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Abstracts of the Proceedings of the Chemical Society, Vol. 3, No. 45 |
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Proceedings of the Chemical Society, London,
Volume 3,
Issue 45,
1887,
Page 135-147
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ABSTRACTS OF THE PROCEEDINGS OF THE CHEMICAL SOCIETY. No. 45. Session 1887-88. December 15th, 1887. Mr. William Crookes, F.R.S., President, in the Chair. Messrs. Herbert E. Kirby, John Norman Collie and Sydney Martineau were formally admitted Fellows of the Society. Certificates were read for the first time in favour of Messrs. Samuel Banner, Sherwood, Sefton Park, Lirerpool ; Arthur G. Bloxam, Royal Agricultural College, Cirencester ; Lewis Walter Hawkins, 18, Burr Street, London, E. ; Stevenson J. C. G. Macadam, Brighton Home, Portobello, Edinburgh ; Sidney Skinner, B.A., Christ's College, Calmbridge; Charles Francis Townsend, Ashley Road, Epsom ; Alfred Edwin Tutton, 12, South Parade, Brompton, S.W. The following papers were read :-92. "An Apparatus for Comparison of Colour-tints." By Alfred W.Stokes. In operations such as Nesslerising in water analysis, when it is necessary to compare a number of depths of tint with one another, it is very inconvenient to have to make up a large series of standard tints. The author has devised an apparatus which obviates this necessity. It consists of a,base-board on which lies a sheet of white opal glass. Placed obliquely a lit'tle way above this is a sheet of glass on which rest the Nessler-tubes containing the solutions whose tints are to be compared. The mouth-ends of these tubes recline in gi-ooves hollowed in a horizontal bar. This bar is supported by two pillars, on one of which slides a ring clasping a calibrated glass tube ; this tube has a side tubulure at the ba.se, and is thus and by means of a short india-rubber tube connected with a similar but uncalibrated.tube resting on the glass plate. A known quantity of the standard colour being placed in the tube carried by the ring and diluted up to the top mark with water, if the movable tube be raised, this standard solution will flow into khe tube resting on the glaas plate. The movable tabo is oalibrated to show how much is present in the other tube. Henoe, if a Nessler-tube containing liquid of un-known depth of tint be placed beside the tube on the glass plate, and the tube in the sliding ring be raised OF lowered till the tints agree in the two tubes resting on khe glass plate, a simple inspection of the level of the liquid in the calibrated tube will give the quantity of standard colour the unknown solution is equal to.The apparatus is especially useful in Nesslerising ; also in determi- nations of the quantity of lead prese,nt in wahers; and in other cases where comparison of tint depths is necessary, 93. “The Alloys of Copper and Antimony and of Copper and Tin.” By E. J. Ball, Ph.D. The author gives the results of experimenhs instituted with the view of abtainiug further evidence as to whether the alloys CuzSband Cu,Sb, which are indicated by changes in the direction of the curve by which the electi-ical conductivity of the copper-antimony alloys is expressed, are or are not compounds. Copper, antimony and lead were melted tagether in varying proportions, lead being a metal which alloys only to a very slight extent with copper. Mixtures of CuzSb and lead were first made, the first alloy containing 95 per cent.of lead ; the second 90 per cent. of lead ; and so on For the remainder of the series. No alloys could be formed between the one with 20 per cent. and that with 65 per cent. of Cu2Sb, The intermediate mixtures that had separated on solidification were all melted up together and allowed to cool slowly, with the resulC that owing to the partial oxidation and consequent loss of antimony in the successive fusions and castings, the metal was found to have separated on solidification into three alloys of different densities. The upper of these had t,he composition CukSb, the alloy which occupies the lowest posi- tion on the conductivity curve.The mixture of 75 lead and 25 Cu,Sb, the first that separated after fusion, when cast in a cylindrical mould, separated an cooling into two concentric cylinders the inner of which had the same composition as that of the last alloy that formed before the separation of the fused mixture into two alloys, i.e., 80 lead and 20 Cu2Sb. The author is of opinion that this represents the satu- rated solution of CuzSb in lead. The alloys were then cast into discs, which were ground to the same size and examined by the aid of the Hughes’ induction balance. The curve of relative conductivity so obtained was practically a straight line between the terminal points. In view of this fact, and since in their general appearance the alloys resemble both in colour and structure mixtures of CnzSb and lead, it would appear that Cu,Sb exists in these alloys as snch.In the second series of alloys, the first mixture consisted of 95 antimony, 25 lead and 2.5 copper ; the second of 90 antimony, 5 lead and 5 copper. These alloys were all more or less grey in colour, and their fracture became conchoidal as the alloy approached in composi-tion CurSb. The induction balance curve rose gradually, till the copper and antimony were almost in the proportions: necessary to form CuzSb, and then fell again as this point was passed. In hhe third series, the first alloy formed contained 95 copper, 2.5 lead and 2.5 antimony; the second contained 90 copper, 5 lead and 5 0f antimony.All the alloys of this series formed, except tho one with 50 copper, 25 lead and 25 antimony; this separated on cooling into an alloy which was again found to have the compositioii CusSb and lead containing antimony and copper. The induction balance curve of this series, allowing for the dilution of the copper- antimony alloys by lead, is identical with that of the copper-antimony alloys free from lead. Throughout these three series of alloys the lead appears to be wholly without influence on the physical properties except that which it exercises as a diluent, the influence of the alloys forming the tuming points of the conductivity curve, CuzSb and CuaSb, being as marked in the presence of lead as when Chat metal is absent.Hence the aukhor believes that these two alloys are true compounds. When they are fused with silver sulphide, the copper in both Cu,Sb and CulSb is to a, great extent dispboed by silver, without greatly altering the charwter of the alloy. Copper-tin alloss were treated with lead in a similar manner, and in this case also the lead appeared to be without effect on C-he general chayacter of the alloys, the influence of the alloys which are indicated by the turning poinCs of the conductivity curve, viz., CuaSn and Cu4Sn, being as marked as in the case of the turning points of the copper-antimony alloys CuzSband CudSb. DISCUSSION. Professor ROBERTS-AUSTENsaid that the alloy of copper and antimony known as the " Regulus of Venus " is the only alloy having an intense violet colour, which made it an object of great interest to the alchemists, but it had been strangely neglected by their successors in modern times.Lead unites readily with antimony, and it therefore appeared not improba.ble that lead would induce a certain amount of antimony to leave t,he copper and form triple alloys ; but Dr. Ball had shown that the antimony and copper alloys remained intact, and thaf lead merely diluted them. This was specially interesting because, to turn to other metals, it is well known that zinc and lead if melted and mixed in the fused state separate from each other almost entirely on cooling. Notwithstanding this fact, A. and L. Svanberg had shown that in the presence of a third metal, viz., tin, lead and zinc will unite to form a triple alloy ZnSn, + 2PbSn3, which solidifies at 168”C.It was generally assumed that rapid cooling prevented the “liquation” or separation of the constituents of alloys, but the speaker had shown in the case of the silver-copper alloys, that SZOW cooling produced products as uniform in composition as Levol’s alloy containing 71.8 per cent. of silver, the only alloy of the series which was formerly believed to be uniform in cornpositlion. Professor Roberts-Austen added that he was glad of the new evidence afforded by the author’s observations of the delicacy of the Hughes induction balance, an instrument which he had long since predicted would prove to be of great service in studying the molecular constitution of alloys. Dr.C. R. ALDERWRIGHTsaid that the determination of the con- stitu tion of ternary alloys involved the solzltion of some very interest- ing problems, which in certain cases appeared to be of a far more complex order than was generally supposed. A great distinction was to be made between the amount of permanent miscibility possible with fluid metals whilst kept moltten by heat, and tfhe more or less com- plete segregation taking place during solidification on cooling, especially when $lowly effected. In the latter case the separation appeared frequently to be regulated by the formation of alloys of definite constant compositions, atomic or otherwise, which possessed fusing points higher or lower than those of the rest of the masses : so that one portion solidified first, leaving, so to speak, a more fusible mother-liquor. But it was quite different in the former case : with certain metals in certain proportions the mixture when melted, well stirred together and then left quiescent for some time in a molten condition, separahed into Cwo layem, just as a mixture of ether and water, or certain mixtures of ether, alcohol and water would do if shaken up and then allowed to stand; the relative proportions in which the metals divided themselves were doubtless regulated by some law, because one given mass always divided itself in one way, and another in another, and so on ; but this law or guiding principle did not seem to be connected with combination in atomic proportions, nor upon the production of any one particular alloy which formed and separated from the rest of the mass.He was not in a position at present to indicate what really was the guiding principle in such cases, but hoped that some experiments upon which he and Mr. C. Thompson were now engaged would throw light on the question. These experiments were being carried out with various mixtares of lead, zinc and tin or bismuth: thus for example a series of ingots were made by mixing equal weights of lead and zinc in each case with varying amounts of tin, melting together, well stirring and keeping molten for oue to two hours, and then cooling without more delay than was absolutely necessary in order to diminish possible sources of error through incipient segregation during solidification taking place in either the bottoni 01' the top one of the two layers into which the molten mass divided itself during the period of quiescence.The top and bottom portions being analysed and the lead and tin calculated per unit of zinc in the first case, and the zinc and tin per unit of lead in the second, and these pairs of values being plotted off as abscisse and ordinates respectively, curves were obtain- able from comparison of which he hoped to be able to deduce the guiding principle. In each case the amount of zinc taken up by the heavier alioy in which lead predominated, and that of lead in the lighter alloy in which zinc predominated, increased with the amount of tin present; but not always in the same ratio.Moreover, the relative proportions in which the tin divided itself between the bottom and top layers was not constant, but varied with the proportion of tin in the total mass ; so that the production of atomic compounds of the metals, even if it occurred at all, was certainly not the sole ex- planation of the results. The principle of two saturated solutions being formed also appeared to be inapplicable. In answer to a further question by Dr. Ball, Dr. Alder Wright said that his experiments were as yet hardly complete enough to enable him to pronounce definitely, but he thought that the formation of an eutectic alloy would not afford an adequate explanation, because if this were the case, either the top or the bottom layer (presumably the latter, being usually the more fusible) should exhibit constancy o€ composition which was very far fro-being the case ; the principle of eutexia no doubt largely regulated the solidification of molten masses on cooling; but it did not seem to be so closely connected with the miscibility of molten metals kept fluid throughout. As regards avoiding loss by oxidation during fusion and volatilisation of zinc, he had found that a little cyanide of potassium previously fused in the melting pot largely if not entirely prevented both sources of alteration ; and was preferable for this purpose to borax or meta-phosphate of soda, &c., as these substances did not exert any reduc- ing action, but simply cleansed the metal by dissolving any oxide that might be formed.140 94. ''The Constitution of the so-called mixed Azo-compounds." By Francis R. Japp, F.R.S., and Felix Klingernann, Ph.D. The authors find that diazobenzene chloride interacts with ethylic scdiomethacetoacetate to form acetic acid and an ethereal salt, C,,H,,N,O, (m. p. 117"), which by hydrolysis is converted into the acid C',H,,N,O, (m. p. 185'). They have also prepared homologues of these compounds, substituting ortho- and para-diazotoluene for diazo- benzene, and ethylic ethacetoacetate for rnethacetoacetate. They at fiivt regarded the acid C9H,,N,02 as benzene-azo-propionic acid, C,H,*N,*CH(CH,).COOH (see Ber., 20, 2942). It yields on reduc-tion a hydrazo-acid, C9H,,N,0, (m.p. 170"), which proved to be the a-phenylhydmzidopropionic acid of Pischer and Jonrdan, obtained by reduction of phenylhydraainepysuvic acid. On comparing tbe snp-posed benzene-azo-propionic acid with phenylhydrazinepyruvic acid, it was found that tlie two compounds were identical, the melting pint (169') given by Fischer and Jourdan being much too low. It t'herefore appeared probable that the acid was a hydrazide : this view is supported by the followisng proof that "benzene-azo-acetone," hitherto formulated CH3-C0.CH,-N,.C6H5,is in reality a hydrazide of tlie formula CH3*CO*CHN*NHC,H5,derivable from pyruvic aldehyde. By acting on "benzene-azo-acetone " with sodium ethoxide and ethylic chloracetate, an ethereal salt was obtained which on hydrolysis yielded an acid of the formula CliH12N203(m.p. 161-162"). By ri>duction this acid gave anilido-acetic acid, but no aniline, thus proving that it has the formula CH,*CO*CH:N-N(C,H,)CH,*COOH. If "benzene-azo-acetone " had the formula hitherto ascribed to it, the introduction of CH,.COOH into the methylene-group would hare occurred and the resulting compound would have yielded aniline on r?du ction. The above view is confirmed by the fact that the phenylhydrazide of "benzene-azo-acetone " proves to be identical with the dihydraside C:,H,NH*N :CH*C(CH3):N*NHC6H5, recently obtained by von Pechmann from methylglyoxal (pyruvic aldehyde) and phenylhydr- azine. The authors therefore regard the various so-called mixed azo-com-pounds obtained by the action of diazo-salts upon compounds of the ethylic acetoacetate type as hydrazides.They point to the pa,rrtllel case of the formatioil of isonitroso-compounds (hydroximes) by the action of nitrous acid, and suggest that this analogy would be more perfect if free diazobenzene were regarded as the anilide of nitrous acid, thus : ON.NHC,H,. Experiments are being nndertaken in support of this view. They had intended to study the act{ion of reducing agents on the alkyl-derivatives of the benzene-azo-naphthols 141 in order to settle the question, already mooted by Zincke, as to whether the latter are azo-compounds or hydrazides ; but have renounced this intention on learning that Professor Meldola is engaged in investigating this subject.95. " The Interpretation of Absorption-Spectra." By G. H. Bailey. 96. " The Reduction of Potassium Bichromate by Oxalic Acid." By C. H. Bothamley, Assistant Lecturer on Chemistry, Yorkshire College. Potassium bichromate and hydrated oxalic acid, finely powdered and intimately mixed, interact spontaneously after two or three hours, or instantly if heated to 30-35" ; after heating at 110-120" until the weight is constant, a dark friable residue is obtained which is completely soluble in water. If the mixture which has been heated at 110-120" is heated over a low flame, care being taken to avoid fusion, further decomposition ensues, and on treatment with water chromic oxide remains undissolved and a fiolution of potassium chromate free from oxalic acid and chromic salts is left.If dehydrated oxalic acid be taken the interaction does not take place spontaiieously, but occurs instantly at 30-35", the product being a very bulky porous and friable grey solid; the nature and limit of the interaction is, however, the same as with the hydrcited acid. With an excess of oxalic acid, reduction is complete, but with excess of bichromate the interaction is different. The first stage of +he interaction, which takes place at a t'emperature not exceeding 120", is represented by the equation 2KZCrzO7+ 6H,Cz04 = Cr,(C,O,), + 6H,O + 6CO, + 2KzCr04. The decomposition is limited, even in presence of excess of bichromate, by the formation of chromic oxalate, which is not further oxidised at 12d0.At a higher temperature in presence of only a slight excess of bichromate the chromic oxalate decomposes in accordance with the equation Cr2(C2O&= Crz03+ 3CO + 3c02. If, however, a considerable excess of bichromate is present further oxidation takes place thus : 2K2Cr20,+ Cr,(C,04)3 = 2Cr203+ 6CO, + 2K2Cr04. The com-plete oxidation of oxalic acid in presence of a lai*ge excess of potas-sium bichromate is represented by the equation 4K2Crz0, +-6H2Cz04 = 2Cr,03 + 4K2CrOa+ 6H,O + 12C0,. 97. '' The Reduction of Chlorates by the Zinc-copper Couple." By C. H. Bothamley and G-. R. Thompson. When a solution of potassium chlorate is reduced by means of the zinc-copper couple (Thorpe, Trans., 1873, 541) a portion of the reduced chloride is converted into zinc oxychloride, which is 142 insoluble in water but readily soluble in dilute sulphuric acid.The quantity of oxychloride formed is greater the more concentrated the solution. In order to avoid the error due to this cause, the chlorate solution is heated with the couple for about one honr, and pure dilute sulphuric acid is then added until the zinc hydroxide and oxychloride just dissolve. The liquid is filtered, neutralised with calcium carbonate and titrated with silver nitrate. Thus modified, the method gives very accurate results ; the solution should not contain more than 1.5 gram of potassium chlorate in 25 c.c., and should just cover the couple.98. “Preliminary Notice on the Oxidation of Oxalic Acid by Potassiuni Dichromate.” By Emil A. Werner, Assistant in the Chemical Laboratory, University of Dublin. In the course of an investigation of chromoxalates and analogous chromium compounds with other organic acids, the results of which have already been partly published (Trans., 1887, 383), I was led to study the action of oxalic acid on potassium dichromate solutions in presence of sulphuric acid. The results already obtained seem note- worthy, and in view of the fact that a paper on the same or a similar subject is announced, I send the following short note. In the preparation of the blue chromoxalates already described, 9 mols. of oxalic acid are required for the complete reduction of each molecule of potassium dichromate ; in this interaction the oxalic acid is divisible into two distinct portions, viz., 3 mols.which are used up in the reduction of the dichromate, and 6 mols. which combine with the reduced chromium to produce the chromoxalate : e.g., 2KCrz07+ 6H2Cz04 + 3HzCz04 = KzH4Cr2(C204)6+ 7Hz0 + 6630,. I have endeavoured to use instead of the persistent 6 mols. oxalic acid their equivalent of succinic acid, but I find that the interaction proceeded in an entirely different manner; only a partial reduction of the dichromate is effected by the 3 mols. of oxalic acid, and no compound whatever of chromium and succinic acid is produced, the final products of the reaction being :-(1) The red chromoxalate of Crofts, K2Crz(Cz04)4,and (2) free K2Cr207(about two-fifths of the original amount), the succinic acid remaining unaltered.If oxalic acid be added until the dichromate is all reduced, 9 mols. are required, and the interaction proceeds exactly as in the absence of the succinic acid. An attempt to effect a partial replace- ment of the oxalic by succinic acid was attended with the same result. From these results, I was led to investigate more closely the oxidation of potassium dichromate by oxalic acid in presence of sulphuric acid, and while looking over the literature of the subject, 143 I was struck by the following account of the method of preparing chrome-alum in Watts’ Dictionary (3rd Supplement). In the prepara- tion of chrome-alum by the action of sulphuric acid on potassium dichromate, the reduction of the latter may be conveniently effected by oxalic acid, when it is not necessary to add an excess of the reagent, as the reaction is complete when CO, ceases to be evolved, &c.; the equation representing the change is as follows :--K,Crz07+ 4HzS04 + 3HzCzO4 = K2Crz(S04)a+ 6C02+ 7H20.29.5 parts of dichromate are dissolved in 39 parts of sulphuric acid, and the necessary amount of water, and 38 parts of oxalic acid added gradually in small portions (Lielegg, DingZ.polyt.J.,207, 321). The production of chrome-alum by this method is entirely dependent on the “necessary amount of water,” the above equation being only true when little or no water is present, dilution of the mixture causing only partial reduction of tlie dichromate, with production of varying amounts of red chromoxalate and chromium sulphate, the former increasing, and the latter diminishing, with the degree of dilution, and vice versc2.I am at present engaged in investigating this reaction in all its details, with special reference to the influence of mass and temperature. The remarkable affinity existing between chromium and oxalic acid as shown in these reactions, becomes all the more interesting when compared with the not less remarkable inert behaviour of chromium towards succinic acid. All attempts hitherto to obtain compounds corresponding to the chromoxalate containing succinic acid have been unsuccessful ; in fact freshZy precipitated chromic hydroxide is perfectly insoluble in excess of succinic acid solution at the boiling temperature, and when heated in sealed tubes at 120-130’ C., only a mere trace of the chromium enters into solution, 99.“Isomeric Change in the Naphthalene Series.” No. 1. By Henry E. Armstrong. It having been ascert,ained that betanaphthylsulphate, C,,H,.OSOsH, may be converted by mere warming in the water-bath into the iso- meric betanaphtholsulphmic acid (Schaefer’s modification), the study of the conditions under which isomeric change occurs in the case of naphthalene-derivatives became of special importance in determining the laws which govern substitution in the naphthalene series, and indeed generally. Experiment soon showed that there were important differences to be observed : thus bromobetanaphthol gave but little sulphate, being almost entirely-and apparentZy directly-converted nto the isomeric acid which may be prepared by brominating Schaefer’s betanaphtholsulphonic acid; in like manner, betanaphthyl- 144 sulphate when sulphona,ted by chlorosnlphonic acid does not yield, as might have been expected, a sulphosulphate but an isomeric disul- phonic acid.This latter acid is of special interest on account of the readiness with which, by mere warming with dilute sulphuric acid, it is converted into Schaefer’s be tanaphtholmonosulphonic acid : hhere is little doubt that one of the sulphonic groups occupies an alpha- position contiguous to the OH, and hence the readiness with which it is displaced by hydrogen.These observations have not only led to the experiments being made of which the results are described in the following notes, but they have served in connexion with the observa- tions on the sulphonation of naphthalene to favour the assumption that the action of sulphuric acid is in the majority of cases of a very simple character, and that when isomers are produced their formation is very frequently the outcome of isomeric change. The author pro- poses to pay special attention to the investigation of this question, and not only in the naphthalene series. 100. “Isomeric Change in the Naphthalene Series. No. 2. p-Ethoxynaphthalenesulphonic Acids.’’ By E. G. Amphlett and Henry E.Armstrong. In order to determine the course of chemical change when the formation of the sulphate is prevented, the authors have sulphonated by means of chlorosnlphonic acid the ethoxynaphthalene, CI,H,*OC2H6, prepared by ethylating betanaphthol. The product obtained when a cold solution in carbon bisulphide is operated upon is a mixture of two sulphonic acids, one of which is undoubtedly derived from Schaefer’s modification of betanaphtholsulphonic acid, and the other probably from Baeyer’s modification; if the product be heated in the water- bath, the latter acid is converted by isomeric change into the former. The two acids are readily distinguished by means o€ their barium salts :that of the former acid being almost insoluble in water, while t.hat of the latter dissolves easily and crystallises in transparent prisms containing 3H20.On submittiiig the difficultly soluble potas- sium salt from the former acid to the action of bromine, a difficultly soluble’ethoxybromosulphonateis obtained ;and on further treatment with bromine the bromhydroxyquinonesulphonate is produced which may be prepared in a similar manner from Schaefer’s acid. Alto-gether different results are obtained on heating the isomeric ethoxy- acid with bromine. Experiments are in progress with other deriva- tives of both a-and @naphthol in which the hydroxylic hydrogen is displaced by positive and negative radicles. 145 101. “Isomeric Change in the Naphthalene Series. No. 3. P-Chloronapht’halenesulphonicAcids.” By Henry E.Armstrong and W. P. Wynne. The authors have previously fihown that when /3-chloronaphthalene is sulphonated by means of chlorosulphonic acid, the product consists of the two isomeric monosulphonic acids which Arne11 obtained by using fuming sulphuric acid: one of these is the P2P3‘-derivative corresponding to Schaefer’s betannphtholsulphonic acid, and it was of importance to determine whether this acid was a primary product of sulphonation or a product of isomeric change. It is found that a small proportion-very few per cent.-of the p2Ps’acid is formed even when the sulphonation is effected by adding the chlorosulphonic acid to a cold solution of p-chloronaphthalene in carbon bisulphide, and that heating on a water-bath has little or no effect; but that if the product be heated to a temperature at which it is just fused-about 150O-for an hour, an appreciably larger proportion of the p*fiP”’acid is obtained, and that after heating for five hours at 150” the product chiefly consists of this acid.There can be little doubt therefore that the p2/13‘acid is a product of isomeric change. 102. “Isomeric Change in the Naphthalene Series. No. 4. a-Haloidnaphthalenesulphonic Acids.” Ey Henry E. Armstrong and S. Williamson. The authors have previously shown that when a-chloro-, or a-bromonaphthalene is sulphonated by means of chlorosulphonic acid the product mainly consists of the 1:4-derivative together with a very small proportion of what is probably the 1 :2-derivative.They now find that if the product be heated at 150”, isomeric change takes place, new acids being formed of which the constitution has yet to be determined. It has been stated by Gessner that when potassium a-bromo-naphthalenesulphonate in heated with PCI, it is converted into a chloronaphthalenesulphobromide melting at 115”. The authors have obtained the normal product, bromonaphthalenesulphochloride, which melts at 101”; but on heating potassium chloronaphthalenesul-phonate with PBr5, they obtained a substance precisely like that described by Gessner and which gave similar results on analysis: this, however, they find is a mixture or compound of chloronaphtha-lenesulphobromide and bromonaphthalenesulphochloride,and they are inclined to attribute its formation to the presence of free bromine in the PBr5,and that of Gessner’s product to free chlorine in the PCI, used by him.3 oh’s statements regarding the properties of bromonaphthalene- 146 sulphonic acid, which do not accord with their own, are no longer surprising now that the occurrence of isomeric change on heating is established ; the authors have moreover observed that when brorno- naphthalene is heated with excess of sulphuric acid the bromine is displaced, a naphthalenedisulphonic acid being formed ; it is not improbable that the dibromonaphthalene melting at about 160" which Jolin obtained was formed from a naphthalenedisulphonic acid. 103. "The Sulphonation of Naphthalene." By Henry E.Arm-strong and W. P. Wynne. After a very carefid study of the products of the direct sulphonation of naphthalene and of the naphthalenemonosulplionic acids by means of chlorosulphonic acid, the authors are convinced that the initial action is always of a simple character and takes place in accordance with what one of them has termed the alpha-law ;and as they have also failed to obtain any evidence of the occurrence of isomeric change in the case of the sulphonic acids, they are of opinion that the formation of' P-snlphonic acids is due to secondary change, and probably involves the formatioil and subsequent partial hydrolysis of a higher sulphonic acid than that which is eventually separated. Thus they find that naphthalene may be alinost entirely converted into the a-monosul- phonic acid by careful treatment with a single molecular proportion of chlorosnlphonic acid, and that the sole product of the action of 2 mol.props. is the a'a" or ydisulphonic acid ; the pure p-monosul- phonic acid in like manner yields as sole product the p (?)-disulphonic acid previously described by them, which is undoubtedly an a-P-deriva- tive-in all probability the 2 :4' modification. By heating naphthalene with a considerable excess of chlorosulphonic acid at about 150°, they have obtained a trisulphonic acid. This acid yields a very soluble lead salt. Its sodium salt crystallises in aggregates of very slender needles of the composition C,H,( S03Na),.5H20; its sulpho-chloride melts at 194".Experiments are in progress to determine the nature of the trisulphonic acids formed in a similar manner from the /3 (?) and Ebert and Merz's two disulphonic acids. To determine whether the sulphonic acids undergo isomeric change, an aqueous solution of the 13 (?)-disulphonic acid was heated in an air current at a temperature gradually rising to 170-180°, at which it was maintained for several hours : much naphthadene sublimed, and the residue was found to consist almost, entirely of the P-monosulphonic acid. Ebert's and Merz's a-disulphonic acid treated similarly under- went no change. On evaporating the water from a solution of a-monosulphonic acid as far as possible at 100" and then raising the temperature to 115O, hydrolysis immediately sets in.147 ADDITIONS TO THE LIBRARY. I. Donations. Olfactics and the Physical Senses, by C. H. Piesse. London 1887. From the Author. A Short Manual of Analytical Chemistry. Qualitative and Quan- titative-Inorganic and Organic, by J. Muter, 3rd edition. London 1887. From the Author. Experimental Chemistry for Junior Students. Part IV. Chemistry of the Carbon Compounds or Organic Chemistry, by J. E. Reynolds. Lcndon 1887. From the Author. A Course of Quantitative Analysis for Students, by W. N. Hartley. London 1887. From the Publishers. The Elements of Chemistry, a Text-book for Beginners, by I. Remsen. London and New York 1887. From the Publishers. Steven Hoogendijk de Stichter van het eerste Stoomwerktuig in Nederland, door A. Huet. Rotterdam 1887. From the Bataafsch Genootschap. 11. By Purchase. Chimie orgnnique. Essai analytique sur la determinations des fonctions, pa'r P. Chastaing and E. Barillot. Paris 1887. Grundriss der Edelsteinkunde, von P. Groth. Leipzig 1887. Die Beziehungen zwischen dem Siedepnnkte und der Zuaam-rnensetzung chemischer Verbindungen, von W. Marckwald. Berlin 1887. Das Princip der Erhalting der Energie, von M. Planck. Leipzig 1887. Die galvanische Kette mat.hematisch bearbeitet, von G. S. Ohm. Neudruck mit einem Vorwort, von J. Moser. Leipzig und Wien, 1857. Die Presskohlen-Indnstrie, von E. Preissig. Freiberg 1887 Lehrbuch der physiologischen und pathologischen Chemie, von G, Bunge. Leipzig 1887.
ISSN:0369-8718
DOI:10.1039/PL8870300135
出版商:RSC
年代:1887
数据来源: RSC
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