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Proceedings of the Chemical Society, Vol. 6, No. 82 |
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Proceedings of the Chemical Society, London,
Volume 6,
Issue 82,
1890,
Page 61-68
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摘要:
Issued 231411890. PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 82. Session 1890-9 1. April 17th, 1890. Dr. W. J. Russell, F.R.S., Presideqt, in the Chair. Messrs. Fred. A. A.ndersoq, Henry H. Bunting, P. A. Cobbold and D. S. MacNair were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. James Kear Colwell, 2, Lloyd Street, Lloyd Square, W.C.; William Tait, 115, Rylston Road, Fulham, S.W. The following were elected Fellaws of the Society ;-Joseph Barker, Charles Ridgeway Beck, David Corrie, William Dixon, Thomas Flower Ellis, Frederick John Hambly, Andrew Cowan Holburn, B.Ss., C.E., William Frederick Laycock, Ph.D., Arthur Sheridan Lea, Herman Lescher, John Stewart MacArthur, Henry de Mosenthal, George Muller, Pb.B., E.€3. qeville, M.A. Camb,, Harold Picton, Ernest George Scott, James Sibun, Alexander Smith, Willis Brewin Shuttlewood, Frederick Richard M. Stone, James S. H. Walker. The following papers were read :-28. "Phosphorous oxide." Part I. By T. E. Tharpe, F.B.S., and A. E Tutton. The authors describe a method of making phosphorous oxide in quantity by burning phosphorus in air. Pure P~OS~~OI-OU~oxide melts at 22*5O,and solidifies at 21". It boils unchanged in an atmo- sphere of nitrogen or carbon dio,xide at 173". Vapsur-density deter- minations made by Hofmann's method show that its molecular weight corresponds to the formula P406. In this respect it is analogous to arsenious and antimnnions oKides, which are reqpectively represented by the formulsa As406and Sb,Os.A determination of the molecular weight by Raoult's method, using benzene, which has no chemical action on the substance, as a solvent, also indicated the formula PA On heating phosphorous oxide to about 300", it is decomposed, and at 443" it is wholiy changed into phosphorus and phosphorus tetr- oxide, 2P,06= 3P,01 + 2P. Phosphorous oxide is readily acted on by light, and in bright sunshine its colour rapidly becomes yellow and eventually dark-red. Observations by Captain Abney show that the rialet rays are most active in effecting the change. Curves show- ing the results of the photometric observations are given in the paper,As first prepared, phosphorous oxide is obtained in minute crystals, aggregated into 8 mow-like mass.On allowing the melted oxide to 0001, it solidifies in the form of thin prisms Gapped by pyramids ; the orystals frequently attain the length of an inch or more. The crystals appear to belong to the monoclinic system, and exhibit the pinaooidal faces a = (1OO)mPcm and b = (010)03€b, several prism faces, a pair of ortbQdomes and a pair OP complementary pyramidal faces. The extinctions upon a are parallel to the prism edges, whilst those upon b make an angle of about 20" with the prism edges. When the crosaed Nicols are parallel to the orthopinacoidnl edges, the brush passes across the centre of the field in a line parallel to the vertical axis. The optic axial plane, therefore, appears to be the symmetry plane b.The crystallographha1 relations of Pa06, Agio6and Sb,06are discussed in the paper. The relative density of liquid phosphorous oxide was found to be 119358 at z.Its thermal expansion, as determined by dilatometrical4! measurements, is exppessed by the formula V = 1 + O*O391377S -0.061L175:2 + 0:0,38A07t3. Its relative density at the boiling point is found to be 1.6859, whence its specific volume is 130.5, The bearing of this observation on the question of the constitution of phosphorous oxide and on the question of the varying specific volume of combined phosphorus is then discussed. Previous observations by oue of the authors had shown that the specific volume of combined phosphorus is about 25. From the abservations of Pisati and De Frrtnohis and of Ramsay and Masson, the specific volume of free phosphorus is found to be about 20.9.If all the oxygen in phosphorous oxide be considered as single linked, or, in other words, $0 have the specific volume 7.8, the specific volume of the phosphorus in phosphorous oxide is 20.9, agreeing with the observations of Ramsay and Masson. The conclusion to which the authors come is that, whilst the varia-tion in the specific volume of phosphorus may be related to the atomic arrangement of the phosphorus atoms in the molecule of the elemeiit and in that of the phosphorous oxide, both of which contain the same number of phosphorus atoms, this variation is not neces- sarily dependent on or related to the differences in the cornbiiiing power of the element.Determinations of the refractive index of phosphorous oxide for the red lithium line, the sodium D line, the green thallium line and the three brightest hydrogen lines corresponding to C, F and G have led to the following general expression for the refraction of liquid phos- -516,590,000,000.phorous oxide at 27.4":p =1.5171 +817 670 ____~x2 X' The calculated value of p for the line A (wave-length 7604) is 1.5311 : for a ray of infinite wave-length it is the first term of the above expression, viz., 1.5171. As the rel. den. of liquid phosphorous oxide at 27.4 is 1.9300, the refraction equivalent of phosphorous oxide for A is 220 0*5311=60.5 ;for a, ray of infinite waveAlength 1.93 it is 58.9.The bearing of this observation on the refraction equivalent of phosphorus is then discussed. Contrary to the usual statement of the text books, cold water has very little action on phosphorous oxide: many dajs elapse before even a small quantity is dissolved ; it then forms phosphorous acid, H,PO,. Hot water acts upon P,Os with explosive violence, forming the red suboxide, phosphoric acid and spontaneously inflammable pbosphoretted hydrogen. Caubtic alkalis act similarly, On adding ethyl alcohol to the oxide it at once ignites, but with care the two compounds may be caused to interact to farm diethyl phosphite or diethyl phosphorous acid in accordance with the equation P,Os +8CzH60z4P OC2H, +2H20sCHS This substance, which will be described more fully in a subsequent paper by one of the authors and Mr.Parker North, is a, liquid of 15.5intensely disagreable smell, of rel. den. 1.0749 at -and boiling at4 184-185'. Ether, carbon bisulphide and benzene dissolve phosphorous oxide unchanged. Phosphorous oxide spontaneously oxidises to phosphorus pent-oxide on exposure to air or to oxygen, and the process of oxidation is attended under dimiuished pressure by a faint luminous glow, No ozone is formed as the oxidation pmceeds. On gently warming the 64 oxide in oxygen, the glow gradually increnses in intensity until it passes into flame. In warm oxygen the melted oxide at once ignites and burns with great brilliancy. Carc, therefore, is necessary in distilling large quantities of phosphorous oxide to avoid the free access of air ; otherwise dangerous explosions may occur.In contact with ozone phosphorous oxide glows at the ordinary temperature and pressure. A small quantity of the oxide thrown into a jar of chlorine at once inflames, bnt on leading a slow current of the gas over the cooled oxide it is gradually converted into phosphorus oxychloride and the metaphosphoryl chloride of Gustavson : P,Os -+ BC1, = 2POC1, + ‘LP0,CL Phosphorous oxide has a well marked physiological effect, and it is not improbable that the action hitherto attributed to phosphorus, especially as regards its influence on the glycogenic functions of the liver and on tissue change, may be really due to this substance.It is well known that persons employed in the manufacture of lucifer- matches are occasionally attacked by caries of the lower jaw ; this is not due to the action of the phosphorus after absorption into the circulation, but to the direct effect of the fumes upon the bone itself: for it has been found that when a bone of an animal fed by phos-phorus was exposed no carious change took place ; but if one were exposed to the fumes caries was produced, and amongst lucifer-match makers it has been noticed that only those who haye carious teeth suffer from necrosis of the jaw (T. Lauder Brunton, Yha~rnacoZogy,gc., 771). The fumes from phosphorus consist largely of phosphorous oxide ; by drawing air over phosphorus without allowing it to ignite and passing the fumes through a narrow strongly cooled tube a deposit is obtained which melts with the warnit,h of the hand and gives the reactions for phosphorous oxide.Moreover, the smell of the product is identical with that of pure phosphorous oxide, and it is also identical with the peculiar smell noticed in a lucifer-match manufactory during the making and handling of the “composifion ” with which the splints are “ tipped” and which hangs about the benches where the “boxers ” are at work. It is highly probable, as Schonbein long ago surmised, that phosphorus vapour as such is odourless, and that the smell which phosphorus ordinarily possesses is a mixture of that of ozone and of phosphorous oxide. The authors are continuing the study of this compound, and have already investigated the action upon it of ammonia, sulphur, sulphuric acid, the chloridqes of phosphorus &c.; they are also engaged in experiments on its behaviour with a number of organic substances, and they premise a further communication ou an early date.29. ''The action of chlorine on water in the light, and on the action of light on certain chlorine acids." By Professor A. Pedler. After referring to the somewhat discrepant statements on record regarding the action of chlorine on water in the light, the author describes a long series of experiments made in Calcutta, where the inhensity of light is such that a strong solution of chlorine in water, when exposed to the full blaze of the sun during the hot season, is actually seen to effervesce very decidedly.The results show that interaction takes place only under certaiu conditions, and that more than one change is possible. In a first series of experiments, known volumes of chlorine and water enclosed in tubes were exposed to light, and at the conclusion of the exposure the tubes were opened under water: the contrac- tion having been measured, the residual chlorine and subsequently the oxygen which had been produced were estimated. Using 83.5 C.C. chlorine and 4 C.C. water, quantities in the ratio C1, : 64H20, practic-ally no action was found to have taken place after exposiire during a, month to strong diffused daylight, and during a second mouth to the direct action of tropical sunlight; but, the ratio being Cl, :88H20, about 89 per cent.of the chlorine was fo'und to have been active, 6.5 C.C. of oxygen being liberated. Supposing action to have taken place according to the equation 2H20 + C12 = 0, + 4HC1, 7 C.C. of oxygen should have been obtained, an indication that a very small portion of the chlorine had undergone oxidation. The general result of a number of experiments of this ,kind was that, even in very strong tropical sunlight, water and chlorine interact to but a very slight extent when there aye about 100 times as many molecules of water present as of chlorine; when the proportion is about 150H,O : Cl,, ciction takes place to the extent of perhaps hearly 50 per cent. of the possible amount ; and, when more than 400H20 :Clz, interaction takes place much more rapidly, but even then only to about four-fifths of the theoretically possible extent.As the proportion of water is increased, the amount of chlorine which is oxidised becomes some- what larger. Chlorine water saturated at 30-32", the average working tempera- ture in a Calcutta laboratory, contains chlorine in about the ratio 708H20:Cl,. Experiment shows that, when exposed to direct tropical sunlight, such water undergoes decomporsition practically entirely in the sense of the eqnstion 2H,O + 2C1, = 0, + 4HC1, an exceedingly small amount of chloric acid being formed. On exposing it to strong diffused daylight inside an open south verandah, either hypochlorous or chloric acid, or both, were formed in somewhat variable amount, the pi-oportion of oxygen being much below that obtained in the previous experiments in bright sunlight.On exposing the chlorine water to very moderate diffused light opposite the window in a room having a north light, very little, if any, oxygen was liberated, but the chlorine became oxidised to hypochlorous and chloric acids. In no case could chlorous acid or hydrogen peroxide be detected, On exposing dilute solutions of hypochlorous acid to light, it wag found that both oxygen and chloric acid were produced, the pro- portion of oxTgen being larger the greater the intensity of the light. Solutions of chloric acid underwent little or no change. The author concludes that in its first stages, at all events, the action of chlorine on water is quite similar to that which it exercises on dilute cold solutions of sodium and potassium hydroxides ; and that in the subsequent stage it is very similar to that erected in the case of more concentrated and hot solutions of the two hydroxides.30. “Note on the explosion of hydrogen sulphide and of carbon bidphide with air and oxygen.” By Professor A. Pedler. The author finds that when a mixture of hydrogen sulphide, air and oxygen is exploded, a normal result is obtained, sulphur dioxide and water being formed. But when carbon bisulphide vapour is similarly treated, a not inconsiderable proportion of the nitrogen of the air becomes oxidised ; and after the explosion contractioii con- tinues to take place, owing to the formation of sulphuric compounds (chamber crjstal, &c.) under the combined influence of the moisture present and the oxide of nitrogen.The results of a large number of experiments are described, showing the effect of various proportions of oxygen and air. 31. “The action of light on phosphorus, and on some of the pro-perties or“ ‘amorphous ’ phosphorus.’’ By Professor A. Pedler. As part of an exteneive series of experiments on the action of strong light on substances, the author has studied its effect on phos-phorus, and has thereby been led also to examine and compare the several forms of allotropic phosphorus, viz., that produced by the action of light only, that produced at modemte temperatures, the commercial form, and also rhombohedra1 or metallic phosphorus prepared by dissolving phosphorus in lead at high temperatures. The conclusion is arrived at that, the term “amorphous phosphorus” is a distinct misnomer, and that, so far from commercial ‘‘aniorphous ” phosphorus constituting a, separate allotropic modification of the element, it is in reality the same substance as the form called rhom- bohedral or metallic phosphorus, the very slight difference8 in cha- 67 raoter noticed between the substances in question being explained by the difference in the state of division and the slight variations con- ditioned by their mode of formation.Whether the term amorphous phosphorus can be truly applied to the forms made by the action of light is open to grave doubt; even in this case there appears to be distinct evidence of crystalline form, although, in some instances, a form which appeared to be amorphous was obtained.It is mggested that it would be better to altogether discard the use of the term anaorpkozcs y hosphorus. The author finds that when phosphorus is exposed to light in con- tact with liquids containing oxygen, such as alcohol, it tends to enter into action with them. He arrives at the conclusion that neither in cacuo nor at ordinary pressures is there any change whatever of red into ordinary phosphorus at 260" as ordinarily stated ; and that, practically, no change occurs up to temperatures of nearly 358", above which, iiz vaczm, change takes place, but exceedingly slowly, even up to 445".He also describes experiments which tend to show that red phosphorus is not permanent in air, as commonly supposed. 32. ''The action of phosphoric anhydride on fatty acids.'' By F. S. Kipping, Ph.D., D.Sc. In a previous preliminary note published in these Proceedings, the author has described the formation of the ketone stearone by the action of phosphoric anhydride on stearic acid; he now gives a detailed account of his experiments with this acid, and also describes the application of the same method to the preparation of dihexyl ketone, (C,H,,),CO, from heptylic acid. Two experiments gave 33 and 25 per cent. respectively of the theoretical amount of dihexyl ketone; the yield of stearone being 40-42 per cent.of the theo- ret ical. Dihexyl ketone is found to have the properties already described by Uslar and Seekamp (Annulen, 106, 179). Its hydroxime and hydrazone were both obtained as yellow oils. Dihexyl carbinql was prepared by adding a large excess of sodium to an ethereal solution of the ketone placed in a flask together with moderately concentrated soda solution; it crystallises from dilute alcohol in plates melting at 41-42'. ADDITIONS TO TEE LIBRA.RY. I. Donations. Companion to the latest’, edition of the British Pharmacopmia, by Peter Squire. Fifteenth edition, revised by P. W. Squire and A. H. Squire. London 1890. From P. W. Sqnire, Esq. 11. By Purchase. Les Engrais, par A. Miintz et A. C. Girsrd. Deux tomes. Tome I, Alimentation des plantes ; fumiers ; engrais des villes ; engrais vhg6taux.Tome 11, Engrais azot6s : engrais phosphat3s. Paris 1589. A Text-Book of Assaying for the use of those connected with Mines. By C. Beringer and J. J. Beringer. London 1889. The Micro-organisms of Fermentation practically considered. ByA. Jorgensen. Edited from the German by G. H. M.orris. London 1889. SPECIAL MEETING, MAY 8th. Fellows who desire to exhibit objects at the Special Meeting in May are requested to communicate forthwith with the Secretaries, in order to give time far the preparation of a descriptive list of the exhibits. At the next meeting, on May lst, the following paper will be read :--“ The conditions under which hydrogen peroxide is formed from ether.” By Prof. Dunstan and T. S. Dymond. HARRXSON AND SONS, PRINTERS IN ORDINARY TO HER MAJESTY, ST. MARTIN’S LANE.
ISSN:0369-8718
DOI:10.1039/PL8900600061
出版商:RSC
年代:1890
数据来源: RSC
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