摘要:

GDiL AND MEUSEL ON PARAPFIN XLL-On Para$;n and the products of its Oxidation. By C. H. GILL and ED. MEUSEL. THEpara& used in this research was obtained from Messrs. Price. It had a melting point of 56O C. but by repeated crystallisation from carbonic disulphide the melting point was raised to 60" and over. It -was therefore a mixture of various hydrocarbons. By analysis it gave :-C. 85.5 per cent. H. 14.9 , As it did not seem to be quite settled whether paraffin is a marsh gas or an olefhe we endeavoured to clear up this point by the following experiments :-Paraffin digested with Nordhausen sulphulic acid blackens even in the cold but gives no soluble baryta-salt. When treated with English acid of ordinary strength it behaves in a similar manner.With oil of vitriol diluted with one-fifth its bulk of water it blackens slightly on being heated to 60"-80" C. for seventeen days but still gives no soluble baryta-salt. Sealed up in long tubes with hydrochloric acid gas and heated to temperatures varying from 50°-li)Oo C. for intervals of 18 hour to 15 days it undergoes no change of melting point AND THE PRODUCTS OF ITS OXIDATION. 467 and absorbs none of the gas. Aqueous solution of hydrochloric acid is likewise without effect. When heated or exposed to sunlight in contact with bromine and water it becomes soft at the same time that the bromine disappears. However all the bromine which enters into the para& does so by replacing hydrogen none combining directly as is shown by the following experiment :-About 4 grms.paraffin and 14 grms. water were sealed up with 2.518 grms. bromine and the whole was exposed to sun- light for three days by which time the bromine had all disap- peared a very white soft product being left. The tube was opened and the bromine estimated in the form of hydrobromic acid by a standard solution of soda. The bromine so found was 1.26 grms. which is sensibly equal to zo= 1.259. 2 Therefore neither bromine nor hydrobromic acid had combined directly. Paraffin in a state of fine division was treated in the cold and at temperatures above it8 melting point with solutions of hypo- chlorous acid of strength varying from 2 to 4 per cent. It underwent no alteration of melting point nor could any action be observed.Cetene CI6 HS2,as described by Carius combines with hypochlorous acid with evolution of heat. From these experiments together with the fact that paraffii occurs in mkeral oils not known to contain any hydrocarbons of the formula C H,," we conclude that paraffin i8 a marsh-gas and not an olefine. Paraffin resists the action of most oxidizing agents but yields to nitric and to chromic acids. Oxidation by Chromic Acid. 300 to 500 grms. of paraffin were placed in each of three large boltheads and were boiled with 120 grms. potassic di- chromate and 180 ps. of sulphuiic acid diluted with twice its volume of water. A small quantity of manganese dioxide was added to each flask to expedite the reaction which it does to a remarkable extent.After three or four days' boiling the chromic acid was completely reduced. The cakes on its surface were well washed and then boiled witaha very dilute solution * Ann. Ch. Pharm. cxxvii 195. 468 GILL AND MEUSEL ON PARAFFIN of carbonate of soda. By this meam a creamy liquid containing eoap and paraffin and a floating layer of unaltered paraffin were obtained. The lower liquid separated from the layer of paraffin wa8 raised to the boiling point and mixed with nearly its own bulk of spirit of 88 per cent. which caused the separation of the sllspended paraffin. After cooling the paraffin waB removed fiwm the surface of the alcoholic liquid; the latter which had gelathized was strained through linen ; and the solid portions were submitted to strong pressiire.The solid soap so prepared contained acids melting at 62" C. while that in the liquid gave acids melting at 40' C. By re-crystallisation of t,he hard soda soaps from weak alcohol the melting point of the contained acids was raised to 65" C. when suspecting the presence of some very high acid we converted the whole into lead salts and repeatedly exhausted these with strong boiling alcohol A considerable portion of them dissolved ; but some remained and after decomposition gave acids melting at 74-75' C. ; these by many times repeated crystallisstion from alcohol and ether at,last attained a constant melting point at 78' C. and were not then to be distinguished from pure cerotic acid prepared for purposes of comparison &om Chinese wax.A portion wa8 converted into a silver salt by the proceas recommended by Bro die," theii dried weighed and ignited- 0-1553gms. of salt gave 0.972 grms. silver that h 20.41 per cent. A portion of another preparation of the silver salt was burned in a current of oxygen and the following results were ob tained :-0.2179 gims. substaiicp gave 0.1983 , carbonic acid 0.2022 , water 0.456 , silver. By allowing two atoms of oxygen for each atom of silver we find 0-0135grms. of oxygen. These numbers correspond to the peweatages given below in the table which also shows the perceutagea required by the next higher and lower hornologue of cerotic acid :-* Phil. Trans. for 1848. AND THE PRODUCTS OF ITS OXIDATION.$69 CnH53Ag02. CzsHSIAgOa. Cslcnlat,ed. Brodie. Fomd. CBHsAgOp C .. 62-02 62-66 62.5 62.36 63-2 7 H .. 10-01 10.25 -10-31 10.37 Ag.. 21.46 20.9 20.69 20.92 20.34 0 .. -6.19 -6-21 -The acid was therefore cerotic acid. In addition to this cerotic acid there was a great number of the lower acids of the same series some solid and others liquid and volatile ; of these latter acetic acid was the most abundant. Oxidation by Nitric Acid. Paraffin as is well known is powerfully attacked by strong nitric acid with ultimate formation of succinic acid as pointed out by Ho fsta d t er.* When however the action is regulated by using a more dilute acid the result is different. About a kilogramme of paraffin divided into three portions was boiled with five or six times its volume of commercial nitric acid of sp.gr. 1.3 diluted with 19 volume of water. The action at first imperceptible gradually became stronger red hmes were evolved and an odour like that of butyric acid developed itself. The action was continued till the paraffin was decidedly soft when cold. The three cakes thus obtained were washed out with dilute alkali and the paraffin left was again treated with nitric acid and so on till a sufficient quantity of crude soaps was obtained on which to work. These were all boiled with water and alcohol was then added as before described for the purpose of separating suspended paraffin. The soaps which crystallised out of the alcoholic liquid mere after strong pres- sure again and again crystallised from dilute spirit till they gave acids melting at 56" C.These acids were very brown; we therefore distilled them in a current of superheated steam whereby their melting point wa8 raised to 64O C. and their colour was entirely removed. They were then converted into led soaps as those procured from the chromic acid process of oxidation ;only the final cry- stallisation from alcohol and ether wits not continued after the melting point had been raised to 76OC. * Ann. Ch. Pharm. xci 326. GILL AND MEUSEL ON PARAF'FIN A portion of this still impure acid was converted into a silver salt which was found to contain 22-01 per cent. Bilver. The acid nsed was therefore probably cerotic acid containing a portion of some lower acid as its melting point indicated.As cerotic acid had been proved to be the product of the oxidation of paraffin by chromic acid we did not deem it worth while to attempt the further purification of this portion our point being established. A large quantity of the lower acids of the same series waB obtained at the same time as the cerotic acid including among the lower terms acet'ic butyric valeranic and cenanthylic acids which were separated in the ordinary way by fractional satura- tion and distillation then converted into silver salts and the percentage of silver in each salt determined. We wish to remark that cenanthylic acid was present in considerable quantity. The nitric acid which had been used for oxidising the paraffin was found to contain Rome bodies in solution.It was sub-mitted to distillation when a strong odour of prussic acid was noticed. The presence of this body was then proved by dis-tilling it out at a very low temperature into water and apply- ing the ordinary tests. As the nitric acid became more concentrated another reaction set in ; we therefore stopped the distillation neutralized the remaining acid with soda and added ,solution of basic nitrate of lead till no further precipitate could be obtained. The precipitate thus produced gave on decom-position by sulphuretted hydrogen an acid melting at 11'7' C. forming soluble salts with sodium potassium and ammonium and insoluble ones with silver iron lead and barium in pre-sence of ammonia and alcohol.Thus the barium salt pro- mised an easy means of separating the acid or acids ;but we found that it was impossible to remove the barium completely by sulphuric acid as an acid barium salt was always formed which was not decomposed by dilute sulphuric acid. We therefore precipitated the acids as ferric salts by a solution of ferric chloride then extracted them by boiling with ammonia coucentrated the liquid and threw down the acids with nitric acid. They had a melting point of 106OC. They were treated by Ar p pe's process" (slightly modified) four times whereby we obtained two acids the one nearly pure succinic acid melt- * Am. Ch. Pharm. cxxiv p. 86. 471 AND THE PRODUCTS OF ITS OXIDATION. ing at 172' C. and giving a rJilver salt with 63.4 per cent.of silver (succinic acid melts at MOO and gives a silver salt with 64 per cent. of silver); the other anchoic acid melting at 117O -118' C. and givingthe following numbers on combustion:-0.1921 gr. substance gave 0.4021 gr. of carbonic acid and 0.1451 gr. water corresponding to the percentages given in the following table :-Sebacic. Anchoic. Buckton. Found. Suberic. Calculated. Calculated. c . 59-4 57-44 57.02 57.1 55.17 H .. 8.91 8.51 8.68 8.38 8.04 A silver salt yielded from 0.1186 gr. substance 0.0636 Ag. = 53.62 per cent. Ag. (theoretical percentage 53.3). These numbers a8 will be seen agree closely with those given by B u ckt on,' and the properties of the acid are identical with those given by B uckt o n for anchoic acid.We regard this acid as being a product of the oxidation of the cerotic acid previously formed from the paraffin. Commercial nitric acid diluted with four times ih volume of water acts very slowly on paraffi but forms in the course of twelve days' boiling a small quantity of a fatty acid which can readily be purified so far as to melt at 73"C. We were not able to observe the simultaneous formation of any other product either among the bibasic acids or the volatile monobasic ones neither was there any prussic acid formed. From the results of our experiments above detailed we con- clude that parafk is a mixture of hydrocarbons homologous with marsh-gas some of which have a carbon condensation of not less than C2,. These experiments were carried out in the laboratory of University College London. * Chem. Soc. Journ. vol. x p. 16'7.

ISSN:0368-1769    

DOI:10.1039/JS8682100466

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

472 XLIL-QOn th Hydride of Butyro-salicyl and Butpk Coumaric Acid. By W.H. PERKIN, F.R.S INa previous communication* it has been shown that in the formation of coumarin by means of acetic anhydride and hydride of sodium-salicyl the fist product of the reaction is the hydride of aceto-salicyl and that thils body is subsequently transformed into coumarin by the separation of a molecule of water. Eaving obtained homologues of coumarin by substi- tuting other anhydrides for the acetic it appeared desirable to follow up the changes which take place in the formation of one of these new products and at the same time to further esta- blish its relationship to ordinary coumarin by the production of a new coumaric acid. I have therefore investigated the changes which take place in the formation of butyric coumarin and ita corresponding acid.Ifydm'de of Butyro-salicyl. A solution of butyric anhydride in anhydrous ether is left in contact with hydride of sodium-salicyl for two or three days the reagents being used in equivalent quantities. The ethereal solution is then filtered off from the butpate of sodium formed and agitated with a small quantity of a dilute solution of car-bonate of sodium. It is then dried over anhydrous carbonate of sodium and distilled. After the ether has passed over the temperature gradually rises but no very steady boiling point is observed ;the principal product however comes over at about 260°-2700 C. and is collected apart. Three combustions of this body gave the following numbers :-I.-1925 of substance gave .4835of CO, and *lo96of H,O. 11. -2002 of substance gave -5026 of CO, and *1116of H,O. * Vol. vi p. 181. PERI(IN ON HPDRIDE OF BUTYRO-SALICYL,ETC. 473 111. *2508 of substance gave 06289of CO, and 01392of H,O. These results give percentages agreeing With the fomuIa as the following comparisons show :-Theory. Experiment. 7- /I. IT. 4 111. C, ...... 132 68-75 68.50 68.46 '68*38 H, ...... 0 ...... 12 48 - 6.25 25.00 6-32 - 6-19 - 6.16 - 192 1oo*oo The product. therefore represents the hydride oT aalicyl with an equivalent of hydrogen replaced by butyryl its formation being analogous to that of the hydride of aceto-salicyl. C0,H CO,H CHO = ($$;op) (c6$)0) + c:H;O}O 4-c*:;o}o* Hydride of sodium-Butyric Hydnde of 3utyrate of SalicyL anhydride.butyro-salicyl. sodium. The hydride of butyro-salicyl is an oil boiling at about 260'-270" C. It has a slightly butyric odour mixed with that of the hydride of salicyl. It is soluble in all proportions in alcohol and ether. With bisulphite it appears to decompose into butyric acid and hydride of salicyl the latter combining with the bisulphite. A strong solution of hydrate of potassium decomposes it immediately forming a solid mass of the hydiide of potassium-salicyl and butyrate of potassium; this decomposition is attended with a considerable elevation of temperature. Acetic Anlydride and Hydride of Butyro-sulky l A mixture of the hydride of butyro-salicyl and acetic anhy- dride when heated in a sealed tube to 140° or 150°C.for a few hours becomes slightly brown. On opening the tube and leaving the product in contact with water for a day or two 474 PERKIN ON HYDRIDE OF BUTYRO-SALICYL crystals separate ;these when pressed between bibulous paper and twice crystallised from alcohol gave the following numbers on analysis :-02094of substance gave- 04524 of C,O, 01057of H,O. These results give numbers corresponding with those required by the formula C,,=l,O6 as the following comparbons will show :-Theory. Experiment. - C13...... 156 58.64 58.92 H14 .... 14 5-26 5.60 0 ...... -96 36-10 -266 100=00 This formula is that of the compound of the hydride of aceto-salicyl and acetic anhydride.Its identity was confirmed by the determination of its melting point. In the formation of this product the radical butyryl has been replaced by acetyl a mixed anhydride being probably formed at the same time thus- Hydride of butyro-Acetic Hydride of aceto-salicyl and Aceto-butyric mlicy1. anhydride. acetic auhydride. anhydride. Formation of Butyric Coumurin from Hydride of Butyro-salicy1. Hydride of butyro-salicyl when distilled alone does not appear to yield a coumarin but if boiled with a mixture of butyric anhydride and butyrate of sodium for a short time washed from saline matter with water and then distilled the last third of the distillate will be found to solidify on cooling. This solid product when separated fiom oily matter by pressure between bibulous paper and then crystallised from alcohol is AND BUTPRIC COUMARIC ACID.found to be pure butyric coumarin possessing the correct melt-ing point and characteristic odour. The formation of this body is therefore perfectly analogous to that of ordinary coumarin. Butyric Coumaric Acid. Butyric coumarin &solves in boiling aqueous hydrate of potassium. Upon evaporating this solution an oily layer forms and if the liquid be then allowed to cool this oily compound becomes a hard tenacious masg from which the alkaline soh- tion may be easily decanted. This product is apparently a compound of one molecule of coumarin with one of hydrate of potassium and is therefore isomeric with the potassium salt of a butyric cvumaric acid.On heating this body in a dish it fuses and boila up ;it then becomes more pasty and frothy and soon breaks up into soft masses. This fused product is perfectly noluble in water and on the addition of' hydrochloric acid to its solution it beconies a pure white mass of minute crystals. To separate any unchanged butylic coumarin from this product it was dissolved in a little ammonia filtered thrown down with acid washed well with water and dried. Thus obtained it still contains a small quan- tity of butyric coumarin. This is easily separated by digestion with chloroform in which the new body is very difficultly soluble. It is then further purified by crystallisation from dilute alcohol. A combustion of a specimen dried at loooC.gave the following numbers :-01819 of substance gave- 04556of CO, and 01058 of H,O. These numbers give percentages agreeing with the for-mula-C,,Hn*, as the following comparisons will show :-Theory. Experiment. C,,.. ..*. 132 68-75 68-30 H, .... 12 0 ...... 48 6.25 25.00 6.46 192 100*00 476 PERKIN ON HYDRIDE OF BUTYRO-SALICYL ETC. This product ia evidently butyric coumaric acid the third ot the aeries. C H 0 coumaric acid. C,,H,,O propionic coumaric acid (not known). CIIH,,O butyric coumaric acid. It is also isomeric with the hydride of butyro-salicyl. Butyric coumaric acid crystallises in flat prisms having a brilliant lustre. It hses at about 174O C. but undergoes slight decomposition at that temperature.It is extremely rJoluble in alcohol and ether but difficultly so in water and chloroform. It does not colour the solutions of the persalts of iron. It is but feebly acid in its Characters but will decompose a boiling solution of carbonate of sodium with effervescence. Like ordinary coumaric acid it forms only monometallic derivatives. Sodium salt.-This body is prepared by boiling the acid with a solution of carbonate of sodium keeping the a.cid in excess. The aolution is then allowed to stand for a day filtered and evaporated. It is a crystalline and very soluble salt. &lveT salt.-A solution of the sodium salt gives a pale yellow precipitate with nitrate of silver ; this however suddenly changes becoming nearly white and crystalline.It is slightly soluble inwater and also in the above sodium salt. It requires careful drying for analysis as it is apt to blacken at 100"C. whilst a lower temperature does not appear to be sufficient for its complete desiccation. It gave the following results upon analysis :-I. 02012 of substacce gave- -3235 of GO, 00706 of H,O and 00733of Ag. 11. 01338of substance gave- *0480of Ag. These numbers give percentages agreeing with the for-mula-C11H11Ag039 as the following compaiisons will show :- DITTRIAR ON THE VAPOUR-TEK§ION ETC. Theory. Experiment. -__c__ -4 J. 11. C, ...... 132 44.14 43.85 -H, ...... 11 3.68 3.89 -Ag ...... 108 36-12 36-43 39-87 03........ 48 16.06 --299 100*00 Ammonium Snlt.-Buttyric coumaric acid dissolves easily in ammonia but the resulting solution when evaporated decom-poses leaving nothing but the acid behind. From these results there cannot be any doubt I think that the new cournarins are really true honiologues of the natural body.

ISSN:0368-1769    

DOI:10.1039/JS8682100472

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

DITTRIAR ON THE VAPOUR-TEK§ION ETC. By W. DITTMAR. RY the expei*iment,al and speculative labours of H. Kopp we have been made acquitiiited with a number of regularities regarding tlie correlation of chemical composition and boiling point in carbon-coinpounds. These regularities although liable to exceptions and in many cases only approximately in accordance with observation clearly s!iow that the constants determining the iuterdependence in these compounds of temperature and vapour-tension must be dependent on and deducible from the atomic constitution of the inolecule. It will take an enormous amount of experimental data such as can only be firrnished by the co-operation of a great number of investigators before an approach towards the discovery o€ the great law expreming the correlation of chemical constitation temperature and vapour- tension will be possible.But chemists should not shrink from t'rying to accuiiiulate these experimental data the less so as even a mere empirical knowledge of the tension-curves of a consider- alde number of conipounds would be invaluable as a means for ciiaracterising them and thus place in our hands a most power- ful instrument of research. VUL. nr. 2 31 478 DITTMAR ON THE VAPOUR-TENSION OF FORMATE A mongst the different boiling-point regularities pointed out by Kopp there is one which it seemed to me might perhaps at the expense of comparatively little experimental work be expanded into a proposition regarding the dependence of vapour- tension generally on chemical constitution.We know that in the homologous series of ethers formed by the union of fatty alcohols and fatty acids a difference of n x CH in the molecules of two terms corresponds to ?a x a constant difference in the boiling points and that consequently any two or more metameric ethers of the group must have the same boiling-point. .Hence it would appear that the tension- curves of each group of metameric ethers have at least one point in common and that in case of all groups this point always corresponds to the accidentally chosen pressure of 760 mm. It is certainly not going beyond the legitimate limits of induction to coiijecture that possibly each sizch group has only one common tension-curve. In order to test this hypothesis I decided upon undertaking a comparixon within a certain range of temperatures of the tensions of the best known metameric ether6 of this series namely of formate of ethyl and of acetate of methyl.I have made two independent seiies of com-parisons employing in both of them methods which were in principle the same as Magnus's only simplified so as to bring them within reach of my resources. First Series. t In these experiments which were finished about a year asgo,the following apparatus wa8 used:-A U-tube of about 10 mm. inner diameter was drawn out at a short distance from one end so as to produce a narrow neck into which was ground a well-fitting glass stop- per. Each of the limbs wa8 provided with a millimetre scale.The U-tube was placed iii a vertical position partly filled with mercury and the levels of the mercury in both limbs were read in order to find out which points in the two scales were situated in the same horizontal plane. More mercury was now added through a so as OF ETHYL AND OF ACETATE OF METHYL. to bring its level in b up to very near the neck. A quan-tity of formate of ethyl was poured into b boiled for a short time and then the stopper was inserted so as to shut up a part of the liquid within the apparatus and leave the rest in the funnel b. Some mercury was now poured iiito this funnel a spiral of steel wire introduced and at last the opening closed with a well-fitting cork so as to press the spiral against the top of the stopper and at the same time hermetically close this end of the apparatus.At last the greater part of the mercury contained in limb a was taken out by means of a pipette. A similar apparatus was charged with acetate of methyl and the open ends of both were connected with the same syphon-barometer a bracch off the connecting tube leading to a syringe by means of which it was possible to rarefy or condense the atmosphere within the apparatus. The barometer was made out of a Frankland’s gas-apparatus and as the “pressure-tube” of this apparatus was more than 1metre long it was possible by means of it to measure pressures sorne-what exceeding that of the atmosphere. To execute the determinations both U-tubes were plunged iiito the same water-bath (care being taken to make the tubes as exactly as possible vertical and to bring the two ethers into close proximity to each other) and exposed to the desired temperature.The pressure within the apparatus was by means of the syringe adjusted so as to produce a convenient volume of each vapour ;the water in the bath continually kept iii motion by means of a current of carbonic acid; and after the temperature had been kept constant for a sufficient time to ensure equilibrium of temperature the four levels of mercury in the U-tubes and then the two in the barometer were read off and thus all the data were obtained for calculating the tensions of bot>h vapours. Before giving the results I will describe the methods used for preparing and testing the substances operated UpOL The formate of ethyl was prepared according to Lowig’s method i.e.by distilling oxalate of ethyl (1mol.) with dehy- drated oxalic acid (1mol.). In this process the temporarily formed ethyl-odic acid breaks up into CO and formate of ethyl. The crude formate was purified by washing with water then dehydrating with chloride of calcium and at last distilling it in an apparatus constructed so that the vapours before reaching 2M2 480 DITTMAR ON THE VAPOUR-TENSION OF FORMATE the condenser had to pass through an ascending tube kept at about 56" C. The distillate was collected in fractions and the fractions were separately tested by titration with Rtandnrd baryta-water when it turned out that the best fraction still colltained about 1per cent.of impurities. After ail unsuccessful attempt to remove the latter by repeated washing with water and drying with chloride of calciuni it was at last got rid of by digestion with and distillation over dehydrated sulphate of copper. The ether thus purified giving on titration numbers corresponding to 100 per cent. of real forrnate was considered sufficiently pure and used for the tension experiments. To prepare the acetute of methyl a kind of purified wood- spirit which at the time was to be had in commerce under the name of '' Eschwege's wood-spirit," Rerved as raw material. The spirit was first dehydrated by means of lime and then by distillation with its own weight of dehydrated oxalic acid clianged into crystalline oxalate.The oxalate of methyl was by means of a powerful press freed from mother-liquor and for flirther purification heated to near its boiling point in a current of hydrogen when however no liquid distillate was obtained. This oxalate was originally intended to be next changed into methyl-alcohol but I ~oonfouiid out and availed myself of a process for directly converting it into acetate. If glacial acetic acid arid oxalate of methyl are heated together there is scarcely any action observable; if however a small quantity of fuming hydrochloric acid be added a complete double decomposition takes place and acetate of methyl and oxalic acid are produced. The following modus operandi was ultimately adopted :-lo0 grs. of oxalate 100 grs. of glacial scetic acid 8 C.C.of (nearly saturated) hydrochloric acid were heated together in an apparatus in which the vapours formed had before reaching the condenser to pass through an ascending tube placed in an open water-bath. The intermediate con-denser was first for a short time kept cold and its tenipera- ture then raised to mid kept at about 56" so that the acetate distilled over at the rate at which it was formed. The crude acetate was shakeii with a solutiori of acetate of soda (wliicli dissolves less of the ether than pure water does) kept in con- tact with and distilled over recently fused acetate of potash and finally again distilled with fractional condensation at about 56O. The &stl fraction of the dist'illate titrated a few OF ETHYL AND OF ACETATE OF METHYL.tenths less than 100 P.c. and was used for the tension-deter- minations. The following table gives the results of a series of tensioii-determinations executed in t,he manner above described :-Vapour-tension reduced Difference of temperature expen-Centigrade. No.o! Temperature to 15" C.* $-a,+ :orresponding ment. to $-a. Formate Acetate f. a. --I____ ---mm. mm. mm. 1 16 9 174.1 165.3 8.8 } 0'9O la 16*75 174.5 165.2 9-3 2 25 *O 257'7 243.9 13.8 1.2 3 28 65 } 300.3 282.3 { 17.7 } 1.5 3a 28 .6 18'2 4 38.35 435.8 421.7 14.1 0.7 5 50 -1 670.9 663-8 7*1 0.3 5a 50 .6 680'7 G7P5 8 '2 0'3 6 56 .3 1-5 0.06 } 823.7 823'3 { 6a 66 -2 -0.7 0'03 From these numbers it appears that the tension of the speci- men of formate always exceeded that of the acet'ate; that from the temperature of' 16' upwards the difference of the tensions increased until it attained a maximum and then decreased again so that at 56.2" it became practically = 0.It would have been extremely interesting to see by a few experiments at higher temperatures whether the tension-curves fiwm 36' upwards continue to coincide or deviate again. An attempt towards this end unfortunately failed arid as I had just then to suspend work for some time I was not in a position to repeat the experiment. Secoid Se93ies. Since Regnault has shown to how great an extent the vapour-tension of n substance ma,y be affected by the admixture of even small quantities of impurities it would be hasty to * The numbers in these two columns can only be considered as rough approxima- tions ; see end of memoir.t. Respecting the numbers in this column it is to be remembered that they are independent of the manorneter-readings. 4132 DITTMAR ON THE VAPOUR-TENSION OF FORMATE apply to the ideul substances results arrived at in experiments on one set of specimens. In resuming my experiments therefore I considered it necessary first of all to prepare new specimens improving upon the methods of preparation and analysis so as to bring the eubstaiices as nearly as possible to the state of absolute purity. I chiefly directed my attention to the titration of the ethers and tried to give this process a higher degree of precision than I had previously been able to attain.The chief sources of error in the analysis of ethers by means of standard alkalies are those introduced :-1. By the presence of free acid. 2. By the action of the alkalies on glass. 3. By the uncertainty in case of weak organic acids in thc determination of the point of saturation. Finding it extremely difficult to keep at Ieast the formate of ethyl neutral for any length of time I tried to find out a process for determining the amount of free acid in the ethers and learned that this can be effected by means of a standard solution of ammonia containing about 2 eq. (-$?-) grammes per litre. This liquid acts so dowly upon the ethers that in employing it it is easy to hit the point at which the free acid is saturated and the ether begins to be acted upon.Respecting the second source of error it was found that in case of the two compounda in question it can practically be avoided by effecting the decomposition of the ethers (with alkali) in the cold. I have satisfied myself that after a few hours’ standing the decomposition is quite complete. Caustic baryta and soda act about equally well ; the latter however was found to offer .this advantage that the liquid to the elid of the titration remained perfectly clear while in case of baiyta there was generally a slight precipitate formed which carried down the litmus and greatly diminished its sensibility as an indicator of alkalinity. A solution of pure soda (made of metal) containing about 4equivalent in grammes per litre and freed from CO by admixture with a slight excess of pure baryta was ultimately found to be the most convenient standard alkali for the purpose.Regarding the third source of error I had no difficulty with the formate the point of neutrality being quite sharply defined. In the titrations of the acetate there was some degree of uncer-tainty whivli I mas not able entirely to remove. In order to OF ETHYL AND OF ACETATE OF METHYL. reduce the error hereby introduced to a minimum the point of saturation was in each case determined several tiine8 by succes- sive addition of measured quantities of standard hydrochloric acid and saturation with standard alkali and the mean of the results was taken.* In the preparation of the formate of ethyl for the new deter- minations I first proceeded in the same way ah before with this difference only that the crude formate was previous to being washed with water first shaken with ammonia when a small quantity of oxamide separated out.The washed ether was dried first with chloride of calcium then with dehydrated sulphate of copper distilled with partial condensation at 55'-56" and collected iii four fractions. Fractions I and 111 when analysed by titratioii with baryta gave numbers corresponding to respectively :-I. 111. 98-5 99.86 per cent. of real formate. On titratioii with ammonia it was found that while fraction I. contained only a trace of fi-ee acid fraction 111. contained a quantity corresponding to 1.4 p.c. of (decomposed) formate so that in reality it was not any more pure than fraction I. Seeing the impossibility of removing by mere wmhing with water the last traces of impurities I tried to get rid of them by means of concentrated sulphuric acid. The ether was cautiously mixed with about one-fifth of its volume of distilled sulphuric acid and the mixture was distilled from a paraffin bath at a temperature below 100O. The strongly acid distillate was treated with recently fused formate of potash and again dis- tilled. In both distillations tlie vapour underwent partial condensation at 56". The final product was found free from acid and titratecl 100 p. c. (taken 922 mllgs. ; found 922.3). It was preserved for the tension-determinations.Immediately before use it was tested with standard ammonia when it was found to contain a quantity of free acid corresponding to &,th Jt I hoped to be able completely to eliminate the uncertainty in the titration by decomposing the ether with excess of baryta precipitating the excem with C02 with the aid of heat and determining the amount of carbonate precipitated. But finding that a solution of neutral acetate of barium (prepared by precipitating an acid solu-tion of the salt with alcohol) when warmed and treated with C02 gave a precipitate 1had to reject this method. of its weight of deconposed formate. I did not think that this small amount of impurities could materially affect the results and therefore used the ether as it was.In the preparation of' the acetate the former process was improved upon in so far as the mixture of oxalat,e of methyl acetic acid and hydrochloric acid was heated in a paraffin bath in order to avoid overheating which might possibly have led to the formalion of formate of methyl. The crude acetate was this time not washed but at once poured on a large quantity of recently fused acetate of potash the mixture allowed to. stand for some hours arid then distilled from A paraffin-bath with partial condensation at 56-58'. The distil-late was tested for and found to be free from chlorine and oxalic acid but titration showed it to contain 2.6 p. c. of other im- purities. These were easily removed by successive distillations firstly with concentrated sulphuric acid secondly with recently fused acetate of potash the operations being conducted exactly as in the case of the formate.The ultimate product was found on titration with pure soda to contain 99.8 p. c. of real acetate of methyl. (Taken 931.6 mllgs. ; found 929.4.) It was perfectly neutral and remained 80 up to the time of its being used. The improvements introduced in the physical part of the work consisted chiefly in this that the two tubes containing the ethers were made to communicate so that the two vapours pressed against each other through a continuous mass of mercury. The determination of the difference in ten- sion was thus reduced to that of the differ- ence of level of two menisci a measure- ment which was effected by means of a cathetometer constructed by Dr.Meyer- 8 t ein of Giittingen. The water-bath used consisted of a rectangular iron case provided on two opposite sides with plane glass plates parallel to which the system of tubes coil- taining the ethers was placed. An apparatus shaped like fig. 2 was F f.C L 2 niade out of glass txbiiig of about 12 mm. OF ETHYL AND OF ACETATE OF METHYL. inner diameter. It was half filled with pure mercury the open ends connected with ail air-pump and after exhaustion the mercury was boiled for a considerable time. After cooling a and b were drawn out iieitr the ends so as to produce very narrow-necked funnels and more mercury was poured into the apparatus through the middle tube the well-known precautions being taken to avoid as much as possible the formation of air-bubbles.Of the few bubbles formed none were seen to travel over to the side tubes. About 18c. c. of formate of ethyl were now introduced into one of the side tubes and the end of this tube was drawn out and broken off so as to produce a capillary orifice; the ether was then kept in ebulli- tion for some time to expel the air and the end of the tube sealed up. After the other side-tube had in the same way been charged with’ acetate of methyl the greater part of the mercury contained in the middle tube was taken out with a pipette and the end of this tube was closed with a perforated cork through which a glass tube passed provided at tlie end with H cemented-on two-way stopcock of steel with two appendages shaped 60 as to form one-half of a ‘‘ Regnault’s coupling.” The a,pparatns was placed in the water-bath and to one branch of the two-way cock there was coupled on a glass tube with soldered-on branches connected severally by means of black india-rubber tubing with a syphon-manometer a hollow copper ball of about 5 litres’ capacity and a syringe constructed so as to serve for exhausting as well as condensing.The two-way cock afforded the means of making the TV-tube comniunicate at will with the atmosphere or the manometer or of shutting it off from either and served to regulate the pressure within the apparatus. The object of the copper ball was to eliminate the influence of slight leakages in the joints and of sudden changes in the temperature of the atmosphere.In the experiments at pres- sures exceeding one atmosphere the cork in the middle tube was fast<ened down with wire arid the india-rnbber joints were made pressiwe-proof by bandaging them over with strips of calico tied on with wire. The modus ope~ancliin the tension-determinations scarcely needs description. After the desired temper:tture had been established in the water-bath and the pressure within the apparatus properly adjusted tlie temperature was kept constant niici unit‘orni by 4&6 DITTMAR ON THE VAPOUR-TENSION OF FORMATE well known means; and while one person kept the water in the bath continually in motion and observed the thermo- meters another by means of the cathetometer took the levels of the menisci in the ether-tubes first in a then in b and then again in a.In most cases the result was checked by altering the pressure within the apparatus keeping the temperature as nearly as possible constant and taking another series of readings. The temperatures up to 50° inclusive were determined with a very sensitive thermometer divided into fifths of degrees obtained from Geisler in Bonn and corrected for a difiplacement (of + 0-2O) in the zero-point of the instrument. The higher temperatures were taken with an ordinary lab_oratory-thermometer divided into whole degrees. This second thermometer had been cornpared with Geisler's at a series of temperatures below 50" ; and its 'indications having been found to exceed the latter by a constant difference of 0*So its readings above 50"were also corrected by deducting 1".All this is of course no perfect guarantee for the exactness of the temperature-determinations ;* but considering t4hat as is seen from the table below the differences of tension vary only very slowly with the temperature a rectification of the errors in the scale of temperatures would probably not very materially alter its position towards that of the differences of tension. The following table gives the resutts of thirty experiments carried out in the way described. "t" stands for the mean of the temperatures observed during the respective experiment ; '6 A t " for the maximum deviation from this mean ; "f"for the ZeveZ of the meniscus in the forniate-tube ; ''a" for that in the acetate-tube.? Consequently the column headed ''f-a," gives the excem of the tension of the formate over that of the acetate measured by a column of mercury of to; the followiiig column gives the fjame difference of pressure in mercury of 15"C.f I hope before long to be able to furnish a correction table for the temperatures given founded on a calibration of the instruments or on comparisons with a "weight-thermometer." C As observed with the cathetometer the zero-point of which was at the upper end of the scale. 487 OF ETHYL AND OF ACETATE OF METHYL. ExperimentNO. t. A t. f-a. mm. f-a. -educed to 15O. -_I_ 1 18.0 0 15.35 15-35 2 18.0 0 15-22 15-22 3 4 23'3 24.4 0.3 0 18-408*02(?) 18*02(?) 18.40 5 24'4 0 16.77 16.77 6 26'3 0.03 17-15 17.15 7 89.5 0.07 21.67 21.61 8 29.6 0.03 21-75 21-69 9 29-75 0.05 21.85 21.79 10 29.8 0 21.70 21-64 11 34-4 0 24.90 24.81 12 34.4 0 25-10 25-01 13 39.3 0-07 28-47 28-34 14 38-9 0.1 28.00 27.87 15 43.5 0.1 31-75 31.59 15a 43.4 ..30.75 30'59 16 42.95 0-05 31-01 30-85 17 43.0 0.03 30-80 30'64 18 48.55 0-05 35-52 35-29 19 48% 0 36-37 36'14 20 55.0 0 40-87 40.58 21 55'15 0.05 41.75 41-46 21a 55-35 0.05 41.25 40.96 22 54.05 0.1 5 38.80 38.51 23 53.7 0.03 39.40 39'1 1 24 65.2 0.2 40.55 40.26 25 54'4 0'03 39.95 39-66 26 63.7 0 48.35 47.91 27 63.7 0.03 48-20 47-76 28 69.0 0 53.27 52.74 29 78.95 0.05 59-90 59-18 30 7a75 0.15 60.80 60'09# It will be seen that the results of this series of determina-tions do not agree with those of the first.The differences cannot be accounted for by the more refined method of' measurement employed in the second series but must be owing to the different degree of purity of the two sets of sub-stances used. Feeling sure that the ethers used in the secoGd series of determinations were at least very nearly pure I think we may safely assume that the results arrived at would sub-stantially hold also for the ideal substances and conclude that. at temperatures between 19O and 80' C the vapour-tension of formate of ethyl is greater than that of acetate of methyl * The ahsolute amount of the tensions at this temperature was about two atmo-spheres.4aa DE LA RUE AND MULLER ON A and that the difference is the greater the higher the tempera- ture.” I cannot conclude without returning my cordial thanks to my friends,Mr. Cranst on and Mr. r) ewar,for the valuable assistance they have frequently given me in the course of this research. University Laboratory Edinburgh.

ISSN:0368-1769    

DOI:10.1039/JS8682100477

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

DE LA RUE AND MULLER ON A XLIV.-On a New Form of Constant Batteiy. By WARREN DE LA RUE and HUGOMULLER. ALTHOUGH there are several voltaic batteries which possess the esseptial quality of continuous action yet when a very large number of elements is required it is found that they are all in some respects inconvenient. For example it is very troublesome to charge a battery of several hundred elements in which two liquids and a porous cell are required; moreover diffusion of the two liquids eventually takes place and produces a great amount of local action whenever the battery is left for a long time with the electrodes disconnected. We believe therefore that the instrument which we herein describe will be foiind useful to the chemist and the physicist as a ready source of dynamic electricity always at hand and that especially where from a few hundreds to several thousand elements are requisite it will be found to be valuable handy and compact.In its construction no porous cell is needed and the electrolyte is solid and very nearly insoluble so that practically the electro-positive metal is scarcely attacked even when the elements are left im-mersed with the electrodes disconnected for several weeks. We may state that this iristrurnent was designed for the express * A few of the values for f-a were reduced to differences in temperature the calculations being founded upon the ahsolute determinations of the tension of acetate in series I. ; the results which I give only as rough approximations were us follows.The temperatures of equal vapour-tensions are respectively For formate .. . . 20 26 '33 43 53" * 54.9 , acetate .... 21 7 27.8 34.7 44.5 54O.4 56.3 Difference . . . .. 1.7 1.8 1.7 1.5 1",4 1'4 * According to H. Kopp. NEW FORM OF CONSTANT BATTERY. object of facilitating experiments on the direct voltaic discharge in highly rarefied media that is as an ‘‘intensity ” rather than as a ‘‘ quantity” battery. It will be recollected that a battery consisting of ten of our elements was described and exhibited in action at the meeting of our Society 011 February (5th last. At the soir4e of the President of the Royal Society on March 7th one liuiidred elements were shown in action; and at that of the Chemical Society on March llth and on several other occa- sions two hundred elements were exhibited.But we have delayed giving a more detailed account of the instrument for publication until we had an opportunity of making fur- ther experiments with it and more especially of testing its electromotive force. 111 om battery the generating or electro-positive metal is zinc which it is better to amalgamate although it is not essential to do so; the negative metal is silver aiici the electrolyte solid chloride of silver thewhole being immersed ill a solution of chloride of sodium or chloride of zinc. The solu- tion we generally use contains 25 grammes of common sslt to t~ litre of distilled water (219 grains to a pint). It is not clesirable to use common water for dissolving the chloride of sodium as the carbonates prcseiit cause a cloudiness by precipitating the zinc as carbonate when the battery is in action.The form of the battery which we have adopted is represented in Figs. 1and 2 but where a very large number of elements is wanted it is more economical and convenient to employ a rnodi- fication presently to be described and shown in Fig. 3. The zinc elemeiit is formed of Belgian zinc wire (English zinc being too impure to be used advantageously) 2+ inches (6 ceutinietres) long and 0.2 inch (5.1 mm.) diameter. The electro-negative element coiisists of a wire of pure silver 0.03 inch (0.77 mm.) in diameter ;and round this is cast* a cylinder of chloride of silver 0-22 inch (5.6 mm.) in diameter. The silver wire projects about 0.2 inch (5 mm.) beyond the bottom end of the chloride of silver * In making these cylinders a mould which was designed for casting rods of lunar caustic (nitrate of silver) was found to be convenient.The mould contained a series of receNe8 which permitted of several rods being cast at a time. The silver wire was held firmly in the centre of the cylindrical recess by passing through ;t hole in the bottom of the mould and by a series of arms projecting over the mouth of each recea at a sufflcient distance to permit of the fused chloride being poured i~tothem DE LA RUE AND MULLER ON A and about 1; inch (3.8 centimetres) beyond the top end of it so as to permit of its connection with the zinc of the next pair of elements.The cells are conveniently formed out of 1-ounce vials by cutting off the necks with a diamond or an ignited spliu t-coal. The zinc and chloride of silver rods pass through and are sup-ported by a lath or bar of varnished mahogany A A which is pierced for that purpose. The ends of this bar are also pierced wit11 two larger holes through which the two supporting glass rods B B pass ; it slides up and down these rods freely and is retained in any required position by means of the vulcanized caoutchouc collars C C on which it rests these grip the rods 23 B with adequate firmness to support the bar but at the same time permit of its being moved up and down with suffi- cient freedom to immerse the elements partially or wholly a8 in Fig. 2 or to raise them entirely out of the liquid as in Fig.1. ‘l’he raising is conveniently performed by placing the two fore- fingers of each hand under the collars C C and pressing the thumbs on the top of the glass rods B B ; the lowering of the bar can be effected by pressing down the two ends. These glass rods should not be varnished on that portion over which NEW FORM OF CONSTANT BATTERY. the vulcanized collars have to slide as the varnish cawes too much friction and a liability to jerking ; below this point they may be varnished with advantage. They are cemented into the base of varnished mahogany D D in which is made a serieg of recesses to fit the cells E and keep them in their places. This base rests on feet of vulcanite to increase the insulation.The rods of zinc and chloride of silver are prevented fi-om falling through the holes in bar A A by means of heads formed in the zinc by hammering the wire while it is held in a properly shaped tool and on the chloride of silver by suitably shaping the upper end of the mould into which it is cast ; a collar of caoutchouc is placed on the lower end of the zinc element to prevent contact between it and the rod of chloride of silver. Another plan of support is however more advantageous where a very numerous series of elements is used as shown in Fig. 3 for it permits both of economising the chloride of silver and of readily renewing it from time to time. Pieces of gutta-percha or ebonite I I are well fitted into the bar A; they are pierced with a hole just large enough to permit of the silver wire M being drawn through them.The zincs are held in position by means of the vulcanized collars N?while a second collar 0,serves as a clip for making connection with the silver wires M which is done by passing the wire between the zinc and the collar 0. DE LA SUE AND MULLER ON A It should be observed that as the chloride of silver becomes reduced the resulting spongy silver is of greater diameter and less regular in form thau the original rods of chloride; it is evident therefore that the reduced silver cannot be mitlidrawn though the holes in tlie bar A A with the arrangement shown in Figs. 1aiid 2 ; moreover that portion of the chloride which remains out of the liquid in the arrangement of Figs 1and 2 is not reduced and although no silver is ultimately lost yet a portion of the useful effect of its chloride is sacrificed and coil- sequently the arrangement of Fig.3 is both more economical and convenient. When the chlorine is more or less completely exhausted by the reductioii of the cylinders through their entire thickness the resulting rods of spongy silver should be placed in a vessel of water acidulated with hydrochloric acid and some rods of zinc in order to reduce any undecomposed chloride especially at their upper ends. After removal of the zinc the spongy silver must be treated with dilute hydrochloric acid and well washed to remove all traces of zinc. Very little if any,'loss of silver occurs and the cost of ienewal of the electrolyte is chiefly one of labour.If the battery be left in action after the complete reduction of the silver there is always some reduction of chloride of zinc and the amount of this secondary action we hope hereafter to investigate ; but we con-iine ourselves for tlie present to a description of the effects of the primary action of the battery and reserve for a future coin- riiunication the total useful effect of the battery for an equiva- leiit of zinc aiid chloride consumed. Before entering on the details of the experiments there are om or two matters worthy of notice. In the first place the physical properties of chloride of silver render it especially ad- vantageous as a Rolid electrolyte for it is extremely tough and therefore not liable to crumble away ; it is sufficiently soft to be cut with a knife and may even be rolled out in a rolling machiiie ; ulthougli soft enough to be cut yet it ia so elastic as to give off' inusicd sounds when struck.It conducts electricity 80 feebly that it must be classed with insulatorrj :and it is on this account iiecessary that the silver wire should pass right through the chlo- ride of silver in order to touch the ~aline solution and the circuit has to be closed for about a quarter to half an hour the first tiizze tJ:iebattery is wed in order to effect a sufficieut reduction on the surface ofthe cylinders. When the action hag once commenced NEW FORM OF CONSTANT BATTERY. 493 it may be continued until the whole of the chloride is decom- posed.Although we have made batteries with plates of chloride of silver and zinc instead of cylinders the arrangements we have described are far more efficacious in proportioii to their size. In order to test the electromotive force of the battery we availed ourselves of the kindness of Dr. Matthiessen and of Mr. Hockin who placed at our disposal the apparatus they have employed iu determining the conductivity of metals and alloys aiid who were so good as to conduct the experiments with which they are more familiar than ourselves. By way of comparison a Daniell's battery was made in which the electro- negative metal was pure electrotype copper immersed in a solution of pure sulphate of copper saturated at about 20' C. (68' I?.) and the electro-positive metal wag pure zinc amalga- mated and immersed in a solution containing 14 per cent.of pure sulphuric acid and 86 per cent. of water. The charge of the chloride of silver battery was 25 grammes of common salt to a litre of water (219 grs. to 1pint). Two cells of the chloride of silver battery produced in a circuit of resistance of 31,170 Brit. Assoc. units a current of &om 2 to 4per cent. less than two of the Daniell's cells through the same resistance. But when the bat- teries were joined zinc to zinc and the negative elements were connected with the extremities of the coil no current was apparerit the electro-motive force of the batteries was therefore identically the same or at all events did not differ by 0.1 per cent.when only two cells of each battery were opposed. The internal resistance of 10 cells of t'he chloride of silver battery estimated by the current produced through 31,200 B. A. units compared with the current produced by them through a circuit resistance of 10 units besides their own resistance was 56 units giving 54 units for each cell. In general terms it may be said that the chloride of silver battery has about the same electro-motive force as a Daniell's battery. During our experiments with the resistance coil it wa8 noticed that there occurred in the readings of the galvanometer pulsations which indicated a greater accumulation of force from time to time. The instrument could only show the pulsations of comparatively long interval ; but this observation could not fail to point out that possibly periodic accumulations and dis- charges may occur in what we usually consider as a continuous current whose periods are so small that it would require special YOL.XXI. 2N DE LA RUE AND MULLER ON A apparatus to reveal them. Their investigation might throw some light on the stratifications of discharges in highly rarefied media. In order to test its cmstancy a series of 10 cells was charged with a solution of common salt and the circuit completed for half-an-hour. It was then connected from time to time wit11 a voltameter in which the electrodes were made of platinum wire about &th (5.1 mm.) of an inch in thickness. When the current had become sensibly constant the voltameter was read 0% when it was found that the mixed gases were collected at the rate of 5-5 cubic inches (90.12 c.c.) per hour.The volta- meter was then disconnected and the circuit left unclosed for 14 days the elements being allowed to remain immersed. At the end of this time it was necessary to add water to replace t'hat which had evaporated from the cells. On again completing the circuit by means of the voltameter 5.6 cubic inches (91.76 c.c.) of mixed gases per hour were collected and this quantity was given off from time to time for several days whenever the voltameter was made to close the circuit. A very slight local action had taken place on the zinc rods during the period of fourteen days that the elements had been left immersed and the circuit broken.Subsequently a trial was made with 100 cells arranged so as to form a battery of 10 cells of ten times the surface aiid connected with the same voltameter. On this occasion 53 cubic inches (868.46 c.c.) per hour were collected. Of course very little advantage was obtained in passing the current of 100 elements arranged in seiies through the voltameter over the current of 10 of the aame elements. Some experiments were made by ourselves and Professor Abel with the battery in order to test its value for igniting his artillery and blasting fuses. It required from 15 to 18 elements to fire the fuses with certainty; therefore 20 elements would be quite sufficient for the purpose. 100 ele-ments fired four of the fuses linked so as to form a chain.A battery constructed as shown in fig. 3 gave when the whole of the chloride of silver was immersed 2 C.C. of mixed gases per minute or 120 C.C.(73.2 cubic inches) per hour. The rods of chloride of silver weighed each 11-5 grammes ; this corresponds to a total evolution of 1427.27 C.C. at 60'Fah. (15.ci0C.) and the normal pressure so that if used continuously at its maximum force the chloride would be used up in 11-89 NEW FORM OF CONSTANT BATTERY. hours. It is easy however to regulate the consumption by immersing the elements a short distance at first and gradually lowering them so as to make the chloride last for several days’ continuous action. Moreover for experiments where the circuit is closed for a short interval only from time to time the battery would remain available for several weeks without renewing the chloride.For special requirements the cylinders of chloride may be made of larger diameter. One hundred elements gave a bdliant arc with boxwood charcoal points which could be sustained when the points were withdrawn one-sixteenth of an inch (1.58 mm.) ; with a series of two hundred elements the arc could be maintained when the charcoal points were separated one-fourth of an inch (6.32 mm.). We have not hitherto constructed a larger series than that just described as some slight improvements in construction have fi*om time to t8ime suggested themselves ; but we anticipate that from 1,000 to 2,000 cells would permit of the investigation of the electric discharge in vacuo much more conveniently than with any other battery.Ten cells occupy a length of 15 inches (38-1 centimetres) and a width of 2 inches (5.1 centimetres) so that 1,000 elements mould stand on five trays 18 inches (45.7 centimetres) wide and 48 inches (1.292 metre) long and afford space for the supports. Although we have said that the battery was chiefly intended for me when ‘‘ intensity ” is desired yet it will be seen that the amount of decomposition of water in the volta-meter shows that the amount of chemical force transmitted is very considerable in proportion to the size of the instrument Lastly it must be borne in mind that the source of power is the chloride of silver and consequently that this is consumed as the sulphuric acid in Smee’s battery the sulphate of copper in Daniell’s battery and the nitric acid in Groves’ battery just in proportion to the amount of work done and t,hat it requires renewal just as these substances do ; the chloride of silver battery however possesses this great advantage that it is more simple to charge and bring into action than any porous cell-battery and that it may be allowed to remain for a considerable time immersed without detriment.Notwithstanding this latter property it will be better to remove the elements from the solution whenever the experiments are likely to be interrupted particularly as the construction of the battery permits of this being done so readily.

ISSN:0368-1769    

DOI:10.1039/JS8682100488

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

496 Ry WM.H. DARLING. Being the results of an investigation for which the Dalton Chemical Scholarship at Owens College was awarded October 1867. THEsynthesis of carbon compounds forms perhaps the most important and interesting branch of modern chemical inquiry. By the- most recent developments of these synthetical pro- cesses it has been ascertained that the chemical properties of a carbon compound depend upon the position of the atoms of whichits molecule is built up. From Fr an kl and's original observations concerning the difference between the action of chlorine 011 the so-called di- methyl ::3} obtained by the electrolysis of an alkaline acetate 3 obtained from ethyl coni-I-and on the hydride of ethyl '22 pounds the existence of a difference in the four combining powers of a carbon atom was rendered probable.The subsequent researches of Sch o rl em m er have however proved that onlp one hydrocarbon of the formula C,H exists iiia>smixchas he succeeded in preparing ethyl chloride from the hydrocarbon di-methyl CH3-L CH3 I ' obtained by the electrolytic decomposition of an alkaline acetate (Pr0c.R. Soc, xiii. 225) ; as well as from ethyl-hydride obtained from ethyl compounds." It appeared of great interest to repeat this synthesis and to prepare the chloride in larger quantity from which to obtain ethyl compounds and ascertain their chemical and physical properties. At the request of Mr. Schorlemmer I undertook this in- vefitigation. I take this opportunity to express my thanks to that gentleman and also to Professor Roscoe for the kind assistance rendered to me throughout this research.* Chem. SOC. J. [Z] ii 262. DARLING ON DI-METHYL. 497 I. PREPARATIONDI-METHYL OF BY SCH~TZENBERGER'S PROCESS. When peroxide of barium acts on acetic anhydride a gas stated to be di-methyl is gil-en off t'he reaction being repre- sented as follows :-It was found that if the peroxide was heated with the anhy- dride as Schutzenberger directs a violent explosion oc-curred breaking the apparatus. In order to avoid this the peroxide was mixed with dry sand; this had the desired effect if the decomposition was allowed to begin at once. If how-ever the flask containing the mixture was cooled to begin with the action after a time became so violent probably owing to the formation of peroxide of acetyl that explosions occurred.20 grms. of anhydride were weighed into a two-ounce flask and an intimate mixture consisting of 20 grms. of powdered peroxide of barium and 40 grms. of dry sand was poured in mixed by shaking and immediately connected with a bent glass tube whereby all the air was displaced. The gas evolved was collected in a Pepys gas-holder and afterwards displaced by pressure ; it was purified by passing first through a. strong solution of caustic potash to absorb the carbonic acid afterwards through concentrated sulphuric acid to absorb any vapour of acetic anhydride present. The gas thus prepared burnt with a feebly luminous flame. In order to form the chloride the gas thus prepared was treated with an equal volume of chlorine in the following manner:-A white glass bottle of about 2.5 litres capacity full of water was exactly half filled with the purified gas in a pneumatic trough the remaining water displaced by pure chlorine and the bottle tightly corked.The bottle thus filled was exposed until nearly colourless to diffused sun- light after allowing time for the two gases to mix and the action was completed by means of direct sunlight. The bottle was then opened under warm water ; the hydrochloric acid absorbed was equal to half the capacity of the bottle. The remainder * Comptes Rendua 1865 lxi 487. DARLING ON DI-METHYL. of the gaseo us contents not absorbed was displaced by warm water into a receiver in which a few pieces of stick potash were placed and which was surrounded by a freezing mixture of salt and ice.In this tube a small quantity of liquid was con-densed. After using the anhydride obtained from one pound of phosphorus with the exception of a small quantity reserved for future analysis of the gas the total volume of liquid ob-tained did not exceed 25 c.c. and began to boil at 40' C. the temperature iising up to 80"C. This quantity proved too small to admit of being fractionated in order to separate any more highly chlorinated products. In order to ascertain the cause of 80 small a yield of chloride the gas was analysed according to Bunsen's method after freeing it from carbonic acid and vapour of anhydride by means of caustic potash.It was first tested for earbonic oxide by means of cuprous chloride and yielded the following result :-Vol. at 0"C. A. / Volume. Presaure. Temp. C. and lm. Gas originally employed (moist). . 122.7 0.7151 14.0 83.47 After absorption of carbonic oxide ..................,...I 1 Pressure. (dry) 116.65 0.7273 17.0 79.86 The composition as determined by analysis A is Carbonic oxide ............ 3.61 22}.................. 79-86 -c H4-83.47 The following absorption analysis B was made with fuming sdphuric acid to determine the presence of olefines. B. Vol. at 0' C. Volume. Pressure. Temp. C. and lm. Pressure. --I_-Original volume of gas (dry) .... 116'65 0.7273 17.0 79.86 Afier absorption with fuming sul-phuric acid (dry) ............119.40 0*7082 18.0 79.32 DARLING ON DI-METHYL. Hence the composition from B is Carbonic oxide ............ 3.61 C,H .................... 0.54 $$} ........:......... 79.32 83-47 For the det errniiiation of t,he remaining constituents which could only consist of di-methyl and methyl hydride a com-bustion analysis was made. C. Vol. at 0"C. Volume. l Pressure. Temp. C. and lm. Pressure. ----__.--Original volume (moist) ........ 203.5 0'1684 18.0 32.16 After addition of air (moist). . .. 527'1 0'4783 19-4 235.4 Y? , oxygen (moist) . . 618.5 0.5647 21'5 323.8 , explosion (moist) .......... 551'5 0.4992 20.2 456-4 , absorption of carbonic acid (dry)........................ 495.2 04658 16.2 217.8 Original volume of gas .... 32.16 = A Contraction .............. 67-40 = C Carbonic acid ............ 38-60 = B. Since 1volume of di-methyl givea 2-5 volumes of contrac- tion and 2 volumes of carbonic acid and 1volume of methyl hydride gives 2 volumes of contraction and 1volume of carboiiic acid then if y represents the former gas and x the latter X+ y=A x+2y=B y = B -A x = 2A -B. By substituting the numerical values x + y = 32.16 x + 2y = 38.6 y = 38.6 -32.16 x = 64.32 -38.6 y = 6.44 x = 25.72. The contraction C gives a third formula 500 DARLING ON DI-METHYL. 2x+zy=C x+y=A 5 y = 2(C -2A) x = A -2(C -2A). Again substituting values 2x + 5 y = 67.4 x + y = 32.16 y 2i6'7.4 -64.32) x = 32.16 -2(67*4 64.32) y = 6.16 x = 26.00.Taking the mean of the results x = 25.86 y = 6.30. From these analyses the following numbers were obtained :-Carbonic oxide ........ 3.58 4.29 Olefines .............. 0.54 0.63 C,H6. ................ 15.49 18.57 C H,.................. 63.84 76-51 93.45 100-00 This analysis clearly shows that Schiit zenberger's descrip- tion of the above decomposition is incorrect the greater part of' the gas consisting of hydride of methyl. This method being found not to yield the required product a,nd not to be pure di-methyl I endeavoured to procure this substance in quantity by the action of zinc upon methyl iodide. 11. PREPARATIONDI-METHYL OF BY F RANKLAND'S PROCESS. In order to prepare pure di-methyl I took advantage of the directions given by Schoyen* for the preparation of pure di-ethyl.Into stout glass tubes closed at one end metallic zinc made rough on its surface was introduced; the open end was then softened before the blow-pipe thickened and drawn out into a. strong capillary which was bent twice at right angles as described by Frankla n d. Through this capillary the methyl iodide was introduced and afterwards the ether equal in volume to that of the iodide both of which had been dried as far as * Ann. Ch. Pharm ,cxxx 233. DARLING ON DI-METHYL. possible over metallic sodium. The air in the tube was dis-placed by boiling the ether and closing the capillary and the end was thickened after cooling the tube.Tubes thus prepared were maintained at a temperature of 130' C. until all the zinc was dissolved then allowed to cool and afterwards opened by softening the end of the capillary before the blo w-pipe when any marsh-gas which by presence of some moisture might have formed escaped. The tube after heating until the contents began to boil was again sealed and heated at 150"C. for several hours. After the tubes had attained the temperature of the room they were immersed in a mixture of salt and ice; one end of a narrow tube of thick caoutchouc was drawn over the capillary the other end being attached to a gas holder containing a saturated solution of common salt; and the end of the capillary was broken off. The gas then rushed into the holder the internal pressure frequently projecting some of the liquid contents into the holder where in contact with the water decomposition took place it being almost impossible to decompose all the zinc-methyl.The di-methyl obtained from iodide of methyl and zinc by this process and purified by fuming sulphuric acid and caustic potash was treated with chlorine as in the previous case whereby a liquid was condensed which began to boil at 11"C. and rose above 80" C. The quantity obtained was however but small in consequence no doubt of the presence of marsh-gas from zinc-methyl which was carried over ; and as it became apparent that considerable difficulty would be encountered in preparing large quantities of the pure gas this method was abandoned.To substitute mercury for the solution of salt would not be desirable as the mass of mercury then required would be unmanageable. That pure di-methyl is obtainable by this method is clearly shown by the following analysis; this gas was however col- lected in a mercury gas holder as deacribed in Bunsen's Gasometry. The following analysis of di-methyl thus prepared was made according to Bunsen's method :-VOL. XSI. 20 DARLING ON DI-METHYL. Sol. at 0"c. Volume. Pressure. Temp. C. and lm. Pressure. ----. ---Original volume of gas (moist) . . 145.62 0,1205 11.0 18-71 After addition of oxygen (moist). . 2~3.~7 0.2563 11'8 69.74 air (moist). ..... 539.23 0.50'75 11.8 262-3 9, .. explosion (moist). ......... 495.06 0'4637 11.5 220-3 , absorption of carbonic acid (dry) ..................456.53 0.4268 11.9 186'8 , addition of hydrogen (dry) . 579.12 0.5461 13.2 301.8 .. explot3ion (dry). ........... 476.92 0.4351 11.4 199.4 Found. Calculated. Gas employed ...... 16.71 -Contraction ........ 42.30 41-77 Carbonic acid. ...... 33.50 33-42 III. PREPARATION OF DI-METHYL OF BY ELECTROLYSISAN ALKALINE ACETATE. I prepared the di-methyl by the electrolytic decomposition of acetate of potash according to the process described by Kolbe. The gas evolved &om a platinum plate contained in a porous cell was passed first through a solution of caustic potash to absorb the carbonic acid afterwards through Nordhausen acid and over pumice-stone moistened with oil of vitriol to fiee it fkom a trace of oxide of' methyl or hydrocarbon absorbable by this acid and fmally through a solution of caustic potash to absorb acid fbmes any carbonic acid which had escaped the first wash bottle or traces of sulphurous acid.The gas thus prepared had a very slight odour and burnt with a non-luminous flame. The following analysis of di-methyl was made according to Bunsen's method:- Vol. at Oo C. Volume. Pressure. Temp. C. and lm. Pressure. ~~ ~~ ~~ (1) Ori'ginal vol. of gas (moist} .. 183~3 0.1402 8-5 2494 (2) After add. of oxygen , .. 333.41 0.3919 8.0 12'7'00 (3) all-,9 0' 567'52 om21 8.5 287-5 99 79 (4) , explosion 505.38 0.4591 9.2 224.7 (6) , absorption of carbonic J> acid (dry) ..........447-58 0.4156 12.3 173.9 DARLING ON DI-METHYL. Coiitractioh observed ,. 62.80 .. calculated for C,HG.. 68-85 Carbonic acid , .. 50.80 .. 9) 99 .. 49-83 On similar treatment with chlorine as in the previous cases and subsequent displacement with warm water into a receiver containing pieces of potash and surrounded by a freezing mixture of salt and ice a colourless volatile liquid was condensed in the tube. If the gas or the chlorine was not pure being mixed with air very little 01-no liqnid was condensed being carried off by the current. The same fact was noticed by Mr. Schorlemmer. This will probably account for FranE- land's obsermtion that no liquid was condensed at -18" C. One hundred grammes of chloride were prepared by the repetition of this process.This first product was separated by distillation into two parts one which distilled below 30" C. and the other above 30" C. On still further fractionating the first distillate a portion was obtained boiling at 11-13O C. whose specific gravity was 0.9253 at 0' C. Pierre found the specific gravity of ethyl chloride to be 0.9241 atf the same temperature. The chloride boiling below 30' C. gave on heating in sealed tubes with acetate of potash and glacial acetic acid to a tem- perature of 130"-143° C. for three or four hours a volatile fragrant liquid having the characteristic odour of acetic ether which after drying over chloride of calcium and magnesia boiled at 74*0-75*5' C. Kopp gives the boiling point of ethyl acetate at 74.3 under a pressure of 760 mm.of mercury. In order to prepare the alcohol the acetate was heated with crystals of baryta hydrate in sealed tubes for one or two hourtJ to a temperature of 120' C. After cooling the liquid was distilled and the distillate treated with dry carbonate of potash until it separated into two layers; and the upper one was decanted upon fused carbonate and afterwards upon anhydrous baryta from which it was distilled when it had assumed a light amber colour. It began to boil at 78*1°,the whole coming over before the temperature exceeded 79.0"C. Kopp gives the boiling point of ethyl alcohol prepared by fermentation at 78.4' C. under a pressure of 760 mm. mercury and the specific gravity at 0" C.as 0.8095 ; calculating by means of his coefficient of expansioll the specific gravity at 6" C. would be 0.80146 whilst I found the same to be 0.80302 at the same temperature. The alcohol thus prepared had very little odour agreeing in 202 504 DARLING ON DI-METHYL. this respect with the observation of Mendelejeff* though the specific gravity is slightly higher than his at the same tempera- ture calculated from his coefficient of expansion viz. 0-80123. On submitting this liquid to combustion analysis the following numbera were obtained :-No. 1. 0.2834 grm. of liquid gave 0.5357 grm. of carbonic acid and 0.3314 grm. of water. No. 2. 0-5533 grm. of liquid gave 1,0481 grm. of carbonic acid and 0.6480 grm. of water. No. 1. Percentage No.2. Calculated from the formula C2H60. C .. 51-56 .... 51.65 .... 52-17 H .. 12.99 .... 13.02 ..I. 13.04 0 .. 35.45 ... . 35-33 ..,. 34-79 -_I 100*00 100*00 100*00 The numbers are not all that could be desired when compared with the calculated composition ; this is however owing to the difficulty in burning so volatile a liquid and to the small quan- tities taken. Dumas and Boullayt state that in order to obtain accordant results upwards of a grm. of liquid was neces- sary ; in one combustion 1-742 grins. was used; with ether a dill greater quantity was required. The alcohol still remaining in the carbonate of potash and in the dilute solution was separated by distillation ; this distillate was oxidized by a mixture of bichromate of potash and sul- phuric acid when the characteristic odour of aldehyde was recog-nised ; and the oxidation was continued until it had disappeared.On distilling to dryness an acid distillate was obtained this was neutralized with pure carbonate of soda and yielded on evapora-tion needle-shaped crystals of acetate of soda. The mother- liquor was distilled to dryness with sulphuric acid; and the distillate was neutralized with pure carbonate of silver and filtered boiling. On cooling it yielded colourless transparent flat needles! which after drying over sulphuric acid gave on analysis the following numbers :-No. 1. 0.4142 grm. of salt gave 0.21363 grm. of metallic silver. f Zeitschrift fur Chemie 1865 p. 257. .F Ann. Ch. Phys. 182’7[3] xxxvi 299.DARLING ON DI-METHYL. No. 2. 0.5095 grm. of salt gave 0.3274 grm. of metallic silver. No. 3. 0-3650 grm. of salt gave after drying at 100' C. in a water-bath for one hour 0.2349 grm. of metallic silver. No. 4. 03483 grm. of salt gave after drying at 100' C. in a water-bath for two days 0.1604 grm. of metallic sil-ver. Estimation No. 1gave 64.30 per cent. of silver. 9 2 , 64.25 9) 7) 3 , 64-36 ¶ 79 4 , 64.60 97 Calculated from the formula C2R30[Ag.64-68 per cent. of silver. 0,acetate of silver yielda That portion of the mixed chlorides which distilled above 30" C. was fractionated when two-thirds of the total volume distilled over between 57"-59" C. and consist as the following analyses prove of the monochlorinated chloride of ethyl.The specific gravity of this liquid was found to be 1.198 at 6.5" C. Regnault found the sp. gr. to be 1.174 at 17" C.? and the boiling point to be 64" C.* B eilst einf has shown that mono-chlorinated ethyl chloride and chloride of ethylidene obtained by acting on aldehyde with perchloride of phosphorus are identical ; the boiling point of the latter as observed by Wurtz is 58-59" and the specific gravity as determined by Geuther is 1.189 at 4.3' C.;-these numbers agree with those I found. Beilstein remarks that the higher boiling point as observed by Regnault would result from the presence of more highly chlorinated products. The following numbers were obtained by analysis :-No. 1. 0.5206 grrn. gave 0.3691 grm. of chlorine.No. 2. 0.4491 0.3186 99 99 No. 3. 0.4292 , after drying over solid caustic potash for a week 0*3010grm. of chlorine. Percentage of chlorine found by No. 1 70-89 79 ,? ? 2 70.94 7 77 9 3 71.76 Ann. Ch. Phys. [2] Ixxi 355. t Ann. Ch. Phwm. cxiii 110. 306 F. B. MILLER OW TEEE APPLICATION OF CHLORINE GAS The percentage required by the formula of monochlorinated ethyl chloride C2H4gi] is 71.73. Hence the mono-chlorinated ethyl chloride was formed in quantity by the action of excess of chlorine on di-rnethyl. The foregoing results confirm the conclusion that oiily one hydrocarbon C,H, exists and that this substance from what-ever source it may be prepared always yields ethyl chloride when treated with chlorine.

ISSN:0368-1769    

DOI:10.1039/JS8682100496

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

$06 F. B. MILLER ow TEE APPLICATION OF CHLORINE GAS XLVL-OOn the Application of Chlorine Gas to the 2bughening and Refining of Gold. By FRANCIS MILLER F.C.S. Assayer in the Sydney BOWYER Branch of the Royal Mint. THEmethods at present in use for refining gold viz. by alloy-ing it with a certain proportion of silver and treating the metal so alloyed either by sulphuric or nitric acid necessitate a large and costly plant besides causing a considerable delay before arriviiig at the desired end; whilst the processes used for toughening brittle gold are all more or less objectionable ; the use of mercuric chloride on account of its expense as well as its obnoxious vapours ;and t,he employment of oxide of copper or of nitre and borax from their corrosive action on the melting pots and the unavoidable introduction in the former case of copper into the gold so toughened.The consideration of these facts and objections suggested the desirability of instituting experiments for the purpose of deter- mining whether it was not.possible in one operation to satisfy all the requirements of the case more siniply and cheaply. The chemical part played by the mercuric chloride in the common process of toughening brittle gold due as it is to the action of its chlorine upon the baser metals which are thereby converted into more or less volatile chlorides naturally sug- gested the use of chlorine gas ; and the well known property of this gas to form argentic chloride when passed over red-hot TO THE TOUGHENING AND RFJ?INING OF GOLD.507 silver encouraged the anticipation that it might when applied to the alloys of gold and silver give rise to the same compound. The chief diEculties which presented themselves as opposing the practical adoption of such a method were the volatility of the so formed argentic chloride when exposed for a considerable time to a very high temperature and its liability to be absorbed by and filter through the pores of clay crucibles. To overcome these difficulties and thus to open a way for a practical application of chlorine gas to the before mentioned purposes the following experiments were made. A clay crucible was dipped into a hot saturated solution of borax in water so as to be thoroughly impregnated therewith.Into this crucible when dry argentic chloride was introduced and a well-fitting lid luted to it and the whole was submitted to a high temperature in a furnace for 25 minutes. It was then removed from the fire and when cold broken. No absorption of chloride by the crucible was found to have occurred and the residual cake of argentic chloride weighed nearly the same as before the operation. Thus a ready means was indicated for obviating the infiltra- tion and consequent loss of the fused chloride when treated in an ordinarF clay pot. The next and not less important question which had to be experimentally decided was the volatility of the argentic chlo- ride at high temperatures. Indeed so much does this question seem to involve the whole success of the application of chlorine gafi to the purposes in view that there can be little doubt but tfhat a foregone conclusion on this point has hitherto prevented such a process fiom receiving earlier attention and trial.The following experiments however were sufficient to set this question at rest. I. 922.63 grains of argentic chloride together with 1,660 grains of fused borax were introduced into a weighed porcelain crucible loosely covered with a porcelain lid and the whole was submitted to the highest heat of an assay muffle for 1 hour and 35 minutes. The crucible and its contents were found to weigh after this operation only 53 grains less than they did before the experiment was begun. 11. 102 ounces of fine silver and 3 ounces of fused borax were melted in a clay crucible previously prepared by dipping it into a solution of borax as before described and covered with $08 F.B. MILLER ON THE APPLICATION OF CHLORINE GAS a well fitting but not luted lid through R hole in the centre of which a clay pipe reaching down to the bottom of the pot was introduced as soon as the whole contents were in a atate of fusion. Through this pipe a current of chlorine gas was allowed to pass for upwards of an hour which was effected quietly and FVitliout any projection of globules. At the end of this time the crucible was withdrawn and allowed to cool. On breaking the crucible a cake of silver was found at the bottom; on this rested a la'yer of argentic chloride ; and on this again a thin stratum of borax tinged with a delicate pink colour.The argentic chloride thus produced weighed 14.93 ounces yielding on reduction 10.81ounces of silver. An ingot of silver was obtained unacted on by the chlorine weighing 90.83 ounces. The pot on being crushed and washed gave of dver 0.08 ounces. And the borax yielded 0-06 ounces ;summarized thus :-Weight before experiment ............ 102 ounces. Ounces. Silver recovered as ingot ........ 90.83 Y? Y9 .. .. ......fr. chloride fi. pot ......... 10.81 0.08 ?) ¶ fi. borax.. ...... 0.06 - 101*78 Loss.. .......... 0.22 oz. 102*00 In these experiments the small addition of borax appears to have prevented all but a very minute volatilization of argentic chloride. Encouraged by these results as well as by those obtained with small quantities of alloys of gold and silvar similarly treated trials on a large scale were instituted.From these trials the resultfi of which are appended in a tabular form it will be seen that with the imperfect apparatus employed the time required for the operation was only a few hoim in order to bring the gold to a fineness of say 993 parts in 1,000 and that the apparent loss of gold is very little more than what is known to occur in ordinary gold melting being TO THE TOUGHENING AND REFINING OF GOLD. 509 2igb partp in 10,000 whereas in ordinary Mint melting the appa-rent waste is about 2 parts in 10,000. By “apparent Zoss” is meant the loss at the end of an operation without taking into account the amount recoverable from “ sweep,” &c.The apparent waste of silver it will be seen is about $per cent. of the gross weight operated on or 3 per cent. of the silver con- tained in the alloy :but a large proportion of this is recoverable from the flue more especially if a small condensing chamber is constructed in its course. In the experiments referred to in the table the gold to be operated on was melted with a little borax in French clay crucibles duly prepared by dipping into a solution of borax in order to render them less liable to absorb the melted argentic chloride. It was found that black-lead pots would not answer for the purpose as they exert a reducing action on the chloride pro- bably fiom a small quantity of hydrogen contained in the mate- rials of which they are composed.The crucible was covered with a closely fitting but unluted lid with a small hole bored through it and when the metal was melted a long ordinary tobacco-pipe stern (no suitable clay tubes being than procurable in the colony) was inserted through this hole so as to dip into the molten gold down to the bottom of the pot. The upper end of the pipe stem was conriected by a vulcanized india-rubber pipe with a large stone bottle (warmed by a water-bath) in which chlorine was generated and with this simple arrangement quantities of gold weighing upwards of 400 ounces were refined. The gas was used undried just as it issued from the generator no advantage being obtained when dry chlorine was employed.The chlorine generator was fitted with a safety tube 7 feet long dipping at its lower end into the liquid in the generator; and the liquid standing in this tube at such a height as was nec,essary to overcome the pressure of the column of melted gold in the crucible afforded a ready means ef detecting at once if any accident had happened to the clay pipe by the immediate alteration of the height of the column. One inch depth of gold in the crucible was equivalent to about 16 inches of liquid in the safety tube. The india-rubber pipe when protected from the direct radiation of the fire was found to stand the heat well; and if plunged 510 F. B. MILLER ON THE APPLICATION OF CRLORINE GAS into weak ammonia at the end of each operation lasted uniii-jured for some time.No difficulty was experienced from the projection of globules of gold as might perhaps have been anticipated would be the case. The greater part of the chlorine appears to be ab-sorbed at once and no violent ebullition consequently takes place. It was foirnd advisable not to introduce the stream of gas into the molten metal until a11 the atmospheric air had been expelled from the generator and only pure chlorine gas was issuing fkom the eduction pipe; for the air passed through the gold without being absorbed and caused rather more bubbling of the molten gold and possible loss by projection than was the case with pure chlorine which was almost wholly taken up by the silver. It is difficult to obtain proper apparatus in the colony; but with the defective arrangement here described about 8 ounces of metallic silver per hour were separated as chloride fiomgold alloyed with it and at nearly a uniform rate whether the gold contained much silver or little.An assay of the contents of the pot was taken from time to time by dipping into it a clay pipe warmed to prevent it from cracking when plunged into the molten metal. A little column of gold rose in the bore and the pipe if at once withdrawn after the manner of a pipette while the gold was partially cooled within it retained a sample in the form of a little wire of gold ; this was rapidly alloyed approximately and thus the progress of t.he operation was ascertained. When the refinage was complete the crucible was withdrawn from the fire and allowed to cool until the gold therein had set and the still liquid chlorides were then poured from its surface into a mould so as to form a slab.The Borax was in this operation retained in the crucible in effecting this no difficulty was experienced as the borax was quite viscid and consequently much less fluid than the chlorides. The fused argentic chloride appeared to have the property while hot of holding a little chlorine gas in solution which escaped from it with sluggish effervescence as it cooled. The fine gold remaining in the crucible was re-melted and cast into ingots. The reduction of the chloride of silver to the metallic state was effected by placing the slab between two flat pieces of TO THE TOUGHENING AND REFLN€NB OF COLD.511 wrought iron and immersing them in water acidulated with sulphuric acid where it was left for 24 hours by which time the reduction was usually complete but the metal thus obtained always contained a little gold; it was therefore necessary to dissolve the reduced silver in nitric acid when the undissolved gold was separated by decantation and melted while the silver was precipitated as chloride and again reduced to the metallic state. [Since these experiments were completed however it haa been found that the chloride of silver can be obtained free from gold without the necessity of dissolving the reduced silver a matter of much importance in a practical point of view.] On reducing the slab of argentic chloride with iron as above described and dissolving the spongy reduced silver in nitric acid the gold remained as a flaky residue resembling precipi- tated metal and not in rounded globules as would probably have been the case had it been mechanically thrown up from the molten alloy by the gas during the operation.This fact rather appeared to indicate that a chemical combination of gold silver and chlorine had been formed a view of the case which was further confirmed bj-the quantity of the two metals obtained from the slab of chlorides as compared with the amount that should have resulted from calculation and fi-om the circumstance that the residual gold was nearly pure. It was found that a part of the gold was readily separated in the metallic state and obtained as a button on submitting the slab of chlorides to fusion at a red heat but that a portion still remained with the chlode of silver.This leads to thecon-elusion that if some agent could be found that would reduce the chloride of gold without affecting the chloride of silver the whole of the gold might be separated by simple fusion. The only substance likely to effect this reduction seemed to be metallic silver ; this therefore was tried and found completely to effect the desired object when tried on a small scale; experi- ments on larger amounts are necessary and will immediately be made. The mode of operation adopted was as follows :-A slab of argentic chloride containing a small quantity of gold obtained from the refinage of silvery gold by chlorine and weighing 13-22 ounces was fused in a borax-prepared clay crucible at a bright red heat for five minutes; half an ounce of carbonate of 512 F.B. MILLER ON THE APPLICATION OF CHLORINE GAS potash was then gradually dusted into the crucible which was allowed to remain in the furnace for twenty minutes longer. The effect of the carbonate of potash was by reducing a small quantity of chloride to produce a shower of minute globules of metallic silver which as it descended through the fused argentic chloride exerted its reducing action on any chloride of gold that might exist therein. After withdrawing the crucible from the furnace it was allowed to cool until the chlorides appeared black but were still quite liquid; these were then poured off into a mould and there remainedat the bottom of the crucible a button of silvery gold together with a spongy mass appearing to consist of'sub- chloride of silver which is less fusible than the chloride.The crucible was now replaced in the furnace with the silvery button and the spongy residize and a little carbonate of soda added to reduce any silver chloride &c. and the whole was brought to a red heat for five minutes. A button of silvery gold was thus obtained weighing yvv of an ounce and con- taining 0.28 08. of gold and 0.27 oz. of silver. On reducing the slab of argentic chloride to the metallic state and dissolving the silver obtained in nitric acid it was found to be quite free from gold.It seems therefore probable that this plan will afford a con- venient means of separating the small quantity of gold existing in the chlorides obtained in the method of refining above described without the necessity of dissolving the reduced metal in acid and again reducing the dissolved silver to the metallic state. With regard to the amount of chlorine wasted and passing up the chimney in the operations described in the earlier part of this paper it appears calculating from the materials employed in the generator that the quantity so wasted does not exceed in amount that reqiiired to chloridize the silver in the alloy operated on. One cubic foot of chlorine will theoreti- cally convert eight and a quarter ounces of silver into argentic chloride; not.more than twice this quantity is actually required in practice and probably less. Thus in refining 1,000 ounceB of gold containing 5 per cent. (or 50 ounces) of silver six cubic feet of chlorine would! theoretically be required and practically twelve cubic feet are amply sufficient; and this waste six feet is not all vomitted fortjh from the chimney at TO THE TOUGHENING AND REFINING OF GOLD. 513 once but is gradually evolved during several hours. It can be readily intercepted in a small chamber furnished with a trickling stream of milk of lime. To determine approximately the amount of chlorine required to effect' the refiiiage the following experi- ment was made :-A known quantity viz. 8.65 gallons of chlorine was passed through an dloy of gold and silver containing an excess of the latter that is to say more than the chlorine employed would theoretically be able to convert into argentic chloride.At the end of the experiment 9.23 ounces of chloride of silver were obtained so that the 8.65 gallons of chlorine converted 6.62 oz. of silver into chloride whereas this amount of chlorine was theoretically capable of chloridizing 11.62 oz. of silver. The waste therefore of chlorine in this operation amounted to 44 per cent. of the quantity employed. I am greatly indebted to my brother officer Mr. Robert Hunt the gentleman in charge of the melting department and to Dr. Adolph Leibius my colleague in the Assay Office of the Sydney Mint for their valuable suggestioiis and assistance in reducing this plan of refining to a practical and workable method and for 'their earnest encouragement under diAi-culties.Table showing results of Experiments in Rejning Gold by Chlorine Gas. Prs. Bowyer Miller's Patent Royal Mint Sydney ;amw Weight containing %d Of1t$O9 according to Apparent loss 3: %; in operating. 2s after Assay* I 2% the h$ .% k opera-gg On [Gold. Silver. g$ Gold. Silver. 4 -____~ -ozs. ozs. ozs. 02s. 02s. ozs. ozs. 02s. 078. 135.35 129'85 5'410 4.700 130.460 1?9%40 0.620 0.010 0.120 959.4 194.925 166'076 28 -300 27.173 166'801 165'966 0.835 0.110 0'292 852'0 276'499 255'165 20 '765 18'135 256.820 255.080 1.800 0 085 0.830 922% 377.96 336'309 39.651 32.950 341-090 336'212 4.874 0.093 1-827 889.8 40925 375'280 32.740 29 ' 600 377.050 375'111 1.939 0.169 1-201 917'0 229.80 212-100 17 *510 15.580 213.620 212.090 1*530 0.010 0'400 923.0 XOTE.-B~4L Apparent loss " is meant the loss shown at the end of each experiment without taking into account the amount recoverable from '' sweep" and flues which is a considerable pro-portion of the whole loss

ISSN:0368-1769    

DOI:10.1039/JS8682100506

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

514 XLVII.-Note on t7be Specijc Gravity and Boiling Point of Clzwomyl Dic7tlovide. By T. E. THORPE. IN the course of an investigation the results of which will shortly be made public I had occasion to prepare a consider-{: able quantity of pure chromyl dichloride CrO and con-seqiiently took the opportunity of repeating the determination of the boiling point and specific gravity of this substance. To the best of my knowledge the only determiiiations hitherto pub- lished were made some years ago by Walter." The following results but incompletely confirm those obtained by that che- mist. The chromyl dicldoride employed in these experiments was prepared by distilling an intimate fused mixture of 10 parts sodium chloride and 12 parts potassium diclnornate with 30 parts strong sulphuric acid.In order to ensure the expulsion of the free chlorine the liquid was repeatedly distilled in a current of dry carbonic acid and on the fifth distillation it was received in a flask provided with a long narrow neck into the side of which near its upper extremity a tube had been fused in order to convey the vapours into Liebig's coiidensw. The determina- tion of the boiling point was made in this flask the thermo- meter being so disposed that the entire length of the mercurial column was within the vapour. The weight of the liquid employed was about 60 grammea. Under a barometric pressure of 733 millimetres it began to boil at 114"C. the height of the colunin quickly rose to 116O C. and remained perfectly constant at 116O4 C.the quantity distilling over at this latter point being about five-sixths of the whole. Walter observed 118' C. under a pressure of 760 millimctres. When the necessary allowance is made for the difYerence in the pressures the two determinations ma)-be said to agree completely. It appears however not to be possible to distil chromyl dichloride without slight decom- position. To determine its specific gravity a portion of the distillate * Am. Chim. Phys. [2] Ixvi 387; Pogg.Ann. xlv 154. THORPE'S ANALYSIS ETC. obtained during the observation of the boiling poht wag trans-ferred to a small weighed bulb the neck of which was narrowed and provided with an accurately fitting stopper to prevent the decomposition of the liquid by atmospheric moisture.The following are the results of the various weighing :-Weight of specific gravity bot>tle ............ 3.5312 grms. Bottle and water. Temp. 25OC. ............ 7.6549 , Weight of bottle after emptying and drying it and before the introduction of the chromyl- dichloride .............................. 3.5311 ) Bottle and chromyl dichloride. Temp. 25OC. .. 11.4692 , On calculation these numbers give 1.920 as the specific gravity of chromyl dichloiide at a temperature of 25O C. At 21' C. Walter observed 1-71. I may state as some confirmation of the former number that the accidental observation that this body immediately sinks on being dropped into strong sul- phuric acid originally led me to re-det'ermine its specific gravity. It is worthy of remark that the atomic volume of this compound calculated from the corrected number agrees per- fectly with that of its analogue sulphuryl dichloride. At. wt.. Sp. gr. At. YO]. Sulphuryl Dichloride SO c1 135'0 1.66 81.8 Chromyl Dichloiide CrO 155.5 1.92 81.2 Heidelberg September 1868.

ISSN:0368-1769    

DOI:10.1039/JS8682100514

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

THORPE’S ANALYSIS ETC. XLVIIL-Analysis of the Ashes of a diseased Orange Tree (Citrus Aurantium). By T. E. TEORPE, Dalton Scholar in the Laboratory of Owens’ College Mancheater. THE orange plantations along the south-eastem coast of Spain and in the adjacent Balearic Isles have recently been visited with a severe epidemic the rapid progress of which waB THORPE’S ANALYSIS OF THE ASHES naturally viewed with no little anxiety by the people since the culture and exportation of oranges constitute one of their prin-cipal industries. This disease is said to have made its appear- ance at Valentia and to have spread to the islands during the summer of last year. The first symptoms of the sickening manifest themselves in the leaves which turn yellow and in time drop fi-om the branches.During the progress of the disease the roots exhale a most disgusting odour arid within a very few days after the attack the tree succumbs. But the true nature of this remarkable disease hitherto unknown in these parts is very imperfectly understood; its origin is involved in complete obscurity and as yet it has baffled all attempts at remedial measures. Happily however its violence which at one time threatened destruction to the entire plantations in the islands has within the present year considerably abated and the disease seems to be gradually dying out. For these particulars I am indebted to the kindness of Pro-fessor Bunsen who visited the Balearic Isles during the summer vacation of last year and as it appeared interesting to ascertain the nature of the inorganic constituents of the diseased trees and to compare it with that of the ashes left by the combustion of perfectly healthy specimens procured all the necessary materials for analysis.Accordingly analyses of the ashes of the roots stern branches and fruit were made in the laboratory of the University of Heidelberg under Professor Buneen’s direction and superintendence. The results of these analyses form the subject of the present communication. The following was the method of analysis adopted :-From 4 to 5 grammes of the ash obtained by burning in a muffle at the lowest possible temperature were placed in a glass cylinder of about 500 C.C. capacity provided with a well fitting stopper.About 50 C.C. of distilled water was then added and carbonic acid passed into the cylinder the delivery tube of the apparatus (which did not dip below the surface of the liquid) being fre- quently withdrawn the stopper inserted and the liquid shaken in order to promote the absorption of the gas. When the caustic bases were completely neutralized and the solution saturated (which was evidenced by the cessation of the partial vacuum and also by the bubbles passing “upwards” between the bottle and its stopper when the latter was cautiously lifted after vigorously slinldng the liquid) the total contents of the cylinder OF X DISEASED ORANGE TREE. were washed into a porcelain dish evaporated to complete dry-ness again heated with a sinall quantity of water just about sufficient to dissolve the soluble portion and after stanang R short time filtered through a weighed filter.The filtrat.e together with the washings was again evaporated nearly to dryness and allowed to stand for some time to effect as far a8 possible the complete precipitation of the calcium sidphate which was separated and when its aniuunt was but small weighed immediately ; if large it wits added to the main quantity of the insoluble portion of the a& which IVXR then dried at 100"C. and weighecl. 1. Azcnlysis qf' the Itt~olddePortioii. In the insoluble portion are contained he niagiieaia femk oxide silica plioaphoric sulphuric and carbonic acids. The carbonic acid was estimated by the usual method that is by determining the loss of weight which cz known quantity of the ash suffered on treutnieiit with clilute hydrochloric acid ; the sulphuiic acid was afterwards determined in this solutioii by precipitation as barium sulpliatc.The phosphoric acid was separated by means of tin. For its estimation together with that of the bases and the silica about 1 gramme of the inao- liible portion was dissolved in nitric acid and after separation of the silica in the usual nirtnner the solution was again evapo- rated nearly to dryness and dilute nitric acid added until the bases were completely dissolved ;strong fuming i&ric acid was then added until the calcium nitrate began to separate when the slight precipitate was immediately re-dissolved by the addition of a few drops of dilute acid.The nitric acid solution of the bases ~vczsthus in the highest posfiible state of concentration aid on warining sncli a solution the tin-foil is rapidly oxidized to the niasiiniiiii degree of oxidation Tvldst thc supernatant liquid remains perfectly clear. The prelimillary heating of t11e solution is absolutely necessary sirice in the cold t8hemetal becomes passive aiicl refuses to oxidize. The yuaiitity of tin foil added amounted to about six tiines the weight of the phos- phoric acid that could possibly be present and care was always taken to keep the nitric acid in sufficient excess in order to prevent the forination of the monoxide wlkh renders the solu-tion inconveniently turbid. When a11 action wa~ at an ~xd.and I VOL.SS?. -1 1' THORPE’S ANALYSIS OF THE ASHES the tin fully oxidized the contents of the dish were evapo- rated fiearly to dryness in order to remove the excess of nitric acid; water was then added and the solution filtered. The precipitate contains all the phosphoric acid ; tlie bases are found in the filtrate Thils precipitate detached as far as possible from the filter waa digested in the smallest possible quantity of highly concentrated potash-solution ; on the addition of watw thia mixture dissolves to a perfectly clear liquid provided no great excess of the alkali hag beeu employed. The trifling amount of the precipitate still adhering to the filter was dissolved in the same manner and added to the main portion of the sohl- tion.The liquid was then saturated with sulphuretted hydrogen acetic acid added in very slight excess and the precipitated tin sulphide separated by means of Bu 11sc 11’s filter pump. The filtrate wag next concentrated to a small bulk the slight amount of tin sulplde which invariably precipitates on evaporation being removed and the phosphoric acid determined in the usual manner as magnesium pyrophosphate. This slight departure from the indirect method usually enzployecl is only renclered possible by the aid of the filtering apparatus iiivciitecl by Buns en ;it liaa the advantage that the whole of the phosphoric acid admits of direct determination a point of some iniportaiice when its amount is but relatively sniall aud moreover the saving of time it effects is considerable.Tlie filtrate from tlie tin oxide containing the ferric oxide lime and imgiiesia may also con-tain no incoiisiderable quaiitity of foreign metals for example. lead and copper existing as impurities in the foil ; tliese were removed by mlphuretted hydrogen before the determiiiation of the bases which were then separated in tlie usual way tlie iron by ammonia and the lime and niagiiesia respectively by mirno-liiuni oxalate aiid socliuin phosphate II. i-lnctlysis of the Soluble Portion. The solutioii of the soluble portion of the ash was filtered from the calcium sulphate (separated by evaporat,ioii in the manner above described) through as sinall a filter as possible into a weighed flafirk provided with a tubulus drawn out at tlie side to admit of the more convenient weiglring off of aliquot portions of the weighed liquid.The total quantity of liquid was divided as near a8 possible into six equal parts to serve for OF A DISEASED ORANQE TREE. the determination of the sdphuric acid alkalies chlorine aolu-Ble pliosphoric acid and carbonic acid the sixth portion being reserved 111 case of accident. The carbonic acid was determined volumetrically by &normal dphuric acid and litmus solutions; the sulphuric acid and chlorine in the ordiiiary way by precipitation asbarium sixiphate :tnd silver chloride and the phosphoiic acid separated after con-siderable concentratiou of the solution as the double salt of Inagnesium and ammonium and weighed as pyrophosphate.In order to determine the amount of the alkalies the aolutiofi was boiled with excess of baryta-water in a porcelain dhh filtered and the excess of baryta removed by ammonium carbonate ahd ammonia; the solution wag then evaporated to dryness in a platinum dish gentlyheated re-dissolved in a few drops of water; ammonia and ammonium carbonate again added; and after Mtandizlg a considerable time the solution was again filteredand evaporated to dryness heated and by the cautious addition of' liydrochloric acid converted into chlorides in which forin the alkalies were weighed. The potassium chloride was then sepa- rated in the usual way by platinum chloride. In cases where the amount of the soluble portion of the ash was comparatively large iuore than traces of magnesia ntill remained in solution with the alkaline chlorides even after repeated treatment with ammo-iiiuiii carbonate and ammonia.This small quantity of magnesia ww found in the filtrate from the double Bait of potassium and platinum; its amount was easily estimated by evaporating the alcoholic solution to dryness re-dissolving in water and transfer- ring the aolution to a small flask provided with a tightly fitting cork pierced with two holes to admit of the introduction of glass tubes. This little piece of apparatus has the disposition seen iii the annexed figure. Hydrogen is led through the 4- + tube (A) and the end of the exit tube (B) within the flask is sufliciently long to reach just above the surface of the liquid 80 as to ensure the complete expulsion ofthe air by the gas.When the vessel is completely full of hydrogen the ends of the tubes (A) and (B) are closed during the actual transmimion of the gas either by mrew-clamps or by glass rods and the whole is phced in the direct sunlight wlien the platilium is quickly reduced to the metallic state and the solution ultimately becomes perfectly 2P2 TRORPE’S ANALYSIS OF THE ASHES coloiurless. The process of reduction may if necessary be faci-litated by heating the solution on a vater-bat8h before the trans- mission of the gas. If the capacity of bhe Aask is small it may be requisite to re-fill it once or twice with hydrogen to emure the complete reduction of the platinum; it is then desirable to displace the remaining-gas by a rapid current of carbonic wid ;otherwise an explosion might possibly occur particularly if the contents of the flask are warm owing to the surface action of the finely divided metal on a mixture of air and hydrogen.The clear solution was then filtered from the finely divided platinum and after concentration the magnesia was precipitated in the uaual way by sodium phosphate and ammonia and its weight deducted from that of the mixed chlorides. This method is recommended to be used in all accurate separatioiis of the alkalies from inag-nesia; it moreover offers a rapid and eaay mode of recovei+q?,- the excess of platinum used in the determination of potash. (A.) Analysis of the Ash of the Root$. 413.4 grms.of the roofs freed as far as possible fioiii adhering sand and Boil left on burning 5.686 grins. of a&. Amount taken for analysis 4.9315 grms. After treatment with car-bonic acid the insoluble portion weighed 5.081 G grins. the solution of the soluble portion 66.2125 grms. I. Composition of the Insohble Portion. Amount in total insoluble portion grms. grms. grms. 1.1431 gave Silica ...................... 0*0710 Silica ........ 0.31554 Magncgium PJrophosphate ,,. 0*173E Xagnesia ...... 0-2’7787 Ferric oxide ................ 0.01 00 Ferric oxide .. 0’01444 Lime ...................... 0.5021 Lime ........ 2.23145 Magnesium pyrophosphate *. , 0.0199 Phosphoric acid 0.05655 1.2273 , Do. do. .... 0‘0214 D@.. 0.05668 0.5868 lost on treatment with dilute acid ,.0’2289 Carbonic acid .. 1.98230 Tot,al weight of Calcium Siilphate ................OfJOBO 11. Composition of thc Solnble Portion. Amount in total soluble portion. grms. grms. grms. 10.1446 solution gave Barium sulpliate .., ,. 0.0751 SoIphuric acid. . 0*16827 9.6667 .... Silver cliloride.. ...... 0.0191 Chlorine ...... 0‘03236 10.3215 .... Mixed chlorides ...... 0’1290 Potash ........ 0.21331 Plztinum-salt ........ 0.1968 Soda ......... 0.23466 9*2150 , reqnirc-d11 C.C. C;O,H-sol. (I 1i G*C@22) Carbouic wit1 , 0.17332 OF A DISEASED ORANGE TREE. 521 (H.) iicdysis of the ltsh of the l%>~~~. JIacle by Hwr Giitscliow. 122.5 grma. of' tlie wood left 4.00 grim. of ash. rlniouiit taken for analysis 2.9551 ems.After treatment with carbonic acid the iiisoluble portion weighed 2.6687 grms. the solution of the soluble portion weighed 40.5186 grma. I. Composition of the Insoluble Portion. Amount in total insoluble portion. grms. grms. grmfi. 0.8945 gave Magnesium pyrophosphate .,., 0.0955 Magnesia.. .... 0.10269 Do. do. ...... G-0175 Phosphoric acid 0-03340 , Lime.. ...................... 0.4465 Lime ........ 1.33210 0.471 9 lost on treatment with acid.. ........0.1983 Carbonic acid . . 1.08750 IT. Composition of the Soluble Portion. Amount in total solution. grms. grms. grms. 8.4638 solution gave Silver chloride ........ 0.0652 Chlorine ..,.. 0.06542 8'1861 , , Barium sulphate ...... OwO420 Sulphuric acid.. 0.07147 '1.7'051 , , Magnesium pyrophosphate 0'0050 Phosphoric acid.0.01684 8.1500 , , Mixed chlorides ........ 0.0882 Platinum salt ..........0.2204 Potash ........ 0.20225 Mnpefii urn pyrophosphate 0'0 030 Soda.. ........0.06081 8.0736 , required lU.7 C.C. S04H2solu-Carbonic acid . . 0'05916 tion (10.7 x 0'0011) (C.) Analysis of theilsh of the Branches. Made by Herr H. Knop f. Amount taken for analysis 5.0115 grms. After treatment with carbonic acict the insoluble por- tion weighed 4.8286 grms ; the so1utio.u of the soluble portion 47.7822 grms. I. Composition of the Insoluble Portion. Amount in total insoluble portion. grins. grms. grme. 1.3815 gave Silica.. ...................... 0.0260 Silica ........ 0.09037 Magnesium pyrophosphate , .. ,. 0*0622 Phosphoric acid. 0.14004 Ferric oxide. ................. 0.0042 Ferric oxide 0*01460 Lime ........................ 0.8837 Lime ........ 2.38950 IIagiicaium yj-rophoaphak ..... 0.0992 Magnesia ...... 0'12498 0-j.52.jlost on trcatniciit with acid .......... 0'2104 Carbmi: acid .. 1.63340 11. Composit'ion of the Soluble Portion. grms. grms. 11*0066sdution required 5 C.C. normal HC1 solution. 6.9950 , gave Mired chlorides .. . . . 0.0293 Platinum salt .. .. . . . . 0.0770 6.9592 , Barium sulphate 0.0050 7.0647 . 0'0016 THORPE'S ANALYSIS OF THE ASHES grms. Carbonic aoid . . 8*0476 8oda.. . . . . . .. 0.02186 Potash . . . . . ,. 0.10110 Sulphuric acid. 0.0116 Chlorine 0*0027 (D.) Analysis of tle As7~of the FT*uit.Amount taken for analysis 5.5482 grms. After treatment with carbonic acid the weight of the insoluble portion WRY 2.2948 grms. that of the solution of the soluble portion was 59.9210 gnus. I. Compoaition of the Insoluble Portion. F grms. a 0.9339gave Silica.. . . . ,. . . a. . . . . . . .. . 0,0085 Magnesium pvophospbate ... . . . 9.2970 I .. . . 0.3834 0.5149 lost on treatment with dilute HCl .. . . 0.1 045 Amaunt in total insoluble portion. g.IUlS. Silica .. .. . . . 0-02062 Phosphoric acid 0,46085 Ferric oxide.. . . 0.00560 Lime.. ,. .. . 0,94191 Nagnesia .. , , 0.17667 Carbonic acid .. 0.45978 Total weight of calcium sulphate . . . . . . . ,. . 0*02930 11. Composition of the SQlublePortion.gm0. grms. 6.0420 solution gave Barium sulphate.. .,. . . . 9.0395 5.1163 , , Silver chloride,. .. . . . . . . 0.0304 9.8770 , ) Magnesium pyrophosphate 0.0059 7-9500 ) ) Mixed chlorides.. ... . .. 0.4497 Platinum salt . . . . . ,. .. 1.4246 Magnesium pyrophosphate 0-0017 6.2297 , required 42.1 C.C. S04Hz soln-tion (42*1x 0'0022). Amount in total solution. grme. Sulphuric acid.. 0.13442 Chlorine .. . . .. 0.08805 Phosphoric acid. 0-02305 Potash . . . . . . I. 2006950 Soda.. . . . . . . . . 0*05800 Carbonic acid .. 0.89086 Reducing all these results to percentages after dedncting the amount of carbonic acid the composition of the ash of the root? skaa hwhes and fruit irJ found to be aa follows :- OF h DISEASED ORANGE TREE 523 Root.Stem. Branches. Fruit. Potash.. .................. 6 '74 10 -79 3 -49 51 *64 Soda.. . . .. ...... . . . ....... 6'50 3 -22 0 -75 1'45 Lime .. . . .... . . .... . ,.. .. 61 '82 '70.67 82 '49 23-50 Magnesia ......... . . . .... 7 '70 5 *92 4 *31 4 -41 Ferric oxide .. . . ...... .... 1'23 0 '51 0 .14 Chlorine .... . . ...... . ... . . 0 '90 3*48 0'09 2 -19 Phosphoric acid.. . . . . . ...,. 1-57 2 *66 4 '83 12 -07 Sulphuric acid .... . .... .. 4 '66 3 -26 0.40 3 -35 Silicic acid .... . .. . ,.. . . ... 8 9'4 3 '13 0 *52 Calcium sulphate . . ...... . ---.. 0 '73 0 *14 lo@-00 100~001 lo@*oo 100 so0 For the sake of comparisoii I here append the results of ;I similar series of analyses made some years ago by Messrs.Rowney and How of ashes obt.ained from perfectly healthy trees grown in the island of St. Michael.* In the last colunz~i I also add an analysis of the entire fruit by Dr. Richardson.? Tlie results of these analyses are here represented in per- centages after deduction of the unessential constituents i.~. carbonic acid sand and charcoal. Fruit Root. Stem. Leaves. Fruit. Seed. (Richard- son). I-Amount of ash left by 4.48 2-74 13-73 3.94 3.30 }1 1 100 pts. m . . . .I .* * . 11.69 18.51 36.42 40.28 38.72 3'07 1.68 13-42 0.92 '7.64 Lime..... ........... 49.89 55.13 56.38 24.52 18.97 22-99 Magnesia . . . . ..... . . Ferric oxide.. ..... . .. 6-91 1.02 6-34 0'57 5-72 0.52 8.0 6 0*46 3.7'4 0.80 6.55 1.7'42 Sodium chloride . . .... 1-18 0.25 6.66 3.87 0.82 trace Phosphoric acid .. .... Sulpliuric acid.. .. . .. . Silicic acid . . . . . . .,. 13.47' 5-78 1.75 17.09 4.64 1.22 100'00 I 3.27 4.43 4-83 10oao01 23-24 5.10 1.13 100~00 14-17 2.95 5.25 100~00 11.07 3.74 0.44 100~00 It will at once be noticed on instituting the compariscn that the coiiiposition of the ashes of the healthy tree differs widely * Reports &c. Royal College of Chemistry 1847 Journal of Chemical Society. f Ann. Ch. Pharm. lxvii 3'17 1848. Ferric phosphat,e from that of the diseased specinlens. The waut of analogy is inore particularly seen in the undue proportion of limc and the comparative lack of phosphoric acid in all parts of tho unlieitlthy tree with the exception of the fruit; but the concentration of potash in the latter is remarkablc.TVhether however these deviations may in any way be connected Tvitli tho source of the disease or are themselves its results reinains still to be demonstrated. Hitherto the culture of the orangc has no~v11er.e been carried to a greater degree of perfection than in the Balearic Ides; but the yield of fruit seems to have been forced by excessive manuring to a most unnatural extent ;and pro- bably in this ’injudicious overworking of the trees inay be found the cause of their sickening. Heidelberg September 186%

ISSN:0368-1769    

DOI:10.1039/JS8682100515

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

INDEX. A. Absorption of ammonium salts by hydrated ferric oxide and hydrate of alumina 11 14. -of phosphoric acid by soils 2. -of potassium-salts by hydrated ferric oxide and alumina 6 13. -of vapours by charcoal on the by John Hunter 186. Absorptive action of soils on the part taken by oxide of iron and alumina in the by R. Warington 1. Acetamide action of permanganate of potash on 30. Acetate alkaline preparation of dime-thy1 by electrolysis of 502. -of methyl absorption of its vapour by charcoal 188. -preparation of 480,484. -rapour-tension of 481 487. Acetic anhydride action of peroxide of barium on 497. - - compound of with hydride of aceto-salicyl 181. --hydrate of butyro-dcyl 473. Acetone absorption of its vapour by charcoal 192.Aceto-salicyl,on the hydride of by W. H. Perkin 181. Acid anchoic produced by oxidation of paraffin with nitric acid 470. -arsenious on the occurrence of prismatic by F. Claudet 175. -benzy1-salicylic,125. -bromoglycollic 203. -butyric coumaric 475. -caproic synthesis of by J. A. Wanklyn and R. Schenk 31. -carbolic on the reducing action of peroxide of hydrogen and by J. Parnell carbonic reduction 356. of to oxalic acid by E. Drechsel 121. -cerotic produced by oxidation of paraffin 468. -chromic action of on paraffin 467. --coumai*ic,butpic 62. and valwic 63. Acid dimethyl-norhemipinic 368. -dimethyl-noropianic 362. -dinitromethyl-hypogallic 361. -glyoxylic on the constitution of by W.H. Perkin and B. F. Duppa, 197. -hemipinic action of hydrochloric and hydriodic acids on 360. -crystalline forms of 361 366. -hydriodic its action on hemipinic acid 360. -meconin 360. narcotine 363. -opianic acid 358. -hydrochloric its action on hemi-pinic acid 360. -meconin 360. -narcotine 363. -opianic acid 358. -methin-trisulphonic on by Dr. Theilkuhl 196. -methyl-hypogallie 361. -methyl-norhemipinic 362. -methyl-noropianic or monomethyl normal opianic acid 358. -nitric action of on paraffin 469. -nitric note on the estimation of in potable waters by E. T. Chsp-man 172. -nitric and nitrous estimation of in potable waters 85 101. -nitromethyl-noropianic 360. -norhemipinic 362. -noropianic 362.-opianic action of hydrochloric and hydriodic acids on 358. -reduction of to meconin by the action of sodium amalgam 359. -oxalic reduction of carbonic acid to by E. Drechsel 121. -phosphoric absorption of by soil 2. -separation of from bases by tin 517. -picramic action of nitric acid on by John Stenhouse 150. -picric preparation of chloranil from 144. -pyrophosphamic 65. -pprophosphodiamic 67 526 IN 3EX. Acid pyrophosphotriamic 68. -salicylic absorption of its vapour by charcoal 189. -valeric on the isomorphism of by A. Pedler 74. _I vanadic 339. Alcohol ethylic absorption of its vapour by charcoal 190. -methylic absorption of its vapour by charcoal 190. Alkalies separation of from magnesia 519.Alumina absorption of ammonium salts by 12. -potassium salts by 10. -and oxide of iron on the part talicn by in the absorptive action of soils by R. Warington 1. hides pyrophosphoric on the by 3. H. Gladstone 64. -tetraphosphoric on the by J. H. Gladstone 261. Animonia action of perrnanganate of potash on in strongly alkaline solu- tions 29. -estimation of in potable waters 87 103. -evolved by alkaline perrnanganate acting on organic nitrogen compounds 161. -Nessler test for 103 161. Ammonia-carbonate direct conversion of into urea by A. Basaroff 194. Amy1 nitrate action of zinc-ethyl on 174. -nitrite action of zinc-ethyl on 171. Amylamine oxidation of 162. Analysis of gases on by W.3. Rus-sell 128. -some experiments on the applica- tion of the measurement of gases to quantitative 310. -of potable waters on the by E. Frankland and H. E. Armstrong, 7’7. I_ note on the preceding by J. A. Wanklyn E. T. Chapman and M. H. Smith 152. -water- on a simple apparatus for * determining the gases incident to by E.Frankland 109. Animal heat source of 47. Antimony symbol of 4M. Aqueons vapour Regnault’s table of the elasticity of 119. Armstrong and Frankland. See Fr ankla nd. Arsenic symbol of 421. Arsenious acid on the occurrence of prismatic by F. Claudet 175. Asparagine oxidation of 162. B. Barium peroxide action of on acetic anhydride 497. Basalt devitrification of 257. Basaroff A.on the direct conversion of ammonia-carbonate into urea 194. Battery on a new form of constant by Warren Ye la Rue and Hugo Muller 488. Be 1 1 J. C. on the solubiIity and crystal- lisation of plumbic chloride in water and in water containing various per- centages of hydrochloric acid of 6p. gr. 1.162 350. Beiizyl chloride its action on gaulthcrstc of sodium 124. -on the hydride of sodium salicyl, 122. BenzyIic derivatives of the salicyl series on some new by W. H. Perkin 122. Benzyl-salicyl hydride of 123. Benzyl-salicylates 126. Bismuth freezing of 71. -symbol of 442. Bisulphide of carbon absorption of its vapour by ch~rcoal,192. Bivanadates 340. Boron spbol of 435. Brodie Sir B. C. the calculus of chemi-cal operations; being a method for the investigation by means of symbols, o€ the laws of the distribution of weight in chemical change.-Part I.On the con,ptruction of chemical sym-bols 367. Bromine symbol of 418. Bromoglycollate of silver its resolution into silrer bromide and glyoxylide 20P. Bromoglycollide 203. Brucine oxidation of 164. Butyric coumaric acid 475. Biityric coumarin 56. -formation of from hydride of butyro-sslicyl 474. Butyro-salicyl on the hydride of by W. H. Perkin 472. C. Cadmium symbol of 448. Calculus of chcmicd operations on the by Sir B. C. Brodie 367. Calorimeter for determining the amount of heat evolved in the combustion of various substances with potassic chlomte 34. Carban~nt~ of iimmonk it F r1ircc.t con--\weion into urea 194.ISDES. 527 Carbanilie ethm on by Din. Wilm niid Dr. Wirchin 192. Carbon estimation of organic in potable waters 87. -proportion of in various kinds of steel 281. -symbol of 42'7. -bisulphide :sbuolption of its \-apour by charcoal 192. Carbonate of ammonium absorption of by alumina 12. -by ferric oxide 11. -potassium absorption of by alu-mina 10. --by fei~ic oxide,6. C'habot P. jun. obituary notice of xxxir. Chance Henry on the manufacture of glass 242. Chapman E. T. note on the estima- tion of nitric acid in potable waters 172. Chapman E. T. and Smith M. H. action of zinc-ethyl on nitrous and nitric ethers 170. Chapman and Wanklyn. See Wank- lyn.Chapma 11 Mi $11k 1y n aud 'S ni i t h. See Wanklyn. Charcoal on the absorption of vapoiirs by by John Hunter 186. Chemical equations construction of from the data afforded by experiment 402. Chemical Society Anniversary Meeting of March 30 1868 i. -Balance-sheet of 1868 xxxvi. Chemical substances symbols of the units of tU>& -symbols on the construction of by Sir B. C. Brodie 367. Chloranil action of sulphurous acid on 146. -analyses of 144. -on by John Stenhouse 1411. -preparation of from picric acid 144. Cldorate potassic determination of heat evolved by burning of various sub-stances with 34. Chlorhydranil 145. Chloride of ammonium absorption of by ferric oxide 12. -diamylamine oxidation of 162.I_ potassium absorption of by ferric oxide 10. -silver non-volatility of st high temperatures 507. Chlorine gas application of to tho toughening and refining of gold by F. B.Miller 506. Chlorine symbol o€,415. c'1i~o.omyl clichloride note on the specific gravity and boiling point of by T. E. Thorpe 514. Church -\.,~licmicd researcheson new and rare Cornish minerals 277. Clark Dr. Thomas obituary notice of, ... v111. Clauclet F. on the occurrence of pris-matic arsenious acid 175. Codeine oxidation of 164. Colloid silica obtained by dialysis on the occurrence of organic appearances ill by IT. C'. Eoberts 274. Comwallite examination of by A. H. Chnrch 276. Coumarin on the artificial production of and formation of its hornologues by TV.H. Perkin 53. -acetic 55. -butpic 56 474. -raleric 55. -formation of from the hydride of aceto-salicyl 185. Cruy Walter obituary notice of XT11. D. Darling W. H. researches on dime-thyl 496. Daubeny C. (3.B. obituzry notice of xvll1. De la Rue Warren and Euliiller Hugo on a new form of constant battery 488. Diamylamine oxidation of chloride of 162. Diazo-dinitrophenol,.produced by the action of nitric acid on picramic acid 151. Dimethyl researches on by W. H. Darling 456. -action of chIorine on 503. -preparation of by electrolysis of an alkaline acetate 502. -by Frankland's process, 500. -by Schutzenberger's pro-cess 4.97. Dime thy 1-normeconin ,362. Dinas brick Welsh analysis of 297.Diphenyltartramide oxidation of 163. Diptyl 61. Dittmar W. on the vapour-tension of formate of ethyl and of acetate of methyl 477. Divanadyl monochloride 348. Donat>ions to the Library of the Chemical Society (1867-1868) xliv. Drechsel E. the reduction of carbonic aciil to oxalic acid 121. ,528 INDEX. Duppa and Perkin. See Perkin. Forbes David on chemical geology E. Electrolysis of acetic acid by 11. Kolbe 195. -alkaline acctate preparation of dimethyl by 502. Energy actual clcvcloped by 1gram of various articles of food when burnt in oxygen 49. -when oxidized in thc body, 49. Equations chemical constriwtion of from tlic data affordod by experiment 402. -fundamcntnl chemical 392.Ether carbanilie 011 by 311.. Wilm and Dr. Wischin 192. 13iiws action of zinc-otly.1 on nit:*ous and nitric bv E. T. C11~p111an miit 31.H. Smitil ITO. Ethyl formate preparation of 4i9,493, -vapour-tension of 481 487 Ethyl iodide absorption of its raponr by cliarcoal 186. Ethylamine absorption of its yapoui-by ~hareoiil,188. Ethylglyouylate of ct?iyl 205 Ethylic sulphocyanate note on by MY. Irelan 193. F. Faraday Michael obituarJ notice of xxi. Ferric oxide absorption of ammonium dts by 11,14. L_ -. potassiuni salts 6 13. Pick and Wislicenus amount of work performed by in' the ascent of the Faulhorn as compared with the amount of muscle consumption 39. Fluorides neutral of the alkalis etch- ing on glass with 256.Food actual energy developed by 1 gram of vaPious articles of when burnt in oxygen and when oxidized in the body 49. -weight and cost of various articlcs of required to be oxidized in the body jn order to raise 140lbs. to the height of 10,000 feet 50. -weight of various articles of required to sustain respiration and circulation in the body of an average mau during twenty-four hours 51. -results of experiments with dried at 100"C. in heat-unit% 48. 213. Formate of ethyl prepamtion of 478 4.83. -vaponr-tension of 481 487. Poster and Matthiesscn. See Mat- t 11i e s s en. Frankland E. on the origin of mus-cular power 33. -on %.simple apparatus for deber-mining the gases incident to water analysis 109.Frankland E.,and Armstrong IT. E. on the. analysis of potable waters 77. Freezing of water and bismuth by A. Tribe 71. G. Gamgec and Waiiklyn. See Wank-lyn. Gas analysis on by W. J. Russell 128. Gases application of the measurement of to quantitative analysis by W. J. Russell 310. -on a siinple nppmatus for deter-mining the incident 13 water analysis by E. Frankland 109. Gas-furnace on the wgcneratiye as applied to tho milnufacture of cast-steel by C. M. Siemens 279. Bnultherate of sodium action of benzj 1 chloride on 124. Geology on chemical by D a v i cl Forbes 213. Gill C. $1. and Meusel Ed.,on para€-fin and the proclucts of its oxidation 466. Gladstone J. II. on the pyrophos-phoric slides 64.-on the tetraphosphoric amides 261. Glass on tlic mariufactnrc of by Henry Chance 242. -change of colour of by exposure to sunlight 251. -etching on by hydrofluoric acid and neutral alkaline fluorides 256. Yjoxylide 204. Sold on the application of chlorine grs to the toughening and refining of by F. B. Miller 506. H. fa ttg h t on Rev. D. determination of the amount of dual energy dere-loped in the bodies of military vegeta- rian prisoners engaged at shot-drill ISDES. 529 as coinpared with the niiioant nf muscle consumption 43. Heat animal source of 47. Herlcpath William obituary notice of xxiv. Hu nt e r 5oh11 on the absorption of vapours by charcoal 1%. Hydride of aceto-salic;rl on tlic bp TV.H. Perkin 181. -benzyl-aalic,vl 123. -butyro-salicTl 011 tlic and butgric coumaric acid Ly W. H. Perkin 272.-forination of but@ couniarin from -474. -diuin-salicF1 action of b:iizyl-chloride on 122. -salicyl absorption of its rapour by charcoal 188. Hydrogen on the reducing action of pc~ oxide of and carbolic acid by J. Pnrnekl 356. -symbol of 405. I. loclide of amyl absorption of its KL~OUP by charcoal 189. -ethyl absorption of its vapour bp charcoal 180. -methyl-strScliiiiiie oxidation of 164. Iodine symbol of 417. Irelan on ethylic suIphocyttnate 193. Iron oxide absorption of aianionium salts by 11,14. -potassium salts 6 13. J. Jones H. Bence on the solubility of xanthine (uric oxide) in di1ut)e liydro-chloric acid 211.K. Kol be H. chemical contributions by, 192. -on the eleotrolysis of acetic acid 193. L. Lxng Victor von on tlie crptallinc form of some products obtaiiied from narcotine 365. Library o€ the Chemid Society dona. tions to the (1867-1868) xliv. iog. (1 + *003665t)'l60 table of for ea,ch-i$. of a degree from Oo to 30' C. 120. M. dlgiiesia separation of fi*om allralia ,519. higanese in steel 252. bIatthiessen h.,mid Fostcr GI. C'. pesearclies into tlIe clwitiical constitn- tion of I~PL'O~~UC tr17(1 of its pxducts of ciecomposit ion.-Fart TI 357. Ueconin actioii of lipdrochloric and hydrioclic aciiis on 360. -crptalline fom of acid CgH804, derired froin 365. -forination of from opianic aci(l I)p the nction of sodium mialgam 359.Neetings of the ~heinicnl Society rc-ports of Proccedings nt (Session 1867-1868) i. 3lercii.y sj111T)ol of,423. Metaranndntes 340. Methyl acetate ahcoi*ptionof its vnpour by charmil ISS. -pwpamtioii of 1S0 484. -=-w.poiir-tPii~ionof 481 487. WetIi~-lic nlcoliol ; absorption of its Tapour by charcoal 190. nIethT1 iodicie production of dimeth~l bj-action of zinc upon in sealed tubes 500. Methyl-normeconin 360. Methyl-nornsrcotine 364. Metliyl-strychnine oxiclation of iodidc Of) 16$. Meuscl and Gill. Sec Gill. Miller F. B. on the applicatioii of chlorjne gas to the toughening anci refining .of gold 506. Nonomet h$-nonnal meconin 360. Monovanadates 339.Morphine oxidation of 164. Miiller and De la Rue See Dc la Rue. Musculrtr power on tlie origin of by E. Frankland 33. N. iXaplitJialeiie abaolption of its rnpw by cliarcoal 189. Xarcotiiic action of hydrochloric and hydriodic acids on 363. -researches into the chemical conl-position of and of its products of decomposition by A. Matthiesee11 and G. C. Foster.-Part 11 353. Xicotin?. oxidation of 163. Nitrale of aiuuoniuiu absoi-ption of by ferric oxide 12. -nmyl action of zinc ethyl on 171. -potassium absorjjtiou of by alumina 11. -by ferric oxide 9. Nitrite of ainyl action of zinc-ctlijl on 171. Xitre rough notes on the formation of as observed in the north-western pro- vinces of India by W. J.Palmer ,318. Nitrides of vanadium 349. Nitrogen est,imation of in the form of nitrates aiid nitrites in potable waters 101. -estimation of organic in potable waters in steel 87. 282. I_ table for the reduction of cubic centimetres of to grams 118. -compounds ainmonia evolved by alkaline peruianganate acting on or-ganic 161. Nitrobenzol absorption of its vapour by charcoal 189. 0. 0bituai.g notice of P. J. Chubot xxxiv. -Dr. Thomas Clark viii. -Walter Cruni xvii. -Dr. D a 11b e n y xviii. --William Herapath xsiv. J. Michael Faraday xxi. T. Pelouze YXV. -John Tenneut xxix. -Robert Warington sssi. -William Winsor xxxiv. Opcmtions Calculus of chemical hg Sir B. C. Brodie 367. Orange-tree analgsis of the ashes of fi diseased by 'l'.E.Thorpe 5:s. Orange-trees anal-pis of the ashes of healthy 523. Organic and other volatile niattera esti- mation of in pDtable waters 79. .__ carbon and nitrogen estimation of in potable waters 87. -compounds action of oxiclizing agents on in presence of emes of alkali 161. Oxdic ether absorption of its raponi. by charcoal 188. Oxide of iron absorption of arnmoniuni-salts by 11 14. -potassium-salts 6 13. -and alumina on the part taken by in the absorpti-ve action of soils by P. Wqrington 1. 0s) gen clcieiininxtion of the necwzs:.y to osidise the organic matter in potn- ble waters 81. -symbol of 407. P. Palmer JV. J.,rough notes on the for-mation of nitre as observed in t!ic north-western provinces of India 318.Paparerine oxidation of 164. Paraffin on and the products of its oxi- dation by C. H. Gill and Ed. Meu- eel 466. -oxidation oE by chromic acid 467. nitric acid 469. Pnrnell John on the reducing action of peroxide of hydrogen and carbolic acid 356. Pcdler A. on the ieomeric forms of vnleric acid 74. Pelouze J. T. obituary notice of XXV. Perchloritle of carbon absorption of its vapour by charcoal 192. Perkin W.H. on the artificial pro-duction of coumarin and formation of its homologues 53. -on some new benzylic derivatives of the salicyl seyies 162. I_ on the hydride of nceto-snlicyl 181. -butyro-salicyl and butyric coumaric acid 472. -and Duppa B. F. on the consti- tution of glyoxylic acid 197.?en*n~anganate ammonia evolved by alkaline acting on orgnnic nitrogen compounds 161. -of' potash on the action of on urca aiiimoiii:i and acetmiide in strongly nlltalinc solutions by J. A. WanG-lyii and Arthur Clamgee 25 Peroxide of bariiini action of on acetic anhydridc 4.0'7. Piperine oxidation of 162. Phosphorus ill stcel 288. -symbol of 420. Play fair's determiiiatioiis of' tIic amount of work performed by various lnbourey? as compared with the amount of muscle consumption 45. 'I~unbic chloride on the solubility of in water and in dilute Iiydrocldoric acid of various strengths by J. C. Bell 350. 'rime factors apparent exceptions to the law of 454. 'roceedings at tho meetings of the Chemical Society (1867-1868) i.'yrophoaphoi*iu aniides on the by J. 11. GlatLslulic 64. INDEX. 531 Qniiiine oxidation of sulphate of 165. R. Regenerative gas-furnace description of 287. -on the as applied to the inanufatts- ture of cast-steel by C. W. Siemens 279. Report of the President and Council of the Chemical Society March 30 1868 i. _I_ Treasurer March 30 1868 xsxrl. Roberts W. C.,on the occurrence of organic appearances in colloid silica obtaiiied by dialysis 2’74. Roscoe H. E. researches on mnadiiiin~ 322. Rowley rag:,devitrification of 257. Russell W. J. on gas analysis 12% -some experiments on the applica-tion of the measurement of gases to quantitative analysis 310. S Palicy1 hydride absorption of it3 VR~W by chai*cqal 188.Salicyl scmes on some new henzylic deihtives of the by TI’. R.Perkin 122. Salicylic mid absorption of its mapour by charcoal 189. Schenck and Wanklyn. See Wank-lyn. Selenium symbol of 414. Shot-drill experiments to determine the amount of actual energy developed in the body compared wit?i that of muscle consunystion 43. Piemeiis C. W. on the reZencratiT2 Smith and Chapman. See Chapman. Sni it 11 C 11apni an and W an k 1p n. See TVanklyn. . Soclium gaultlerate action of beiizrI-cliloride on 18s. Sodiuin-salicyl action of b~~~zyl-c!ilo~ide on the hydride of 122. Soils on tlie part taken by oxide of iron and alumina in the absorptive action of by R. Warington 1. Solid constituents estimation of total in potable waters 78 87.Steel effects of various elements 011 tlie propeyties of 282. -its power of retaining magnetim increased by the presence of tungsten 284. -nature of 280. -’ on the regeneratire gas-fhrnare as applied to the manufacture of cast by C. W. Siemens 279. _I various processes for making 28 C. -proportion of cerboii in verioi?s kinds 281. Stenhouse John action of nitric a4 on picramic acid 150. -on chloranil &c. 141. Strychnine oxidation of la. Sulphate of ammonium absorption of by almnina 13. -by ferric oxide 12. -cinchonine oxidation of 1%. -potassium absorption of by olu-mina 11. -by ferric oxide 10. -quinine oxidation of 165. Sulphocyanate ethylic 011 by Mr. Irelan 193.Sulphur in steel 882. -symbol of 413. S~mbo!0 in cdculus of chemical opera- tions 385. -1 in calculus of chemical opera- tions 390. F~i~lHbo:H,01 t1.c co-ietmctioii of cliemi-gas-fuimacc as applied to the ~1sild>~-ture of cast steel 25’9. Silica orgnnic appearances in co!lofd 274. Silicate of soda production of by tle-composition of common ~nlt with Rilieic acid 2%. Silicon in steel 253. -symbol of 433. Silver symbol of 449 Silver cliloride non-yolatility of at high temperatures SOP. Smith E. detemination of the ainoiiii+ of energy clereloped in the body of men engaged in treadwheel wo~k,2s compared with the ainonnt of inn4:le eon~iiinption,43. cal by Sir l3. C. Bl-odie 357. -of chemical operations 384.-of simple weights 397. T. Tennent John obituary notice of xxix. Tei~chlo~~~o~nliydroqi~itioiie~ 14.9. Terchlo~~l~ronzqv.i~oiie, 249. Terchlorhydroquiuone 146. Terchlorqninone 147. Tetraphosphodiainic acid 269. I_ amnoniated 273. Tdrq~liosphoricamiclrs on the bp J. IT.fll;1~?~!<~i?c, ?GI. INDEX. Tetraplzosphotetriniate of silver 2'70. Theilkuhl on inethia-trisulphonic acid 196. Tlror~e,T. E. note on the specific gmvity and boiling point of chromjl dichloride 514. -analysis of tho ashes of n diseased orange-tree 5 1 5. -analysis OC tlie water of the Holy Well a medicinal spring at Hrunplirey Head North Lancashire 19. Tin use of to separate phosphoric mid from bases 517.7symbol of 4444. Treadwheel experiments to determine the amount of actual energy developid in tlie body as compared with the amount of muscle consumption 41. Tribe A. on the freezing of water and bismuth 71. Triethylamine absorption of its Fapour by cI~arcoal,188. Tungsten its effect in increasing the power of steel to retain magnetism, 284. U. Urea action of mangnnate of potash on 28. -permanganate of potash on in strongly alkaline solutions 25. -note on the preparation of by J. Williams 63. -rational formula of 31. -direct conversion of ammonia-car-bamate into by 4.Basaroff 104. Uric oxide or xanthine it.s solubility in dilut,e hydrochloric acid 211. V. Valeric couiarin 330 344. Vanadates 339.Vanadium compounds occurrence and preparation of 326. -dioxide 3344. -minerals occurrence of phosphorus in 329. I_ nitrides 349. -oxycldorides 341. -pentoxide 339. -researches on by H. E. Roscoe 322. -tetroxide 338. -trioxidc 336. Vanaclyl 334,. iliehloridc 347. Vansdyl liionochloride 34% -trichloridc 3.31. lrapours on the absorption of by chnr-coal by John Hunter 186. Vapour-tension of formate pf ethyl aid of acetateof methyl by W. Dittniar, 4i77. Wanklyn J. A. and Chapman E. T. on t'he action of oxidizing agents on organic compounds in presence of alkali.-Part I. Ammonia evolved by alkaline permanganate acting on or-ganic nitrogen compounds 161. -and Gamgee A. on the action of permanganate of potash on urea; am-monia and acetamide in strongly alkaline-solutions,25.-and Schenck R. synthesis of caproic acid 31. -Chapman E. T. and Smith, M. H. note on Frankland and Arm- strong's memoir on the analysis of potable waters 152. Warington R. on the part taken by oxide of iron and alumina in thc absorptive action of soils 1. I_ obituary notice of sssi. Water freezing of 71. -analysis on a siinplc apparatus for determining the gases incident to by E. Frankland 109. -of the Holy Well at Humplirey Head North Laneashire analysis of by T. E. Thorpe 19. Waters on the analysis of potable by E. Frankland and H. E. Arm-strong 77. i. Estimation of total solid consti- tuents 78 37. ii. Estimation of organic and other volatile matter 79.iii. Determination of oxygen neces- wry to oxidize the organic matter 81. iv. Estimation of nitrous and nitric acids 85 101. F. Estimation of ammonia 87 103. vi. Estimation of organic carbon and nitrogen 87. -on the estiination of nitric acid in potable by E. T.Chapman 168. Weights on the symbols of simple 397. Williams J. note on the artificial preparation of urea 63. Wilin and Wiscliin on carbanilic ether 192. Winaoy W. obituary notice of ssxiv. ISDEX 5 33 X Z Xanthine on the solubility of in dilute Zinc action of on mdhyl iodide in hydrochioric acid by H. B eiice sealed tubes 500. Jones,211. Zinc symbol of 426. Zinc-ethyl its action 011 nitrous and nitric ethers by E. T. Chapman and M. H. Smith 170.

ISSN:0368-1769    

DOI:10.1039/JS8682100525

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

ISDEX. 533 ERRATA. Page. Line. 185 7 from bottom foil byacetate P~ULZ biacetate. xliv 18 from bottom ufter ‘‘Metals ” iiasert Part 11. HARRISON AND SOXE3 PRINTERS IX ORDINARY TO HER MAJESTY FJT. MARTIN’S LANE.

ISSN:0368-1769    

DOI:10.1039/JS8682100533

出版商:RSC    

年代:1868

数据来源: RSC