend. Accad. Sci. Pis. Mat. Napoli 1910 [iiia] 16 159-1GS).-The products of the recent volcanic eruption of Etna have been studied in the same manner as those of Vesuvius (this vol.ii 290). The smallest radio- activity is possessed by the volcanic sands followed in ascending order by the lava the scoriie and the sublimed products and incrustations. The maximum activity agrees with that of the materials obtained fiom the preceding eruption and is greater than that of corresponding materials from the last eruption of Vesuvius in which however the same relative order is observed. C. H. D. Radioactivity of Italian Minerals. RAFFAELO NASINI and MARIO G. LEVI (Gazzetta 1910 40 ii 101-122. Compare Abstr. 1909 ii 7 110).-A complete account of the work on this subject carried out by the authors and others. R. V. S. A Determination of the Ratio of Mass to Weight for a Radioactive Substance. L. SOUTHERNS (PYOC. Boy.Soc. 1‘310 A 84 325-344).-The ratio of mass to weight of the oxides of lead and of uranium have been compared by filling the hollow bob of a specially constructed rigid pendulum with these t w o substances and no difference between them has been indicated. The ratio is the same €or the two substances within one part in 200,000. I?. 8. Electrical Purification and Conductivity of Liquid Sulphur Dioxide. J. CARVALLO (Con@. rend. 1910 151 717-719).- When a current is passed through liquid sulphur dioxide free from air between platinum electrodes the difference of potential being V it is found t h a t the currenc 1 diminishes with time until a limit is attained. The negative electrode becomes slightly brown and the liquid under- goes purification by prolonged passage of the current.When V i s 200-500 volts the limiting current does not vary as a simple function of K With a difference in potential of 1000 or 2000 volts the current is much smaller than that passing with lower tensions. Curves plotted for 1’=f(V) are in accordance with Ohm’s law when Vdoes not exceed 100 volts. The limiting conductivity for higher voltages is not in agreement with this; the law governing i t under these conditions appears to resemble the laws for the conduct- ivity of gase; and will be fwther studied. The limiting specificGENERAL AND PHYSICAL CHEMISTRY. ii. 1027 resistance under 100 volts was 7.6 x lo9 ohms; under 2350 volts 4-9 x 1O1O ohms and under 4000 volts 4.9 x 1010 ohms per cm. w. 0. w. Electrical Conductivity of Solutions in Aniline Methyl- aniline and Dimethylaniline.AL. SACRANOFF (J. Russ. Phys. Chem. Soc. 1910 42 683-690).-The object of the research was t o determine the connexion between the chemical nature of an amine and its dissociating power and its power of giving conducting solutions. Since the dielectric constants of the three amines are very close t o one another any difference that may exist in their dissociating powers would be due t o the difference in their chemical constitutions. The following salts were employed ammonium iodide pyridine hydro- bromide aniline hydrobromide silver nitrate and lithium iodide and tables and a curve for aniline solutions are given showing the relation of concentration t o electrical conductivity. All the solutions show a rapid diminution of their molecular electrical conductivity with increasing dilution this probably being due to the formation and dissociation of complex salts such as NH4I,2PhNH AgNO,,ZPhNH,.Aniline gives the best conducting solutions methylaniline comes next whilst the solution in dimethylaniline seems to be on the border between conducting and non-conducting solutions. The conclusion is drawn that the chief factor determining the ability t o give conducting solutions is the chemical constitution of the amine. Z. K. The Potential of the Sodium Electrode. GILBERT N. LEWIS and CHARLES A. KRAUS (J. Amer. Chern. Xoc. 1910 32 1459-1468). -A method of obtaining the difference of potential between metallic sodium and a solution of sodium ions of normal concentratmion is described This consists in determining the potential difference between a dilute sodium amalgam and a n aqueous solution of sodium hydroxide and also the E.M.F.of the cell metallic sodium I sodium iodide dissolved in ethylamine I sodium amalgam. The E.H.F. of this galvanic combination is independent of the medium in whicb the sodium salt is dissolved and ethylamine was chosen because it is not acted on by the alkali metal. The E.M.F. of the combination sodium amalgam (0.206% sodium) I 0*2N-sodium hydroxide I normal calomei electrode was found to be 3.1986 volts. Assuming that the sodium hydroxide is ionised to the extent OF 82*8% this gives for the E.M.F. of the cell sodium amalgam I aqueous solution containing Na ions in normal concentra- tion I normal calomel electrode 2.1525 volts. The potential difference between sodium and 0906% sodium amalgam is 0.8456 volt,aud these data when combined give for the 8.M.F.of the combination sodium 1 aqueous solution containing 1N-sodium ion 1 normal calomel electrode 2.9951 volts at 2 5 O . The temperature-coefficient of the sodium-sodium amalgam cell is -0*0000408 volt per degree and from this i t is calculated that the heat of solution of 1 gram-atom of sodium in 0206% sodium amalgam is 19,790 cal. The precautions to be observed in the preparation of pure sodiumii. 1028 ABSTRACTS OF CHEMICAL PAPER% amalgam and of anhydrous ethylamine are described in detail. If these are followed the observed potential differences can be re- produced with great accuracy. Oscillographic Investigation of Some Electrolytic Processes.111. D. REICEINSTEIN (Zeitsch. Elektrochem. 1910 16 916-944. Compare Abstr. 1909 ii 960).-Using a more sensitive oscillograph (on the photographic record a deflexion of 1 mm. on the ordinate axis is given by a current of 0.0004 ampere whilst 1 mm. on the axis of absciss2e corresponds with 0.0006 second) the author has studied the polarisation of an electrode produced by a fairly strong current lasting a few hundredths of a second and its subsequent decay. The cases examined are the anodic and cathodic polarisation of platinum ( a l s ~ mercury and silver) in 28% sulphuric acid ; the anodic polarisation of copper silver lead,and nickel in solutions of their salts and the cathodic polarisation of palladium in sulphuric acid and in acid zinc sulphate.I n all the experiments the experimental electrode is combined with a large unpolarisable electrode. The results are as a rule given in the form of reproductions of the oscillograph curves. The main result however is that during the passage of the polarising current the difference of potential between the electrode and the solution is always much larger than the equilibrium P.D. when no current is flowing and the difference increases with the current. The rate of disappear- ance of this excess depends on the nature of the product of electro- lysis and of the electrode. The phenomenon is met with in every case examined ; it is hardly possible to give the details and also the possible mechanisms which the author suggests in explanation of them in a brief abstract.It may be said however that the view is taken that the primary products of the electrolysis are not identical with the stable substances finally formed the decay of the excess polarisa- tion being due t o the transformation of one into the other. The P o t e n t i a l s of Chlorine Bromine and Iodine in Methyl and Ethyl Alcohol. J. NEUSTADT (Zeitsch. Elektrochern. 19 10 16 866-869).-The E.2CI.F. of a cell Ag 1 saturated solution of AgCl I C1 is independent of the solvent used. It is given by E = E A ~ - E C ~ + RT/nF(log[Ag’] + log[Cl’]). The quantity in the brackets is the logarithm of the solubility product of silver chloride and €Ag and rc1 are the normal potentials of silver and chloride in the solvent used. From the value of I3 for aqueous solutions and determinations of the solubility products of the silver haloids in the alcohols the differences of the normal potentials of the haloids in alcoholic solutions are therefore easily calculated.The solubility products in alcoholic solutions are obtained by measurements on concentration cells of the type Ag I O*lN-AgNO I O*lN-KCl saturated with AgCl 1 Ag. The concentrations of the silver and chlorine ions in the alcoholic solutions are calculated from the conductivity measurements of Dempwolff (Abstr. 1905 ii 9). The mean values of the solubility products at 25” are Methyl alcohol. Ethyl alcohol. H. M. D. T. E. ......................... Age1 1 *95 x 10-13 1.85 x AgBr 1-1 x 10-l5 6-4 x 10-l6 ........................... AgI ............................. 1.5 x 1-1 x10-1sGENERAL AND PHYSICAL CHEMISTRY.ii. 1025 Electrode reversible with reference to anion. Saturated solution of zinc sul- phxte in contact with the reference to cation. stable solid phase of the salt. Electrode reversible withii. 1030 ABSTRACTS OF CHEMICAL PAPERS tho passage of 96,540 coulombs and 7r is the pressure. The factor v 2 - q has been determined directly by puLting pure zinc sulphato heptahydrate in a pyknometer filling up with toluene as indif’l’erent liquid and finding the change of volume after transformation to the hexahydrate. Substituting in the above equation the value Eso0 - Eo = 0.00058 volt is obtained as compared with the experimental value 0-OOlOt! volt. Further the Cllausius-Clapeyron equation dI’/dp = 10,3331’(~ - T)/427.2~ where (a-T) is the change of volume in the transition of zinc sulphate heptahTdrate and v is the accompanying thermal effect can be employed to fmd the effect of change of pressure on the transition temperature.Inserting the appropriate values of ((r-T) and Y it is found that dp/dT= 0*003Z0 whereas the experimental value is 0.0036°. Finally another equation is derived thermodynamically by means of which dp/dY‘ can be calculated by means of electrical measurements. It leads t o the value of dp/dT=0.0027’ instead of the experimental value given above. G. S. Thermo-[electric] Forces of Solid Solutions of Metals and Schenck’s Law. AUGUST L. BERNOULLI (An7t. Phpsik 1910 [iv] 33 690-706).-Thermo-electric measurements have been made for various solid solutions of metals in order to test Schenck’s formula T = R/3e.log(k’/af k/u) in which 7r is the thermo-electric diEerence of potential between the pure metal and a solid solution containing a second metal k and cr are the thermal and electric conductivities of the solvent metal and k’ and cr’ the corresponding quantities for the solution.Solutions of thallium and tin in silver of mercury in cadmium and of tin zinc and nickel in copper were investigated. For sufficiently dilute solutions the observed thermo-electric potential difference agrees with that calculated from Schenck’s formula and this agreement is particularly good when the atomic weight of the solute metal is considerably greater than that of the solvent metal. As the concentration oE the solutions increases the agreement becomes less satisfactory.I n tho case of the copper zinc alloys the observed potential differences are much larger than those obtained by calculation and this is attributed t o the formation of the compound Cu2Zna. H. M. D. Electrophoresis of Lamp Black. ALBERT REYCHLER (Bull. Xoc. chirn. Belg. 1910 24 345-354).-Using an apparatus similar to that described by Coehn (Abstr. 1909 ii 841) the author has investigated the electrophoresis of lamp black (Kahlbaum’s) which bad been subjected to different methods of purification in order to obtain a suspension in water. These methods were ( a ) treatment with a mixture of potassium dichromate and concentrated sulphuric acid for eighteen hours and subsequent washing with dilute hydro- chloric acid and finally with water ; (6) trituration with concentrated sulphuric acid and then washing as in ( a ) ; ( c ) warming with a diluteGENERAL AND PHYSICAL CHEMISTRY.ii. 1031 solution of sodium in ordinary alcohol and subsequent washing with alcohol and water; ( d ) no purification was attempted but a suspension was obtained directly by introducing the lamp black into dilute alcohol which was slightly alkaline. Suspensions could not be obtained when it was put directly into water. The suspensions obtained were investigated as such and after the addition of enough potassium hydroxide or hydrochloric acid to make them from iV/llO to N/11,000. All alkaline suspensions showed the phenomenon of anaphoresis and were fairly stable. Suspensions which were very feebly acid still showed anaphoresis but when the acidity was increased (iV/110} they were flocculated so rapidly that it mas impossible to observe whether they showed catapboreeis (compare Perrin Abstr.1905 ii 13s). Details are also given of actual stability of the different suspensions and of the effect of filtration. The remainder of the paper is occupied with a discussion of the detergent action of soap special reference being made to the theories of Spring (this vol. i 6 ) and of Chevreul. T. S. P. The Nature of the Coloured Films Formed on the Alkali Metals by Electric Discharges. JULIUS ELSTER and HANS GEITEL (Physikal. Zeitsclh. 1910 11 1082-1083. Compare this vol. ii 379). -The coloured substances which are formed on the surface of the alkali metals when subjected to the influence of the glow discharge in hydrogen a t low pressure have been described as colloidal solutions of the metals in the corresponding hydrides.It is pointed out that the colours of the different substances are identical with those of the corresponding modifications of the alkali metals obtained by Fificher and Schroter (this vol. ii 609) by the disintegrating action of the arc discharge 0.n alkali metal electrodes immersed in liquid argon. The two series of coloured substances obtained by the two methods are considered to be identical. The presence of hydrogen is supposed to facilitate the formation of the colloidal metals under the influence of the glow discharge by form- ing hydrides which act as solvents for the metals. Since hydrogen was in all probability present in the arc discharge experiments of Fischer and Schroter the formation of the colloidal metals in these circumstances may bo in some measure due to the preliminary formation of hydrides.When potassium is subjected to the glow discharge at the tempera- ture of liquid air the coloured film is not formed to any appreciable extent and this is attributed to the absence of the hydride which is not formed in consequence of the low vapour pressure of the alkali metal at this temperature. H. M. D. Specific Heats and Gas Equilibria from Explosion Experii ments. 11. MATHIAS PIER (Zeitsoh. Elektrochem. 19 10,16,897--903). -The manometer previously used (Abstr. 1909 ii 789) is improved by fixiug the mirror directly to the corrugated diaphragm about midway between its centre and its periphery.By exploding acetylene (a) with excess of air (6) with excess of 70-2ii. 1032 ABSTRACTS OF CHEMlCAL PAPERS. oxygen and (c) with excess of carbon dioxide data are obtained from which the ratios of the specific heats of carbondioxide or of oxygen to that of nitrogen are calculated. The molecular heat of oxygen up to 2200° is the same as that of nitrogen (4*900+0*00045t). The formulse of Holborn and of Langen do not represent the results obtained for carbon dioxide; a new equation is therefore proposed for the mean molecular heat of carbon dioxide between 0" and to at constant volume c 6.800 + 3.3 x lo-% - 0.95 x 10-%2 + 0.1 x 10-9t3. This represents both the author's results between 1600" and 2100' and those of Holborn and Henning (200-1364") with sufficient accuracy.The molecular heat of sulphur dioxide is obtained from explosions of carbon disulphide with oxygen It is the same as that of carbon dioxide up to 2000". The dissociation of carbon dioxide is calculated from the results of explosions of mixtures of carbon monoxide and oxygen on the assump- tions that carbon monoxide has the same molecular heat as nitrogen and that the above expression for carbon dioxide holds up to 3000°. The results are too high which is taken to indicate that the specific heat of carbon dioxide increases more rapidly above 2000". An attempt to measure the equilibrium CO + H = H,O + CO also failed for reasons which are not clearly understood. T. E. Critical Phenomena of Ethyl Ether. F. B. YOUNU (I'M Mag.1910 20 793-828).-0bservations relating to the nature of the critical phenomena in ethyl ether are described and discussed in reference to Andrews's theory. It has been frequently observed that when a liquid in contact with its vapour is heated to the critical temperature the meniscus dis- appears whilst the density of the liquid is still distinctly greater than that of the vapour and that this difference of density may persist for a considerable time even when the temperature is raised above the critical temperature. Various explanations of this have been offered some of which attempt to reconcile it with Andrews's theory whilst others regard it as evidence of the incompleteness of this theory. The ethyl ether used in the experiments was purified as completely as possible and elaborate precautions were taken to free it from traces of air for observations made with different tubes containing extremely small quantities of gaseous impurities indicate that these may visibly modify the critical phenomena.The Jena glass tubes containing the ether were heated in an aniline vapour-bath the temperature of which could be adjusted very exactly by regulation of the pressure. Sliding freely inside each tube was a bell-shaped piece of tubing sealed on to a closed tube containing iron filings which enabled the bell to be raised or lowered by means of an electro-magnet. This arrangement was found to give a very delicate means of testing the contents of the tubes for traces of gaseous imparities. The conclusion drawn from the observations is that the critical phenomena observed with the pure substance can be explained in accordance with Andrews's theory and that the phenomena advanced in support of the insufficiency of this theory are to be observed onlyGENERAL AND PHYSICAL CHEMISTRY ii.1033 in tubes which contain traces of impurities. The part played by hydrostatic pressure is in all probability negligibly small and the differences in density which are observed on the disappearance of the meniscus are apparently due to slight differences in temperature. From a study of the phenomena of opalescence the author considers that the opalescence is not due to the formation of an emulsion but to variations in the temperatures of the individual molecules as has been supposed by Kuster. I n an appendix a vapour thermostat for experiments on critical phenomena is described.The vapour-jacket is connected with a large flask which communicates with a closed mercury manometer This is provided with a short arm in which is a float which makes electrical contact with a platinum-tipped needle. When contact is made a relay is actuated and a current is sent through a coil of fine wire contained in the large flask The heat developed causes the air to expand until the consequent rise of pressure breaks the contact. By wrapping the coil of wire in cotton wool the change of pressure is made to take place less suddenly and the mercury in the gauge is thus enabled to follow the change of pressure more closely. H. M. D. Influence of the Surface of a Solid Phase on the Latent Heat and on the Melting Point.P. N. PAWLOFF (J. Russ. Phys. Chem. Soc. 1910 42 677-680. Compare Abstr. 1909 ii 19 295). -The formula obtained by the author connecting the melting point with the surface energy of a phase is now deduced by another method and a further formula is given showing in what direction the melting point of small particles varies as compared with that of large ones. I f small particles have a smaller heat of fusion then the temperature at which they melt is lower than that of the large particles; if their heat of fusion is greater then the melting point is higher than that of the large ones. If the free surface energy of a solid phase is less than the free surface energy of the liquid phase then the increase of surface of the solid phase is accompanied by a rise in its heat of fusion and vice versa.I f the free surface energy of the solid and liquid phases are equal then the change in the size of the surface exerts no influence on the latent heat of fusion (see further this vol. ii 1043). Z. I(. Influence of Degree of Dispersrion of Solid Crystalline Substances on their Melting Points. P. P. VON WEIMARN (J. Russ. Phys. Chem. SOC. 1910 42 647-653).-8 short discussion of the author’s previous work on this subject. The properties of the surface layer of a crystal resemble although they are not identical with those of the interior of a strongly compressed liquid whilst the superficial layer of a liquid resembles the interior of a strongly com- pressed gas; therefore with an increase in the degree of dispersion a solid crystalline substance becomes more active chemically more volatile more soluble and more readily fusible.The two most important factors in determiuing the structure and properties of the surface layer of a crystal are ( A ) the unilateral action of the vectorial molecular forcesii. 1034 ABSTRACTS OF CHEMICAL PAPERS. on the molecixles forming the free surface of the crystal. (B) The dynamic (kinetic molecular) processes occurring on the free surface of the crystal. A gives rise to the capillary pressure which is superadded to the external pressure on the surface and increases with the degree of dispersion ; consequently as the degree of dispersion increases so A tends to diminish the similarity between the surface of the crystal and a liquid the melting point in general (except in cases such as ice) rising with an increase in pressure.B on the other hand tends to increase the similarity between the surface of a crystal and a liquid and since a fine disperse system is almost always more active than a coarse one B acts as a more energetic factor than A . Intaddition the melting point is lowered in a system of great dispersion by the fact that the surface of the crystals dissolves the surrounding medium until saturated ; consequently the melting point and other physical properties of a disperse system varies with the nature of the medium by which it is surrounded or from which the crystals have been separated and the greater the degree of dispersion the more marked is this variation. 21. K.The Spontaneous Crystallisation and the Melting- and Freezing-Point Curves of Mixtures of Two Substances which form Mixed Crystals and Possess a Minimum or Eutectic Freezing Point. Mixtures of Azobenzene and Benzylaniline. FLORENCE ISAAC (Pvoc. Roy. SOC. 1910 A 84 344-369).-From freezing- and melting-point observations with mixtures of azobenzene and benzylaniline it has been found that these substances form a eutectic mixture which solidifies at 26' and contains 19% of azo- benzene. Mixed crystals are formed by mixtures containing more azobenzene than the eutectic but not by mixtures which contain less. The form of the melting-point curve was confirmed by analysis of the mixed crystals. The temperatures at which different mixtures undergo spontaneous crystallisation were also determined by two different methods and in this way the supersolubility curve was obtained.This curve exhibits a minimum for liquids which have approximately the composition of the eutectic mixture and for the most part it runs nearly parallel to the freezing-point curve. The supersolubility curve on the other hand cuts the melting-point curve at three different points. The mixed crystals which separate out on spontaneous crystallisation along the supersolubility curve have been determined for various liquid mixtures of the two substances. Microscopic examination of sections cut from the solid solutions indicates that gradual changes take place i n these mixed crystals at the ordinary temperature. H. M. D. Freezing Mixtures. JACQUES DUCLAUX (Comnpt.rend. 19 10 151 715-716).-A description of a simple method for attaining low temperatures. Two liquids which produce a fall in temperature on mixing are allowed to flow through two long glass tubes (diameter 1 mm.). The liquids leave the tubes a t the rate of 1 to 2 drops per second and then mix. The mixture is caused to flow over tho tubes before leaving the apparatus thus lowering the temperature of the iuaorning liquids. By this iwthod a temperature of - 48" canGENERAL AND PHYSICAL CIIEMISTRP. ii. 1035 be maintained for long periods employing 100 C.C. of carbon disulphide and 70 C.C. of acetone per hour. I n one experiment a volume of 20 C.C. was kept at -43.5' with this mixture in a double-walled silvered glass tube the external temperature being 22'.W. 0. W. Condition of Substances in Solution in Absolute Sulphuric Acid. V. GIUSEPPE ODDO and E. SCANDOLA (Gazxetta 1910 40 ii 163-209. Compare Abstr. 1909 ii 377 798 and Hantzsch &ti ii 973).-Since in the opinion of the authors the condition of alcohols in solution in absolute sulphuric acid has now been settled they have proceeded to the study of the ethers and esters. In a polemical appendix the objections raised by Hantzsch are discussed further inaccuracies in his results are suggested and finally the authors' views on the whole question under examination are set forth. I n calculating from the cryoscopic measurements the molecular weights of the substances in solution a correction is introduced for the proportion of the dissolved substance which has been acted on by the sulphuric acid the correction being obtained by neutralising the remaining sulphuric acid with barium hydroxide and weighing the barium sulphate obtained.When this is done it is found that the molecular weights amount to very nearly 50% of the theoretical in the case of all the following ethers ethyl ether propyl ether n-butyl ether isoamyl ether n-heptyl ether dimethylpyrone. Hence all these ethers yield an acid oxonium sulphate which dissociates. In the case of the esters ethyl acetate and ethyl monochloroacetat-e it is found thatjdecomposition (to the extent of 15.35% and 32*9% respectively) occurs although Hantzsch has stated otherwise in regard to the former substance. Taking this decomposition into account the molecular weights are 55% and 62% respectively of the theoretical values showing that the esters are weaker oxonium bases than the ethers the weakness being greater the more negative the radicle which they contain.The authors consider that when an ester is diseolved in absolute sulphuric acid three changes occur (1) formation of the acid oxonium sulphate which dissociates into two ions ; (2) molecular dissociation of part of this salt ; (3) partial decomposition of the ester into two acids namely the alkyl hydrogen sulphate and the acid corresponding with the contained radicle Of these the second tends to give values above SO% the third values below that. Hence the mere cryoscopic measurement may indicate 50%. Results according with this view were obtained also with isoamyl formate isoamyl acetate and iaoamy 1 bu tyrate.Experiments with ethyl nitrate isoamyl nitrate and isonmyl nitrite show that with increase in the negative character of the acid radicle (as compared with those of the ethers and esters already mentioned) the acid decompositionof the molecules reaches a maximum and no indication of an oxonium salt can be found. sec.-Butyl nitrate gives results indicating that the difference between primary and secondary alcohols already noticed (Zoc. cit.) exists also in the case of the esters. Methyl sulphate has not the normal molecular weight as stated by Hantzsch On the contrary the authors advance reasons for supposing that st large part of it i s decomposed to form theii. 2036 ABSTRACTS OF CHEMICAL PAPERS. acid ester and that in addition complex molecules such as Me,(HSO,) also exist in the solution.Some Molecular Weights in Phosphoryl Chloride as a Cryoscopic Solvent. PAUL WALDEN (Zeitsch. anorg. Chern. 1910 68 307-3 16).-Phosphoryl chloride has been used as a cryoscopic solvent by Odd0 (Abstr. 1901 ii 492,; 1904 ii 236) who found the melting point to be - 1.7S2° and the cryoscopic constant 70.16. The author finds the melting point to be +1.25' and the cryoscopic constant determined as the mean of experiments with several compounds 76.8 corresponding with a latent heat of fusion of 19.8 Gal. Simple molecular weights are given by the compounds TCl ICN N,O C1,07 and OsO,. Phosphoric oxide chromic acid and iodine pentoxide are practically insoluble in phosphoryl chloride. Both solid a- and liquid P-iodine chloride are unimolecular in bromoform.LUIGI MASCARELLI and L. VECCHIOTTI (Atti R. Accad. Lincei 1910 [v] 19 ii 410-414)- For the purpose of comparison with cyclohexane (Abstr. 1909 ii 19 972) the behaviour of dicyclohexyl C,jHI1*CGH1l prepared by the reduction of diphenyl by hydrogen in the presence of nickel has been examined. The solubility of most substances in this solvent in the cold is small. Phenol propyl alcohol and acetic acid are associated even in dilute solution The general behaviour of ketones and nitro-compounds in dicyclohexyl closely resembles that of the same substances in cyclohexane. Tetra- nitromethane however is normal Vapour Pressure Curves. DEMETRIUS E. TSAKALOTOS (Zeitsch. physikal. Chem. 1910 '75 743-746. Compare this vol.ii 266).- The minimum of vapour pressure in the binary mixture chloroform- ethyl ether is probably connected with the formation of a compound Et,O:CHCl,. From the results of surface-tension and vapour pressure measurements it appears that liquid oxygen is polymerised whereas according to Walden's boiling-point formula (Abstr. 1909 ii 122) it is unimolecular. G. 8. Studies in Vapour Pressure. 111. A Static Method for Determining the Vapour Pressures of Solids and Liquids ALEXANDER SMITH and ALAN W. C. MENZIES (J. Arner. Chem. Soc. 1910 32 1412-1434; Ann. Phpsik 1910 [iv] 33 971-978. Compare this vol. ii 687 688).-The sources of error involved in vapour pressure measurements are discussed and a critical resume is given of the variouq methods which have been employed in such determinations.A new form of apparatus called the static iso- teniscope is described and it is claimed that by means of this apparatus more trustworthy measurements of vapour pressures can be made than by the older methods. It consists of a small U-tube one limb of which is connected with a small spherical bulb and the other with a long vertical tube which communicates with a mercury R. V. S. The ci*yoscopic constant of bromoform is 144. Dicyclohexyl as a Cryoscopic Solvent. C. H. D. The cryoscopic constant has a mean value of 145.2. C. H. D.GENERAL AND PHYSICAL CHEMISTRY. ii. 1037 gauge and with a large iron bottle which in turn can be put into communication with (1) the atmosphere (2) a vacuum reservoir and water pump or (3) a pressure reservoir and compression pump.The lower half of the U-tube is occupied by a confining liquid and to prevent the ascent of this into the spherical bulb containing the vaporising liquid or into the long vertical tube small bulbs are blown on the upper end of each limb of the U-tube. The liquid under investigation may be conveniently employed as confining liquid. In the manipulation of the apparatus the temperature of the liquid bath in which the isoteniscope is immersed is fixed and the pressure in the iron bottle is then adjusted until the liquid in the bulb boils freely. After the removal of all air and dissolved gases the pressure is cautiously increased until the levels of the confining liquid are the same in both limbs of the U-tube. To ensure that all foreign gases have been expelled the process of boiling and adjusting of the pressure is repeated until constant pressure values are recorded on the gauge.To test the results obtainable with this apparatus the authors have measured the vapour prmsure of water between 50° and 90° the isoteniscope being immersed in a thermostat the temperature of which was determined by means of a resistance thermometer. The data obtained are in close agreement with the measurements of Holborn and Henning. H. M. D. Studies in Vapour Pressure. IV. A Re-determination of the Vapour Pressures of Mercury from 250" to 435". ALEXANDER SMITH and ALAN W. C. MENZIES (J. Arner. Chem. Soc. 1910 32 1434-1447; Ann. Physik 1910 Liv] 33 97-9-988).- The measurements were made by means of the static isoteniscope (compare preceding abstract).From the vapour pressures 106-52 mm. at 264*16' 760 mm. at 356*95O and 2598.67 mm. at 433*96O a Kirchoff-Rankine-DaprB formula has been obtained which may be written log p = 9.9073436 - 3276.628/8 - 0.6519904 log 6. The ex- perimental data which agree well with the pressures calculated from this equation are compared with bhe older measurements of Gebhardt Regnaulc Ramsay and Young and with the probable values calculated by Laby (Abstr. 1908 ii 1039) from the several known series. The divergences between the authors' measurements and the values adopted by Laby are not inconsiderable the difference amounting to 15 mm. at 450O. A table is given showing the vapour pressures of mercury for every 2' between 0" and 450"; these pressures are the values obtained from the formula given above.The temperatures re€er to the thermo- dynamic scale and the pressures to the normal value of gravity. H. M. I>. Studies in Vapour Pressure. V. A Dynamic Method for Measuring Vapour Pressures with its Application to Benzene. and Ammonium Chloride. ALEXANDER SMITH and ALAN W. C MENZIES (J. Amer. Chem. SOC. 1910 32 14413-1459 ; Aria. Yhysik. 1910 [ivl 33 989-994).-The authors describe a modified form ofii. 1038 ABSTRACTS OF CHEMICAL PAPERS apparatus for the dynamic measurement of vapour pressures (compare this vol. ii 687 6SS). The apparatus which is immersed in a well- stirred liquid bath consists of a small bulb which communicates through a narrow tube with a small reservoir containing a suitable confining liquid.The tube is sealed through the upper wall of the reservoir and terminates beneath the surface of the confining liquid. By means of a long vertical tube the reservoir can be put into communication with a pump or compression apparatus. This so-called dynamic isoteniscope has been employed for the measurement of the vapour pressure of benzene between 65' and 120" and that of ammonium chloride between 280' and 333.5O. The results are compared wich those of previous observers who have used both static and dynamic methods of measurement I n the case of ammonium chloride the authors' vapour pressure curve lies between the curves representing the data of Ramsay and Young and those of Johnson (ASstr. 1908 ii 157). 111. The Influence of Temperature on the Composition of Solutions.M. S. VREVSKY (J. Russ. Phys. Chem. Soc. 1910 42 'i02-714).-The solutions of ethyl methyl and propyl alcohol in water have been investigated. Curves are given showing the relation between tbe %molecular composition of the solutions and the%molecular composition of the vapour at various temperatures for each pair of liquids and the compobition of the constant boiling point solution of propyl alcohol and water is deduced graphically. As the temperature of the solution of methyl and ethyl alcohol in water rises the relative proportion of water in the vapour increases whilst in the case of propyl alcohol the proportion of alcohol in the vapour increases under similar conditions. These facts are deduced theoretically and shown to agree with experiment.Micro-distilling Apparatus. A. GAWALOWSKI (Zeitsch. anal. Chem. 1910 49 744-745).-The apparatus consists of a very small flask (or test-tube) the neck of which is shaped like the head of an alembic. For very volatile liquids by means of a cork a small inverted condenser is attached the tube from which is bent slightly so t h a t the liquid which drops from it will fall into the annular space in the alembic head. Measurement of Heats of Combustion with the Calorimetric Bomb and Platinum Resistance Thermometer. FRANZ WREDE (Zeitsch. physikal. Chem. 1910 75 81-94).-A number of other determinations of heats of combustion has been made by the method already described (Abstr. 19OS ii 155). The heats of combustion in joules per gram are as follows phenylacetic acid 28.618 ; a-methyl glucoeide 18.175 ; naphthalene 40.314 ; furoin 23.941 ; glycine 13.035 ; dl-alanine 18.218 ; d-alanine 18.217 ; dl-valine 25.045 ; glycine anhydride 17.441 ; d-alanine anhydride 23.163 ; dl-leuayl- glycine 24.367 ; formyl-dl-leucine 24,134 ; diglycylglyciae 15.732 ; triglycylglycioe 16.1 19 ; glycylglycinecarboxylic acid 11.234 ; mefhyl- uracil 18.68s ; and isoserino 13709.H. 1sI. D. The Composition and Vapour Tension of Solutions. Z. K. L. DE K.GENERAL AND PHYSICAL CHEMISTRY. ii. 1039 The sources of error in the work of previous observers and the possibility of applying corrections to their data are discussed. G. S. Solutions. 11. Variation of Density of Binary Mixture8 with Temperature. F. SCHWERS ( B d . Soc. chirn. 1310 [iv] 7 937-940).-In previous papers (Abstr.1909 i 80 ii 794) it has been shown that if changes of volume are expressed in percentages of the initial volume the volume-temperature curve for a binary liquid mixture is sinuous and shows characteristic inflexions. It can be superposed on that illustrating the relationship between refractive index and temperature for the same mixture (this vol. ii 913) and is similar in form to the curve expressing the relationship between heat developed and temperature of addixture for the same mixture. These observations cannot be explained by the hydrate theory of solutions and the following explanation is suggested. Admixture of two liquids may cause disintegration of associated molecules the existence of which was proved by Ramsay and Shields (Trans.1893 63 1089). Such disintegration causes according to van Laar (Abstr. 1900 ii 189) a diminution in volume. In a mixture this may be counterbalanced in part or overbalanced by an increase in volume due t o a new association between different molecules. I n raising the temperature of such a system each complex formed will undergo disintegration in accordance with its own constant of dissociation and since this constant is not a linear function for a single liquid it is conceivable that such changes occurring in a mixed system may be represented by a sinuous curve. GERVAISE LE BAS (Chem. News 1910 102 226-229).-The volumes of a number of atoms or groups in straight chain compounds or in the side chains of ring compounds have been calculated as described in previous papers (compare Abstr.1907 ii 754; 1908 ii 667). The results are as CO = 22.2 = 6H (except in COOOH group where CO = 25.9 = 7H) ; C€IO=25*9=7H. Oxygen in the hydroxyl group generally in the phenolic ethers and in aldehydes and ketones = 2H ; in the carbonyl group and in the aliphatic ethers it is equal to 3H. Doubly linked oxygen in a ring is also equal to 3H. The volumes of a number of ring compounds containing oxygen are tabulated and i t is shown that ring structure is accompanied by considerable contraction which varies in magnitude with the size and complexity of the ring. The relative volumes are however the same in spite of the contraction. Method for Determining the Lower and Upper Limits of Elasticity. The Hardening of Metals. 0. FAUST and GUSTAV TAMMANN (Zeitsch.plqsikal. Chem. 1910. 75 108-126).-The lower limit of elasticity of a metal can be determined by subjecting a piece of which one side is highly polished to pressure or to a pull and observing microscopically the point at which the polish just begins to disappear. The elasticity can be iricreased by alternately slowly T. A. H. New Theory of Molecular Volumes. follows OH = 11.1 = 3H ; CO*OH = 37.0 = 10H ; CO = 33.3= 9H ; G . S.ii. 1040 ABSTRACTS OF CEEMICAL PAPERS. increasing the pressure beyond the first limit of elasticity and then releasing until finally an upper limit of elasticity corresponding with the limiting pressure which produces flow in the metal is reached. The metal has tharefore been hardened by slowly increasing the pressure. Some of the data for the lower and upper limits of elasticity are asfollows lead lower limit 25 kilog./cm.2 upper limit 102 kilog./cm.2; zinc drawn lower limit 75 upper limit 770 kilog.lcm.2 ; copper drawn lower limit 1200 upper limit 2780 kilog./cm.2.The lower limit depends greatly on the previous treatment of the sample. The hardening of metals is ascribed not to formation of a harder crystalline form or to a change to the amorphous condition but to a diminution in the size of the crystallites of which the metal is composed owing to the formation of systems of sliding surfaces. The hardening is therefore a preparation for flowing the latter occurring when the systems of sliding surfaces have sufficiently increased. Detailed evidence in favour of this view of hardening is advanced.G. S. Viscosity of Isodynamic and Motoisomerides. FERDINAND B. THOLE (Zeitsch. physikal. Chem. 1910 '74 683-686).-Muhlenbein (Bisseytcction Cothen 1907) has found that the densities and viscosities of nitrobenzene and of quinoline altered on keeping and ascribed this result to the existence of these compounds in two isomeric forms. The author has prepared pure specimens of these compounds and finds no difference in the viscosities or densities immediately after distilla- tion and after twenty-two hours. For nitrobenzene Di5 1.1987 viscosity at 25O= 0.018224 ; for quinoline DF 1.08994 viscosity = 0,033724. The statement of Schaum (Abstr. 1898 i 629) that the density of ethyl acetoacetate alters when kept is confirmed ; the viscosity alters in a corresponding manner.The viscosity of the diethyl derivative of this ester which cannot have an enolic constitution and of ethyl malonate did not alter on keeping. G. S. Viscosity of Albumin Solutions. LEONOR MICHAELIS (Biochem. Zeitsch 19 10 28 353-354).-Polemical against Pauli and Wagner (this vol. ii 830). The author maintains the validity of his measure- ments of the isoelectric point. G. s. Influence of Chemical Affinity in Certain Adsorption Phenomena. LEO VIGNON (Compt. rend. 1910,151,673-675 ; Bull. Xoc. chirn. 1910 [iv] 7 985-988. Compare this vol. ii 272 273 692).-The phenomena of adsorption may be divided into two classes those due to attraction between chemically inert substances in colloidal solution or in suspension and those due to chemical affinity between two substances one of which is insoluble whilst the other is in true solution or between two insoluble substances having some degree of chemical activity.Thus inert compounds like calcined silica or asbestos have no attraction for picric acid in aqueous solution whilst in the case of zinc oxide or aluminium hydroxide the acid is adsorbed. Quartz adsorbs the alkali hydroxides or carbonates but not theGENERAL AND PHYSICAL CHEMISTRY. ii. 1041 chlorides of sodium or magnesium. Brigg's results (Abstr. 1906 ii 13) are discussed from this point of view. w. 0. w. Adsorption of Gases by Charcoal. ALEXANDER TITOFF (Zeitsch. physikal. Chem. 1910 74 641-678. Compare Homfray this vol. ii 77 I).-The adsorption of hydrogen nitrogen carbon dioxide and ammonia by cocoanut charcoal has been measured between - 79' and +151*5' by the usual method.Between -SOo and +SOo the adsorption of hydrogen follows Henry's law while the behaviour of the other gases at constant temperature is represented by the familiar formula at = up$/% where at represents the amount of gas adsorbed at the pressure pt and u and l/m are constants When both pressure and temperature are varied the results are represented by the formula logut=loga - (x - ylogp)t where x and y are constants bearing a simple relationship to a and 1/12. Deviations from these formula? occur in the cases of carbon dioxide and ammonia at the higher pressures under which conditions the gases are probably partly liquefied. Ammonia was adsorbed to the greatest extent; at 0' and 10 cm.pressure 1 gram of charcoal adsorbed 71 C.C. of this gas. The heats of adsorption p of nitrogen carbon dioxide and ammonia gases were determined by means of an ice calorimeter. The mean values of q a t 0' for 1 C.C. of gas are as follows nitrogen 0.203 cal. carbon dioxide 0.31 cal. and ammonia 0,386 cal. each about 50 cm. pressure the results for the last two gases being in good agreement with those obtained by Chappius (Abstr. 1883 702). The values of q diminish considerably with increasing pressure. The heats of absorption have also been calculated from the isothermal adsorption curves by means of the formula - q = n12T2(x x ylogp)/22.410ge and there is fair agreement between the calculated and experimental values. IDA F. HOMFRAY (Zeitsch.physikal. Chem. 1910 74 687-688. Compare this vol. ii 771).-A few slight corrections to the former paper (Zoc. cit.) and some additional references are given. G. S. G . S. Absorption of Gases by Charcoal. Adsorption of Solutions [by Charcoal]. GERHARD C. SCHMIDT (Zeitsch. physikal. Chem. 1910 74 689-737. Compare Abstr. 1895 ii 39).-In the great majority of the experiments the adsorption of acetic acid from aqueous solution was studied. The rapidity with which equilibrium is established depends on the nature of the charcoal ; with some specimens it is practically instantaneous a t room temperature. At low temperatures the equilibrium is reached very slowly ; increase of temperature enormously accelerates the adsorption. This is due at least in part to the more rapid removal of gases adsorbed (chiefly air) in the fine pores of the material as the temperature is raised.When equilibrium is attained and the solution then diluted the new equilibrium point is rapidly reached the rate being the greater the more the concentration is altered. If on the other hand a more concentrated solution is added to a system already in equilibrium the new equilibrium point is only slowly attained. It is shown by experiments with acetic acid in aqueous solutionii. 1042 ABSTRACTS OF CHEMICAL PAPERS. that on grrdually increasing the concentration a maximum of adsorption is reached a fact which shows that the usual adsorption formultle cannot be valid within wide limits. A new formula Iog[X/(S- x)] - Ax = C(cc/v) is derived X representing the maximum of adsorption x the amount adsorbed a the total amount of the solute v the volume and A and C are constants depending on the amount and nature of the coal.This formula represents the experimental results fairly satisfactorily. There are therefore three determining factors in adsorption X the maximum adsorption K (proportional to C) the activity coefiicient of the material and A which is a measure of the falling 08 in the attraction between absorbing surface and solute as the amount adsorbed increases. From experiments with iodine and acetic acid in chloroform solution it is shown that the amount of two dissolved substances adsorbed from a solutiou containing both is less than the sum of the amounts adsorbed separately. Further when charcoal is in equilibrium with one solute and a second is added ‘ it partially displaces the first substance from combination.Some experiments on the adsorption of acetic acid from solution in ethyl acetate are described. Dissociation of Ferric Sulphate. MAX BODEXSTEIN and TATSUJI SUZUKI (Zeitsch. Elektrochem. 19 10 16 9 12-91 6).-The measure- ments of Wohler Pliiddemann and Wohler (Abstr. 1908 ii 290) of the partial pressure of sulphur trioxide in equilibrium with ferric sulphate gave values three or more times larger than those of Keppeler and D’Ans (Abstr. 1908 ii 289). The authors have therefore repeated both sets of experiments taking every precaution to avoid accidental errors and have obtained results which agree very well with the original measurements in both cases. I n Wohler’s method the total pressure of the mixture of sulphur di- and tri-oxide and oxygen evolved by the heated ferric sulphate is measured and the partial pressure of the trioxide calculated from Bodenstein and PohI’s measurements of the equilibrium constant.It is shown that the gases really are in equilibrium and that this method of calculation is therefore justified. On the other hand in Keppeler’s method of passing air or nitrogen over the heated ferric sulphate although the partial pressure of tri- oxide found is independent of the velocity of the gas within the rather narrow limits tried the ratio between the oxides of sulphur and the oxygen is not in agreement with Bodenstein and Pohl’s measurements oE the dissociation of sulphur trioxide; there is always too little trioxide.The deviation diminishes as the temperature rises. It appears therefore that the low results obtained in Keppeler’s experi- ments are due to equilibrium not being established. If ferric sulphate dissociates directly into ferric oxide and sulphur trioxide an excess of trioxide would be anticipated instead of a deficit hence the mechanism of the reaction is probably more complicated. G. S. T. E. The Theory of Transpiration Diffusion and Thermal Con- duction in Rarefied Gases. MARYAN SMOLUCHOWSKI (Bull. Acad. Sci. Crucow 1910 7 A 295-312).-The paper consists of threeGENERAL AND PHYSICAL CHEMISTRY. ii. 1043 sections. The first and second are concerned with a criticism of Knudsen’s recent papers on the dynamics of rarefied gases ( Abstr 1909 ii 216; Ann. Physik 1910 31 205 633) from the theoretical standpoint.It is stated that the treatment of the problems is in- validated by the neglect t o take into account the modification of the Maxwell-Boltzmann law of distribution of velocities during thermal conductivity and diffusion. An expression is deduced for the in- crease of thermal conductivity of gases produced by molecular surface currents. An analysis for the condition of low pressure where the mean free path of the molecule is large compared with the dimension of the vessel leads to results somewhat similar to those of Knudsen but it is claimed by a simpler and more rigorous method. The last section contains a discussion of the experimental results of Soddy and Berry on the conduction of heat through rarefied gases (this vol.ii 180). An exact calculation of the theoretical conduction of heat gives as the result that their values should be multiplied by the factor Jp/6=Om7236 and by the term 1 -/?I1 +/I where /3 is a coefficient representing the fraction of the total number of molecules ‘‘ reflected” from the surface without change of kinetic energy. A re-calculation of their results shows that /3 can never be neglected the interchange of energy between the surface and the molecule impinging upon it being the less perfect the lighter the molecule and the greater its intramolecular energy. I?. s Methods of Investigation of Capillary-chemical Problems. P. N. PAWLOFF (Zeitsch. Chem. I n d . Kolloide 1910 7 265-26’7).- From a consideration of surface-energy relationships von Weimarn arrived a t the conclusion that a substance in a very fine state of sub- division should melt at a higher temperature than t h a t found for the substance in the form of coarse particles.Since this conclusion is contradicted by experiment some doubt has been thrown on the validity of the deductions made on the basis of surface-energy con- siderations The author points out that the conditions under which a melting-point determination is carried out in the ordinary way preclude the possibility of observing the effect which is to be expected on the basis of Laplace’s theory of capillarity. von Weimarn’s views relative to the nature of the surface layer of crystalline snbstances are also criticised. The assumption that the properties of the surface layer approximate to those of the inner layers o€ a highly compressed liquid is tantamount t o the view that the surface layer is isotropic whereas the geometric an3 physical characteristics of crystalline substances indicate that the surface layer is anisotropic (compare this vol.ii 1033). H. M. D. Osmotic Equilibrium between Two Fluid Phases. L. GAY (Compt. rend. 1910 151 754-756. Compare this vol. ii 935).- The mathematical considerations advanced in a previous paper lead t o the proposition that for two fluid phases in osmotic equilibrium with a common constituent at infinite dilution at the same temperature and pressure the variations in volume and thermal effects should be equalii. 1044 ABSTRACTS OF CHEMICAL PAPERS. whatever the temperature and pressure.Some theoretical conse- quences of this conclusion are discussed in the present communication. w. 0. w. Diffusion [of Dissolved Substances]. OSCARRE SCARPA (Nuouo Cimento 1910 [v] 20 212-225).-Vanzetti (Abstr. 1908 ii 20 88 ; 1909 ii 978) has compared the coefficient of diffusion of certain electrolytes by allowing them to diffuse towards each other in a capillary tube filled with distilled water and finding (for example with silver nitrate and alkali chlorides) where a precipitate begins to appear. The author has deduced an equation which permits of the calculation of the coefficient of diffusion of one of the electrolytes in terms of that of the other of the concentrations of the two electro- lytes and of the position in the tube where the precipitate begins to form.It is shown that some of the assumptions of Vanzetti for example that the distances traversed by the salts are proportional to the co- efficients of diffusion are untenable. The values of the diffusion coefficients obtained by the above method agree neither with the theoretical values nor with those determined by the standard methods ; the method is therefore not adapted to the study of diffusion. The suggestion of Vanzetti that certain of his results are due to the hydrolysis of sodium chloride and other salts in very dilute solu- tion is shown to be untenable. An equation is given which permits of the calculation of the hydrolysis of a salt of a strong base and a strong acid and it is shown that the degree of hydrolysis is almost independent of the dilution and therefore the quantity of salt hydrolysed diminishes with dilution whereas Vanzetti has assumed that it increases. G.S. Fundamental Law for a General Theory of Solutions. EDWARD W. WASHBURN (J. Chim. PAYS. 1910 8 538-568. Compare this vol. ii 39 1 ).-The interdependence of the colligative properties of solutions (osmotic pressure b. p. .f. p. vapour pressure etc.) follows from the laws of thermodynamics and has no bearing on the question of the actual condition of solvent and solute. An ideal solution is one in which neither association nor dissociation of the solute nor association of solute with solvent (solvation) occur. I n dilute solutions the molecular concentration of the solute is unaffected by solvation so that dilute solutions of substances which neither associate nor dissociate behave as ideal solutions.The author develops the following general equation of state for solutions which whilst closely related to that advocated by van Laar is expressed in terms of colligative properties rather than thermodynamic potentials d r = ( -RT/V)dlogN where is the osmotic pressure Y the molecular volume and N the molecular concentration of the solvent. Physical properties in idaal solutions or mixtures are additive. The vapour tension of any volatile component such as the solvent p=p,N where p is the tension of the pure component. This rule is known to hold in the case of many mixtures of analogoils organic substances such as were examined by Young (Trans. 1903 83 68).GENERAL AND PHYSICAL CHEMISTRY.ii. 1045 Somewhat complex expressions are deduced for freezing point boiling point and the effects of concentration and temperature on chemical equilibrium in ideal solutions. These laws of ideal solution apply to dilute solutions a n d t o certain liquid mixtures but in most concentrated solutions they are set aside by the unknown factors of association and dissociation. R. J. C. A Simple Method of Measuring the Afflnity between the Solvent and the Dissolved Substance P. P. VON WEIMARN (J. Russ. Phys. Chem. Xoc. 1910 42 646-647).-1f a solvent Y contains in solution the substances xl X2,. X . . . xk the solutions being of considerable and equal concentrations and another solvent 2 completely miscible with Y but practically not dissolving XI X2 X3 . . . xk be added these substances will be precipitated when sufficient of 2 has been added and the more affinity the dissolved substance bears to Y the more of 2 will be necessary.Thus the quantity of 2 necessary to completely precipitate Xl Xz . .. . xk from unit value of Y solution will be a measure of the affinity X I X2 . . . X bears to Y. The method has been applied to the solutions of various salts etc. Z . K. Partition Law in Mixed Solvents. 11. WALTER HERZ and ALFRED KURZER (Zeitsch. Elekti-ochem. 1910 16 869-872).-1n addition to the cases previously studied (this vol. ii 399) the partition of boric acid between water and mixtures of amyl alcohol and carbon disulphide of iodine between chloroform and mixtures of water and glycerol of bromine between water and mixtures of carbon tetra- chloride and carbon disulphide are investigated.The partition constants for mixtures of two solvents usually differ from the values calculated from the constants of the pure constituents in the sense that the solute is less soluble in the mixture. Two more complicated cases (the partition of picric acid between water and mixtures of chloroform and toluene and that of iodine between a solution of barium iodide and mixtures of carbon disulphide and carbon tetra- chloride) are also examined and found to follow the same laws which hold for single solvents. The results in the second case indicate the existence of BaI molecules in the aqueous solution. T. E. Diminution of Velocity of Cryatallisation by Addition of Foreign Substances. HERBERT FREUNDLICEC (Zeitsch.physikal. Chem. 1910 75 245-256).-0n the basis of the experimental data of von Pickardt (Abstr. 1903 ii 66) and of Padoa and Galeati (Abstr. 1904 ii 714) it is shown that the diminution in the maximum velocity of crystallisation of supercooled liquids due to the addition of foreign substances is represented by the formula Go - G - where Go is the velocity of crystallisation of the fused solvent G that of the solution c is the concentration and E and vz are constants; l / n usually lies between 0.2 and 0.7. This can be accounted for on the assumption that the solvent is adsorbed at the crystal faces and that the diminu- tion in the velocity of crystallisation is proportional to the amount adsorbed (compare Marc Abstr. 1909 ii 983). G. S. VOL. XCVIII.ii. 71ii. 1046 ABSTKACTS OF CHEMICAL PAPERS. Crystallisation of Agar-agar and Gelatin i n Connexion with the Mechanism of Gelatinisation. P. P. VON WEIMA~LN (J. Russ. Phys. Chem. Xoc. 1910 42 653-657).-The author rejects the generally accepted theory that solutions of gelatin agar-agar albumin or other 'high molecular compounds are disperse systems liquid + liquid which are termed emulsoids and t h a t the gelatinisation of these systems is merely a separation of the two liquids into layers. The solution of such high molecular substances must on the contrary be regarded as true solutions and their gelatinisation as being identical with the process of crystallisation. To obtain emulsoids and sus- pensoids a solid substance X is dissolved in a solvent A and another solvent B which is miscible in all proportions with A but does not dissolve X is added. If the solution is concentrated the addition of B will a t first cause the formation of an emulsion which will rapidly separate into two layers X soon crystallising from the layer of A con- taining it.If a large volume of B is added and the mixture stirred vigorously X may separate at once. If however a fairly dilute solu- tion of X in A is taken then the addition of B will produce a more stable emulsion and emulsoid which will only crystallise after very long standing and the crystals may be microscopic ultramicroscopic or even smallel' whilst if the solution is very dilute the addition of H will at once produce a stable suspension and suspensoid. These con- siderations have been verified by experiments with manganese sulphate lithium chromate potassium carbonate hydrogen carbonate and formate A beiug water B an alcohol.With slight modifications similar experiments with agar-agar and gelatin gave the same results To obtain a partial precipitation of agar-agar and gelatin the sus- pensoid was alternately boiled and cooled alcohol being added to replace that lost by evaporation. The precipitate thus obtained con- sisted of very minute long crystalline grains rounded at the edges. Z . K. Behaviour of Salts of Organic Acids on Melting. DANIEL VORLANDER (Bey. 1910,43,3120-3135).-1n previous papers (Abstr. 1906 i 317 ; 1907 ii 70 337 441 442; 1908 i 641 ; ii 22 88) attention has been directed to the connexion between the chemical constitution of substances and their power of forming liquid crystals and in the present paper this investigation is extended and it is shown that liquid crystals are formed by salts of aliphatic and aromatic acids and by metallic derivatives of phenols but not by aliphatic hydro- carbons acids esters alcohols or ketones.The liquid crystals belong to the same system as those described previously (Abstr. 1908 ii 88). The salts of the optically active acids are not pleochroic but certain of them show a play of colours in the liquid crystal state (compare Abstr. 1908 i 641). The formation of liquid crystals is shown to depend on polarity of structure in the molecule and their stability and capacity for growing in the direction of the principal axis is due mainly to intramolecular energy difference.[With R. WILKE and M. E. H u ~ ~ . l - T h e sodium and potassium salts of the normal fatty acids from acetic to cerotic were examined,GENERAL BND PHYSICAL CHEMISTRY. ii. 1047 and it was found that the property of forming liquid crystals begins with butyric acid and ends with s t e a k cerotic acid forming ‘‘ resinous crystals” in the case of the sodium salt and doubtful “resinous crystals ” in that of the potassium salt. A large number of salts with other metals particularly for the lower acids were also examined and details of the behaviour of these on melting are given. Tetramethyl- ammonium stearate forms a liquid crystal phabe. Sodium allylacetate is a good material for the demonstration of liquid crystals and the sodium salts of undecylenic elaidic erucic and other unsaturated acids also show this phenomenon.[With M. E. HTJTH.]-T~~ tendency to form liquid crystals is greatly influenced by the branching of the chain of carbon atoms at least among the sodium salts of fatty acids; thus isovaleric and isopropyl- acetic acids yield sodium salts which form liquid crystals whilst a-methylbutyric and di-a-methylpropionic acids do not but the potassium salts of all four show this phenomenon. The alkali salts of the di- and tri-basic fatty acids do not give liquid crystals as a rule. The alkali salts of the aromatic acids in many cases yield liquid crystals but no general correlation with constitution can be deduced. Among substituted benzoic acids the salts of ortho- meta- and para- derivatives show equal facility in giving liquid crystals but the ortho- compounds are usually monotropic whilst the isomeric meta- and para- substances are enantiotropic.Among phenols only the potassium derivatives of 0- and p-nitro- phenol show the phenomenon. I n carrying out these investigations great difficulty is experienced in observing the two melting points and the use of the polarisation microscope with crossed Nicols is unadvisible owing to the difficulty of observing the temperature. For substances of high melting point Rinne’s heating apparatus as constructed by Fuess is used and for substances of low melting point a small melting tube with a stirrer of capillary glass tube or a platinum wire. Approximate first and second melting points for a long series of salts of organic acids thus determined are given in the original.T. A. H. Proof of the Movements of Dissolved Molecules Demanded by the Molecular Kinetic Theory. THE SVEDBERG (Zeitsch. physikal. Chem. 1910 74 738-742).-1n a previous paper (compare this vol. ii 772) it has been shown that the movements of particles in a colloidal solution is such that the mean deviation from the average number of particles in a definite volume of solution corre- sponds with that required by the kinetic theory. The same is now proved to be the case for dissolved molecules as a result of experi- ments with a solution of polonium chloride A small portion of the solution was covered with a screen coated with zinc sulphide and the number of a-particles produced in a given time numbered by observing the impacts on the screen in the usual way. When allowance is made for the deviation from the mean Qwing t o the irregular breaking-down of the radioactive atoms it is found that the momentary differences of 71-2ii.1048 ABSTRACTS OF CHEMICAL PAPERS. concentration in a limited volume of a true solution correspond with the requirements of the molecular-kinetic theory. G. S. [History of the Orientation Theory of Matter.] P. P. VON WEIMARN (Zeitsch. Chern. h d . Kolloide 19 10 7 256-265).-An historical accouut is given of the views which have been put forward a t different times in reference to the nature of the “amorphous ” state. Quotations are given from papers by Fuchs Frankenheim and Lehmann. H. M. D. Coagulation of Colloids. V.A. VOLSCHIN (J. Russ. Phys. Chem. Soc. 1910 42 863-876).-The non-agreement between the numbers obtained by various authors for the coagulating power of the same and analogous coagulating substances is probably due to the various methods employed for obtaining colloidal solutions the different methods of experiment and to the varying concentrations of the colloid investigated. To characterise the coagulating power of an ion by a number it is necessary to investigate (1) the connexion between the concentration of the coagulating ion and the concentra- tion of the colloid precipitated. (2) Whether this relation is identical or not for ions of different valencies. (3) Whether this relation remains the same for different colloids. The present paper is the first of a series to determine these questions.Soluble Prussian-blue Fe,[e(CN),] as obtained directly by the interaction of ferric chloride and potassium ferrocyanide and the insoluble blue KFe”’Fe”(CN),,. in oxalic acid solution were used as colloids and sodium potassium and ammonium chlorides as coagulating electrolytes. The main portion of the latter was added from a burette to the colloid of given concentration and the rest added in very small portions or drop by drop a small portion of the mixture being withdrawn by a capillary pipette and examined under the microscope after each addition. The commencement of the coagulation could thus be accurately determined. Tables and curves are given showing the number of gram-mols. and concentration of electrolyte necessary to coagulate colloid solution of varying concentration.The curve for each electrolyte is of exactly the same character resembling the crystallisation curves in a mixture of two salts. It consists in each case of branches the breaks coming a t exactly the same points on the abscissa (where are marked the total volume of colloid + electrolyte at coagulation point). The ordinates (gram-mols. of electrolyte) corresponding with these points are in the ratio NaCl NH,Cl KCl = 4 2 1 for KFe”’Fe”(CN) and KaCl NH,Cl KCl= 1 4 2 for Fe,[Fe(aN),] and these relations are true whatever the concentration oi the colloid. Coagulation by means of electrolytes although in some respects a purely physical phenomena may yet exhibit laws characteristic of purely chemical processes and this is particularly the case with the substances dealt with here.Z. K.GENERAL AND PHYSICAL CHEMISTRY ii. 1049 Filtration of Colloidal Solutions. A New Filter. A. SCHOEP (Bull. 8oc. chirn. Bdg. 1910 24 354-36’7).-The addition of a certain quantity of glycerol to an ethereal-alcoholic solution of cellulose nitrate increases the permeability of the collodion membrane made from such solutions. The membrane however is not stable on exposure to the air as it contracts and glycerol is exuded. I f castor oil is added as well as glycerol a stable membrane is obtained which does not contract on exposure to the air and can be preserved for a long time between filter paper in order to keep away moisture. It can be used as an ultra-filter which works under the pressure of the liquid contained in it no extra pressure being necessary.To prepare it for use it is simply soaked in water to dissolve out the glycerol. The solutions which gave the best membranes cootained four parts of cellulose nitrate 3.5 parts of castor oil and 2.5 3 4 and 5 parts respectively of glycerol the alcohol and ether used to form the solution being in the proportion 10 parts of alcohol to 80 parts of ether. Experiments on the filtration of colloidal solutions classified according to the size of the particles (compare Bechhold Abstr. 1908 ii 24 823j showed that the smaller the particles the smaller is the amount of glycerol which should be used to obtain membranes which will retain the particles. The membranes so made can only be used for the filtration of colloidal solutions containing particles varying in size from those of colloidal arsenic sulpbide to colloidal Prussian-blue (compare Bechhold Zoc.cit.). The author has succeeded in separating colloidal arsenic sulphide from Prussian-blue by filtration through the membrane containing 4 parts of glycerol to 4 and 3.5 parts of cellulose nitrate and castor oil respectively. T. S. P. The Action of Chloroform on Lipoid Suspensions D. CALUGAREANU (Biochem. Zeitsch. 1910 29 96-101).-The appear- ances are described when cholesterol and other lipoids in colloidal solution are shaken with chloroform and other solvents which are not miscible with water. The particles of the lipoid increase in size and in the case of cholesterol lose their crystalline form and form a kind of precipitate on the surface of the chloroform when this solvent is employed in the experiment.The phenomenon is ascribed to the adsorption of the chloroform on the surface of the lipoid and is contrasted with the phenomena observed when colloidal metals such as gold and silver are shaken with mercury. Here no adsorption takes place and the difference of action is ascribed to the fact that the mercury in contrast to chloroform is not soluble in water. S. B. S. The System Chlorine-Sulphur Dioxide. ANDREAS SMIW and W. J. DE MOOY (Proc. K. Akad. Wetensch. Amsterdam 1919. 13 339-341).-The nature of this system has been investigated by freezing-point measurements. The melting points of chlorine and sulphur dioxide are - 100*45O and - 75.6O respectively. The data obtained in the dark indicate a eutectic point at -102*3O theii.1050 ABSTRACTS OF CHEMICAL PAPERS. composition corresponding with 1.5 mols. % of sulphur dioxide. From the form of the freezing-point curve the authors conclude that mixed crystals are formed Measurements in which the mixtures were subjected to sunlight or the light from a quartz mercury lamp show that sulphuryl chloride is formed very rapidly in these circumstances. A mixture con- taining 47.1 mols. % of sulphur dioxide in which equilibrium had been established in sunlight was found to exhibit initial solidification at - 80° which is very much higher than the temperature corresponding with the freeling-point curve for the system in the dark. H. AT. D. Critical End-Points in Ternary Systems.ANDREAS SMITS (Proc. K. Akccd. Vetensch. Amsterdam 1910 13 342-352).-The gradual changes which the critical solution phenomena exhibit when :I third eub3tance is added to a binary system are discussed. The third substance is of such a nature that i t does not yield critical end-points with either of the components of the binary system and is completely miscible with these components in the liquid state. The binary sjstetn t o which special reference is made is that of ethyl ether-anthraquinone which has been previously examined in detail and the third substance is ethyl alcohol H &I. D. Critical Phenomena of the T e r n a r y S y s t e m Ethyl Ether Anthraquinone and Naphthalene. ADA PRINS (Proc. K. A kccd. Wetensch. Amstertlam 1910 13 353-359).-Experiments hare been made to ascertain the nature of the critical solution phenomena which are exhibited when the binary system ethyl ether-anthraquinone is converLed into a ternary system by the addition of naphthalene.For small quantities of naphthalene the two critical end-points which are characteristic of the binary system are still observable. As the propartion of naphthalene increases the end-points approximate to one another and the spacial region bounded by the critical curves dis- appears as a result of this approximation when the proportion of n lphthalene added amounts to 4.5%. IT. 3%. D. The Ternary Systems Alkali-Phosphoric Acid-Water. JOH. D'ANs and 0. SCHREINER (Zeitsch. physikal. Chew,. 1910 75 95-107). -The equilibria in these systems have been determined by solubility measiirements at 25' in the usual way and the results are given in tabular form and also represented graphically.In the system containing sodium salts the solid phases met with were the cwmpounds Na,P04~12H20 Na2HP04 12H,O Na2HP04,7 H,O NaH2P04,2H,0. Trisodium phosphate dodecahydrate has a transition temperature a t 70.75 k Oslo. The corresponding disodium salt has two transition points the first represented by the equation Na,HP04,12H,0 Na2HP04,7H20 -t 5H,O a t 35.4 k 0.05' ; the second Na2HP0,,7H20 ~ L Y H ~ I ~ P O ~ ~ H ~ O + 5R,O at 48.35 +_ 0 O.-,O. The solubility in grams anhydrous salt per 100 gtams of water is 46.11 a t the former and 79.00 a t the latter transition point. The region of the acid mono-GENERAL AND PHYSICAL CHEMISTRY. ii 1051 sodium phosphate described by previous observers was not reached ; i t is stable only in the presence of practically pure phosphoric acid In the system containing potassium salts only the three anhydrous salts K3P0 K,HP04 and KH,PO were met with.The investigation was difficult owing to the extremely high solubility of the di- and tri- potassium salts. The region within which K,HPO exists is very narrow lying between the ratios K PO = 6.9 4.15 and K PO = 4.8 3 or K PO = 1.66 1.60. The region of the acid monosodium phosphate KH,PO H,PO described in the literature was not reached. In the system containing ammonium salts the compounds (NH,),PO,,SH,O (NH,),HPO and NH,*H,PO were met with as solid phases. The diammonium salt exists only within narrow limits of concentration.For all three alkalis the systems in which the solution and the solid phase have the ratio PO alkali = 1 1 represent an absolute minimum in the solubility of these compounds; in other words the solubility of the monoalkali phosphates is increased by the addition of alkali as well as of phosphoric acid. Stability of the Two Crystalline Modiflcations of Phenol. GUSTAV TAMMANN (Zeitsch. physikd. Chem. 19 10 '75 75-80).-The conditions of stability of the different forms of phenol have been further investigated (compare Abstr. 1909 ii 983) by an improved experimental method. As a preliminary to the preparation of phenol I1 (the denser modification) in open vessels at atmospheric pressure curves are plotted giving the temperatures and corresponding pressures at which the velocity of transformation of phenol IT.to phenol I in the presence of both phases becomes appreciable. Further the conditions under which spontaneous transformation of phenol I1 to phenol I (ordinary phenol) takes place are tabulated. At - 39O the latter change takes ppce at 154 kilog./cm.2 pressure ;at - 28.2' 410 kilog. ; at + 3*5" 1025 kilog. and at 2 9 O 1625 kilog. A t - SOo no appreciable change takes place in a considerable time at atmospheric pressure. Phenol I1 was prepared at 15' under a pressure of 3000 kilog./ cm.2. The cylinder of nickel steel containing it was then cooled at - SOo and the pressure gradually lowered to 1 kilog. After some further manipulations phenol I1 was obtained and freed from its wrappings in a mixture of light petroleum and chloroform cooled to - SOo in which it sank whereas a piece of ordinary phenol floated in themixture.The diminution of volume when phenol I changes to phenol I1 is 0-06 cm. per gram. [Temperature-coefficient of Chemical Reaction Velocities.] Correction. MAX TRAUTZ (Zeilsch. physikal. Chem. 1910 74 747). -A correction is applied to one of the author's formulae on this subject (compare this vol. ii 24) which simplifies it and renders it more accessible to experimental investigation. MAX BODENSTEIN and WALTER KARO (Zeitsch. physikd. C'hem. 1910 '75,30-47).-Ewan (Abstr. 1895 ii 213) found that the rate of oxidation of sulphur is proportional t o G. S. G. S. G. S. Slow Combustion of Sulphur.ii. 1052 ABSTRACTS OF CHEMICAL PAPERS. the square root of the pressure of the oxygen but the present authors have obtained entirely different results. The sulphur was heated at constant temperature (252’) with oxygen in a glass tube for definite intervals the mixture of oxygen and sulphur dioxide transferred to a measuring vessel and the proportion Gf sulphur dioxide in the mixture determined by observation of the pressure before and after absorption of the sulphur dioxide with an iodine-potassium iodide solution.The rate of reaction is directly proportional to the pressure of the oxygen and is roughly proportional to the surface of the sulphur. The rate increases in the ratio 1-87 1 for a rise of temperature of 10’. From these observations the conclusion is drawn that the controlling reaction is a chemical one which takes place in the adsorption layer on the surface of the sulphur.The excellent agreement of the velocity- coeficients shows that the sulphur dioxide which must accumulate in the adsorption layer has no influence on the reaction velocity and the authors show that this can be reconciled with their view as to the mechanism of the reaction. A t 159O the temperature at which Ewan worked the rate of oxidation of sulphur is extremely slow and this observer must there- fore have measured some other reaction. His heated sulphur was near a soda-lime tube (used for absorbing the sulphur dioxide) and it is suggested that the sulphur distilled over to the soda-lime forming polysulphides and thiosulphate which were very rapidly oxidised by the oxygen. G. S. Specific Stereochemical Behaviour of Catalysts. KASINIR FAJANO (Zeitsch.physikcd. Chern. 1910 75 232-234. Compare this vol. ii 599).-The Doint at issue between the author and Rosenthaler I (this vol. ii 232) requires further experimental investigation. G. S. Dead Spaces. RAPHAEL ED. LIESEGANG (Zeitsch. angew. Chem. 1910 23 3124-2125).-A small glass tube open a t both eDds and filled with a 10% jelly containing sodium chloride is immersed in a solution of silver nibrate. When the diffusion of the silver nitrate and the precipitation of silver chloride is complete a clear space of several mm. is left in the centre of the tube where no precipitation has occurred. It contains silver nitrate but no chloride. This “ dead space ” is due to the fact that the sodium chloride has diffused away to the places where precipitation of silver chloride has occurred.Such a “dead space” is not formed when the substance dissolved in the jelly is not diffusible for example when the jelly contains albumin and the tube is immersed in metapbosphoric acid. If the jelly contains potassium dichromate instead of sodium chloride a “dead space ” is still formed in the middle of the tube. The silver chromate deposit is not continuous however as in the case of silver chloride but in the form of rings with clear spaces between (the ordinary Liesegang phenomenon). The latter clear spaces are not identical with the “dead space ” in the centre of the tube if a “dead space” is defined as one where no chemical reaction has taken place,GENERAL AND PHYSICAL CHEMISTRY.ii. 1053 since silver chromate has been formed in them and while in super- saturated solution has diffused to the places where precipitation has taken place. These results make it doubtful whether the phenomena observed by Liebreich (Abstr. 1891 1150) are really due to the occurrence of I ‘ dead spaces.” The importance of these phenomena in connexion with for example the occurrence in many bones of zones poor in lime is pointed out. T. S. P. Repeating Figures in the Atomic Weight Values. F. H. LOEING (Chern. News 1910 102 228-229).-1n the International Tables for 1911 there appears to be a tendency for the figure in the unit’s place to recur in the second .place of the decimals for example Ag = 107.87 Fe = 55.85 but this may be accidental. A New Valve.Aua. EUMM (Chern. Zeit. 1910 34 1136).- A valve for preventing the return of water into vessels while being exhausted by the filter-pump is described. A glass rod is supported on the mouth of a vertical glass tube by means of an expansion covered with indiarubber. During suction the valve is raised but if the pump is stopped or if water returns the rubber-covered expansion makes a tight joint with the tube. Modified Drying Tube. EDWIN DOWZARP (Amer. J. Pharrn. 1910 82 509-510).-By inserting a stopcock in the lower part of a Pelligot drying tube the exhausted sulphuric acid may be removed and replaced with fresh acid by suction at the side-tube without dismounting connected apparatus. A small test-tube is suspended under the stopcock to catch drops of exuding acid. Extraction Apparatus. R. P. NOBLE (J. Arner. Chem. Xoc. 19 10 32 1533).-A form of apparatus f o r the extraction of substances by means of mixed solvents is described. It consists of a glass tube the bottom of which is connected with a syphon tube to the upper end of which a side-tube is attached. The substance t o be extracted is contained in a cartridge and the solvent is removed by actuating the syphon G . S. C. H. D. T. A . H. The apparatus avoids the use of any stopcock. H. M. D. Lecture and Laboratory Apparatus. JAMES A. SCHOFIELD (Austral. Assoc. Report 1909 167-172).-The following forms of appar- atus are described. 1. Apparatus for showing the composition of nitrous and nitric oxides. Instead of the original method devised by Davy for heating sodium in the gas the sodium is contained in a deflagrating spoon and fired electrically. The gas is confined in one limb of a manometer the electrical connexions passing through a rubber cork a t the top of the tube. 11. Apparatus for the preparation of ammo- nium hydroxide solution concentrated and dilute from liquid ammonia. 111. A rapid form of condenser for distilled water. The condenser is practically a reversed tubular boiler nine &-in. tin tubes 1 f t . long forming the condenser. IT. A cheap demonstration balance. Fitted to the centre of the beam and projecting above it is a light aluminiumii. 1054 ABSTRACTS OF CBEMICAL PAPERS. pointer about 21 inches long playing over n cardboard scale. This scale and pointer are turned towards the class the ordinary scale and pointer being towards the lecturer. The aluminium pointer is counter- balanced by a binding screw clamped on to the ordinary pointer. V. Nickel crucibles for the Laurence 6mith method of determining alkalis in silicates. These crucibles are used for the decomposition of silicates with calcium carbonate and ammonium chloride and give the same results as platinum ones. T. s. P. Apparatus for Laboratories and Lecture Experiments. JOHANNES THIELE (Annalen 19 10 376,279-2S5).-Chlorinntions and brominations and also the detection of feeble fluorescence can be accomplished very successfully in the light of an arc lamp instead of in sunlight. Apparatus for the demonstration of the production o€ water in quantity from its elements and of tho combustion of nitrogen are described and also electrically heated filter funnels boiling-point apparatus etc. Many lecture experiments in which the reagents a r e heated to boil- ing can be performed in very much shorter time by placing a little of tho not too dilute reagents in an upright cylinder and adding much boiling water. The hydrolysis of ferric alum the formation and decomposition of copper hydride the hydrolysis of carbonates and o F sucrose the decomposition of mercuric nitrate and the hydrolysis of ferric chloride are thus readily demanstrated. c. s.

ISSN:0368-1769    

DOI:10.1039/CA9109806013

出版商:RSC    

年代:1910

数据来源: RSC

摘要:

ii. 1054 ABSTRACTS OF CQEMICAL PAPERS. Inorganic Chemistry. Preparation of Pure Hydrogen7 Peroxide for Medical Purposes. OTTO SCHMATOLLA (Pharm. Zeit. 1910 55 888-889).- The method used consists essentially of (1) solution of commercial barium peroxide in hydrochloric acid phosphoric acid being added t o precipitate metals such as iron ; (2) precipitation from the solution of hydrated barium peroxide by means of sodium hydroxide; and (3) preparation of the solution of hydrogen peroxide in the usual way by the addition of the hydrnted barium peroxide to sulphuric acid. T. S. P. Formation of Hydrogen Peroxide. K. V. CHARITSCHKOFF (J. Buss. Pl~ys. Chern. Soc. 1910 42 900-904).-Papers prepared with cobalt naphthennte are very sensitive to hydrogen peroxide turning from pink to olive-green (compare t h i s vol.ii 238). I n bright sunlight or by w rise of temperature they become still more sensitive it being possible to detect one part i n 1,000,000 of water. Water containing oxygen when exposed to bright sunlight gives the hydrogen peroxide reaction after the following intervals a t 9-22' after- twelve days ; 19-31° after eight days ; 20-41°,after seven days.INORGANIC CHEMISTRY. ii. 1055 If the oxygen is replaced by air no hydrogen peroxide is formed. I n similar experiments with radioactive barium chloride and also the nitrates of barium lead thorium UI anium and bismuth hjdrogen peroxide was formed only in the presence of radioactive barium salt and of lead nitrate. When however the experiment was made in the dark even radioactive barium produced a negative result ; i t is t,herefore considered that it is not the radium emanation which induces the reaction 2H,O = H,O + H but that the radium salt acts as a catalyst.Hydrogen peroxide is also formed on the surface of moist porous substances such as wood asbestos and so forth. Z. K. Formation of Hydrogen Peroxide in t h e Combustion of Detonating Gas. K. v. CHARITSCHKOFF and AMBARDANOFF (J Russ. Phys. Chem. Xoc 1910 42 904).-Using the cobalt naphthenate papers (compare preceding abstract) hydrogen peroxide was detected in the products of combustion of detonating gas 0.000476 C.C. hydrogen peroxide being produced from the combustion of about 25 litres of hydrogen in oxygen. Hydrogen peroxide could not be detected in the combustion of benzene or of alcohol.Z. K. Colour of Iodine Solutions. JOEL H. HILDEBEAND (Zeitsch. physikal. Cl~em. 1910 ’74 679-682).-The author answers some adverse criticisms of Waentig (this vol. ii 11 7) on his and Glascock’s work on this subject (compare Abstr. 1909 ii 225). I n particular the standard solution (for comparison purposes) was prepared by adding to the violet soIution of known iodine concentration sufficient of the “active” solvent to be investigated to chauge the violet colour completely to brown so that Waentig’s objection that the authors had assumed the colour of the additive compound to be the same for all the solvents used is not valid. G. S. Solubility of ‘( Insoluble ” Sulphur (Sp). ALBERT WIGAND (Zeilsch. physikal. Chew,. 1910 75 235-244. Compare Abstr.1910 ii 228).-Wben amorphous insoluble sulphur Sp is treated with carbon disulphide or carbon tetrachloride a small proportion of it (usually not exceeding 3 per cent. with carbon disulphide) goes into solution the proportion depending on the time of action the tem- perature and the nature of the solvent but being independent of the amount of solvent. This is ascribed to a partial change of Sp to solu5le sulphur Sh under the influence of the solvent. Further a small amount of Sp under ordinary conditions less than 1 in 1000 goes into solution unaltered probably in the colloidal form. The author maintains the accuracy of his figure 118.95 for the melting point of monoclinic sulphur. G. S. The Supposed Nitrososulphonic Acid of Raschig (Sabatier’s Nitrosodisulphonic Acid) and t h e Theory of t h e Lead Chamber Process WILHELM MAKCHOT (Zritsch,.angew. Chem. 19 10 23 2 1 13-2 114).-Raschig’s theory of the lead chamberii. 1056 ABSTRACTS OF CHEMICAL PAPERS. process assumes the intermediate formation of nitrososulphonic acid HO-NO*SO,H (compare Abstr. 1908 ii 30) the solution of which in concentrated sulphuric acid has a blue colour; in more dilute acids there is a slight red colour. This blue colour is also produced by the action of a mixture of sodium nitrite and mercury on sulphuric acid but disappears after a time nitric oxide being evolved. The author finds that the solution of nitric oxide in pure sulphuric acid is colourlees ; if however the sulphuric acid contains iron a red coloration is produced. The red coloration observed by Raschig in some experiments of his (Abstr.1905 ii 23 700) and also a solu- bility of nitric oxide in sulphuric acid considerably greater than that observed by the author are due to the use of impure sulphuric acid. The “purple acid” from the Gay Lussac tower is nothing more than a solution of the ferrous or ferric sulphate compound of nitric oxide. The brown coloration produced by the solution of nitric oxide in an aqueous solution of ferrous sulphate is not due to the formation of ferrous nitrososulphonate ON<iE:>Fe as assumed by Raschig since the same colour is produced Gith ferrous chloride and ferrous hydroxide. The compounds formed contain one molecule of nitric oxide to one atom of iron and are probably of the type NO-FeCl (compare Abstr.1907 ii 93). For similar reasons it is probable that Raschig’s copper nitrososulphonate does not exist (compare this vol. ii 956). Thus the existence of a nitrososulphonic acid has still to be proved. The same objections may also be raised to Sabatier’s nitrosodisulphonic acid. T. S. P. Revision of the Atomic Weight of‘ Nitrogen. Exact Analysis of Nitrogen Tetroxide. PHILIPPE A. GUYE and G. DROUGIKINE (J. Chim. Phys. 1910 8 473-514).-The atomic weight of nitrogen has been determined by decomposing weighed quantities of nitrogen tetroxide with incandescent iron wire. The possibility of obtaining pure nitrogen tetroxide for the purpose depends on the following considerations. Nitrogen trioxide is easily oxidised a t the ordinary temperature t o tetroxide.The tetroxide is not further attacked by oxygen although it is oxidised by ozone; on the contrary the pentoxide undergoes spontaneous decomposition into tetroxide and oxygen. The equilibrium between nitrogen tetroxide and nitric oxide plus oxygen has been determined and the result shows that the dissociation of tetroxide is negligible under the conditions of experiment. The calculations are not affected by the question a s to whether the formula of the tetroxide is NO o r N,O,. The vapour- pressure curves of nitric oxide nitrogen tetroxide and nitrogen trioxide (prepared by Baker’s method) were determined in an apparatus specially designed to protect the surface of the mercury by a buffer of air from corrosion by the tetroxide. The curves which are in accord with those of Rarnsay and Young indicate that although the tetroxide should be easily separated from nitric oxide by distillation the removal of trioxide would be difficult.Accordingly the tetroxide was prepared by mixing purified and carefully dried nitric oxide withINORGANIC CHEMISTRY. ii. 1057 excess of purified oxygen and was distilled in a vacuum a t least ten times in presence of free oxygen precautions being taken to free the final product from dissolved oxygen. The absence of traces of trioxide was inferred from the colourless nature of the liquid product. Throughout the mainpulations phosphoric oxide was used to exclude moisture. The decomposition apparatus consisted of an oval bulb placed with its major axis horizontal and provided with a stopcock at the top and a tubulure for condensing the gas at the bottom. A spiral of iron wire which traversed the bulb could be heated electrically. It was prepared for use by alternate oxidation and reduction in a low pressure current of dry hydrogen.From one to two grams of dry nitrogen tetroxide of f. p. -9.6' mere distilled into the bulb and solidified in the tubulure by a freezing mixture. The bulb having been evacuated and closed was allowed to warm up and weighed. After passing the current and removing the residual nitrogen by the pump the bulb was weighed again. The mean of seven determinations gives 14.010 as the atomic weight OF nitrogen or neglecting the two first determinations the remaining five give a mean value 14.009 ( 0 = 1 6 ) . Considering the possible sources of error the atomic weight could not be less than 14.005 and probably not less than 14.00s.The values obtained are in good agreement with those deduced from analyses of nitrous oxide by Guye (14.0107) and analyses of nitric oxide by Gray (14*0097) bat are opposed to those recently ,calculated by Richards from analyses of silver nitrate namely 13.990 to 14.002. The authors consider that the various direct measurements of nitrogen- oxygen ratios are more trustworthy and agree better amongst them- selves than the indirect (silver) values and that i t wowld be reasonable to make the atomic weight of silver depend on the directly determined value for nitrogen since this is supported by the physical comtants of nitrogen. R. J. C. Formation of Nitric Oxide in the High Tension Arc.FRITZ HABER ADOLF KOENIG and E. PLATOU (Zeitsch. Elektrochem. 1910 16 789-796).-The apparatus and method of experiment have been described in 'previous papers (Abstr. 1908 ii 34 940). Two sets of experiments were made. I n the first set the length of arc and the current (0.27 ampere) were kept constant and the pressure of the air varied. The results show a very decided maximum yield a t 150 mm. the gas leaving the arc containing 8.16% of nitric oxide at this pressure. The second set was designed to determine the relation- ship between the energy consumed in the arc and the quantity of nitric oxide produced. Owing to the distortion of the voltage curve by the discharge through the gas the curves of voltage and current are not in the same phase which introduces some difficulty in the measurement of the energy used in the arc. The methods of measurement are described in detail.The best yield in twenty-four experiments with air at 140 mm. pressure was 57 grams of nitric acid per kilowatt-hour with 3.4% of nitric oxide in the gas leaving the arc. T. E.ii. 1058 ABSTRACTS OF CHEXICAL PAPERS. Formation of Nitric Oxide from Air by means of High Frequency Alternating Electrical Discharges. FRITZ HABER and E. PLATOU (Zeitsch. Elektrochern. 1910 16 796-803).-The electrical measurement of the energy consumed in an unsteady arc produced by an high frequency alternating current is impossible. The authors have therefore measured i t by immersing the apparatus in which the discharge occurs in a calorimeter consisting of a Dewar’s tube filled with parafin oil.The platinum resistance thermometer also serves as a stirrer and the hot gases leave the discharge tube through a silver tube filled with silver filings which is immersed in the oil and serves to cool them. The discharge takes place between platinum wires placed closed together at their lower extremities and diverg- ing at their upper ends. Good results are only obtained when con- siderable quantities ef energy are used in the arc and when it is well spread out in a fan-shape. With a current of about 500 periods per second and air at atmospheric pressure the yield is as high as 54 grams of nitric oxide per kilowatt-hour ; with about one hundred times higher frequency slightly worse results were obtained (48.7 grams of nitric acid per kilowatt-hour) whilst diminishing the pressure t o 387 mm.reduced the yield to about 20 grams. The lower yields are however ascribed to the tendency of the arc to hang to one spot on the platinum wires instead of travelling along them and the authors thinksthat neitjher pressure nor frequency have any specific influence on the yield obtainable. T. E. Yield of Nitric Oxide in the Combustion of Air in the Cooled Direct-current Arc. WILHELN HOLWECH and ADOLF KOENIG (zeitsch. Elektrochem. 1910 16 803-810).-An iron mire 2 mm. diameter surrounded by a quartz tube served as cathode. The anodes were water-cooled copper capillary tubes of from 0.5 to 3 mm. bore. The electrodes were usually placed 2 to 5 mm. apart and the air was drawn off through the capillary tube by means of an air pump; the arc is thus drawn into the cold capillary tube and the greater part of its length which varies with the rate at which the air flows is within the tube.The cathode was not heated as in Holwech’s experiments with the same arrangement (this V O ~ . ii 578) but this had no effect on the results. The yields are always better when the capillary anode is vertically below the cathode and the air therefore drawn downwards than it is when their positions are reversed. The yield increases with the velocity of the air current (the percentage of nitric oxide in the gas of course decreases); with the 0.5 mm. capillary a yield of 74.3 grams of nitric acid per kilowatt-hour was obtained using air with 1.94% of nitric oxide in the gas the arc taking 0.29 ampere a t 290 volts.The best results were obtained with the 2 mm. capillary tube 84.8 grams of nitric acid per kilowatt hour being reached with 2.3% of nitric oxide in the gas a current of 0.2 ampere and 280 volts. Attempts to concentrate more energy into the arc gave worse results; reversing the poles and using alternating current also were less successful. T. E.INORGANIC CBEMlSTRY. ii. 1059 Formation of Nitric Oxide from Air in the Arc under Pressure. FRITZ HABEH. and WILHELM HOLWECH. (Zeitsch. Elektvo- chem. 1'310 16 810-813).-The arc is formed in a vertical steel tube between a cooled copper cathode and an iron anode placed respectively a t the top and bottom of the tube. The air is blown in at the bottom tangentially to the walls of the tube.In one arrangement cold air mas used in another it was heated by passing over the outside of the steel tube before entering it. With the first arrangement 0.55 to 1.5 ampere at 700 to 2075 volts were used and pressures varying from 2 to 21 atmospheres. The best yield was 76 grams of nitric acid per kilowatt-hour with 2 atmos. pressure and 0.36% of nitric oxide. The same yield mas obtained at 11 atmos. with only 0.29% of nitric oxide in the gas. With pre-heated air using currents of 0-5 to 0.6 ampere and 1200 to 1460 volts the yields were better 82.8 grams of nitric acid per kilowatt-hour being obtained with 4 atmos. pressure and 0.76% of nitric oxide. At higher pressures the yields were rather lower. T. E. Formation of Nitric Oxide during the Combust.ion of Hydrogen.A. WOLOKITIN (Zeitsch. Elektrochem. 1910 16 814-826).-The experiments of Htlber and Coates (Abstr. 1909 ii 997) on the formation of nitric oxide during the combustion of carbon monoxide in mixtures of oxygen and nitrogen are extended to hydrogen using the same apparatus and methods of experiment. The results are very similar; the combustion of hydrogen in air a t the ordinary pressure yields no nitric oxide; when the pressure is increased to 20 atmospheres or more about 0.3 mol. of nitric oxide is formed per 100 mols. of water. With a mixture of equal volumes of oxygen and nitrogen the yield is small at low pressures but increases with the pressure nearly 3 mols. of nitric oxide per 100 mols. of water being obtained at 15 atmos. pressure. Further increase of the pressure up to 50 atmos.produces but little further increase in the yield. A mixture of oxygen and nitrogen with 80% of the former behaves in much the same way as the mixture of equal volumes. The theoretical calculation of the yield made in che manner adopted by Haber and Coates indicates a maximum yield of about 4 mols. of nitric oxide per 100 mols. of water using a mixture of equal volumes of oxygen and nitrogen ; the actual yields are less than the theoretical ones whereas Haber and Coates obtained t4he opposite result with carbon monoxide. T. E. The Behaviour of Nitrous Gases towards Water and Aqueous Alkalis. FRITZ FOERSTER and J. BLICH (Zeitsch. ungew. Chem. 1910 23 2017-2025. Compare Abstr. 1908 ii 941 1031). -The rizt>e of oxidation of nitric oxide by air under different con- ditions has been determined by absorbing the product in sodium hydroxide and determining the ratio of nitrite to nitrate formed.In the authors' apparatus the gases issuing from the large oxidation chamber pass through two vessels containing water after which the mixture contains nitric oxide as well as peroxide. The third vesselii. 1060 ABSTRACTS OF CHEMICAL PAPERS. contains sodium hydroxide. Lengthening the path between the water and alkali increases the completeness of the oxidation but no improve- ment is brought about by interposing heated glass spirals. Experi- ments in which air and nitric oxide pass together into a heated vessel containing broken glass show that the reaction 2NO + 0 = 9N0 proceeds less rapidly as the temperature rises.This result has also been observed by Bodenstein and is best explained by the assumption that a molecular oxide is first formed NO + 0 -+ NO*O NO.0 + NO -+ ZNO (compare Raschig Abstr. 1907 ii 455). The experiments also show that alkalis absorb nitrogen trioxide more rapidly than nitrogen peroxide. It appears probable that in a partly oxidised mixture the equilibrium NO +NO t N,O exists although the quantity of trioxide is small and that the water absorbs the gases in this form (compare Le Blanc Zeitsch. Elektrochern. 1906 12 544). When pure liquid nitrogen trioxide is added to sodium hydroxide solution a t - 2 2 O it is instantly absorbed whilst liquid nitrogen peroxide only reacts slowly. HUNPHREY 0. JONES and J. I(. MATHEWS (Proc.Cccm6. Phil. Xoc. 1910 15 529-530),-When nitrosyl chloride and ethyl mercaptan react in ethereal solution a t - 80° small quantities of hydroxplamine hydrochloride are formed. The action of other reducing agents on nitrosyl chloride has therefore been studied but the formation of hydroxylamine hydrochloride has only been observed when nitrosyl chloride and hydrogen are passed over reduced platinum cooled in a freezing mixture. Even in this case t h e hydroxglamine hydrochloride only forms 576 of the ammonium chloride produced. When the contact substance is nickel the product is ammonium chloride. With palladium the products at the ordinary temperature are palladium chloride nitric oxide and nitrogen ; at higher temperatures ammonium chloride is formed. Hydrogen sulphide and nitrosyl chloride interact at a low tempera- ture in ether or light petroleum the principal reaction being C.H. D. The Reduction of Nitrosyl Chloride. NOCl + 3H2S = NH,Cl + H,O + 3s. C. H. D. Presence of a Small Quantity of Carbon Monoxide in the Atmosphere of Coal Mines. P. MAHLER and J. DENET (Compt. rend. 1910 151 645-647. Compare this vol. ii 607 ; Boudouard Abstr. 1909 ii 234).-.Carbon monoxide has been found to occur in the air of well-ventilated coal mines to the extent of about 0.002% by volume; the maximum amount found was 0.004%. Iodic anhydride was employed to estimate _the carbon monoxide and precautions were taken to avoid the influence of traces of dust or unsaturated hydro- carbons. w. 0. w. Silicates with Linked Silicon Atoms. WILHELM MANCHOT (Ber.1910 43 2603-2604).-1n his lecture before the German Chemical Society (this vol. ii 780) W. Pukall represents the constitution of ‘‘ kaolin-acid ’’ as there being a double linking OH*Si*O*O* AI(OH) OH*& 0 0 *A1 (OH),lNORGANIC CHEMISTRY. ii. 1061 between the two atoms of silicon. A similar constitution is given to kaolin. The author points out that such substances should evolve hydrogen when treated with hydrofluoric acid or with hydrofluoric acid followed by alkali (compare Abstr. 1905 ii 165; 1908 ii 46) and that therefore the above formula is an impossible one. Moreover the doubly linked atoms of silicon would indicate that a reduction of silicic acid had taken place in the preparation of the compound whereas no reduction could take place according to the method of preparation described by Pukall.Such a linking would be broken by the action of alkali and not be stable as postulated by Pukall. T. S. P. Preparation of Argon. GEORGES CLAUDE (Compt. rend. 1910 151 752-’i53).-Details are given of n laboratory method for preparing argon a t the rate of 2-3 litres per hour. The compressed oxygen of commerce when obtained from liquid air contains over 3% of argon and is a convenient source of this element. The oxygen i R absorbed by reduced copper and the small amount of nitrogen by heated magnesium. w. 0. w. Determination of the Velocity of Sound in Potassium Vapour and the Monatomicity of its Molecules WILHELM WENZ (Ann. Physik. 1910 [iv] 33,95 1-97O).-Measurements of the velocity of sound in potassium vapour have been made by Quincke’s resonance method at 850’.The vapour was contained in a steel tube surrounded by a wider porcelain tube which was heated electrically. The one end of the steel tube was closed by a thin mica plate serving as a vibrating resonance diaphragm. I n order to obtain satisfactory results with this at the high temperature it was found necessary to protect the inner surface with a thin layer of silver. The other end of the tube was formed by a piston which could be moved up and down and by this means the length of the column of vapour could be varied. The distances between successive positions in which resonant vibration was obtained were determined and compared with the corresponding lengths for air. The measurements give 1-77 for the ratio of the specific heats.From this the author concludes that the vapour of potassium consists of monatomic molecules. H. 1sI. D. Equilibrium in the System Potassium Iodide Iodine and Aqueous Alcohol. CHARLES L. PARSONS and H. Y. CORLISS (J. Amer. Chem. Soc. 1910 32 1367-137S).-The solubility of iodine and potass- ium iodide in aqueous-alcoholic solutions containing varying amounts of potassium iodide and iodine respectively has been measured a t 25O. In an alcohol-water mixture containing 60% of alcohol two solubility curves are obtained which intersect at a point corresponding with a solution containing 20.0% of potassium iodide and 72.5% of iodine. Similar results were obtained with a solvent containing 40% of alcohol the point of intersection of the two curves corresponding in this case with 22.5% of potassium iodide and 70.8% of iodine.The limiting solutions VOL. XCVIII. ii. 72ii. 1062 ABSTRACTS OF CEEMICAL PAPERS. indicated are those which are simultaneously saturated with respect to iodine and potassium iodide. The solubility data afford no evidence of the formation of solid polyiodides and the absence of these has been confirmed by analyses of the solid phases in contact with the saturated solutione. The question of the existence of polyiodides in solution is discussed and experiments are described wbich show that the iodine and potass- ium iodide in an aqueous solution of these substances can be partly separated by diffusion. These results are interpreted as indicating that polyiodides are not formed t o any appreciable extent.The increased solubility of iodine in an iodide solution as compared with pure water is attributed to the high solvent power of the dissolved solid. H. M. D. Sodium Tellurides. GIOVANNI PELLINI and E. QUERCIGH ( d t t i R. Accad. Lincei 1910 [v] 19 ii 350-356. Compare Tibbals Abstr. 1909 ii 728)-With a view to throwing further light on the analogy between tellurium sulphur and selenium the authors have investigated the sodium tellurides by thermal methods. The cooling curves of mixtures of the two elements were observed in an atmosphere of nitrogen a quartz vessel being employed and the temperatures measured by means of a platinum and platinum-rhodium couple. The results obtained are also exhibited in a curve from which it follows that under the conditions of the experiment three compounds can exist namely Na2Te Na3Te2 Na3Tel.Only the first melts unchanged. It is whitish in colour but rapidly darkens in the air and is very deliquescent. I n these circumstances it was not possible to obtain the compound Na2Te3 prepared by Tibbals (Zoc. cit.). The formulae of these tellurides differ from those of the selenides (compare Mathewson Abstr. 1907 ii 682) and sulphides except in the case of the type Na2Te. The other two have a grey metallic aspect. R. V. S. The Equilibrium Diagram of the Silver-Sodium Alloys. E. QUERCIGIH (Zeitsch. anorg. Chem. 1910 68 301-306).-Sodium does not react appreciably with silver below 700". The alloys may be prepared in all proportions by fusion in a current of nitrogen and separation into two liquid layers does not take place.The freezing- point curve falls rapidly at first then slowly and then from 90 atomic % Na very rapidly. The eutectic point lies not more than 0.1' below the freezing point of sodium. Solid solutions of sodium in silver are formed up t o 13 atomic % Na. C. H. D. Photo-Halides. I. WILLEM REINDERS (Chent. Weekblad 1910 '7 961-973).-Crystalline photo-chlorides of silver have been prepared by crystallising silver cbloride from dilute aqueous solutions of ammonia in presence of sunlight. The crystals were indigo-blue in colour the depth of tint depending on the intensity of the light and the duration of the crystallisation. The darkest crystals contained about 1% of free silver. Exposure under blue glass during crystal-INORGANIC CHEMISTRY.ii. 1063 lisation did not affect the colour of the resulting crystals but with green or yellow glass the tint was much lighter and with red glass colourless crystals were formed. During exposure to light for several days the colour of the crystals changed to reddish-brown and they became opaque. Longer exposure to light produced a grey colour with metallic lustre. These colour changes are caused by superficial reduction to metallic silver. The free silver present in the photo-chloride is in the colloidal state. Crystallisation from a solution of colloidal silver was effected by. addition of a small proportion of formaldehyde to a saturated solution of silver chloride in ammonia ( 4 N ) slow reduction to a colloidal solution of silver taking place.In transmitted light the resulting crystals were light yellow to reddish-brown in colour whilst in reflected light they were yellow chocolate-brown or green. They did not contain more than 1-2% of free silver. I n diffused sunlight they changed slowly in colour from yellow to indigo-blue with production of iritermediate shades of red I eddish-violet and violet-blue. A. J. W. The So-called Emulsion of Silver Iodide. JOHN K. THUM (Amer. J. Phawn. 1910 82 507-508).-When silver nitrate reacts with potassium iodide dissolved in a solution of egg-albumin the greater part of the precipitated silver iodide is maintained in colloidal solution. Irish moss mucilage gives fairly good results as a substitute for egg-a1 bumin. Solutions of gelatin (0*1-0-50/,) in water also give good sus- pensions.I n this medium the precipitates a t first fall to the bottom of the flask but permanent almost perfect suspension can then be obtained by agitation and the suspension improves on keeping. T. A. H. The Tellurides of Silver. GIOVANNI PELLINI and E. QUERCIGH ( A t t i R. Accad. Lincei 1910 [v] 19 ii 415-621).-The mixtures of tellurium and silver are melted in a current of nitrogen. The freezing-point diagram indicates the formation of two compounds Ag're and Ag,Te the first being marked by a break in the curve at 4M0 and the second by a maximum at 959O. There are two eutectic points a t 351' and 33.3 atomic % Ag and a t 872Oand 86 atomic % Ag respectively. The compound AgTe undergoes a transformation a t 4 1 2 O but a polymorphic change of Ag,Te which is identical with the mineral hessite is not observed. The alloys are crystalline and metallic in appearance changing from grey to white as the silver increases.The brittleness diminishes from tellurium to silver. C. H. D. The Absorption of Bromine by Lime. W. A. R. WILKS (Proc. Camb. Phil. Soc. 1910 15 526-528).-Solutions of bromine in carbon tetrachloride react with slaked lime with the formation of a brown product. Using weak solutions of bromine the concentration of the bromine in the lime increases with the concentration of the solution the ratio C,/C,l'J being sensibly constant pointing to the 72-2ii. 1064 ABSTRACTS OF CHEMICAL PAPERS. formation of an adsorption product. With more concentrated solutions of bromine the quantity taken up is independent of the concentration and the ratio Ca(OH) Br = 4-42 1 indicating the formation of a compound.With dry slaked lime the ratio soon becomes constant at 14.9 1 the equilibrium concentration of bromine being thus much lower a iesult similar to that observed with bleaching powder. The colour of the product increases until the constant concentration is reached. C. H. D. G. CALCAGNI and a. MANCINI (Atti R. Accad. Lincei 1910 [v] 19 ii 422-427).-The double sulphates of calcium and the alkali metals have been studied by D'Ans (Abstr. 1909 ii 401). The freezing-point curve of mixtures of calcium sulphate and sodium sulphate has now been determined. Pure calcium sulphate decomposes so readily at 1000° that its freezing point cannot be determined but extrapolation of the curve gives 1375'.Sodium sulphate melts a t 887' and undergoes a polymorphic change at 234'; this transformation is not observed in mixtures containing more than 7% of calcium sulphate. The curve has a single maximum at 949O corresponding with the compound 3Na2S04,CaS04 an analogue of vanthoffite 3Na,S04,MgS0,. The eutectic point is at 917O and 51% Na2SO corresponding with the composition of the mineral glauberite. It is possible that other double salts may exist at lower temperatures especially glauberite and the pentacalcium sulphate. Between 73% and 82.6% of sodium sulphate two liquid layers are formed C. H. D. Anhydrous Sulphates. [Calcium Silicides.] ADALBERT KOLB (Zeitsch. anorg. Chem. 1910 68 29'7-300).-A reply to Hanigschmid (this vol.ii 503) maintaining the accuracy of the author's formihe for the calcium silicides (this vol. ii 35). HERMANN NOLL (Zeitsd. angew. Chern. 1910 23 2025-2029. Compare Abstr. 1908 ii 435). -The solubility of calcium carbonate in water free from carbon dioxide is lessened by the presence of magnesium carbonate. Experi- ments are described to determine the influence of magnesium salts and of organic substances on the temporary hardness but without definite result. C. H. D. C. H. D. The Temporary Hardness of Water. Preparation of Crystalline Strontium. ANTOINE GUNTZ and GALLIOT (Compt. ?*end. 1910 151 813).-A mixture of an- hydrous strontium oxide with the calculated amount of aluminium is heated for four hours at 1000° in a steel tube (10 cm. long 3 cm.diam.) which is placed in an evacuated porcelain tube. On cooling the inner tube is found to be coated with silver-white crystals of strontium containing 99.4% of the metal. The product has D 2.63 w. 0. w. Solubility of Strontium Nitrate and Strontium Hydroxide in the Presence of Each Other. CHARLES L. PARSONS a i d C. L. PERKINS (J. Amer. Chem. Soc. 1910 32 1387-1389).-The solubility and the yield is 76% of the theoretical.INORGANIC CHEMISTRY. ii. 1065 data obtained at 2 5 O can be represented by means of two curves intersecting at a point which gives the composition of the solution saturated with respect to both substances. This solution contains 1.76 parts of strontium oxide and 51-06 parts of strontium nitrate per 100 parts of water. The curves are quite similar to those obtained in the case of barium nitrate and barium hydroxide (compare following abstract) and show that no basic nitrates of strontium are capable of existence at 25’.H. 35. D. Solubility of Barium N i t r a t e and Barium Hydroxide in the Presence of Each Other. CHARLES L. PARSONS and H. P. CORSON (J. Amer. Chem. Soc. 1910 32 1383-1 387).-These measurements were made to ascertain whether a basic barium salt analogous to the calcium salt Ca0,Ca(N03),,3& H,O is capable of being obtained. The graphical representation of the solubility data for 25’ gives two curves meeting at a point corresponding with a solution which con- tains 5-02 parts of barium oxideand 11.48 parts of barium nitrate in 100 parts of water. This solution is saturated with respect to both Ba(OH),,8 L3,O and Ba(NO&. The saturated solutions of the two substances separately contain respectively 4-29 parts of barium oxide and 10.30 parts of barium nitrate per 100 parts of water.The solu- bility of each substance is increased in presence of the other. The data show that basic nitrates of barium are not formed at 25’. H. M. D. The Action of Solutions of Borax on Zinc Salts. FRIEDRICH BORCHERS (Zeitsch. ccnorg. Chem. 1910 68 269-291).-The compo- sition of the precipitate obtained from borax and zinc salts is very variable. The possible equilibria have now been studied in detail. The reaction may be expressed thus [B~0,”][H20]3[Zn’.]= k[H3B03]2[Zn(B0,),]. The borax is employed in most of the experiments as a saturated solution but also-occasionally in the solid firm or as a supersaturated solution.For the analysis a part of the filtrate is precipitated with sodium carbonate to remove zinc neutralised with standard hydro- chloric acid with methyl-orange as indicator and after boiling to remove carbon dioxide glycerol is added and the solution is titrated with potassiuru hydroxide using phenolphthalein as indicator. Boric acid does not react with zinc oxide or hydroxide to form solid zinc borate although some zinc goes into solution but boric acid and zinc carbonate react readily. The largest yield of zinc borate is obtained by adding a concentrated solution of a zinc salt t o a slight excess of saturated borax solution. The maximum proportion of borax thus precipitated as zinc borate is 38.676 using solid zinc sulphate.Higher. results are obtainable from supersaturated borax solution or solid borax. An excess of zinc salt diminishes the yield complex zinc salts being formed. Indifferent salts have a similar effect a large excess of magnesium chloride for instance preventing precipitation completely. If the hydrolysis of the borax is checked by the addition of boric acid the whole of the borax and even a part of the added boric acidii. 1066 ABSTRACTS OF CHEMICAL PAPERS. may be precipitated by means of a zinc salt. Borax does not produce any precipitate with sodium zincoxide but by addition of only small quantities of sodium hydroxide the precipitation is rendered more complete. If the zinc borate is removed by filtration and an excess of sodium hydroxide followed by zinc sulphate is added to the filtrate a further precipitate is obtained and this process may be repeated until 94% of the borax has been converted into zinc salt.Sodium carbonate has less effect than sodium hydroxide and the addition of sodium chloride or sulphate then modifies the reaction. Mnnganous salts behave similarly to zinc salts. C. 13. D Hydrates of Cadmium Nitrate. ALEXIS 3%. VASILIEFF (J Russ. Phys. Chem. Soc. 1910 42 562-567).-Cadmium nitrate which crystallises from aqueous solution with 4H20 can be obtained like the correspondiDg silver salt in the anhydrous state by the evaporation of the hydrate. Contrary to Funk's statement (Abstr. 1899 ii 209) no salt with 2H,O or 6H20 could be obtained. At low temperatures however a salt with 8H,O was produced.The anhydrous salt melts a t about 350' and dissolves in water with development of much heat. The solubility cuive of the anhydrous salt Cd(N0,)2 in the hydrate Cd(N0,),,4H20 (investigated in the solid condition in Flawitsky's apparatus Abstr. 1909 ii 886) has a break beyond the m. p. of the hydrate 595O descending to 44.5" which is the eutectic point of the mixture and corresponds with the composition Cld(N0,),,2.65 H,O ; the curve then rises continuously to the m. p. of the anhydrous salt about 350O. Z . K. The Binary and Teinary Alloys of Cadmium Bismuth and Lead. WILLIAM E. BARLOW (J. Amer. Chem. ~ o c . 1910 32 1390-1412).-From observations of the rate of cooling of the molten alloys the author has determined the freezing-point curves for the pairs of metals lead-cadmium and lead-bismuth.By combination of these results with the data obtained in experiments on alloys contain- ing the three metals the solidification diagram for the ternary system has been deduced. Lead and cadmium give rise to two curves intersecting in a eutectic point which corresponds with 82.6% of lead and a temperature of 247-3'. On the cadmium side the form of the curve points to a slight solubility of lead in solid cadmium and on the lead side cadmium appears to dissolve in the solid lead t o the extent of about 3%. Lead and bismuth yield a similar diagram the eutectic temperature being 124-3-1 24-8' and the composition corresponding with 56 5% of bismuth. On the bismuth side the data indicate that bismuth dissolvl s in solid lead to the extent of about 11%.From the very numerous observations which hare been made with allojs containing the three metals a triangular diagram has been constructed. The ternary freezing point is sharply defined a t 91*4-91*5O and the compobition of the ternary eutectic is given as 40.2% lead 51.65% bismuth and 8.15% cadmium. H. M. D.INORGANIC CREMISTHY. ii. 1067 Equilibria in t h e Precipitation of Lead Hydroxide WALTER HERZ (Zeitsch. anorg. Chem. 1910 68 421-424).-When lead oxide is shaken with an alkali halide and water the whole mass becomes pasty and i t is therefore necessary to approach the equilibrium from the other side. The formation of basic salts may be left out of con- sideration. The constant [PbCI,][KOH]2/[ KC1 32 is found to tie 0 00073 and for the corresponding reactions with ammonia and methy lamine 0.00082 and 0*00066 respectively.The solubility of lead hydroxide is calculated to be 0.93 x lo-*. C. H. D. Basic Lead Carbonates. LEOPOLD FALK (Chem. Zeit. 1910 34 937-938).-When lead carbonate is shaken with a solution of basic lead acetate three parts of carbonate withdraw two parts of oxide from solution as shown by titration! but the washed precipitate always contains too much carbonate for the formula. If boiled with the basic lead acetate solution the ordinary basic carbonate 2PbCO,,Pb(OH) is obtained. Crystalline and amorphous lead carbonates differ in their chemical behaviour. Thus whilst the crystalline compound reacts readily with lead oxide in preAence of lend acetate the amorphous modification only reacts rery slowly.The formulae CO<o>Pb and 0 are proposed for the two modifications and a similar polymerisation is assumed in the case of white lead. Structural formulz for the basic carbonates are proposed. Hydrogen sulphide only reacts very slowly with crystalline white lead but rapidly with the amorphous variety. C H. D. Solubility of Lead Sulphate and Lead Chromate and of Mixtures and Oil Colours Containing the two S a l t s in Dilute Hydrochloric Acid. The Equilibrium between Chromate and Dichromate in Solution. KARL BECK and PH. STEGUULLER (Arb. K . GesundL-Amt 19 10 34 446-483).-Measurements have been made of the solubility of lead sulphate and lead chromate in O-lN- to O.6N-hydrochloric acid a t 1S0 254 and 37O. The data for lead sulphate show that a t constant temperature the solubility is approximately proportional to the concentration of the hydrogen ions.In the case of lead chromate the solubility in the more dilute solutions is nearly proportional to the bydrogen ion concentration but in the more con- centrated solutions it is more nearly proportional to the square of the concentration of these ions. The increase in solubility with rise of temperature is linear for both salts the increase per 1' being 2.1% for the sulphate and 3-5-4% for the chromate. The equilibria in the solutions have been examined theoretically and it is shown that the observed differences in the dependence of the solubility of the two salts on the concentration of the acid is due to the formation of dichromate ions in accordance with the equation 2HCr0,' = Cr,0/ + H20.In acid solutions less concentrated than 0*3N the effect of this changeii. 1068 ABSTRACTS OF CHEMICAL PAPERS. is not very marked but in the stronger solutions it results in a considerable increase in the :amount of lead chromate dissolved per mol. of acid present. In connexion with the analysis of the equilibrium in solution measurements were made of the solubility of lead sulphate in 0.1 to O.4N-solutions of sodium chloride and nitric acid and of lead chromate in 0.1 to 0-6N-nitric acid. From these data the following equilibrium constants are calculated [H'].[CrO,"]/[H?0,'3 = 3.7 x TO-? l O - l 3 [H'][Cr,O ]/[HCr20,1] = 1.0 x 10-3 [H']2.[CrOpN]2/[Cr20{'] = 3.4 x [KCr0i]2/[Cr20,1'] = 2.5.Data are also recorded showing the quantities of lead dissolved by 0.1 to 0*4N-hydrochloric acid solutions in presence of both sulphate and chromate and these are supplemented by observations showing the rate at which oil colours containing these two substances are attacked by dilute hydrochloric acid solutions. H. M. D. The Ternary System Copper-Antimony-Bismuth. NICOLA PARRAVANO and E. VIVIANI (Atti R. Accad. Lincei 1910 [v] 19 ii 343-449. Compare this vol. ii 956).-In this paper are siven the results obtained in the examination of the ternary system Cu3Sb-Cu-Bi the second of the two systems into which the system Cu-Sb-Bi resolves itself. The diagram constructed from them differs from that which was deduced on general grounds because both copper and bismuth and Cu3Sb and bismuth €orm eutectics which practically coincide with bismuth.Photomicrographs of some typical alloys are given. I n conclusion the space of miscibility in the liquid state is discussed the limits of the space in the two systems being obtained by analysis of the two layers in equilibrium at about 670° which is very near the initial temperature of solidification of alloys in that region. Uniting the two systems Cu,Sb-Cu-Bi and Cu,Sb-Sb-Bi in one diagram it then becomes possible to exhibit on it the closed curve representing the boundary of the space of miscibility. All alloys within the curve separate into two layers whilst those outside it are miscible in all proportions. R. V. S. Action of Chlorine in Carbon Tetrachloride Solution and of Carbon Tetrachloride on Metallic Oxides.ARTHUR MICHAEL and ARTHUR MURPHY jun. (Amer. Chem. J. 1910 44 365-384).- This investigation was undertaken originally with the object of ascertaining the relation between the position of metals in the periodic system and the behaviour of their unsaturated oxides towards chlorine. The following experiments were made with a 10% solution of dry chlorine in carbon tetrachloride. With ferrous oxide a violent action occurs even when the chlorine solution is cooled to - lSo with formation of ferric oxide and chloride 6 FeO + 3 C 1 ~ 2 Fe,O + ZFeCI,. Manganous oxide reacts less violently ; nickelous oxide reacts readily at the ordinary temperature but the reaction is not complete for a considerable time; in the case of cobaltous oxide the mixture must be heated at 100' in a sealed tubs in order to complete the reaction.These reactions may be represent6 I by the gene1 a1 equation 3M0 + C1 = M20 + 31C12. Stannous oxide reacts violently with the solution,INORGANIC CHEMISTRY. ii. 1069 with formation of stannic chloride and a light brown oxide probably identical with the oxide Sn0,20Sn021 obtained by Schiff (Annalen 1861 120 52) by treating stannic acid with a solution of stannous chloride. Cuprous oxide requires to be heated at 250' with the solution in order to effect a reaction; cupric oxychloride Cu,0Cl2 is thus obtained as a dark brown amorphous powder. Antimony trioxide reacts with the chlorine solution at 100' in a sealed tube in accordance with the equation Sb,O + 3CC1 + 2C1 = 2SbC1 + 3COC1,.I n the case of silver oxide the following reaction takes place at the ordinary temperature Ag20 + C1 + UCI = 2AgC1+ COCl + Cl,. The chlorine evidently behaves as a catalyst since when the oxide is heated with carbon tetrachloride in the absence of free chlorine carbonyl chloride is not produced until a temperature of about 250' is reached. Lead oxide reacts with the solution at 100' in accordance with the equation 2Pb0 + GI = PbO + PbCl,. Mercuric oxide although reacting readily with chlorine gas even at Oo is not affected by a solution of chlorine in carbon tetrachloride unless the mixture is heated at looo in a sealed tube ; the products thus obtained consist of mercuric chloride and some basic chlorides. When molybdenum dioxide is heated with carbon tetrachloride in a sealed tube at 250° it is converted iuto the tetrachloride. Molyb- denum trioxide reacts with carbon tetrachloride at 280' with formation of the pentachloride.When the trioxide is heated with a solution of chlorine in carbon tetrachloride at 200° the product consists of a yellowish-green oxychloride mixed with unchanged trioxide; at 225' a mixture of yellow and green compounds is obtained probably consisting of the dioxy-dichloride and the oxytetra- chloride ; at 240' the pentachloride is produced. The pentachloride is also obtained when the oxide Mo,? is heated with carbon tetra- chloride at 240O. When tungsten trioxide is heated with the chlorine solution the oxychloride WOC1 is formed at 240° and the hexa- chloride at 280'; in the absence of free chlorine reaction does not occur a t 240° but at 280'the hexachloride is produced.Uranium dioxide if heated with carbon tetrachloride at 350° yields the tetra- chloride whilst the oxides UO and U,O when heated a t the same temperature give the pentachloride. CHARLES L. PARSONS and W. W. EVANS (J. Anzer. Chem. SOC. 1910 32 1378-13S3).-Solu- tions of alum when allowed to undergo diffusion into distilled water through a parchment or agar-agar diaphragm are more or less com- pletely separated into the component simple sulphates. Similar results were obtained a t 25' and at 0'. The separation is more complete in the case of the chrome alums than in that of the alumiuiurn alums. The authors draw the conclusion that the dissolved alums are more or less completely resolved into the simple sulphates.Composition of Some Greek Vases. WILLIAM FOSTER (J. Amer. Cl~arnz. SOC. 1910 32 1259-1264).-A study has been made of the nature and composition of the black glaze of vases of the black- figured and red-figured Attic styles and the red glaze of the Mycenaean E. G. Diffusion Phenomena of the Alums. H. M. D. style.ii. 1070 ABSTRACTS OF CHEMICAL PAPERS. The black colour of the glaze of fragments of some Greek vases was found not to be due to manganese as has been suggested but to the presence of ferrous iron probably existing as silicate. The red colour of the glaze of a fragment of a Mycenaean vase was found to be due to the presence of ferric iron. A fragment of a vase of the Mycenaan style has been analysed and the results are compared with those recorded for Attic and Campanian pottery.The Mycenaan pottery contains considerably less silica and much more lime than the other varieties and yields a large quantity of carbon dioxide. The percentage of aluminium is about the same in each case but the Campanian ware contains about twice as much ferric iron as the Mycenzan and Attic. The amount of magnecium is about the same in the Mycenzean and Attic varieties but is much less in the Campanian. E=. G. The Structure of Cast Iron in the Graphitic Condition. OTTO KROHNKE (MetuZZu?*gie 1910 7 674-679).-When cast iron is transformed into the '' graphitic " condition by corrosion the ferrite is removed from the pearlite whilst cementite and iron phosphide remain unaltered. The graphite retains its position in the mass but is partly convei.ted into a white or grey substance graphitite the composition of which is unknown.White cast iron does not undergo such a change the constituents being resistant to corrosiori. Wrought iron although containing pearlite in small quantities does not corrode in this way the presence of graphite being necessary to produce the requisite electrolytic couples. C. H. D. Case-Hardening. SYDNEY A. GRAYSON ( J . ITon Sted Inst. 1910 81 287 -302).-The case-hardening of steel by means of carbonaceous mixtures takes place best at 950-1000". A t 900-950° diffusion being very slow a highly supersaturated external layer is produced. Sulphur diffuses in a Fimilar manner to carbon a t tthe same temperature. C. H. D. The Crystallography of the Iron-Carbon System. ADOLPHE KROLL (J.Iron Xtoel I n s t . 1910 81 304-385).-When steel is heated and cooled in an inert gas relief-patterns are obtained in- dicating the volume changes which have taken place at the critical points. The microscopical examination of etched sections shows that cjrdinary cementite is hexagonal but that the carbide entering into solution in y-iron is regular. A modified equilibrium diagram is proposed in which a gap exists between two series of solid solut,ions one of carbide in y-iron and one of y-iron in cementite the latter solution being identical with troostite. This system is formed in tempering. A theory of the constitution of iron-carbon alloys haced on the crystallographic development is proposed for the metastable systems the only stable chemical equilibrium being that of ferrite and graphite.C. H. D. The Influence of Sulphur on the System Iron-Carbon. THEODOR LrEscHrNG (,Wetdurgie 1910 7 565 -571).-The distribu-INORGANIC CHEMISTRY. ii. 1071 tion of iron sulphide in alloys of iron and carbon has been studied microscopically. The ferrous sulphide appears in low-carbon alloys in the form of thin films surrounding the crystals of ferrite. When the sulphur exceeds 2% in an alloy high in carbon two liquid layers are formed of which the lighter sulphide layer does not contain cnrbon. C. H. D. The Influence of Silicon on the Maximum Solubility of Iron Carbide in 7-Iron. CH. SCHOLS (iVetcclZurgie 1910 7 644-646).-The solubility of iron carbide in y-iron is known to be diminished by the addition of silicon.Thermal and microscopical investigations of alloys prepared from iron and ferro-silicon show that the maximum solubility which is at 2.2% C in the absence of silicon is lowered to 1.9% by 1.34% Si to 1.5% by 1.80/ Si and to 1.2% by 5.6% Si. The pearlite trans- formation point is slowly raised by the addition of silicon but becomes imperceptible above 1*2%C if the alloy contains 5.6% Si or above 1.5% C in the presence of 4.5% Xi. JOHN 0. ARNOLD and ARTHUR A. READ (J. Iyon Steel Inst. 1910 81 169-181).-The carbides isolated from alloys of iron manganese and carbon by electrolysis show an increase in the ratio of manganese to iron as the proportion of manganese in the alloy is increased becoming constant in steels containing from 4-98 to 13.38% Mn afterwards increasing still further. The results do not decide whether double carbides or a mixture of the two carbides are present.Tested by the colour test carbides of this kind indicate a lower percent,age of carbon than pure iron carbide. Up tso 10% Mn the colour is only that due to the iron carbide present showing that manganese carbide does not give a coloration with nitric acid D 1.20. Alloys containing 11 (.r 14% Mn give a higher coloration with nitric acid. Some Physical Properties of 2% Chromium Steels. ANDREW MCWILLIAM and ERNEST J. BARNES (J. I ~ o n Steel Inst. 1910 81 246-267).-The t'hermal analysis of steels containing 2% of chromium and varying quantities of carbon shows that the critical point Ac2 is depressed below Acl when the carbon is between 0.2 and 0.5%.The three critical points become identical in steels containing 0.65 (;r 0.85% C. The saturation point lies between the last two values. The microscopic structure does not indicate the form in which ,t,he chromium is present in the steel. HAROLD MOORE (J. Iron Steel Znst. 1910 81 268-275).-The determination of the critical points of steels conta.ioing more than 3% of chromium shows that the posit'ion of Acl is progressively raised by the addition of chromium and that a new critical point appears below A c l . The fact that the new point coincides with the temperature at which the magnetic properties of the steel disappear on heating proves it to be identical with Ac2. An elmtromagnetic method is employed to determine this point (compare preceding abst>ract).The eutectic point remains constant a t 1120'. CI. H. D. Iron Manganese and Carbon. C. H. D. C. H. D. The Ac2 Point in Chromium Steel. C. H. D.ii. 1072 ABSTRACTS OF CHEMICAL PAPERS. Reduction of Ferric Oxide by Solid Carbon. GEORGES CHARPY and S. BONNEROT (Compt. rend. 1910 151 644-645. Compare this vol. ii 215).-The authors have studied the speed of reaction between ferric oxide and carbon at low pressures (0.001-8 mm.) to avoid as far as possible the catalytic action of gases. The mode of procedure was similar t o that employed when examining the cementation of iron under similar conditions. The conclusion drawn is that carbon is incapable of reducing ferric oxide below 950" a temperature considerably higher than has hitherto been supposed necessary.w. 0. w. The System Nickel-Sulphur. KARL BORNEMANN (MetaZZurgie 1910 7 667-674. Compare Abstr. 1908 ii 292)-The experi- ments with mixtures high in nickel have been repeated using magnesia vessels and quartz protecting tubes for the thermo-couples. Care being taken to avoid undercooling the break in the freezing- point curve formerly observed at 4 atomic % S disappears apd only a single series of solid solutions rich in nickel is observed extending from 0 to 0.5 atorriic :L S. The complicated transformations in the solid state are confirmed. C. H. D. Preparation of Anhydrous Chromic Chloride by Bourion's Method. JOSE RODRIGUEZ MOURELO (Anccl. Pis. Quim. 19 10 8 196-1 99).-Although chlorine in presence of carbon attacks chromium sesquioxide prepared by gently igniting chromium hydroxide it is without action on the crystalline sesquioxide or the sesquioxide obtained by ignition a t a high temperature.But by Bourion's method (Abstr. 1909 ii 220) these indifferent substances are rapidly converted into beautifully crystalline scales of chromic chloride ; it is only necessary to pass the vapour of sulphur chloride (b. p. 137-139") over the oxide heated gradually to a red heat and after the action is complete to cool in a current of dry hydrogen chloride. W. A. D. Uranium Salts. I. and 11. ALEXIS M. VASILIEFF (J. Russ. Phys. Chem. Soc. 1910 42 570-581).-Uranium nitrate gives three hydrates U02(N0,),,6H,0 U0,(N03),,3H,0 and the dihydrate U0,(N03),,2H,0 but the nitrate UO,( N03),,l+H20 does not exist.The hydrate U02(N03),,6H20 melts a t 60*2O and when further heated just above this temperature is transformed into the trihydrate but if heated at a higher temperature a basic salt is formed which however dissolves in water to a yellow solution. The trihydrate m. p. 121*5" forms crystals belonging to the mono- clinic system and can also be obtained by crystallising a strongly acid solution of the sesquihydrate in nitric acid (D 1.4). The dihydrate m. p. 179.3' forms small thick square plates probably of the rhombic system very bright and with a green fluorescence. It is formed when the sesquihydrate is kept for some time in a desiccator at the ordinary temperature or when the latter hydrate is treated thus a t looo and the product which now contains slightly less than 2H,O is dissolved in nitric acid D 1.502 and then allowed to cryatallise.When the substance containing less that 2H20 is treatedINORGANIC CHEMISTRY. ii. 1073 with water the sesquihydrate separates. Tables and a curve are given for the solubility of the sesquihydrate in water and the theoretical significance of these are discussed. Contrary to Oechsner de Coninck's statement (Abstr. 1901 ii 104) the constitution of the solution at 13.5' is about UO,(N@,) + 19H,o. The constitution of the cryohydrate is UO,(NO,),,28~93H,O at - 18.1'. Uranium nitrate is one of those salts for which the number repre- senting the degree of dissociation increases with increasing concentration of the solution. Z. K. The Solution and Precipitation of Titanic Acid. KARL BORNEMANN and H.SCHIRMEISTER (Metulluvgie 1910 7 646-649).- Contrary to the usual statement in text-books titanic acid which has been heated to 1000' is practically insoluble in sulphuric or hydro- fluoric acid. It the temperature of ignition does not exceed 700° solution in concentrated sulphuric acid is complete in fifteen minutes. Hydrofluoric acid has a rather greater solvent power. Fusion with potassium hydrogen sulphate readily brings about complete solution. It is not necessary to dissolve the product in cold water for if dilute sulphuric acid (1 2) is used solution takes place completely even if the liquid is boiled. After fusion with alkali carbonate and solution in hydrochloric acid the residue is difficult to wash and readily passes through the filter.This is avoided by the use of sulphuric acid (1 2) instead of hydrochloric acid. Orthotitanic acid may be precipitated from hot strongly acid solu- tions by the addition of ammonia without destroying it8s solubility in dilute acids. When metatitanic acid is dissolved in concentrated sulphuric acid boiling for more than a few minutes must be avoided or an insoluble precipitate is formed. No difference in this respect is observed between ortho- and meta-titanic acids. C. H. D. Zirconia and Erbia from Titanium Minerals. KARL A. HOF- MANN (Ber. 1910 43 2631-2636).-Hauser and Wirth have found that the zirconia contained in a number of zirconium minerals is not accompanied by a strange earth (this vol. ii 713) ; the author finds that the principal mineral investigated by him which differs from typical euxenite in that it has a very high titanium content contains zirconia which gives some strange lines in the arc-spectrum and also has a higher equivalent weight than zirconia prepared from zirconium silicat,e The mineral used was euxenite from Brevig and had the com- position Loss on Cb,O,.TiO,. Rare earths. SiO,. PbO. ZrO Fe,03. UO,. CaO heating 4'65 45.74 36.17 0.53 0-33 2-83 2-06 2'73 1.60 2 80% The zirconia was identified by the preparation of the double fluoride with potassium and from the mother liquors obtained in the recrystallisa- tion of this salt zirconia was prepared the arc-spectrum of which showed unknown lines (451 9.6 4322.65 3682.43 3662.29 3253.83 The rare earths comprised didymium erbium and holmium.ii.1074 ABSTRACTS OF CHEMICAL PAPERS. 3194.30 and 3031 -32) together with the known lines due t o zirconium and titanium. These lines still persisted after the titanium had been removed. The remainder of the paper deals with neo-erbium compounds. The erbium compounds contained in the rare earths mentioned above are purified from holmium and dysprosium by fractional crystallisation of the ammonium double oxalate (compare Abstr. 1908 ii 189). Fractional crystallisation of the acetylacetone compound from alcohol may also be used. Thulium and ytterbium may be readily separated from almost pure erbium sulphate by heating to 845Ofor ten hours ; on treating the residue with water the less basic portions remain undis- solved. The solution is evaporated to dryness the residue heated to 950' for thirty minutes and then treated with water when erbium oxide remains undissolved.By using the above methods an erbium material was obtained which gave a constant spectrum and a constant equivalent weight. After freeing it from impurities derived from the vessel used a bright rose-red oxalate was obtained Er2(C204\37 10H20. Former analyses have given 9H20. On drying in a vacuum over phosphoric oxide the ti*ihydrate is formed. The oxide results on heating the oxalate to 575"; it is obtained pure a t 8 4 5 O and then forms a rose-coloured powder which does not glow in cathode rays but gives a green discontinuous light in the bunseii flame. The reflexion spectrum is not altered by dilution with other oxides when no compound is formed. Atomic-weight determinations were made by transforming the sulphate into the oxide by heating a t 1055O and gave the mean value 167.68 (three determinations 0 = 16 S= 32.07).At 845' a basic sulphate Er20,,S03 is obtained. T. S. P. Colloidal Zirconium Silicide. EDGAR WEDEKIND (Zeitsch. Chem. Ind. Kolloide 1910 7 248-25 l).-Zirconium silicide obtained by the action of excess of silicon on potassium zirconium fluoride in the electric furnace has been converted into a colloidal form by Kuiel's method. The finely divided substance was treated successively with dilute acid and alkaline solutions at a temperature of 50-60' the treatment in each case being continued for about twenty-four hours. After a considerable number of such operations a dark brown colloidal solution of the silicide is obtained.Under the microscope the solution which has been kept for some time appears to be homogene- ous but the want of homogeneity is clearly seen in the ultra-microscope. The colloidal particles move towards the positive pole and are there- fore negatively charged. On the other hand colloidal zirconium is positively charged and coagulation takes place when solutions of the metal and of the silicide are mixed. Colloidal zirconium silicide is coagulated by various electrolytes but in comparison with the colloidal metal it is not a t all readily acted on by solutions of alkali hydroxides. Coagulation of the silicide is also brought about by freezing the solution and in this respect also it differs from the colloidal solution of zirconium. H. &I.D.INORGANIC CHEMISTRY. ii. 1075 Basic Thorium Sulphate. OTTO HAUSER (Bey. 1910 43 2776-277S).-The author claims priority to Barre (this vol. ii 718) in showing that Demarcay’s salt (Compt. rend. 1860 96 728) 3Tn(SO4),,ThO(S0,),4H,0 is really a mixture of Th(S0,),,2H20 and ThO(S0,),2H20 (compare Abstr. 1909 ii 54). He also confirms Barre’s result that a t 100’ the stable basic sulphate has the compo- sition ThO(S0,),2H20. At 125-180’ the stable basic sulphate is ThO(SO,),H,O. The author’s and Barre’s results show that in moderately dilute solutions of thorium sulphate the basic sulphate ThO(SO,) is produced which according to the temperature crystallises with one or two molecules of water. I n very dilute solutions the sulphate may be completely hydrolysed to the hydroxide.T. S. P. Preparation of Vanadium. WILHELN PRANDTL and BENNO BLEYER (Bey. 1910 43 2602-2603. Compare Abstr. 1909 ii 1022). -Vanadium may readily be obtained by the thermite reaction using the following mixture 100 parts of fused and powdered vanadium pentoxide 49.5 parts of aluminium powder 20 parts of calcium fluoride. The action is carried out in a magnesia crucible or better still in a box made of fluorspar. I n the latter case it is not necessary t o add the calcium fluoride to the reaction mixture. The vanadium regulus obtained is 70-80% of the theoretical quantity and is 95% pure. The impurity is chiefly oxygen ; possibly a lower oxide of vanadiumremains dissolved in the excess of vanadium and escapes the reducing action of the aluminium.T. s. P. Red Platinum as Analogue of Purple of Cassius. LOTHAR WOHLER and A. SPENGEL (Zeitsch. Chern. Ind. Kolloide 1910 7 243-249).-Experiments have been made to determine the cause of the red colour which appears when solutions of platinum salts are acted on by stannous chloride. These show that the red substance consists of colloidal metallic platinum in a very fine state of sub- division and that the formation of this in place of the more usual brown colloidal metal is due to the action of stannic chloride and its products of hydrolysis as protective colloids. The red colloid is also formed when the reduction of platinum salts is effected by means of a solution of phosphorus in ether if gelatin is added as a protective colloid. The identity of the two red substances has been established by spectroscopic observations. If the colloidal solution obtained by reduction with stannous chloride is shaken up with ethyl ether ‘or ethyl acetate the organic solvents take up the red colour and this is found to be connected with the solubility of stannic chloride in these media in which it plays the part of protective colloid. When the aqueous solution is diluted with a large volume of water or when the ethyl acetate solution is poured into water a chocolate- brown precipitate is obtained. According to Schneider (Ann. Phys. Chem. 1869 [ii] 136 105) this substance has the composition Pt,Sn,Olo. It is now found however that no definite compound is formed but that the composition of the precipitate varies very con- siderably with the conditions under which it is produced. Analogousii. 1076 ABSTRACTS OF CHEMICAL PAPERS. to purple of Cassius it appears to be a mixture of colloidal platinum and colloidal stannic acid and this view is supported by the similarity in the properties of the two substances. The blood-red colour which appears on reduction of silver nitrate by stannous nitrate in dilute nitric acid solution is similarly due to colloidal silver and not to the formation of what have been described as silver stannates. On account of the instability of the red colloidal silver the red solution quickly turns brown and deposits a reddish- brown precipitate. The red modification of silver cannot be obtained by reduction by means of an ethereal solution of phosphorus. H. 31. D.

ISSN:0368-1769    

DOI:10.1039/CA9109806054

出版商:RSC    

年代:1910

数据来源: RSC

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ii. 1076 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Probable Identity of Podolite with Dahllite. WALDEMAR T. SCHALLER (Amer. J. Sci. 1910 [iv] 30 309-3lO).-A comparison of the characters and analyses of dahllite (Briigger and Backstrom Abstr. 1890 714) and of podolite (W. Tschirwinsky Abstr. 1907 ii 481) [ = carbapatite of P. N. Tschirwinsky 19061 suggests the identity of these minerals The composition of dahllite was expressed as 2Ca3P2O8,CaCO3,~H2O ( = H,oCa70P4,C,o0,,,) and of podolite as 3Ca,P,0s,CaC0 ( = Ca70P42C70,s9). Action of Carbon Tetrachloride Vapours on Minerals and Application to Quantitative Analysis. PAUL JANNASCH (Bey. 1910 43 3135-3136).-8 claim for priority over Camboulives (this vol. ii 202 ; compare Abstr. 1909 ii 728 767). The following analyses of a fluorapatite from Renfrew County (Ontario) are given L.J . S. Deduct from P,O,. CaO. MgO. Fe,O,. K,O. Na.j3. H,O. F. 0 for P. Total. 39.68 54.67 1-34 0'49 0.50 0.92 0.12 3-75 -1.57 99'90 39'74 54-74 1.22 0'48 0.47 0'90 O.fO 3-68 -1.54 99.78 T. S. P. Identity of Stelznerite with Antlerite. WALDEMAR T. SCHALLER (Amer. J. Xci. 1910 [iv] 30 31 1-312).-For the orthorhombic stelznerite from Chili described by Arzruni and Thaddeeff (Abstr. 1899 ii 563) the formula was given as CUSO,,~CU(OH)~ whilst for the massive antlerite from Arizona described by Hillebrand in 1889 the formula 3CuSO 7Cu( OH) was deduced. A microscopical exam- ination of the latter shows that its optical characters so far as these can be determined do not differ from those of stelznerite and it is pointed out that the analyses of antlerite approximate to the simpler formula.The name antlerite having priority i t is suggested that this should stand for the species [but how far this rule should apply in the case of incompletely described or incorrectly determined minerals is doubtful 3. L. J. S.MINERALOGICAL CEEMISTRY. ii. 1077 New Kind of Vanadate in the Cupriferous Deposit of Bena (d)e Padru near Ozieri isassari). DOMENICO LOVISATO (Atti R. Accad. Lincei 1910 [v] 19 ii 326-333).-Analysis of the new mineral by Silvio Manis gave V,05. P,05. PbO. ZnO. CuO. Fe,O,. MnO. H,O. Total. 19.87 0.18 53-76 2.45 13-13 6'54 0.05 3.45 99'43 Its hardness is inferior to that of calcite,and it has D10'5 5.716. R. V. S. Further Occurrences of Tantalum and Columbium in Western Australia.EDWARD S. SIMPSON (Austral. Assoc. Report 1909 310-315).-The following analyses are given (I) Fergusonite from Cooglegong D 5.82-6*65 ; (11) Euxenite from Cooglegong D 5.37; (111) Microlite from Wodgina D 5.422 ; (IV) Ixiolite (5) from Wodgina D 7-36 ; (V) Cissseterite from Greenbushes. Ta205. Cb,O,. TiO,. SnO,. Tho,. Y,O,. Er,O,. Ce,O,. Di,O,} CaO. I. 55.51 2-15 2 20 - 1-02 23.00 8'38 0'94 - 2-18 II. 23.10 4-38 30.43 - 1.76 15.76 9'27 1'82 1-73 1'02 III. 73.54 3*62 - 0.90 - - - - 13.46 IV. 70.49 7-63 - 8-92 - - - - - 0.42 FeO. MnO. MgO. UO,. A1,03. K,O. Na,O. Ignition. Total. I. trace 0.87 - 1'18 - - - 3-36 100.79 11. trace 0-34 0.35 6'69 0.76 - - 2 *82 100-20 I I I . 3'64 0'60 0.42 - - 0.20 1-66 1 -28 99-32 IV. 1'34 10.87 0.37 - - - - 0.18 100.22 - - 100*00 V.0'61 - The analytical results for fergusonite agree with the usually accepted formula R,O,,Ta,O ; those for ixiolite with the formula 3Mn0,STa205,Sn02. T. 5. P. F. HART (Chem. Zeit. 1910 34 1168).-A fossil palm-tree found in a bed of clay of Xiocene age at Cuxhaven on the Oste a small tributary of the Elbe gave :- La,O - - - - - - V. 1.76 - - 97.63 - - - - - Analysis of a Fossil Wood. Insol. inHC1 Soluble in HC1 \ /I --___ Alkalis Moisture. CO,,H,O*. SiO,. (AI,Fe),OS. SO,. A1,0,. Fe,O,. CaO. MgO. SO and diff. 1-45 8.21 51.72 0.26 0'25 26'80 2-68 7'04 0'21 0'23 1.15 * Organic matter soluble in soda was also present. Two samples of the clay gave SiO,. ( A1 Fe),O,. CaO. MgO. SO,. Loss on ignition. 50.45 30.00 1-86 2.50 0'60 14'40 60.50 26.60 2.00 2 5 0 0'60 7 -95 The ratio of silica to sesquioxides is very nearly the same in the fossil as in the first of the clay analyses (namely 1.76 and 1-68 respectively ; in the second clay analysis it is however 2.27) ; but whilst in the clay the sesquioxides are insoluble in hydrochloric acid in the fossil they are almost wholly soluble.To explain this it is suggested that a t the time of the deposition of the clay when this was suspended in a very finely divided state or in colloidal solution the VOL. XCVIII. ii 73ii. 1078 ABSTRACTS OF CHEMICAL PAPERS. cellular organic matter of the wood exerted an adsorptive action and resolved the clay into aluminium hydroxide and hydrated silica. L. J. S. Barbierite a Monoclinic Soda-felspar. WALDEMAR T. SCHALLER (Amer.J. Xci. 1910 [iv] 30 358-359).-Barbier and Prost (Abstr. 1908 ii 863) have recently established the existence of a monoclinic soda-felspar (NaA1Si30,) isomorphous with orthoclase and dimorphous with albite. For this the name barbierite is proposed. The felspar from Kragero with only 1.15% K,O is nearly pure barbierite. Other analyses of soda-rich orthoclases have been given by Barbier (this vol. ii 419). L. J. S. [Minerals in Dacite from Victoria.] ERNEST WILLIKCTON SKEATS (Quart. J. Geol. Xoc. 1910 66 450-46S).-In a description of the rocks of the Dandenong district the following analyses by Plante and Richards are given of dacite (I) from Upway and of the minerals isolated from this namely biotite (11) formula 2( K,H)20,4(Fe,Mg)0,A1203,6 (Si,Ti)O ; hypersthene (111) formula 1 2(Fe,Mg)0,(Al,Fe)20,,16Si0 ; ilmenite (IV) formula (Fe,Mg)0,2TiO2.H2O. H20. SiOz. Ti02. A1203. Fez03 FeO. MnO. CaO. MgO. K2O. NazO. (105").(>105"). P&. Total.Sp.gr 1I.t 39 86 1 95 11.13 1'39 15'10 058 trace 9'SS 6.73 0'35 0'43 3.20 trace 99-60 3 16 111. 50'42 351 4.06 2.10 23'54 0'24 1.30 13.04 0-69 trace 0 10 0'6 0.92 99'98 3% I." 63'27 !'30 16'50 0 6b 5-1C) 0 0 3 4'18 2-48 2 6s 3 36 0 0 9 0'52 0.15 99'50 2-76 IV. - 07.28 - - 31.92 trace - O'SO - - - - - 100'00 4.56 * Also S (in pyrites) 0.16 ; LizO trace. t Also LizO trace. L. J. S. [Minerals Associated with Diamond in Rhodesia.] FREDERIC PHILIP MENNELL (Quart. J. Geol. Xoc. 1910 66 353-375).-1n a description of the geological structure of Southern Rhodesia the following analyses by W.C. Hancock are given of minerals from the '' blue ground " of the new Colossus diamond mine thirty-five miles north-east of Bulawayo I deep red pyrope; 11 small orange- coloured garnets from eclogite fragments in the '' blue ground '' ; 111 a more reddish garnet also from eclogite; IV deep green augite (chrome-diopside) with a pronounced parting parallel to the ortho- pinacoid. SiO,. A1,0,. CrzO,. Fe,03. FeO. MnO. CaO. MgO. H,O. Total. Sp. gr. I. 40'43 19'13 2'12 4.94 8.66 0.12 4.44 20.33 - 100'17 3.72 11. 40.44 23.69 0.32 6'51 11.38 0.60 9'86 7.72 - 100'52 3.75 111. 39-87 2147 0.28 4-95 8'10 0'23 12.32 12-89 - 100-09 3-64 IT. 53-93 1'90 0.70 5-97 2.67 - 13'11 20 08 1'63 99'99 - L. J. S. The Nature of the Pseudonepheline from Capo di Bow near Rome. FERRUCCIO ZAMBONINI (Rend. Accad. Xci. $'is Mat. Napoli 1910 [iiia] 16 83-88).-The pseudonepheline or pseudo- sommite of Capo di Bove has been re-examined. The crystallographicPHYSIOLOGICAL CHEMISTRY. ii. 1079 characters agree with those of nepheline but the refractivity is rather higher and the double refraction lower. SO,. A1,0,. Fe,O,. CaO. Na,O. K,O. Total. 39'91 33-04 2 '14 2.55 12-75 10.06 100.45 corresponding with (Na,K)AlSiO whilst nepheline always contains a higher proportion of silica. Pseudonepheline has therefore a com- position between that of kaliophilite KhlSiO and the silicate NaAlSiO which has only been obtained artificially. Analysis shows C. H. D.

ISSN:0368-1769    

DOI:10.1039/CA9109806076

出版商:RSC    

年代:1910

数据来源: RSC

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PHYSIOLOGICAL CHEMISTRY. Physiological Chemistry. ii. 1079 Relative Influence of the Heat and Chemical Impurity of Close Air. LEONAND E. HILL R. A. ROWLANDS and H. B. WALKER. The Influence of Alcohol on the Power t o Eold the Breath and Work. J. F. MACKENZIE and L. E. HILL. Compressed-air Illness I. Solubility of Compressed Air in Water and Oil. J. F. TWORT and L. E. HILL. 11. The Desaturation of the Arterial Blood as Measured by the Nitrogen Dissolved in the Urine. L. E. HILL J. F. TWORT and H. B. WALKER. Effect of Breathing Oxygen on the Nitrogen andoxygen of the Urine. L. E. HILL J. P. TWORT H. B. WALKER and R. A. ROWLANDS (Proc. physiol. Xoc. 1910 iii-iv iv v-vi vi-vii viii; J. Ph~siol 41).-In hot closed chambers with no ventilation the discomfort is caused by moisture rather than by chemical impurities.Half an ounce of alcohol extends the time during which a man can hold his breath while performing work. Various results showing that air is more soluble in oil than water are confirmed ; fat men should be excluded from caisson work. During decompression the nitrogen in the urine sinks; the nitrogen does not get into equilibrium with the atmospheric pressure under ten to fifteen minutes. During the breathing of oxygen the renal epithelium checks its entry into the urine; some of the dis- solved nitrogen can be got out of the body by this means but not so much as was expected. W. D. H. A Respiration Apparatus for Isolated Organs and Small Animals. OTTO COHNHEIM. The Gaseous Metabolism of the Musculature of the Small Intestine.0. COHNHEIM and DIMITRI PLETNEFF. The Gaseous Metabolism of the Stomach Mus- culature. 0. COHNHEIM and D. PLETNEFF. The Gaseous Meta- bolism of the Musculature of Stomach and Intestine during Insufficient Oxygen Supply and under the Influence of Barium Chloride 0. COHNHEIM and D. PLETNEFF (Zeitsch. physiol. Chern. 1910 69 89-95 96-101 102-105 106-107).-The apparatus described was constructed on the principle of the Atwater- Benedict machine and was used in the experiments on stomach and 73-2ii. 1080 ABSTRACTS OF CHEMICAL PAPERS. intestine which follow The intestine of cats is treated with mercuric chloride which destroys the cell9 of the mucous membrane and bacteria but leaves the muscle in active movement in Ringer’s solution. This produces 80-90 mg. of carbon dioxide per 100 grams of intestine per hour and uses up a corresponding amount of oxygen. The gaseous metabolism is furthered if oxygen is circulated direct through the capillaries.In the stomach musculature in strocg activity 170-175 mg. of carbon dioxide are produced per 100 grams per hour. In a previous research on intestinal muscle (Abstr. 1908 ii 209) a smaller figure was given. This is due to insufficient oxygen supply and not to the use of barium chloride in the experiments for that salt does not affect the amount of carbon dioxide produced. No reference is made to the work of Brodie and others on gaseous metabolism of the small intestine during rest and activity (this vol. ii 518). The figures there given are in terms of C.C. per gram per minute.Cohnheim’s figures for the intestine muscle (85 mg. of carbon dioxide per 100 grams per hour) may be reduced to the same terms and compared with Brodie’s C.C. of carbon dioxide in intestinal muscle 0.0071 (Cohnheim). Y 9 9 7 y epithelial cells of small intestine 0.0378 (Erodie’s The respiratory quotient is 0.78. ,9 Y ’ ’ 9 ) whole small intestine at rest 0.02 (Brodie) estimate). Brodie’s further estimate is taken as fairly accurate that the muscular coat accounts for 40% and the mucous membrane of the small intestine for the remaining 60%. If 60% of the intestine is producing carbon dioxide a t the rate estimated by Brodie and the remaining 40% at the rate determined by Cohnheim the whole intestinal wall will produce 0.23 C.C. of carbon dioxide per gram per minute; that is t o say a figure is obtained a little higher than that actually determined by Brodie and his colleagues.The correspondence is however very close taking into account that in Cnhnheim’s experiments the muscle was in active movement. The research illustrates again the low metabolism of muscle as compared with secreting epithelium. W. D. H. Composition of the Blood-gases in Chloroform Anaesthesia. GEORGE A. BUCKMASTER and JOHN A. GARDNER (J. Plhysiol. 1910 41 246-262).-The total gas in the blood of cats as compared to dogs is low (this vol. ii 969); as anzsthesia deepens this is increased and the increase is mainly due to carbon dioxide. The amount of oxygen sinks and the blood is dark in colour; this is probably because the chloroform unites with the haemoglobin and so prevents it combining with so much oxygen.This may explain the effect on the respiratory centre. Full analytical details are given including the amount of chloroform in the blood. W. D. H. The Permeability of Red Blood-corpuscles in Physiological Conditions especially to Alkali and Alkali-earth Metals. HARTOG J. HAMBURGER and F. BUBANOVIC (Proc. K . Akad. TVetensch. Amsterdam 1910 13 258-27O).-If a disturbance within physiological limits inPHYSIOLOGICAL CHEMISTRY. ii. 1081 the composition of the blood is produced between the corpuscles and serum a redistribution of the inorganic constituents takes place both as regards anions and cations.. Thus if 0.2% sodium chloride is added to serum sodium magnesium and calcium enter the corpuscles and potassium leaves them.If the serum is diluted with 10% of water sodium enters whereas potassium magnesium and calcium leave the corpuscles. Calcium enters the corpuscles when the blood is shaken with 5 vols. % of carbon dioxide. The fact that the corpuscles are permeable to cations is against the current view which is based on Gruber’s work. Griiber’s methods and results are criticised. W. D. H. Comparative Investigations on the Rotatory Properties of the Plasma and Serum of Dog’s Blood under Varying Conditions. I. EMIL ABDERIIALDEN and PAUL KAWOHL. 11. E. ABDERHALDEN and PAUL HAHN (Zeitsch. physiol. Chenz. 1910 69 1-22 50-56)-I. Plasma has a stronger Izevorotatory power than serum. Repeated bleedings lower the rotmation in both fluids but the change is not a great one.Feeding on 50-500 grams of meat causes no more change than occurs without feeding; there is no rise in the rotatory power. Some preliminary experiments on feeding with carbohydrates are also given but no noteworthy effect is seen unless large amounts of monosaccharides are given ; thus lzevulose raises and dextrose depresses the Isvorotation. Hunger causes considerable variations but nothing typical. There is no difference between the optical properties of carotid and jugular blood but the portal blood has always a higher rotation than that from other parts. 11. Injection of dextrin into the blood stream lowers the l~evorotation but the effect passes off in about twenty minutes. The lowering of rotation produced by bleeding lasts longer in fasting than in well-fed animals.W. D. H. The Influence of Large Quantities of Water on the Optical Properties of Blood-plasma and Serum. EMIL ABDERHALDEN and ERNST RUEHL (Zeitsch. physiol. Chem. 1910 69 57-59).-Large quantities of water mere given by the alimentary canal and this caused a noteworthy sinking of the rotatory power of the plasma and serum; this lasts for about four hours. SIGMUND FRANKEL and ALADAR ELFER (Biochem. Zeitsch. 1910 28 330-331).-Attempts by various methods of evaporation do not yield good results. A perfectly dry powder was obtained by the addition of anhydrous sodium sulphate (670 grams per litre of ox-serum). Autolysis of Normal Blood. J. C. SCHIPPERS (Biochem. Zeitsch. 1910 28,418-426).-Defibrinated blood undergoes autolysis which is accelerated by acetic acid ; proteoses leucine and tyrosine were found in the autolysed fluid.The active agent is destroyed by heat. The change is believed however to be in part due to a spontaneous cleavage of the protein molecule Blood-serum shows no autolysis but the red corpuscles do. W. D. H. A Method for Drying Serum. W. D. H. \V D. H.ii. 1082 ABSTRACTS OF CHEMICAL PAPERS. Hzemolyeis. 11. Haemolysis by Sodium Carbonate. OSRAR GROS (Arch. exp. Path. Yharm. 1910 63 341-346. Compare this vol. ii 51).-H~molysis produced by sodium carbonate runs on the same lines as that caused by ammonia. Within definite limits of concentration the time of induction is inversely proportional to the concentration of the salt and proportional to the amount of blood. W. D. H. The Hydrochloric Acid of the Gastric Juice of the Selachian Fishes.ERNST WEINLAND [with A. GROHMANN and TH. STEFFEN] (Zeitsch. Biol. 1910 55 58-69).-The method of Sjoqvist for estimating hydrochloric acid is not practicable in the presence of chlorides of the alkali earths. Hydrochloric acid is found even though none be present in the free state if an organic acid is present also. The gastric juice of the dog fish and other selachians contains little or no free hydrochloric acid. Statements to the contrary are due to the non-recognition of the two facts mentioned above. W. D. H. Variations in Quantity and Composition of the Pancreatic Juice during Secretions Provoked by Secretin. S. LALOU (Compt. rend. 19 10 151 824-827).-Repeated injection of secretin into dogs enables a regular supply of the pancreatic fluid to be obtained during several hours. The alkalinity and diastatic activity of the juice thus obtained gradually diminishes however the variation in lipolytic power being more marked than the diminution in tryptic or amylolytic activity.w. 0. w. Physiology of Digestion. 11. Total Chlorine of the Animal Body. RUDOLF ROSEMANN (Y’uger’s Archiu 1910 135 1’77-195. Compare Abstr. 1907 ii 706)-The author’s previous work on the hydrochloric acid of the gastric juice led to the present research. The methods used and results obtained by previous workers are summarised. The fetus is richer in chlorine than the new-born animal and the percentage amount diminishes still more after birth. The author’s values for the fully-grown dog average 0.12% of chlorine.I n the cat and mouse the figure is a little higher. W. D. H. Metabolism Experiments as Statistical Problems. H. L. RIETZ and H. H. MITCHELL (J. Biol. Chem. 1910 8 297-326).- Metabolism experiments should be studied mathematically as observa- tions on heredity are in order to exclude the deviations which occur in physiological processes and take place although surrounding conditions are made as constant as possible. W. D. H. Metabolism of Development. 11. Nitrogen Balance during Pregnancy and Menstruation in the Dog. JOHN R. MURLIN (Amer. J. Physiol. 1910 27 177-205. Compare this vol. ii 729).- Menstruation causes a retention of nitrogen which is to be regarded in part as a compensation for the blood lost. The first half of normal pregnancy is characterised by a loss of nitrogen from the mother’s body.This is probably due to the action of proteolytic enzymesPHYSIOLOGICAL CHEMISTRY. ii. 1083 produced by the embryo and not yet limited by the placenta in their action to the maternal blood. Nitrogen retention occurs in the last half of the pregnancy. W. D. H. The Importance of the Mechanical Part of the Work of Digestion in Relation to Metabolism in t h e Ox. KARL DAHM (Biochem. Zeitsch. 1910 28,456-503).-8 very important contribution to the much discussed question as to whether the work of the digestive organs is an important factor in metabolism as Zuntz maintains,.or not. A number of oxen were fed on different diets and their meta- bolism and heat production determined by examining faxes urine and gaseous interchanges. The results confirm Zuntz’s views.W. D. H. Digestion of Cellulose in Dogs and the Methods for Estimating Cellulose. HANS LOHRISCH (Zeitsch. physiol. Chem. 19 10 69 143-161).-The author’s previous conclusion that dogs are able to digest cellulose he finds on further work to be incorrect. Dogs do not digest cellulose. He still holds however that cellulose is digestible to some extent by man in spite of the criticisms of Scheunert. The Simon-Lohrisch method for the estimation of cellulose is regarded as the best. W. D. H. The Work of Digestion a f t e r Carbohydrate Food and its Dependence on the Physical Condition of the Nourishment. OTTO MULLER (Biochern. Zeitsch. 19 10 28,427-455).-Investigations on the gaseous metabolism of dogs show that this is much more increased by giving starch than by giving an equivalent amount of dextrose; the effect is also more prolonged after starch feeding.Older investigations on the question in which the gaseous interchanges were not examined are criticised. The original paper must be consulted for full analytical details and methods for calculating results; the main conclusion is that in starch feeding for every 100 calories of the starch digested 9.23 calories are produced over and above the inanition figure ; for dextrose the figure is only 5.61. When the carbohydrates are given in small quantities the difference is not noticeable. The low respiratory quotient found is due to the fact that the animals had fasted for two days before the experiment therefore much of the carbohydrate given would be stored as glycogen and fat used for combustion.W. D. H. Carbohydrate Metabolism in Carcinas mamas. E GRAF VON SCHONBORN (Zeitsch. Biol. 19 10,55,70-82).-In the crabs investigated glycogen is found in important amounts ; after twenty-five days’ inanition it does not wholly disappear ; its amount diminishes at first rapidly then slowly. On then feeding upon fish or injecting dextrose it is again laid on until its amount may reach 2.7% of the body-weight. I n the period of chitin formation in the shell the amount of glycogen is lessened. W. D. H.ii. 1084 ABSTRACTS OF CHEMICAL PAPERS. The Influence of Carbohydrate and Fat on Protein Meta- bolism. 11. The Effect of Phloridzin Glycosuria. E. YROVAN CATHCART and M. Ross TAYLOR (J.Physiol. 1910,41 276-2S4).- I n phloridzin glycosuria if the carbohydrate in the food is insufficient there is no excretion of creatine. The carbohydrate cannot be re- placed by fat. The output of creatine persists only as long as the glycosuria lasts. There is no apparent causal relationship between acidosis and excretion of creatine. The experiments were made on dogs. W. D. H. Parenteral Administration of Protein. KORNEL VON KOROSY (Zeitsch. physiol. Chem. 1910 69 313-326).-If a foreign protein is injected into the circulation it has been held that provided circula- tion through the alimentary canal is prevented it passes like a foreign substance into the urine. This is not the case proteins and proteoses pass into the urine in minimal amounts only even though the stomach and intestine are extirpated. The injected protein remains therefore in the organism but whether it is built into the tissues as is protein given enterally is as yet an open question. W.D. H. Metabolism Experiments with Elastin. EMIL ABDERHALUEN and ERNST RUEHL (Zeitsch. physiol. Chem. 1910 S9 301-309).- Elastin contains glycine in abundance leucine and very little glutamic acid ; histidine has been found in so-called hemi-elastin but trypt@ophan is absent In the present research on dogs elastin was prepared from the neck ligament of the ox; on artificial gastric digestion hemi-elastin was obtained but tryptophan was present although whether this was due t o impurities is doubtful. It is badly absorbed the faxes containing a high percentage of nitrogen; the animals lost weight and elastin is regarded as inferior to other proteins although it “ spares ” them to some extent. It is superior t o gelatin.After feeding on elastin Borchardt (Abstr. 1908 ii 957) stated that hemi-elastin was discoverable in the blood and urine these experiments were repeated with a wholly negative result. W. D. H. The Assimilation of Natural and Artificial Nourishment. 11. ARNOLD ORGLER (Biochem. Zeitsch. 1910 28 359-3’73).- Puppies of the same litter were fed some on cow’s milk and some on their mother’s milk. They were killed and analysed some a t four and some a t six weeks of age. Those fed in the natural way grew more rapidly in weight and strength than the others and their bodies con- tained more fat nitrogen ash and calcium.The puppies fed on cow’s milk took i t freely and were found with enlarged stomachs after death. The putting on of fat per kilo. of body-weight was more rapid than in those artificially fed. If the figures are reckoned on the fat- free body the naturally-fed animals show a higher percentage of dry residue but the nitrogen ash and calcium are about equal in the two sets of animals Dog’s milk is richer than cow’s milk in protein and ash and is of greater calorific value. Analytical details are given in full and compared with those of previous workers. w. 1>. H.PHYSIOLOGICAL CHEMISTRY. ii 1085 Distribution of Fluorine in the Human Organs. EMIL ZDAREK (Zeitsch. physiol. Chem. 1910 69 127-137).-Fluorine is widespread in the organs; the quantity is always small and is relatively greatest in liver kidneys and bone Analyses are given in full.W. D. H. Detection of Phosphates [in Tissues] with the Molybdate Reagent. RAPHAEL ED. LIESEGANG (Chenz. Zeit. 1910 34 1158).- Experiments showing that for histological purposes the application of the ammonium molybdate-nitric acid reagent does not localise the phosphates in tissues. L. DE R. Incineration of Microtome Sections. RAPHAEL ED. LIESEGANG (Biochem. Zeitsch. 1910,28,413-417).-An attempt was made in the direction of localising the occurrence of certain elements in micro- scopic section by incinerating them. In the early stages of heating the blackening indicates the position of carbonaceous material and here as also in the later stages of complete incineration it is still possible t o identify the tissue elements especially in thin sections. Attempts thus to localise iron microchemically were not successful as the iron is again " masked " as oxide.A similar failure attended attempts to localise iodine in the thyroid and the various reactions for the detection of phosphorus are either not sufficiently characteristic or worthless. W. D. H. The Aldehydase in Animal Tissues. FR. BATELLI and LINA STERN (Biochem. Zeitsch. 19 10 29 130-151).-By aldehydase is meant the ferment which can convert an aldehyde into a mixture of the corresponding alcohol and acid. I n the absence of oxygen the activity can be measured by estimating the amount of acid produced. I n the presence of oxygen certain aldehydes are oxidised further t o the acid although in many tissues the amount of alcohol-oxydase is very small.Acetaldehyde is changed in most tissues more rapidly than salicylaldehyde. Calf's spleen is an exception in this respect. Formaldehyde does not readily undergo the change. The aldehydase is contained in most tissues especially in the liver of the horse. Preparations containing aldehydase can be produced by precipitation of the tissues by acetone. The ferment acts best in slightly alkaline medium the optimum temperature being 60". The rate of reaction was also studied. s. B. s. Lipoids of the Brain. 11. A New Method for the Prepara- tion of the Galactosides and of Sphingomyelin. OTTO ROSENHEIM and M. CHRISTINE TEBB (Proc. physiol. Xoc. 1910 1-11 ; J. Physiol. 41. Compare Abstr. 1909 i 282).-Cholesterol is first removed by extraction with cold acetone and then lecithin and kephalin by extraction with ether or light petroleum; the residue is then reduced to a fine powder and extracted with cold pyridine; the extract is reddish in colour and shows an absorption spectrum similar to that of haemochromogen; it is poured into acetone and a bulky precipitate of impure galactosides (phrenosin and kerasin) is thusii.1086 ABSTRACTS OF CHEMICAL PAPERS. obtained ; these can be separated by fractional crystallisation from 85% alcohol at 30" and O" and subsequently purified by several methods. If the residue is now extracted with warm pyridine (40-45O) sphingomyelin is dissolved out which is precipitated by cooling to room temperature and subsequently purified.Molisch's reaction is a very delicate one for the detection of the galactosides. W. D. H. Lipoids. XIII. Composition of the Spinal Cord. SIGMUND FRANKEL and LUDWIG DIMITZ (Biochem. Zeitsch. 1910 28 295-319). -The spinal cord contains 74% of water 18% of lipoids (being the part of the central nervous system richest in these substances) and 8% of the proteins described by Halliburton who however put the percentage higher. The amount of water increases with age. The cholesterol present (4%) is in the free condition as in the brain. A great part of the unsaturated phoephatides consists of kephalin ; the saturated lipoids are only present to the extent of 1.5%. W. D. H. Union of Certain Poisons with Cardiac Muscle. HORACE M. VERNON (J. Physiol. 1910 41 194-232).-Alcohol added to Ringer's fluid perfused through the tortoise heart lessens the amplitude of the heart's contraction ; after about twelve minutes the amplitude remains at a small but constant level ; this effect is removed by perfusing with pure Ringer's solution. Ether and chloroform act in the same way but smaller doses are required to produce the same effect as alcohol ; their action is also reversible ; the concentration of the poison does not affect this result.Hydrocyanic acid acts in the same way except that the effect is not proportional to the con- centration ; greater concentrations than O*Ol% permanently injure the heart. Probably the same amount of poison is united to the cardiac substance in spite of variations in its concentration. Sodium fluoride acts somewhat in the same way ; on washing out with pure saline the ventricle usually shows one to three huge waves of tonus oscillation.Formaldehyde very slowly reduces the contractions to a constant level proportional to the concentration (0.001 to O*OOS%) and recovery on washing out is very slow. Alcohol ether and chloroform slow and may stop the heart. Formaldehyde hydrocyanic acid and sodium fluoride seldom stopped the heart absolutely and in many experiments did not affect its rate. Hearts depressed in vitality are more sensitive to the action of poisons especially of chloroform. It is regarded as probable that alcohol ether and chloroform enter into a loose union with the colloidal lipoids or other constituents of the cardiac tissue by means of. molecular valencies whilst hydrogen cyanide sodium fluoride and formaldehyde enter into definite chemical combination by means of atomic valencies.W. D. H. Autolysis. WALTHER LINDEMANN (Zeitsch. Biol. 1910 55 36-52).-Autolysis in the livers of rabbits cats and dogs was studied under aseptic conditions. Protein hydrolysis acid formation and development of gas occur only if the organs are kept a t 37O.PHYSIOLOGICAL CHEMISTRY. ii. 1087 Carbon dioxide and hydrogen appear in most variable proportions ; hydrogen may be absent in the case of the rabbit. No constant relation- ship mas found between the production of carbon dioxide and volatile fatty acids ; this is against a fatty acid fermentation of carbohydrate. The possibility of the acids arising from protein was shown by the occurrence of de-amidation.W. D. H. The Behaviour of the Fat of Organs in Autolysis and on Preservation Under Aseptic Conditions. KOHSHI OHTA (Biochem. Zeitsch. 1910 29 1-12).-To investigate the question as to whether fat can be formed from proteins liver and heart muscular tissues were preserved in the cold and a t 37-40’ with chloroform water and the amounts of fatty acids in the unchanged tissues together with the cholesterol in the changed and unchanged tissues were estimated. It mas found that there was no increase of fatty acid produced under any conditions in the liver tissue whereas the results in the heart muscular tissue were irregular probably owing to the want of homo- geneity in the original tissue. Owing to the small quantities of cholesterol and the conseyuent uncertainties due to experimental error no conclusion could be drawn as to whether this substance increases in amount or not.s. B. s. The Oxidation Processes of Lipoids of the Spinal Column. E. SIGNORELLI (Biochem. Zeitsch. 1910 29 25-30).-1t has already been shown by Scaffidi that the nervous tissue especially during degeneration absorbs relatively large amounts of oxygen. The author now shows that the lipoids prepared from fresh nervous tissue also absorb oxygen owing probabiy to the presence of unsaturated lipoids. The experiments were carried out by means of a microspirometer. S. B. S. The Amount of Erepsin in Blood-free Organs. OTTO COHNREIM and DIMITRI PLETNEFF (Zeitsch. physiol. Chern. 1910 69 108-1 12).-Vernon found the duodenal mucous membrane to be richest in a peptolytic enzyme (erepsin) whilst among the organs the kidneys possessed most and the blood least.He determined this colori- metrically by the biuret test. Abderhalden uses the splitting off of tyrosine from glycyl-tyrosine as his test for such enzymes. In the present research a slight modification of Vernon’s method was employed to test the presence of erepsin in cat’s organs (kidneys lungs muscles); the results confirm those of Vernon; the organs were freed from blood by Ringer’s solution. Erepsin or a t any rate a peptolytic enzyme is therefore present in the tissue cells independently of the blood. W. D. H. The Isolated Kidney. The Influence of Pulse Pressure upon Renal Function. DONALD R. HOOKER (Amer. J. Physwl. 1910 27 24-44).-A perfusion apparatus for the dog’s ,kidney is described which yields a pulsatile wave of pressure similar to the normal pulse The amount of urinary filtrate and the rate of blood flow vary directly as the magnitude of the pulse pressure; the amount ofii.1088 ARSTRACTS OF CHEMICAL PAPERS. protein varies inversely as this magnitude; in all cases the mean perfusion pressure was constant. W. D. H. The Cortex of the Suprarenal Body. K. KAWASHIMA (Biochem. Zeitsch 1910 28 332-339).-Extracts of the cortical region of the horse’s suprarenal contain no enzyme capable of destroying adrenaline Small quantities of adrenaline or a related substance are present. W. D. H. The Behaviour of the Chromaffine Substance of the Suprarenal Body in Hunger and Under the Influence of Potassium Iodide.F. VENULET and G. DMITROWSKP (A~ch. exp. Path. Pharm. 1910,63,460-464).-1n inanition the chromaffine sub- stance of the suprarenal is diminished ; administration of adrenaline under these conditions prolongs life Potassium iodide is inhibitory towards the secretion of adrenaline and this in addition t o its depressor action is considered to explain its therapeutic use in arteriosclerosis. W. D. H. The Peptide-splitting Enzyme of Ovaries. A. KOBLENCK and WALTHER LOB (Biochem. Zeitsch. 1910,29 102-103).-The ovaries of rabbits and pigs contain an enzyme capable of hydrolysing glycyl- tryptophan. S. B. S. Changes in the Skin following the Application of Local Anesthetics. I. Ethyl Chloride. SHEPHERD IVORY FRANZ and WILLIAM C. RUEDICIER (Amer. J.Physiol. 1910 27 45-59).-Ethyl chloride is au anaesthetic and analgesic ; analgesia (insensibility to pain) being the more persistent. This is in favour of the view that pain is a sensation subserved by nerve- and end-organs distinct from those concerned in tactile impressions. Sensations of temperature are dulled. W. D. H. Laxatives and the Calcium of the Intestine. RICHARD CHIARI (Arch. exp. Path. Phaym. 1910 63 434-440).-Saline purgatives which precipitate calcium ions increase the calcium in the intestinal wall and calomel and alkaloids lessen it. W. D. H. Is the Stoppage of Rhythmic Contractions in a Solution of Pure Sodium Chloride Due to Increased Rate of Oxidation? JACQUES LOEB and HARDOLPR WASTENEYS (Biochem. Zeitsch. 1910,28 350-352).-Direct measurements show that there is no increased absorption of oxygen due to the presence of sodium chloride in solutions containing organisms which undergo rhythmic contractions so that the question in the title is answered in the negative.The retarding action of sodium chloride on the rhythmic contractions of Medusa is not removed by addition of sodium cyanide. G. S. Production of Light by the Firefly. JOSEPH H. KASTLE and F. ALEX. MCDERMOTT (Amer. J. Physiol. 1910 2’7 122-151).-Three thingsare concerned in the production of light by living organisms thePHYSIOLOGICAL CHEMISTRY. ii. 1089 photogenic substance water and oxygen. The first is characterised by extreme irritability but its composition is unknown. Chemical stimuli especially ether chloroform carbon disulphide carbon tetra- chloride nitrobenzene and nitrites of certain metals cause a con- tinuous formation of light in the firefly whereas normally light emission is intermittent resembling a series of luminous explosions.Of the substances tried sulphur dioxide is the most toxic. Great diminution of atmospheric pressure causes emission of light in the living animal and in the detached luminous organ. The photogenic material can be dried in a vacuum and retains its power to emit light when moistened for at least thirteen months. W. D. H. The Secretion of the Infundibular Lobe of the Pituitary Body and its Presence in Cerebrospinal Fluid. HARVEY CUSHINGI. and EMIL GOETSCH (Amer. J. Physiol. 1910 27 60-86).-The view that the active principle of this gland is secreted into the ventricular cavity is supported by the discovery that the cerebrospinal fluid con- tains s substance which acts on blood-pressure like ‘‘ pituitin.” This can be demonstrated in concentrated specimens of the fluid.Pituitin is believed to be a product of the hyaline substance of the pars nervosa. W. D. H. The Reducing Properties of Milk Liver and Yeast. LEOPOLD ROSENTEALER (Zeitsch. Nahr. Genussm. 1910 20 448-453).-From the results of experiments in which the action of milk on phenylgly- oxylic acid was investigated the author comes t o the conclusion that the reducing power of milk on such substances as the methylene-blue of Schardinger’s reagent (Abstr. 1903 ii 190) etc. is due to bacterial action and not to that of enzymes. The analogous actions of liver D.ACKERMANN and FRIEDRICE KUTSCHER (Zeitsch. physiol. Chem. 1910 69 265-272).-The name aporrhegma is given t o the decomposition products of protein amino-acids formed by physiological processes in the living plant or animal and includes the common ptomaines and acids formed by putrefaction. Attention is drawn to the fact that although methylated nitrogenous compounds are presert in large quantities in vegetable tissues they are rarely met with in animal tissues. Methylated glycine has been extracted from the muscles of Crangon vulgaris Astmusfluviatilis and Acanthias vulgaris but does not appear to be present in the muscle of mammalians. It is suggested that in warm-blooded animals the nitrogenous products are got rid of by processes of oxidation but that in plants and cold- blooded animals they are removed by means of complete methylation.Methylation can occur in the case of warm-blooded animals when oxidation is stopped to an appreciable extent for example in cases of phosphorus poisoning. A list of aporrhegma and their corresponding amino-acids is given and also a list of methylated aporrhegma. A New Aporrhegma Prepared by Bacterial Agencies. D. ACKEBMANN (Zeitech. physiol. Chem. 1910 09 273-281. Compare this vol. i 419).-Lysine mixed with Witte’s peptone and dextrose and yeast are due to the same cause. w. P. 5. Aporrhegma. J. J. S.ii. 1090 ABSTRACTS OF CHEMICAL PAPERS. undergoes bacterial putrefaction in the presence of a small amount of putrefying pancreas and after nineteen days at 364 yields appreciable amounts of pentamethylenediamine which can be isolated as the picrate or aurichloride.A small amount of a product which yields a readily soluble platinichloride is also formed. Arginine under similar conditions yields tetramethylenediamine and 6-aminovaleric acid but not agmatine and glutamic acid yields y-amino- butyric acid (compare Schotten Abstr. 1883,813 ; Gabriel ibid. 1890 360) by the elimination of carbon dioxide. It has not been found possible to isolate methylamine and ethylamine from the products formed by the action of anaerobic bacteria on glycine and alanine. J. J. S. A Methylated Aporrhegma from Animal Tissues. R. ENGELAND and FRIEDRICH KUTSCHER (Zeitsch. yhysiol Chem. 19 10 69 282-285).-The y-aminobutyric acid obtained from glutamic acid (compare Ackermann preceding abstract) is identical with the synthetical acid.The aurichloride C,H-902N,HAuCl crystallises in glistening plates m. p. 138'. When methylated the y-amino-acid yields a product from which an aurichloride C7H,60,N,HAuCl can be obtained identical with the aurichloride m. p. 603O from y-butyrobetaine chloride isolated by Takeda (this vol. ii 797) from the urine of dogs poisoned by phosphorus. has m. p. 222' (decomp.). The occurrence of this betaine in substances of animal origin is due to the decomposition of glutamic acid and the methylation of the y-aminobutyric acid. The a-hydroxy-y-butyro- betaine formed in muscle extract is probably the first oxidation product of y-butyrobetaine. J. J. S. The platinichloride of the ethyl ester (C6H,,N0C1O,Et),PtCl6 Distribution of Nitrogen in the Intestinal Excreta.HENRI LABBI~ (Compt. rend. 1910 151 822-824).-Normsl human faxes were extracted successively with ether benzene aqueous sodium carbonate and glacial acetic acid. Nitrogen was determined in the original faxes in each extract and in the insoluble residue. The results are given in tabular form. The benzene extract appeared to contain the substances of the lecithin type whilst the alkaliae extract probably contained the amino-acids. w. 0. w. The Secretion of Urine. JOSEPH BARCROFT and HERMANN STRAUB (J. Physiol. 1910 41 145-167).-The diuretics studied fall into two groups (1) those which produce urine without alteration in the gaseous exchange of the kidney (Ringer's solution and sodium chloride in hyper- and hypo-tonic solutions) ; (2) those which cause increased gaseous exchange (urea caffeine sodium sulphate phloridzin).I n the case of urea and caffeine there is a definite poisoning action as shown by subsequent depression of the gaseous exchange. The dis- tinctive features of the urine produced by the second class are attained by a process of secretion on the part of the tubules and not by a process of re-absorption. After poisoning the cells by corrosivePHYSIOLOGICAL CHEMISTRY. ii. 1091 sublimate or by the diuretics of the second class a flow of urine can still be produced by the first class of diuretics; the urine so produced appears to be isotonic with the blood-serum. Clamping the kidney vessels for fifteen minutes after washing out with Ringer’s solution does not abolish its power of secretion.The special interest of the research is the action of diuretics of the first class and these produce urine independently of secretory activity (as judged by the absence of increased metabolism) and so their action must be attributed to mechanical filtration ; the experimental methods adopted were such that changes in rate of blood flow or of blood pressure could be excluded. The proteins of the blood-plasma in virtue of their osmotic pressure would attract water into the blood; the capillary pressure would drive water into the urine. Suppose for instance that the capillary pressure is equal to 27 mm. of mercury and that the osmotic pressure of the proteins is a little lower say 25 as it probably is in normal circumstances then the available pressure for filtration would be 2 mm.If the amount of protein in the blood-plasma were reduced to half the osmotic pressure will be reduced to 12.5 and the available filtering pressure is thus 14.5 or seven-fold increase and diuresis will occur. This argument was justified by testing it as follows the animal was bled very considerably and the blood replaced by Ringer’s solution containing blood corpuscles in suspension ; the diuresis so produced was very considerable although the blood-pressure was very low and this was attended with no increase in the gaseous exchange. W. D. H. A Comparison of the Total Nitrogen Excretion of either Kidney in Normal Individuals. THEODORE B. BARRINGEB jun. and BENJ. S. BARRINGER (Amer. J. Physiol. 1910 27 119-121).- Observations were made on eleven young men.One ureter was catheterised a bladder catheter collecting the urine from the other kidney. Details are given of the quantity of urine in periods varying from twenty to one hundred and twenty minutes secreted by each kidney also the total nitrogen and the sum of urea and ammonia nitrogen. The differences noted are usually small. W. D. H. The Excretion of Perenterally Administered Creatine in Mammals. CORNELIS A PEKELHARING and C. J. C. VAN HOOCEN- HUYZE (Zeitsch. phpsiol. Chem. 19 10 69 395-407).-1njection of creatine into the blood-stream of rabbits led t o the result that this substance is in part decomposed in the body and partly excreted as creatinine by the kidneys. The liver appears to be specially concerned in its destruction and in its conversion into creatinine.W. D. H. The Excretion of Organically United Phosphorus in Urine. KURA EONDO (Biochem. Zeitsch. 1910 28 200-207.).-Previous work on the organic phosphorus compounds of the urine in health and disease have shown that they are increased by the administration of glycerol-phosphates and lecithin. I n the present research a dog was fed on horse-flesh and lard and then to this were added for two or three days’ periods brain casein and thymus. On normal days theii. 1092 ABSTRACTS OF CHEMICAL PAPERS. organic phosphorus in percentage parts of total phosphorus averaged 2.7 on thebrain days3.3 and on the casein and thymus days 1.5. W. D. H. The Influence of the Fat of the Food Ingested on the Excretion of the Acetone Substances.GUNNAR FORSSNER (Chem. Zentr. 1909 ii 1759; from Xkand. Arch. Physiol. 1909 22 349-392).-The excretion of acetone and P-hydroxybutyric acid depends on the food ingested. After meals there is a regular increase in the excretion of acetone substances and the missing of a meal causes a distinct change in the regular curve representing the excretion and a marked diminution in the amounts excreted. The excretion depends on the fat ingested ; no difference could be detected between the action of the higher fatty acids (lard etc.) and the lower fatty acids (butter). When the store of glycogen in the body had diminished relatively small quantities of fat caused acidosis similar to that of severe diabetes. S. B. S. The Influence of Muscular Work on the Excretion of Acetone Substances with Diets Poor in Carbohydrates.GUNNAR EORSSNEE (Chem. Zentr. 1909 ii 1760; from Xkand. Arch. Physiol. 1909 22 393-406).-On different days certain amounts of muscular work were performed (marching) which were in the ratios of 1 2 3 and 4. The average diet consisted of 111.7 grams protein 239 grams fat and 59.4 grams carbohydrates. Muscular work was found to diminish the body reserve of carbohydrates which are concerned in the formation of acetone substances. This diminution was however only proportional to the amount of work performed within certain limits. The maximal action under the condition of experiments was attained by a forced march lasting for two to thirty-six minutes. S. B. S. Melanuria. HANS EPPINGER (Biochenz.Zeitsch. 1910,28 181-192). -The origin of the black pigment which occurs in certain malignant tumours and passes into the urine is obscure and the suggestion that it originates trom tyrosine by the action of a tyrosinase is due to experiments in vitro only. The present research shows that this pigment (melanin) originates from tryptophan. By feeding with tryptophan the excretion of the pigment is increased threefold whereas tyrosine and phenylalanine the parent substances of homo- gentisic acid have no effect. The urine is sometimes darkly coloured when passed sometimes the darkening comes on after exposure to the air but in all cases of melanotic tumour i t appears on the addition of oxidising agents; the material in the urine is then not melanin but melanogen.This can be precipitated from the urine with sulphuric acid and mercuric sulphate and can then be dissolved out from the precipitate by a method which is described in full and finally obtained in crystalline form. These crystals show all the colour and other reactions of melanogen as contained in the original urine. The following formula was calculated from its percentage composition C,H,,O,N,S and it is regarded provisionally as a hydroxy-N-methyl- pyrollidinecarboxylic acid in the form of an ethereal sulphate. AnotherPHYSIOLOGICAL CHEMISTRY. ii. 1093 substance was separated from the same urine ; it is probably related to the first but this requires further investigation. W. D. H. Acapnia and Shock. VII. Failure of the Circulation. YANDELL HENDERSON (Amer.J. Physiol. 1910,27 152-176. Compare this vol. ii 622).-The essential factor in the circulation in shock is not heart failure but failure of the veno-pressor mechanism which consists in part of the tonus of the tissues and in part of osmotic processes. Tonus is largely dependent on the carbon dioxide they contain and when the tension of carbon dioxide (regulsted by the respiratory centre) is diminished in acapnia the blood stagnates in the venous reservoirs. Acapnia upsets osmotic processes ; water passes out of the blood into the tissues and is ultimately followed by tissue asphyxia and acidosis W. D. H. The Fundamental Constituents of Tumour Cells. EMIL ABDERHALDEN and FLORENTIN MEDIBRECEAKU (Zeitsch. physiol. Chem. 1910 69 66-71).-Tyrosine glutamic acid and glycine were estimated in the cell proteins derived from various malignant tumoms.The different kinds of tumours all yielded the three amino-acids in approximately the same proportion. W. D. H. The Theory of t h e Wassermann Reaction. E. GATZ and R. INABA (Biochem. Zeitsch. 1910 28 374-391).-Sachs and Rondoni have shown that dilution of the alcoholic extract Lo€ the syphilitic liver with salt solution causes a cloudiness which varies as the dilution is effected slowly or rapidly. The manner of dilution influences the power of the extract in uniting with complement and they explain this as due to a physical cause namely the size of the particles in suspension. There is an undoubted alteration as Sitchs and Rondoni described and t h i s disappears on cooling ; moreover the difference does not run parallel to the change in hzmolytic power ; the latter however does not remain unaltered.Sharper results are obtained in extracts diluted slowly and those who use the Wassermann reaction for the biological detection of syphilis must recognise the importance of this factor. It appears doubtful if the explanation is wholly physical. W. D. H. Serological Studies with the Help of the Optical Method. XI. Parenteral Administration of Carbohydrates. EMIL ABDERHALDEN and GEORG KAPFBERGER (Zeitsch. physiol. Chem. 1910 69,23-49).-Sucrose injected either into the blood or subcutaneously is inverted in the blood but great differences are seen in different animals. Lactose is also affected but not raffinose. After the injection of lactose dog's serum or plasma inverts sucrose and lactose but not raffinose. The action of the these fluids on the two disaccharides is noticeable seven to eight hours after a subcutaneous injection of either and lasts a t least fourteen days.Whether the urine has the same power has not yet been investigated. The agent in the blood that acts on the sugars dialyses into distilled water. A temperature of 60" destroys the power and of 4' lessens it. W. D. H. VOL. XCVIII. ii. 14ii. 1094 ABSTRACTS OF CHEMICAL PAPERS. The Influence of Pharmacological Agents on Oxidation in the Organism. JULIUS BAER and WILHELM MEPEHSTEIN (Arch. exp. Path. Pharm. 1910 63 441-459).-The importance of oxidation as a source of energy and the way in which body functions are influenced by drugs acting on oxidation processes are well illustrated by recent work on narcosis.In the present research the point investigated was acetone formation in the liver perfused with various drugs namely potassium cyanide chloral hydrate trichloroacetic acid dimethylbarbi- turic acid or ethylbarbituric acid (veronal) salicylic acid salicyl- aldehyde saligenin p-hydroxybenzoic acid and aldehyde and m-hydroxy- benzoic acid and aldehyde. All of these inhibit acetone formation in varying degrees but the figures given show that the variation is not proportional to their effect on oxidation ; indeed some increase oxida- tive processes. I n the oxidation of butyric and hydroxybutyric acids in the liver two different processes or factors have therefore to be dealt with W. D. H.Behaviour of Phloridzin a f t e r Extirpation of the Kidneys ERICH LESCHKE. Answer t o t h e Preceding. KARL GLAESSNER and ERNST P. PICK (P-iiger’s Archiv 1910 135 171-175 176. Compare this vol. ii 53O).-Polemical. Both sides maintain their original position. W. D. H. Quantitative Investigations on the Chemistry of Stroph- a n t h i n Action. WALTHER STRAUB (Biochem. Zeitsch. 1910 28 393-407).-Alkaloids which act on certain organs such as the heart can be washed out and re-obtained in the washings and their action is thus reversible. This is not the case with the digitalis glucoside. Strophanthin is in this relation similar to alkaloids and its action is largely reversible. Tested on a frog’s heart by perfusion the reaction is proportional to the concentration of the drug and there is probably a chemical action between the cell constituents and the glucoside although very little of the latter is used in the combination or inter- action and there is no storage in the heart muscle.W. D. H. The Systolic and Diastolic Heart-Action of Strophanthin. N. WERSCHININ (Amh. exp. Path. Phccrm. 19 10 63 386-404).-This drug in Ringer’s solution applied to the exterior or interior of the frog’s heart leads in small concentrations to diastolic stoppage in medium doses t o systolic stoppage and in high concentrations to diastolic stoppage and paralysis. Mixed with blood-serum the toxic power is much increased. This is in part due to the lipoids present and lecithin exerts a similar action but the effect in producing systolic stoppage appears to be specially due to the salts of the serum particularly those of calcium but calcium salts only exert this influence when applied endocardially.W. D. H. The Action of Strophanthin on the Blood-Vessels. MAX K ASZTAN (Arch. exp. Path. Pharm. 19 10 63 405-423).-The effect of members of the digitalis family in raising arterial pressure is in part due to vaso-constriction and large doses will soon contract thePHYSIOLOGICAL CHEMISTRY. ii. 1095 kidney blood-vessels and lessen the flow of urine. The present research specially takes up this point and the organs of cats rabbits and dogs were perfused with strophanthin in Ringer’s solution. Solutions OF one or more per million coilstrict the blood-vessels of kiduey and intestine ; concentrations below this dilate them but here a difference between the kidney and intestine is noted for smaller concentrations which constrict the intestinal will still dilate the kidney blood-vessels. W.D. H. [Physiological] Action of Atropine Pilocarpine and Physos- tigmine. ARTHUR R. CUSHNY (J. Physiol. 1910 41 233-245).- Pilocarpine causes contraction or inhibition of the cat’s uterus accord ing to the condition of the organ in this resembling the effects of adrenaline or hypogastric stimulation. Its contractor action is antagonised by ergotoxine as is that of adrenaline or electric stimulation. It diff ors from adrenaline in being antagonised completely by atropine whether it contracts or inhibits the uterus. Physostigmine contracts the uterus and is antagonised by atropine. It is suggested that pilocarpine and atropine act on receptive substances associated with the nerve impulse path t o the uterus but do not lie actually on this path.Physostigmine may probably affect the receptors associated with the augmentor path only. I n the case of other abdominal organs the same explanation is regarded as tenable whilst in other cases the receptive substances are regarded as lying on the impulse path since this is interrupted by atropine. W. D. H. The Behaviour of Morphine in the Frog. BRONISLAW FRENKEL (Arch. exp. Path. Pharm. 1910 63 331-340).-Most previous workers on morphine have employed warm-blooded animals. Frogs differ from these in the prolonged period of primary excitation culminating in tetanus and in manifesting no immunity. Morphine is retained for a long time in the frog’s body ; after eight days it is however all eliminated mainly by the alimentary tract from which 65% of the amount given is recoverable ; comparatively little (10%) is destroyed in the body.None is found in the central nervous system b,ut the liver and next to that the muscles contain most. The des- truction is increased by an elevation of body-temperature and of oxygen tension. W. D. H. Influence of the Concentration of Hydroxyl Ions in a Sodium Chloride Solution on the Relative Anti-Toxic Action of Potassium and Calcium. JACQUES LOEB (Biochent. Zeitsch. 1910 28 176-180).-The poisonous action of sodium chloride on the developing fertilised eggs of the sea-urchin is neutralised to a greater extent by potassium than by calcium in neutral or slightly acid solution; in alkaline solution on the other hand calcium is more effective than potassium. I n all cases the effect of a mixture of potassium and calcium is greater than the sum of the separate effects.Addition of alkali to a mixture of potassium and sodium chloride increases the poisonous action whereas alkali renders a mixture of sodium and calcium chloride less poisonous. G. S. 74-2ii. 1096 ABSTRACTS OF CHEMICAL PAPERS. Why Does Sodium Cyanide Diminish the Poisonous Action of Sodium Chloride on Sea-Urchin’s Eggs ? JACQUES LOEB and HARDOLPH WASTEKEYS (Biochem. Zeitsch. 1910 28 340-349).- Warburg (this vol. ii 628) accounts for the poisonous action of sodium chloride on sea-urchin’s eggs on the assumption that it increases the oxidation processes to such an extent that the egg is disadvantageously affected the favouring effect of the calcium being due to its property of bringing back the rate of oxidation to the normal value The authors have determined the amount of oxygen used up when the eggs develop in different solutions and show that in sodium chloride solution there is no increase but if anything a decrease in the amount of oxygen absorbed.Warburg’s observation that more oxygen is used up in a given time in a solution containing sodium chloride and cyanide than in the same solution with the addition of calcium is confirmed but no final explanation is advanced. The anti-toxic effect of sodium cyanide in a solution con- taining sodium chloride is ascribed to the former substance retarding the development of the egg or the oxidation changes accompanying development.G. S. The Inhibition of the Toxic Action of Certain Poisons on the Eggs of Sea-Urchins Due to Depression of Oxidation in the Eggs. JACQUES LOEB (Biochem. Zeitsch. 19 10 29 80-95).-1t was found that the stoppage of oxidation in the eggs either by sodium cyanide or by driving out oxygen from the artificial sea-water by hydrogen inhibited the toxic action of the following classes of sub- stances (1) Neutral salt solutions ; (2) sugar solutions ; (3) hyper- andhypo-tonic solutions ; (4) narcotics (chloral hydrate phenylurethane chloroform and alcohol). This action of deficient oxidation cannot be due to inhibition of the bifurcation process for it inhibits the toxic action of substances like chloral hydrate which themselves inhibit the bifurcation of the egg. The Removal of t h e Poisonous Effects of Eydrocyanic Acid by Substances which Split off Sulphur. JOSEF HEBTING (Biochem. Zeitsch. 1910,28 208-21 2).-Lang found that hydrocyanic acid compounds led to the excretion of thiocyanates and in minced organs the change of potassium cyanide into thiocyanate also occurs the sulphur arising probably from the cystine of protein. He further showed that various sulphur compounds protect the organism against the poisonous effects of hydrocyanic acid. Reid Hunt and others have confirmed this. In the present research on rabbits the antidotes investigated were sodium tetrathionate cystine P-thiolactic acid and a- and P-dithiodilactylic acids and Lovh’s trithio-compound C6H100,S,. All were protective in some degree but none reach thiosulphate in efficiency. S. B. S. W. D. H. T h e Supposed Immunity of Toads to their own Poison (Secretion of Skin Glands). HERMANN FUHNER ( h c h . exp. Path. Pharm. 1910,63 374--385).-It has been generally stated that toads like snakes are immune to their own poison. The cutaneous secretionVEGETABLE PHYSIOLOGY AND AGRICULTURE. ii. 1097 of toads contains several active constituents namely a haemolysin called phrynolgsin and two substances bufonin similar to cholesterol and an easily soluble substance bufotalin. The last two substances produce the main toxic symptom namely a digitalis-like action on the heart. It is shown in the present research that the hearts of frogs are easily affected by the toad’s poison stoppage and systolic con- tracture being produced; the same occurs also in the toad’s heart. This action is to a great extent annulled by previous treatment of the secretion with cholesterol. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9109806079

出版商:RSC    

年代:1910

数据来源: RSC