摘要:

Issued 14/5/04 PROCEEDINGS OF THE CHEMICAL SOCIETY. VOl. 20. No.280. ~~-~ May 5th, 1904. Professor W. A. TILDEN,D.Sc., F.R.S., President, in the Chair. Messrs. C. M. Beadnell, C. T. Bennett, and T. U. Walton mere formally admitted .Fellows of the Society. Certificates were read for the first time in favour of Messrs. W. Eddington Field, 65, Sutherland Road, Armadale, Melbourne, Victoria, Australia. John Hulme, 3, Albert Terrace, Stockport. A ballot for the election of Fellows was held, and the following were subsequently declared duly elected : William Barbow, M.A., B.Sc. William Davidge Page. R. H. Durward Benn. Gerald Pinchbeck. Robert Currie Bridgett, M. A., B.Sc. Thos. Linton Daniel Porter, B.Sc. Ellis Clayton. Louis John Ezekiel Riley.Robert Steel Fiulow, B. Sc. Franklin Ernest Robertson. Harold Sankey Hammond. Thomas George Shacklady. George Mathieson Horn. Clarence Smith, D.Sc. Percy Kent Le May. Henry Herou Smith. Alfred Mander. Reginald Harry H. Stanger. Tom Sidney Moore, B.A., B.Sc. Robert de J. Fleming-Struthers, B.A. Gerald Oscar Morgan Smith. Walter Tong. Lauiel Cecil Francis Oldfield. 106 The PRESIDENTannounced that the following persons were proposed by the Council for election as Foreign Members. Henri Becquerel. Madame Marie Curie. Cornelis Lobrg de Bruyn. Carl Liebermann. Frank Wiggleswort h Clarke. Edward Williams Morley . and stated that in accordance with Bye-Law IT. the ballot for their election would take place at the next meeting of the Society on Wednesday, May 18th.The PRESIDENTannounced that the following letter had been received from Sir Henry Roscoe in reply to the address of congratulation from the Society on the occasion of the celebration of the Jubilee of his Doctorate. (‘‘To the Conncil and Fellows of the Chemical Society I offer my hearty thanks for the honour they have done me through the President, Professor Tilden. ‘Instituted in 1841 for the purpose of stimulating chemical research in this country by the leaders of our science of that day, aniongst whom Thomas Graham stands pre-eminent, the influence which the Society has exerted during more than half a century on the progresq of English Chemistry bas been far greater than its Founders could have foreseen.‘During the last fifty years our Science has undergone not one but many revolution$, each one widening and deepening its foundations. ‘In this wonderful series of changes, thanks to the zeal and ability of its Fellows, both young and old, the Chemical Society has borne no inconsiderable part., and for its still wider influence and its still greater activity no one has warmer wishes than myself. (Signed) HENRY E. ROSCOE.’ ” Of the following papers, those marked * were read : “72. “ The slow combustion of ethane.” By William Arthur Bone and William Ernest Stockings. The authors have studied (1) the interaction of ethane and oxygen at 250-400°, under pressures of 1.75 to 2.33 atmospheres, in boro-silicate glass bulbs (compare Trans., 1902,81,536) ;(2) the oxidation of ethane in contact with a surface of porous porcelain at 400--500°, under reduced pressure, in the circulation apparatus described in a previous paper (Trans.,1903, 83, 1074), and (3) the slow combustion 107 of ethyl alcohol and acetaldehyde.The main conclusions deduced from the experiments are as follows : (1) The proportions of ethane and oxygen most favourable to chemical change are equimolecular (1 :l), although interaction takes place nearly as rapidly in mixtures containing ethane and oxygen in the ratio 2 : 1. At all temperatures, ethane is oxidised much more rapidly than is methane, other conditions being equal. (2) When ethane is treated with proportions of oxygen insufficient to oxidise the whole to carbon monoxide and steam, there is no prefer- ential combustion either of hydrogen or carbon.In the absence of secondary phenomena, the interaction is always marked by a diminu-tion in the pressure of the cold products witbout any deposition of carbon or liberation of free hydrogen. (3) The combustion proceeds in several well-defined stages, among which the following have been distinguished : (i) A primary oxidation to acetaldehyde and steam. (ii) A further rapid oxidation of the acetaldehyde to formaldehyde, carbon monoxide, and steam. (iii) The final oxidation of formaldehyde to carbon monoxide, carbon dioxide, and steam, which may best be considered as due to two simultaneous interactions (i) CH,O +0, =CO, +H,O, (ii) 2CH,0+0,=2CO+2H20.(4) The combustion of the hydrocarbon may be accompanied by the following secondary phenomena : (i) Hydrogen or methane, or both, may appear in the products with- out any liberation of carbon, as the result of the purely thermal decompositions of formaldehyde and acetaldehyde vapours respectively, the latter giving rise to methane and carbon monoxide, whilst the former yields hydrogen and carbon monoxide, although its decom- position is a more complex process than that of acetaldehyde. (ii) Small quantities of ethylene and bydrogen may appear in the products as the result of the thermal decomposition of ethane. (iii) If the heat liberated during the initial stages of oxidation is sufficient to raise the temperature of the interacting gases to the ignition point, an explosion takes place, during which the excessof hydro- carbon, and probably also of aldehyde vapours, is decomposed, carbon and hydrogen being liberated together with some acetylene and ethyl- ene.There is no liberation of carbon below the ignition point. (5) Although ethyl alcohol has not been detected among the oxida- tion products of ethane, its absence may be explained by the fact that it is oxidised far more rapidly than is ethane under similar con- ditions. (6) The view taken of the mechanism of the combustion of ethane is supported by the experiments on ethyl alcohol and acetaldehyde. 108 *73. “The action of radium rays on the halides of the alkali metals and analogous effects produced by heat.” By William Ackroyd.The author has studied the action of y-rays from radium bromide, in its violet glass tube, on the chlorides of lithium, sodium, potassium, rubidium and caesium, and deduces the following conclusions : (1) The colour changes produced divide the compounds into two sub- groups: I. LiCl, NaCI, azd II. KCI, RbCl, CsCI, and in the effects observed : LiCl, white ; NaCl, orange ; KCl, violet ; RbCI, bluish- green, and CsCl, green, each sub-group conforms to the constitiitive- colour law (Chena. News,1893, 67,27). (2) The division into these sub-groups is also indicated by their differences of molecular aggregation as expressed by l/sp. vo1. (3) There is relative stability of the colours produced while they remain in darkness, and their rate of disappearance or decay in day-light varies with the intensity of the light.(4) The relative expendituie of energy in the y-rays effecting the colour changes decreases with increase of molecular weight, or, in other words, the sensibility to the action of the y-rays increases with the molecular weight. (5) When the induced phosphorescence has decayed so as to be no longer visible, it can be revived by invisible heat. In the case of fused lithium chloride, a temperature of 37” is sufficient for the purpose. (6) These various features correspond in many respects with the thermal effects produced in other substances, and the whole of the evidence points to the conclusion that both are physical changes.“74. ‘‘The mutarotation of glucose and of galactose. Solubility as a means of determining the proportions of dynamic isomerides in equilibrium.” By Thomas Martin Lowrg. The method formerly described (Proc., 1903, 19, 156) and applied to the case of P-bromonitrocamphor has now been used in order t.0 deter-mine the proportion of a-glucose and of a-galactose in the mixt!ires of dynamic isomerides which are formed when these sugars are dis-solved in alcohol or in water. The solubility of a-glucose in an-hydrous methyl alcohol gradually increases in the course of a week in the ratio of 0.53:1 and that; of a-galactose in the ratio 0.50: 1. The increment of solubility is due to the formation in solution of the stereoisomeric P-glucose (Tanrot’s y-glucose) and P-galactose ;when equilibrium is reached, the quantity of sugar in solution is nearly twice 109 as great as when the a-form alone is present, and the stereoisomerides must therefore be in approximately equal proportion and be almost equally stable.This result differs from that obtained by Jungius in the case of the methyl-glucosides, for which the ratio was found to be a :/3 = 3 : 1 instead of 1 : 1. In a mixture having approximately the cornposition EtOH + H,O, the solubility of a-galactose was found to increase in the ratio 0.39 : 1, and in a mixture having approximately the composition PrOH + 2H,O in the ratio 0.35 : 1. The decrease of the ratio in the aqueous-alcoholic solutions may be attributed to the presence in the solution, along with the stereoisomeric a-and 6-galactoses, of a consider-able proportion of the hydrated aldehydic form of the sugar, which is probably an intermediate product in the isomeric change (compare ITrant~.,1903, 83, 1316); this conclusion is in harmony with the fact that the rate of change is many times greater than in the anhydrous me thy1 -alco holic solutions.Similar experiments were made on the dissolution of a-glucose in mixtures having approximately the composition 2EtOH + H,O and EtOH + H20, but in each case the gradual increase of solubility was preceded by a more or less rapid decrease owing to the conversion of the solid a-glucose into a less soluble hydrate. '75. " A study of the substitution products of ar-tetrahydro-a-e tr ah ydro-a-napht hylamine and nap ht hy lamine.4-Bromo-a~t nr-tetrahydro-~-naphthylamine-4-sulphonicacid." By Gilbert Thomas Morgan, Frances Mary Gore Micklethwait, and Herbert Ben Winfield. The acgl derivatives of ar-tetrahydro-a-naphthylamine(Bamberger and Althause, Ber., 1888, 21, 1895), when brominated with one molecular proportion of the halogen or hypobromous acid, ultimately undergo substitution in the aromatic ring, the entrant bromine atom assuming the para-position with respect to tbe aminic nitrogen. The homo-base obtained on hydrolysis was shown to be 4-homo-ar-tetrahyclro-a-nccphthyZa~~in~(m. p. 42O) by furnishing successively 1-bromotetrahydronap hthalene and 1-bromocZinitrotetrahydl'onccphth-cclene (m.p. 9 1'). The isomeric 2-tromodinitrotetrahydronaphthuZene prepared from ar-tetrahydro-P-naphthylaminefor the purpose of comparison melted at 105-106°. On treatment with diazo-compounds, the bromo-base yields diazoamines of the type C,oH,oBr*NH*N2X. .For example, 4 :4'-dibrorno-l-diuzo-l-aminotetmhy&-onaphthaZene prepared by the irteraction of the base with its own diazonium salt, decomposes violently at 190-1 94O, and when treated with cold concentrated hydrochloric acid undergoes fission, yielding the hydrochlorides of its 110 generators, the diazonium chloride being identified by the formation of 4-bromotetrahydronuphthaZeneaxo-~-naphthoZ(m. p. 2 15O). 4-Bromo-a-naph thylamine, unlike the analogously substituted tetra- hy dro-base, condenses with diazo-compounds to form ortho-azo-derivatives having the general formula XN,*C,,H5Br*NH,.The CLXO-compound, NaSO,=C,H,*N,*C,,II,Br*NH,, yields, on reduction, sulphanilic acid and naphthylene-1 :2-diamine. ar-Tetrcchydro-a-naphthylamine-4-sulphonicacid, NH,*C,oH,,*SO,H,H,O, produced by sulphonating ar-tetrahy d ro-a-naph thy lamine, was con-verted into tetrahydronaphthazene-1-suZpI.onicacid by eliminating its amino-group, the same product being also obtained by replacing this radicle in ar-tetrahydro-a-naphthylamineby the SO,H group and oxidising the tetrahydrona~htiLaZene-l-s~~pi~inicacid thus produced. Tetrahydronaphthalene-1-sulyhonic chloride and the corresponding anilide melt at 70.5’ and 144-145’ respectively.cw-Tetrahydro-a-naphthy lamine-4-sulphonic acid differs from a-naphthy lamine-4-sulphonic (naphthionic) acid in yielding diazosmino- derivatives and not azo-compounds. The azo-derivatives of ur-tetrahydro-a-naphthylaminewere shown to be para-azo-compounds like the corresponding azo-a-naph thy lamines, for, on reduction, they give rise to ar-tetrahydronaphthylene-1:4-diamine. These results indicate that although ar-tetrahydro-a-naphthylamine resembles a-naphthylamine in forming para-azo-compounds with greater facility than a benzenoid amine, yet its para-substituted derivatives, unlike those of a-naphthylamine, do not yield ortho-azo- compounds, and in this respect behave like p-bromoaniline and other similarly substituted bases of the benzene series.bb*76. Studies in the tetrahydronaphthalene series. Part IT. Halogen derivatives of ar-tetrahydro-p-naphthylamine.”By Clarence Smith. In a previous paper (I’mns., 1902, 81, 900), it was shown that ar-tetrahydro-p-naphthy lamine resembles primary benzenoid nmines in giving diazoamino-compounds, and this resemblance is exemplified further in its behaviour towards the halogens. Aceto-P-naphthalide yields only 1-bromo;tceto-p-naphthalide at the ordinary temperature, even with excess of bromine. ar-Tetrahydro-ace to-P-naphthalide reacts with one molecular proportion of bromine to form two compounds, namely, 1-bromo-ar-tetrahydroaceto-p-naphthalide and 4-bromo-c~r-tetrahydrortceto-/3-naphthalide.The following compounds have bean prepared : 1-BromotetrahydronaphthaZene,C,,H,,Br, obtained from .ar-tetra- 111 hydro-a-naphthylamine by the Sandmeyer reaction, is a colourless, refractive liquid with an odour resembling that of halogen compounds of the benzene series; it is volatile in steam and dissolves readily in organic solvents (b. p. 255-257"/751 mm. ). 2-Brornotetrahydi*onaphthaZene,prepared from ay-tetrahydro-a-naphtfr ylamine, resembles the preceding compound and boils at 238-239' under 758 mm. pressure. l-Bromo-w-tetruh ydroaceto-P-naphtha Zide, C, ,H, ,ONBr, resulting from the action of one molecular proportion of bromine on an equivalent quantity of ar-tetrahydroaceto-P-naphthalidedissolved in glacial acetic acid, separates from alcohol in colourless, octahedral crystals (m.p. 125.5"). 4-Bromo-ar-telrahydroaceto-P-naphthalide,obtained from the mother liquor in the preparation of the preceding isomeric 1-bromo-compound, separates from alcohol in colourless needles (m. p. 151'). 1-Bromo-ar-tetrahydro-/3-naphthyZarnine,C,,H,,NBr, is prepared by hydrolysing the corresponding acetyl derivative ; it separates from light petroleum in colourless, silky needles (m. p. 52.5'). It dissolves easily in alcohol or acetone, and is volatile in steam. 4-Bromo-ar-tetrahydro-~-napl~thylaminecrystallises from light petrol- eum in colourless needles (m. p. 52"); it is not readily volatile in steam. "77. Studies in the tetrahydronaphthalene series.Part 111. Reaction between ar-tetr ahydro-P-naphthylamine and form- aldehyde." By Clarence Smith. Evidence of the benzenoid nature of acr-tetrahydro-p-napht hylamine is obtained from the study of the behaviour of the base towards form-aldehyde. The product is methylene-ar-tetrahydro-P-naphthylamine, analogous to methyleneaniline. There is no tendency to produce an acridine, which would be evidence of its naphthalenoid character. The following compounds have been prepared : Methylene-ar-tetrcchydro-P-nccpl~thyZamine,(ClllH13N)3,is obtained to- gether with a polymeric modification, (Cl1Hl3N)%,when a solution of formaldehyde is added slowly to ar-tetrahydro-P-naphthylamine. The trimolecular form separates from acetone or light petroleum as a felted mass of small, white needles ; it melts at 121' and gives an intense blood-red coloration with glacial acetic acid.The polymeric modification is a white, amorphous powder which, when heated, darkens at 156' and fuses at 164". It is almost insolu- ble in acetone, light petroleum or benzene, but dissolves in hot alcohol and becomes converted mainly into the trimolecular form. MethyZ-ar-tetrahydro-/3-naphthyZamine,C,,H,,*NH*CH,, obtained by 112 the reduction of methylene-ar-tetrahydro-P-naphthylamineby sodium and amyl alcohol, is a colourless, refractive, oily liquid which boils at 26’7~5~under 2 10 mm. pressure. The hydrochloride, C,,H,,N,HCI, crystallises from water in white needles. The nitrate, C,,H,,N,HNO,, separates in needles when an ethereal solution of the base is shaken with dilute nitric acid.The nitrosoarnine, C,,H,,N(CH,)*NO, is a yellow oil, which gives Liebermann’s reaction. 78. “Note on the hydrolysis of starch by diastase.” By John Simpson Pord. The writer finds that Kjeldahl’s “ law of proportionality ” is true for the diastase of barley and air-dried malt, as well as for that of kiln-dried malt. 79. “The resin acids of the Conifer@. Part I. The constitution of abietic acid.” By Thomas Hill Easterfield and George Bagley. The resin acids of the Conifem as a class have the following points in common : (1) they readily become superfused, and then set to a resin Gr glass, which crystallises if fused and maintained for some time at a temperature slightly above the initial melting point; (2) they nitrate without difficulty in glacial acetic acid solution ; (3) in a fused state, they readily absorb oxygen from the air; (4) their esterification velocity is extremely low ;(5) with hydriodic acid, they yield hydrocarbons of nearly the same composition as the diterpenes, with which they have erroneously been regarded as identical.Colophony, on distillation under diminished pressure or in super- heated steam, yields a product which gives analytical results agreeing accurately with those required for abietic acid (m. p. 160-165’). By the slow distillation of abietic acid, even under reduced pressure, a hydrocarbon, C18H28, is produced, which is undoubtedly the ‘‘colophene ” obtained by Deville on distilling colophony, but is not the ‘‘colophene” which the same author produced by polymerising turpentine by means of sulphuric acid.In order to avoid ambiguity, the name “abietene” is proposed for the compound derived from abietic acid. Kriimer and Spilker, by distilling colophony under pressure, obtained a hydrocarbon to which they assigned the formula C18H28,regarding it as being derived from abietic acid by the loss of carbon dioxide. Abietene, C18H28,boils at 199-200” (13 mm.), 247-250” (82 mm.), 340-345” (760 mm.), has a sp. gr. 0.9’73 at 19”/19”, and n, 1.537 at 113 20’ ; it is thus identical with the ‘‘ diterebenthyl ” (C,,H,, 1) which Renard (Compt. rend., 1887, 105, 865) isolated from resin oil.Abietene is produced when abietic acid is heated with fuming hydriodic acid at 200’ ;the gases formed at the same time have been analysed and were found to consist of 90 per cent. of carbon monoxide and dioxide approximately in the ratio 9CO : lCO,, the volume of oxides of carbon formed after 2 hours’ heating being 80 per cent. of that required for the elimination of one carboxyl group from abietic acid. Abietene, when distilled with one-third of its weight of sulphur, yields a small quantity of retene (m. p. 99’), but with twice this pro- portion of sulphur an isomeric hydrocarbon is obtained melting at 86’ ; at the same time, a hydrocarbon boiling at 330-360’ (30 mm.) is produced, which is still under examination. If the distillation with sulphur is conducted under reduced pressure, retene is the principal product.These two hydrocarbons are also formed by distilling Merck’s ‘(retene puriss.” with one-fifth of its weight of sulphur. The foregoing observations support the view that hydrogenated retenes are probably normal constituents of resin oil (Bey., 1889, 22, 3368 ; 1903, 36, 647), and that resin oil is undoubtedly a hydrogen-ated retene. This conclusion is further strengthened by the observation that abietene, when reduced with hydriodic acid and excess of phosphorus at 240°, takes up two atoms of hydrogen and yields a hydrocarbon, dihydronbietene, which appears to be identical with the dodecahydro- retene obtained by Liebermann and Spiegel (Bey., 1889, 22, 779) by reducing retene under similar circumstances.The above observations lead to the conclusion that abietic acid is decahydroretenecarboxylic acid, but the accepted formula for retene would not account for its low esterification velocity. There is, horn- ever, no experimental evidence for the assumed para-position of the methyl and isopropyl groups in retene. That these groups are really in the meta-position in abietic acid and in retene is rendered probable by the observation of Kolbe (Ber., 1880, 13,888) that resin spirit is rich in m-cymene, but contains only small quantities of ordinary cymene. 80. 6c The additive products of benzylideneaniline with ethyl acetoacetate and ethyl methylacetoacetate.” By Francis Ernest Francis and miss Millicent Taylor.It was shown that the additive product of benzylideneaniline andethyl methylacetoacetate exists in one form only, being unaifected in solu- tion by traces of either piperidine or sodium ethoxide. This confirms Schiff’s view of the constitution of such substances. The various data 114 in connection with the additive products from ethyl acetoacetate and benzylideneaniline were indicated, and Morrell and Bellars’ work on the subject was criticised. 81. “Studies on ethyl carboxyglutarate. Part I. Action of halogens on ethyl sodiocarboxyglatarate.” By Oswald Silberrad and Thomas Hill Easterfield. When halogens were allowed to act on ethyl sodiocarboxyglutarate, no condensation occurred, but instead of ethyl carboxydiglutarate the haloid derivatives of the original ethyl carboxyglutarate were formed.The reaction may be thus represented : C,H,*CO,*CH,aCH,~CNa(CO,*C,H,),+I, = NaI + C,H,*C0,*CH,~CH,*CI(C0,*C2H5)2 The products proved to be identical with the compounds subsequently obtained by the direct halogenation of ethyl carboxyglutarate. 82. “Studies on optically active carbimides. Part I.” By Allen Neville and Robert Howson Pickard. The authors have investigated (i) the preparation of some optically active carbimides, (ii) the use of such compounds for the resolution of synthetical alcohols and amines containing asymmetric carbon atoms, (iii) the measurement of the velocity of reaction between such com-pounds and various alcohols and amines with the object of contrasting the influence of (1) the constitution of the alcohols and amines, (2) the temperature, (3) the solvents, and (4)various catalytic agents on the velocity of such reactions. The compounds described were : bornylcarbimide (compare Forster and Attwell, this vol., p.91), ethyl bornylcarbamate and dibornyl-cccrbamide, 1-menthylcarbimide, mth$ ethyl and propyl l-menthyl-cccrbumcttes, and di-1-menthylcarbarnide. 83. ‘‘The comparison of the rotation values of methyl, ethyl, and n-propgl tartrates at different temperatures.” By Thomas Stewart Patterson. Methyl tartrate was first shown to be capable of existence in a solid form melting at 61*5O. Data for the variation of rotation with change of temperature of methyl, ethyl, and propyl tartrates mere given.Comparisons of the rotation values of these substances at identical temperatures were shown to be of little value, especially at low temperatures. Since, however, the rotation of methyl tartrate vanishes at Oo, that of ethyl tartrate probably at -34O, and that of propyl tartrate probably at -60°,it may be assumed that the three substances are in corre- sponding optical conditions at these temperatures, and, in general, inethyl tartrate at TO, ethyl tartrate at (T -34O), and props1 tartrate at (T-60°)will also be in corresponding conditions as regards rotation. It is shown that comparisons of rotation effected at corresponding temperatures are much more satisfactory than those obtained for identical temperatures, and that if the rotations are taken at corre-sponding temperatures, the increment of 2CH, in passing horn methyl to ethyl tartrate rather morc than doubles the rotation, whilst the next increment of 2CH, in passing to propyl tartrate increases the rotation to 1-41 times that of ethyl tartrate.The rotation of propyl tartrate is therefore almost three times that of methyl tartrate. These results hold within wide limits of temperature. 84. "Note on the action of hydrogen sulphide on formaldehyde and acetaldehyde solutions." By Julien Drugman and William Ernest Stockings. Although the conditions under which various thio-derivatives are formed when hydrogen sulphide reacts with aqueous solutions of formaldehyde and acetaldehyde respectively have been thoroughly investigated by Hofmann (Bey., 1868, 1,176 ; 1869, 2, 152 ; 1870, 3, 584), Pinner (Ber., 1871, 4,257),Klinger (Bey., 1876, 9, 1894 ; 1877, 10, 1879; 1878, 11, 1023), Baumann and Fromm (Ber., 1889, 22, 2600; 1890, 23, 69; 1891, 24, 1434, 1457) and others, it is not generally known that provided hydrochloric acid or other strong mineral acid is absent, the reaction affords a sure means of detecting form- aldehyde, even in the presence of acetaldehyde or other higher fatty aldehydes. (1) When a dilute aqueous solution of formaldehyde is saturated with hydrogen sulphide in the absence of hydrochloric acid, and the test-tube set aside in a warm place (30-50°), no visible change occurd for about 21 or 4 hours, but afterwards a white, amorphous, flocculent precipitate is gradually deposited.This substance, when dried in a desiccator over sulphuric acid, melts, with decomposition, between 85" and llOo. This characteristic thio-derivative is precipitated from Formaldehyde solution by hydrogen sulphide even in the presence of acetaldehyde, methyl and ethyl alcohols, acetone, or acetic acid ; the melting point of the product formed in presence of acetone or acetic acid is fairly 116 definite, namely, 98-103', and sometimes quite sharp at 98'. According to Baumann (Zoc. cit.), the compound has the composition 3(CH,S),CH,O ; it is distinguished from the odourless, crystalline tri-thioformaldehyde, (CH,S),, both by its lower melting point and atrong odour.The presence 0:'even 0.1 per cent. of formaldehyde in aqueous solution may be easily detected by means of this reaction. (2) The crystalline trithioformaldehyde, (CH2S)3,first prepared by Girard by the reduction of carbon disulphide by means of nascent hydrogen (Compt. rend., 1870, '70,623), and afterwards fully investi- gated by Hofmann (Zoc. cit.), results when hydrogen sulphide acts on a solution of formaldehyde previously strongly acidified with hydro- chloric acid. The crude product melts indefinitely between 180' and 205", but it crystallises from hot acetone in white needles which melt at 216'. (3) When a solution of acetaldehyde is saturated with hydrogen sulphide in the absence of hydrochloric acid or other strong mineral acid, and the test-tube set aside in a warm place, the liquid soon assumes a milky appearance, owing to the separation of minute, oily particles, which gradually collect in drops.or, the bottom and sides of the test-tube, leaving the rest of the liquid perfectly clear and trans-lucent.No solid product is ever obtained under these conditions, a circumstance which at once differentiates the behaviour of acet-aldehyde from that of formaldehyde. (4) Several distinct crystalline thio-derivatives can be obtained by the action of hydrogen sulphide on aqueous or alcoholic solutions of acetaldehyde previously acidified with hydrochloric acid. Among these may be mentioned the volatile bimolecular compound, which melts at 61°, and the a-,p-, and y-trithioacetaZde?Lydes, (C,H,S),, which melt at lolo, 135--126O, and 76' respectively. The character of the products and the relative proportions in which they are formed depend entirely on the experimental conditions.When, however, a dilute (1 to 20 per cent.) aqueous solution of acetaldehyde, acidified with about one-fifth of its volume of strong hydrochloric acid, is satur- ated with bydrogen sulphide and the test-tube set aside in a beaker over a water-bath kept at 50-60', a very characteristic and striking phenomenon is observed. At the outset, the liquid assumes the milky appearance described under (3), then gradually becomes clear, and finally, after some hours, a volatile thio-compound sublimes on to the cooler portions of the tube in the form of long, glistening needles, which, after crystallisation from acetone or dilute alcohol, melt at 75-78'.The sublimate is not, however, formed if the original solu- tion contains formaldehyde as well as acetaldehyde. In this case, the 117 mixed t-hio-compounds separate together from the liquid as a crystal-line precipitate. Moreover, if the original solution contains a volatile solvent, such as acetone or alcohol, the sublimate will only appear after the solvent in question has nearly all evaporated. (5) Aqueous solutions of propaldehyde or isobutaldehyde saturated with hydrogen sulphide, without a,ny addition of hydrochloric acid and set asidein a warm place, exhibit a similar behaviour to that of acet-aldehyde solutions under the same conditions. The oily thio-compounds obtained soon fall to the bottom of the test-tube, leaving the super- natant liquid quite clear.The presence of hydrochloric acid does not materially alter the character of the appearances observed, except in the case of isobutaldehyde when, after a very long time, a slight crystalline sublimate may be formed. 85. The viscosity of liquid mixtures.” By Albert Ernest Dunstan. The following conclusions were drawn from the author’s investi- gation on the viscosity of liquid mixtures : (1) Aqueous solutions give abnormal results. This is true for all known cases, which, however, are always solutions of two associated liquids, as, for example, alcohol and water. (2) Wherever chemical affinity is existent to any marked extent in the two liquids of a mixture, abnormal results occur.In many such cases, definite complexes have been isolated. (3) Wherever marked abnormalities present themselves, it is noted that they do so near points of definite molecular composition, but these points of abnormality are not constant, and shift with change of temperature. At a sufficiently high temperature, they would pro- bably vanish, as then no formation of complexes would be possible. (4) When points of minima are obtained in the viscosity curve, it is difficult to say whether association or dissociation is proceeding. It certainly seems due to some change in molecular aggregation. (5) Substances containing the hydroxyl group (and associated) have a higher viscosity, as a rule, than monomolecular substances.Hence the rise of viscosity in the case of alcohol-water is probably due to the formation of complexes. A further examination of hydroxylic substances is in progress. 86. (‘The conversion of isopropyl alcohol into isopropyl ether by sulphuric acid.” By Frank Southerden. In the course of some experiments on etherification by the agency of small quantities of sulphuric acid at high temperatures, it has been 118 found possible to prepare isopropyl ether. The yield is very poor, and therefore without improved conditions the method cannot be said to compete with that involving the use of alkyl iodide (Erlenmeyer, Annulen, 1863, 126, 305), but it is interesting as an example of the production of a secondary ether from its alcohol.Previous observers have obtained only propylene in this reaction. When, however, 3 C.C. of H,SO, were employed for 100 C.C. of iso-prop91 alcohol (b. p. 81-83O), and the mixture heated for 6-12 hours at 150-ldO0, the ether was formed along with propylene. After removal of the unchanged alcohol by prolonged treatment with sodium, the whole distilled at 70-70.5O (uncorr.). Zander (Annalen, 1882, 214, 164) gives 685-63' as the boiling point of the ether. The iso-prop91 ether has an intense odour resembling peppermint ; bromine in carbon tetrachloride solution is not decolorised by it. Two vapour density determinations obtained by Victor Meyer's method gave 51.3 and 51.4 whereas the calculated value for (C,H7),0 is 51.ADDITIONS TO THE LIBRARY. Donutions. British Fire Prevention Committee. First International Fire Pre- vention Congress. . , Report 1903. pp. 207. ill. London 1903. From the Committee. Carnot, Adolphe. Trait6 d'analyse des substances minerales. Tome 2. Mitallorides. pp. 821. Paris 1904. From the Publishers. Clowes, Frank, and Houston, A. C. The experimental bacterial treatment of London sewage, being an account of the experiments carried out by the London County Council between the years 1892 and 1903. pp. xii + 242. ill. London 1904. From Professor Frank Clowes. Engelhardt, Viktor. The electrolysis of water, processes and applica- tions. Authorised English translation by Jo>eph W. Richards.pp. 140. ill. Easton, Pa. 1904. From the Publishers. Gadd, H. Wippell. Drugs, their production, preparation, and properties. pp. xi + 180. London 1904. From the Author, Giinther, R. T. A history of the Daubeny Laboratory, Magdalen College, Oxford. To which is appended a list of the Writings of Dr. Daubeny, and a Register of the Names of Persons who have attended 119 the Chemical Lectures of Dr. Daubeny from 1862 to 1867, as well as of those who have received instruction in the Laboratory up the present time. With some additional papers, pp. vii + 137+clxiv. ill. London 1904. From the Author. Hittorf, J. W., and Plucker, J. On the spectra of ignited gases and vapours, with especial regard to the different spectra of the same elementary gaseous substance.pp. 39, ill. 1904. From Professor W. A. Tilden, F.R.S. Merrill, Elmer D. A dictionary of the plant names of the Philippine Islands. pp. 193. Manila 1903. From the Author. Muir, M. M. Pattison. The elements of chemistry. pp. 554. ill. London 1904. From the Author. Pictet, Am& The vegetable alkaloids, with particular reference to their chemical constitution. From the second French edition, rendered into English, revised and enlarged by H. C. Biddlo. pp. 505. New York 1904. Prom the Publishers. Schmatolla, Otto. Neue Entdeckungen aus dem Gebiete der Chemie und Physik. Die unbegrenzte Teilbarkeit der Masse, der Aufbau der Korper. pp. S4. Berlin 1904. From the Author. Trait& de chimie minerale. Publie sous la direction de Henri JCoissan.Tome I., 1, and HI., 1. pp. ix+528, 672. ill. Paris 1904. From Professor H. Moissan. Pamphlets. Brougb, Bennett H. Cantor lectures on the mining of non-metallic minerals, delivered before the Society of Arts, November and December, 1903. pp. 48. ill. London 1904. Burg;, R. T. Der Elektronather. Beitrage zu einer Neuen Theorie der Elektrizitat und Chemie. pp. 47. Berlin 1904. Dymond, T. S., and Bull, B. W. Variation in the milk of a dairy herd during the summer months. Chelmsford, Essex 1904. Kunz, George F., and Baskerville, Charles. The action of radium, actinium, Roentgen rays, and ultra-violet light on minerals and gems. (From Science, N.S., 18.) Long, J. H. The electrical conductivity of urine in relation to its chemical composition.Part 11. The conductivity of mixed solutions, (From the J. Amer. Chern. Soc,, 26.) Richards, Theodore William, and StulI, Wilfred Newsome. New method for determining compressibility. pp. 45. ill. Washington 1903. Senier, Alfred. On acridines. Abstract of a paper read before the British Association, Southport meeting, 1903. (From the Chemica2 News, 88.) 120 ERRATA. PROC.,1904, Vol. 20. Page. Line. 88 14 for ‘‘[u]~’’yead ‘‘aD.” 88 20 delete ‘‘veratric acid.” RESEARCH FUND. A Meeting of the Eesearch Fund Committee will be held in June next. Applications for grants, to be made on forms which can be obtained from the Assistant Secretary, must be received on or before June 6th. At the next Ordinary Meeting, on Wednesday, May 18th, 1904, at 5.30 p.m., tho following papers will be communicated : “Action of nitrosyl chloride on pinene.” By W.A. Tilden. “The electrol~tic estimation of minute quantities of arsenic.” By H. J. 8. Sand and J. E. Hnckford. “The decomposition of the alkylureas. A preliminary note.” By C. E. Fawsitt. “ The action of sodium methoxide and its homologues on benzophen- one chloride and benzylidene chloride. Part 11.” By J. E. Mackenzie and A. F. Joseph. “The formation of periodides in nitrobenzene solution. 11. Periodides of the alkali and alkaline earth metals.” By H. M. Dawson and Miss E. E. Goodson. R CLAY AND SONS, LTD., BREAD ST. HILL, L.C., AND BUNGAY, SUE’FOLK.

ISSN:0369-8718    

DOI:10.1039/PL9042000105

出版商:RSC    

年代:1904

数据来源: RSC