the nitrogen of the atmosphere is directly combined with its accompanying oxygen without utilising any other chemical substances, the process consisting essentially of a powerful arc furnace through which air is forced, causing at this high temperature the nitrogen to combine with the oxygen, forming nitric oxide, NO. Second.-Methods of fixing nitrogen by means of electric furnaces or combustion where the energy of chemical combination is utilised, causing the nitrogen to combine with some substance with which there is a pronounced energy of chemical combination. These processes include furnaces utilising calcium carbide, with which nitrogen readily combines to form calcium cyanamid, CaCN2, and various processes for making combinations of nitrogen and a basic or alkaline earth metal such as calcium nitride Ca3N2, or magnesium nitride Mg3N2, or aluminium nitride AIN, the chemical action usually forming a nitride or carbo-nitride. Third.-Processes for producing ammonia, NH3, directly from nitrogen and hydrogen. These include the effort to use the various forms of electric discharge by which the nitrogen molecule may be decomposed and, in the presence of hydrogen, form ammonia. As ammonia decomposes at a very low temperature (500 to 1000° C.) only the silent discharge seems available, and the yields are not commercial, The most promising of all direct ammonia processes seems to be that of Haber. In this process a catalytic agent is used, and under a heavy pressure the nitrogen molecule is decomposed and united to the hydrogen, thus forming ammonia. Salts of uranium seem to be preferred as the catalytic agent, and have the power of acting on nitrogen at a temperature of about 500° C. Fourth.-Production of a high temperature by combustion, utilising either catalytic agents or simply by producing a high temperature by means of the explosion or combustion of gases directly combining the nitrogen and oxygen to form nitric oxide, NO. This method, early used by Bunsen in the combustion of hydrogen to form water, has been applied to coke oven gases by Hausser. A bomb is used and the mixture of gas and air is fired electrically, the small amount of NO formed is recovered and converted into nitric acid, HNO3. The chemical form in which the commercial supplies of combined nitrogen appear on the market is due largely to existing commercial conditions. The nitric acid combined as sodium nitrate occurs in this form simply on account of being naturally produced in this form. The ammonia appears on the market as ammonia sulphate largely on account of the cheapness with which sulphuric acid can be obtained, and the widely distributed plants for its manu. facture, making it one of the cheapest and most convenient forms of combining with ammonia. It is probable that in commercial nitrogen fixing plants, if both ammonia and nitric acid are manufactured, one of the most convenient forms of marketing this product will be by using nitric acid in place of sulphuric acid, making ammonia nitrate, NO NH4. This product is on the market at present, but is only manufactured from sodium nitrate and from ammonia, or in some of the plants where nitric acid is manufactured, ammonia is shipped to the nitric acid plants to be manufactured into ammonia nitrate. The advantage of ammonia nitrate is that it has a nitrogen content of 35 per cent, in this respect being a much more concentrated nitrogen product either for the processes of manufacturing other compounds of nitrogen or for use in the fertiliser industry. Physical Limitations and Those Fixed by Natural Sources. The competition with natural sources will fix the commercial limitations or selling prices for these various nitrogen compounds, and in considering the possible developments of the processes it will be interesting to see to what extent they have definite theoretical limitations, as these will greatly affect any comparison of possibilities. Before considering in detail these processes we might endeavour to investigate whether our present con ception of the physical and chemical reactions involved impose real limitations, or whether there is an uncertain boundary which further developments may encroach upon, perhaps thus continually improving the efficiency and possibilities commercially. If, for instance, the nitric oxide processes which utilise only 2 per cent to 4 per cent of the energy supplied to the furnace are limited to this amount by the inefficiency of the apparatus, there are much greater possibilities of development than would be the case if the process has definite physical or thermo-dynamic limitations, and the present apparatus utilises a favourable percentage of this possible ultimate limit. To some extent these theoretical limitations are not always sharply defined, and research will extend this horizon, but we may determine some of these limitations quite definitely. II. Theoretical Limitations. As we are considering this subject from its engineering aspects, it may be excusable to examine some of the theoretical limitations imposed by the laws of physical chemistry, and in reviewing what may be termed elementary formula it is interesting to note that the investigation of these theoretical limitations has been of funda. mental importance to physical chemistry in extending the application of the laws of chemical dynamics. Molecular Inertness of Nitrogen. The elements carbon (C) and nitrogen (N) possess a marked similarity in the fact that the molecule of each is composed of two or more atoms united together with a bond representing a large amount of energy. Nitrogen, having an atomic weight of 14, has a normal molecular weight of 28, indicating two atoms to the molecule, and in this molecular form it occupies 79.2 per cent of the volume of the earth's atmosphere. To separate this molecule into its constituent atoms and cause these atoms to combine with other elements is the problem of the fixation of nitrogen. Unless combined in the atomic form the enormous bond between the atoms causes them to combine upon themselves into the inert form of molecular or atmospheric nitrogen. The ordinary compounds of nitrogen are formed only by expenditure of a large amount of energy, the union of molecular nitrogen, N2, and molecular oxygen, O2, to form nitric oxide, NO, being represented by the formula N2+ O2 = 2NO=-43,000 calories. Or in other words, to form 1 grm. molecule of nitric oxide, NO, requires the expenditure of energy amounting to 21,500 calories. The general similarity to carbon in this molecular inert ness makes an interesting comparison. Thus C2 + O2 =2CO=58,000 calories. 2CO+O2=2CO2 134,000 calories. The formation of 1 grm. molecule of CO therefore represents the liberation of 29,000 calories, while the formation of 1 grm. molecule of CO2 and CO represents 67,000 calories, or a total of 96,000 calories in the formation of CO2 from the original elements C and O. When amorphous carbon, therefore, is caused to assume the gaseous condition and unite with a molecule of oxygen, there is liberated 29,000 calories, but after assuming this condition in which the molecule is no longer composed of the inert carbon molecule, a second grm. molecule of oxygen unites with the CO and liberates 67,000 calories additional. The second molecule of oxygen therefore liberates 38,000 calories more than the first molecule, and as the oxygen molecules were alike this energy represents the bond uniting the carbon atoms and the energy necessary to break down the bond between these atoms and produce a gaseous condition from the amorphous condition. Returning to the nitrogen molecule, it is apparent that the formation of the grm. molecule of NO requires 21,500 calories in comparison to carbon liberating 29,000 calories to form CO; that is, the nitric oxide reaction is endo NEWS thermic while the carbon monoxide reaction is exothermic. Upon adding a second molecule of oxygen to the nitric oxide to form the peroxide we find 2NO + O2 = 2NO2 = 27,000 calories, or 13,500 calories per grm. molecule are liberated after previously expending 21,500 calories to form NO. Since there is liberated only 13,500 calories, upon adding a second molecule of oxygen the net energy required to form NO2 would be 8000 calories. The first molecule of oxygen required 21,500 calories, whereas the second required only 8000 calories, so that 13,500 calories were required by the nitrogen molecule to prepare it for combination with the oxygen. Dynamic Equilibrium.-These heats of combination developed by the atoms combining upon themselves indicate a very stable or inert molecule, and in liberating this energy to assume this more stable form the forces exerted are of large magnitude. It is readily apparent from this, for instance, how carbonaceous gases can readily form soot and cinders and other amorphous forms when the union with oxygen is disturbed, as the tendency of the atoms to unite with oxygen or to form carbon molecules will depend upon an adjustment of the surrounding conditions. This ever-changing condition of equilibrium con. stitutes the dynamic conception of equilibrium displacing the static equilibrium of the older theories of chemistry. In order to more carefully consider some of the theories that have been advanced it may be of interest to follow further some of the concepts of physical chemistry. The fact that the nitrogen atom has this strong tendency to combine upon itself with a liberation of energy greater than the combination with the oxygen atom indicates that in any reaction, when the combination with oxygen has made possible a changing of the atoms, there will be continuously in progress an action and a reaction, and the equilibrium will be indicated by the expression N2+022NO, the sign of equality being displaced by the two arrows indicating that the action proceeds in each direction; that is, it is a reversible reaction, and the equilibrium will be dependent upon conditions, the two most important conditions being temperature and the active masses of the substances present. Considering, first, the effect of the active masses present, if it be assumed that the collision of molecules causes the rearrangement of the atoms comprising the molecule, and that of these collisions only a certain number will cause the rearrangement to proceed in one direction, the rearrangement will be greater the more frequently the collisions take place, there being some ratio for each individual case, and the collisions possible will obviously be proportional to the concentration presentthat is, the collisions will be proportional to the number of molecules present. With two substances present, the collisions will be proportional to the molecules of each present and hence to their product. (To be continued). Attempts to Prepare Closed-Chain Compounds Analogous to Indazols by means of Nitrated and Bromonitrated o-Anisidines. - E. Noelting and F. Steimle. By the elimination of acid or water the diazoic salts and the free diazo-compounds of substituted orthotoluidines give closed-chain compounds, the indazols. It seemed not improbable that by using the diazoic derivatives of substituted orthoanisidines analogous compounds containing an extra oxygen atom would be obtained. The authors found, however, that this is not the case. When the diazoic compounds of the nitrated or bromo-nitrated anisidines are decomposed normally into phenols the quantity of nitrogen liberated corresponds to two atoms, while if derivatives with closed chains were formed it would be less, or even none at all, according to the proportion of cyclic derivative obtained.-Bull. Soc. Chim. de France, xvii.-xviii., No. 19-20. 1916 PROCEEDINGS OF SOCIETIES. SOCIETY OF CHEMICAL INDUSTRY Ordinary Meeting, January 3, 1916. Mr. ARTHUR R. LING in the Chair. Or the following papers those marked * : * were read:"Action of Boiling Acetic, Propionic, and Butyric Acids on Aluminium. with a Note on the Action of Formic and Some Higher Acids." By RICHARD SELIGMAN and PERCY WILLIAMS. The experiments described in the paper were carried out to clear up certain anomalies in the literature on the action of acids on aluminium. Prominence is given to the action of boiling concentrated acetic acid on aluminium on account of the fact that whilst alnminium stills used for a number of years for distilling acetic acid have in general given satisfaction, certain parts are liable to corrosion. With the development of the colour industry in Great Britain this question became important. The authors were at first inclined to attribute the phenomena to the presence or absence of air, but their investigation has shown, that, whilst ordinary concentrated acetic acid is almost without action on the metal, the acid if perfectly anhydrous attacks aluminium with great violence. As little as o'05 per cent of water is sufficient to stop this reaction. The same applies to propionic and butyric acids. The authors conclude from these facts that where aluminium plant is used in connection with the lower fatty acids, precautions must be taken to prevent these from becoming absolutely anhydrous, either by avoiding undue dephlegmation, or by introducing a trace of water vapour at the threatened points. In the course of their work the authors obtained new aluminium salts of the acids examined. "Action of Certain Chlorinated Hydrocarbons on Some Metals." By SOSALE GARALAPURY SASTRY. Certain chlorinated hydrocarbons in the presence of moisture and under the influence of heat are liable to hydrolysis, especially if they are impure. Carbon tetrachloride, dichloroethylene, trichloroethylene, tetrachloroethane, and pentachloroethane were examined. Many such compounds are used to extract oils and fats from vegetable seeds, and experiments were conducted in which the solvents, with and without seeds, were heated under a reflux condenser, in presence of strips of metals (1 inches by inch), the heating being continued for ten hours. The metals were weighed before and after the experiment. Wrought iron, mild steel, nickel, copper, aluminium, and lead were examined, and tables are given in the paper showing the effect of the chlorinated hydrocarbons on them. Tetrachloroethane and pentachloroethane hydrolysed most readily, and aluminium was the most easily attacked of all the metals. The author comes to the conclusion that dichloroethylene and trichloroethylene are the safest of these solvents now on the market. "Viscosity of Oils in the Redwood and Ostwald Viscometers." By CHARLES A. SAVILL and ARTHUR W. Cox. This work was undertaken with a view to proving the connection existing between viscosities given by the Redwood viscometer (the one used in commerce) and the "absolute" type, and also of suggesting a simple method of conversion the one to the other. The viscosities of a series of oils have been ascertained in the Redwood and Ostwald viscometers and it is found that the two sets of results of any oil when plotted on a graph give parallel curves. It is, therefore, evident that Redwood and Ostwald viscosities are easily interconvertible, and, incidentally, that Redwood viscosity depends directly on the lubricating value of the oil. The results of the series of oils in both instruments are then taken and those obtained in one instrument plotted along one axis of a graph, and those in the other along the other axis. By reference to this graph it is then a simple matter to convert viscosities determined in one instrument into the corresponding figures in the other. "Estimation of Carbon Dioxide in Air by Haldane's Apparatus.” By ROBERT C. FREDERICK. For the estimation of small quantities of carbon dioxide in air this is the most convenient apparatus to use, and in skilled hands it is a quick and sufficiently accurate method. The principle is that the CO2 is absorbed by caustic potash and the consequent diminution in volume, being measured on the graduated scale, gives a direct reading of the quantity present per 10,000 parts of air. If the potash solution is coloured with methyl orange movements of the liquid are made more apparent. Stress is laid on the importance of agitating the water in the water jacket, and considerable effort is avoided if a blowing bulb is used to provide the air current instead of blowing by mouth. A full and detailed account of the manipulation of the apparatus is given both when employed direct in the space to be tested and when used for the testing of air samples; in the latter case, a mercury bath is required. The sample bottles are two ounce, narrow-mouth stoppered, and the sample is collected by placing a rubber tube in the bottle and drawing a deep breath through the tube. A simple device is described for making the ordinary, Haldane apparatus record up to 500 parts per 10,000 instead of 100, and also a labour-saving apparatus for propelling the mercury reservoir which prevents the mercury and potash being brought together accidentally and has other advantages. "Method for the Determination of Free Alkali in Soap." By F. H. NEWINGTON. The method is based upon the principle of salting out the soap from its aqueous solution by means of sodium sulphate. Any free caustic alkali is thus obtained in aqueous solution together with the sodium sulphate after the soap has been removed. The caustic alkali in this solution is titrated with N/10 H2SO4 using a 5 per cent solution of silver nitrate as a spot indicator. With care the method will detect with accuracy o'r per cent of free sodium or potassium hydrate in either toilet, household, or soft soap. Silicates and borates do not interfere. Exhibits. Mr. C. A. HILL exhibited some preparations of analytical reagents, and in the course of a description of them explained the methods he had adopted in purifying them to meet the requirement of the specification laid down by the Joint Committee Institute of Chemistry and the Society of Public Analysts. Mr. SHERARD COWPER-COLES sent an exhibit of leadlined vessels. Dr. E. C. B. WILBRAHAM exhibited and described natural and synthetic succinates. Mr. T. D. MORSON (Hon. Sec.) exhibited and described glass filter cloths suitable for filtering corrosive liquids. Exhibits of British glass chemical apparatus were made by Messrs. J. MONCRIEFF, Ltd., of Perth, and by Messrs. BAIRD & TATLOCK, Ltd., of London. Dr. Travers gave a brief description of Messrs. Baird & Tatlock's manufacture, which has been put on the market under the name of "Duro" glass. Both these makes of British glass are said to be equal in their resistance towards chemicals to Jena glass. Messrs. DOULTON & Co. sent an interesting exhibit of porcelain ware for chemical purposes. NOTICES OF BOOKS. Relativity and the Electron Theory. By E. CUNNINGHAM, M.A. London, New York, Bombay, Calcutta, and Madras: Longmans, Green, and Co. 1915. IN this monograph the relation of the principle of relaivity to the electron theory is explained with as little mathematical analysis as possible. The modifications which the principle has forced upon our notions of space, modern ideas concerning momentum and energy are time, and motion are first discussed at some length, and explained. The general conclusions to be based upon the principle of relativity are summarised, and the question of the existence of an objective ether is discussed. The author has condensed his material and provided a comparatively complete survey of his subject, but in so doing he has, no doubt unavoidably, made the book rather difficult to read and follow, and it seems doubtful whether the general reader, spoken of in the preface, will be able to make much use of it, though physicists and those who know something of the work of Lorentz and Einstein will find it a useful summary. Historical Introduction to Chemistry. By T. M. LowRY, D.Sc., F.R.S. London: Macmillan and Co., Ltd. 1915. IT may well be believed that the course of work given in this book has been proved by experience to be both interesting and instructive to all classes of students, as stated in the preface. The author has in his mind particularly the mixed classes in training colleges and medical schools, some of the students being beginners, while others have a considerable knowledge of elementary chemistry. For and this book provides just what they need, and will moresuch classes the historical method is undoubtedly the best, over be found very valuable by teachers. It gives an account of classical experiments and theories often in the actual words of the original descriptions, and contains many illustrations of the apparatus used by early workers in the science. It is divided into two parts, the first dealing with the discovery of the facts of chemistry, while Part II. discusses chemical theories, beginning with a full treatment of the atomic theory. In both parts recent work is included; thus some account is given of Moseley's investigation of the high frequency spectra of the elements. Short summaries of each chapter are provided, and a bibliographical index is included, which gives in tabular form, with dates, lists of the works of the most prominent investigators. Cuadro Sinoptico de la Doctrina Bioscosmica de la Gravitacion Universal y de la Jeneracion de los Mundos. ("Synoptic Table of the Biocosmic Doctrine of Universal Gravitation and of the Generation of Worlds"). By Dr. ARISTIDES FIALLO CABRAL. Santo Domingo: La Cuna de America, Vuida de Roques and Cia. 1915. In this thesis a series of cosmic problems is stated, such as, "What is contained in interplanetary space?" "What are the comets?" "What is the origin of life upon our planet?" and the answers and explanations given by the classical theories are briefly stated as well as those provided by the biocosmic theory. These latter, which usually take the form of dogmatic assertions, are given at some length, but no attempt is made to state what the author's premises are, nor how much is to be regarded as deduction from untested hypotheses. The author possibly wishes the table to be regarded as providing a statement of debatable questions for further argument, and thus deliberately refrains from enlarging upon reasons and proofs. CORRESPONDENCE. GROWING MEDICINAL HERBS. To the Editor of the Chemical News. SIR, -It has been decided to start an organisation for growing medicinal herbs in this country, to be called the Herb-growing Association, affiliated to the Women's Farm and Garden Union. Members may join on payment of 2s. 6d. per annum. Those who already belong to the Women's Farm and Garden Union may join on payment of Is. per annum. These terms are for original members, and may be altered later. Members will be entitled to advice on herb-growing and the preparation and disposal of herbs. By cooperation the growing of different herbs will be regulated so that the market may not be overstocked with some and be short of others. Anyone wishing to help in the development of this industry and to hear details of the proposed working of the scheme is requested to communicate as soon as possible, as it is now that the supply from Central Europe is stopped that it is possible to keep the industry in this country. Communications should be addressed to the Secretary of the Herb-growing Association, 45 (6), Queen Anne's Chambers, Westminster, S.W. Hoping you will kindly give publicity to this organisation, we are, &c., EDITH L. CHAMBERLAIN, F.R.H.S., Members of the Herbal Sub-Committee. concentration has been reached, the sugar exercises a protective action upon itself and accumulates. With glucose or invert sugar the curve is very nearly a straight line, and the precipitation of the copper soon becomes total for a given quantity of reducing sugar. CI Hydroxylamine Complexes of Divalent Platinum. L. Tschugaeff and J. Tschernjaeff.-When Peyrone's chloride is digested with hydroxylamine in aqueous soluNH3 CI tion the compound [(NH3)2Pt(NH2OH)2] Cl2 is readily obtained. It yields the complex by >Pt< NH2OH the action of hydrochloric acid at the temperature of the water bath. This readily fixes two molecules of hydroxylamine to give [Pt(NH2OH)3NH3] X2 and two molecules of ammonia to give [PtNH2OH(NH3)] X2. By the action of hydroxylamine in aqueous solution on Reiset's base the following transformation is effected : Bulletin de la Société Chimique de France. Vol. xvii.-xviii., No. 19-20, 1915. Some Colour Reactions of Triphenylmethane Derivatives.-E. Noelting and A. Kempf.-Bayer and Villiger have shown that triphenyl carbinol dissolves in concentrated sulphuric acid, giving an intense orange coloration. This is due to the formation of a salt, the triphenyl carbinol group possessing feeble basic properties. If the hydroxyl or methoxyl groups are introduced into the triphenylcarbinol the coloration is increased in intensity and the basic properties of the complex are accentuated, the OH group having the stronger influence. Rosolic acid and its hexamethoxy derivative both behave like basic dyes, and trianisylcarbinol has the same action. The authors have prepared the carbinol corresponding to phenyl-deorthomethoxyl-cresylmethane by oxidising the leucoderivative with lead dioxide in acetic solution, and the paracresol derivative similarly. The former gives CHEMICAL NOTICES FROM FOREIGN a red coloration with sulphuric and the latter a Bordeaux SOURCES. NOTE. All degrees of temperature are Centigrade unless otherwise expressed. Comptes Rendus Hebdomadaires des Séances de l'Académie des Sciences. Vol. clxi. No. 21, November 22, 1915. Action of Saccharose on Cupropotassic Liquid.L. Maquenne.-The action of cupropotassic liquid upon saccharose at the temperature of boiling water is quite different from its action on invert sugar. The latter is attacked chiefly by the caustic alkali which the reagent contains, and the action is slightly dependent only upon its richness in copper, whereas saccharose is greatly affected by the latter, its reducing power increasing very rapidly with the quantity of dissolved metal. The duration of boiling also has an influence, and in order to investigate the reaction thoroughly the author used the same reagents always and kept the volume of liquid as low as possible, in order that the heating could be better regulated. He constructed a curve, taking the weights of sugar as the abscissæ and the corresponding reductions as ordinates, and observed that at first it rose very rapidly, then had a point of inflection, became horizontal, and finally fell. Thus, after a certain red colour. If amino groups are introduced into triphenylcarbinol in the para position with reference to the original carbon basic carbinols are obtained which give strongly coloured salts, dyeing silk, &c., with a molecule of acid. "Oil MEETINGS FOR THE WEEK. TUESDAY, 18th Institution of Petroleum Technologists, 8. Storage," by H. Barringer. Royal Institution, 3. "The Physiology of Anger and Fear," by Prof. C. S. Sherrington. "The Common WEDNESDAY, 19th.-Royal Society of Arts, 4.30. Lands of London-the Story of their Preservation," by Lawrence W. Chubb. "The Utilisation of Energy THURSDAY, 20th.-Royal Institution, 3. from Coal-The Chemistry and Economics of Coal and its By-products," by Prof. W. A Bone. Chemical, 8. "The Colouring Matter of Cotton "Studies on the Flowers," by A. G. Perkin. Oxidation of Unsaturated Fatty Oils and Unsaturated Fatty Acids-Part I., Formation of Acrolein by the Oxidation of Linseed Oil and Linolenic Acid," by A. H. Salway. "Synthesis of Keto-indo-pyranols," by S. G. Sastry and B. Ghosh. "Vapour Pressure of Glyceryl Trinitrate (Nitroglycerin)," by A. Marshall and G. Peace. "Problems in Capillarity," by Prof. Sir James Dewar. FRIDAY, 21st-Royal Institution, 5.30. SATURDAY, 22nd.-Royal Institution, 3. Angelo," by C. J. Holmes. "Raphael and Michael STEREO-PYROMETER (English Patent 10617/1905). For ascertaining any temperature from 550o C. to 2000o. No Delicate Mechanism to get out of Order. This is undoubtedly the simplest and most reliable form of Pyrometer for practical use in works. It can be used for ascertaining the temperature of : Price complete 48s. Write for Descriptive Circular from the Sole Makers Porous Terra Cotta. net. F. E. BECKER & CO., 17-27, HATTON WALL, E.C. BRITISH DYES LIMITED. The Directors of the Company are now or ganising the RESEARCH DEPARTMENT under the direction of Professor W. H. PERKIN, F.R.S., and are prepared to receive applications from Senior or Junior CHEMISTS. Letters, containing full particulars of training and experience, should be addressed to BRITISH DYES LIMITED, EMPIRE HOUSE, KINGSWAY, LONDON, W.C. ALFRED JÖRGENSEN LABORATORY FOR THE PHYSIOLOGY AND ECHNOLOGY OF FERMENTATION. 30, FRYDENDALSVEJ, COPEnhagen, v., denmark. STUDENTS' SECTION.-For Beginners and Advanced Students with Practical (Brewers, Distillers, &c.) or Scientific purposes in view. NEW METHODS for DISTILLERIES and YEAST FACTORIES |