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4#34 CALVEltT AXD JOHNSON ON TIIE XLL-Action of Acids upon Metals und Alloys. By DR. CRACE CALVERT F.R.S. and RICHARDJOHNSON F.C.S. IT has frequently occurred to us in the course of our investiga-tions into the physical properties of metals and alloys that it would be interesting both in a scientific and practical point of view if we were carefully to examine the action of some of the acids upon them. We therefore submitted copper zinc and tin and the two classes of alloys which are obtained from these metals viz. brasses and bronzes to the action of sulphuric nitric and hydrochloric acids. In this series of researches we have followed the same plan as when we experimented upon the ‘‘conductibility,’’ the ‘‘specific gravity,” &c. &c. of metals and alloys ; viz.we first examined the action of these acids upon the pure metals and after- wards upon the alloys composed of the pure metals melted together in equivalent and multiple proportions. Our experiments having been very numerous and therefore having extended over a long- period of time me have deemed it advisable to divide our paper into two parts. First-The action of sulphuric acid upon zinc copper and tin and of nitric and hydrochloric acids on the same metals. Secondly-The action of the same acids upon their alloys viz. brasses and bronzes. ACTION OF ACIDS UPON METALS AND ALLOYS. 433 On the marked influence which an Oxidized Surface has on the subsequent action of Xukhuric Acid of various strengths on Zinc. Before entering into the details of our experiments it is neces- sary that we should state that it was only after considerable time aiid experience that me mere able to determine the exact condi- tions under which we were to operate if we wished to obtain constant and correlated results owing not only to the extreme difficulty attending the preparation of perfectly pure sulphuric acid and a few ounces of pure zinc but especially to the irregu- larity of the action of sulphuric acid on zinc depending as we observed upon the peculiar state of its surface.Thus we found that cubes which had been made of the same zinc hut at different times were acted upon more or less liy the same acid when placed under the same circumstances ; and these observations gradually led us to the discovery of a curious fact viz.that a perfectly clean surface of zinc will become after a few days sufficiently oxidized by contact with air to modify in a very marked degree the action of sulphuric acid upon it. Thus if a cube of zinc recently filed is placed in snlphnric acid diluted with 9 eq. water the action may be considered as null; whilst if the same cube be gently heated in contact with the air and allowed to cool and be then placed in the same strength of acid the attack is 10 times greater as proved by these results. TABLE. Quantity of acid ............ 50 cent. cube. Surface of zinc acted on ...... 1 , Time of action.. ............ 2 honrs. STRENGTH OF ACID URED Quantity of zinc dissolved. Used a clean file carefully kept free from grease to S03,9H0........*32{ clean surfaces of cube. S03,9H0........ *03 After filing washed with alcohol to remove grease. *08{After filing heated in gas flame-allowed to cool S03>9H0 * * '* * * * * before using-surface oxidized. On the Action of Xulphuric Acid of various Strengths on Zinc. In looking over the table following these remarks and con-taining our results on the action of various strengths of sulphuric 212 CALVERT BSIl JOHNSON ON THE acid on pure zinc with an nnoxidised surface it will be observed firstly that they are contrary to the general view entertained by chemists of the action of sulphuric acid upon that metal for this acid has no action at ordinary temperatures on zinc; also that it requires a temperature of 130' C.before concentratcd acid begins to shorn any marked action and that it is only at 150" C. that the action of sulphiiric acid with 1 and 2 equivalents of water is fully developed. Secondly on perusing our resuJts the following curious facts will be observed viz. that mono- and bi-hydrated sixlphuric acids exercise a comparatively limited action on zinc at a temperature of 130"C. as compared with that of the tri-hydrated acid ; thus whilst SO,,HO and S03,2H0will dissolve only respectively 125 or 236% grammes zinc on a square metre surface S03,3H0 will in the same space of time dissolve 9860 grammes or 7 to 8 times the amount. Further the same extra- ordinary difference of action of these various strengths of acids is maintained when their temperature is raised to 150" C.A similar difference of action is observed when the action of diluted sulphuric acids on the unoxidized surface of pure zinc is studied ; thus alien S03,6H0 acts upon such a metal only 561-6 grammes per metre surface are dissolved in two hours whilst S0,,7HO dissolves in the same space of time as much as 5260% grammea but in this case the temperature employed was only 100" C. or that of the boiling point of the latter acid. The reactions of sulphuric acid of ctifferent strengths upon an unoxidized surface of pure zinc are far more complicated and interesting than chemists admit. To understand them it is neces- sary that they should be classed uncl2r two distinct heads viz.the action of S03,H0 in which case the metal is oxidized solely at the expense of the acid sulphurous acid being produced whilst with S03,2H0 and especially with S0,,3HO not only is sul-phurous acid given off but also simultaneously with it sulphu-retted hydrogen. It is interesting to obseilve two distinct chemical reactions taking place simultaneously ; thus we have an action similar to that which sulphuric acid exercises on the metals of the alkalies or alkaline earths giving rise to hydrogen and a sulghate of the metal and that which sulphuric acid has viz. on the fifth group etc. viz. mercury generating sulphurous acid and a sulphate of the metal. Lastly it will be observed on lookirhg over the table that sul- ACTION OF ACIDS UPON METALS AND ALLOYS.437 phurous acid gradually disappears whilst the quantity of sulphu-retted hydrogen increases until in its turn it also disappears and is replaced by pure hydrogen. TABLE1. Action of SulpJwric Acid of diferent strengths upon pure Zinc. Quantity of acid ................... 50 cent. cubes. Surface acted on ................. 1 , , Time of action .................... 2 hours ~ ~~ a 4 2 4 Strength of Temperature :2 acid. degs. cels. .-"e 2 Remarks. $ I+ I+ I_-Ordinary 130" 475 12; 0 SO2 evolved. 150" *232 386.6 SO2 erolved. No HS. Ordinary -002 3 -3 130" #I42 236.6 SO2 evolved. A little HS. 150" *345 575 .o HS given off and SO2. Ordinary '002 3 -3 130" 5.916 9860 *O Large quantity of HS.A trace of SO2. Violent action. Large 130" 4.916) 8193 *3 quantity of ZnOSO undissolved 150' 5,450 9083.3 Same action as above. Ordinary -005 83 130' 3.080 5133 3 Large quantity of I-ISgiven off,wit,h 130" 2.389 4731 6 a litrle SO:. Violent action. Quantityof ZnOSO notdissolved. Ordinary .049 81 -66 130" .456 760.0 Acii nearly hiling. HSgivcn off. Trace of SO-. Ordinary .027 45 *o 130" .337 561.6 Boiling point of tliis acid. HS evolved. Ordinary *018 33 .O Violent action at first ; after about loo0 3.161 5268 -3 20 minutes Ftoppt d. ZnO,SO 3 .SO0 6333 '3 . undissolved. Surf;lce apparently Y? , 3 060 5100 .o coated with no HS. Trace of SO,. Attack irregnlar. Ordinary *035 58.3 Ordinary *005 8.3 Ordinary .033 55.3 Action of Sukhuric Acid on Copper.The following is the action of 50 cubic centimetres of sulphuric acid of different strengths upon 1 cent. cube of pure copper duriug a period of two hours and at the temperature of 130' and 150° c. CALVERT AND JOHNSON ON THE TABLE2. Action of SuZphuric Acid of diferepht strengths upon pure copper. Surface acted upon.. .................. 1cent. cilbe. Quantity of acid. .................... 50 #I 7) Time of action ....................... 2 hours. Temperature ....................... 130" and 150" C. Calculated Sulphnric Temperature Loss by acid on emplojed. dega. cels. 1cent. cube. 1 sq. metre. Remarks. -__I. so,,Iro .... 130" *554 1423 *3 Surface of cubes covered with CuS ;SO2was also ................ 1Sb" -704 1 -678 1173.3 2796.7 evolved. There mas also a residue S032H0 .... .... 130" 150" -008 *063 13.3 105 *O insoluble in the acid and composed princi- pally of CuS and cuo,so:(.Very slight action. S013H3 . . ,. 130" *004 6.6 Sd:4HO .... ,I .. 150" 150" ,006*ooo 9 .9 These results suggest to us the following remarks :that the tem- perature at which copper is first attacked bp sulphuric acid SO,HO is 130°C, and that even at a few degrees below that tem- perature copper is not ,acted upon ;further that at 150' C. the quantity of copper dissolved by this acid under the same circum- stances is nearly the double of that which S03,2H0 SO3,3HO could dissolve whilst S03,4H0 have little or no action upon that metal. We further noticed that the decomposition of S03H0 by copper is far more complicated than it is generally admitted to be; for the action does not consist simply in the decomposition of the acid into oxygen which oxidizes the copper and sulphurous acid which escapes but the affinity of copper for oxygen is such that the whole of this gas is removed from a certain portion of the sulphuric acid leaving free sulphur which combines with the copper to form sulphide of copper The reason which leads us to believe that the formation of this compound is due to the direct Combination of the sulphur with the copper and not as in the case of zinc to two chemical actions taking place simultaneously is that if water were decomposed into its constituent elements its oxygen uniting with the copper whilst its hydrogen would c?m- ACTION OF ACIDS UPON METALS AND ALLOYS.439 bine with the sulphur of the reduced sulphuric acid to form sul-phuretted hydrogen which in its turn would act upon oxide of copper to produce the sulphuret of copper some sulphuretted hydrogen would undoubtedly have been given off and under the influence of heat must have escaped and have been easily detected. Another proof that sulphuric acid is decomposed into oxygen and sulphur and that water does not participate in the chemical action which ensues is that free sulphur volatilizes and condenses in the neck of the small balloons employed which in our expe-riments were placed in an oil-bath maintained carefully at the required temperature.This remarkable reduction of sulphuric acid by a metal is further corroborated by the action of sulphuric acid upon tin in which case sulphur is also liberated in con- siderable quantity but no sulphidc of tin produced owing probably to t.he fact that sulphur has less affinity for tin than for copper. TABLE3. Action of Sulphuric Acid of diferent strengths upon Tin. Calculated Sulphuric I'empcrature Loss by on acid employed. degs. eels. 1 cent. cube. 1sq. metre. Remarks. SOJIIO . . . . . 150" 3.010 5016.6 A large quantity of SO2 given off Xo HS. No SSn but some free sul-phur. S0,,2HO.. . . 150" .640 1066 *6 SO given off. No HS. SU33H0 . . .. 150" *470 783 *3 SO2given off and a little HS. S0,4HO .... 130" *215 358.3 A large quantity of HS given of with a little so2.S0,5HO . . .. 130" -140 233 *3 kid nearly on the foil. HS given of and only a little SO.,. It will be observed in examining the results contained in this table that the action of various strengths of sulphuric acid upon tin differs entirely from that which they exert upou copper and in some respect.s on zinc; S0,HO exerts the maximum action upon copper but it gradually decreases as the acid becomes more diluted; whilst with ziiic as before statcd the actioii is cornpletcly differeut CALVERT AND JOHNSON ON THE according to the strength of acid; but there is still this similitude between the action of sulphuric acid upon tin and zinc viz. that with a certain strength of acid sulphurous acid and sulphuretted hydrogen are given off simultaneously; but this action does not take place with SO,,HO or S0,,2HO as the first indication of sulphuretted hydrogen occurs with S03,3H0 and it is only with SO3,5HO that large quantities of sulphuretted hydrogen are given off and only a trace of sulphurous acid.From these results we conclude that when strong sulphuric acid acts upon tin the metal is oxidized like on copper through the action of the acid whilst with weaker acids water is decomposed the oxygen fixing itself on the tin or zinc whilst the hydrogen unites with the sulphur to produce sulphuretted hydrogen; therefore the action of dilute sulphuric acid upon tin niay be considered as two chemical actions occurring simultaneously ;moreover sulphate of binoxide of tin is produced and not the corresponding salt of pro-toxide.The action of sulphuric acid upon tin throws much light on the formation of sulphide of copper for in the case of tin as there is no intense affinity between sulphur and that metal we ob-serve the production of a large quantity of sulphurous acid no sulphuretted hydrogen but a large quantity of free sulphur float-ing in the liquid showing a complete deoxidation of the sulphuric acid by both metals; but with this difference that in the case of tin sulphur remains free whilst in that of copper it combines with it producing a sulphuret. Action of Nitric crnd Hydrochloric Acids on Tin Zinc and Copper. -We shall reserve details of our experiments until we describe the results obtained by acting with the same acids on the two classes of alloys formed by these metals viz.brasses and bronzes; for it was found by direct experiment that to arrive at any correct data it mas necessary to employ acids of peculiar strength or ctherwise the reactions were so complicated that no comparative results could be obtained of the action of these acids on the various groups of alloys. The following facts will we believe illustrate these statements :- ACTION OF ACIDS UPON METALS AND ALLOYS. 441 TABLE4. Action of Nitric Acid upon an Alloy of Copper and Zim. Surface acted upon.. ........... 1 cent. cube. Quantity of acid.. ............. 100 , Time of action ................ 24 hours. 50 .941 Composition of Brass { z: i::,9”r :: 49 *059 Strength of nitric acid employed.Total quan-tity dissolved on 1 C.C. Composed of Per cent. Average per cent. Sp. gr. 6*421 3 -093 cu 3 *328 Zn 48 -232 Cu 51 *768Zn 6 -421- 100 -000- 48.258 Cu 51 -742 Zn 3.936 1 -898 Cu 2 -038Zn 48 -283 Cu 51 717Zn 0 so00 3 *936- 100 *ooo- 1 *504 0 -252 Cu 16.856 Cu 1 -243 Zn 83.144 Zn -I 1.495 100 moo0 16 -741 Cu 83.259 Zn 0 *340Cu 16 -626 Cu 1 -2.034 1 5’05 Zn 83 a374 Zn 100 ‘000 --I 2 ‘045 100 .ooo In perusing the above table it will be seen that whilst nitric acid of sp. gr. 1-14dissolves the metals composing the brass in the exact proportions in which they exist in the alloy employed whilst an ncid of about half the strength or of sp. gr. 1.08,dissolves nearly the whole of the zinc contained in the alloy and only a small quantity of copper.This result among others showed us the necessity of employing a given strength of acid in order to con-duct a series of comparative experiments on various alloys and we consider the action of nitric acid of sp. gr. 1.14 a normal action as it attacks both zinc and copper in the proportions in which they exist in the alloy whilst that of a stronger or weaker a2 CALVERT AND JOHNSON ON THE acid is abnormal as it acts according to its strength more or less on each of the metals composing a brass alloy. These results were further confirmed by a cube of an alloy composed of equal parts of zinc and copper being left for several days in hydro- chloric acid of full strength the whole of the zinc or nearly so of the alloy being dissolved leaving a cube which had the samc diameter as if it had only been experimented upon and was com-posed of nearly pure copper.The following table illustrates this fact :-TABLE 5. Action of Strowg Hydrochloric Acid on the AUoy ZnCu. 1eq. copper .................... 49.059 I ey. zinc. ...................... 50.941 100 *ooo Strength 01 acid used. Weight of cube. Remarks. 1 *20 grammes.cu 4.403 grammes. grammes. 1 *20 Zn 4.577 8 *986 cu 4 *467 Zn 4.638 _- 4 *443 4 -330 -130 *308 The cubes after the experi-ment have copper -like colour and have the same diamet,er as before but are qiiite soft. A trace only of copper dis- solved. 9 *lo5 Action of weak Nitric Acid on Brasses.We shall now proceed to describe the action of weak nitric acid sp. gr. 1.100 on various alloys of zinc and copper combined in equivalent and multiple proportions. We decided to use this strength of acid as we found after many experiments that this was the best strength of acid that could be employed to obtain constant results. The table which follows these remarks contains a summary of our results and gives an idea how varied is the action of the same strength of nitric acid on the same class of alloys and what an extraordinary influence a few per cent. of copper or zinc more or less exerts in preventing or promoting thc action of this acid. ACTION OF ACIDS UPON METALS AND ALLOYS. 443 Further in perusing the table it will be observed that the action of the acid is comparatively violent on all the alloys containing an excess of zinc and that it is nearly 1,000 times less active on all thvse in which there is an excess of copper ; and we cannot in this case refrain from drawing special attention to the action of the acid on the alloy ZnCu as compared with that which it exerts upon Zn,Cu although there is only a difference of 17 % of zinc.It is necessary that we should explain how we have arrived at t,he data found in the fourth column. The figures represent the calculated results of the amount of metals which should have been dissolved had the metals been free and had not the presence of one of the metals interfered with the chemical action. It will be observed in comparing these figures with those which represent the quantity of alloy actually dissolved that in the first four alloys of the table viz.those which contain an excess of zinc the quan- tity of alloy dissolved is in excess of that which theory indicates whilst in the alloy composed of equivalents of each metal and those which contain an excess of copper the action is 40 or 50 times less. These facts appear to us not only interesting in a scientific point of view hut important in ;their applications to manufactures especially for brass taps pipes &c. The following is a summary of our experiments:- TABLE6. Actioii of Nitric Acid sp. Or. 1 -100,on Alloys of Copper and Zinc (Brasses). Surface acted upon. ............ 1 cent. cube. Quantity of acid................ 25 , )> Time of action.. ................ 15 minutes. Temperature .................. 20" C. 1 Metals and Calciilated to the y:z composition of loss on 1 sq. composition of alloys. metre. the alloys. --.---Copper 0.009 15.000 15 *OOO Zinc 1 760 2933.3 2938 3 ZnjCu Zn 83.70 2.025 3375.0 2457 -645 Cu 16.30 100 00 I 4444 CALVERT AND JOHNSON ON THE TABLE6-Coritinued. -Metals and compasition of alloys. Loss on 1C.C. Calculated loss on 1 sq. metre Loss calculated wording to the composition of the alloys ZndCu Zn 80.43 15'40 2900 *O 2362 '2 Cu 19.57 100 .oo- Zn3Cu Zn 75.36 1*695 2886 '0 2214.25 Cu 24.64 ~ ~~ 100 .oo- Zn,Cu Zn 67.26 1*530 2550 .O 1977 -8 Cu 32.74 100 .oo- ZnCu Zn 50.95 0.027 45,000 1494 .O Cu 49-05 100 00- ZnCu Zn 33.94 0.015 25.000 1005 *48 Cu 66.06 - 100 00 ZnCu3 Zn 25.52 0 -013 21 *66 759 -75 cu 74.48- 100*oo- ZnCu4 Zn 20.44 0 *015 25 *oo 611 '50 Cu 79.56- 100 '00- ZnCn5 Zn 17 *05 0 no10 16 -66 512 -57 Cu 82-95 100 *oo - ACTION OF ACIDS UPON METALS AND ALLOYS.445 Action of Hydrochloric Acid sp. gr. 1.05 on Alloys of Zinc and Copper (Brasses). It will be observed in perusing the results consigned in the table following that the action of this acid is :nearly equal to that which theory indicates on the alloys Zn,Cu and Zn,Cu whilst in the next alloy Zn,Cu which contains only 5 % more copper than the preceding one the attack is only half of that indicated by theory.But certainly the most iinexpected result arrived at is the complete inaction of hydrochloric acid upon all the alloys con- taining an excess of copper and especially on the alloy composed of equivalent proportious of each metal ; and it is very remarkable that whilst half the cube of the alloy Zn,Cu is dissolved in the space of oue hour the alloy with equal equivalents of each of the metals remains perfectly unattacked. The fourth column in this table also gives the theoretical quan- tity tliat should have been dissolved if the metals had been free md not alloyed. TABLE7. Surface acted upon ............ 1 centirnetre cube. Quantity of acid.. .............. 50 .. 9) Time of action ................1 hour. Calculated iI Loss calculated Metals and composition of Loss on loss on 1 sq* ,according to tile composition of alloys. 1 C.C. the allo~s. ~ CopperZinc 0 .ooo 0 200 0 000 333.33 I 0 000 333 33 ZnjCuZn 83.70 0 *155 268 334 I 279 00 Cu 16 30 100 .oo- Zn,Cu Zn 80.43 0.155 258.334 268 .O cu 19 57 100 .oo- ZnJ!u Zn ‘75.36 0 -065 10s 334 251.2 Cu 24.64 100 .oo CALVERT AND JOHNSON OX THE TABLE7-Continued. Metals and Calculated Loss calculated composition of Loss on loss on 1 sq. according to the alloys. 1 C.C. metre. composition of the alloys. Zn,Cu Zn 67’26 0*050 83 *334 224 *2 Cii 32.74 I00 .oo ZnCu Zn 50.68 0 -000 0 -000 168 ‘933 Cu 49-32 100 .oo -ZnCu Zn 33.94 0-000 0 *ooo 113 *133 Cu 66.06 -100 -00 -ZnCu, Zn 25.52 0 -000 0.000 85 -066 Cu 74-48 100 -00 7 ZnCu, Zn 20.44 0 -000 o*ooo 68.133 Cu 79.56 100 -00 ~--ZnCu5 Zn 17*05 0 *ooo 0 *ooo 56 ‘83 cu 82.95 -roo -00 Action of Sulphuric Acids S0,HO and s033H0 on Alloys of Copper and Zinc.We now pass on to the action exerted by the-two above mentioned strengths of sulphuric acid upon brasses the results of which are not less instructive than those already referred to But before drawing attention to the leading facts observed it is necessary that we should give the reason why we em-ployed in preference S03,H0 and S03,3H0 for our experiments. They are that S03,H0 is the only acid which attacks copper in any marked degree ; S0,,3HO the only one which has a corres- ACTION OF ACIDS UPON METALS AND ALLOYS.447 ponding action upon zinc and therefore by employing these SUC-cessively upon the same alloy at a temperature of 150°C. we were acting under favourable circumstances for appreciating the exact mode of action of these acids on both metals entering iuto the composition of the alloy. TABLE8. Action of Monohydrakd Sulphuric Acid on Brasses. Surface acted npon .............. 1cent. cube. Quantity of acid employed ........ 50 .. Time of action ................. 2 hours. Temperature.. .................. 150" C. 0 sq. metre. Action on 1c. c. of copper ........ 1.678 = 2797 .. zinc .......... *232 = 3367 Calculated Compositionofallojs. Loss on 1 c.c. loss 1 sq. metre on surface. Theoretical loss. Bemarks. CuZn 83.7 Zn 16.3 Cu 1 /so2 given off. NO HS and only Zn dissolved. 100 -0- ,098 163 *33 779 *5 J CuZnl 80.43 Zn 19 .ti7 Cu 1 1 and only Zn dissolved. I so2given off. NO HS 100 .00- 97'4 123.33 858 *3 CuZnR 75 *36Zn SO2 given off. No HS, 1 and only Zn dissolved. 24.64 Cu 100 -00 el80 300 *O 980.5 -__ -CuZn 67.26 Zn 32 *74Cu 100 .oo -083 153.3 1175.8 SO given off. -SO given off. No HS. Strong action. Insoluble residue consists of ZnO, 1 S02,Cu0,S0,. Also a CuZn small quantity of CuS 50.68 Zn and S. i 49.32 Cu Thequantitiesof themetals i dissolved were found to 100 -00 1 297 2161.6 137'5 -7 be in the exact propor- tion of those in t,he allors.-J 448 CALVERT AND JOHNSON ON THE TABLE 8-Continued. Calculated Compositionof alloys. Loss on 1 c. c. loss 1 sq.m&re on surface. Theore tical loss. Remarks. Cu,Zn 33 .Q4Zn 66.06Cu 100 .oo- 1 -292 21 58 *3 2015 0 I so2 given off. NO HS. A small quantity of free S and CuS.i J Cu3Zn 25 *52 Zn 74'48 Cu 100 '00 - 1 *747 2211 *66 2182 so1 Ditto Cu4Zn 20 -44Zn 79 *56 Cn 100 -00- 1 -328 2213 -0 2304 47 Ditto Cu,Zn17.05 Zn a2 -95 cu *605 1008.33 2386 *19 Ditto In examining the results contained in this table several interest- ing data are brought out viz. that in all the alloys in which there is an excess of zinc over the quantity of' copper the attack is exceedingly limited whilst in all those in wbich there is an excess of copper the action is most marked and very similar in fact to that which acid exerts on pure copper.It is certainly interesting to observe the extraordinary preven- tive influence which a metal like zinc has on the action of such a powerful acid as SO,,HO on copper ; and certainly a priori such a result could have been expected. And we cannot help drawing attention to the striking difference between the action oE SO,,HO on the alloys ZnCu and Zn2Cu and therefore the influence which only 17 % of zinc exercises in preventing the action of the acid the action on ZnCu being nearly 15 times as violent as on Zn,Cu. It may be further observed that when SO,,IIO acts upon the above alloys in all those containing an excess of zinc not only does the zinc prevent the action of the acid upon ACTION OF ACIDS UPON METALS AKD AILOYS.4-49 the alloy itself but it so thoroughly preserves the copper from the action of the acid that whatever may be the amount dissolved it is represented by zinc only; whilst in the alloys containing an excess of copper the copper is attacked also and dissolved in large quantities As to the general result of the chemical action of SO,,HO on the same group of alloys we may add that the secondary products are the same as when SO,,HO acts upon copper itself. Action of S0,3HO on Brasses. It will be seen in perusing the results contained in the table which follows these remarks how very different is the action of SO3,3HO as compared with SO,,HO on the same alloys when placed under identical circumstances for all the alloys which contain an excess of zinc are those most attacked whilst this strength of sulphuric (S0,,3HO) acid exerts little or no action upon the alloys containing an excess of copper; and what enhances the value of these results is that all the alloys which contain an excess of either copper or zinc are attacked more or less whilst the alloy CuZn is not acted on and therefore this alloy could be employed with marked advantages for many purposes the more so that when well prepared it has a fine and rich brass appearance notwithstanding the large proportion of zinc ; it contains about 15 % more than the poorest brass alloys usually found in commerce.Lastly it will be observed that among the secondary pro-ducts formed during the chemical action of S03,3H0 there is no sulphide of zinc produced as in the case when SO,,HO acts upon the same alloys of zinc and copper.TABLE9. Surface acted upon .............. 1 centimetre cube Quantity of acid ................ 50 , , Time of action .................. 2 houra Temperature.. .................. 150" C. on sq. metre of surface. Action on 1 c. c. of copper ........ '006 = 10*000 , .. 1 , zinc ........ 5.450 = 9085'150 VOL. XIX. 2K CALVERT Ah'D JOHNSON ON THE TABLE9-Cont.inwd. Calculated. Composition.of alloys. Loss on 1c. c. on 1 sq. metre. Theore tical quantity. Remarks. CuZn ...... CuZn. ...... CuZns ...... -135 *130 -120 225 -0 216 -0 200 -0 7605 *73 6848.86 7308.95 S0,givenoff.NoHS deposits. CuS. Ditto. A trace of HS. Ditto CuZn2 ...... CuZn ...... -115 so00 191 *6 - 6113 -77 4609 -2 Ditto - Cu2Zn ...... Cu3Zn ...... a119 -006 198.33 10 .o 3090 *05 2325 55 SO2given off. Ditto Cu,Zn ...... Cu,Zn ...... ,007 -006 11 -6 10 -0 1864 *95 1557 29 Ditto Ditto Action of Acids on Bronzes or Alloys of Copper and Tin. We shall follow the same order in examining the action of vari-ous acids upon bronzes as we have done in describing their action upon brasses; thus we shall first examine the action of nitric acid then that of hydrochloric acid and finally that of sulphuric acids; and it is easy to conceive that the action of these various acids upon bronze alloys must be very different nitric acid pos-sessing the property of acting upon both metals hydrochloric acid of acting only upon tin and not upon copper whilst suZphuric acid only acts upon both metals but under the influence of heat.We shall now proceed to examine the action of each acid separately. TABLE20. Action of Nitric Acid sp. gr. 1.25 on Alloys of Copper and Tin (Bronzes). Surface acted upon .............. 1 cent. cube Quantity of acid ................ 25 .. Time of action .................. 16 minutes Calculated loss Metals and com- Loss Calculated on according to the position of alloys. on 1C.C. 1sq. metre. composition of the alloys. Copper.. ........ 1.920 3200 -0 3200 -0 Tin............. 0.505 841.667 841 *667 Sn5Cu Sn .. 90.27 cu .. 9.73 100*OO 1 *130 1883 '33 1071 -132 ACTION OF ACIDS UPON METALS AND ALLOYS.451 TABLE10-Continued. -Metals and com-position of alloy1 Sn4Cu Sn .. 88.14 Cu.. 11 '86 I00 .oo _. Sq,Cu Sn .. 84.79 Cu .. 15 21 -100 .oo -Sn?Cu Sn .. 78.79 cu *. 21.21 100 00 -SnCu Sn .. 65.02 Cu .. 34 98 100 00 -SnCii, Sn .. 61 a3 Cu .. 48.17 100 *oo -SnCu3 Sn .. 38 21 Cu .. 61-79 100 .oo -SnCIi, Sn .. 31.73 Cu .. 68 27 100.00 LIWI SnCu, Sn .. 27 10 cu .. 72 90 100~00 Loss on 1 C.C. 0 -725 0 -590 0 240 0 110 0-126 0 560 0.910 0.485 Calculated 01 1 sq. metre. 1208 33 985 -33 400 00 183 -334 208.534 933 *334 1516.66 808 381 Calculated lose according to the composition of the alloys.1121-36 1200 *36 1341 .869 1666 G 1977.676 2295 .a8 2453 *384 2577 *725 CALVERT AND JOHNSON ON THE The first result which attracts attention is that none of the alloys are acted on to the same extent as pure copper; therefore the presence of tin in the alloys counteracts to a certain extent the action of nitric acid on bronzes; but the preventive influence of tin presents this particularity that the action of the acid increases as the proportion of tin increases; thus the alioy CuSn is attacked ten times more than the alloy CuSn. It should also be noticed that the quantity of metals dissolved is less in all the alloys contairiing an excess of copper as well as in the two alloys Sn,Cu and Sn,Cu than theory indicates but it is especially with the alloys Sn,Cu and SnCu that this result is observed.TABLE11. Action of Hydrochloric Acid sp. gr. 1-10,on Alloys of Copper and Tin (Bronzea). Surface acted upon ............ 1 cent. cube. Quantity of acid.. .............. 50 .. Time of action ................ 1 hour. ~~ ~~ Calculated loss Metals and com- Loss on Calculated on tccording to the position of alloys. 1 C.C. 1 aq. metre. composition of the alloys. Copper ........ Tin ............ 0.002 0 011 3 ~334 18.334 3,334 18.334 Sn,Cu .......... Sn,Cu .......... Sn3Cu .......... Sn,Cu .......... SnCu .......... SnCuz .......... 0 017 0*016 0 *015 0 *012 0.006 0 $006 28.334 26 *667 25 ,000 20 .ooo 10 000 10 .ooo 16.874 16 *554 16 *052 15*152 13,086 11 .lo7 SnCus ..........0 *005 8 *334 9*065 SnCu .......... SnCuj .......... 0-004 0.003 6 *667 5.000 8 -093 7.398 In this series of experiments the action of hydrochloric acid upon tin is marred by the presence of copper the action of acid on the bronzes decreasing as the quantity of copper in the alloy increases. ACTION OF ACIDS UPON METALS AND ALLOYS. 453 Composition of alloys. CuSn 9 '73 cu 90 '27 Sn 100 *oo - CuSn4 11.86 Cu 88 *14Sn 100.oo - CuSn 15-55 Cu 84 *45Sn loo no0 CnSn2 21 -21 cu 78"79 Sn 100 .oo - CuSn 34*98 Cu 65 -02 Sn 100 -00 - CuaSn 51*83Cu 48-1'7 Sn 100-00 TABLE12. Action ofSui@huricAcid (SO3HO) upon Bronze.Sui+face acted on .............. I cent. cube Quantity of acid .............. 50 .. Time of action ................ 2 hours Temperature.. ................ 150" C. sq. metre. Action upon 1 c. c. Cu = 1-678 = 2797 -2 , Sn = 3*010= 50.17 -6 JY ~~ Calculated Loss on Calculated loss accord-1 cent. cube In 1squarc ing to the Remarks. metre. :ompositior If the alloy. -656 1.093-3 4801*55 SO2 given off. No ITS. -546 910 *o 4754*26 Ditto Ditto *634 1056.6 46'72 -32 Dit,to Ditto *525 875 .O 4546 65 Ditto Ditto -632 10.53'3 $240 -9 Ditto Ditto '797 1328 -3 3866 -76 Ditto Ditto 456 CALVERT AND JOHNSON ON ACIDS ETC. TABLE12-Continued. Compositionof allop. Loss on cent,. cube Calculated loss on 1 square metre.. Cdculated loss accord-ing to the composit ion of the alloy. Remarks. -._- Cu3Sn 61‘79Cu 38 -21 Sn- 100*oo- *820 1366-6 3645-6 SO2 given off. No HS. Cu4Sn 68*27Cu 31 ‘73 Sn 100-00- *450 750 -0 3501.33 Ditto Ditto Cn5Sn 72-9 Cu 27-1Sn- 100*00 *372 620*O 3391 *93 Ditto Ditto In examining the results contained in this table it will be observed that copper retards the action of the acid upon tin none of the alloys being attacked in the ratio of the quantity of tin it contains compared with that of copper; in fact an alloy Sn5Cu although it contains 90 % tin and only 10 % copper is not attacked more than an alloy SnCu which contains 65 % tin and 35 % copper Again two of the alloys which contain a great excess of copper vix.SnCu and SnCu, are less attacked than any of the other alloys comprised in the series and it is difficult to understand why the two alloys SnCuz and SnCu should be attacked with such violence as compared with the two bronzes which contain a larger amount of copper ; the only explanation we shall offer of this exceptional result is that in our experiments on the conductibility for heat by metals and alloys,” we found that those two alloys had conducting power which differed from all the rest of the alloys of copper and tin and we submitted at that time the opinion that it was highly probable that those two alloys were not simply mixtures of metals but definite compounds and the exceptional action which S0,HO has on these alloys as compared with that it exerts upon the rest of the series appears to substautiate this view.

ISSN:0368-1769    

DOI:10.1039/JS8661900434

出版商:RSC    

年代:1866

数据来源: RSC

摘要:

455 XLI1.-On Determining the Weight of Heterogeneous Liquids. By HERMANN SPRENGEL THErelation between mass volume and density furnishes a ready means of determining the weight of a body and is often resorted to when the result cannot be conveniently arrived at by means of the balance. This for obvious reasons applies especially to liquids and moreover to large quantities of liquids. If the liquid is homogeneous and the space which it fills easily measurable no difficulty will be experienced in the determination; but if either one of these conditions be unftilfilled the case is different. It is probable indeed that errors often arise from want of attention to the heterogeneity of liquids. Take for example the determination of the weight of sulphuric acid accumulating at the bottom of the leaden chambers.In this case we have on the average an area of about 2,000 square feet covered with acid of a heterogeneous gravity and varying in height from fractions of an inch to 12 inclies or more. We have then to ascertain in the first place the volume of this liquid and in the second its average specific gravity. Determination of fhe Vohme. As the area of the pan containing the acid once determined remains the same in all future determinations we merely need on repeating them to take notice of the altered height of the level. This is commonly effected by plunging a dry gauge per= pendicularly into the acid; but by the use of the instrument which I am about to describe we may dispense with the necessity for a separate determination of the height and ascertain it in a similar but perhaps superior may in the course of determining the average specific gravity.A graduated scale etched on a plate of glass forming part of the side of the chamber would doubtless be the most direct and certain way ; but practical objections render it inapplicable Graduated syphons U tubes and communicating vessels in general are useless for the determination of the* height of heterogeneous liquids as the he.ights of the two liquid columns wheu in equili- 456 SPRENGIEL ON DETERMINING THE WEIGHT brium will of course be inversely proportional to the specific gravities of the liquids they respectively contain. Determination of the Average Specijk Gravity.A heterogeneous liquid in equilibrium may be regarded as con-sisting of an infinite number of laminae of different gravities of which the lighter ones are buoyed up by the heavier. Suppose now that we have to determine the average specific gravity of such heterogeneous liquid which we cannot convert into a homo- geneous one by mechanical agitation it is obvious that if a vertical section of this liquid could be procured the gravity of that section would represent that of the whole provided that the bottom of the vessel were parallel with the surface of the liquid. FIG. 1. With this object I have constructed the instru- ment represented in the annexed diagrams. A B (fig. 1) is a graduated cylindrical glass tube of about 1inch diameter and 18 inches in length.It is essential that the calibre of this tube be as nearly as possible the same throughout the whole length. On plunging such a glass tube open at both ends vertically into the acid the liquid will stand at the same height both inside and outside the tube and at corresponding altitudes will possess the same specific gravity. This cylinder of acid cut so to speak out of the whole mass has to be withdrawn its height read off on the scale and its specific gravity after mixture determined in the usual way. The idea which first suggests itself is to affix to the end A a valve (opening towards the inside) which would on the tube being raised preveut the liquid from running out. As however a cer-tain pressure equivalent to the resistance of the valve is required to keep it open the level inside the tube will always be lower than out- side.The chief obstacle to this plan lies in the poasible presence of solid particles which might happen to prevent the valve from shutting and would render the whole determination useless. To obviate these difficulties I have adopted the follow- OF HETEROGENEOVS LIQUIDS. 457 ing expedient. Supposing the liquid column inside the tube were hermetically shut ofi' above its level from the outer air and in such a manner that no air whatever remained enclosed with the liquid it is evident that theoretically the column might be raised out of the acid without any loss. As we know that these con- ditions cannot practically be fulfilled I have approached them by supplying the tube with a moveable piston attached to another glass tube of small calibre which serves to ad- FIQ 2.just the position of the piston to the height of the acid and for the escape of air while the acid is entering from below. After this is done the pistou-tube having at its upper end it piece of black india-rubber tubing is closed with a com-mon pinch-cock. The instrument might now be lifted out of the acid and as a tube of this size would lose its charge directly I have prevented such escape by attaching to its end A a sort of cap as shown in fig. 2. This cap which in the diagram is represented detached from the tube consists of a thin plate best made of plati- num of a diameter a trifle larger than that of the glass tube.To prevent its slipping off it is fixed unto the tube by means of two springs each of which is supplied with a small pin fitting a corresponding hole bored in the side of the glass tube without of course completely per-forating it. There are also as will be noticed in the figure four small pieces of platinum fixed opposite to each other round the margin of the cap. These prevent the rim of the glass tube from touching the plate and thus leave a small -space of about &th of an inch between the ttlbe. and the cap by which the acid can enter. The piston is made of vulcanised india-rubber cut out of a flat block of that substance with a sharp cork-borer well lubricated with oil. As the-accunte fit of the piston is essential I may mention that a piston a little too small may be enlarged to the required size by boring the central hole somewhat smaller than the piston-tube it is to receive.To secure a sufficient attachment of the piston to the piston-tube the end C of the latter is SPRENGEL ON DETERSIINING THE WEIGHT roughened with a file and the upper part of the piston bound with a strip of india-rubber.* The piston-tube is of course as long as or even a little longer than A B and its diameter about 0.3inch while that of the bore ought to be not much less than0-08 inch; for on immersing A B in the acid the levels inside and outside the tube ought to be always equal and as no acid can enter without pressing a propor-tional bulk of air through the capillary tube the motion down- wards would become inconveniently slow if the bore were much less.To keep C D in the centre of A B a loose cap of ebonite is affixed at B serving as a guide. The scale on A B is etched into the glass as described in Bunsen’s Gasometry. The division is 0.1 inch subdivided into five parts. Fig. 2 is intended to represent the natural size. The 0-point is placed near the rim say 0.4 inch above the lower surface of the platinum-plate when affixed to the tube This value 0.4has consequently to be added to all readings so that 5 inches read on the scale is in reality 5.4 inches. As the naked eye can without difficulty distinguish the half between two of these small divisions we are able to read in this manner 0.01 inch.This accuracy is not superfluous since in this case one of these small divisions represents a weight of about 300 lbs. of acid. As the piston for the sake of accurate reading must be placed high enough not to be in contact with the surface of the acid (or more properly the meniscus) and as a certain amount of air remains also enclosed in the capillary tube C D the amount of both (which we will henceforth call u) necessarily leads to an error when the in- strument is withdrawn from the bulk of the acid For whereas v was previously under the full pressure of the atmosphere it is now under the pressure of the atmosphere minus the weight of the column of acid in A B. The bulk of v will consequently expand and expel a proportional quantity of acid.All readings will therefore f This tying of india-rubber tubing etc. with india-rubber I manage as follows I cut from a sheet of clean black india-rubber a strip say a quarter of an inch broad and of the requisite length. Then after warming it I proceed to coil it round the place I wish to tighten stretching the strip as much a8 it will bear without tearing and thus extending it into a long fine membrane. Though each round of such elastic binding exercises only a slight pressure the sum of all these pressures amounts to something considerable and the coils compress each other into a solid compact collar of considerable strength. This binding of india-rubber 1 recommend as supe- rior to string or wire as it withstands the action of acids excellently and does not cut the substance bound with it.0.F HETERUQENEOUS LIQUIDS. 459 be this much too low. This error is however small as will be seen from the following calculation. Suppose that the distance of the piston mere always kept 0.2 inches above the level of the acid what mould the error amount to at different heights and different gravities of acid if the instru- ment had the dimensions previously given? The volume of v in this instance was found to be 0.232566 cub. inches easily deducted from the weight of water filliiig 0.2 inches lineal of A B and the whole of the capillary tube C D. Supposing the acidin the chamber be 1.5 sp. gr. and its height 1 inch v under the atmospheric pressure minus 1 inch acid of 1.5 sp. gr.... . ... . .. = 0.233800 cub. inches v under the atmospheric pressure .... .. = 0.232566 , Increaseof v .............. = Oa000834 , Now we know from the determination of the volume of v that 0.125226 cub. inches occupy 0.2inch lineal of A B hence 0.125226 0.2 = 0.000834 x. x = 0.00133 inch representing the number which expresses in lineal inches the increase of v 011 the scale of our instrument if it is withdrawn from a depth of 1 inch of acid at 1.5 sp. gr. This number which represents the error me mill call e. In like manner are obtained the values of e in the annexed table at the specified heights and gravities :-1.5 sp. gr. 1.6 SP. gr. 1.7 sp. gr. e at 1 inch = 0.00133 0.00150 0*00152 e , 6 , = 0.00855 0.00922 0.0097'3 e , 11 , = 0.01605 0.01728 0.01832 We learn from this the ratio in which e increases within limits seldom exceeded in practice.Thus we have e at 6 inches of 1.5 sp. gr. .... = 0.00855 > 1 >> ,> .... = 0.00133 Increase of e for 5 inches.. = 0.00722 consequently >> , 1 . . = 090144 ,> SPRENGEL ON DETERMINIKG THE WEIGRT being the average expansion-coefficient for v for every inch from 1 to 6 inches. In the same way are found the expansion-coefficients of the following table :-Expansion co-efficient8at 1% sp. gr. at 1.6 sp. gr. at 1.7 sp. gr. From 1to 6 inches .. 0.00144 0-00154 0.00164 , 6 , 11 , .. 0*00150 0*00161 0.00172 Supposing we had read off 5.4 inches as the height of the acid which was found to have a sp.gr. of about 1.6 we should have to make the correction by adding 5.4 x 0.00154 or 0.008316 to the 5.4 inches observed as being the real height of the acid inside the chamber The error consequently is so small that for low levels it may be altogether neglected as well as the slight error arising from the loss of the small portion of acid which influences the average specific gravity Having described the nature of the instrument I may now briefly explain how to use it. After having wetted the piston which is necessary for its easy motion it is pushed into the tube to a position high enough not to touch the level of the acid of which a sample is about to be tak.en. The pinch-cock is now remoyed to open C D and the instrument slowlylowered into the acid till it touches the bottom.After C D is closed again with the pinch-cock the instrument has to be raised and the level reached by the acid read off on the scale. On again opening the pinch-cock the acid will run out. This samplehas to be rejected having merely been drawn to ascertain approximatively the height of the level in order to adjust the piston to its proper place i.e. 0.2inches above the level. Before the next sample is drawn it will be well to blow through the piston-tube in order to remove any portion of liquid which might have obstructed the passage. All the rest of the operation is then repeated as before only with more care especially in lowering the instrument with a slow uniform and perpendicular motion. After the acid adhering to the outside of A B has drained off and the height of the level been read (the eye being carefully placed in a line with the surface) the pinch-cock is opened the acid collected in a glass cylinder and after mixture testedin the usual manner.When the acid in the chamber stands at a low level it might be found troublesome to have to repeat the drawing of samples until a quantity of acid OF HETEROGEKEOUS LIQUIDS. is obtained in which hydrometers of the usual size can float. This objection is easily met by employing smaller ones made on purpose. Being now in possession of the means of ascertaining with accu- racy the height and average specific gravity of the horizontal sec- tion of any liquid,* I may add a few words on the horizontal sections of the acid accumulating on the bottom of the chambers.For reasons mentioned hefore the sample has actually to be drawn from the inside of the chamber which is generally effected by making a cavity of suitable dimensions in the side of the chamber placed a foot or so above its bottom. A hole is pro- vided in the bottom of this 'cavity for access to the acid under-neath. If the bottom of the chamber be parallel with the surface of the acid one determination is sufficient to fix the absoiute weight of the whole. It will often happen however that though the chambers were built level at first they will in time become otherwise. If that is the case one determination is insufficient and the number and places of these determinations will depend upon the geometrical figure assumed by the vertical section of the acid.If the figure of this vertical section became too irregular the task of fixing the accurate weight in this manner would haw to be given up. The heaviest acid mill invariably gravitate to the lowest point in the chamber. Equal altitudes have equal gravities and if samples drawn with the above instrument from the same chamber have different gravities it is caused by irregularities in the level of the bottom. Although the importance which is attached to these determina- tions lies less in the knowledge of the absolute weight of acid prevent at the time in the chamber than in that of the exact quantity of acid which has been formed during a certain period tbere is no possibility of knowing the one without the other.By fixing the level to-day and at the same point to-morrow we learn from the altered height the volume formed in the interval but uot its weight or at least only conditionally that is only under the assumption that the determinable part of acid x has * The intimate mixture of large quantities of liquids demands considerable time and labour. As the average specific gravity after mixture is generdlly taken as the guide for fixing the desired proportion between two liquids to be mixed numeroua experimental mixtures aud tests of t,he whole bulk may be avoided by the taking of samples with the above instrument. SCEIUNCK ON SOME PRODUCTS DERIVED the same specific gsavity as the indeterminable part y and such might seldom be the case.If therefore y be of a higher specific gravity than x x will become heavier at the expense of y anct me assume a greater yield of acid than me have actually made during the period in question. If y is weaker the reverse takes place. The intervals between these determinations are generally so long that the acid has to be removed from the chambers. In its further treatment it undergoes such a change that it becomes a homo-geneous liquid or a well-defined sulphate in which state it is weighed. By this means all the errors arising from the hetero- geneity of the acid are the more diminished the larger the pro-portion of homogeneous to heterogeneous acid. In other words the longer those periods are the nearer the calculation will come to the truth; on the other hand the shorter they are the more particular have we to be in all details which fix the weight.

ISSN:0368-1769    

DOI:10.1039/JS8661900455

出版商:RSC    

年代:1866

数据来源: RSC

摘要:

462 SCEIUNCK ON SOME PRODUCTS DERIVED XLIIL-On some Products derived from Indigo-Blue. SCHUNCK, By EDWARD Ph.D. F.R.S. [Abatract from the third volume of the third series of Xemoirs of the Literary and Philosophical Society of Manchester. Session 1864-5.] MY experiments on the formation of indigo-blue an accoxnt of which I had the honour of presenting to this Society several yetvs ago led me to make some inquiries regarding the processes em-ployed in tropical countries for the production of indigo from the various plants yielding that dye-stuff. I found that all the authors who have written on the subject agree in affirming that the pro-cess of fermentation which is the one usually adopted for the purpose of extracting the colour from the plant requires to be conducted with the greatest care in order to yield a successful result.Unless certain precautioirs are adopted a product of very inferior quality will be obtained ;in some cases indeed the colour- ing matter is entirely lost. This will not be surprising to any one who considers that though indigo-blue when once formed is a very stable compound thc substaiice existing in the cells of the FROM INDIGO-BLUE. plant from which it originates and which I have named indican is decomposed with the greatest facility in various ways; that indigo-blue is only one of its products of decomposition and may be formed or not according to the nature of the process to which it is submitted. With this sufficiently obvious explanation I should have been inclined to rest contented had I not acquired a knowledge of some other facts relating to indigo-blue to which the same explanation cannot be applied but which evidently belong to the same class.It is well known to those dyers who employ the so-called woad-vat in which the reduction of the indigo-blue is effected by the action of various organic matters such as woad madder and bran together with lime that if the process be not carefully managed it may change its character entirely the contents of the vat entering into a state of complete putrefaction-a change which results in the total destruction or at least disappearance of the colouring matter. Now this phenomenon the reality of which cannot be doubted though its nature has never been subjected to scientific scrutiny cannot be explained in axordance with what is at present known regarding indigo-blue which is considered by chemists to be a body of such a stable character as not to be decomposed by any except very potent agents such as chlorine bromine and nitric acid.In no work on scientific chemistry is it stated that indigo-blue may be decomposed by any prpcess of fermentation or putrefaction in the same way as sugar or albumen. In my experiments on indigo-blue I have generally employed for its reduction and purification the process of F,ritzsche which consists in acting on it with a mixture:of alcohol grape-sugw and caustic soda. The colouring matter dissolves when the mixture is heated and is again deposited on exposure to the atmosphere in crystalline needles.Now in performing this operation with very small quantities of indigo-blue and an excess of alcohol and grape- sugar I found that the colouring matter did not make its appear- ance again on agitating the solution with air. The yellow colour of the liquid passed as usual through red to green; but instead of the indigo-blue being precipitated the whole became yellow or brownish-yellow and the colouring matter disappeared entirely. In this way I had the mortification of losing a quantity of indigo- blue which I had prepared with much labour from human urine though the loss resulted as it afterwards turned out in some gain of information. 46% SCHLTNCK ON SOME PRODUCTS DERIVED This fact was also difficult to account for since it is usually supposed that by the combined action of reducing agents and alkalies indigo-blue merely takes up an atom of hydrogen and then dissolves and by the action of the atmospheric oxygen is again precipitated unchanged and undiminished in quantity.In order to ascertain on what the disappearance of the colouring matter in this case depends I first dissolved a small quantity of indigo-blue by means of grape-suga;. and caustic soda using water as a solvent instead of alcohol; but though the indigo-blue was kept for a long time in solution and heat was applied at the sanie time to assist the action it made its appearance again on exposure to the air apparently undiminished in quantity. In another expe- riment in.which alcohol was used as the menstruum and protoxide of tin as the reducing agent the same result was arrived at. It was therefore apparent that the disappearance of the colouring matter was due to the combined action of the alcohol and the grape-sugar not to the separate action of either. By the use of a great excess of these two agents together with caustic soda and the long-continued application of heat to the solution I succeeded in causing several grammes of indigo-biue to disappear entirely. avoid the word decompose because as I shall show the colouring matter is not decomposed but enters into new forms of combina-tion. It now occurred to me that since by the action of caustic alkalies on sugar acetic and formic acids are formed the effect produced by the grape-sugar in this process might in reality be due to the presence of one or both of these acids rather than to that of the sugar itself.My supposition mas completely verified by experiment. On treating some pure indigo-blue with alcohol to which an alkaline solution of protoxide of tin was added until it dissolved then adding acetate of soda and digesting at a mode- rate heat the indigo-blue after some time ceased to be deposited on exposure to the air or even agitation; it had entirely dis-appeared. The same thing occurred when formiate of soda was employed in the place of acetate. It was evident therefore that in this process acetic or formic acid was capable of playing the same part as grape- sugar ;and as the use of the latter might have tended to introduce complications in consequence of the forma-tion of secorrdary products I ceased to employ it in my subsequent experiments.The objcct of the present communication is to give an account of tlic combined action of alcohol acetate of soda FROM INDIGO-BLUE. and caustic alkali on indigo-blue and the products thereby formed. At the commencement of the investigation I imagined that it wa8 an essential condition that the indigo-blue should be in a state of solution; but 1 soon found that this was not necessary. The operation succeeds equally well if indigo-blue freshly precipi- tated or in fine powder be employed. The plan which I adopted was quite simple Pure indigo-blue was introduced into a large quantity of ordinary spirits of wine and the mixture after being well agitated was raised to the boiling-point.A quantity of pure acetate of soda previously deprived of its water of crystallisation and a little solid caustic soda were then added and the boiling mas continued for several hours. A reduction of a portion of the indigo-blue took place in the first instance as was evident from the deep red colour of the liquid On agitating with air this red colour disappeared for a moment the indigo-blue being precipi- tated in powder to be again dissolved on boiling the liquid; but after some time the liquid acquired a dark-brown colour and de-posited nothing on exposure or agitation. The process mas then completed. There sometimes remained a residue of indigo-blue which obstinately resisted the action of the boiling liquid ; but on pouring off the latter and adding fresh materials it generally disappeared rapidly.I found it advisable to employ ody a small quantity of indigo-blue at a time as the process is a slow one and requires a great excess of alcohol and acetate of soda. The pre- sence of caustic alkali I found to be quite essential as no percep-tible action took place without it ; but the quantity required was not large. The stronger the alcohol and generally speaking the freer from water all the substances employed were the more rapidly was the process completed. In order to obtain the products resulting from this process I proceeded as follows :-The dark-bromu alcoholic liquid containing them was first mixed with sulphuric acid until it had acquired a slightly acid reaction and it was then evaporated.During eva- poration brown resinous masses mere deposited ; and on adding water when the evaporation was nearly completed a fresh quan- tity of resin-like matter was thrown down. The liquid filtered from this matter was still brown. It was evaporated to a syrup which after standing some time became solid from the formation of crystals consisting chiefly of acetate of soda. The whole ma- of crystals was then dissolved in boiling alcohol and tolerably VOL. XIX. 2L SClIUNCK ON SOME PRODUCTS DERIVED strong sulphuric acid was added to the solution until no more sulphate of soda mas precipitated care being taken to avoid an exmss of the acid.The liquid after standing some time was filtered and evaporated so as to drive off the acetic acid as well as the alcohol. When the cvaporation was nearly completed water was added mliicli threw down a large quantity of a brown pulverulent substance as well as a little brown resin which after filtration were added to the resinous matter previously obtained. The filtered liquid had lost much of its brown colour. 1shall return to it presently. The products insoluble in water obtained in this manner consist partly of resinous partly of pulverulent substances. Among these products there are at least five distinct substances which I have succeeded in separating from one another by the use of various solvents; but it is probable that small quantities of other sub- stances closely resembling them are also formed at the same time.Unfortunately these bodies are all amorplioiis and possebs very few characteristic properties. It is indeed only their origin and mode of formation that impa~t to them any interest; and I shall therefore refrain from adding to the already cumbrous mass of terms with which organic chemistry has to deal by inventing narces for them but shall simply distinguish them by the letters of the alphabet. The process adoptcd for the separation of these substances from one another was as follows :-The whole of the mass iiisoluble in water mas first treated with boiling water in order to remove all the sulphate and acetate of soda. It was then dried finely pounded and treated with successive doses of ether as long as anything dissolved.The ethereal liquid which had a rich reddish- brown colour was filtered and evaporated when it left a resin-like residue of the same colour. This residue was digested with weak caustic ammonia which dissolved a great portion of it. The por- tion insoluble in ammonia was filtered oE washed dried and then treated with ether which generally left a small quantity of brown powder undissolved. The filtered ethereal solution was evaporated and the residue was dissolvecl in cold alcohol which left behind a little resinous matter. The filtered liquid left on evaporation a brittle brownish-yellow resin which I assume to be an unmixed substance and shall distinguish by the letter A. The matter dis- solved by tlie ammonia was precipitated by acid in thick flocks which af er being filtered off waslied and dried were treated FROM INDIGO-BLUE.with ether. The ether left some brown powder undissolved which was separated by filtration. The liquid was evaporated and the residue was again treated with ether in order to separate a little more of tlie brown powder. The substance was then introduced into a hot solution of carbonate of ammonia which if not too concentrated dissolved the greatest part of it leaving only some brown powder behind. Ii; as sometimes happened the solution of carbonate of ammonia was not suficiently dilute very little was dissolved by it the greater part of the substance sinking to the bottom of the vessel as a viscid resinous mass which dissolved however almost entirely on pouring off the liquid and adding pure water.The addition of acid to the filtered solution produced a brown flocculent precipitate which was filtered off washed with water and treated with cold alcohol. The filtered alcoholic solu- tion left on evaporation a resinous body hardly to be distinguished in appearance from the preceding; this I will denote by the letter B. The matter insoluble in ether constituting by far the larger part of the whole mass mas first treated with a little cold alcohol to which it communicated a dark-brown colour. The filtered alcoholic liquid lei% on evaporation a brown resinous residue which was not further esczmiiid since it w3s sure to contain some of that well-known product of decomposition which is formed by the action of caustic fixed alhlies on alcohol and which being also resinous I saw no prospect of being able to separate from any product derived from indigo-blue that might be mixed with it.The portion left uridissolvcd by the cold alcohol mas aftcr being dried a brown powder consisting of three substances. In order to separate these from one another the mixture was first sub-jected to the action of boiking dilute caustic soda-lye in which one of the three mas found to be insoluble. The alkaline liquid which mas of a dark brown colour was filtered and the residue left undissolved was again treated with alkali in order to remove the hole of the soluble portion and it was then treated with a boiling alcoliolic solution of caustic soda in which the greater part dissolved with ease.The dark-brown solution was filtered and then mixed mitli an excess of liydrochloric acid which pre-cipitated tlie greater part of the substance as a dark-bromn powd2r. This mas collected on a filter washed with alcohol until the acid and chloride of sodium were removed and dried. This body I will distinguish by thc letter C. The caustic 3odcz-lye SCHUNCK ON SOME PRODUCTS DERIVED contained the two other substances in solution and it was accord- ingly mixed with an excess of acid which produced an abundant brown flocculent precipitate. This was collected on a filter well washed with water and then treated with a boiling solution of acetate of soda which dissolved part of it thereby acquiring a brown colour.The liquid was filtered boiling hot and the residue was treated with fresh solution of acetate of soda the process being repeated as long as the boiling liquid acquired any colour. The residue left undissolved by the acetate of soda was treated with boiling alcohol containing a little ammonia in which it dissolved with ease forming a dark-brown solution from which the greatest part was again precipitated on the addition of an excess of hydrochloric acid as a brown powder. This was filtcred off well waslied with alcohol and dried. This body may be denoted by the letter D. The substance held in solution by the acetate of soda was precipitated by sulphuric acid in brown flocks which were filtered off well washed with water and then treated with boiling alcohol in which they dissolved completely.The alcoholic solution deposited on cooling a brown powder which was collected on a filter washed with a little cold alcohol and dried. To this product I apply for the sake of distinction the letter E. The acid liquid filtered from the mixture of substances insoluble in water still contained in solution a product of decomposition derived from the indigo-blue. It was evaporated until crystals began to appear on its surface and mas then set aside and allowed to stand for some time when a large quantity of crystals mas gradually deposited. After separation from the mother-liquor these crystals appeared of a brown colour; but by re-crystallisation from boiling water and decolorisation with animal charcoal they were rendered white and pure.They were then found to have the properties and composition of anthranilic acid the well-known product formed by the action of caustic alkalies on indigo-blue. The mother-liquor of the crystala left on evapo-ration a thick brown syrup which seemed to be a compound of anthranilic acid and acetic acid. On dissolving it in water adding sulphuric acid to the solution and evaporating I obtained a quan-tity of crystals which were purified by crystallisation first from water and then from boiling alcohol. They differed in appear- ance from anthranilic acid and consisted indeed of a compound of the latter with sulphuric acid The same compound is obtained FRON INDIGO-BLUE.469 in place of uncombined anthranilic acid if a great excess of sulphuric acid beyond what is required to unite with the free soda and that combined with acetic acid and the various products yielded by the process has been employed in the first instance. The sulphate being more soluble in water than the free acid does not crystallise so easily from the brown syrup which the liquid always leaves on evaporation and hence it is advisable not to use an excess of sulphuric acid in the process above described for the separation of the anthranilic acid. As regards their properties the products insoluble in water present very little that is of interest. The body A is a brittle amorphous brownish-yellow resin traiisrarent in thin layers At a temperature of 100' C.it becomes soft and semi-liquid. When heated on platinum foil it burns with a bright flame leaving much charcoal which on being heated disappears without leaving any ash. It is decomposed by boiling nitric acid yielding a product of decomposition in crystalline needles. It is quite insoluble in alkaline liquids such as caustic potash soda and am-monia even when a reducing agent such as protoxide of tin is added; but it is decomposed on being heated with dry soda-lime giving off alkaline fumes having a peculiar penetrating odour. The body B can hardly be distinguished by its external appear.. ance from A with which it has also many properties in common; but it is easily soluble in caustic and carbonated alkalies yielding yellow solutions from which it ir precipitated by acids in brown flocks.The compounds with baryta lime lead silver and copper prepared by double decomposition are bronn or yellow and insoluble in water. When treated with boiling nitric acid it behaves like A yielding also a product of decomposition crystal- lising in needles. The body C is a brown powder which on being heated burns without previously melting ; it is insoluble like A in watery solutions of a!kalies and very little soluble in alcohol alone but easily soluble in an alcoholic solution of soda. 11 resembles C in most of its properties but differs from it by its soluhility in caustic and carbonated alkalies. E is a reddish-brown powder soluble in alkalies and more easily soluble in alcohol than C and D but distinguished from the others chiefly by its solubility in acctate of soda.The composition of these bodies is however a matter of some interest since it is only from a knowledge of their composition that any light can be thrown on the nature of this curious process. 2L2 SCHUNCK ON SOME PRODUCTS DERIVED I shall therefore proceed to give a short account of the results yielded by the analysis of these products which mill lead to a few remarks regarding their mode of formation and probable con-stitution. From the results of their analyses the following formulz were respectively assigned to them :-1c80H44N2010 C62H39N '8 '8 C52H35N '8 C56H22N!208 C56H24N208 'Phe compound D was formed in abundance C and E in small quantities only.All the products were conceived to be produced by the combination of indigo alcohol and acetic acid and in the case of A of carbonic acid (probably formed correlatively to the anthranilic acid) with elimination of water. To the specimens of A and B prepared at different times though very similar in pro-perties each to each different formulze had to be assigned which however are derivable from similar modes of formation thus :-C16HsNO2 + 8C4H602 + 3CJAdO4 + 2CO1 = C62H39NOs + 26H0 A{ 2c16HSNOj + 9C4Hb0z -t ZU,H+Oj -t 4C02 = CMH44N20lo + 28HO. Anthranilic Acid. Though there could be no doubt after an examination of the properties of the crystallised acid formed in this process of its identity with anthranilic acid stili I conceived that its analysis if riot altogether indispensable might prove of some interest.The results obtained mere as follows :-1. 0,3135 grrn. dried at 100" C. gave 0.7035 grm. carbonic acid and 0.1500 grm. water. 0.4050 grrn. burnt with soda-lime gave 0.2890 grm. metallic platinum. II. 0,1664 grm . gave 0.3720grm . carbonic acid and 0.0780grm. water. 0.5590 grrn. gave 49 cc. of moist nitrogen at 7" C. and 759.2 millims. pressure eqriivalent to 47.25 cc. dry nitrogen at 0" C. id '760 niillims. pressure or 00593 grm. FROM INDIQO-BLUE. 47 1 These numbers correspond with the formula C,,H,NO, which is that of anthranilic acid as the following compa-rison of the composition with that required by theory will show :-Calculation.I.Experiment.11. C, ........ 84 61.31 61.19 60.97 H,........ 7 5.10 5.31 5.20 N ........ 14 10-21 10.13 10.58 0 ........ 32 23.38 23.37 23-25 -7 7--137 300.00 100~00 100~00 Since under ordinary circumstances this acid can only be obtained by the long-continued action of boiling concentrated alkaline lye on indigo-blue its formation in this process in which only a small quantity of caustic soda dissolved in a large quantity of alcohol was employed is remarkable. There can be little doubt that its formation in this case is connected in some way with that of the other substances and could not be effected by the mere action of a dilute alcoholic solution of caustic alkali on indigo-blue. The experiments just described suggest a few general remarks on this process and the products to which it gives rise.1. Though I have no doubt that the products of the properties and composition of which I have just given an account are dis- tinct chemical compounds still it might be objected that some of them were not free from an admixture of products of decomposi-tion derived from alcohol alone the action of caustic alkali *on alcohol being a process not very well understood. In order to satisfy myself on this point I took an alcoholic solution of caustic soda boiled it for some time and then evaporated it in contact with the air. The solution hecame brown; and on adding water and an excess of acid after evaporation of the alcohol I obtained a brown flocculent precipitate which being filtered off and washed was dissolved in alcohol.The solution left on evaporation a dark brown resinous residue which I found to be quite insoluble in ether. That portion of the products obtained in this process which was insoluble in water and ether but easily soluble in alcohol and alkalies was therefore certain to contain some of this resinous matter; and I therefore hid the whole of it aside and SCHUNCK ON SOME PRODUCTS DERIVED gave up all further examination of it. It is certainly true that by the action of alkali on alcohol in closed vessels a totally different product is obtained-a product which differs from the other by its solubility in ether and its total insolubility in alkalies and shows a striking resemblance to the body A which is also soluble in ether and insoluble in alkalies.Still as my process was conducted in open vessels and not under pressure I think it is not probable that any of this substance was formed.* 2. From what has been stated above it follows that all the pro- ducts except anthranilic acid are formed by a very simple process which consists merely in indigo-blue combining with alcohol and acetic acid in various proportions and yielding compounds in vhich none of the constituents as such can be detected. It is therefore not a process of decomposition but rather a synthetical process a building-up of complex bodies from others of a simpler constitu- tion. This is proved by the fact of water being eliminated during the process whereas in all cases in which complex organic sub-stances are decomposed into simpler ones water is absorbed.This elimination of water proceeds so far that some of the products notwithstanding that they are formed by the addition to indigo-blue of many atoms of alcohol and acetic acid (bodies having much less carbon and more oxygen) are found to contain even more carbon than indigo-blue itself a great -proportion of the water both of the alcohol and the acetic acid having been separated. Is it not possible that processes of a similar nature may go on within the cells of plants the chief function of which * According to Liebig the colour which an alcoholic solution of caustic potash asmmes in contact with the air is due to aldehyde-resin the product of decomposi-tion formed by the action of caustic alkalies on aldehyde.Weidmbusch (Ann. Ch. Pharm. lxvj 5. 153) however states that the true aldehyde-resin is almost insoluble in 'alkalies; and in consequence of the discrepancy in the accounts of this body I requested Mr. A. Mylius to make some experiments on the action of caustic alkalies on alcohol in sealed tubes. He obtained by this action a resin of a fine reddish-yellow colour soluble in ether but totally insol~ble in watery solutions of alkalies. Its properties so nearly resemble those of the true aldehyde- resin as described by Teidenbusch and its composition differs so little from that of the latter that it seems very probable that the two resins may be identical. If so it follows that aldehyde-resin is certainly formed by the action of caustic alkalies on alcohol but only under pressure in sealed tubes.The resin formed in open vessels in contact with the air is totally different. For further particulars regarding this peculiar action I must refer to the account of Mr. Mylius's experiments contained in the Proceedings of the Manchester Literary and Philosophical Society February 21st 1a65. FROM INDIGO-BLUE. is known to consist chemically speaking in the construction of complex bodies from others of a simpler composition ? Is not the power residing in the vegetable cell which enables it to neutralise very potent chemical affinities somewhat of the same nature aa that which in this process causes the acetic acid to leave the strong base with which it is combined in order to unite with alcohol and indigo-blue for which it cannot be supposed to have any strong chemical affinity? 3.The physical properties of theae compounds do not Eeem to depend in any way on those of their constituents. Nevertheless it is to be observed that those containing the largest proportion of alcohol are insoluble in alkalies whilst those in which the indigo- blue preponderates are the least soluble in alcohol and ether. 4. No law or rule can be detected determining the number of atoms of alcohol and acetic acid which are capable of uniting with the indigo-blue. Were the series more extensive it is probable that some such law might be found to prevail. It may be re-marked however that all the products insoluble in water with one exception contain either 8 or 10 equivalents of oxygen.5. Regarding the rational formulze or probable interhal consti- tution of these compounds 1 hardly venture to indulge in any speculations. They might be considered as conjugated compounds -compounds of which organic chemistry affords so many exam- ples; and it might consequently be possible to obtain from them by decomposition some of the simpler bodies which are known to have entered into their composition. I have however been unable to discover any facts in favour of this view. Neither indigo-blue nor any of its products of decomposition can be obtained from them by any means which I have tried. In this respect these compounds resemble some of the secondary products which are formed during the decomposition of indican by acids and from which no indigo-blue can be obtained though they must be supposed to contain the elements of that body and of various organic acids such as formic acetic and propionic acids.Indeed the resemblance between the two series of compounds extends also to their physical properties. For instance the body A resembles indifulvin one of the products derived from indican both being brownish-yellow resins insoluble in alkalies. B is very SCHUNCK ON sonm PRODUCTS DERIVED similar to indiretin; and D is so like indifuscin that the two can hardly be distinguished from one another. There may in fact be some analogy in the composition of the two last-named bodies.Indifuscin may as I have shown on a former occasion be considered as a compound of indigo-blue and propionic acid minus water as may be seen by the following equation :-Indifuacin. lndigo-blue. Propionic acid. C44H&& -t 2HO = 2(C16k15N02) + 2(C,H,04). In like manner D may be supposed to contain the same elements combined in a different proportion since D. Indigo-blue. Propionic acid. c56H24N2O1 lOHO = ~(C~GH~NO~) + 4(C6H604). Analogies such as these unsupported by experimental proof may he only fanciful. Nevertheless they may prove of some use in facilitating the classification of facts. At all events the cir- cumstance of indigo-blue yielding by the combined action of alcohol acetic acid and alkalies bodies so closely resembling the products obtained along with indigo-blue in the decomposition of indican seems to afford a striking confirmation of the view which I have taken regarding the composition of these products.There is another point of view from which these bodies may be considered. They may be representcd as substitution products of indigo-blue one or more of the atoms of hydrogen in the latter being replaced by one or more organic radicals. For instance the body C may be looked upon as the hydrate of a compound in which one atom of the hydrogen of indigo-blue is replaced by phenyl (C,,H5) since C,8H,,N04= CI6H,(Cl2H5)NO2+ 2H0. In order to obtain some confirmation of this hypothesis I took some of the body D of which I had a considerable quantity and which differs from C only by containing more mater and subjected it to the action of hydriodic acid and phosphorus in a sealed tube.By the action of the nascent hydrogen I expected that indigo- blue might possibly be regenerated but the experiment led only to a negative result ; for though the tube was heated in the mater- bath for several days the substance on its being opened was found to be almost unchanged a small part only having been con- FROM INDIGO BLUE. 47% verted into a resinous matter easily soluble in alcohol. A similar negative result was obtained when an amalgam of sodium was employed as a source of hydrogen. After these failures I felt but little encouragerrient in making further experiments in this direc- tion; and this part of the subject must therefore be left in its present state of obscurity.6. The occasional disappearance of the indigo-blue in the woad- vat in consequence of mismanagement now admits of an explana- tion which will probably be allowed to be the correct one. By the fermentation of the sugar contained in the madder and other materials employed alcohol is generated which in its tixn may yield some acetic acid; and alcohol acetic acid and a base (lime) being present nothing further is required for the development of the process above descrihed. By neutralizing a portion OF the lime when necessary the danger of losing colouring matter is to some extent obviated; but I would venture to suggest as a means of rendering it still less the avoiding all materials containing much sugar or starch-substances which might by their decomposition lead to the formation of alcohol.When in the process above described formiate of soda is em- ployed instead of acetate of soda exactly the same phenomena are observed. ?'he indigo-blue gradually disappears and a dark brown alcoholic liquid is obtained which is found to contain bodies closely resembling those formed by means of acetate of soda. By operating on a tolerably large quantity of material I was enabled to ascertain the presence in this liquid of anthra- nilic acid and of three products corresponding to and having the same physical properties as the bodies B D and E. They were separated fcom one another by the:same means as the latter the first being a brownish-yellow resin easily soluble in alcohol and ether as well as in alkalies; the second a brown powder soluble in alkalies but soluble with difficulty in alcohol and ether ; whilst the third was a reddish-brown powder distinguished by its solu- bility in a boiling solution of acetate of soda-a property which afforded a ready means of separating it from the others.No compounds insoluble in alkalies and corresponding to the bodies A and C were produced with formiate of soda. The analysis of the compound resembling B led to the formula C4BH29N010' 476 SCBUNCK ON SOME PRODUCTS DERTVEn FROM ETC. Calculation. Experiment. C, .......... 288 '70.07 69-70 H29.......... 29 7-05 7-20 N .......... 14 3.40 3.32 0, .......... 80 19.48 19.78 411 100-00 100~00 Its formatioh may be represented by the equation C16H,N0 + 6C4H6O2 i-4c2FI,04= c,,H29~~o,, 4-20HO.The analysis of the substance corresponding to E yielded humbers which may be approximately represented by the for- mula C'26H13N08* Calculation. Experiment. C26........e. 156 63.15 62.61 €Il3.. ........ 13 5-26 4.64 N ......... 14 5-66 5.61 0,.......... 64 25-93 27.14 247 100~00 looooo Assuming this to be the correct formula the formation of the compound may be represented by the equation :-It will be seen that the same law regarding the number of atoms of oxygen prevails here as in the case of the bodies before described this number being either 8 or 10. If in this process ordinary alcohol is replaced by methylic alcohol the same effect is produced provided acetate of soda is employed ; but a mixture of methylic alcohol formiate of soda and caustic soda does not act in the same manner on indigo-blue which remains unchanged however long it may be left in contact with the boiling liquid.It appears therefore that one of the two agents ethylic alcohol or acetic acid is quite essential. One of the two may be replaced by an homologous body ;but wherl both are so replaced the indigo-blue remains intact.

ISSN:0368-1769    

DOI:10.1039/JS8661900462

出版商:RSC    

年代:1866

数据来源: RSC

摘要:

CHAPNAN AND THOItP ON 1LIE RETATTON ETC. 477 [Contributions from the Laboratory of the London Institution ] XL1V.-The Relation bctzoeen the Products of gradual 0xiclatiG.n and the Mo 'ecular Constitution of the Bodies Oxidiscd. By ERNEST THEOPHRON CHAPMAN and WILLIAM THORP. WE believe it will be generally allowed that the greatest probleni now occupying the attention of chemists is that of isomerism. There are two methods bj7 wliich this problem may be attachl. WC may eitlier spnthctica?ly form the isoweric compounds and compare them or v7e may decompose the already formed isomeric compounds into their proximate constituents. The first rnzthod requires assistance from the second because as isomeric bodies frequently have almost identical physical properties a difficulty may arise in determining whether such bodies are not really iden- tical and not only isomeric.All tests .such as the boiling-point fusing-point &c. are liable to be rendered fallacions by the pre- sence of traces of foreign matter. We therefore require a method by which we may determine what are the proximate constituents of isomeric bodies. We believe that gradual oxidation fulfils this requirement. But before adopting this method it is requisite to examine its action on bodies the molecular grouping of which is well understood and also on those products which may be termed proxiinate oxidation-products more particularly the acids of the acetic series. We have made such an examination and though at present it has been confined to substances connected with the vitiic series it has led us to the couclusion that by the gradual oxidation of complex organic molecules simpler groups are produced ; that these simpler groups represent the radicles entering into the com-position of the substances oxidized ; and finally that these repre- sentative groups themselves can only with great difficulty be further oxidized.1. All bodies derived from the viuic series that we hm7e yet oxidized have yielded acids of the acetic series and in some instances carbonic acid. The first step therefore in this investi- gation is to examine the action of oxidizing agents on this class of VOL. XIX. 2M 478 CHAPMAN AND THORP ON THE RELATION BETWEEN acids. With this object three solutions were prepared containing respectively 3 5 and 8 per cent of bi-chromate of potash.They were prepared by dissolving the requisite quantity of biclirornate of potash in water and adding sufficient sulphuric acid to combine with the potash as bi-sulphate and with the chromium as sulphate of sesquioxide. To these solutions small quantities of pure acetic acid were added the mixtures sealed up in digestion-tubes and heated for twelve hours in the water-bath. On examining the tubes the 3 and 5 per cent solutioiis had not sensibly altercd their colour the 8 per cent. had slightly changed but no gas mas evolved on opening any of them. All three tubes were sealed up again and heated as before for 24hours along with a similar tube containing the 8 per cent.mixture without acetic acid; at the end of this period the contents of the tubes had slightly altered in colour though not perceptibly more so than the tube contain- ing no acetic acid; still little or no gas was evolved. All four tubes were now heated for four hours to 130"C. ;on opening gas escaped from all four though only in minute quantities from the 3 and 5 per cent. tubes; both the 8 per cent. tubes yielded rather more. Tbe gas from the 8 per cent. tube containing acetic acid was tested for carbonic acid of which it contained a small quan- tity. The contents of all three tubes were now distilled the dis- tillates boiled with excess of carbonate of baryta filtered evapo- rated on the water-bath and the percentages of barium deter- mined.The results were as follows :-Substance Ra2S04 Per cent. Theoretical Acid to which this taken. found Ba found. per cent. corresponds. (1) 0*4366 0.3978 53.51 53.726 (2) 0-2984 0*2$20 53 -60 (3) 0.3308 0 *3015 53.59 J> ?9 (4)0.4082 0.3718 53.65 (5) 0.3464 0 -3154 53 '54 9) >> (6) 0.4688 0 *4272 53-58 ?I Numbers I and 2 are from the 3 per cent. tube. J 3 ¶ 4 I9 5 7 9 3, 5 > 6 8 I From the foregoing determinations it is evident that acetic acid withstands the action of this oxidizing agent very perfectly. THE PRODUCTS OF GRADUAL OXIDATION ETC. 479 2. Propionic acid was tlie next member of this series experi- mented upon. It was prepared from cyanide of ethyl. It was heated with the 5 per cent. mixture for 24 hours at 300° C.The contents of the tube were diluted and distilled-diluted because the boiling-point of the mixture is considerably above that of water ; therefore had this been omitted the experiment would nut have been a fair one. The distillate (free from sulpliuric acid) wa3 neutralised with staridard solution of potash eiiough sulphuric acid added to combine with two-thirds of the potash tlie mixture distilled the distillate converted into a baryta-salt and the per- centage of barium determined. Substance Ba2S04 Per cent. Theoretical Acid to which this taken. found. I3a found. per cent.. corresponds. -_I----0.4032 0.3306 48.22 48 *41 Propionic acid 0.4648 0.3815 48.27 99 2) ,7 This fraction of the propionic acid wasI therefore unaltered.Now if any acetic acid whatsoever were produced it would remain in combination mitlh the potash in the retort ; excess of sulphuric acid was therefore added to the contents of the retort and those contents distilled; the distillate as before was con- verted into a baryta-salt and the percentage of barium deter- mined. ~~~~ 1 1 I Substance Per cent. Theoretical Acid to which this taken. BaiSo4 Bafound. per cent. corresponds 0.3975 0.3266 1 48.33 48 *41 Propionic acid 0.3624 1 0.2976 49.28 1 , Y9 1) These numbers prove the absence of acetic acid. There can therefore be no doubt that propionic acid also will endure long-continued digestion with dilute chromic'acid at 100' C. ; at a higher temperature however propionic acid is easily decomposed by oxidizing agents.Four hours' digestion with an 8 per cent. solu- tion of chromic acid at 130' C. is sufficient to cause a large evolu- tion of carbonic acid.* * In thc oxidation of his ketone from carbonic oxide and sodium-ethyl Wanklyn 2 M '2 3. Valerianic acid was next suhjccteci to the action of oxidiziiag agents. Like the preceding acid it withstands their action at the temperature of boiling water but at 130"C. is pretty rapidly decomposed. As in the case of acetic acid three simultaneous experiments were made with 3 5 and 8 per cent. solutions the digestion being continued for twelve hours in the water-bath. The 3 and 5 per cent. tubes yielded no gas on opening the 8 per cent. gave forth a little. The contents of all three tiihes were diluted and distilled and the distillates from the 3 and 5 per cent.tubes were at once converted into baryta-salts. The distillate from the 8 per cent. tuFe was neutralised with standard solution of caustic potash arid divided into three fractions by the addition of the necessary quantity of sulphuric acid and by distillation. The first and third fractions were converted into baryta-salts. The following table contains the percentages of barium" in these salts and also in the salts from the 3 and 5 per cent. tubes :- Substance taken. Ba.,S04 Per cent. Theoretical Acid to which it foucd. I3a found. per cent. corresponds. -II I -I-I--I From 3 per cent. tube 1 1 1 0.3608 0,2457 40.05 40 -:13 Valerinnic acid 0.4114 0.2808 40.13 >, 79 From 5 per cent.tube 0 -2998 0.3670 8 per cent. tube 1st fmc. 0 8938 0 307'8 0 .4054 3rd frac. 0.3726 From this table it appears that the above trcntment hit not affected valeriauic acid.? heated this substance which yields acetic acid and propionic acid for many hours in a digestion tube together with exccss of hichromate of potash and dilute sulphuric acid. No carbonic acid was formed thereby proving that in this experiment neither acid had undergone decomposition.-( Chcrn. SOC. J. August 1866 page 326 of this volurne.) * In this tsble the barium was determined as sulphate by precipitation. t One sample of this acid was found to decompose on treatment like that described III the text; it decomposed readily and produced Lutyric and carbonic acids.The acid which split up in this way was furnished by one of the London druggists but we eoultl iiot learn its history ; it could not have been a primary acid. THE PRODUCTS OF GRADUAL OXIDATION ETC. 481 4. Lastly caproic acid was submitted to the action of oxidizing agents. Two samples of this acid were employed the one obtained from cyanide of arnyl the other from it ketone obtained by the distillation of ricinolate of potash ; this ketone when oxidized yields caproic and carhouic acids. Both these samples were ex-posed to the action of 5 per cent. chromic acid solution for twelve hoiirs at the temperature of the water-bath ;neither underwent any perceptible change though in both instalices the bichromate was slightly discoloured.Both samples were separated by distil-lation from the chromic acid and converted into baryta-salts. Determinations 1 and 2 in the following table are from the caproic acid prepared from cyanide of amyl; 3 and 4from the other sample. ~ ~~~ Substance BalS04 taken. found. corresponds. (1) 0 ,4444 0.2824 37.37 37.33 Caproic acid (2) 0 -3886 0.2472 37 -48 J¶ 79 99 (3) 0 .4306 0.27’28 37.25 >) 9% 9s (4) 0.3946 0.2497 37 *21 $9 )9 >9 It is perhaps worth while to remark that in converting the higher acids into baryta-salts hydrate of baryta is preferable to the carbonate. The action of diiute permanganic acid mas then investigated. This substance when dilute has little or no action on acetic and propionic acids even when boiled with them.In its concentrated &ate however it decomposes them pretty rapidly. But as it mas not our intention to work with this aubstance we did not further investigate its action on the acids of the acetic series. We think we are justified by the above experiments in our state-ment that under ordinary circumstaoces and at the te1rrpera- ture of the water-bath these acids are not attacked by dilute chromic acid. We will now mention a few exceptional circumstances which have great effect on the rapidity of the action of chromic acid. The following circurnstances promote the action :-1st. Presence of large excess of concentrated sulphuric acid. 2nd. Presence of free chromic acid i.e.chromic acid that has been actually separated from potash. 482 CHAPNAN AND THORP ON THE RELATION BETTVEEN 3rd. Presence of a very small qnantity of binoxide of man-ganese. In the first case it is to be observed that acetic and propionic acids are not affected by the excess of sulphuric acid unless this be so great as to develope heat on mixing with water. We are unable to account for the more violent action in the second and third cases. On the other hand if we substitute phosphoric for sulphuric acid we obtain an oxidizing mixture which appears to be absolutely without action upon the acids of this series though it is quite capable of oxidizing alcohol &c. Havirrg now proved that if the acids of this series be once formed by oxidation they are not destroyed by excess of the oxi- dizing agent me are in a position to observe the effects of this oxidation on a series of compounds the molecular constitution of which is well understood.The substances selected for this series of experiments were the following :-1. Ethyl-alcohol ‘7. Nitrite of amyl 13. Ethylamine 2. Amyl-alcohol 8. Nitrate of ethyl 14. Propylamine 3. Acetate of ethyl 9. Nitrate of methyl 15. Arnylamine 4.Acetate of methyl 10. Iodide of ethyl 16. Ethyl-amyl-5. Acetate of amyl 11. Iodide of amgl arnine 6. Valerianate of aniyl 1.2. Iodide of isopropyl We will call the products obtained by carrying this oxidation as far as we can without endangering the acids produced proximate oxidation-products ; and those obtained either by limiting the period of action or employing an insufficient quantity of the oxi- dising agetit mediate products.1. EthyZ-aZcohoZ.-In the first place it was necessary t.0 obtain chemically pure alcohol. The test employed to determine its purity was to oxidize a portion of it with excess of chromic acid distil off the acids formed nearly neutralize the distillate with potash and distil again carrying the distillation to dryness. As all the acids of the acetic series at any rate all the lower mem-bers of that series are expelled from their compounds by acetic acid it follows that had any homologues of alcohol been present they would by their oxidation have furnished acids differing from acctic acid in their saturating capacity and that these acids wdd THE PRODUCTS OF GRADUAL OXIDATION ETC.483 all accumulate in the small fraction described above. When there- fore a sample of alcohol yielded nothing but acetic acid by this treatment it was obviously free from homologues; and as it had previously been digested with caustic potash it must also have been free from compound ethers. It was oxidized with chromic acid in insufficient quantity to produce the proximate products of oxidation; aldehyde and acetic acid were obtained and also a neutral liquid not completely miscible with water and smelling of acetic ether. It was digested with potash excess of sulphuric acid added and the acid thus liberated distilled off it proved to be pure acetic acid Another portion of the alcohol was heated with excess of chromic acid in a sealed tube for about three hours ;the co‘ntents of the tube were distilled aid the distillate examined by Liebig’s method for fractionating acids.We could detect no pro- duct excepting acetic acid. 2. Amyl-a2cohoZ.-A portion of this alcohol was digested with 5 per cent. solution of chromic acid for one hour; the contents of the tube were distilled ;and the distillate saturated with sulphate of soda whereby the oily layer on its surface was greatly aug- mented ;this oily layer mas decanted distilled and treated with solution of carbonate of soda whereby a portion mas dissolved. The remainder (supposed to be a compound ether) was decanted and digested with alcoholic solution of potash.It was then treated with escess of sulphuric acid and distilled. The solution in carbonate of soda was treated in the same manner. The original distillate which had been saturated with sulphate of soda was re-distilled ; all three distillates gave an acid reaction and smelt and tasted of valerianic acid. They were converted into baryta-salts ; the pcrcentap of barium obtained from them are tabulated below Another sample of the amyl-alcohol vas digested for six or seven hours with 5 per cent. chromic acid solution; no gas was evolved. The contents of the tube mere dilnted and distilled; the distillate which was totally soluble in alkalis divided into three fractions by Liebig’s method and the first and third fractions converted into baryta- salts ;the perceiitagcs of barium obtained from these salts will be found on Llie next page.As viil be seen the whole of the above percentages correspond to valerianic acid. 484 CHAPMAN ANL TIIOI'IP ON TIIE RELATION BETWEEX Substance taken. Ba,SO.b Per cent. Theoretical 'Acid to whicli'this 1 found. Ba found. I per cent i corresponds. .-!-I--1 (I) Free acid- 0 5782 0.3960 40.27 40.413 Valerianic acid (2) Free acid rcmaining in distillate- 0 4362 0 *2991 40.32 99 f> tJ (3) Acid from ether 0.3774 0 *3814 o ,2588 0.2620 40.32 40 38 1) )9 0.2998 (4) First fraction- 0 *2053 0.3228 0.2215 0.3436 (5) Second fraction- 0.2353 The first oxidation of both the foregoing alcohols yroiiuc;d a complicated result.In both the corresponding aldehyde was 110 doubt formed in both we had a compound ether formed and in both we had the acids formed. As will be seen below we have proved that these two compound ethers-acetate of ethyl and valerianate of amyl-yield the one nothing but acetic acid the other nothing hut valerianic acid whcn oxidized. Therefore the apparent complication of the products has in reality no effect on the ultimate result. 3. Acetate of Ethyl. -This compound was oxidised both with chromic and permanganic acids; by the former at the boiling- point of water by the latter both in the cold and at the boiling- point. The prodricts of dl three operations were scparately dis- tilled and each of the three converted into baryta-salts; thc percentages of barium obtained from these salts will be found iu the annexed table all corresponding to acetic acid.I 7:;::; I I I Per cent. Theoretical 1 Acid to which this Substance taken. Ba found. per cent. corresponds. I---I-I-I---Chromic acid- 0.4264 0.3885 Acetic acid 0.3712 0.3384 53*67 >Y 9) Permanganic acid hot- 0.4212 0.3846 53.70 >f 9) 9Y Permanganic acid cold-0.3455 0 3153 53.6ti J) >> ?Y 'HIE PRODUCTS OF GRADUAL OXIDATION ETC. 485 41. Acetate of Methyl.-This compound was oxidis2d with chromic acid ; it yielded a.cetic and carbonic acids. Formic acid also was tested for and found though the greater proportion of this acid had evidently split iip into carbonic acid and water. 5. Acetate of AmyZ.-This compound is not very easy to oxi- dize requiring several hours' heating in the water-bath with five per cent.chromic acid solution. If it be imperfectly oxidized valerianic aldehyde is apparently formed. If however the osida- tioii be carried far enough acetic and vttlerimic acids orily are produced. This was proved by diluting the contents of the diges- tion tube distilling dividing the distillate into thrce fractions by Liehi g's method converting the first and last fractions iuto baryta-salts and deteriiiining the percentages of barium. They corresponded the first to valerianate the second to acetate as will be seen in the next table :-Substance taken. Theoretical Acid to which this per cent. corresponds. ___I-I--I--First fraction -0 *4416 1 0.3029 1 40 33 40 413 Valerianic acid 0.4764 I 0-32581 1 40 .21 2) 9) 9) Third fractiou- 0.4145 0.3'165 53.46 53 *726 Acetic acid 0 3624 0.3297 53-49 >2 32 7) 6.Valeriunale of Amyl.-"r his substance is even more difficult to oxidize than the corrcsponcling acetate. It will not bear a temperature much higher than 10GOC. nor the action of a very concentrated solution of chromic acid. However by using a great excess of dilute chromic acid the oxidation was effected pretty easily. On distillation and fractionation of the distillate by Liebig's method it became evident that we were dealing with valerianic acid. The first and last fractions were converted into baryta-salts and the percentages of barium obtained which we give in the annexed table :- 486 CHAPMAN AND THORP ON THE RELATION BETWEEN Subatance taken.Ba,S04 Per cent. Theoretical Acid to which this found. Ba found. I per cent. corresponds. II First fraction- 0 *4286 0.2938 40'30 40.413 Valerianic acid 0.3578 0.2454 40.33 1) #J >> Third frwtion- 0.3582 0.2454 40.28 P) These numbers all correspond to valerianic acid. 7. Nitrite of ArnyZ.-This substance as elsewhere shown,* yields by oxidation nitric and valerianic acids and if the oxida- tion be incomplete valerianate of amyl. 8. Nitrate of Ethyl.-By oxidation this compound yields nitric and acetic acids 9. Nitrate of Methyl.-From this substance we obtain nitric and carbonic acids by oxidation. 10. Iodide of Ethyl.-This compound oxidizes without difficulty Iodine is liberated in abundance during the digestion.The con- tents of the digestion-tube were diluted and distilled the distillate treated with mercury to remove the iodine redistilled and divided into three fractions. The first and last fractions were converted into baryta-salts and the percentages of barium in the annexed statement obtained from them :-Substance taken. Ba2S0.1 Per cent. Theoretical /Acid to which this found. Ba found per cent. corresponds. ---___---~ First fraction- 0 '3989 0.3637 53 '61 63 *$26 Acetic acid Third fraction- 0.3838 0'3500 53.62 39 ># 98 Both correspouding to acetic acid. 11. Iodide of AmyZ.-This compound is somewhat difficult to oxidize ; nevertheless by treatment similar to that described in the last paragraph it was made to yield an acid.This acid when * Journal of thc Chcni. So(*. August lP6d. TIIE PRGDUCTS OF GRADUAL OXIDATION ETC. 487 freer1 from iodine was found to be pure valerianic acid. This was proved by dividing it into three fractions and converting the first and third into baryta-salts; from these salts the annexed num-bers mere obtained :-Substance taken. Per cent. Theoretical (Irid to which this 1 1 1 found. 1 Ba found. per cent. corresponds. First fraction-0.4226 0,2899 40.34 40 *413 Valerianic acid 0 -4074 0.2796 40.36 Y $> 22 Third fraction- u 2788 0.1918 40.45 9 22 ) 12. Iodide of bopropyZ.-This substance yielded much gas during its oxidation which proved to be carbonic acid.The con-tents of the digestion-tube were treated as in the case of iodide of ethyl the first and last fractions so obtained were converted into baryta-salts and as will be seen from the annexed barium deter- minations were nothing but pure acetic acid :-Substance taken. RasSOl Per cent. Theoretical Acid to which this found Ba found. per cent. corresponds. Ill I First fraction- 0.3570 0.3249 53.51 53.726 Acetic acid Third fraction- 0.3672 0 3349 53.63 ?> 99 Jf 13. Ethylamhe.-It has already been proved that this com-pound yields by oxidation acetic acid." 14. PrupyZamine.-We know that isopropyl compounds do not yield propionic acid by oxidation also that it is possible to prepare a propyl compound viz.propylarnine. Now it is probable that we shall ultimately succeed in converting the alcoholic ammonias into the corresponding alcohols and thus effect the ascent of the alcohol series. This being the case it was obviously most important to determine whether the proplamine obtained from * Wanlilyn and Chapman Chem. SOC.J. August 1866. 488 CHAPIMAN AXD THOPP ON THE RELATION BETWEEN cyanide of ethyl was a primary OF a secondary compound. If the method of investigation above described be of any value it mould decide this question at once. We have therefore oxidized pro-pylamine. The experiment was carried on in a digestioii-tube with three per cent. clironiic acid solution at a tempcraturc of 100" C. When the digestion was complete the tube mas opened the escaping gas being collected over mercury.Not the slightest absorption occurred on the introduction of potash iiito this gas thus proving the absence of carbonic acid. The contents of the digestion-tube were diluted and the acid formed was distilled ofY. It was converted into a baryta-salt ; the fcllowing table coutaiiis the percentages obtained from it all corresponding to pro-pioriate :-Per cent. Theoretical .\cia to which this Ba found. per cent. corresponds. 0 *60'72 0,4166 48.29 48-41 Propionic acid 0.3238 0 *2656 48.23 15. Arnylanzin.e.-The oxidation of this substance rcquires care ; it is not very easily or rather not very rapidly effected. We found that the quickest way to oxidize it was to treat it with concen- trated chromic acid but at a temperature not higher than YOo or 80" C.After half an hour of this treatrcent; the fluid was diluted and the digestion continued at the teniperature of the water-bnth. The first treatment with concentrated acid appears to start the reaction after which the dilute acid easily completes it. Much time is snved by this metiiotl of treatment both iii this and the following case. The acid formed v as distilled off and converted into a \)nryta-s;llt which Fielded thc following numbers corres- ponding to va\c:~*iai;at~ :-Ba,S04 Per ceilt. Theoretical Acid to which this Substance tzken. found. Ba found. per cent. corresponds. 0.4066 0.2784 40.35 40.413 Valerianjc acid 0 *2662 0.la24 40 *29 THE PRODUCTS OF' GRADUAL OXIT)ATION ETC.489 Z6. EthyZ-a~?~ylami~~e.-Tliis compcund is more rapidly attacked t,hough it takes a long time to complete the re-action. The pro-ilucts of the digestion were diluted distilled and fractionated and the first and last fractions converted intcj hryta-salts from which the fdlowing percentages were obtained. They correspond to valerianic and acetic acids :-Per cent. Theoretical Acid to which this Substance taken. Ba found. per cent. corresponds. ::':!! I- First fraction- 0 *3824 0 -3266 0 2619 0 2240 40.29 40 *32 40;413 >> Valeiianic acid Last fraction- 0 *4338 0 *3945 53.47 53.726 Acetic acid Observations.-The whole of the foregoing oxidations were conducted in sealed digestion-tubes and in no instance was the temperature employed higher than that of boiling water generally from 10' to 20" below it.With the exception of the last two oxidations the chromic acid employed was in no instance stronger than 8 per cent. and generally less than 5 per cent. Nearly all these experiments have been repeated twice and some of them three times. The greatest possible care was taken to obtain pure suhtances. The four corri-pouiid et?:ers-:Lcetate of ethyl acetate of methyl acetate of aniyl and vderianate of amyl-were all titrated i.e the per- centage of acid which they yielded to caustic potash determined which it is obvious is a complete guarantee of their purity. The acetate of amyl and valeriariate of amyl were obtained by acting with iodide of amyl on acetate and valerianate of potash.The object in adopting this method of preparation was to eliminate any possible action of sulphuric acid on the molecular arrangement of the alcohol in q1:estion. The fractionations were performed in the following manntr :-The contents of the digestion tube having been diluted and dis- tilled the distillate was tested for sulphuric acid which was invariably found to be absent when the distillation had been care- fully conducted. It was then neutralized with standard solution of caustic potash and suEcicnt standard sulphuric acid added to 490 CHAPNAN AND THORP ON THE RELATION BETWEEN combine with a third of the potash employed thereby liberating an equivalent third of the acids operated upon. The liberated acid was then distilled off a sample of it converted into a baryta-salt and the percentage of barium in this salt determined.If it corresponded to any one of the acids of the acetic series we pro-ceeded no further with this fraction. If it did not but differed considerably from any known member of the series the process was repeated. This was however hardly ever requisite as froin the nature of the substances operated on we never had occasion to separate any acids excepting acetic and valerianic acids and in that case the valerianic acid gencrally distils over in the first fraction in a state of perfect purity. A second third of sulphuric acid was now added to the original distillate and the acid thereby liberated distilled off. Excess of acid was employed to obtain the third fraction and this third fraction treated in precisely the same manner as the first.If the percentages obtained from the first and third fractions corresponded it was obvious that we were dealing with a single acid and therefore it was unnecessary to examine the second fraction. If however they differed the second fraction was always examined though we hive not thought it necessary to give the details of these examinations. The barium was unless otherwise stated determined as sul-phate by heating the dry salt with concentrated sulphuric acid. ‘Phis method is exceedingly rapid and perhaps the most accurate known. The annexed table will show precisely the nature of the results obtained in the foregoing portion of this paper :-Table showing thc proximate oxidation products of the following substances.A Zcohols. Ethyl alcohol.. . . . . . . C2H,,0 + 02 = C-H,OJ + HzO Amyl , ......,.CjHliO + 02 = CUH.,02 + Ha0 Compound Ethers. Acetate of Ethyl,. ... . C2H3(C2H5)02+ OL = 2C.,H402 , Methyl ... C2H3(CH3)O2+ OJ = C21-I,02 + CO? t HaO , Amyl .. .. C2H3(C5H11)0S+ O2 = CjH1,,02 + C2H1O2 Valerianate of Amyl .. C5Hg(C5H1JO4i-OL = 2C5H1,,Ot Nitrite of , .. CSHIINOL + 0.3 = C,FIl,,O + FINO Nitrate of Ethyl .... .. C2HjNOJ + O. = C_H40 + HNOi , Methyl ... CHJNOj + OB = C02 i T-INO.; + H,O THE PRODUCT8 OF GRADUAL OXIDATION ETC. 491 Iodides of Alcohol-radicles. Iodide of Ethyl . . , . . 2C2H,I + 05 = 2CzH402 i H,O + 12 , Amy1 .. .. .. 2C5H111 + O5 = 2C5H1,02 i I&O + I2 , Iso-propyl ..2CH,(C2B5)I + Oil= 2C2H402 + 2C02 + 3H20 i I2 Ammonia-bmes. Ethylamine . . . .. C2H5.H2N + O2 = C2H402 + NH3 Propylamine . . . . C3H,.H2N + 02 = CJH602 + NHS . . . . . C5Hll.H2N + 02 = CSH1002 + NH3 Amylamine (C2HSHN+ 04 = C5H& -I-C2H402+ NH3 Ethyl-amylamine (C5H11) The first application made by us of the knowledge acquired hy the foregoing experiments was the oxidation of certain of the olefines an account of’ which was read at the Nottingham meeting of the British Association Ethylene.-This substance is not easy to oxidise by the action of dilute chromic acid but it yields without difficulty to hot con- centrated solutions. The results are carbonic acid and water. We could not detect formic acid. AmyZene.-This substance was digested for many hours with a moderately concentrated solution of chromic acid.When the amylene had disappeared the contents of the tube mere diluted distilled and fractionated the first and last fraction converted into baryta salts from which the following percentages were obtained :-Ra2S04 Per cent. Theoretical Acid to which this Substance taken. found Ba found. per cent. c0 rresponds. I-I First fraction- 0.4826 0 *4318 52-61 53-726 I Acetic acid 0.3014 0 -2720 52 *67 J> Third fraction-0.6089 0 *5566 53 -75 1 ”” These numbers show that the substance in hand is acetic acid. The determinations in fraction 1are sligIitly too lorn. This is due without question to a trace of impurity in the substance employed.Carbonic acid was evolved in abundance during the oxidation. In an experiment made to determine the amount of acid produced from amylene by oxidation 4 grm. of aniyleue yielded 6.12of acetic acid or 153 per cent. If 1 eq. of amylene yields 2 eqs. of acetic acid the percentage should have been 171.4. It yielded therefore 89.3 per cent. of the theoretical quantity. Now as the tube had been opened to allow of the escape of car-bonic acid and as therefore some amylene was without doubt lost this is quite sufficiently near to prove our point viz. that 2 eqs. of acetic acid are formed. The above work was repeated under circumstances the most varied as to concentration of chromic acid &c. but always with the same result.Acid solution of permanganate produced the same result no matter whether used cold or hot The decomposi- tion of arnylene therefore by nascent oxygen is as follows :-C,H, + 70 = H20 -t CO + 2C,H,02. &Hex:yZene.-Four grammes of this substance were digested with moderately dilute solution of chromic acid in the water-bath. The tube was cooled and opened to allow the escape of gas (carbonic acid) twice. When the digestion was completed the contents of the tube were diluted and distilled. The distillate was free from sulphiiric acid. It was rieutralised with staxidarcl solution of potash of which it required a quantity corresponding to 3-16 grammes of potassium. Had it yielded 2 eqs. of acid it would have required 3.515. It therefore yielded 82 per cent.of the required quantity which considering thc loss wliich must have occurred when tlic tube was opened is a sufilciently close 211-proxim rttion. ‘l’he acids combined with the potash were now suhmittetl to fractionation the fractions converted iiito baryts-salts mid the percentage of barium determiued :-Substance taken. 7:;’:; Per ccnt. The retical Acid to which this Ba foand. per cent. con esponds. -__-t-First fraction-I 0.3140 0 2577 1 Propionic acid 0.3336 0 -2734 48.19 Secoiid fraction- 0,3745 0 3144 intermedir,te Third fraction- 0 4355 0.4759 Acetic acid 0.4998 0 -4569 THE PRODUCTS OF GRADU,4L OXIDATION ETC. 493 From fraction 1we learn the presence of propionic acid frac- tion 3 proves the presence of acetic acid and fraction 2 proves that no other acids were present.P-Hexylene like amylene was oxidized in a variety of ways and always with the same result ; we therefore conclude that it is decomposed by nascent oxygen thus- + 70 = H,O + CO + C2H,0 + C,H602. A few weeks prior to the publication of the above results but unknown to us M. Truchot published a paper on the oxida- tion of the olefines. His results differ remarkably from ours but we believe we can explain the cause of the difference. M. Truchot states that amylerie yields acids of the acetic series when oxidized with permanganate of potash but that hntyric propionic acetic and formic acids are all formed. Now it is obvious that if this were really the case gradual oxidation would be valueless as a method of research for no possible information could be derived as to the molecular constitution of a body if molecules of every degree of complexity were formed by such oxidation.We have repeated the experiments of M. Truchot and can to a certain extent verify his results; ie. if we oxidize amylene with permranganateof potash we find that we can isolate acids the salts of which contain a smaller proportion of base than corresponds to acetate. This however occurs only when the oxi-dizing agent is alkaline and we fitid that even when it does occur these higher acids may be made to split up by the action of oxidiz- ing agents into acetic and carbonic acids. We conclude there- fore that M. Truchot has insufficiently oxidized this olefine.It is however possible and indeed probable that he may have operated upon a mixture of isomeric olefines in which case the complicated result obtained would be fully accounted for. The following table shows the results of the oxidation of the olefines :-Ethylene ....,..... C4H4 + Ob = 2CO4 + 2Hz0 Amglene .......... C5HI0 + O7 = 2C2H402 + CO + H20 P-Hexylene ........ C6& -1. 0;= C3H602 + CZH402 .t CO2 + HpO These results induce us to propose the following graphic formulze :-VOL. XLX. 2N 494 CHAPMAN AND THOHP ON THE HXLATION BETWEEN Ethylene C,H,. Amylene C5H,,. /3-Hex ylene C,H 12. Whether these formulae be correct or not is a question for the answering of which there are no data extant. There is how-ever nothing inherently improbable in them they represent the grouping indicated by the oxidation-products and this con-sideration will we trust derive greater weight firom the foregoing work.We would draw attention to the relation subsisting between the oxidation-products of these two olefines and those of the secondary alcohols obtained from they. The sny mylene yields a secondary alcohol the oxidation-produd o?‘k?h~‘~’ c 9are according to Wurtz,* identical with those of the olefine itself. He obtains as the oxida- tion-products of amglene acetone and acetic acid; that is to say he obtains acetic acid and a substance which by further ouidation yields acetic and carbonic acids; and moreover he observes that it is somewhat difficult to obtain the-acetone thus confirming our statement.From the oxidation of the corresponding alcohol he obtained the same products and in addition a small quantity of a substance having the compovlition of bntjlic rilcohol. The method af its formation is not very clear. The assumption that oxidation has simply removed CH, and left the substance from which this molecule has been subtracted still in the 6:rm of an alcohol ap- pears to us untenable. It seems to us possible that the substance in question may have been a mixture perhaps of &altered second-ary amyl-alcohol and acetone. This view derives some probability from the fact that it is rather difficult completely to remove acetone from amyl-alcohol by the aetion of bisulphitcs. We have made such a mixture and find that even after 24 hours’ standing sepa- ration is not complete.We desire further to point out that this butyl-alcohol if as assnmed by Dr. Debus it be a secondary alcohol would yield acids of a lower carbon condensation than itself to the action of oxidizing agents. The alcohol obtained from R-hexylene does nQt yield the same oxidation-products as P-hexylene itself. This may possildy arise from the fact that the alcohol is not obtained from the olefine in the same manner as in the case of amylene. If this Be the true reason we should obtain a different alcohol by using oxide of silver to convert the iodide of P-hexyl into the alcohol. In a former part of this paper we remarked that we had met with a sample of valerianic acid which did not resist the action of oxidizing agents.It split up and yielded carbonic and butyric acids. In a similar way there exists an amyl-alcohol which does not yield valerianic acid when oxidized ;at least so we infer from tbe following observations. It has long been known that ampl-alcohol is not alwap found to boil at 132’. In fact one variety of it boils at 128O. When we were searching for a pure sample of arnyl-alcohol to be employed in the foregoing experiments we received a sample from a distillery Ann. Ch. Pbarm. Oet 1864 p. 134. 2N2 496 CHAPMAN AND THOKP ON THE RELATION BETWEEN l(li!l'J ' in which rice was employed though mixed with other grain or at any rate spirit from other-grrtitMiictslmixedwith rice-spir& Before rectification.* After the fusel-oil had been put through all the ordinary purifying processes such as washing drying digestion with potash and repeated fractionation it was found impossible to get it to boil at a constant temperature.In fact it began to boil between 127' and lZS' the thermometer going up gradually and evenly to about 131'. With so small a difference between the boiling-points it was obviously useless to attempt anything like a complete separation of the two liquids composing this mixture. Still by repeated fractionation especially as we had large quanti-ties of the substance at command we might accumulate a larger proportion of the substances of lower boiling-point in one fractiun than existed in the original mixture. After many distillations a fractiou was obtained which though its boiling-point still rose to 131' towards the close of the distillation passed over fur the most part at a lower temperature.On the other hand another fraction was obtained the boiling-points of which were from 128' to 13g0 the greater proportion of the liquid passing over near the latter. The former of these fractions we will designate fraction A the latter fraction B. Two combustions were made of fraction A. Both yielded numbers corresponding to amyl-alcohol:- Substance taken co2 a20 I. .... 02248 0.5604 0*2?'42 11. .... 0.2646 Ob6589 0.3'I76. From these numbers we deduce the percentages :-I. 11. Theory C. .... 67*97 6791 68.18 H .... 13.55 13.33 13.63 The combustions were made with oxide of copper chlorate bf potash being employed at the close of the operation.HFaction A was then oxidized with chromic acid in the manner so frequently before described and the products of the operation fractionated. Carbonic acid was liberated during the oxidation. * We state the above factson the authority of &hedistiller fkom whom we w-ceived this sample of fuselsil. THE PRODUCTS OF GRADUAL OXIDATION XTC. 497 I 1-I Per cent. Theoretical Acid to which this 1 1 Substance taken. BazSo4 Ba found. per cent. found. corresponds. First fraction- 0.3748 0 -4164 0 *2800 0 -3107 43.92 43 *87 44 -052 Butyric acid trtet fraction- 0 -3768 0.2583 40 *34 40 *413 Valerianic acid 0 -4002 0 -2757 40 -51 These acids are somewhat difficult to separate requiring several repetitions of the fractionating process before the separation can be looked upon as complete.Carbonic bntyric and valerianic acids appear therefore to be the products of the Oxidation of this mixture. If the substance of lower boiling-point be really a secondary alcohol yielding carbonic and butyric acids as its oxida- tion-products we ought to have equivalent quantities of these substances produced. To determine this point 1.2128 grm. of frac-tion A were introduced in a sealed bulb into the digestion-tube which already contained bi-chromate of potash and sulphuric acid ; the neck of the tube was drawn out to a long fine point and the digestion proceeded with. When it was jiiciged that the digestion was complete an india-rubber tube was slipped over the point and connected with aLie hi g’s potash-apparatus containing concentrated sulphuric acid.A second potash-apparatus charged with potash which had been weighed was connected with the first. The point of the digestion-tube was then snipped off and the carbonic acid escaping through the extremely small aperture was dried by its passage through the sulphuric acid and absorbed by the caustic potash. As soon as the passage of gas had corr?pletely ceased the point of the digestion-tube was broken off somewhat lower down though still within the iudia-rubber tube and the contents heated until they boiled. The steam of course expelled the whole of the carbonic acid arid by judiciously cooling the india-rubber tube and when necessary the top of the digestion-tube any dan-gerously rapid absorption by the sulphuric acid was avoided.The potash-bulbs were then detached and reweighed. Of course their increase of weiglit gave a most accurate measure of the amount of carbonic acid liberated. A precisely similar experiment was performed with fraction B. 4Q8 OHAPMAN AND THBRq WV*Slri RELATION EX. As will be seen from th' ahkh&i-nunibers the amount of car-bonic acid differed consideraTJ$ in-tlie two cases :-_. Substance employed. Carbonic acid found. Per cent. of carbonic acid. 1 Fraction A. 1,2128 0.4096 3 3-77 Fraction B. 1.5728 0.3636 2.3.09 i Samples of each of the alcoliols were oxidized AS before the coriteuts of the digestion-tulles diluted and distilled almost to dryness arid samples of each acid distillate converted into barjta-salts.The annexed table exhibits the perceiitages of barium contaiued in these salts arid also those wliicli would have been obtained on the assumption tliat an nmourit of butj-ric acid equi-valelit to the carbouic acid was produced aiid tliat this butjric aeid m;is the representative of the seco:idary alcoliol contained in the two fractions. It is further assumed that the primary alcohol prodnced nothing but valerianic acid. Substance takeu. Ba.,SO found. Per cent. Ba Calculated per found. eentage. _L_I_-Fraction-A. Fraction A. 0.4092 0.2975 42.56 42.801 0.3834 0.3784 43.69 Fraction B. Fraction B. 0'319'2 0.22SG 42.1 I 42.016 0 420'; 0,3003 41.97 Finall! a portion of the valerianic acid obtained !)y the oxida tion of orie of the samples of ;iico11ol was digested with dilkte chi*oniic acid (fii e per cent).No carbonic acid was liberated thereby poviiig tliat tlie butJric atid carbonic acids did not owe their existence to tlie deconlpositioii of' tlie valeriaiiic acid. l3.e thiiili that we liave tliits f8irly proved the existence of a seconcl isort:eric :m>1-alcoliol in tlic sample we were operating upon thon;h we were iiiiabIe to isol:tte it. We will IIOM consider what iiiforniatiori the metliod of research. by gradual oxidation is capabaapfdbrding us with regard to the molecular constitution of bodies. Tlyisquestion is best answered by considering how many isomers it is capable of revealing to us in any one case.Take for instance amyl-alcohol. We know that there are many possible isomers of this body but gradual oxida- tion or at least oxidation carried far enough to produce those substances which we have agreed to term proximate products of oxidation could only reveal to us the existence of a portion of them ;for it is o-13vious that we may have a pseudo-primary amyl-alcohol i.e. an alcohol containing a pseudo-amyl say for instance propyl-ethyl; and we may have a secondary amyl-alcohol con-taining propjl and ethyl. Both these compounds mould we believe yield the same proximate oxidatiou products though doubtless the former would in the first instance yield pseudo-valerianic acid. This would at once distinguish it from the real primary alcohol but would not distinguish it from the secondary alcohol which would yield the same oxidation-products.Still though the so-called proximate products of oxidation would not fnrnish us with information on this pint the mediate products taken in conjunc-tion with the proximate products would. We have not in the foregoing paper considered the case of bodies in which the ratio of carbon to hydrogen is such as to render it impossible to account for the whole of the carbon in the form of acids of the acetic series. It is obvious that such bodies must either yield substances of an altogether different class or the carbon must be converted into carbonic acid.

ISSN:0368-1769    

DOI:10.1039/JS8661900477

出版商:RSC    

年代:1866

数据来源: RSC

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XLV.-On the Strength of Solutions of Phosphoric Acid of Variozis Densities. By‘Mr. JOHN WATTS, Senior Bell Scholar in the Laboratories of the Pharmaceutical Society. [From the Proceedings of the British Pharmaceutical Conference 1865 p. S9.l IN the compilation of a table of this kind the first thing is to know at what specific gravity to start ;accordingly finding that a thick syrupy acid of 1.5 p. c. sp. gr. oontained nearly 50 per cent. PO, 1 made that the starting-point and proceeded regularly 500 J. WATTS OM THB STRENGTH 03' SOLUTIONS OF downwards as far ars sp. gr. 1.006. The interval between these two numbers contairis 47 specific gravities therefore 49 in all and as the acid of each specific gravity was analysed at least three times in order to obtain a correct mean it entailed the work of about 150 analyses.The table when completed stands ae follows:--A.t:3&* -,g:3 G; -$!$ $!$a3-$9 &Z AQ$5 0 - s~5 &#2 .-.r( VP -6L2&$ - I 1.608 49.60 1.392 40.86 8211 1-185 1'08 1 10-4 4* 1.492 48.41 1.384 40.1 2 31-94 1.173 1073 9.53 1.4'76 47 10 1.376 39-66 31'03 1'162 1.066 8.62 1.464 45-63 1.369 39-21 30.13 1-158 1.056 7-39 1.453 I *442 45.38 44.13 1.256 1.347 38.00 37'37 29'1% 28-24 1.144 1.136 1.047 1.031 6.17 4.15 1.484 Pa95 l"33.9 36.74 27.30 1'1 24 PO22 3'03 1-426 43.28 1.328 .36*15 26.36 1'113 1'014 1:91 1.418 42.61 1.315 34.82 24-79 1-109 3 '006 -79 1-401 41.60 1-802-33'49- 23.23 17096 I I would next notice the method empIoyed for its analysis. After essaying arid testing the various advantages of a great many diferent processes of which I will speak hereafter 1 came to the conclusion that with a pure solutioo of phosphoric acid no method is more simple msre accurate or less liable to error than the method employed in the British Pharmacopceia viz.''the evapo- ration down of a weighed quantity of the solution with a known excess of pure protoxide of lead." I coilfess I was somen~hnt disappointed when first employing this method owing to the discordant results obtained notwith-standing that at first sight it seemed exceedingly straightforward and plain; but I afterwards found it entirely arose from not operatirig with pure oxide. I had used the commercial article and though previously to each anriljsis it had been carefully ignited there nevertheless remained so much carbonate and OtheJ iiapuritics as to render it practically wdrtliless no tivo results agreeing nearer than 2 or 3 per cent.Finding this to be the case I looked about for some other sub-stance to use instead and for this purpose tried the oxixie of zirlc. BritiSJr Phamacopceis. PHOSPHORIC ACID OF VAUIOUS DENSITIES. 501 Analysis with this latter oxide eve perfectly accurate results as regards numbers but was open to a great objection inasmuch as the phosphate of zinc readily fuses; and upon ignition towards the end of the analysis to get rid of the last traces of water the fusing of the phosphate and its adhering tenaciously to the bottom of the crucible from which it cannot be subsequently removed entirely spoils the vessel for a second operation.Oxide of mag-nesia answered uo better for this unlike the oxides of lead and zinc forms a hydrate when put into water; and as is the case with many magnesia salts either the last traces of this water of hydration or the atom of basic water assimilated when neutralizing the phosphoric acid is so difficult to expel totally even after powerfid ignition that one can never be certain that the whole of the water is driven off unless the capsule hasbeen allowed to cool and re-ignited several times which with such a number of similar analyses causes much unnecessary trouble. The volumetric nitrate of uranium process was also tried hut as the results never approached nearer than 5 to 6 per cent.a discrepancy too great to be allowed in a case like this it wns given up. Determined then to revert again to oxide of lead and to prepare a pure oxide myself 1 took red led (BPbO.PbO,) and dissolving out the protoxide with dilute nitric acid washed well the resulting binoxide ; this by careful ignition over an air-flame loses its extra oxygen-atom and passes with incandescence to the state of protoxide. Working with oxide prepared in this manner I ob-tained highly satisfactory results and subsequently used this method only for the completion of the analyses in the table. By examining the gradation of the numbers on the table it is seen that the percentage increases or decreases regiilarly accordingly as the specific gravity rises or falls proving that the strength cau be correctly deduced from a knowledge of its density and t.hat unlike acetic acid it presents no anomaly in this respect; also that when a strong acid is diluted with water though a consider-able quantity of heat is evolved no condensation in volume follows.The correctness of the numbers may be also somewhat checked in the following manner :-Take 100 Jluid grains of 1*5@8acid this will weigh 150.8grs. and contain 74.79 grs. by weight of PO ; dilute this with 100 A. grs. of water the whole will weigh 250.8 grs. and contain 74.79 grs. by weight of PO ; each 100 parts by weight will be therefore of sp. gr. 1.254 and contain theoretically 29.7 parts by weight of acid; by referring to the latter sp. gr. on the table we find by ~~~~s~ number to contrtin 29.16 per cent.Again 100 fi. gm'of acid 1.385 sp gr. will weigh 128.5 grs. and contain 41.03 gre. by weight of PO,; diluted with 100 fl. grs. of water it will weigh 228.5 grs. and contain 41.03 grs. of acid being of sp. gr. 1.142 ;each 100 parts of acid of this sp. gr. should contain then 17.9 by weight of PO,. Reference to the table shows us 17.89 per cent. A great many numbers 6aGe been checked in this manner and they were all fouhd to be correct. The temperature at which all the specific gravities were taken was 15.5 C. (60"Fahr.). This is of course an important point in using the table as the volume of liquid varies considerably according to the temperature; and as at different heights of the thermometer comparison of volumes no longer holds good com-parison of percentages would be equally fallacious.I may add that the acid used was prepared from common phos- phorus in the ordinary manner; but I have since made several examples of acid from amorphous phosphorus as first mentioned by Mr. Groves and decidedly prefer this latter method; the phosphorus is readily acted upon its use entails no danger and a product is obtained in a few hours which ordinarily would take as many days. One little objection appeared which is apt to make one think that the product is not.absolutely pure vie. that in the concentrated state it was more or less coloured possessing a brownish or yellow tint; this might have arisen from the par-ticular specimen of amcjrphous phosphorus operated on probably another sample would not show this defect.

ISSN:0368-1769    

DOI:10.1039/JS8661900499

出版商:RSC    

年代:1866

数据来源: RSC

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X&VI.-Note on Messrs. Calvert and Johnson’s paper c4 0%the Action of Acids upon Metals and A-lloys.” (November 1866 p. 434.) By A. MATTHIESSEN, F.R.S. INmost of the tables given in this paper (Tahles 6-12) tbere will be found a column headed “Loss calculated according to the composition of the alloys.’’ The numbers given under this head-ing are honever all faulty as the authors have calculated these MATTEIBSSm OM THE AWEION CXFAACIDS ON ALLOYS. 503 values fim the weights of tk~~daih -posing the alloy using the co-efficients as they may be called of the action of the acid on their surface as the co-efficients of the action of the acid ofi their weights; thus in TaMe 7 p. 445 they give the follow-ing :--Metalsand Calculated Loss calculated according to composition of Loss on loss on 1 sq.wmpoaitian of 1 C.C. a€loys. metre. alloy. Copper .,.... . .. 0 -000 0 *ooo 0 .coo Zinc. ... . . . . . ... 0-200 333 -33 333 *33 1st alloy. Zn&u ZP .. 83-70 0 *I55 268 854 279 .OO Ca .. 16.30 -100 -00 La0t 81loy. ZnCUr, Zn .. 17'*05 0 -000 0 *ooo 56 *83 Cu .. 82 95 100 00 -Now 100grms. of the first alloy consist of 83.7 = 11.7 C.C. 7.10 16.3 zinc (for 1C.C. weighs 7.15 grms.) and -= 1.8 C.C. of copper 8.95 (for 1C.C. copper weighs 8-95 grms.) ;or 1C.C. of the alloy consists of 0.86 C.C. zinc and 0.14C.C. copper. The loss on 1 C.C. zinc by the action of hydrochloric acid being 0.200,on 0-86C.C. it will be 0.272,and that of the acid on copper being 0-000,the calculated loss on 1 C.C.alloy is 0.172; or the calculated loss on the square meter deduced from the composition of the alloy will be 287 instead oE 279 as given in the table. Similarly the calculated loss on the alloy ZnCu will be 68 instead of 56.83. The authors' method of calculation is as stated the use of weight instead of surt'ace ; thus their calculated values are found 'by multiplying the weight-percentages by the co-efficieats and dfoididg by 100; for 83.7 x 3.3333 = 279; and 17.05 x 3*8333= 56-83. ROSCOE ON THE ISOMORPHISM OF The whole of these results therefore need recalculation. It would have been of interest Imd the authors stated how they made the copper-zinc alloys in exactly their combining proportions as they must have had great difficulty in doing so owing to the volatility of zinc.

ISSN:0368-1769    

DOI:10.1039/JS8661900502

出版商:RSC    

年代:1866

数据来源: RSC

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ROSCOE ON THE ISOMORPHISM OF XLVII.-Qn the Isomorphism of ThalZium-Perchlorat; with the Potassium and Ammonium-Perchlorates. By Prof. €1. E. ROSCOE, F.R.S. &c. [From the Proceedings of the Literary and .Philosophical Society at Mancheater October lS 1866.1 THErecently ascertained isomorphism of the thallium-and ammonium-sulphates* renders it highly probable that the per- chloratev of these metals also exhibit isomorphous relations. Thallium-perchlorate equals the alkaline-perchlorates in stability. It can be readily prepared either by dissolving metallic thallium in aqueous perchloric acid or by the double decomposition of thallium-sulphate and barium-perchlorate. From solution the anhydrous salt is easily deposited in colourless rhom bic crystals which .re transparent bright well-defined and non-deliquescent.The spmific gravity of the crystals is 4.844 at 15O.5 C.; they dissolve iu 10 times their weight of water at lb" and in about %ths of their weight of water at 100"; the salt is also slightly soluble in alcohol. Thallium-perchlorate does not lose weight when heated to 200" C. and the temperature may even be raised to within few degrees of the boiling point of mercury without producing tke slightest decomposition of the salt. On the further application of heat a black mass is formed and the salt finally volatilises as thallium-chloride. The crystalline form of thallium-perchlorate is that of a right rhombic prism (ppl),in which the faces of the rhombic octohedron (ml) and the basal faces of the prism (c) generally appear the crystals being lengthened,.as is the case with the alkaline-perchlo- rates sometimes in the direction of the prismatic and sometimes in the direction of-the octohedral faces.A careful measurement * Lang Phil. Mag. xxv 248. THALLIUM-PEEOHLORATE,ETC. 505 of the crystals gave the mean value of 102' 50' for the anglepp ; and that of 102' 6' for the angk rr on c. Hence the relation of the axes is 0.79'78 1 0.6449. The angles observed by Mitscherlich (Pogg. Ann. xxv. 301) in the case of potassium and ammonium-perchlorates agree exactly with the above; for the first of these salts pp = 1C3" 58' rr on c = 101"19'; and for the second,pp = 103' 11' and rrl on c = 4' giving the relation of the axes to be (1) 0.7817 :1 0.6408 and (2) 0.7926 1 :0.6410.An analysis made in my laboratory by Mr. T,E. Thorpe shows that the formula of the salt is T1 C1 0,. (1.) Determination of ThaZliurn.-The crystals were well dried in vacuo over sulpburic acid and precipitated with platinum-tetra-chloride the passage of the finely divided precipitate through the fitter being avoided by evaporating to dryness on the water-bath and taking up with absolute alcohol. (a) Salt prepared by direr$ solution of the metal in perchloric acid ;0.1831 salt yielded 0.2476 chloroplatinate. (b) Salt prepared by double decomposition ; 0-4502 salt yielded 0.6060 chloroplatinate. (2.) Determindion of Perchtoric Acid.-A solution of potassium-acetate was added to the thallium-perchlorate and the whole eva-porated to dryness on a water-bath the acetates of thallium and potassium washed out with absolute alcohol and the insoluble potassium-perchlorate collected on a weighed filter; 0.4570 thallium-perchlorate yielded 0.2100potassium-perchlorate. Hence Calculated. Found. I. XI. 111. T1....,. 204.0 67-21 67-38(a) 67'18 (b) C1...... O4 .... 3505 6$0 21.09 11TO 132.96 __I 308.5 100.00

ISSN:0368-1769    

DOI:10.1039/JS8661900504

出版商:RSC    

年代:1866

数据来源: RSC

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MEETINGS OF THE CHEMICAL SOCIETY 1866. January 18th. Dr. Miller F.R.B. President,in the Chair. Robert Henry Smith Rodney-street Pent~nville ; James Spier Newcastle-on-Tpe; Thomas Boverton Redwood 19 Montague-street Russell-square ; John Conroy Oxford ; were elected Fellows ; and John Bones Newport ,&tonmputhshire was re-admitted a Fellow. The fdowing papers were read :-‘I On Pyrophosphotriamic Acid :” by Dr. Gladstone. ‘‘On the Action of Carbonic Oxide upon Sodium-ethyl :” by Prof. Wan kly n. ‘I On Glyoxylic Acid :” by Dr. Debus. February Pat. Dr.,&filler F.R.S.,Preqident in the Chair. Franklin Epps 112 Great Russell-street ; William Thorp 13 York-terrace Kingsland-road ; Edward Purser Jun. 116 Fenchurch-street ; Arthur Ellson D rtvies Surgeons’ Hall Edinburgh ; were elected Fellows.Dr. Gilbert delivered a discourse (( On the Composition Value and Utilisation of Town Sewage.’’ PWCEEDINGS OF TE%3CHEMICAL SOCIETY. 807 February 15th. Dr. Frankland F.R.S. Foreign Secretary in the Chair. G. B. Ferguson Magdalen Hall Oxford ; W. H. Walenn 19 Talbot-road Tufnell Park West ; Benjamin Nichols Making- place Hall Rippenden near Halifax ; were elected Fellows. Twelve Fellows were removed from the Society for non-payment of their subscriptions. The following papers were read :-‘‘ On the Action of Nitrous Acid upon Nayhthylamine ?’ by Ernest T. Chapman Esq. “On the Action of Heat on Ferric Hydrate in presence of Water :” hy Edward Davies Esq. ‘‘On the Prognosis of New Alcohols and Aldehydes:” by Prof.Kolbe. March 1st. Dr. Williamson Vice-president in the Chair. Robert Bell Queen’s College Kingston Canada West ;W. H. Corfield Pembroke College Oxford; G. W. Webster Bridge-street Warrington ; were elected Fellows. The following papers were read :-‘‘ On New and Rare Cornish Minerals :” by Prof. Church. On the Numerical Relations between the Atomic WeigEts of the Elements :” by J. A. R. Newlands Esq. u On a New Method of forming Organo-metallic bodies :” by Prof. Wanklyn. “On the Chemical Action of Sunlight upon Sensitive Photo- graphic Papers :” by C. R. Wright B.Sc. March 15th. DF.Miller F.R.S.,President in the Chair. Samuel Crawley Training College York ; Charies Pat- more Phillips 109 Fenchurch-street ; were elected Fellows.The following paper qy,~&;r ‘# On Hgdrocy an-rosaniline :’p by Dr. fia go M u 1 1e P. Dr. Fiankland gave a verbal acconnk &some ‘fiVakktions in the Cothpbsitibn bf the Waters supplied ’ to-the Metropolis during the past year.” March 29th. Anniversary Meeting Dr. Miller F.R.S. President in the Chair The following report was read by the Prersident :-On this 25th anniversary of the establiehment of the Chemical Society the Council are again able to congatdab the Fellows upon a steady advance in their ntmibers and.aprosperous condition of their finances. On the last I anniversary the numbers en&dled as Fellows smounbd to 453 whilst on t%e present .occasion4432 appear upon OUT fist.These numbers are accounted for aa follows :- Numher of Fellows at last annirersary (1865) ...... 453 Elected and paid since .......................... 47 -i5w Removed on aceaunt of arrears. ................... 1.2 Fellows withdrawn ............................ 3 .. deceased. ............................... 3 -19 Present number of Fellows (1866) !*. .............. -482 NumSer of Foreign Member@,last Anniversnry ...... 38 Deceiwed ...................................... -Presentnumber .I....r..r........~....r..,,.cr. 37 PROCEEDIKGS OF TIIE crmixc,iL SOCIETY. 609 ‘I’he naues of the B’ellows ‘witldrawn are:-J. 33. Davidson R‘m. Wskefiel,d Samuel Parr. Tbe names of the Fellows deceased are :-Prof. W. T. Brmde Dr.Dauglish Mi*.George Smith of the firm of Messrs. Smith and CO. distillers ;Professor Rafaelle Piria. The name of Mr. Brande has been for more than fifty years familiar to the public as one of the most prominent chemists of this country. Contemporary in his prime with D av y Da1t o n and MTollaston he was one of the few survivors of a generation mlio formed the connecting link between the great chemists of the last century Watt Priestley and Cavendish and those who are engaged in carrying forward their work at the present time. Win. Thomas Brande D.C.L. F.R.S. was descended from a family of Hanoverian extraction and was the younger son of Mr. Brande the apotliecary to George 111. and Queen Charlotte. He mas born in 1786 and educated at Westniiiister School.As a boy he attracted the notice of Mr. Hatchet t of the Mint from whom he appears to have derived his first taste for chemistry. When he left scliool he went for a time to Hanover and on his return to England entered as a medical student at St. George’s Hospital where in 1805 and 1806 he attended the chemical lec- tures of Dr. Pearson and Mr. Accum. In 1808 he made a chemical examiiiation of the calculi in the Hunterian Museum and in the same year conimenced his career as a pnblic lecturer by delivering a course on Pharmaceutical Chemistry in Dr. Hooper’s Medical School in Cork Street. Shortly afterwards he joined the Medical School in Windmill Street where for several years he lectured on general chemistry. Iii 1813 on the recommendation of Sir H.Davy he mas appointed as his successor in the chair of chemistry in the Royal Institution. The chemical classes of St. George’s Hospital and of the Windmill Street School were afterwards transferred to the Royal Institution so that in addition to his ordinary duties as Professor he gave an extended course of chemical lectures in the laboratory of the Institution. In this course Mr. Faraday was associated with him in the year 1827 and for nearly twenty years they lectured‘ together. He con-tinued to hold his professorship until the year 1852 when he resigned his active duties and was appointed Honorary Professor to the Royal Institution. As a lecturer Mr. Brande mas highly successful being distinguished for the clearness of his VOL.XIX. 20 5 10 PROCEEDINGS OF TRE CnEMICAL SOCIETY. style for the methodical arrangement of his matter as well as for the admirable selection and performance of his experimental illustrations. In 1809 he was elected a Fellow of the Royal Society and in 1816 succeeded Dr. Wollaston as one of its secretaries in which‘ capacity he acted until the year 1824. He received the Copley Medal of the Society in 1813 for his researches on the propor- tion of alcohol in wines and for his experiments on some of the compounds of carbon and hydrogen ; and in 1828 he received the Fullerian Medal of the Royal Institution. Having in 1812 been requested to‘report upon the laboratories belonging to the Society of Apothecaries in London he was shortly afterwards appointed Professor of Chemistry and Materia Nedica to that corporation and in 1851 filled the Chair of Ma3ter of the Company.We learn from the autobiography of the late Sir B. Brodie that about the year 1812 Mr. Brande became a member of a small scientific society the Animal Chemistry Club which in- cluded Sir E. Home Sir H. Davy Sir B. Brodie himself Mr. Hatchett Dr. Babington Mr. Children and some other distinguished chemists and physiologists. It was chiefly a social gathering intended especially to stimulate researches upon physio- logical chemistry. In the year 1818 Mr. Brande married Mr. Hatchett’s youngest daughter and this lady has survived him. In 1825 he received the appoiiitment of Keeper of the Dies at the Mint and on the chnnge in the management of the Mint in 1852 he was appointed Superintendent of the Coining department.As a scientific writer Mr. Brande is well known. The first edition of his Manual of Chemistry appeared in 1815. It passed through six editiorrs the last of which was published in 1848. Since that time it has not been republished; but in connection with Dr. Taylor in 1863 a joint work on chemistry Based largely upon Mr. Brande’s manual appeared. For sixteen years from 1816 to 1832 he conjointlp with Mr. Faraday edited the Quarterly Journal of Science and Art.” He was also the author of a “Dictionary of Pharmacy,” as well as of a work entitled “ Outlines of Geology,” besides acting as editor of a ‘‘Dictionary of Science Literature and Art,” upon the second edition of niliicli he was occupied at tlik time of his death.Tn 1836 Mr. Brande was named one of the original Fellows PROCEEDXNGS OF THE C’REMlCAL SOCIETY. of the University of London and a member of its Senate; in 1846 he became one of their Examiners in Chemistry in which capacity he continued to act until the year 1858. On the instal- lation of Lord Derby as Chancellor of the University of Oxford ‘Mr. Brande received the honorary degree of D.C.L. in that Uni- versity. He was also a Fellow of various scientific societies both in this country and abroad. His name mill always be connected with the early history of the Chemical Society. On the establishment of the Society in 1841 Mr. Graham became its first Yresident and Mr.Brande and Professor Daniell with Mr. J. T. Cooper and Mr. R. Phillips were nominated Vice-presidents. In March 18417 W. Braride was elected to the office of Pzesident and as it wa3 in this year that the Society obtained its charter of incorporation his name appears as its President in the deed of incorporation. 3t mas during Mr. Brande’s Presidency that the Society began the publication of a Quarterly Journal to which he contributed ;L short paper on the Well-water of the Mint. To the last he preserved his vigour both of body and mind so that even at the advanced age of 81 the news of his death after a short illness was received almost with a feeling of surprise. Dr. John Dauglish was born in the year 1824,in th9 parish of Bethnal-green London.He was educated at the school of Dr. Alexander Allen at Hackney and began the study of medicine in 1852 at the University of Edinburgh where he sub-sequently took his degree of M.D. He was elected a Fellow of thc Chemical Society June 30th 1861. He has not communicated any paper to its Transactions but is well known in connection with a patented process for making unfermented bread which bears his name and which has come extensively into use. In this process carbonic anhydride is liberated from chalk by the action of sulphuric acid the gas is received into an ordinary gasholder and is thence pumped into a strong cylindrical vessel containing water by which means a solution of carbonic acid con- taining three or four times its bulk of the gas is obtained.Thc solution of carbonic acid is drawn off into a strong closed vesscl where it is mixed under pressure by means of a revolving agitator with the proper proportion of flour and salt. When the incor- poration lins been properly effected a valve at the bottom of the 202 . 1. . 'sic 512 PBOCEEDTRGS OF THE CIIEMICAL SOCIETY. ''(> f<'>Ifj! I/!'i,' 1' mixing vessel is opened thei;@$,e$capes and on corning into the outer atmosphere immediatelb becomes vesicular owing to the expansion of the imprisoned gaseous carbonic anhydride,' as soon as it is released from the pressure to which it has been subjected. It is immediately tratuferred to thc oven and baked. This process is a substantial addition to the supply of bread iu the country ; for besides ensuring cleanliness by dispensing with the ordinary method of kneading by the naked hands 'or feet it saves a sensible percentage of the flour which was wasted in the old process of fermentation.It also dispenses with the necessity of tile use of alum formerly resorted to for pre-venting tile conversion of starch into gjucose wIiic1i is so 1ial)Ie to occur in flour from the more highly azotiscd wheats; and it is even more digestible than the bread fermented upon the ordi- nary plan. Dr. Dauglish died on the 14th of January 18GG at the early age of 42. Those who knew him have to regret the loss of an able and accomplishcci man and the Society that o$ an engrgetic practical workerd ,I ' Mafaelle Piria was born at Scilla in Calabria on the second of August 1815.Tn 1838 he was a pupil of M. Dumas in whose laboratory he made his classical research on Salicin and its derivatives. This laboriaus investigation surrounded as it was with many and formidable difficulties he carried out :with the most persevering industry establishing the proximate constituents of salicin to be grape-sugar and saligenin. The latter substance he transformed by dilute acids into saliretin by concentrated sulphuric acid into rutilin by cold nitric acid into helicin and by inore powerful oxidiziiig agents into formic acid and hydride of salicyl. The latter substance mas soon recognised as the essentid oil of meadow-sweet the constitution of which was thus for the first time clearly established.This splendid investigation to which we owe almost exclusively our very complete knowledge of the salicyl series of organic bodies is justly regarded as a model of analytical accuracy and logical reasoning. M. Piria was not content with the reputation which this great work secured for him but continned down to a recent period to contribute numerous memoirs to chemical literature. Amongst the most important of these his papers on Aspxagin Papulin and Nitrosalicylic Acid may be mentionccl. His last memoir however is. perhaps aiiic chemistry the most important and described a method of general of organic acids into the:corresponding aldehydes by distilling their calcium-salts with calcic formiate. The truc significance of this reaction is at once pcrceived when it is remembered that it furnished the first step in the passage ’from the acid into the alcohol family the second haviag been since supplied by Wur tz in the transformatiou of the aldehydes into their corresponding alcohols by nascent hyilrogen.Soon after the contribution of this valuable discovery M. Piria’s energies became absorbed in a movemeiit which could not fail to sttract the services of Italy’s best intellects. He became a senator in the Parliament of the new kingdom; nevertheless he did not allow himself to be entirely withdrawn from science but continued to hold his professorship at the University of Turin until his death which took place at Turin on the 18th of July 1865. List of Papers read at the meetings of the Chemical Society from March 30 1864 to Narch 30,1865 :-1.u On a New Bro@noderivative of Camphor :” by Mr W. H.. Per kin 2. ‘r On il Deposit of Sulphate of Ammonia from Dried Blood :” by Mr. J. A. R. Newlands. 3. Lr Laboratory Notices :” by Prof. Bloxam. 4. ‘‘ OH Phosphide of Magnesium :” by Mr. J. P. Blunt. 5. rc On the Periodides of some Organic Bases :” by Mr.-W. A. Tilden. 6. ‘‘ On the Specific Refractive Energies of Elements and their Compounds :” by Dr. Gladstone. ’. On the Transformation of the Lactic into the Acrylic Series of Acids :” by Mews. Frankland and-Duppa 8. ‘‘ On the Action of Nascent Hydrogeb on Azo&naphthyl- diamine :” by Mr. W. H.’Perkiu. 9.‘‘ On Some New Cornish Minerals :” by Prof. Church. . 10 “ On the Caprylic and CEhanthylic Alcohols :” by Mr. E. Chapman. 11. ‘‘ On the Absorption of Gases by Charcoal :” by Mr. John €Iu 11 t er. 32. “ On Nitro-,Compounds :” by Dr. S. 5. Mills. 13. “ On I’!.roPl~osp?io-rliarnic AcAl :” by Dr. Gladstone. 514 PROCEEDINGS OF THE CHEMICAL BOCIETP 14. “ On Phenyl-Phosphoric Acid :” by Dr. H. Muller. 15. “ On the Material to be Employed for Mural Standards of Length :” by Mr. James Yates. 16. On Pyrophospho-triamic Acid :” by Dr. Glads tone. ‘I 17. ‘; On the Action of Carbonic Oxide on Sodium-ethyl :” by Prof. Wanklgn. 18. ‘(On the Constitution of Glyoxylic Acid :” by Dr. Debus. 19 ‘‘ On the Action of Nitrous Acid upon Naphthylamine :” by Mr.E. Chapman. 20. ‘‘ On the Action of Heat on Ferric Hydrate in presence of Water :” by Mr. E. Davies. 21. On the Prognosis of New Alcohols and Aldehydes:” by Prof. Kolbe. 22. “ Further Researches on New Cornish Minerals :” by Prof. Church. 23. “ On the Numerical Relations of the Atomic Weights of the Elements :” by Mr. J. A. R. Newlands. 24. On a New Mode of forming Organo-Metallic Bodies :” by Prof. Wanklyn. 25. u On the Chemical Action of Sunlight upon Sensitive Pho- tographic Papers :” by Mr. C. R. Wright. 26. (‘On Hydrocyan-Rosauiline :” by Dr. H. Muller. Lectures have also been given. 1. cc On Some Points in the Analysis of Potable Waters:” by Dr.Miller President. 2. On the Composition Value and Utilisation of Town Sewage :” by Messrs. Law es and Gilbert. The following Fellows mere elected Officers and Council for the ensuing year :-President.-W. A Miller M.D. F.R.S. Vice-presidents who have Jilled the Ofice of President.-Sir B. C. Brodie F.R.S.; C. G. B Daubeny M.D. F.R.S.; Thomas Graham F.R.S.; A. W. Hofmann LL.D. F.R.S.; Lyon Play-fair Ph.D. C.B. F.R.S.; A. W. Williamson Ph.D. F.R.S.; Colonel Philip Yorke F.R.S. Vice-Presidents.-F. A Abel F.R.S.; Walter Crum F.R.S.; Warren De la Rue Ph.D. F.R.S.; John Stenhouse LL.D. F.R.S. PROCEEDINGS OF TEE CHEMICAL SOCIETY. Secretaries.-William Odling M.B. F.R.S. ; A. V.Har-court M.A. Fore$n .ISecretary.-E. Fr ank1 an d Ph.D. F.R.S. Treasurer.-T h eoph ilus TLe dwood Ph.D. Other Members OJ the Council.-F. Crace Calvert F.R.S.; Dugald Campbell W. Crookes F.R.S.; H. Debus Ph.D. F.R.S.; F. Field F.R.S.; G. C. Foster; E. A. Hadow; H. Letheby Ph.D.; Hugo Muller Ph.D.; H. M Noad Ph.D. F.R.S.; W. J. Russell Ph.D.; Maxwell Simpson Ph.D. F.R.S. It was resolved that the fourth Bye-law,,relating to the removal of Fellows be altered as recommended by a resolution of Council passed at a meeting held on January 18th. It was resolved that a new form of Nomination paper for the proposal of Gentlemen as Fellows of the Society as approved by the Council should be adopted. The thanks of the Society were voted to the President Officers Council and Auditors for their services during the past year.The Treasurer presented the Balance-sheet of the Society DRS. T!IE TliEASURER IN ACCOUNT WITH THE CHEMICAL SOCIETY. Cas. - 1; 4 1865-6. f 3. d. 1865-6. s. d. $ s. d. 3lsrch 25. I-0 Ealmcc on hand 25th March 18C5 ........................ 792 8 11 Journal. By Editor's Salary .........................................i 96 0 0 , Dividends on 21,301)Consols ................................ 38 7 0 , Printing Joufial ....................................... 168 17 0 , Sundry Receipts from 26thMarcli 1865 to 5thhIarch , EnWVing for ditto .........:........................... 1 15 4 . 0 1866 :-, Distributing ditto ....................................... 44 1 5 e 3. d , Beporting Proceedings ..............................17 17 0 Admission Fees ........................... 92 0 0 , Translation .;.............................................. 0 12 0 Life Compositions ....................... 100 0 0 341 7 5 27 Subscriptions for 1864 nnd pre- Proceedings , Anmal Subscription for Proceedings sent. to vious years .............................. 38 0 0 of lloyal the Fellomii,oftlie Chemical Society ............ 50 0 0 83 Subscriptions for 1865 ............... 142 0 0 Society. 5000 280 Subscriptions for 1866 ............ 478 0 0 Library. ? Librarian's Salary. ....................................... 25 0-0 ,I Subscriptions overpaid carded to ac-Eoohe,and Magazines ..,................................. 3 16 0 count .......................................0 4 , BOokbinding.,A,... ....................................... 7 . 9'7 -6 850 4 6 I' $6 5 T j 8 Printing , Printing hTotiGesr.............:........................... Stationery Stationery ,.:; ....;;........................................ y; 0" 1 2. 4 ZolIector an( , ColleCtor's CommiGsion ....;............................ Clerk , Clerk .........................................................- j 40 10;s '..I ,-i tc* , stamps ......................... ;............................ I-! 4 12:j House , Roy& Sotiets. Share of Tea Expenses ............ , T.J. Hm Salary ........................................ % 1 ,...- -L. Expenses. ,, ,? , , . ,,,W. Petty Expens* per.Boo!i ............... Giu Account ..............................2 3 4 i) Y 0 I. 0 0 Page Cleaning........................................ , Gate Porter ......A...... .................................. 2 2 0 -i-44 6 S Furniture , Ventilating Meeting ~oom,and Mtcring,~ooli-and Altera- .. CaBeS ...................................................... I i23 '7 0 tion of , Purchase of f30Q 3 per Cent. Coneols ............ %3 7 cj Meeting Ealance at Messm Coutts ...................... ....... 762 8 I1 horn. 2 1031 0 5 I-f 1681 0 t ASSETS. We have examined the accounh of the Chemical Society from the ?5th March 1865 tQ'the 23rd € S.' d. March 1866 inclusive compared them with the vouchers &lid found them correct. We flnd the 1:nlance zit Coutts'3 ...................................................762 8 11 balance in dvour of tie Society to be ST62 8s. lld. which ib-at the society's banken. Invested in Thrcc per Cent. Consols .............................. 1.WO 0 0 JOHN ATWIELD, .€?,W:! 8 11 London,March 27th 1866. CHe HI$ISCH ) April 5th. Dr. Hofmann F.R.S. Vice-president in the Chair. Rpbcrt McCalmont Belfast ; TVm. Carr Stevens Mark Lane ; Thomas Vosper Nightingale Mancl-sester were elected Fellows. The following papers were read :-“On the Estimation of Phosphorus in Iron and Steel:” by J. Spiller Esq. “On Magnesium :” by Prof. Wanklyn and E. T. Chspman Esq. “Note m Mercury-ethyl :” by E. T. Chapman Eq.-“Contributions to the History of the Periodides of the Organic Bases :” by W.A. Tilden Esq. ((Onthe Formation of Acetylene :” by H. McLeod Esq. On the Synthesis of Gutmidine :” by Dri Hofmaon. Apyil 19th. Dr. Miller President in the Chair. J. T. Drown Oxford Villa Sudbiiry; James Gale Belsiae Park Hampstdad; Win. Huggon Park Row Leeds; Joseph Ricliardson Dawson-street Manchester ; Wm. Marsh all Watts B. Sc. University Laboratory Glaegow were elected FelIows. The following papers were read :- On Picric Ether :” by Dr. Steiihouse and Dr. H. Miiller. On Styphnic Ether :” by Dr. Stenhouse. Professor Cary Foster delivered a discourse ‘‘On the Ttnermd Phenomena accom pan yiiig Chemical Action .” May 3rd Dr. Miller P.R.S. President in the Chair. Marshall Hall Cieveland-terrace Hyde Pdc ; J ulin Robinson Oxford; J.J. Lundy Leith ; were elected Fellom. 518 PEQOEEDINGS OF THE CHENICAL SOCIETY. Professors Rammelsberg Wolcot Gibbs and Weltzien were elected Foreign Members. The following papers were read :-IC On Pyrophosphodiamic Acid :” by Dr. Glad stone. c‘ On the Phosphates of Calcium and the Solubility of Tri-calcic Phosphate:” by R. Warington Sun. Esq. May 27th. Dr. Miller F.R.S, President in the Chair. The following papers mere read :-“On the Production of Acetic and Propionic Acids from Amylic Alcohol :” by I3.T. Chapman Esq. ‘I On the Oxidation of Ethplamine :” by Prof Wanklyn and E,T. Chapman Esq. I‘ On the Action of Acids on Naphthylamine :” by E. T. Chap-man Esq. On some Compounds obtained from Acetone :” by SirRobert Kane.“On Formulze for the Expansion of Gases by Heat :” by the Rev. B. W. Gibsone. On the Nitro-prussides :” by E. A. Hadow Esq. June 7th. Dr. Miller F.R.S. President in the Chair. Wm. Arnot Bachelor-street Liverpool; E. H. Davies Har-ley-road Brompton ; C. Wilson Bridgewater Smelting Com-pany St. Heleu’s; C. R. A. Wright B. Sc.; were elected Fellows. The following papers were read :-‘I On the Oxidation-products of the Propione produced from Carbonic Oxide and Sodium-ethyl :” by Prof. Wanklyn. “On Phthalic Aldehyde:” by Prof. Kolbe and G. Wirchin. “On Chrysammic Acid:’’ by Dr. Stenhouse and Dr. H. Muller. On Chrysammic Ether :” by Dr. Stenhouse. PROCEEDINGS OF THE CHEIIICAL SOQZBTTr 519 u On the Platinum-bases :” by E.A. Hadow Esq. ‘‘ On Decompositions of Nitrite of Amy1 :” by E. T. Chap-man Esq. “ On a Cyanogen-derivative of Marsh-Gas :” by Henry Bas-sett Esq. Mr. A. Vernoii Harcourt delivered a lecture “On the Obser- vation of the course of Chemical Change.” June 2lst. Dr. Williamson Vice-president in the Chair. Arthur Gamgee M.D. Edinburgh; James H. Lighbown Manchester ; W. F. K. Stock Darlington Durham; Edward J. Sparks Oxford; were elected ‘Fellows. The following papers were read :-rf On the Action of Acids upon Metals and Alloys :” by Prof. Crace Calvert and H. Johnson Esq. Dr. Debus delivered n lecture “On the Constitution of some Carbon-compounds.” July 5th. Extra Meeting. Dr Miller F.R.S. President in the Chair.I Mr. James Yates exhibited and descrihed some new Mural Standards of Length made in Porcelain by Mr. Casella The following palms wcre read :-’I On the Constitution and Representation of Organic Com-pounds :” by Dr. Williamson. ‘I On the Reduction of the Oxides of Nitrogen by Metallic CCJpller in Organic Analysis :” by w. Thorp Esq. “On the Hydrocarbons contained in Crude Benzol;” by C. S cliorlemmer Ph.D. “On Ethyl-hcxyl Ether :” by C. Schorlemmer Ph,D. ’ Novemkir 2%; 1866 Or Miller F.R,S. Presiilcut in the Chair. Itr. C h aiitller Roller ts Camberwell New Road Keiinirigton Park ; l3 P. 11. 1-anghail Gaisford-street Kentisli l’fi~ii,mere elected F‘ello~s. fl 1lie follon ing papers TT’CFC rend :-‘‘On an Instrumeiit for Taking the Specific Gravities of Hetero-gmeous Liqnids :” by Dr.N. Sprengel. ‘‘ On the RelatSon between the Products of Gradual Oxidation and the Molecular Constitution of the bodies Oxidised:” by E. T. Chapman &q. and W. ‘l’horp Esq. Dr. Miller F.R.S. President in the Chttir. W €1. Gossage Melbourne Victoria; R. Biggs Charles-streef Bath; David Page Galibecli Powder Mills Kendal were elected Fel1o~ve . The folloving payers were react :-I‘ Ou Atmospheric Ozone ;” by Dr DaulJeiiy. ‘(On a Chlorosulphide of Carbon :” by W. K. Hartiey Esq. ‘‘ On the relation between the Products of Gradual Oxidation and the Molccular Constitution of the bodies Oxidkerl :’” Part II. by E. T. Clialirnan Bsq. and W. Thorp,’Xsq. ‘(Oil the SyiitIiesis of Butylerie :,’ by E.T.Chapman Esq. December 6th Dr. Miller F.R.S. President iii the Chair. A. C. Cook Pi1.D. King’s College London; Hearg Dirckq C.E. Bucklersbury ;Jaines l~ol.rcst,’AsliburnlLrnR ond Creenwicli ; Wn1. I-Iutchinson Gray’s Inn Raad ; A. 17. Narrcco Newcastle College of Medicine ; J. Hancoclr Ricliarclson 3Tcwcastlc-on-Tyne were elected Fellows. ‘~III~I~ICAL PROCEEDIRGSOF ~IE’ soc?d+ki 521 The folIowing papers were rg+$.iglc{J,,t cj ‘(Ou the Synthesis of Formic Acid :” by E. T.C h apman Esq‘ r4 On the Alloys of Magnesium:” -by Jas. Parkinson Esq. ‘< On the Oxidation of Ethylic Benzoate:” by B. €1. Smith Esfi Decciuber 20th. Diigtlld Campbell Esq. in the Chair. Jultn Brou gh ton Esq. Government Ciiichona Plaulatiou Mdri~~ Presidhcy ;Watson S mith Portland Qrwwnt Mandies-tcr ; ,Walter Noel H nrtley Esq.Pathological Laboratory St. Tliomas’s Hospital ; Alex. &lo Prison Tbomson D.Sc. University of Sydney New South W-ales were elected Fellows. The following papers were read :- On the Basicity of Tmtaric Acid :” by W. II. Perkiri Esq. “ On the Absorption of Vapours by Charcoal :” by J. Hunter M.A Oh Soine Readions of Hydriodic Acid :” by E. T.C 11 apm 88 xsq. ‘‘ On a New Continuous Aspirator :” by H. McLeod Esq. Donatiohs to the Library in the year 1866 :-“A Dictionary of Chemistry and the Allied Brancbes of other Sciences :” by €1 en ry Watt o. Parts XXXII1.-XXXVI. from Iaessrs. Longmap and Co. r‘ Lcctures oa Animal Chemistry delivered at the Roial College of Physicians :” by William Odling M.B.from the Author. “Elements of Chemistry Theoretical and Practical,” 3rd Edi-tion Part 111. by William Allen Miller KD. LL.D. from the Author. Lecture Notes for Chemical Students embracing Mineral and Organic Chemistry :’’by E. Frankland Ph.D. F.R.S. from the Author; “Lessons on Elementary Chemistry :” by Henry E.&oscoe B.A. F.R.S. from tbe Authori ‘r Chemical Handicraft :” by J J. Griftin from the Author 522 PROCEEDINGS OF THE CHEMICAL SOCIETY. “Synoptic Tables of Chemistry :” by A. P. Fourcroy from George Whipple Esq. The Chemical Laboratories of the Universities of Bonn and Berlin:” by A. TIr. Hofmann Ph.l). F.R.S. from the Author. “Chemical Addenda being a brief exposition of the salient features of Modern Chemistry :” by the Rev.B. VC’. Gibsone from the Author. cc Little Experiments for Little Chemists :” by M. IS. W a1 enii from the Author. “The Toxicologist’s Guide :” by J. C. Horsley from the Author. ‘‘Mineral Resources of Central Italy including a description of the Mines and Marble Quarries :” by W. P. Jervis from the Author. “On the Application of Disinfectants in arresting the Spread of the Cattle Plague :” by William Croolres F.R.S. from the Author. rr The Book of Quinte Essence or the Fifth Being; that is to say Man’s Heaven :” edited from the Sloane MS. 73 about 1460-70 A.D. by Federick J. Furnivall M.A. and published by the Early English Text Society from the Editor.‘‘Report on Experiments undertaken by order of the Board of Trade to determine the Relative Values of Unnialted and Malted Barley as Food for Stock by J. B. Lawes Esq. from the Author. ‘‘First Report of the Commissioiicrs appointed to inquire into the best means of preventing the Pollution of Rivers (Rirer Thames) :” Vol. I. Report Appendix and Plans; Vol. 11. ?+ti-nutes of Evidence and Index from the Commissioners. ‘‘Abridgements of Specifications of Patents relating to Elco-tricity and Magnetism :” compiled by Mr. H. W almera from the Compiler. Address on the Presentation of the Gold Medal of the Royd Astronomical Society to John Conch Adams Esq. RLA. :” by the President Warren Dc La Rue Pii.D. P.R.S. -from the Author..‘(On the Source of Muscular Power:” lip E. Frankland 3’h.D. F.R.S. from the Author. Synthetical Researches on the Ethers No. 1 ; Synthesis of Ethers from Acetic Ether :” by E. Frankland and B. F. Dupp a from the Authors. PROCEEDINGS OF THB CHEMICAL SCCIEMYP. 523 “Lord Bacon as Natural Philosopher ; a reply to an article by Baron Liebig bearing the same title :” by G. F. Rodwell from the Author. “Suggestions for a new System of Chemical Nomenclature :” by George Hamilton from the Author. “Analyses of. the Waters of Pyrmont and Driburg :” by R. Fresenius from the Author. Pamphlets by Dr. A. Volcker from the Author. “On the Absorption of Potash.” “On the Functions of Soda-salts in Agriculture.” (( On the Absorption of Soluble Phosphate of Lime by different Soils of known Composition.” ‘< On Peruvian Guano.’ “Salt Experiments and Mangolds.” ‘r On Disinfectants.” On the Composition of Orange Globe Mangolds Bulbs and Tops.” “Annual Eeport of Chemical Analyses :” Pamphlets by C. M. Wetherill from the Author. “On the Crystalline Nature of Glass.” ‘‘Experiments with Ammonium-amalgam .” cc On the Crystallisation of Sulphur and upon the Reaction between Sulphide of Hydrogen Ammonia and Alcohol.” “A brief Sketch of the Modern Theory of Chemical Types :” ‘‘Cows de Philosophie Chirnique ; fait au Colle‘ge de France :” par Adolphe Wurtz (1864-1866) from the Author. c‘Sur 1’Isomdrie :” par M. Rerthelot from the Author. ‘‘ Nouvelles Recherches s~irles Lois r!es Proportions Chimiques sur les Poids Atomiyues et leur Rapports Mutuels:” par J.S. Stas from the Author. ‘‘ Sur le Dosage de 1’Acide Tartrique :” par 3lr. Ber thelot from the Author. “Sur 1esOxydes duNiobium:” par AX. l\larc Delafontaine from the Author. “MatAriaux pour servir ii l’histoire des rne‘taux de la C6rite et de la Gadolinite:” par M. Marc Delafontaine from the Author. 524 PR&OEEDIBGS OF THEl CHEAtICAL SOCIETY. ‘‘ Rechtwklieu sur lcs Combhaimns du Xiobiuin (deuxi8me me’moire):” par C. Marignac from the Author. “La Vie et l’muvre de Charles Fre‘de‘ric Gerhardt :” par J. H. F. Papillon from the Author. I‘ Considkrations sur la Science et les Savant.s? par F. Papii-Ion from the Author. “Introduction h 1’Etude de la Philosophie Ckimique :” par F.Pnpillon from the Author. “De 1’Identitb d’origine de Composition et de Propridte‘s Mgdicales des Sources Mine‘rales du Bassin de Vichy :” par N. Larbaud from the Author. ‘I Systemstische Zusammenstelluiig der Organischen Verbin- dungen:” von C. Weltzien from the Author. ‘CInductioii and Deduction :” von Justus Liebig (Rede gehalten in der Sitzurig cler Iianiglichen Akademie der Wissen-schaften zu Muuchen am 28 Marz 1865). Entstehung und Begriff der Naturhistoiischen Art :” von Dr. Karl Nageli (Rede in der ijffentlichen Sitzungder Koniglichen Akademie der Wissenschaftcu zu Muachen am 28.Marz 1865. Periodicals :-‘(Philosophical Transactions,” 1864 part 111 ; 1865 parts I and TI from the Royal Society.‘I List of Officers and Fellow8 of the Royal Society for the year 1865 :” from the Royal Society. rC Memoirs of the Royal AstronoEical Society,” vol. XXXIV. c( Monthly Notices of the same 1866 :” from the Society. cc Quarterly Journal of the Geologisal Society,” for 1866 from the Society. ‘l Qnarterly Journal of Science,” for 1866 from the Editor. ‘‘Proceedings of the Royal Institution of Greet Britain,” vol. IV. part 7,8. ((List of Members Officers and Professors of the same,” for I866 from the Royal Institution. “Calendar for the year 1866 of the Science and Art Depart- ment of the Committee of Council on Education :” from the Department. Journal of the Pliotographic Society,” for 1866 from the Society. Pharmaceutical Journal and Transactions,” for 1866 from the Editor.fF Annual Report of t&e;~:~L’Philosophicalwd Literary Society ’’ (1864+-65) ‘.11 from the Society. I‘ Proceedings of the Literary and Philosoptiical Society of Liverpool ’’ (1864-65) from the ’Society. (‘Mehoirs of the Literary and Philosophid Society of Man-Chester;’ third series vol. 11. from the Society. “Promedings of the aatne,” vois. HI. IV. from the Society. Journal of the Society of Arts,” 1866 from the Society. cc Chemical News” for 1866 from the Editor. ‘‘The Reader ” for 1866 from the Editor. CcAmerican Journal of Science and Art,” from November k8S4,to September 1866 from the Editors. ‘‘Journal of the Franklin Institute,” from November 1865 to October 1866?’ from the Jnstitute.‘‘Transactions of the American Philosophical Society,” vol. XIII. part 2 from the Bociety. lC Praceedings of the American Philosophical Sooiety (1866) from the Society. ‘I Catalogue of the Library of the American Philosophical Society :” from the Society. ‘(Proceedings of the Academy of Natural Sciences at; Philadel-phia ” (1565) from the Academy. “Annual Report of the Board of liegents of the Smithsonian Institution ” (1865) from the Smithsonian Institution. ‘‘Circular No. 6 War Department Surgeon-General’s Office Washington. Reports on the Extent and Nature of the Materials available for the Preparation of the Medical and Surgical History of the Rebellion :” from the Surgeon-General. ‘‘ Cosmos,” 2nie Sbrie Tome 111.:” from the Editor. “Bulletin de l’Acsd6inie des Sciences de St. Petersbourg,” Tome TX, Fenilles 1-9 from the Academy. ‘‘ Bulletin cte l’Acad6mie Royale de Belgique,” 1866 “Annuaire de l’Acad6mie Royale de Belgique,” 1866 from the Academy. Giornale di Scienze naturali ed economiche publicato per cura dal Consiglio di Perfezzionamente annesso a1 R. Institute technic0 di Palerrno,” Volume I. Fascicoli 2 3 4 ‘‘Denlischriften der Kaiserlichen Akademie der Wissenschaften in Wien (Math.-pliys. Classe),” Band XXlV. ‘‘Sitzungsberichte derselben,” Erste Abth. und Zweite Abth. LII. LIII. from the Imperial Academy of Sciences at Vienna. VOL XIS. 2P “Sie;z~iii,vsl)ei.ic~~te dcr Koniglicli-baiel.i.cllcrl hlrademie der JVisscnschaftcn 211 ilIii1lcl~c11,”1Ztl.TI IIcfte 3-6 from tlie Royal Bavarian Academy of Sciences. Abhand1ungen (1er 11at11r \\ isseo~ch aft1ich e Ti t e clin iscli en C:oni -niissioii der Kbniglichen AEadirnir der Wisscn schaften Z~I Jliinclien,” Band I. (1857) from the Academy. “Jahrbuch der li. 1;. g-eokyiischen Reichsanstalt zu Wen,” Rd. SIT- IIeftc 1-4 (Jiiniiel.-S:ei~teniber 1864) ; Bd. XV &If&4 fvom the Iustitnte. “Zeitsclirift fiir Chemie und Pharmacie,” Iierausgegeben ~’qn E. Erlenmeyer Hd. TrlI Hefte 19-28,-Neue Folg-e liemus-gegdlien vdn A. Hiibuer Bd. 11 Hefte 2-17 from the Editors. ‘‘J-erhnndlungen der Naturforschenden Gesellschaft in Basel,” Abth. IT,1Ieft 2 from the Soaiety. ‘‘Jenaische Zeitsbhrift fiir Medicin imd ~atiirwisSensc’haft~’ Bd I Heft 2 from the Edibr.‘I Kieuwe Verhandeiirigen van het Bataafsch G enootschag der proef‘ondervindeiijkeWijsbegeerte te Rotterdam,‘? l%Deel 2 e.3 Stuk 1865 flora the Society. ‘l bfversigi af Usgl. T’etenskaps Altadomiens F5rhandlinga.r:” frbm the RQyal Academy of $ciences at Stockholh.

ISSN:0368-1769    

DOI:10.1039/JS8661900506

出版商:RSC    

年代:1866

数据来源: RSC

摘要:

INDEX. A Acetate of amyl oxidation of 4.85. ht&% of ethyl oddation of 484. -methyl 485. Acetic ether synthesis of ethers from by 3%. P)a.akIshd sand B. F. Dupps, 395. -action of sodium and ethylic io&de F% 3f64 Acetone relation to paeudo-propylic aIcohol 260. -diethylated 402. -di-methylated 4+4. -etxyfated 465. -methyked 416. Acetylene amodificationofBerthelot’s experiment for the formation of by ipxperfeet combustion,161 Acld yetkJormatios of by oxidation of amylene Wit. -amylic acetate 485. -amylic alcohol 333. -ethylamine 487. -ethylamylamine 489. -ethylic acetate 484. -ethylic iodide 486. -ethylic nitrate 486. -(3-hexylene 492. -isopropylic iodide 487. Acid acetic and alcohol their action on indigo-blue 464.Acid benzoyl-chrysammic 322. Acid anthranilic its formation from indigo-blue 470. Acid carbonic formation of by oxida- tion of amylene 492. -amylic alcohol 333. -ethylene 491. -/3-hexylene 492. -isopropylic iodide 487. -methylic acetate 485. Acid chrysammic crystalline form of 321. Acid chrysammic on the preparation of by J. StenhouseandH. Muller 319. Acid ethacetic 4.08. Acid formic and alcohol their action on indigo-blue 475. Acid hydriodic its action on nltriko amyl 339. Acid hydrochloric its action on alloys ofcopper and &c 462,446. -alloys of copper and tin 462. Acid nitric its action upon brad Ml 443.-bronze 461. Acid nitrous action of on naphthyla- mine by E. T.Uhapmarl 1M.Acid nitrobenzoia 364. Acid phosphoric on the strength of solutions of of vationb >dcnsitiee! by J. Watts 49. Acid propionic formation of by oxida-tion of propi6& ‘327. Acid propionic formiltion of from amylic alcohol 333. -cT.kyh.e 48% -7 propylamine 488. Acid pyrophosphodiamic notea on by J. H. Gladstone 290. Acid pyrophosphotriamic on by J. H. Gladstone 1. Acid pykoracemic or pyruvic 267. Acid styphnic action of chlorine on 237 Acid sulphuric its action on brasses 447. -bronzes 453. -copper 438. -nitrite of amyl 337. -tin 4.39. -zinc 437. I_I_ determination of the weight of accumulating at the bottom of the leaden chambers 455. Acid valerianic formation of by oxida-tion of amylamine 488.-amylic acetate 485. -amylic alcohol 483. -amylic iodide 487. -amylic valerianate 485. Acids action of on metals and alloys :by F. C. Cnlrert and R. Johnson 434. Acids action of on naplithylnmine by E. T. Chapman 329. Acids fatty constitution of 429 Alcohol and acetic acid t.heir action on indigo-blue 466. 2P2 525 INDEX -Alcohol and fodc acid their action on indigo-blue 475. Alcohol and grape-sugar their action on indigo-blue 463. Alcohol amylic oxidation of 483. -ethylic oxidation of 482. Alcohols and aldehydes prognosis of Dew by H. Kolbe 54. Aldehyde phthalic preliminary notice on by E. Kolbe and Gt. Wirchin 339. Alloys specific heat of 195. -and metals action of acids 011 by F. C.Calvert and R. Johnson 434. Ammonia per gdlon and estimated value of total coixkitucnts in one ton of sewage at different dilutions 101. Ammonia grains of per gallon in differ-ent samples of nietropolitan sewage 90. -highest lomest,andaverage amounts of and total solid matter in mixed samples of Rugby sewage at different times 93. Ammonium pyrophosphodiamate 294. Ammonium pyrophosphotriamate 10. Amyl on some dccompositions of nitrite of by E. T. Chapman 336. Amylamine oxidation of 488. Amylene oxidation of 491. Amylic acetate oxidation of 455. Amylic alcohol gradual oxidation of with sulphuric acid and bichromate of potash 483. Ainylic alcohol production of acetic and propionic acids from by B.T. Chap-man 333. Aniylic iodide oxidation of 4.96.Amylic iodide and sodium action of upon acetic ether 418. -nitrate oxidation of 4.87. -valerianate oxidation of 485. Analysis on the reduction of the oxides of nitrogen by metallic copper in or-ganic by W. Thorp 359. Aniline chloTine- and bromine-substitu- tion products of 61. Anniversary Meeting of the Chemical Society (March 30 lS66) 508. Antunite 135. drseniates specific heat of 201 228. Arsenides specific heat of 196 225. Atomic heat and atomic weight or composition relations between 203. Average specific gravity of heterogeneoue liquids determination of 456. B. Bdame-sheet of the Chemical Society (1866) 516. Barium pyrophosphotriamates 6. Bargtic-nitrobenzoate action of heat on 369.Bases a further contribution to the his-tory of the periodides of the organic by W. A. Tilden 145. Basset t H. on a cyanogen-derivative of marsh-gas 352. Benhydrol 289. Benzol note on the hydrocarbons con-tained in crude by C. Schorlem- mer 356. Borates specific heat of 225. Boron specific heat of 187. Bran d e W. T. obituary notice of 509. Brass action of hydrochloric acid on 442 -445. nitric 441 443. -sulphurjc 447 449. Bromine-compounds specific heat of 197 225. Bromine-substitution-products of ani-line 61. -Bronze action of hydrochloric acid on 452. -nitric 450. -sulphuric 453. Brown J.,tables for the calculation of vapour-densities 72. C. Cadmium pyrophosphotriamate of 9. Caffammonmm iododichloride of 147.Calcium chrysammate of 321. Calcium researches on the phosphatea of and on the solubility of tricalcic phos- phate by R. Warington junr. 296. Calorimeter used by H. Kopp for de- termining the specific heats of solid bodies 172. Calvert F. C. and Johnson R. action of acids on metals and alloya 430. Carbinols 54q. Carbon specific heat of 189. Carbonate ethylic diethacetone 4xIo. -e thylic dimethacetone 412. -ethylic ethacetone 404. -ethylic methacetone 412. Chapman E.T. action of acids on naphthylamine 329. -action of nitrous acid on naphthy-lamine 135. -on mercury-ethyl 150. -on some decomposition of nitrite of amjl 336. -production of acetic and propionic acids from amylic alcohol 333.Chapman E. T.,and Thorp W. the relation between the products of gradual oxidation and the molecular constitution of the bodies oxidised 477. Chapman and Wanklyn. See Wenklyn. Chemical Society Balance-sheet of the (I€%) 516. -donations to the library of the (1866) 521. -proceeding8 at the meetings of the (1M) ax. Chlonttes epecific heat of 201,328. Chlorine action of on sdphuric acid 237. Chlorine-compounds spec& heat of 197 225. Chlorine-substitution-products of aniline 64. Chloropicrin action of potassium-cyanide on 352. Chloropicrin formation o€guanidine from 251. Chromium pyrophosphotriamate of 10. Chrysammates 321. Chrysammic ether on by J.St en h o u se 324. Church A. H.chemical researches on new and rare Cornish minerals 130. Cobalt pyrophosphotriamate 9. Composition and atomic heat relations between 203. Constitutional formi& 375. Copper actmion of sulphuric acid on 438. Copper and tin alloys of see Byonze. Copper and zinc alloys of see Brass. Copper on the reduction of the oxir?es of nitrogen by metallic in organic analysis by W. Thorp 359. Copper chrysammate of 323. Copper pyrophosphotriamates of 8. Cornwallite 135. Crops to which sewage is most applicahle 104. Croydon sewage see Sewage. Cupric aluminum sulphate hydrated 130. Cyanogen-derivative of marsh-gas on R new by H. Basae t t 352. Cyanopicriu 352. D. Daugliah J. obituary notice of 511. Davies E. action of heat on ferric hy- drate in presence of water 69.Debus H. on the constitution of aome carbon-compounds 17 256. Dimetone-carbonate ethylic 4~30. Diazo-amidobenzol 57. -action of bromine on 60. -nitrous acid on 60. Diazo-amido-komobenzol 63. Diazo-amido-chlorobenzol, 62. Diazo-amido-dibromobenzol, 65. Diazo-amido-dichlorobenzol, 66. Diazo-amido-nitranisol,68. Diazo-amido-nitrobenzol 64. Diazo-amido-toluol 67. Dicarbinols 56. Diethacetone-carbonate ethylic 480. Dimethacetone-carbonate,ethylic 412. Dimethylated acetone 414 Dry-systemof collecting manurial matter 83. Donatioiis to the Library of the Chemical Society (1866)) 521. Duppa and Frankland ; see Prank-land. E. Elements atomic heat of 209. -considerations on the nature of tiiz chemical by H.Kopp 230. Elements nomenclature and notation for expressing the different states of condensation of 16. Elements specific heat of 195. Erinite 135. Etliacetone carbonate ethylic 404. Ether acetic action of s9dium and a.my-lic iodide upon 410. -action of sodium ai:d ethylis iodide upon 396. -action of sodimn and methylic iodide upon 411. -constitution and chemical wk-tions of the ethereal salts and ketone- derived from the duplication of the molecule of 419. -exaniination of the products depending upon t,he duplication of the molecule of 399. -examination of the products derived from the substitution of ethyl for hydrogen in the methyl of 406. -chrysammic 324. -diathacetic 409.-dimethacetic 417. -dimethylene- carbon-ethylene-sodic 404. -dimethylene-carbon-ethylene, 406.. -disodacetic 409. -ethacetic 407. -ethyl-hexylic,note on byE. Scho r-lemmer 357. -picric 235. -pyrophosphodiamic 224. -sodacetic 407. -styphnic or oxgpicric 236. Ethers carboketonic 422. -synthetical researches on by E. Prankland and B. F.Duppa 935. 530 Ethyl-aIcohol ij&$&on of 482?. '*5'iJ; I j?)l lflf Ethylamine on the aiidation df' :<' J. A. Whnklyn hnd E.T.Chap111&2 Pfa'dov E.,A. on the ~YI 328. 341. Ethylamylamhe oxi'dation of 488. -the pliLt.in~m-bhse8 i the bat mode Ethylene oxidation of 491. of obtaining and identlfging %b; Ethylic acetate oxidation of 484.some new bonygmndd 5-65. : -acetone carbonate 421. -diethacetone carbonate 400. Heat action of dn f69riehydmte in pre-sence of water by E. D avie 8 69. -himethacetone carbonate 402 -on a-hydric nitrobenzoate -ethacetone carbonate 404. and on barytic nikobenzoates 369. -iodide oxidation of 4236. -atomic ; see Atomic heat.- -iodide and sodium action of upon -specific ; see Speciflc heat' * . ' acetic ether 396. -methacetone carbonate 415. H&erogeneops Iiquide oa de6eraixiing the weight of by H. Gprengel 45. -nitrate oxidation of 486. P-Hexylene oridatioa &rf 49% Expansion of water on the by A. iU a t-Hofmann A. W. on the synthesis of thiessen 30. guanidine 249. Human voidniga amount of nitrogeeh reckoned as ammonia and &timated vaIne of total constituents in 96 I F.Hydrated cupric-aluminum sdphate a new 130. Fatty acids constitution of 429. Hydric nitrobenzoates 364. Ferric hydrate action of heat on in Hydrocarbons note on the contained in presence of water by E. Davies 69. crude benzol E. Sehorlemmer Fluorine-compounds specific heat uf 356. 197,226. Hydrochrysammide 324. Hydrogen bn n liew class. of1 mgenic Fordae constitutional 315. compounds in which it is replaoed by Frankland E. contributions to the notation of organiQ and inorganic nitrogen (Part iii.) by Peter Ukiees I1 compounds 3'72. ' 5?. -the water supply of the me- .I tropolis during the year 1865-66 239. Frankland E. and Duppg B. F. I synthetical researches on ethep : No.1,synthesis of ethers from acetic Indigo-bhe 6n some firuducts derived ether 395.from by E.Schunck 462. -formation of slzrthraailic acid from 470. Inorganic and organic eompounds con-tributions to the notation of by by E. Frankl'and . Iodides amylic ethylic rnethyl.2 &c. ; Gilbert J. H. and Lawes J. B. on see amylic ethylic methylic iodide the composition value and utilisation &C. of town sewage 80. 1odlne-compounde;'ep ecific heat of 197, Gladstone J. H. note on pyrophos-225. phodiamic acid 290. Iodo-dichloride,of caffammofiium,149. -on pyrophosphotiamic acid 1. Iodo-dichloride of tetrethylammoninm, Graphite specific heat of 190. 147. Grass quantities of green obtained and Iron and steel on the estimation of of sewage spplied per acre per annum phoephorus'in by J.Bpilhr 14& in experiments made at Rugby 108. Iron pyr~phosphot~iamate of 9. Qriess Peter on a new class of organic Is0 ropylic iodide oxi&tion of 40. * compounds in which hydro en is re- Jbgnson and Olthert; Bee Oalvert. placed by nitrogen (Part iii.f 5'7. Guanidine on the synthesk of by A. W. Hofmann 249. K. Guano relation of sewage to Peruvian in amount of nitrogen reckoned as am-Ketones and ethereal salts derived from monin 103. the duplication of the rndectklwof acetic ether conq#xtion and chemical relations of 419. b=a&41,.6E.u~ ilpl0~0skof mew &ahPfs and aldehydes 54. I.. -ad. Wir&i,a .J,,.pwIi+$iimy .notice on phWo aklehp-le 339. Eopp H. iystiptiom vf the specific .&& of bdes 154 L Lawes 3. B.;qnd Gilbert J,B. on tbs composition,value ad utilisation of town sewage 80. Lead preption of pare protoxidq fof fwm,red lead 501. Lead-pyrophosphotriamatesof 7. Library of the Chemical Society dam-tjons-to the (lSSS) 521. Liquids on determining td weight of hehogeneous by H. Sprengel 4%. London Institution contributiqns from the laboratory of the :-1. The oxidation-products of the p-pime produced from carbonic axide and sodium-ethyl by 3. Alfred Wanklyn 326. 2.On theo~datiopof ethylamiqe :b . J. .A.Wanklyn -and Erpest !I! Clapmsn 328. 3. Action of acids on naphthylamhe by Ernest T. Chapman 329. 4.Production of acetic and propionic rtcids from araylic alcohol by Ernest T.Chapman 333. A Oasome decompositiappof nitrite of amyl; by Ernest T. ,Chap-man,336. 6. The reiation between tlpe products of gradual oxidation and the mob-eular constitution of the bodies oxidised by E. T. Chapmsa and W. Thorp 44% . I$agnwiqm,,pn :by J-BWanklyn and . P. %Ghaprn&n,&41. , -chryeammate of 323. -pyrophosphotriamate og10. Mggpeaiuu@hyJ on by E. T. Chap-man 160. -Gdaii of by the action of % anerqury and m4gnesipm on sodium-ethyl 129. Manganese chrysammste of 323. -pyrophosphotsiamate of 10. Manurial matters,‘ dry system of collet:t-‘. bustion 151. Meetings of the Chemical Society pro- ceedings at the (lSSS) 506. Melaconite 135. Mercury-ethyl formation of by the action of mercury with copper iron or silver on sodium-ethyl 130.-note on by E.T. Cba man l$O. -pyrophosphotriamate ol 11. Metals and alloys action of acids upon by F. C. Calvert and R. Johnson 434. -note on the same by A. Mat-thiessen 503. Metapbosphetee specific heat of 201 228. Methacetone carbonate ethylio 415. Methyl of acetic ether examination of the products derived from the substi-tution of ethyl for hydrogen ha the m.‘ Methylrmted rtcetone 416.’ Methylic acetate oxidetion d,4$5. -iodide and sodi~un,dm of npon acetic ether 411. -nitrate bxidation of 486. Metropolitan sewage Bec Sewage W’. Mills E. J. on nitro-compounds. ,Part . ii. appendix 363. Minerals chemical researches on new and rare Cornish by A. H. Church 130. Molybdates specific heat of 200 227.Miiller H. andL‘Stenhouse J. on pisric ether 235. N Naphthylamine eian of acids on by E. T.Chapman 329. -acttop oEnitrous acid on by. $. T. Chapman 135. flickel-pyrophosphotriaslate,9. Nitranieidiye 68. Nitrate of ethyl oxidation of, -meth,pl o&datioa of 486. Nitrakes apecifio heat ~f, 226 2 Nitrite of amyJ,pn sanlq de of by E. T. Chapmsn, -oxi+tion of 486. Nitrobenzo+e j n&y;dric 3t+ ’ ’ .h --P-hydricj’.@S TNDimG. 632 Nitrobenzoate y-hydric 367. --a-hydric 368. ?%trobenzoatee action of heat on a-hy-dric and barytic 369. Nitro-compounds by E. J. Mills 369. Nitrogen amount of reckoned as ammo-nia and estimatad value of total con- stituents in human voidings 96.-on a new class of organic compounds in which hydrogen is replaced by (Part iii) by Peter Griess 57. -relation of sewage to Peruvian guano in amount of reckqned as am- monia 103. on the reduction of the oxides of by metallic copper in organic analysis by W. Thorp 359. Nitroprussides on the by E. A. Ha dow 341. Nomenclature and notation (Wanklyn’s) for expressing the different states of condcnsatiou of a giren element 16. Notation of organic and inorganic com- pounds contributions to the by E. Frankland 372. 0. Obituary notice of W. T. B r a nde 509. I_-John Dauglish 511. -Rafaelle Piria 512. Organic analysis on the reduction of t>lie oxides of nitrogen by metallic copper in by W. Thorp 359.-bases a further contribution to the hidory of the periodides of by W. A. Tilden 145. -compounds specificheat of 202,228. -and inorganic compounds contri- butions to the notation of by E. Frankland 372. Organo-metallic bodies on a new method of forming by J. A. Wanklyn 128. Orthocarbonate of ethyl formatioil of guanidine from 254. Orthosilicate of ethyl action of ammonia on 255. Oxidation the relation between the p~o- ducts of graduitl and the molecular constitution of the bodies oxidised by E.T.Chapman andW.Thorp,4.7’7. Oxides specific heat of 198,226. -of nitrogen see Nitrogen 359. Oxidisod Burface influence of on the subsequent action of sulphuric acid of various strengths upon zinc 435. Oxidising agents action of on nitrite of amyl 326.Oxygen atomic weight of 16. Oxypicric or styphiiic ether by J. Stcnhonse 236. P. Perchlomtee and permmganates specific heat of 201 228. Periodides of the organic barns a further contribution to the history of the by W. A. Tilden 14.5. Phosphates of calcium resewcheson,and upon the solubility of tricalcic phos- phate by R. Warington Junr. 296 -specific heat of 200 228. Phosphorus on the estimation of in iron and steel by J. Spiller 148. -preparation of phosphoric acid from amorphous 502. Photographic papers contributions to our knowledge of the chemical action of sunlight upon sensitive by C. R. Wright 33. Phthalic aldehyde prelimiiiary notice on by H. Kolbe and G. Wirchin 339.Picricether by H. Muller and J.Sten- house 235. Piris R. obituary notice of 512. Platinum-pyrophosphotriamate,12. Platinum-bases on the by a. A. Hsdow 345. Potassium-pyrophosphotrirsmates,10. Proceedings at the meetinga of the Che- mical Society (1866) 506. Propione on the oxidstion-prodncts of the produced from carbonic oxide and sodium-ethyl by J.A. Wanklyn,326. Propylamine oxidation of 487. Propylene and its derivatives 274. Propyl-glycol 270. Pprophosphates specific heat of 201 2%. Pyrophosphodiamates 295. Pyrophosphotriamates 4. R. Report of the President and Council 508. -Treasurer 516. Roscoe H. E. on the isomorphism of thallium-perchlorate with the potas- sium and ammonium-perchlombes 504. Rugby sewage seo Sewage.S. Schorlemmer E.,note on ethyI-heq-1 ether 357. -note on the hydrocarbons contained in crude benzol 356. Schunck E. on some products derived from indigo-blue 4,62. rn&X Sewage ammonia per gallon and esti- mated value of total constituents in one ton of at Uerent dilutions 101. -composition and vdue of town 8'7. -crops to which it is most applicable 104. -experience of common practice in the utilisakion of,123. -quantitiee of applied and of grecn grass obtained pcr acre per annum in experiments made at Rugby 108. -relation of to Peruvian guano in amount of nitrogen reckoned as am. monia 103. -results of direct experiment on the utilisation of 107. -Croyclon partial analyses of before application of the drainage water from the irrigated land and of the river Wsndle above and below the irrigated land 121.I_ Metropolitan grains of ammonia per gallon in diffesent samples of and estimated value of the constituents in one ton 90. -Rugby ammonia and solid matter in mixed samples of 93. -detailed composition of sam-pies of before application and of the drainage-water from the irrigated land collected July 1864 118. -mean cornposition of 94. -mean compoeition of before application and of the drainage-water from the irrigated land in the seasons of 1862 and 1863 116. Sew-aged and uiisewaged gsxis results obtained at Rugby on COWS fed on 112. Sewage-irrigated meadows at Edinburgh, table relating to 122.Silicates specific heat of 199 226. Silicium specific heat of 193. Silicotriamine 255. Silrer pyrophosphotriama tes of 4. Sohum and anylic iodide action of upon acetic ether 418. -and ethylic iodide action of upon acetic ether 396. -and methylic iodide action of upon acetic ether 411. Sodium-ethyl on the action of carbonic oxide on by J. A. Wanklyn 13. -action of mercury in conjunction with other metals on 129. Sodium-ethyl and carbonic oxide on the oxidation-products of the propione produced from by J. A. Wan klyn 126. Specific gravity determination of the average of heterogeneous liquids 455. Specific heat of solid bodies inrestiga- tiom of the by H. Kopy! 154. Spiller J. on the estimation of phos-phorus in iron and steel 148.Sprengel H.,on determining theweight of heterogeneoua liquids 455. St en h ou se J. on chryssmmic ether 324. -on styphnic or oxypicric ether 236. Stenhouse J.,and Miiller H. on the preparation of chrysammic acid 319. -on picric ether 235. Sdphate a new hydrated cupric dumi-num from Coimwall 130. Sulphates specific heat of 200 22'7. Sulphides specific heat of 196,225. Sulphur specific heat of 185. Sunlight contributiona to our knowledge of the chemical action of on sensitive photographic papers by R. Wright 33. T. Tetrethylammonium iododichloride of 146. Thallium-perchlorate on by H. E. Roscoe 504. Thallium pyrophosphotriamate of 8. Thorp W. on the reduction of the oxides of nitrogen by m&ilic copper in organic analysis 359.-and Chapmen see Chapman. Tilden W. A. a further contribution to the history of the periodides of the organic bases 145. Tin action of sulpuric acid on 439. Tin and coppi' allloya of see Bronze. Titano triamine 255. Tom sewage on the composition value and utilisation of by J. 13. Lames and J. H. Gilbert 80. Tricalcic phosphate solubilitr of 296. Tricarbinols 56. Tungstates specific hat of 200 227. V. Vderianate of amyl oxidation of 485. Vapour-density determinations tables for the calculation of by J. T. Brown 72. Voidings human amount of nitrogen, reckoned as ammonia and estimated vdue of total constituevlts in 96. Volume of liquids measurement of 455.W. 534 IYDEX. Wanklyn J. A. on tho coiistitutioii of' carbonic oxide 15. -on a new method of foriiiing organo- metallic bodies 128. -the oxidation-products of the pro- pioiie produced from carbonic oxide and sodium-ethyl 326. -and Chapman E. T. on magiie-sium 141. -on the oxidation of cthyla-mine 329. Warington R. jun. researches on the phosphates of calcium and upon the solubility of tricalcic phosphate 296. Water action of heat on ferric hydrate in presence of by E. Davies 69. Water supply of the metropolis during the year 1865-66 by E. Frankland 239. Watts J. on the strength of solutions of phosphoric acid of various varieties 499. Weight, atomic and atomic heat rcla-tions between 203. Wirchin J.and Kolbe H. prelimi-nary notice on phthalic aldehyde 339. Woodwardite a new cupric aluminum sulphate from Cornwall 130. Wright R. contributions to our know-ledge of the chemical action of sun-light on sensitive photographic papera 33. Zinc action of sulphuric acid on 435 437. -and copper alloys of see Brass. _I pyrophostriamate of 9. Zinc-ethyl formation of by the action of mercury and zinc on sodium-ethyl 129.

ISSN:0368-1769    

DOI:10.1039/JS8661900527

出版商:RSC    

年代:1866

数据来源: RSC

摘要:

534 IYDEX. ERRATA. Page. Line. 54 3 for publications read lectures. 56 11 from bottom , C4 c? J> 56 4 from bottom , CsO C,Op 29 56 2 from bottom ,,{ :64 } {S$> } )) 380 ,,CooBa } ,) { COL/} coo co:, 384 bottom line , isopropylic acid , isoyrvpylic alcohol. 339 ) desoxalic serifs , desoxalic orglyoxyloYd series. 392 , diopside { ~~Cao’Wgo” read diopside k;Cao”Mgo‘. 393 top line , ditanic rea.d dititanic. 303 ,) dolonnite { $GCao”Mgol’ read dolornite~00C~o//~r6of’. 393 for mercuroso-diammonic dichloridc read mercuroso-dinmmo-nic dichloric NH:C,Hg} NH ClHg 394 for porcelain clay of Passan { gg3’Al’’’204H02)iYread porcelain clay of Passau gg::~A~,o,HO,)~V. 394 jor Lanarkite { ~~2Pbo”2, Teud Lanarkite Ez2Pbot’2. PRINTED BY HARRISON AND SONS ST. MARTIN’S LAXY.

ISSN:0368-1769    

DOI:10.1039/JS8661900534

出版商:RSC    

年代:1866

数据来源: RSC