|
1. |
Proceedings of the Chemical Society, Vol. 22, No. 307 |
|
Proceedings of the Chemical Society, London,
Volume 22,
Issue 307,
1906,
Page 77-91
Preview
|
PDF (980KB)
|
|
摘要:
Issued 22/3/06 PROCEEDINGS OF TIIF, CHEMICAL SOCIETY. VOl. 22. No.30'7. Thursday, March 15th, 1906, at 8.30 p.m., Professor R. MELDOLA, F.R.S., President, in the Chair. Messrs. S. L. Courtauld, L. H. Durrans, and R. W. L. Clarke were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs : Ernest Barrett, B.Sc., 56, Elswick Road, Lewisham, S.E. Percy Garratt Chamberlain, M.A., 3, Market Place, Rugby. Cecil Wyatt-Edgell, B. A., Cowrey Place, Exeter. 0. Bertram Foy, 16, Burlington Road, Dublin. John Adam Watson, 8, Powis Gardens, Notting Hill, W-. A certificate has been authorised by the Council for presentation for ballot under Bye-Law I (3) in favour of : Ram Chandra Mukerjee, B.A., of Jaipui; Rajputana, India.The PRESIDESTannounced that Dr. G. T. Morgan had found it necessary to resign the Editorship of the Society's publications, and the Council had appointed Dr. J. C. Cain to succeed him. Attention was drawn to the fact that the Sixth International Congress of Applied Chemistry will be held in Rome, beginning on April %th, 1906. 78 Of the following papers, those marked * were read : *53. u The interaction of well-dried mixtures of hydrocarbons and oxygen.” By William Arthur Bone and George William Andrew. The results of experiments carried out chiefly with mixtures of ethylene and oxygen, well dried by previous long contact with redistilled phosphoric oxide, do not support the view that the presence of steam is essential to the combustion of a hydrocarbon.It mas shown that an amount of desiccation which almost inhibits the combination of hydrogen and oxygen (electrolytic gas) at 525’ does not appreciably retard the oxidation of ethylene. The authors therefore conclude that oxygen is directly active in hydrocarbon combustion. “64. ‘‘ The explosive combustion of hydrocarbons.” By William Arthur Bone and Julien Drugman. The authors showed, as the result of an exhaiistive study of the explosive combustion of a number of diff ereit gaseous hydrocarbons, including paraffins up to butane and olefines such as ethylene, propylene, and the butylenes, that the theory of the preferential combustion of carbon completely breaks down when applied to hydrocarbon flames. The results of the research constitute a strong argument in favour of tlie view that there is no essential difference between the slow and mpid combustion of a hydrocarbon, and that explosive cornbustion prob- ably involves the initial formation of unstable hydroxylated molecules, which subsequently undergo thermal decomposition into simpler pro-ducts.Very striking differences as regards the composition of the end-products are obtained when explosive combustion occurs in the system C,H, + x/202,according as the hydrocarbon is n paraffin or an olefine. In the case of a paraffin, there is always a separation of carbon and a large formation of steam, whereas in the case of the corresponding olefine there is no separation of carbon, and the cooled products consist almost entirely of carbon monoxide and hydrogen in accordance with the empirical equation C,,H,,, + n/20,=nC0 +mH,.In the case of an olefine, it was shown that on reducing the proportion of oxygen much below that indicated by the expression CfiH2,&+ m/202, not only does carbon separate in the flame, but also a large formation of steam occurs, a result which is quite incompatible with the theory of the preferential combustion of carbon in hydrocarbon flames. Comparative experiments on the explosion of mixtures correspond- ing to C,H, + 0,, C,H, + H, + 0,, and C2H,+ 2H, + 0, respectively prove that the process cannot be regarded as involving the primary dissolution of the hydrocarbon, followed by a distribution of the oxygen between free carbon and hydrogen.Incidentally, it wis shown that the affinity of hydrocarbons for oxygen at high temperatures is enormously greater than that of hydrogen, so that whenever mixtures of hydrocarbons and hydrogen react with a supply ol oxygen lew than is required to complete the initial combustion stages of the hydrocarbon, the latter is burnt almost to the entire exclusion of the hydrogen. Hence, in hydro- carbon flames, the initial stages of the oxidation of the hydrocarbon probably take precedence of all other chemical processes. DISCUSSION. Professor SMITHELLSsaid that he was very ready to confess auy mistake he might have made in giving currency to the idea of a ‘‘preferential oxidation ” of carbon in the combustion of hydro-carbons.He admitted at once that the expression was not universally applicable, and he mould endeavour in future not to use it without the necessary qualifications. He wished, however, to remind Fellows what the history of the matter really was. When he began to experi- ment with flamec, he was under the conviction, which he believed was shared by chemists in general, that when a hydrocarbon was burned with a restricted supply of oxygen, carbon rather than hydrogen would remain unoxidised. That view lay at the root of the explanation of the luminosity of hydrocarbon flames then current. When, experi- menting with the aerated flame of ethylene, he had found that the interconal gases contained a large quantity of free hydrogen and no unoxidised carbon, and when he had found this to be true of hydro- carbon flames in general, he felt that a complete revolution must be made in our views, and it was then that he used the expression preferential combustion of carbon. In describing chemical changes, it was customary to name the substances used and the subsfances ultimately obtained.Whatever transitory products might be formed, however the mechanism might be regarded, it was the custom to say, for example, that zinc and strong sulphuric acid give sulphur dioxide, zinc sulphate, and water. We might suppose that zinc first displaced hydrogen from the acid and that the hydrogen reduced some more of the acid, or that the zinc was oxidised by the acid and the oxide then dissolved in more acid. Then, again, hydrogen sulphide and free sulphur were to some extent formed. In such an apparently simple reaction as this, we coulcl affirm nothing with certainty about the actual mechanism.Therefore, we said simply that zinc and sulphuric acid give sulphur dioxide, water, and zinc sulphate. In like manner, it might be said that in the case of hydrocarbon flames burning with a restricted supply of oxygen the carbon was preferentially oxidised. With regard to the probable course of the oxidation, he considered that Dr. Bone had made out a very strong case. It was undoubtedly possible that all the stages which the author had indicated might be passed through; he did not think the explanation presented great difficulties from the standpoint of the kinetic theory of ga,ses.On the other hand, it was undoubtedly possible that the final condition of equilibrium might be reached in one bound, just as a stone under impulse might reach the foot of a hill in one bound instead of folIow-ing the contour of the slope. It was a question of the balance of evidence. The most serious piece of experimental evidence he knew against Dr. Bone’s view was that in those parts of a flame where the partial combustion of hydrocarbons is taking place there is to be seen a spectrum which he believed to be ouly known where carbon and oxygen were uniting to form carbon monoxide. That spoke for a direct attack of the oxygen on the carbon. The solution of the question was one of extreme difficulty, and, as he had said, it involved the careful weighing of circumstantial evidence.Having dealt, Dr. ARMSTRONGsaid, with Dr. Bone’s work elsewhere, and being in agreement with him on the main issue, there mere but few matters to which he need refer. One of the most striking points brought before them was the incombustibility of hydrogen as compared with hydrocarbons-he thought that it mould have to be recognised that hydrogen ras not the active, attractive element it was commonly supposed to be in hydrogen compounds, but that more often than not it simply became pushed aside, as it were. The carbon appeared to be primarily the attractive element, and in this restricted sense Professor Smithells was justified in speaking of the preferential combustion of the carbon in hydrocarbons.As to the influence of moisture on the com- bustion of hydrocarbons, it was to be expected that a hydrocarbon-oxygen mixture would be much more sensitive to change than one of hydrogen and oxygen. Such questions must be regarded from the point of view of some consistent theory of chemical change ;it would be very difficult to obtctin direct experimental proof that conducting water was essential to the occurrence of %he combustion. The view he had expressed twenty years ago in that room, that a mixture of hydrogen and oxygen alone would be found to be incombustible, was now accepted, however, and he did not hesitate to assert that it mas necessary to extend the argument from hydrogen to hydrocarbons but would not be surprised if another twenty Sears passed before it were recognised that a mixture consisting simply of a hydrocarbon and oxygen mas incombustible.Dr. BONE,in reply, remarked that the discussion bad not elicited any definite criticism of the views he has1 advanced in the paper. His own position mas simply this. In conjunction with Dr. Drugman, he had discovered certain facts which proved thzt preferential combustion of carbon did not take place in hydrocarbon flames, but which could be perfectly well explained on the supposition that hydroxylated or oxygenated molecules were initially formed. He had endeavoured to form a mental picture of the processes going on in the flame, but, beyond expressing the conviction that the oxygen is in some way actually incorporated with the hydrocarbon before the system breaks down into simpler products, he did not wish to put forward any theory otherwise than as a working hypothesis.“55. The occurrence of methane amongst the decomposition products of certain nitrogenous bases as a source of error in the estimation of nitrogen by the absolute method.” By Paul Haas. The gas collected over caustic potash in a SchiE’s nitrometer during the estimation of nitrogen by the absolute method was found in the case of more than twelve different compounds to contain methane. The accumulation of this gas was prevented by replacing the copper oxide ordinarily used in such analyses by lead chromate, which effectually oxidises any methane formed.DISCUSSION. Mr. CARRremarked that the different results obtained when the base or its hydrochloride are burnt and the inhibitive influence of cuprous chloride confirmed the results obtained by Prof. Dunstan and himself. These experiments had shown that methane can only be burnt with great difficulty by passing it over strongly heated copper oxide. From the evidence now adduced he thought that the use of cuprous chloride in determinations of nitrogen by the absolute method should become general. More methane is obtained by the ‘‘ carbon dioxide ” method than by Frankland and Armstrong’s racuum method. Mr. W. A. DAVIS staled that in 1896, shortly after thc! publication of Prof. Dunstan and Mr.Carr’s results, he had found that l-nitro-2- methoxynaphthalene gave abnormally high results for nitrogen esti- mated by the absolute method and that the ‘‘ nitrogen ” collected was inflammable. The numbers obtained with the substance agreed closely with those required for a dinitro-derivative, but the fact that normal results were obtained with the derived 1-amino- and l-acetglamino-2- methoxynaphthalene, clearly established the true nature of the compound. It was doubtful whether the formation of methane could be attributed to any special structure, lout it seemed, under exceptional conditions, to be associated with the presence of a methyl or methoxyl group. Dr. BONE said that, with regard to combustions over a hot surface of copper oxide, he had found that the rate of disappearance of hydrogen when electrolytic gas, 2H2+0,, was circulated over copper oxide at 200° was only about 1/30th of the corresponding rate when a mixture of 2H, +K, mas employed.The oxygen in the electrolytic gas was condensed on the hot surface, forming a film which actually protected the copper oxide from the reducing action of hydrogen. Posbibly other gases would be siibilarly condensed on the surface. He was not at all sure that t,he usual practice of using oxygen instead of air in ordinary combustion analyses over copper oxide was a good one. 56. “Studies on comparative crgoscopy. Part IV. The hydro- carbons and their halogen derivatives in phenol solution.” By Philip Wilfred Robertson.The hydrocarbons and their halogen derivatives are characterised by the fact that they give low molecular depressions, which decrease slowly with the concentration. This phenomenon appears to be intimately connected with the associ&ion of the solvent, as it is not exhibited to the same extent by the les associated substituted phenols, 0-cresol, thymol, guaiacol, and o-nitrophenol. It is also shown that benzene does not differ in behaviour from the other hydrocarbons examined, and hence its low molecular depression cannot be attributed to the formation uf a solid solution, as Bruni endeavours to prove (Gucxxettcc, 1898, 28, i, 249). By employing van Bijlerts’ method, his results show that the benzene forms a 30 per cent. solid solution in the phenol.From this it is concluded that van Bijlerts’ method is not always trustworthy, and, moreover, it is not justifiable to assume the existence of a solid solution when the observed molecular depression differs only slightly from the theore tical. 57. ‘(The displacement of acid ions. Part I.” By Alfred Frclncis Joseph. The author described his investigations on the quantitative action of hydrochloiic acid on the nitrates of potassium, sodium, and stroutium, aud of nitric acid on the correspondiug chlorides. An equivalent of the salt in aqueous bolution is mixed with x tquivalents of the acid, the mixture evqoritted to dryness on the water-bath, and the propor- tion of chloride in the residue determined by titration with standard silver nitrate solution.If ihe quant.it,yof salt transformed be y, then it is foubd that ,the 83 equation y = cdogl~z+ b holds good over a considerable range of values of x,a and b being constants depending on the particular acid and salt used. These constants increase and decrease simultaneously with the ratio of the solubilities of the two salts concerned in the transforma- tion. It was found that to transform half the nitrate into chloride by one evaporation with hydrochloric acid requires about 1.5 equi-valents of acid in the case of sodium nitrate, 2.9 for potassinm nitrate, and 12 for strontium nitrate. On the other hand, to transform nioe-tenths of the chloride into nitrate requires 1.6 equivalents of niCric acid in the case of sodium chloride, 1.4 for potassium chloride, and 1-05 for strontium chloride.58. b1 Additive compounds of arylamines with aromatic nitro-derivatives." * By Charles Loring Jackson and Latham Clarke. The following additive compounds have been prepared by the authors in addition to those already described (Bey., 1904, 37, 176). 4 :6-Dibromo-1 :3-c2initrobenzenedimethyZuniline, ~C,H,Br,(NO,),,C,H,.~Me,, which is precipitated as a heavy, red oil. When alcohol is added to a solution of the nitro-compound in an excess of dimethylaniline, it quickly solidifies to short, deep red prisms melting at 50'. 0.3487 gave 0.33'13 A4gBr. Br= 41.12. 0.1762 ?, 0.1705 AgBr. Br=41-16. C,,,H1508NF,Br4 requires 4 1-39 per cent I The conipound is extremely unstable and readily loses dimethylaniline when exposed to the air.4-Chloro-l : 3 :.5-tribromo-3:6-Jinitroberrxene dimethyZuniline, C,ClBr,( NO,),, ?C,H5*NMe,, obtained in the same way as the preceding compound, crystallises in slender, yellow needles and melts at 105'. 0.086 gave 0.0889 AgCl and AgBr ; C1+ Br =40-25. C20H,,0sK',C1,Br6 requires C1+ Br =40.43 per cent. The following compounds give red colorations with dimethylaniline ; in certain cases the colour is removed by the addition of solvents, and in no case has a definite crystalline additive compound been isolated. Nitrobenzene, a-nitronaphthalene, o-nitrophenol, m-dinitrobenzene, 4-bromo-1 :3-dinitrobenzeneY4 :6-di-iodo-1:3-dinitrobenzene, 1:3 :5-tri-* The investigations on additive compounds of trinitrobenzene with amines formerly described (Ber., 1904, 37, 176) and in this paper were undertaken before a copy of J.J. Sudborough's second paper (Trans., 1903, 83, 1334) had been re-ceived by the authors, who thereupoii discontinncd their experiments. chloro-2 : 4-dinitrobenzene, 4-bromo-3 :5-dinitrobenzoic acid (which yields a salt melting at 120-1 25’), 4-ethoxy-3 : -5-dinitrobenzoic acid, 4-isoamyloxy-3 : 5-dinitrobenzoic acid, and picric acid. Methylaniline and s-trichlorotrinitrobenzelle yield ail unstable additive compound, which crystallises in red plates melting at about 78’; it becomes colourless when exposed to the air or when washed with ether, chloroform, or acids. Several of the compounds of toluidines wit’h trinitrobenzene and trinitrotoluene have been prepared (compare Hepp, Aimalesz, 1882, 215, 344 ; Noelting and Sornmerhoff, Ber., 1906, 39, 76).The coin-pounds with trinitrotoluene are much less stable than those with trinitrobenzene. The additive compound of p-toluidine and trinitrotoluene, which Sommerhoff could not obtain, may be prepared by fusing a mixture of the two components, adding a very small amount of toluene, and allow- ing to cool ; it crystallises in dark red needles melting at about 68’. 0.2845 gave 41.4 C.C. of moist nitrogen at 20’ aid 768 inm. N = 16.82. C,,H,,0,N4 requires N = 16-76 per cent. s-Trichlorotrinitrobenzene and pyridine form an extremely unstable additwe compound, C,Cl,(NO,),,C,H,N, which crystallises in slender, red crystals.0.1232 gave 0.1224 AgCl. C1= 54-56. C,,H,O,;N,CI, requires 26.S7 per cent. When kept for a short time, this substance sets to nblack resin. 59. ‘‘Influence of substituents in the trinitrobenzene molecule on the formation of rzdditive compounds with arylamines.” By John Joseph Sudborough and Norman Picton. The formation of additive compounds between a-or P-naphthyl- amine and s-trinitrobenzene derivatives is completely inhibited by the introduction of three methyl-, two methoxy-, or three bromo-radicles into the trinitrobenzene molecule. s-Trichlorotrinitro benzene, however, is still capable of combining with a-naphthylamine. Various additive compounds are described. The compounds derived from the naphthylaii~ines and chloro-deriv- atives of the di- and tri-nitrobenzenes readily lose hydrogen chloride, yielding condensation proilucts of the type of picryl-P-naphthylamine, C,H,(NO,),*N€I*C,,H7.Several compounds of this type have been examined and the following points established : (1) most of the compounds exist in two distinct modifications, namely, a sulphur-yellow and a bright red variety. These may be mutually t,ransformed one into the other by simple methods. (2) They form monopotassium salts which are readily hydrolysed by water. (3) They do not yield acetyl derivatives. (4) Some form extremely unstable additive compounds with arylamines. (5) It has not been found possible to replace the one arylamino-group, *NH*C,H,for example, by another, such as *NH-C,,H7.60. ‘(The relations between absorption spectra and chemical con-stitution. Part IV. The reactivity of the substituted quin- ones.” By Alfred Walter Stewart and Edward Charles Cyril Baly. The reactive power of carbonyl groups in quinones has been shown by Kehrmann (Ber.,1888, 21, 3315 ; J.pr. Chem., 1889,[ii], 39, 399 ; 40, 257) to be greatly influenced by the replacement of the hydrogen atoms of the quinone nucleus by methyl radicle., or halogen atoms. This has hitherto been explained on the assumption that such sub- stituents stericallg hinder the reactions of the carbonyl group in the ortho-position to which they lie. It appeared to the authors that a better explanation might be found in the influence of the substi- tuents on the isorropic process in which the quinone carbonyls are concerned.An examination was made of the absorption spectra of the following quinoc es : p-benzoquinone, toluquinone, p-xyloquinone, thymoquinone, chlorobenzoquinone, bromobenzoquinone, 2 :6-dichlorobenzoquinone, trichlorobenzoquinone, trichlorotoluquinone, dibromothymoquinone, and dichlorothymoquinone ; and from these spectra the following facts may be deduced. (1) Benzoquinone has an isorropic band of long persistence, and shows no sign of benzenoid structure ;(2) the introduction of methyl radicles or of halogen atoms tends to diminish the persistence of the isorropic band and to produce in the spectrum a benzenoid band, the change being greater with chlorine than with methyl ; (3) the benzenoid character of the compound is intensified in proportion to the decrease in the isorropic band.From these facts tohe following conclusions may be drawn. Benzo-quinone exists almost entirely in the quinonoid form. Toluquinone, while existing to a great extent in the quinonoid form, possesses certain characteristics of benzene and probably vibrates in a manner similar to that in which the benzene molecule oscillates. Chloro-benzoquinone, although still possessing cerbain quinonoid properties, is in a state of vibration approximating more closely to the intra- molecular motions of benzene. Trichlorobenzoquinone, in which the isorropic process is practically non-existent, vibrates in a manner closely resembling the vibrations of the benzene ring.Now Kehrmann has shown that the introduction of methyl radicles or halogen atoms hinders the formation of quinoneoximes, and the amount of hindrance observed by him is in complete accord with the change in character from the quinonoid to the benzenoid type which is proved by the spectroscopic evidence. In their previous papers (this vol., pa 33), the authors $homed that in order to bring about the isorropic process the quinonoid structure had first to be produced. As the reactivity of the carbonyl group depends on the isorropic process, it is evident that. the benzenoid character of the compounds examined is alone suficient to explain their non-reactivity, without introducing the question of a purely hypothetical “ steric hindrance.” The facts now submitted, in conjunction with those already com-municated to the Society, tend to show that there is no necessity for the assumption of any such purely mechanical causes underlying the hindrance to chemical reactions.61. ‘‘ The constitution and properties of acyl thiocyanates.” By John Hawthorne. It has been shown (Dixcn and Hawthorne, Trans.,1905, 87,468) that when acetyl “thiocyanate ” interacts with aniline, two changes occur simultaneously : (1 ) double decomposition, the sulphur appearing as thiocyanic acid, AcSCN + PhNH, = HSCN + AcNHPh ; (2) ad-dition, the sulphur now exhibiting thiocarbimidic functions, AcNCS + PhNH, =AcNH-CY-NHPh. At low temperatures the former reaction predominates, and at high temperatures the latter.It has now been shown that, besides temperature, two other factors may have an influence on the course of the interaction between an acyl ‘‘ thiocyanate ” and a base : (1) the nature of the base presented, and (2) the nature of the acidic radicle of the “thiocyanate.” The results are recorded of experiments made at raricus temperatures on the systems o-toluidine-acetyl ‘I thiocyanate ” and aniline-propionyl ‘I thioc) anate,” fr,tin which it appears (1) that o-toluidine causes a great increase of the thiocarbimidic functions of acet’yl “thiocyanate ” as compared with aniline, and (2) that, towards. aniline, acetyl and propionyl ‘‘ thiocyanates ” behave very nearly alike.Since in all the above reactions acetyl ‘‘ thiocyanate ” behaves towards a given b;rse as if it were a mixture of acetyl thiocyanate and acetylthiocnrbiniide in proportions depending on the temperature, a series of determinations of the molccular refraction of the pure substance mas carried out. Within the limits of temperature examined, this value was practically constant, the mean, 45.9, as deduced from the formula ill=(’ d’”’, being inconsistent with $he 87 value required for a compound having the structure hc-S*CiN,but agreeing closely with that corresponding to Ac*N:C:S. 62. “A mode of formation of aconitic and citrazinic acids and their alkyl derivatives, with remarks on the constitution of aconitic acid.” By Harold Bogerson and Jocelyn Field Thorpe.By the condensation of the sodium derivative of ethyl cyanoacetate with ethyl osalacetate, ethyl a-cyanoaconitate, CK*CH(C0,Et) *C(CO,Et) :CH*CO,Et, is produced. This ethyl salt on hydrolysis with acid hydrolysirig agents is conrertetl into aconitic acid, whilst with alkaline hydrolytic agents it is transformed into citrazinic acid. Alkyl derivatives of these conipouncls are formed when alkyl derivatives of ethyl a-cyano- wonitate, prepared either by the direct alkylation of this substance or by the condensation of the sodium derivative of ethyl cyanoacetate with alkyl derivatives of ethyl oxalacetate, are hydrolysed. It was shown that aconitic acid, like glutaconic acid, has a symmetrical struc- t ure, and that a-niethylaconitic and 7-methylaconitic acids are tauto- meric.63. ‘‘ Aromatic sulphonium bases.” By Samuel Smiles and Robert Le Rossignol. It was shown that the action of thionyl chloride on phenetole in presence of aluniiniuin chloride gives rise to 29-phenetylsulphoxide and triphenetylsulphonium chloride ; the latter is produced by the action of excess of phenetole on the sulphoxide. This reaction has led to the discovery of two other methods of preparing these aromatic sulphonium bases : (1) from a sulphoxide and phenetole with a dehydrating agent ; (2) from a sulphinic acid and phenetole with strong sulphuric acid. It is also shown that in this reaction a sulphoxide is formed as an inter- mediate product . 64. (‘A new form of calcium chloride tube for combustion.” By Arthur Edwin Hill.The calcium chloride tube indicated in section in the figure on p. 86 consists essentially of an inner exit tube, A, which is enclosed within a larger inlet tube, B, the latter being fused to the tube A at D and carrying a side-tube, E,provided with the usual form of bulb in which water can collect as liquid. The apparatus is easily filled by inverting it and pouring finely granulated calcium chloride into both the tubes A and 8;before filling, a little glass woo1 should be inserted at the top of both the inner and outer tubes and after charging with calcium chloride niore glass wool is introduced ; a suitable cork is then inserted at G; finally, this cork is cut off flush with the bot'toin of the tube aiicl neatly covered with sealing wax.The bulk of the water produced in the combustion is condensed in the bulb on the tube E, the remainder being absorbed during the pas- sage of the moist gases down B and up A. ,4double scrubbing action is thus obtained by the aid of a comparatively small weight of calcium chloride; this, in fact, in addition to its compactness, is a special feature of the tube and the cause of its efficiency. A certain amount of free space, not packed with the chloride, in the tube R, im-inediately above the point of con-nection with E, is allowed, into which the water vapour can diffuse before coming into contact with the calcium chloride ;by this means, the calciuni chloride is uniformly wetted. The new form of tube presents a number of advantages : (1) The double scrubbing ac-tion, which ensures complete desiccation by means of a com-paratively small quantity of cal- cium chloride.The whole appa- ratus when filled ~eighs only from 3.5 to 30 grams. (2) It can be very easily emptied and refilled. There are no tubes to be sealed off at the blow-pipe and only a single cork is required. (3) It is very compact and strong, the bend which is n point of weak- ness in the ordinary U-tube being got rid of. It is also more easily manipulated than the ordinary form of tube. (4)It can be more easily and rapidly wiped dry before weighing. Several analyses made for the purpose of testing the tube have shown that it gives perfectly satisfactory results.The carbon dioxide pro- (iuced siinultaneously with the water is easily and completely swept from the tube into the pbtash bulbs by the current of air usually employed in a combustion, 89 65. The viscosity of liquid mixtures, Part 111.” By Albert Ernest Dunstan. The author’s prei-ious work and his hypotheses regarding iiiaxiinurii and minimum points in viscosity.concentration curves were summarised and some relations between viscosity and molecular weight were indicated. For liquid mixtures of unimolecular components, it was shown that the general viscosity curve is concave to the axis of percentage com-position, oving to the reciprocal effect of each liquid on the other. MoreolTer, the depression angles which measure these mutual effects we, in general, proportional to the molecular weight of the liquid concerned.The “external angle” lying between the curve and the viscosity axis is shown to be also proportional to the molecular weight of tlie liquid. The fonnule proposed by 9rrhenius was discussed, and it was pointed out that no foriiiula can interpret the curves which does not contain a factor characteristic of each curve. Each allied substance lies on a simple parabolic curve. The curves connecting molecular weight with tlie log,o viscosities are straight lines. The associated lower members of each group diverge somewhat from this line. Water, and formic and acetic acids show anomalous behaviour. If the family to which any liquid belongs is known, the molecular weight of the liquid can be calculated.66. ‘:The action of phenylpropiolyl chloride on the ketonic compounds. Part II.” By Siegfried Ruhemann. The compounds previously described by Ruhemann and Blerriman (Trans., 1905, 87, 1353) have been subjected to a closer investigation. The red compound C,4H1203,which was represented by the formula ?(c6H5)*C(CH3)>C.C0.CH3,reacts with phenylhydrazine to yield aC(0H)---CO pheiiylhydrazone which, on account of its insolubility in alkali, is considered to have the constitution Its formation, therefore, is accompanied by the change of the enolic into the ketonic group. Analogous fornuke should be attributed to the seinicarbazone, C15H1503N3,and the oxime, C14Hl,0,N.The fact that these two compounds are colourless indicates that the colour of the red compound C1,H,,O, is due to the grouping -CO*COH:C< and dis- appears with the change into H$*CO*CO-. The former configura- tion yields blue salts with alkalis. The results thus obtained are used to establish the structural formuh of the derivatives of osalyldibenzyl-ketone (see Claisen and Ewan, Annalen, 1895,284, 245), the properties of which resemble the red substance C11H1203. The former compound with alkalis yields both blue salts and yellow salts. The blue salts owe their formation to the same arrangement of the ketonic and enolic groupings as is contained in the red substance C14H1203, whilst in the yellow salt's t'he ketonic group occupies the P-position with respect to the enolic group.ADDITIONS TO THE LIBRARY. I. Donations. Caven, Robert ;Mccrtin, and Lander, George Druce. Systematic inorganic chemistry from the standpoint of the periodic law. pp. xix +3'74. London 1906. (Red 2/3/06.) From the Authors. Liebreich, Oscar. Third treatise on the effects of borax and boric acid on the human system. Being a critical review of the report of Dr. H. JK Wiley, Chief of the Bureauof Chemistry of the U.S. Depart-ment of Agriculture, to the Secretary of Agriculture. Translated from the German. With diagrams. pp. vii+70. London 1906. (Recd. 9/3/06.) From the Publishers : Messrs. J. 'E: A. Churchill. Metropolitan Water Board. Report on the results of the chemical and bacteriological examinations of the London waters, for the month ending November 30th, 1905, &c.By A. C. Houston. London 1905. From the Board. Rolfe, George TPilZiun2. The polariscope in the chemical laboratory. An introduction to polarimstry and related methods. pp. vii + 320. ill. New York 1905. (Recd. 9/3/06.) From the Publishers : The Macmillan Company. Welch, Geovge Edward. Chemistry lecture notes. pp. 63. London 2905. (Recd. 9/3/06.) From the Publishers : Messrs. Blnckie C! Son. 11. By Purchase. Freund, Ida. The study of chemical composition. An account of its method and historical development. With illustrative quotations. pp. xvi + 650. ill. Cambridge 1904. (Rec1. 3/3/06.) Rutherford, Ernest. Radioactivity. pp. xiv + 550. Cambridge 1905.(Recd. 3/3/06.) 111. Fanaphlets. Day, Arthur L. Miiieritl solution and fusim under high tempera- tures and pressures. (From the Year Book of the Carnegie hastitution of TVasTbington,4)1905.) Paterson, David. Concerning indigo, natural and arcificial. (From the Oil and Colourman’s Journal, 28,1905.) Schroeder, August. B3itrage zur Kennt nis einiger ausliindischen Fette und Ode. pp. 67. Strassburg 1905. Stapleton, Henry Ernest. Sal-ammoniac : a study in primitive chemistry. (From the Memoirs, Asiatic Soc. Bengccl, 1, 1905.) Stapleton, Benq Ernest, and Azo, R.F. Alchemical equipment in the eleventh century, A.D. (From the Memoirs, Asicclic Soc. Bengcd, 1, 1905.) Watts, Prancis, and Tempany, H. The polarimetric determination of sucrose.(From the Test 11zdicc12Bulletin, 67 1905.) ANNUAL GENERAL MEETING. The Annual General Meeting of the Society for the election of Officers and Council and other business will be held on Friday, 30th Harch, 1906, at 5 o’clock in the afternoon. willThe PRESIDENT deliver his address entitled : ‘‘ The living organism as a chemical agency : A review of some of the problems of photosynthesis by growing plants.” At the next Ordinary Neeting, 011 Thursday, April 5th, 1906, at 8.30p.m., the following papers will be read : ‘‘An improved apparatus for measuring magnetic rotations and obtaining a powerful sodium’light.’’ By W. H. Perkin, sen. 6‘ The rusting of irc~n.” By G. T. Moody. ‘‘ The determination of carbon in soils.” By A. D. Hall, N. H. J. Miller, and N. Marmer. The electrolysis of the salts of @dimethylglutaric acid.” By J. Walker and J. I(.Wood. Bromo-and hydroxy-derivatives of &3/3’/3’-tetramethylsuberic acid.” By J. K. Wood. H. CLAY AND SONS, LTD.: BREAD ST. HILL, E.L., AED kUSlfdY, SUFFOLii.
ISSN:0369-8718
DOI:10.1039/PL9062200077
出版商:RSC
年代:1906
数据来源: RSC
|
|