CHEMICAL NEWS, June 24, 1910 Carboxylic Acids of Cyclohexanone. 297 The revised value, 390, of the molecular elevation of | hydrogen chloride, water being formed, the disulphoxide the boiling point of chloroform, recently given by Beckmann, reduced to disulphide, and the mercaptan oxidised to has been confirmed. disulphide :: 144. "The Salts of 8-Hydroxyquinoline." By JOHN JACOB FOX. The The salts of 8-hydroxyquinoline have been prepared and found to dissolve appreciably in benzene and chloroform. The copper, cadmium, and nickel salts are greenish-yellow, the remaining salts being yellow- or buff-coloured. degree of hydrolysis of the sodium salt of 8-hydroxyquinoline and of the hydrochloride was determined by Farmer and Warth's method (Trans., 1901, lxxix., 863). It was found that in a o'r N-solution the sodium salt was hydrolysed to the extent of 11.6 per cent, and the hydrochloride to the extent of 4.2 per cent. 8-Hydroxyquinoline and its salts, 8-ethoxyquinoline and its hydrochloride, 5: 7-dibromo-8-hydroxyquinoline, and 8-hydroxy-1: 2: 3 : 4-tetrahydroquinoline and its hydrochloride were examined spectrographically in alcoholic solution. The yellow colour of the salts was shown to be due to the extension of the bands of the original substances into the visible region, the general form of the curves for absorption being similar in the derivatives of 8-hydroxyquinoline and its salts. The curves obtained from hydroxy. tetrahydroquinoline and its hydrochloride were of a different character from that of hydroxyquinoline, and resembled those obtained from alkylated anilines. 145. "Apparatus for Demonstrating the Volumetric Compositions of Gases." By ALARIC VINCENT COLPOYS FENBY. The apparatus described was devised for the rapid demonstration of the combining volumes of gases and of the compositions of compound gases. The volumes of gases introduced are simple multiples of a unit volume (15 cc.) equal to one division on the burette, which is divided into six parts. The pressure is adjusted to atmospheric pressure at each measurement, and no corrections for temperature or pressure are required. gas The apparatus consists of four parts, namely, (1) the burette, of special design; (2) the levelling tube; (3) a reservoir for filling the burette; and (4) a special form of gas generator and holder, by which fixed volumes of a gas can be passed into the burette. The whole is conveniently supported on a single retort stand. The use of the apparatus for the following experiments was described :-Composition of ammonia by the chlorine method; combination of hydrogen and chlorine in equal volumes; combining volumes of hydrogen and oxygen ; the composition of carbon monoxide and hydrocarbon gases, and the decomposition of hydrogen chloride by sodium amalgam. (C6H5 CH2)2S2O2+4C6H5*CH2 SH= =3(C6H5 CH2)2S2+2H2O. Similarly, benzyl disulphoxide in the presence of glacial acetic acid and dry hydrogen chloride condenses with hydrogen sulphide, forming benzyl disulphide, water, and sulphur :: (C6H5 CH2)2S2O2+2H2S = (C6H5 CH2)2S2 + 2H2O+S2. These condensations are quantitative. Benzyl sulphoxide does not condense in this way when sodium ethoxide or acetic anhydride are used as condensing agents. Benzyl tetrasulphide, together with hydrogen chloride, is formed by the interaction of benzyl mercaptan and sulphur chloride thus : 2C6H5 CH2 SH+S2Cl2 = (C6H5·CH2)2S4+2HCl. The new sulphide is a white crystalline powder, soluble in alcohol, benzene, &c., insoluble in water, and melting at 49-50°. It forms no additive products with methyl iodide or with silver nitrate. Nascent hydrogen reduces it, giving benzyl mercaptan and hydrogen sulphide, and chlorine attacks it in the cold with the formation of sulphur chloride and benzyl chloride. In glacial acetic acid solution it is oxidised by hydrogen peroxide. 147. "The Action of Sodium or Potassium Hydroxides on Sodium Alkyl Thiosulphates and on Disulphides." By THOMAS SLATER PRICE and DOUGLAS FRANK TWISS. The authors referred to the criticism by Fromm and Erfurt (Ber., 1909, xlii., 3816) of their explanation of the course of the reaction between alkalis and the sodium alkyl thiosulphates, and pointed out that there is no satisfactory experimental evidence for the formation of intermediate compounds of the type R S OH, postulated by Gutmann (Ber., 1908, xli., 1650) and favoured by Fromm and Erfurt. In connection with the action of alcoholic potassium hydroxide on benzyl disulphide, it was shown that if benzyl chloride is added to the mixture after the reaction has taken place, and the mixture again heated, the main products are benzyl sulphide and benzoic acid, whereas if benzyl chloride is present from the commencement, a considerable quantity of the benzylmercaptal of benzaldehyde is also formed. From these results it was deduced that the primary result of the action of alkali on benzyl disulphide is the formation of benzyl mercaptan and benzoic acid. Special features of the apparatus include the generation of chlorine in the burette, the method of introducing fixed volumes of gas into the burette from the generator, and the construction of the generator itself and the burette. 146. "Some Reactions of Benzyl Mercaptan. Benzyl Tri- and Tetra-sulphides." By JOHN ARMSTRONG SMYTHE CH2CH2 CH2>co → CH2CH2CH2 148. "Carboxylic Acids of Cyclohexanone and some of its Derivatives." (Preliminary Note). By HENry Dent GARDNER, WILLIAM HENRY PERKIN, jun., and HUBERT WATSON. and AQUILA FORSTER. When a solution of benzyl mercaptan in glacial acetic acid is saturated with sulphur dioxide and hydrogen chloride, a quantitative reaction takes place according to the equation: 4C6H5 CH2 SH+SO2 = = (C6H5⋅CH2)2S2+ (C6H5 CH2)2S3+2H20. Benzyl trisulphide melts at 49°, and possesses considerable crystallising powers. It forms a sparingly soluble additive product, ̊ (C6H5·CH2)2S3,AgNO3 (m. p. 96°), with silver nitrate. The action of sulphur dioxide on benzyl mercaptan thus resembles that of thionyl chloride on mercaptans (Holmberg, Annalen, 1907, ccclix., 81), and the results throw some light on Jones and Tasker's work (Trans., 1909, xcv., 1910). Benzyl mercaptan and benzyl disulphoxide condense in the presence of glacial acetic acid and a current of dry These acids are obtained when the cyclic ketones are treated, in ethereal solution, with sodamide and carbon dioxide. CH2 CHNACO → CH2 CH2 cycloHexanone-2-carboxylic acid softens at 79°, melts and decomposes at 81-820, and, on reduction with sodium amalgam, yields cyclohexanol-2-carboxylic acid (hexahydrosalicylic acid), which melts at 111°. 1-Methylcyclohexan-2-one-3-carboxylic acid is a syrup. d-1 Methylcyclohexan-3-one-2(?)-carboxylic acid, prepared from 1-methylcyclohexan-3-one from pulegone, melts at 103, and has [a] D +97.2°. dl-1-Methylcyclohexan-3onecarboxylic acid, prepared from dl-1-methylcyclohexanone, melts at 100°. 1-Methylcyclohexan-4-one-3-carboxylic acid melts at Ior, and, on reduction with sodium amalgam, yields 1-methylcyclohexan-4-ol-3-carboxylic acid, which melts at 114°, and, when heated, yields a methylcyclohexene carboxylic acid, which distils at 153°/25 mm. and crystallises. This acid is being investigated with the object of determining the position of the double linking. Menthonecarboxylic acid melts at 154°, and thymomenthone carboxylic acid at 150-151°. All those acids which contain the grouping CO CH CO2H give intense colorations when ferric chloride is added to their alcoholic solutions. PHYSICAL SOCIETY. Prof. H. L. CALLENDAR, F.R.S., President, in the Chair. A PAPER on "A Galvanometer for Alternate Current Circuits" by Dr. W. E. SUMPNER and Mr. W. C. S. PHILLIPS was read by Dr. Sumpner. Tests of effects due to change of current, such as induction phenomena, are often hard to carry out because the ballistic galvanometer available is not sensitive enough. Alternate current tests are still less satisfactory owing to special difficulties. The vibration galvanometer overcomes only a few of these difficulties. It must be adjusted to resonance for the best effects, and its indications vary with current frequency. The sensitiveness of ballistic galvanometer tests can be greatly increased by the use of some form of mechanical commutator by means of which a crude form of alternate current is produced. A better method would be to generate the current in the usual way if a suitable instrument existed. The galvanometer here described is the result of an attempt to construct a measuring instrument by means of which inductances and capacities can be compared by bridge methods as accurately as it is possible to compare resistances. The instrument is like a moving coil galvanometer in almost every respect, except that its field is due to a specially constructed electromagnet excited by an alternating voltage. This voltage V is applied to a winding of m turns of the electromagnet, and the core flux N is such that V=rA+mŃ, where is the resistance of the winding and A the current traversing it. The coil and electromagnet are so designed that for currents of the frequencies used the value of rA is negligible in comparison with V. The rate of change of N will therefore be at each instant a measure of V, whatever the permeability of hysteresis of the core. The instrument has a laminated electromagnet formed of stampings of two kinds-a rectangular portion with two straight limbs forming the core of the electromagnet, and a specially shaped stamping between the poles. The moving coil of 50 turns swings in a narrow gap separating the stampings, in much the same way as in a permanent magnet instrument. On the limbs of the magnet are windings of 200, 2000, and 4000 turns. The iron will not be too strongly magnetised if the winding used contains 20 turns per volt or 50 vibration circuits, but the instrument is so sensitive that such excitation will only be needed for exceptional tests. If a voltage V be applied to one of the field coils of m turns, and if the same, or another, field winding of n turns be joined up, through a condenser of K microfarads, to the moving coil, the torque acting on this moving coil will be a measure of i.e., the deflexion is proportional to the square of the voltage. By suitably choosing K, m, and n the voltmeter may be used over a large number of ranges. Thus with the instrument shown a deflexion of 200 mm. on a scale at I metre distance can be obtained either for 200 volts or for 20 millivolts. The deflexion is independent of frequency and wave-form if the field-winding to which the voltage is applied has a resistance negligible in comparison with its impedance. Thus with m= 4000 and n = 200 it was found that the value of V2 required to give a certain deflexion was independent of frequency between 50 vibrations and 100 vibrations, but at 25 vibrations it was 6 per cent less than at 50 vibrations. At any fixed frequency the deflexion will always measure KV2. The instrument may be used with great advantage to compare inductances and capacities by the ordinary bridge methods, the working conditions being (1) the alternating voltage V applied to the field coil of the instrument must also cause the current in the bridge conductors; (2) the alternate current in the bridge must be made in phase with the voltage V by the use of suitable non-inductive resistances; (3) the moving coil must be placed directly across the bridge. The balance can be adjusted with ease to I part in 10,000 when the voltages set up on the coils or condensers are of the order of 1 volt. When a balance of great precision is needed, the minute electromotive force induced in the moving coil by the alternating field of the magnet, tends to cause a small deflexion disturbing the balance. When the moving coil circuit is non-inductive, the current due to e will be in phase with e and in quadrature with the flux so that the corresponding deflexion will be negligible. But in all cases any effect due to e can be accurately elimi nated by working to a false zero. As illustrations of the behaviour of the instrument, the results of tests are given on the measurement of the mutual induction of coils, the comparison of capacities, and the measurement of Specific Inductive capacity. Mr. A. CAMPBELL expressed his admiration of the galvanometer, and in particular of the ingenious method of connecting it with a condenser when voltage is to be measured. He remarked that the instrument was very similar in construction and use to that used by earlier experimenters. Stroud and Oates (Phil. Mag., 1903) described such a galvanometer, and showed how sensitive it was for testing condensers by Anderson's method and for other purposes; and Terry (Phys. Review, 1905) used a similar one for accurate comparisons of condensers. Abraham (Comptes Rendus, April, 1906) described another in which the false zero was got rid of by a compensating arrangement. With regard to vibration galvanometers, there is no difficulty in keeping them in tune on any reasonably steady alternating circuit. In the bridge methods illustrated in the paper, a double adjustment is necessary when a vibration galvanometer is used, and in general an evaluation of effective resistance or leakage resistance can be made simultaneously with the measurement of inductance or capacity. He asked the authors if this double adjustment can be entirely dispensed with when the quadrature galvanometer is used. It would be interesting also to know how the instrument would work with non-sinusoidal waveforms in a case where the balance depended on the fre quency. Mr. W. DUDDELL asked if the authors could supply more numerical data so that the instrument could be compared with other galvanometers of similar design. He pointed out that the tests were simplified owing to a double adjustment being unnecessary. Mr. IRWIN thought that with small modifications the instrument would be useful for tests other than those described in the paper. It might, for example, be used in determining the resistance of electrolytes. He pointed out that errors might arise due to a small amount of magnetic material in the moving coil. Dr. SUMPNER stated, in reply to Mr. Campbell and Mr. Duddell, that the object of the special shape of pole-piece was to increase the impedance of the exciting coil. Electromagnet galvanometers were not new, but the special mode of controlling the magnetic flux by the applied voltage was novel. The behaviour of the instrument was a direct consequence of this device. The vibration galvanometer responded to a voltage irrespective of its phase, and hence in some tests troublesome double adjustments were needed. This was not the case with the new instrument in regard to any of the tests described in the paper. The current taken by the instrument could easily be calculated from data given in the paper. In CHEMICAL NEWS, June 24, 1910 Positive Electrification due to Heating Aluminium Phosphate. reply to Mr. Irwin, the author said that the small deflexion Mr. A. E. GARRETT read a paper entitled "Positive In 1904 Dr. R. S. Willows and the author communicated to this Society the results of some experiments on the halogen compounds of zinc, in which it was shown that those compounds when heated ionised the air around so that both positively and negatively electrified bodies gradually lost their charge. Work in this direction was continued, and the results obtained showed that a large number of inorganic compounds possess properties of a like nature to the above. In 1907 Sir J. J. Thomson found that chlorides, phosphates, and nitrates give off an excess of positive ions when heated, and he incidentally discovered that aluminium phosphate was most active in this direction. As many of the substances previously examined are known to be unstable (and hence the ionisation produced may be the result of chemical change), while aluminium phosphate, on the other hand, is a most stable substance, it was thought that an investigation of the ion producing properties of that compound would be of interest. The apparatus was arranged so that the salt could be heated to the desired temperature (900-1300° C.) on a strip of platinum foil. The pressure could be reduced as required. For most of the experiments a sensitive galvanometer was used as recording instrument. With the usual distance between the electrodes (o'5 cm.) it was found that a difference of potential of 60 volts was sufficient to obtain a saturation current with the positive ions. The way in which the current varied with the time when the saturation voltage was applied was first investigated. For the first half-hour the current was somewhat irregular. This was found to be due to the water present in the salt. The current for the first hour or two appears to be largely influenced by the surrounding gas. Neglecting the preliminary effects due to water, the decay of the current with the time can be represented by a curve having the general formula A(e-t-e-λ)+B(1-e-3). The current finally obtained depends almost entirely upon the salt itself. After five or six hours' heating, no further change takes place in the current obtained under fixed conditions of temperature and pressure. A temporary increase, however, can be brought about by moistening the salt, and also by passing a discharge from an induction-coil through the tube for about half a minute. When the salt is insulated and heated for some time, an extraordinarily large current passes when the field is first put on. This effect increases with the time up to about ten minutes, after which any longer insulation causes no increase of the initial current. With the salt in the final steady state the conditions were suitable for experiments on temperature and pressure effects. It was found that for every temperature tried there was a certain pressure at which the current obtained was a maximum, and the higher the temperature the lower was this pressure. The currents obtained with constant pressure and variable temperature indicate that the relationship between the rate of production of positive ions and the absolute temperature can be represented by the Richardson formula Q ate 20. By using a quadrant electrometer in place of the galvanometer, it was found at pressures of o'o1 mm. that some positive ions are ejected with a velocity of the | 299 order 106 cm. per sec.; and other experiments showed that the ions at very low pressures and acted upon by small electrostatic fields moved with great velocity, so it was thought that this substance could be made use of as a means for rectifying alternate currents. It was found that it could be so used. The values of l/m obtained by Thomson's cycloid method indicate that the smallest of the positive ions present possess a mass comparable with that of the hydrogen atom. Many of the results obtained, in particular (a) those with varying pressures and constant temperatures, (b) those at atmospheric pressure in which after removal of all free ions by a field sufficient to produce a saturation current, a current of equal values for ions of both signs was found at an electrode placed behind that on which the saturation voltage acted, and (c) the loss of charge of a Faraday cylinder when screened from the action of free ions, indicate that one of the products due to heating aluminium phosphate is in the form of neutral pairs or doublets which afterwards split up into negative and positive ions. NOTICES OF BOOKS. A Re-calculation of the Atomic Weights. By FRANK THIS book contains a critical survey of all the information Qualitative Analysis Tables for Use at the Bench. By THESE tables are printed on stout card edged with metal, MISCELLANEOUS. Society for Extending the Rothamsted Experiments.-A meeting of the Society was held at Rothamsted on June 16th under the Presidency of the Duke of Devonshire. The Society has been incorporated with the object of obtaining additional funds for the development of the agricultural investigations which have been carried on so long under the late Sir John Lawes and the Lawes Agri cultural Trust, which he afterwards founded. The immediate object of the Society is to obtain a sum of £5000 in order to secure about 200 acres of land adjoining the present experimental fields, and erect thereon the buildings required for feeding experiments with the crops under investigation. An appeal for subscriptions towards thus securing a small self-contained farm for the Rothamsted Experimental Station is now being circulated, and at the meeting of the Society on Thursday a first list of donations was reported from the Duke of Devonshire, Lord Iveagh, Sir J. T. Brunner, Colonel E. H. Carlisle, M.P., Mr. J. F. Mason, M.P., and Mr. J. Martin White, amounting to £1450. Drawing Office Accessories.-Messrs. Wm. J. Brooks and Co., Letchworth, Herts., have recently introduced several novelties to aid in the preparation of drawing diagrams, &c. Among the most useful are a number of mathematical curves accurately cut and engraved, in transparent celluloid : PARABOLA: Eqn. y = x2; unit 1 inch. Axis, focus, and latus rectum marked. HYPERBOLA (Rectangular): Eqn. xy=1 inch. Axis marked. ELLIPSE Major axis 3 inches, minor axis 2 inches. Axes and foci marked. CYCLOID: Roulette of circle 2 inches diameter. Central ordinate marked. CUBIC Curve: Eqn. y=x; unit I inch. Of these perhaps the parabola is the most useful; with its aid and a sheet of squared paper, square and square roots and other equations can be solved rapidly and with considerable accuracy. For the construction of curves thin flexible steel bands are provided. A simple form with small brass tabs at intervals of about 2 inches enables a curve to be set out and held in position by the fingers of one hand while the line is traced with a pencil. Another more elaborate device consists in a steel band connected to a number of stiffly moving brass links; with this instrument any curve or curves can be given to the steel band and retained by it while the line is being traced. These are made in various lengths. Another ingenious device is sold under the name of "Pinro"; it is an improvement on the common drawing-pin, and consists in a very thin flexible strip of brass with pin points placed every four inches; it is sold in lengths of twelve feet, and will be found useful for a variety of purposes besides the general use of a drawing-pin, and it has the great advantage that it does not roll on to the floor and get lost. NOTES AND QUERIES. Our Notes and Queries column was opened for the purpose of giving and obtaining information likely to be of use to our readers generally. We cannot undertake to let this column be the means of transmitting merely private information, or such trade notices as should legitimately come in the advertisement columns. Castor Seed.-Can any reader inform me if there is a test for the poisonous castor seed in cotton or cattle feeding cake ?-C. S. MEETINGS FOR THE WEEK. THURSDAY, 30th.-Royal Society. "New Method for the Quantitative Estimation of Hydrocyanic Acid in Vegetable and Animal Tissues," by Dr. A. D. Waller. "Comparative Toxicity of Theobromine and Caffeine as measured by their Direct Effect upon the Contractility of Isolated Muscle," by Drs. V. H. Veley and A. D. Waller. "Muhinyo, a Disease of Natives in Uganda" and "The Natural Food of Glossina palpalis," by Colonel Sir David Bruce and others. "Relation of Light Perception to Colour Perception," by Dr. F. W. Edridge-Green. "Anatomy and Morphology of the Leaves and Inflorescences of Welwitschia mirabilis," by Miss M. G. Sykes. "Relative Atomic Weights of Nitrogen and Sulphur," by F. P. Burt and F. L. Usher. MACMILLAN'S NEW and RECENT BOOKS ON CHEMISTRY. Methods Used in the Ex amination of Milk and Dairy Products. By Dr. CHR. BARTHEL. Translation by W. GOODWIN, M.Sc., Ph.D., South-Eastern Agricultural College, Wye, Kent. Illustrated. 8vo. 7s. 6d. net. Theoretical Principles of the Methods of Analytical Chemistry based upon Chemical Reactions. By Professor M. G. CHEsneau. Authorised Translation by Professor A. T. LINCOLN, Ph.D., and Professor D. H. CARNAHAN, Ph.D. 8vo. 7s. 6d. net. Practical Chemistry. By JAMES BRUCE, Ph.D., B.Sc., F.I.C., A.R.C.S., and HARRY HARPER, A.R.C.S., Head of the Chemistry Department of the Trade and Grammar School, Keighley. Globe 8vo. 2s. 6d. EDUCATIONAL NEWS.-"We have pleasure in recommending this book not only to students but to teachers of chemistry, and feel certain it will occupy a high place amongst books on like subjects." Crystalline Structure and Chemical Constitution. By A. E. H. TUTTON, M.A., D.Sc. (Oxon.), F.R.S., A.R.C.Sc. (Lond.). 8vo. 5s. net. [Science Monographs. NATURE." It is a goodly story that he has to tell, and well is it told; without wearying the reader with an unwieldy mass of details, he presents in all essential completeness a vivid picture of an unusually coherent series of investigations. . The book is one that should be read and studied by all interested in crystals, their properties and their formation." FOURTH EDITION, entirely Re-written and Enlarged. Analysis of Oils, Fats, and Waxes. NATURE.-"Well maintains its place in the front rank of works devoted to the study of oils, fats, and waxes. To the chemical technologist it is practically indispensable." MUCH CHEAPER. At least 25 per cent cheaper than any other make. make. MORE ABSORBENT. Effectively absorbs one-third more litharge than any other It is impossible for litharge to run through on to floor fo muffle, thus the muffle can be used over and over again IMPERVIOUS BOTTOMS. More economical in every way. DO NOT CRACK OR SPLIT. REQUIRE NO SPECIAL PACKING. DO NOT GET DAMAGED IN TRANSIT. 5/6 7/9 10/9 14/6 20/- 25/6 35/- 41/ , HATTON WALL, LONDON. NOTICES. EDITORIAL.-All Literary communications, and Books, Chemical SUBSCRIPTIONS, fi per annum, payable in advance, should be ADVERTISEMENTS.-All communications for the Advertisement Department to be addressed to Mr. THOMAS BLYTON, Advertisement Manager. Advertisements should be received not later than first post on TUESDAY morning. Whole page SCALE OF CHARGES. £ s. d. 5 0 O 2 15 0 0 17 6 O 14 O 0 7 6 Half page, or Whole column Contract terms for extended periods by arrangement. SPECIAL PREPAID SOALE for the following classes of Advertisements only:- Five lines in column (about 40 words) 3s. 6d. Each additional line 6d. Where replies are to be forwarded 3d. extra should be sent. Cheques and Postal Orders to be made payable to Sir WILLIAM THE CHEMICAL NEWS, 16, Newcastle Street, Farringdon Street, LONDON, E.C. |