摘要:

THE QUARTERLY JOURNAL OF TWE CHEMICAL SOCIETY. Nov. 4 1850. THOMAS GRAHAM,EsQ. V.P. in the Chair. The following Donations to the Library have been made since the last Meeting ‘‘ The Pharmaceutical Journal,” Vol. X. Nos. 1 2 3 4 and 5 by the Editor. “ Journal of the Franklin Institute,” Vol. XIX. Nos. 5 and 6; Vol. XX. Nos. 1 and 2 by the Institute. “Transactions of the Iloyal Society of Edinburgh,” Vol. IV- XIX ; Part 1 Vol. XX ;and the i‘Proceedings of the Royal Society of Edinburgh,” Parts 35-39 ; by the Society. ‘‘ On the Constitution of Codeine and its Products of Decomposi-tion,” by Thomas Andrews M.D. by the Author. “Report to General Sir Thomas Macdougall Brisbane Bart. on the completion of the publication in the Transactions of the Royal Society of Edinburgh of the observations made in his Observatory at Markerstown,” by John Allen Brown presented by the Author.“On the Isomorphism and Atomic Volume of some Minerals,” by James D,Dana by the Author. Berichte iiber die Mittheilungen von Freunden der Naturwissen- schaften in Wien,” von Wilhelm Haidinger. Band V. and VI. 1848-9. rr Bulletin of the Royal Belgian Academy of Medicine,” Vol. IX? Nos. 3-7 by the Academy. CCQuarterly Journal of the Geological Society,” Vol. VI. No. 23 by the Society. “ Setzungsberichte der Kaiserlichen Akadernie der Wissenschaften Mathematisch -Naturwissenschaftliche Classe.” Erste Abtheilung (Jan. Feb. March April). “Haidinger’s Report,” Vol. V and VI. 1849-50 by the Society of the Friends of Natural Science in Vienna.“ Abhandlungen der Mathemati~ch-physikalischenClasse der KO-niglich Bayerischen Akademie der Wissenschaften.” Band V. 1 2,3 Abtheilungen. VOL. 111.-NO. XII. Y DR. FRANKLAND’S RESEARCHES I‘ Chemical Investigation of the most important Mineral Waters of the Duchy of Nassau,” by Dr. R. Fresenius by the Author. “ Ueber den Antheil der Pharmacie an der Entwickelung der Che- mie :, von Dr. Ludwig Buchner Jun. “Laurent and Gerhardt’s Comptes Rendus,” (from Quesne- ville’s “Revue Scientifique”) Nos. 1-9 by M. Quesneville. “Taylor’s Calendar of the Meetings of the Scientific Bodies of London for 1850-1” by the Publisher. “Silliman’s American Journal for September 1850” by the Editor. (‘Quesneville’s Revue Scientifique from December 1849 to May 1850 by M.Quesneville. “On the Power of Soils to absorb Manure,” by Professor Way by the Author. “ De Cerevisiae Vera Mixtione et indole Chemica et de Methodo analytica alcoholis quantitatem recte explorandi,” scripsit Dr. H. Wackenroder by the Author. The following Papers were read cr On the Magnetic Attraction of Metals,” by Mr. Richard Adie Liverpool. XXVI1.-Researches on the Organic Radicals. BY E. FRANKLAND, PH.D. F.C.S. 111. ON THE ACTION OF SOLAR LIGHT UPON IODIDE OF ETHYL. The action of light in modifying and controlling chemical affinity has frequently been the subject of investigation and the exceedingly curious and interesting results which have already been observed seem to promise that this agent will become a most valuable assistant in chemical research.Gay-Lussac and Thenard were the first to point out that chlorine and hydrogen may be preserved in contact for any length of time without entering into combination if the mixture be carefully preserved from light; but that with the presence of light combination immediately commences and proceeds with a rapidity proportional to the luminous influence. According to Faraday iodine and olefiant gas combine most readily in sun-shine; and the name phosgene gas was given to chlorocarbonic acid because light was found to be essentially necessary to its formation. These are a few of the instances in which light has been observed to produce direct combination ; but the cases in which it effects decom- position and changes the order of elective affinity are much more numerous.Under the influence of light chlorine is enabled to decompose water uniting with its hydrogen and liberating pure oxygen gas and according to Grotthuss the blue solution of iodide of starch ON THE ORGANIC RADICALS. 323 in water is completely decolorized with the production of hydriodic acid. Scheele Seebeck and others found that nitric acid exposed to sunlight is converted into nitrous acid and oxygen whilst many metallic oxides lose the whole or a part of their oxygen thus peroxide of lead is resolved into minium and oxygen ; grey oxide of mercury into metallic mercury and red oxide; whilst red oxide of mercury under water is decomposed into grey oxide and oxygen gas.Oxide of silver is resolved into silver and oxygen; carbonate of silver into silver oxygen and carbonic acid; and oxide of gold into gold and free oxygen Boullay finds that aqueous solution of perchloride of mercury is decomposed into protochloride of mercury hydrochloric acid and oxygen gas. In addition to these curious reactions the highly interesting and important discoveries of Hunt Daguerre Herschell and Talbot need only be men- tioned to establish the great scientific as well as practical importance of this remarkable function of light which is also so completely under the control of the operator admitting of being increased diminished or modified at pleasure that there seems every proba- bility of this agent becoming one of our most valuable means of composing decomposing and ascertaining the rational constitution of organic bodies especially as it allows of being applied in such a convenient manner and under circumstances in which other means are inapplicable.It has been long known that certain inorganic bodies containing iodine such for instance as the iodides of silver and gold undergo decomposition when exposed to light the iodine compounds of the noble metals appearing to be most susceptible of this change. From the close relation of hydrogen to these metals its iodide might be expected to possess the same susceptibility and this is in fact found to be the case; for it is well known that aqueous hydriodic acid even when preserved in closely stopped bottles gradually turns brown on exposure to light from the separation of free iodine but the decom- position only becomes continuous when the iodine is removed as fast as it is liberated; it has also been observed that when hydriodic acid gas is allowed to stand over mercury its volume becomes reduced to one half and the residual gas consists of pure hydrogen; but whether this reaction only occurs under the influence of light has not yet been clearly established.In a former memoir,* I pointed out the very close analogy existing between the functions of the compound alcohol-radicals and those of the simple radical hydrogen as exhibited firstly in the constitution * Chem. SOC. Qu. J. 111 47. Y2 DR. FRANKLAND’S RESEARCHES of the vapours of their parallel compounds; secondly in the decom- position of their respective iodides by zinc; and thirdly in the replacement of hydrogen by methyl cthyl zlrnyl &c.in cacodyl in the new nitrogenous bases of Wurtz and Hofmann and in those of M. Paul Th6nard coutaining phosphorus. In order to add another link to the chain of evidence which already exists in support of this analogy it appeared interesting to ascertain if the action of light upon the iodides of ethyl methyl &c. would yield results corresponding to those obtained from iodide of hydrogen under similar circumstances; and this link seemed to me also of greater importance on account of the results thus produced by the simple action of an imponderable agent being less likely to be influenced by the formation of secondary compounds than in the action of zinc upon these bodies at an elevated temperature.My experiments have as yet been principally confined to the iodide of ethyl and it is the results of the action of light upon this body that I have now the honour to communicate to the Society. It has been remarked by almost all chemists who have had occa- sion to employ iodide of ethyl that this liquid slowly becomes brown from the separation of iodine when exposed even to diffused day- light ;this observation which I have myself of late also frequently had an opportunity of making induced me to hope that a decom-position here occurs analogous to that suffered by iodide of hydrogen under the same influence.I find that the ethyl-compound when exposed to direct solar light rapidly becomes of a dark-brown colour; but as is the case with hydriodic acid this separation of iodine soon ceases and when a certain intensity of colour has been attained no further action takes place; if however the free iodine be removed by agitating the liquid with mercury the action immediately recom-mences and proceeds to the same point as before. This behaviour of the iodide under the influence of light and in contact with mer-cury indicated the method by which the action could be carried on continuously and the products collected and preserved. For this purpose several glass flasks of about 10 ounces capacity were filled with mercury and inverted in a vessel containing the same metal; a few drops of iodide of ethyl being then introduced into each by means of a pipette they were exposed to the direct rays of the sun.The surface of the mercury where it was in contact with the liquid soon became covered with a film of protoiodide which by the further action of the light was converted into binio- dide whilst bubbles of gas were continually evolved and gradually displaced the mercury from the flask finally the whole of the iodide ON THE ORGANIC RADICALS. of ethyl disappeared the gas and biniodide of mercury being the sole products of the decomposition. Although simple exposure to the sun’s rays caused this action to take place with tolerable rapidity yet it was very greatly accelerated by placing each flask near the focus of an 18-inch parabolic reflector which was not however SO highly polished as to cause a very considerable elevation of tempera- ture the heat never rising to the boiling-point of iodide of ethyl (71.6’ C.) in this manner a few hours’ exposure sufficed to fill the flasks with gas which was then transferred to the bell-glass figured in a former Memoir,* and allowed to stand over sulphuretted water for twelve hours.At the end of this time all traces of iodide of ethyl vapour had been absorbed and the gas was fit for the endiome- trical operations. As iodide of ethyl is not in the least acted upon by mercury at a temperature of 150’ C.,? it could scarcely be supposed that the com- paratively low degree of heat to which these materials were exposed in the focus of the reflector could play any importaut part in the decomposition; yet in order to set this question entirely at rest an inverted bell-jar containing iodide of ethyl confined over mercury was surrounded by a glass cylinder and this latter filled first with water then with a solution of chloride of copper and lastly with a solution of bichromate of potash.When the outer cylinder W&S filled with water the decomposition proceeded with as much rapidity as without the intervention of that fluid whilst the temperature of the water was scarcely perceptibly raised during the operation ;the same was the case when solution of chloride of copper was employed ; but on substituting the solution of bichromate of potash scarcely the slightest action was perceptible even after several days’ exposure to bright sunshine.Now since according to Mr. Hunt at whose suggestion I employed these liquids the solution of chloride of copper absorbs nearly all the heating rays and allows about 90 per cent of the actinic rays to pass whilst the solution of bichromate of potash intercepts the actinic and gives free passage to the heating rays it is evident that the decomposition before us is due to the chemical influence of light and is totally independent of the heating rays of the solar spectrum. The gas collected and preserved as just stated was then submitted to the eudiometrical processes minutely described in my former Memoir on the cc Isolation of Ethyl,”$ the observations were also made with similar precautions respecting temperature pressure and formation of nitric acid during the explosion with excess of oxygen.* Chem. SOC. Qu. J. 11 266. j-Chern. SOC. Qu. J. 11,295. ? Chem. SOC. Qu. J. 11 269. DR. FRANKLAND’S RESEARCHES The entrance of atmospheric nitrogen into the gas during the time occupied in its purification from iodide of ethyl vapour by standing over sulphuretted water was sought to be avoided by using a deep bell-jar of comparatively small diameter and an outer glass cylinder,* having its internal diameter only 8 inch greater than the external diameter of the interior jar; thus a very small surface of liquid was exposed to the atmosphere and therefore only a proportionably small amount of nitrogen could be absorbed and transferred to the internal gas.The experiments detailed below show that the plan was effectual as none of the gases examined contained an appreciable amount of that element. A determination of the specific gravity of the gas gave the fol-lowing numbers Temperature of room . 2403~ C. Height of barometer . 767-6 mm. Height of inner column of mercury . 13-6 , Weight of flask and gas . 31.6758 grms. 25*3OC. Temperature in balance-case Weight of flask filled with dry air -31.5559 grms. Temperature in balance-case . 25-7O C. Capacity of flask . 140.79 cbc. From these data the specific gravity was calculated to be 1.7159. To ascertain the composition of the gas it was first subjected to the action of fuming sulphuric acid ; two specimens were then exploded with atmospheric air and excess of oxygen and the residue was treated with recently boiled absolute alcohol.The following numbers were obtained In absorption eudiometer. 1. Difference of Correctedvol. Observed Temp. mercury Baromr. at 00 C. and vol. level. lmpressure. Vol. of gas used )175,4 24*4OC. 603~~ 761*Omm121.51 (dry)* Vola. after action oft 150.6 19~5~ 19.0 , 759.5 , 104-08 8% (dry)= , Vol. after removal of specimen for 19*8O, 62.1 , 766.3 , 57.05 combustion. Vol. after absorp-) o.o tion by alcohol. * See Fig. 2. BB Chem. SOC. Qu. J. 11 266. ON THE ORGANIC RADICALS. 327 In combustion eudiometer. 11. Difference of Correctedvol. Observed Temp.mercury Barom'. at Oo C. and vol. level. Im pressure. Val* of gas used } 94.8 17.40c. 601.0- 7643mm 13% (moist). Vol. after admission 472.2 17.70,, of air (moist). 1 Vol. after admission 567,() 17.90,, of 0 (moist). 1 Vol. after explosion (moist). } 525.7 18.10, '01* after abioqtion 467.8 16.@, of CO (dry). } after admission } 683.3 I?'@,, of H (dry). 20093 , 7644, 24345 112.8, 763.9, 338.30 150.5, 763.6, 29466 2041.7, 765.2, 247.34 11.9, 765.7 , 48436 Difference of Correctedvol. mercury Baroxnr. at 00 C.and level. lmpressure. III. Observed Temp, vol. vol* Of gas used (moist). VOL after admission of air (moist). Vol. after admission of 0 (moist). 98.2 17.30C. 595.4mm 7649mm 1429 511.9 17.60 ,, 1 602.9 18.10,, I.161.5 , 7647 , 282.85 85.1 , 7648, 375.53 123.6, 765.3 , 328.57 176.2, 7644 277.90 '01* after explOsion 559.8 18.20 ,, (moist). 1 Vol. a.fter absorp-1501.9 17*0°,, tion of CO (dry). Analysis No. I. proves that the gas is a mixture and contains in 100 parts Gas absorbable by SO . . 14.34 Gas unabsorbable by SO . . 85.66 100.00 And the perfect disappearance of the gas left unabsorbed by sulphurio acid on subsequent treatment with about an equal volume of absolute alcohol proves the absence of hydrogen and hydride of methyl (light DR. PRANKLAND'S RESEARCHES carburetted hydrogen) as also any appreciable amount of nitrogen which might have permeated the sulphuretted water used to confine it during purification.Analysis No. 11 shows that 13.24 vols. of the gas remaining after the action of fuming sulphuric acid consumed 7'7.72 vols. oxygen and generated 47.32 vols. carbonic acid causing a con-traction on explosion equal to 43.64 vols. According to analysis No. 111. 14-29vols. combustible gas con- sumed 83.34 vols. oxygen and generated 50.67 vols. carbonic acid causing a contraction of 46.96 vols. If we take into consideration the composition of the gases evolved by the action of zinc upon iodide of ethyl,* together with the proof given below that the gas absorbed by sulphuric acid has exactly the composition and state of condensation of olefiant gas there can scarcely be a doubt that the gaseous mixture remaining after the action of sulphuric acid consists of ethyl and hydride of ethyl; and by forming two equations in which the volume of the mixture and the amount of contraction produced by explosion with oxygen are taken into account it is easy to ascertain their respective volumes even independently of the quantity of oxygen consumed and car- bonic acid generated although these latter values may be used to control the result arrived at by employing the amount of contraction only in the calculation.I prefer employing the observed contraction as the known quantity in the second equation to either the volume of oxygen consumed or that of carbonic acid generated because the number representing it is obtained from two readings which are least liable to slight sources of error and contains within itself the results of the entire analysis viz the volume of combustible gas the oxygen consumed and the carbonic acid generated.It will be obvious on inspecting its formula that 1 vol. of ethyl requires for its combustion 6.5 vols. oxygen and generates 4 ~01s. carbonic acid; and as the contraction which occurs on explosion is equal to the volume of the combustible gas + the volume of oxygen consumed -the amount of carbonic acid generated it is evident that the gas in question will cause a con- traction equal to 3.5 times its own volume; arid for similar reasons- since hydride of ethyl consumes 3.5 times its own volume of oxygen and generates twice its volume of carbonic acid-this gas must produce a contraction on explosion equal to 2.5 times its own volume.* Chem. SOC. Qn. J. 11 277. ON THE ORGANIC RADICALS. If then we represent the volume of this combustible mixture by A the contraction produced by explosion with excess of oxygen by B and the volumes of ethyl and hydride of ethyl respectively by x and y we have the following equations x+ y=A 2x+-y=B 75 2 from which the values of x and y are found to be 2B-5A X= 2 7A-2B Y= 2 and by substituting the numbers found in analyses Nos. 11. and III. for A and B we have 11. 111. LI = 10.54 11*23 y = 2.70 3.06 13-24 14.29 Hence the gas unabsorbed by fuming sulphuric acid contains in 100 parts XI. 111. MEAN. Ethyl Hydride . of Ethyl . . 79.61 20.39 78.59 21.41 79.10 2090 100*00 100*00 100*00 In order to ascertain the composition and state of condensation of the gaseous body absorbed by fuming sulphuric acid the original gas before being exposed to the action of that acid was exploded with atmospheric air and excess of oxygen.The following results were obtained IV. Difference of Correctedvof. Observed Temp. mercury Baromr. at 00C. and vol. level. lm pressure. Vol. of gas used 1 96.3 (moist). 9*4OC. 575.9"" 747.5"" 15.16 VOLafter admission 1590.r 9.5*, 68.9, 746.7 , 381*83 of air and 0 (moist) Vol after explosion } 549.2 (moist). 9*7O> 105.4, 746.7 , 335.34 Vol. after absorp- p92.1 tion of CO (dry). 7*4*, 158.1 , 753.1 , 28459 DR. FRANKLAND’S RESEARCHES According to this analysis 15.16 vols.of the gas consumed 82.08 vols. oxygen and generated 50.75 vols. carbonic acid; but analysis No. I. shows that this quantity of gas contains 12.99 vols. of the mixture of ethyl and hydride of ethyl which according to the mean of analyses Nos. 11. and III. would consume 7599 vols. oxygen and generate 46.24 vols. carbonic acid; thus leaving 6-09vols. oxygen and 4.51 vols. carbonic acid as the oxygen con-sumed and carbonic acid generated by the 2.17 vols. of the gas absorbable by sulphuric acid 1 vol. of which must therefore have consumed 2.81 vols. 0 and generated 2-08vols. carbonic acid Vol. of comb. gas. 0 cmsumed. CO generated. 2.17 6.09 451 1 2-81 2-08 When we reflect that in this experiment all the errors of observa-tion are concentrated upon a very small proportion of the gas sub- mitted to analysis the numbers obtained agree sufficiently with those yielded by the combustion of olefiant gas to allow safely of the conclusion that the body absorbed by sulphuric acid is the gas in question; for 1 vol.of olefiant gas consumes 3 vols. oxygen and generates 2 vols. carbonic acid. The composition of the gases evolved by the action of light upon iodide of ethyl in presence of mercury may therefore accordingIto the mean of the above analyses be thus centessimally expressed Ethyl . . 67.76 Hydride of ethyl . . 17.90 Olefiant gas . . . 14.34 100*00 The theoretical specific gravity of 8 gaseous mixture of this composition agrees closely with that found by experimenty as shown by the following calculation C H = 67.76 x 2.00390 = 135.7843 C H, H = 17.90 x 1.03652 = 18.5537 C H = 14.34 x 0.96742 = 13.8728 100~00 168.2108 a = 1.682108 100 Specific gravity as found by experiment .. 1.7159 Hence the decomposition suffered by iodide of ethyly under the ON THE ORGANIC RADICALS. influence of light and in presence of mercury is expressed by the following equation a small portion of the liberated ethyl being at the same time trans- formed into equal volumes of olefiant gas and hydride of ethyl The slight deficiency of olefiant gas as exhibited by the analyses may very probably be owing to the different solubility of the two gases in the sulphuretted water which was used as the confining medium during their purification from the vapour of iodide of ethyl.The action of light upon iodide of hydrogen and iodide of ethyl is therefore perfectly allalogous; in the one case we have the simple radical hydrogen eliminated and in the other the compound radical ethyl. This reaction is also perfectly parallel with that produced by the action of heat upon iodide of ethyl in presence of zinc,* except that in this last decomposition a considerably larger portion of the ethyl is transformed into hydridc of ethyl and olefiant gas. The proportion of ethyl which unde;.goes this transformation in the two reactions just mentioned and in one which I describe below is worthy of remark it is best seen from the composition of the gases left after the action of fuming sulphtiric acid.I Gases evolved by action of zinc upon iodide of ethyl C H C H H=50*03 25.79 = 1.94 1.00 11. Gases evolved by action of light upon iodide of ethyl in presence of mercury C4H C4H5H=79*lO 20.90 = 3-78 1.00 111. Gases evolved by action of light upon iodide of ethyl in presence of mercury and water C Hi C,H5.H = 11.535 3.055 = 3.78 1.00 As the hydride of ethyl occupies exactly the same volume as the ethyl from which it is derived it is evident that in the first reaction * Chem. Soe. Qu. J. 11 281. 332 DR. FRANKLAND'S RESEARCHES exactly &rd and in the second and third very nearly +th of the ethyl evolved undergoes this transformation. It was not without interest to ascertain if the action of light upon iodide of ethyl is modified in any way by the presence of water as was the case in the corresponding reaction with zinc where the whole of the ethyl was converted into hydride of ethyl by the assumption of an atom of hydrogen from the water whilst the oxygen of the latter united with zinc to form an oxyiodide.ACTION OF LIGHT UPON IODIDE OF ETHYL IN PRESENCE OF MERCURY AND WATER. Iodide of ethyl mixed with about twice its volume of distilled water was exposed as before to the direct solar rays precisely the same phenomena were observed as when the iodide alone was used although the production of gas seemed to take place more rapidly when water was present. The gases were collected purified from iodide of ethyl vapour and examined by the methods described above.A determination of the specific gravity of the gas gave the follow- ing numbers Temperature of room . . . 20.3OC. Height of barometer . '765.9"" Height of internal column of mercury . . 12.9 , Weight of flask and gas . . 33.5639 grms. Temperature in balance-case . . 21-3OC. Weight of flask filled with dry air . . 33.4492 grms. Temperature in balance-case . 21*2oc. Capacity of flask . . . 140.65 cbe. From which the specific gravity was estimated at 1.6944. The eudiometrical analysis gave the following readings In absorption eudiometer. I. Observed Difference of Corrected vol. vol. Temp. mercury Barom'.! at 00 C. and level. lmpressure. Of gasused 181.1 20.3OC.55,mm 765*9"" 128.17 1 Vol. after action of } 153,3 18.70, 3.4 , 7'64.9, 109.25 so (dry)* Vol. after admission) o,o __ -0.00 of alcohol. 333 ON THE ORGANIC RADICALS. In combustion eudiometer. 11. Observed Difference of Corrected vol. vol. Temp. mercury Barom'. at OoC. and level. Impresswe. Vol. of gas used) 96.0 19.20~. 585*7mm 7649"" 14.59 (moist) Vol. after admission 516.5 19.40 , 144.8, 7647 , 290.87 of air (moist). I-VOL after'admission } 605.2 19.70 , 649 , 764*5, 385.24 of 0 (moist). VO~.after explosion } 562.3 20.00, 103.1, 764.2, 337f23 (moist). Vol. after absorption } 503.8 18.80, 156.4 , 765.5 , 287.08 of con fdrv). 0 \ dl Vol. after admission } 689.7 21.10 , 2.6 9 762.9 , 486.75 of H (dry).VOL after <xplosion 518.1 21.60 , 153.3, 762-5, 283-27 (moist). } From analysis No. I. it follows that toe gas contains in 100 parts Gas absorbable by SO . . . 14.76 Gas unabsorbable by SO . . 85.24 -100*00 And its perfect absorption by alcohol proves the absence of hydrogen hydride of methyl and nitrogen. Analysis No. 11. shows that 14.59 vols. of the gas left intact by fuming sulphuric acid consumed 83.57 vols. oxygen and generated 50.15 vols. carbonic acid causing a contraction on explosion equal to 48.01 vols. From a simple inspection of these figures it is evident that we have the same gaseous mixture to deal with as in the previous decomposition of iodide of ethyl without the presence of water and on applying the formula given above we obtain the following values for x and y x = 11.535 y = 3.055 14-590 Hence the gas before being acted upon by fuming sulphuric acid consisted of DR FRANKLAND’S RESEABCHES 334 Ethyl .. . 67.39 Hydride of ethyl . . 17.85 Olefiant gas . ‘ . 14.76 100*00 The determination of its specific gravity given above also confirms this result as is seen from the annexed calculation C H = 67.39 x 2*00390= 135.0430 C H H = 17.85 x 1*03652= 18.5019 C H = 14.16 x 0.96742= 14*2791 167*8240 = 1*67824 100 Specific gravity as found by experiment . 1.6944 The presence of water consequently exerts no modifying influence over the decomposition of iodide of ethyl by light the products formed with and without the presence of water being identical both in composition and relative proportion.The transformation of ethyl into hydride of ethyl when its iodide is decomposed by zinc in contact with water is therefore probably owing to the high affinity of zinc for oxygen rather than that of ethyl for hydrogen although both affinities no’doubt take part in causing the resolution of water into its elements. The above decomposition of iodide of ethyl by light depending as it does directly upon the chemical rays furnishes us with the materials for the construction of an actinometer of considerable delicacy since the volumes of gas (corrected for tension of iodide of ethyl vapour &c.) evolved in equal times would give us the relative quantities of the actinic influence falling upon a given surface during these times; thus daily or even hourly readings of the instrument could be made during the time the sun is above the horizon and a register of the actinic influence in different localities be kept with as much ease as registers of the atmospheric pressure and temperature.I have not ascertained how small a quantity of light can determine the decomposition of the iodide; but very weak diffused daylight as for instance on a very cloudy or foggy day is sufficient to produce a very considerable disengagement of gas the volume of which could of course be read off at stated times with the greatest facility and without even interrupting the action of the instrument. I have also studied the action of solar light upon the iodide of ON THE ORGANIC RADICALS.335 methyl as well as upon the iodides of ethyl and methyl in contact with the various metals which has led to the discovery of an entirely new series of organo-metallic radicals possessed of very remarkable and interesting properties; the results of these researches I hope shortly to have the honour of laying before the Royal Society. The foregoing experiments form I think another link in the chain of evidence which establishes the homology of hydrogen with the radicals of the series to which ethyl and methyl belong and the simplicity of the decomposition by which the ethyl is here separated from the iodine by the action of an imponderable agent seems to some extent to disarm of their force several of the arguments lately employed with so much ingenuity by Dr.HofmannX against the formulz which I proposed for these bodies. In order to decide upon the truth or falsity of the views entertained by MM. Laurent and Gerhardt respecting these compounds according to whom their formulz ought to be doubled and the bodies themselves classed amongst the members of the marsh-gas series Dr. Hofmann under- took the examination of the products resulting from the action of heat upon valeric acid in the hope of obtaining the hitherto unknown member of the marsh-gas family represented by the formula c8 HIO which if identical with the gas evolved by the action of zinc upon iodide of ethyl would render necessary the doubling of the formula of the latter gas ; whereas if the body C8 H, were not identical with the so-called ethyl it would afford strong evidence in favour of my formula being the correct one.Unfortunately Dr. Hofmann did not succeedin obtaining this body and thus the question was left in the same condition as before. In a former memoir? I have described two separate series of carbo-hydrogens isomeric with each other the one consisting of the bodies which I consider as the alcohol radicals and the other contain- ing the members of the marsh-gas family which I regard from the mode in which they are formed as the hydrides of these radicals; thus Radicals. Marsh-gas family or hydrides. C H { Hydride of methyl (light carburetted c H,. Methyl hydrogen) } Ethyl C H , ethyl .. . C H,. H 3, Propyl C H prop91 * . C H,. H Butyl c8 H , butyl . C8 €I,. H 3 CI HI,* H &4myl C, Hll amyl &C. &C. * Chem. Soc. Qu. J. 111 121. t Ib. 111 50. 336 DR. FRANKLAND'S RESEARCHES It is obvious on inspecting the above columns that the members on the left hand are isomeric with those on the line next below then1 in the right hand column. Now two of these bodies which are represented as isomeric in the table just given have been already obtained; viz. methyl (C H,) by the electrolysis of acetic acid% and the decomposition of iodide of methyl by zinc;? and hydride of ethyl by the decomposition of cyanide of ethyl (not perfectly anhydrous) by potassium,$ and by the action of zinc upon iodide of ethyl in presence of water,§ and it is therefore only requisite to establish the identity or isomerism of these bodies in order to test the correctness of the two views which have been proposed.As both the bodies in question are gaseous at ordinary temperatures and do not change this condition under a pressure of 20 atmospheres it is evident that their physical properties cannot assist us in deciding the question; besides even assuming them to be isomeric I should not expect any difference either in their boiling points or specific gravities. Under these circumstances chlorine appeared to be the agent best suited to determine the point at issue; because although we could only expect to obtain substitution products yet the nature of these products must at once give us the key to the atomic weight of the bodies before us; for if we found +th of the hydrogen substituted by chlorine then according to the usual interpretation of this pheno- menon we must assume the simplest atom to contain 6 atoms of hydrogen and if under similar circumstances ird of the hydrogen were substituted we should have an equal right for judging the simple atom to contain only 3 equivalents of hydrogen The action of chlorine upon the so-called hydride of ethyl in diffused daylight has already been studied by Kolbe and myself,ll and we find that 1 vol.of hydride of ethyl and 1 vol. of chlorine give 1 vol. hydrochloric acid and 1 vol. of a gas having the formula C H6C1 but which is oiily isomeric and not identical with chloride of ethyl ;we proposed for it the formula which represents 1 atom of methyl conjugated with another atom of the same group in which 1 atom of hydrogen has been replaced by chlorine.From considerations deduced from the production of hydride of ethyl I now regard this chlorine compound as C cfH H > * Chem SOC.Qu. J. 11 173. $ Chem. SOC.Qu. J. I 60. t Ibid. 11 267. 5 Ibid 11 288. 11 Chem. SOC. Qu. J. I 66. ON THE ORGANIC RADICALS. hydride of ethyl in which 1 atom of hydrogen in the group C H has been replaced by chlorine; and this view explains why the body in question is isomeric and not identical with chloride of ethyl. However in whatever way this compound is viewed it is evident that &th of its hydrogen has been replaced by chlorine.It was now necessary to study the action of chlorine upon the body to which I assign the formula C H,. As there are difficulties which I have not yet been able to overcome in the way of procuring this body pure by the action of zinc upon iodide of methyl 1 employed Rolbe's method by the electrolysis of acetic acid. The apparatus used was the same as that described by that chemist in his memoir except that the gases evolved from the positive pole were allowed to stream through a long series of bulbs filled with a solution of caustic potash by which every trace of carbonic acid was removed; behind this bulbed tube were fixed threc Liebig's potash apparatus the first filled with fuming sulphuric acid the second with solution of potash and the third with concentrated sulphuric acid the last being employed to dry the gas perfectly before it passed into the tubes* which were destined afterwards to be used for the experiments the system of tubes terminated in a delivery-tube leading to the mercury- trough.As soon as the gas evolved in this last was perfectly absorbed by recently-boiled alcohol a specimen was collected for analysis and the tubes now filled with the pure gas were hermetically sealed at one end and the caouchouc connecter at the other being securely tied cut and covered with melted wax they were taken asunder and reserved for the subsequent experiments. The specimen of the gas collected as just described was exploded with excess of oxygen and gave the following numbers.Difference of Coriected vol. Observed Temp. mercury Barornr. at 00 C. and vol. level. lm pressure. Of gas used 1100.0 lfj~5OC. 576.4"" 752.5~~~ 15.28 (moist). Vol. after admission of o (moist). 1323.3 17.0°, 330.7 , 751-8, 123.77 Vol. after explosion }2664 (moist). 17*2O, 390.5, 751.6 tf 86.83 ,, To1 afterabsbrption 206.2 16~4~ 455.8 , 749.3 ,) 57.09 of CO (dry). } Vol. after admission 521.6 of H (dry). 1 17,10, 136.0 , 748.9 , 300.83 VOL after 'eiplosion 332.5 16*80, 320.6 , 749.0 , 129.73 (moist) 1 * The form of these tubes is showii in a figure given in t.his JOUIX. Vd.I p. 6 Fig. I e-f. VOL. 111.-NO. XIT. z 338 DR. FRA4NKLAND'S RESEARCHES The proportion between the voluines of combustible gas osygeir consumed and carbonic acid generated may therefore be thus stated VoI.of comb gas. 0 consumed. CO generated. 15.28 51.41 29.74 1 3.36 1.95 The numbers required theoi*etically for methyl are 1 3.5 2 A number of tubes some of the same and others of exactly double the capacity of those containing methyl were then prepared and filled with dry chlorine by displacement ;they were afterwards sealed at one extremity the caoutchouc eonnecter at the opposite end being securely tied and covered with melted wax. ACTION OF CHLORINE UPON AN EQUAL VOLUME OF METHYL. Two tubes of exactly the same capacity the one containing chlorine and the other methyl were quickly connected together by inserting their narrow necks into a strong caoutchouc connecter and securing them by silk ligatures ;they were placed in perfect darkness for 18 hours to allow the gases to become thoroughly mixed.On being afterwards exposed to diffused daylight the colour of the chlorine rapidly disappeared showing that combination ensued. After being allowed to stand in the light for several hours the tubes were hermetically scaled and their contents submitted to eudionietrical examination. On breaking off their extremities under mercury it was evident that no contraction of volume had taken place; but the dense fumes caused by allowing a few bubbles of the gas to escape into the atmosphere proved that hydrochloric acid was one of the products of the reaction and that the two gases had not simply united to form chloride of methyl.The contents of both tubes were trans- ferred into a eudiometer and the volume of hydrochloric acid was estimated by absorption first with a ball of aqueous tribasic phosphate of soda and afterwards with a bullet of fused potash which last also dried the residual gas perfectly. The following numbers were read off Difference of Corrected vol. Observed Temp. mercury Baronir. at Oo C. and vol. level. lm pressure. ON THE ORGANIC RADICALS. Thus it appears that the products of theaction of 1 vol. of chlorine on 1 vol. of methyl are 1 vol. of hydrochloric acid and 1 vol. of another gas which iiiust necessarily liave the empirical formula C H C1 expressing 4vols. This is exactly the result obtained by Kolbe and myself itz acting with an equal volume of chlorine upon the hydride of ethyl obtaiiied by the action of potassium upon cyanide of ethyl and thus up to the present point the experiments seem to prove the identity of the two bodies-the so-called methyl and the hydride of ethyl.But these experiments admit also of a differeiit interpretation; for if we assume that the chlorine acted upon only half of the methyl employed then the following equation mould cxpress the reactinn 2vols. of chlorine acting upon 1 vol. of methyl produce 1 vol. hydro- chloric acid and 1 vol. of chlormethyl C (:<) nhich last remains mixed with the excess of inethyl employed. It would be very difficult to determine directly whether the gas in questioii is a mixture 01’ a single gas; or in other worcXs whether methyl and hydride of ethyl yield identical or isomeric results when acted upon by an equal volume of chlorine; but this question can be easily dccidcd by employing an additional volume of chlorine by which if the view of the reaction just stated be Correct the cxcess of methyl will also uiidergo the pmxss of substitation and the result should be 1vol.of inethyl gas in which 1 atom of hydrogen has been replaced by elilorine (c3(:‘2)-) and 2 vols. hydrochloric acid. H Cl ACTION OP 2 VOLUMES OF CU[LORINX UPOX 1 VOL. OF METHYL. Two tubes wei-e coirnected together the oiie having a capacity exactly twice as great as the other the first being filled with dry chlorine and the last with methyl; as in the former experiment they were excluded from light for 18 hours to secure the perfect mixture of the two gases before allowing the chlorine to act.On afterwariis bringing the tubes into diffused daylight their interior became za DR. PRBYKLAND'S RESEARCHES bedewed with minute drops of an ethereal fluid which however again disappeared after the lapse of a few minutes and on opening the tubes under mercury after the action was completed no con-traction of volume was perceived to have taken place. The contents being transferred to a eudiometer the hydrochloric acid was deter- mined as before. The following numbers were obtained Difference of Correctedvol. Observed vol. Temp. mercurylevel. Barom'. at 00 C. and lm pressure. Vol. of residual gas.Vol. of H C1. 38.19 73.52 1 1.92 Hence it follows that 1 vol methyl and 2 vols. chlorine yield 2 vols. hydrochloric acid and 1 vol. of another gas which must have the formula C H C1 expressive of 2 vols. of vapour ;but this is the formula and state of condensation of the radical methyl in which 1 atom of hydrogen has been replaced by chlorine; and the action of 2 vols. of chlorine upon 1 vol. of methyl is therefore correctly ex- pressed in the equation given above. As a final proof of the correctness of this mode of interpretation and of the isomerism of methyl and hydride of ethyl it remained only to try the action of 2 vols. of chlorine upon 1vol. of the latter body. For this purpose hydride of ethyl was procured by the action of zinc upon iodide of ethyl in presence of water a process which as I have shown,* yields that gas in a state of absolute purity.One volume of this gas perfectly dried being mixed as before described with 2 vols. of chlorine and the intimate mixture then exposed to diffused daylight combination rapidly ensued and the walls of the tubes became wetted with a considerable quantity of an oleaginous fluid which did not disappear or diminish even after the lapse of several weeks during which time the tubes had been hermetically sealed. On breaking off their ends under mercury a considerable contraction was observed to have taken place the residual gas not occupying more than 2rds of the original volume. It was transferred into a eudiometer and on being treated with a ball of phosphate of * Chem.SOC. Q J. 11 291. ON THE ORGANIC RADICALS. 341 soda was so nearly absorbed that the very small volume of gas remaining after its action could not be determined. This experiment allows us to conclude that 2 vols. of chlorine with 1 vol. of hydride of ethyl yield 2vols. hydrochloric acid and a liquid which from the volumes of the gases taking part in its formation has probably the formula C H C1 and the same percentage composition as the oil of olefiant gas (C H C1 + H Cl) ;but whether the oily liquid produced in the above reaction be identical with this body I have not been able to determine as the quantity of the gaseous hydride of ethyl which would be required to form a sufficient amount of liquid to be subsequently purified for analysis would be very great.The results of these experiments on the action of chlorine upon methyl and hydride of methyl do not agree quite so nearly with theoretical calculations as I could wish owing to a slight amount of impurity contained in the methyl as indicated by the analysis of that gas the quantity of oxygen consumed being rather too far below the theoretical volume to be accounted for by possible errors of observa- tion. I have been at great pains to remove this foreign body but without success Dr. Kolbe foiind the same difficulty when he first investigated this gas and attributed the smaller quantity of oxygen consumed to the presence of a trace of oxide of methyl. As the impurity can only be present however in very minute quantity it could scarcely have any material influence upon the results of the experiments and I therefore think they allow us safely to conclude 1st.That there exist two series of hydrocarbons of the form C €Infl,the members of the one series being isomeric with those of the other and 2nd. That the formula of the gaseous hydrocarbon obtained by the electrolysis of acetic acid is C H, its atom being represented by 2 volumes of vapour; whilst the gas procured by the action of potassium upon cyanide of ethyl (not anhydrous) and by the action of zinc upon iodide of ethyl in presence of water has the formula C H, its atom being represented by 4volumes of vapour. As soon as I have succeeded in procuring pure methyl by the action of zinc upon its iodide I intend to repeat these experiments and make them more complete Although Dr.Hofniann regards the decision of the above question as sufficient to establish the correctness of one or the other of the views which have been advanced respecting these radicals on the one hand by M&l. Laurent and Gerhardt and on the other by Dr. Kolbe and myself yet I do not deem it superfluous to offer a few remarks upon the argunients which Dr. Hofmann has used with so much DE. FRANKLAND’S RESEARCHES skill against the formulz we have proposed for the bodies in question especially as several of these arguments appear at first sight very conclusive. The objections which this chemist bas made to these bodies being considered as radicals may be thus expressed 1st.The new radicals do not combine directly with the metalloids ; none of them have been found capable of reproducing a methyl- ethyl- or amyl-compound. 2nd. The voliinie of their vapours are different from that of all other known hydrocarbons. 3rd. The boiling-points of the compounds in question are in favour of their formulix being doubled. 4<th. The decomposition of the iodides of the alcohol-radicals by zinc is not perfectly analogous to that of hydriodic acid. 5th. The formuh of these bodies require to be doubled to remove the discrepancy exhibited by the boiling-points of amylene hydride of amyl and amyl. The first objection follows naturally from the circumstance that up to the time of the isolation of these bodies we were only acquainted with one basic or electro-positive radical in a separate form; viz.cacodyl which has unfortunately been loolred upon by some chemists as a type of all other organic radicals which they therefore expected to find endowed with similar powerful affinities. Such a partial view of the essential characters of a compound radical could not have been formed from a careful coniparison of the varied properties of the simple raclicals which are undoubtedly the true types of their repre- sentatives in the organic world. A slight glance at the habits and afhties ef these elementary bodies exhibits to us the most widely- diEerciit powers of combination. Conimencing with potassium and terminating with hydrogen .gold platinum iridium and nitrogen we have a series of bodies which although they all readily pass from one form of combination to another when already combined yet when once isolated exhibit as we ascend the scale an increasing reluctance to enter into union.Taking these reactions of the simple radicals then into consideration it mould be neither difficult nor visionary to predict that their organic representatives would be found possessed of as great a variety of disposition and that we should have a corresponding series of bodies commencing with cacoclyf zinc-methyl zincethyl stibethyl &c. and terminating with the radicals of the aleohol family (the perfect representatives of hydrogen) euhibiting a siinilnr decrease of combining poxwr ; and since the organic groups arc so instable in their nature and so liable to ntctaniorphosis from ON THE ORGANIC BADICALS.343 the slightest causes that we are unable to expose them without utter destruction to the powerful influences which we can bring to bear upon an elementary body it surely ought to be a matter of no great surprise if the members of the least electro-positive extremity of the series should elude all our attempts to bring them again un- injured into combiuation. If nitrogen were decomposed at a red heat by what means could we recombine that radical when once isolatcd ? I ani at present engaged in filling up the gap in the series between cacodyl and ethyl and have been lately occupied in studying the properties of an organo-metallic radical which seems to occupy a position about niidway in the series entering into direct combina- tion with several of the metalloids but n7ith a degree of affinity iinmensely less than that exhibited by cacodyl or zinc-methyl.Dr. Hofmann objects to the present forizuh of the radicals in the second place because their vapour-volumes are different from those of all other known carbo-hydrogcns. In carefully considering this objection in all its bearings upon the subject I have been quite unable to see its force or to find in this difference of vapour-volume other than a very strong proof in favour of the bodies in question being the true radicals ; for had their vapour-volunies corresponded with those of other carbo-hydrogens it would in i~y opinion have afforded striking evidence of their being no radicals at all.Here in order to seek for analogy we must again return to the siinplc radical hydrogen which presents such close relations to these organic groups and in perfect harmony with them has its atom rep~esented by 2 volcrrnes. The action of chlorinc upon all the other hydrocarbons indicates that they contain an atom of hydrogen in combination with another group aid therefore their siogle atoms like those of the hydridcs of methyl ethyl and amyl are represciited by 4 volumes of vapour and they cannot possibly be brought forrvrzrd as analogies for controlling the foriiiuh of the radicals themsel~ ryith which the members of the series C H and C €In-6are by their properties and reactions placed out of all eonncction.But the ohjection which has the greatest apparent weight arid the one to which Dr. Hofmann evidently attaches the highest importance is the 3rd; viz. “That the boiling-points of the coinpounds iii question are in favour of their forrnulz being doubled.” The apyli-cation of the beautiful and highly-intcresting law of Professor Kopp to the controlling of the forinuh of an entirely new class of bodies should be made with great caution ;for although we can by its means unerringly predict the boiling-points of the members of tlie classes of compounds upon which that law was first founded yet thc extension DR. FRANKLAND'S RESEARCHES of the list of organic bodies has proved beyond doubt that the difference of 18O or 19OC.for each addition or subtraction of the elements C H, by no means obtains when we apply it to other classes of compounds ;in fact these discrepancies might naturally be expected from a consideration of the effect which a difference in the specific and latent heat of different atoms must have upon the thermal properties of the compound; for it could not be expected that the boiling-point of water for instance should be raised through the same number of degrees by the addition of C H, as that of other bodies having a much less specific and latent heat :hence we find that the difference in the boiling-point produced by the addition of the elements C H depends entirely upon the nature of the groups to ivliich these elements are added. In the alcohols and the series of acids C H 0, the elevation in the boiling-point produced by each addition of the dements C H varies from 16" to 21OC.giving the mean number 18*5*C. and it was principally upon these series of bodies containing in addition to water two radicals-viz. ethyl methyl &c. and oxygen that Kopp's law was founded; but if we examine bodies of more simple constitution containing two radicals without water we find the increase of the boiling-point produced by each addition of the elements C H widely different from the above number. Thus at the first step we find between oxide of methyl and oxide of ethyl a difference of at least 51°C.; for according to Gay- Lussac and Dumas oxide of ethyl boils at 35*5'C. whilst oxide of methyl is incondensible at -16OC.The iodides of ethyl and methyl differ by about 30OC. and the chlorides of ethyl and amyl by 9l0C. equivalent to 3OOC. for each term of C H, whilst the difference between chloride of ethyl and chloride of methyl is at least equally great since the boiling-point of the former is ll°C. and the latter is still gaseous at -18OC. the sulphides also exhibit a difference varying from 340 to 4i'OC. for each equivalent of C H,. From these facts it is easily perceived that the difference in the boiling-points produced by the addition or subtraction of the term C H rapidly incyeases as the complexity of the compounds decreases;therefore m7e mkht reasonably expect that the radicals themselves containing as they do only one group consisting of two elements would exhibit a stiIl greater difference which is precisely what is found to be the case; amyl and valyl differ by 47°C.and ethyl and methyl will probably be found to differ to a still greater extent. Although I am averse to drawing analogies from the habits of the hydrocarbon family C H,, coiiceiving its members to have no con- nection with the groiips in dispute pet since the vnpour-uoEunae of ON THE ORGANIC RADICALS. these bodies has been brought forward as an argument in favour of doubling the formuh of the radicals I cannot refrain from referring to the boiling-points of these hydrocarbons C H, which from the fact of their formulz having already been once doubled are not likely to undergo that process again by any discrepancies in this respect.The boiling-points of two of‘ these-viz. butyrene and valerene have been determined with tolerable exactness ; the first was found by Faraday to boil at -17*8*C.; and the last by Balard at 39W. and by myself at 35OC.; but as Balard’s amylene was still mixed with small quantities of a body having a higher boiling-point and the valerene obtained from iodide of amyl contained hyciride of amyl a compound boiling at a lower temperature perhaps the mean 37OC. would be the most correct number. Here then we have two homologous bodies differing from each other by the elements C H, and approaching as near to valyl and amyl in composition as bodies belonging to a different family well could do- for valerene and butyrene differ only from amyl and valyl by con- taining one equivalent of hydrogen less-yet their boiling-points differ to the extent of 54*8OC.,which would require us to multiply their already doubled formuls by 3 to reduce them to the standard of Kopy’s law.Boiling-point. Difference. Valerene (Clo Hlo) . 370 y1 } Butyrene (C8H8) . 17*8O , 548O , It does not therefore seem that any argument in favour of doubling the formulze of the radicals can be drawn from their boiling-points but on the contrary these boiling-points taken in connection with those of their compounds give additional evidence that the formulae assigned to them are the correct ones. A few words will suffice to remove the fourth objection which is founded upon an experiment in which Dr.Hofmann failed to produce the body zinc-hydrogen (Zn H) by passing hydrochloric acid gas over metallic zinc at an elevated temperature. The forma- tion of zinc-hydrogen under these circumstances would have com-pleted the analogy between the decomposition of chloride of hydrogen and iodide of methyl; but as zinc is only very slowly acted upon by dry hydrochloric acid gas even at a high temperature,* the acid gas * Chem. SOC. Qu. J. 111 47. 346 DR. FRANKLAND’S RESEARCHES is always in excess and consequently no other result than the one obtained could be looked for any more than we could expect to preserve potassium in a stream of hot hydrochloric acid; for the series of bodies to which zinc-amyl zinc-ethyl and zinc-methyl belong increase in the energy of their affinities as their atomic weights decrease; therefore we might predict that zinc-hydrogen if such a body exist will be endowed with still more violent reactions than zinc-methyl.Now this last is instantaneously decomposed with explosion in hydrochloric acid gas ; and therefore zinc-hydrogen with perhaps still more powerful affinities could not exist for a moment in a stream of that gas or in other words could never be formed in such an atmosphere. The action of iodide of methyl upon zinc-methyl is however but very slow even at an elevated tempera- ture to which circumstance we owe the presence of this body amongst the products of the decomposition of iodide of methyl by zinc; and if we ever obtain the body zinc-hydrogen it niust be by bringing nascent hydrogen evolved from some nearly neutral body in contact with zinc As the fifth objection ‘‘ that the formulz of these bodies should be doubled to remove the discrepances in the boiling-points of valerene hydride of amyl and amyl,” is not considered by Dr.Hof-mann himself to have much weight on accouiit of the different vapour- volumes of the compounds precluding a propcr comparison I will only remark on this head that the assimilation of an atom of hydrogen with doubling of the vapour-volume and the same assimi- lation without increase of volume are widely different circumstances from which we might naturally expect very different results as regards the boiling-points of the compounds thus produced ; and accordingly when 2 vols.amyl vapour unite vith 2 vols. hydro- gen to form 4 vols. hydride of amyl vapour a depression of the boiling-point from 155O to 3Qo C. = 125O C. takes place; but this cannot be regarded as extraordinary unless it can be proved that the boiling-point of hydrogeii is not 125O C. below that of hydride of arnyl for we are entitled to assume h priori that the boiling-point of such a body would be the mean of those of its constituents. When however 4 vols. of valerene vapour unite with 2 vols. of hydrogen to form 2 vols. of amyl vapour the 4 vols. of valerene are absorbed as it were into the two volumes of hydrogen in other words the 6 volumes are condensed to 2 and the conse- quence is that the boiling-point rises 118O C I have thus endeavonred to remove seriatim the objections which have been so ably and ingeniously made by Dr.Hofinann to thc ON THE ORG.4NIC RADICALS. formuke proposed by Dr. Kolbe and myself for the groups which we conceive to represent when isolated hydrogen-and in ethyl methyl and amyl compounds the hydrogen contained in the parallel combinations of this element. That these groups do not belong to the marsh-gas family as suggested by MM. Laurent and Gerhardt is I think proved by the action of chlorine upon methyl as detailed above; whilst the production d and action of chlorine upon the hydrides of these groups clearly indicates that these hydrides form the so-called marsh-gas family hence we should gain no single advantage by doubling the present formulze of the bodies in dispute but on the contrary we should then either have to assume the existence of a third class of isomeric compounds of undefined constitution or to double our present formula for hydro-gen and represent the simplest isolable molecule of that element by H + H we should then have FI + €i = Hydride of hydrogen.C H + C H = Methyde of methyl. C €3 + C H5 = Ethide of ethyl.* &C. &C. Or adopting the notation of Messrs. Laurent and Gerhardt these formula? would be thus written H H = Hydride of hydrogen. C H C H = Methyde of methyl. C H C H = Ethide of ethyl. &C. &C. which also shows that the views advocated by these chemists on the one hand and Dr. Kolbe and myself on the other exhibit no greater difference with respect to ethyl methyl &c.than they do with regard to hydrogen. * This view of the rational constitution of these bodies was first suggested by Mr. Brodie at a recent meeting of the Society.

ISSN:1743-6893    

DOI:10.1039/QJ8510300321

出版商:RSC    

年代:1851

数据来源: RSC

摘要:

348 MR-J. ARTHUR PHILLIPS Nov. 18 1850. RICHARD EsQ.,President in the Chair. PHILLIPS The following presents were announced cc The Improvement of Land by Warping Chemically considered by Thornton J. Herapath :” by the Author. A donation of 199 volumes by Mr. Griffin; see page 412 ? The following Papers were read “On the claims of the elementary substances Silicon and Selenium to be ranked among metals:” by Mr. Richard Adie of Li-verpool. ((On the existence of Copper and Lead in the Blood and in other portions of the Animal Organism :” by Mr. J. Denham Smith. XXVIIL-On Potasso-gypsite a double Sulphate of Potash and Lime. By J. ARTHUR ESQ. PHILLIPS This substance is obtained as a secondary product in the manu- facture of tartaric acid and it will therefore be necessary to describe the circumstances under which it is produced before detailing the properties and composition of the salt itself.Tartaric acid is as is well known made from the impure bitartrate of potash which reaches this country in such a state as to yield on an average 72 per cent of crystallized acid. The processes employed in the manufacture are briefly as follows Into a large tun capable of containing about three thousand gallons of water are thrown from fourteen to fifteen hundred pounds of mashed chalk which is agitated by means of a revolving arm until the water and carbonate of lime have become perfectly incorporated and a finely-divided mixture is obtained. When this is effected about two tons of crude tartar are added by means of an air-tight trap on the top of the vessel and by the aid of heat obtained by blowing ON POTASSO-GYPSITE.a jet of steam into the mixture and constant agitation of the mass the bitartrate of potash is made to transfer its free atom of acid to the lime giving rise to the formation of insoluble tartrate of lime soluble tartrate of potash and the evolution of carbonic acid which is conveyed away in leaden pipes to be employed in making bicar- bonate of soda. As soon as the decomposition is completed a sufficient portion of sulphate of lime from a preceding operation is added for the purpose of decomposing the neutral tartrate of potash in solution. By the aid of heat and long-continued agitation this is at length effected and the vessel then contains a solution of sulphate of potash together with the insoluble tartrate of lime and small portions of the carbonate and sulphate of the same base arising from the excess of these reagents originally employed.At this period of the manufacture the agitation is arrested the liquor is allowed to settle down and the sulphate of potash drawn off from the tartrate of lime which remains at the bottom of the tub. This is subsequently washed with three successive waters which are added to the solution of sulphate of potash at first obtained. The insoluble tartrate of lime is afterwards decomposed by mlphuric acid with formation of sulphate of lime and production of free tartaric acid which is crystallized in the usual way whilst the sulphate of potash with which we are at present most interested is conveyed away by large leaden gutters for evaporation.At the manufactory of the Messrs. Pontifex these liquors are first drawn in’to a large tubular steam-boiler heated by the waste heat escaping from a set of coke-ovens. In this the potash solution is con-centrated to about two thirds of its oiiginal volume and then allowed to run into a series of large bacs containing coils of iron pipe which are supplied with steam by means of the boiler in which the liquor is concentrated and in these the evaporation is completed. This boiler for concentration and supplying the steam-coils gradually becomes coated by a hard deposit in order to remove which it becomes necessary at intervals of about three months to stop the ovens and run out the liquor.On these occasions the cooling of the boiler and its contents is extremely slow as the mass of brickwork which surrounds it renders the loss by radiation very inconsiderable. When it has sufficiently cooled and the liquor has been run off the greater part of its internal surface is found to be covered with transparent lamellar crystals formed on a hard crystal- line gangue. These are sparingly soluble in water but are easily dissolved by dilute hydrochloric acid. A qualitative analysis showed them to consist of lime potash 350 SIR. J ARTHUR PHILLIPS water and sulphuric acid and a quantitative examination gave the following results FIEST ANALYSIS. 10.05 grs.gave 14*85 grs. platinum-salt. J? 93 3.05 , carbonate of lime 9.28 , 0.51 , water. >> 13.22 ,? sulphate baryta. SECOND ANALYSIS. 10.23 grs gave 15.10 grs. platinum-salt. 3.10 , carbonate of lime. 29 93 5.81 , 0.33 9 water. 8.21 , sulphate baryta. 39 ,5 These numbers afford the following perceiit age results Potash . . 28.52 28.57 Lime . 16.99 16.96 Sulphuric acid . . 48.94 48.55 Water . 5.51 5.67 9996 99.75 The above relations would lead to the empirical formula KO SO,+CaO SO,+HO as may be seen by comparison with the following calculated amounts No. of eqs. Amounts. Percentage. Potash . . . 1 = 47 28.67 Lime. . . . . 1 = 28 17.02 Sulphuric acid . 2 = 80 48.82 Water . . . 1 = 9 5 -49 100~00 Since however a variety of sulphate of lime expressed by 2(CaO SO,) + HO has been found under nearly similar circum- stances,* it appears probable that in reality the water is divided between the sulphates of lime and potash and that the crystals are composed of a double di-hydrated salt of which the true formula is * Johnston Phil.Mag. J. XLII. 325 ; also J. Pr. Chem. XVI 300. ON POTASSO-GYPSITE. represented by 2 (KO SO,) + HO + 2 (CaO SO,) t HO arid to this I propose to give the name of Potasso-gypsite. Professor W. H. Miller of Cambridge who has had the kindness to examine the crystals of this substance dcscribes them as follows PRISM AT1C. Symbols of the simple forms a 100 e 101 u 102 m 110. Angles between normals to the faces ea .. . 46O 28' ee' . . . 87 4 n ua . . 76 38 uu' . . . 26 44r ma . 52 58 mm'. . . 74 4 The crystals exhibit faint indications of cleavage parallel to a plane perpendicular to the faces a gn. The faces a are striated parallel to their intersections with the faces rn. The crystals are very thin in a direction perpendicular to the faces a. The optic axes lie in a plane perpendicular to the faces a rn. Seen in air through the faces a they appear to make angles of 22O 45' with a normal to a and an angle of 45O 30' with each other. The crystalline gangue on which the regular crystals are formed was f'oound on analysis to yield the following results FIRST ANALYSIS. 28.95 0.23 silica. 12.49 carbonate of lime.1.19 phosphate of magnesia. 37)'86 2.95 carbonic acid. 41.96 sulphate of baryta. 39-63 platinum-salt. 0.31 chloride of sodium. 0.30 oxide of iron. O*l& alumina. 9 75-83 0.58 phosphate of magnesia. MR J. ARTHUR PHILLIPS SECOND ANALYSIS. 26.23 0.25 silica. 0.28 oxide of iron. J> 0.21 alumina. >> 0.87 phosphate of magnesia. 25.57 1*90 carbonic acid. 24.12 26.20 platinum-salt. 0.30 chloride of sodium. 9.34 sulphate of baryta. 0.17 phosphate of magnesia. I. 11. Potash . 20.18 20.93 Soda . 0.43 0.61 Lime . 24-16 >> Magnesia. . 1-50 1*24 Alumina . . 0.74 0.80 Oxide of iron . 1.24 1-06 Silicic acid . 0.79 0-80 Sulphuric acid . . . 38.08 38.66 Phosphoric acid 0.49 0.42 0 Carbonic acid .. 7.79 7.87 4.31 Water . 0 >1 Organic matter traces traces 99.71 !l!hese numbers indicate that the uncrystallized portion of the deposit consists of the same substances as the crystals themselves; and if in the first analysis we so arrange them as to form the double sulphate above-described the following percentages will be obtained I. 11. New salt . 64-76 Sulphate of lime . 11.57 Carbonate of lime 1406 Phosphate of lime . 1*06 Carbonate of magnesia . 3.10 Silicate of potash . 2.42 Oxide of iron . 1 *24 Alumina . 0.74 Water . 0.76 Organic matter traces 99.71 ON POTASSO-GYPSITE. In the analysis of the crystala of the pure salt the water was esti- mated by heating to redness in a platinum crucible a portion of the substance which had been kept until it ceased to lose weight under the receiver of the air-pump in which was placed a dish of strong sulphuric acid.The same portion of substance was then dissolved in dilute hydrochloric acid and the sulphuric acid thrown down as sulphate of baryta by chloride of barium in the usual way. A second quantity of substance was then taken and after dissolving it in dilute hydrochloric acid and adding ammonia the lime was precipitated in the form of oxalate and weighed as carbonate. The filtrate from the oxalate of lime was then evaporated to dryness and the residue heated to redness to expel the ammoniacal salts. A slight excess of hydrochloric acid was afterwards added and the potash estimated as platino-chloride of potassium. In the investigation of the uncrystallized deposit the ordinary routine of chemical analysis was employed the phosghoric acid being estimated by the method of Fresenius and the alkalis separated from the alkaline earths by the use of hydrate of baryta.

ISSN:1743-6893    

DOI:10.1039/QJ8510300348

出版商:RSC    

年代:1851

数据来源: RSC

摘要:

ON POTASSO-GYPSITE. XX1X.-On Chlorophosphuret of Nitrogen and its Products of Decomposition. PART11. BY J. H. GLADSTONE,PH.D. F.C.S. In my former Paper upon Chlorophosphuret of Nitrogen,* it was stated that the decomposition which the solutions of that substance in alcohol and ether spontaneously undergo would be reserved for after-consideration. I now return to that part of the inquiry. It was early observed that when the white mass produced by the action of ammoniacal gas on pentachloride of phosphorus was washed with ether to separate the chlorophosphuret of nitrogen and the solution suffered to evaporate other substances beside the crystalline body in question made their appearance. The chloro- phosphuret was coloured pink or red and smelt strongly of hydro- chloric acid; and upon the addition of water it was evident that some body possessing oily properties was also present; whilst the aqueous solution reacted very acid and upon evaporation after the hydrochloric acid had been driven off left a semi-crystalline mass * Chem.SOC. Qu. J. X. 135. VOL. 111s-NO. XII. AA 354 DR. GLADSTONE ON CHLOROPHOGPHURET OF NITROGEN very soluble in water but insoluble or nearly so in alcohol. This was powerfully acid to test-paper was capable of being neutralized by potash and a slightly acid solution gave flocculent white precipi- tates with nitrate of silver and chloride of calcium requiring conside- rable excess of nitric acid to redissolve them. In fact ether was found capable of effecting a gradual but com-plete transformation of chlorophosphuret of nitrogen into hydro- chloric acid the new acid just mentioned and a varying amount of yellowish liquid immiscible in water having an aromatic odour.If the ethereal solution be heated the change is immediately brought about the oily liquid being produced in such quantity as to render the solution turbid. The action of alcohol is equally destructive; but hydrochloric acid and the oily body are the sole products. If some crystals of chloro- phosphuret of nitrogen be placed in a small quantity of alcohol quite inadequate to dissolve them they will be found in a few days to have disappeared the oily body into which they have been trans- formed being taken up by the alcohol. DEUTAZOPHOSPHORIC ACID.The acid produced from chlorophosphuret of nitrogen under the influence of ether crystallizes in feathery crystals or groups of microscopic spiculz. That the substance is free from ammonia is evident from the fact that it does not yield that gas when boiled with baryta-water or weak potash; and as the neutralized solution gives no precipitate when mixed with a metallic salt it cannot con- tain either phosphoric or azophosphoric acid. The acid crystals dried in vucuo at the ordinary temperature do not lose in weight when heated to loooC ;but upon increasing the heat they fuse swell and evolve an ammoniacal salt containing phosphorus in some form and afterwards free ammonia. There remains azophosphoric acid (easily recognized by the immediate production in the cold of the characteristic iron-salt when mixed with a solution of the sulphate of that metal),’.together with some glacial phosphoric acid.Oxidizing agents have little action upon this crystalline acid nitric acid even may be boiled upon it long without causing decom- position. Strong sulphuric acid in the cold has likewise no effect beyond that of dissolving it As the crystals themselves were not very definite in appearance and as some which had been put aside for a few months were found to have undergone a spontaneous change with the formation of AND IT$ PRODUCTS OF DECOMPOSITION. ammoniacal salts it was feared that no good analytical results were likely to be obtained from the acid itself. Its insoluble salts how- ever promised better.Upon the addition of nitrate of baryta to a solution of the crystals a white flocculent salt is formed. This was analyzed; but such differences in the estimation of the base as 43and 60 per cent soon showed that no reliance was to be placed upon the uniformity of composition of this precipitate. One property of this crystalline acid is to produce azophosphoric acid when its solution is boiled with certain metallic salts. If the sulphate of the sesquioxide of iron be added to an aqueous solution of these crystals no precipitate appears proving that azo- phosphoric acid does not pre-exist in them; but it is instantly formed on boiling. Again if the acid be nearly neutralized by an alkali and boiled with a solution of most other metallic salts such as sulphate of copper the azophosphate of the metallic base gradually precipitates.Now this is precisely what occurs when an azophosphate is pro- duced as described in my former Paper. It was there directed that chlorophosphuret of nitrogen should be dissolved in alcohol and decomposed by ammonia; the salts thus obtained were then to be evaporated to dryness redissolved in water and boiled with the sulphate of iron or other metallic salt till the azophosphate was precipitated. It seems probable therefore that the alkali accom- plishes instantaneously the same decomposition which the chloro- phosphuret of nitrogen slowly undergoes when dissolved in ether ; and that the resulting salts are really the combinations of hydro-chloric acid and the new crystallizable acid with the alkali employed.And this supposition is confirmed by the fact that the neutral or slightly acid solution obtained by decomposing chlorophosphuret of nitrogen by an alkali does yield similar flocculent precipitates when niixed with solutions of baryta or lime salts; and if nitrate of silver be employed a precipitate is formed which is very readily acted upon by the light and mixed with a large quantity of chloride of silver. Baryta-suZt.-Various attempts were made to analyze the baryta- salt. Some peculiarities exhibited in its production must be noticed. If a strong solution of nitrate of baryta or chloride of barium be added to a slightly acid solution a precipitate falls; but a more copious precipitate is obtained from a neutral or slightly ammoniacal solution; yet the precipitate is itself wholly soluble in a considerable amount of ammonia and may be regained (perhaps in an altered condition) by evaporating off the large excess.The salt in question AA2 356 DR. GLADSTONE ON CHLOROPHOSPHURET OF NITROGEN is to some extent soluble in water but the presence or absence of different salts in the liquid appears greatly to affect its solubility. The results of analyses of different preparations of this baryta-salt are highly variable and I shall merely give the percentages without details. The base was of course always weighed as sulphate and thus there can be little doubt respecting the accuracy of its determi- nation; but although various means were resorted to €or the estima- tion of the phosphorus and nitrogen I never felt satisfied that the whole amount of either was obtained.The last four determinations recorded below form a series. Some chlorophosphuret was decornposed by means of alcohol and ammonia and evaporated to?dryness ; when redissolved it was slightly acid. A concentrated solution of chloride of barium was added which precipitated a white flocculent salt this furnished result No. 4. Ammonia added to the filtered solution caused a small precipitate which yielded No. 5. The solution separated from this was warmed and more ammonia was added a similar precipitate fell which was collected and the solution on standing yielded a fresh quantity of salt.These precipitates furnished respectively Nos. 6 and 7. The method adopted for analysis was first to heat the salt previously dried at loooC. in a tube per se and collect the water and am- monia evolved in a tube filled with sticks of potash and a Will’s h ydrochloric-acid apparatus annexed to it. The resulting mass was then dissolved in dilute acid and the baryta precipitated as sulpbate ; the solution containing then the free acid not already decomposed was nearly neutralized by carbonate of potash and was boiled with sulphate of sesquioxide of iron to convert as much as possible into the azophosphate. This was separated and the liquid evaporated down and fused with hydrate of potash. The gas evolved was collected and the phosphoric acid contained in the alkaline mass was estimated as usual.In No. 4.the salt was not heated per se. I. 11. 111. IV. v. VI. VII. Baryta 49.8 52.2 51.4 45.0 46 53.2 55.0 Phosphorus 10.8 14.0 19.0 15.9 -22.4 17.3 Nitrogen 1.1 -6.6 -5.0 5.4 I Hydrogen --1 0.7 0.8 The salt evidently varies in composition. There appeared no reason for believing that salts of other bases would be more uniform and the difficulty of obtaining a quantity of the chlorophosphuret of AND ITS PRODUCTS OF DECOBlPOSITION. nitrogen rendered me little disposed to undertake more analyses of so unpromising a character. If the formation of the acid in question be considered we can scarcely entertain a doubt as to its true composition. It is formed from chlorophosphuret of nitrogen by the action of alkalis; the alcohol which is necessary for the success of the process appears to play no other part than that of a solvent.The whole of the chlorine is removed as I have found by direct experiment ;but the phosphorus and nitrogen seem to give rise to no secondary products. NO phosphoric phosphorous or nitric acid is formed; nor have I been able to detect ammonia when potash has been the alkali employed; neither is there any gaseous body evolved. We can only imagine therefore that the chlorine of the chlorophosphuret is replaced by oxygen thus P,N,C15 + 5 KO = P,N,05 + 5 KC1. Again in the decomposition of chlorophosphuret of nitrogen by means of ether no other bodies appear to be formed except hydro- chloric acid and the acid in question the aromatic liquid of which a larger or smaller quantity is usually found accompanying the preparation being a secondary product unessential to the decom- position.This is consistent with the view just expressed but it supposes that the decomposition depends upon the water present in the organic solvent. In order to test this important point some crystals were dissolved in anhydrous ether and the solution kept in a well-stoppered bottle; it was then found that the chlorophosphuret remained unaltered even after the lapse of thirty days. Nor does a solution in anhydrous ether undergo any change upon boiling. The ether then has no specific action on chlorophosphuret of nitrogen beyond that of a solvent; it merely facilitates its coming into contact with water and the real decomposition would appear to be P,N,C1,+5HO=P,N20,+5HC1.Indeed the presence of ether is not absolutely essential; for if some perfectly purc crystals of the chlorophosphuret be allowed to remain in distilled water for several weeks the liquid will be found to react distinctly acid and to be in reality a solution of the two acid products of decomposition given in the formula above. Again this acid or its compounds boiled with certain metallic salts yield the allied body-agophosphoric acid-having the formula Y,NO,. Now if this last arise from P,N,O, it will simply be by the elimination of 1 atom of phosphorus and 1 atom of nitrogen most probably as phoraphite of ammonia by the fixation of the ele- 358 DR.GLADSTONE ON CHLOROPHOSPHURET OF NITROGEN. nients of water. That ammonia is really one of the products of the decomposition I have repeatedly satisfied myself; but I have never succeeded in obtaining clear indications of phosphorous acid ; yet when it is remembered that heat is always employed and that metallic salts are present it is scarcely to be wondered at that so oxidizable a substance should be converted into phosphoric acid; and that is always found. Yet in order to have numerical proof that this new acid really did contain phosphorus and nitrogen in the proportions here assigned to it the last-mentioned reaction was taken advantage of. Some crys- tals formed by the spontaneous evaporation of an ethereal solution of chlorophosphuret of nitrogen and purified by washing with alcohol were dried in vacuo over sulphuric acid.They were then dissolved in water and sulphate of the sesquioxide of iron was added; on boil- ing azophosphate of iron separated which was collected and dried in vacuo. The filtered solution was gently evaporated to dryness and the resulting salt was fused with hydrate of potash in a silver tube and the evolved ammonia and resulting phosphoric acid were estimated as described in previous experiments. 0.219 grm. of the crystallized acid yielded 0.217 grm. of azophosphate of iron (Fez0, P NO, 5 HO) and afterwards 0.1205 grm. of ammonio-chloride of platinum and 0.0655 grm. of phosphoric acid which is As azophosphate. Not as azophosphate. Phosphorus . 0.0571 0.0291 Nitrogen .. 0*0125 OwO078 It appears then that two-thirds of the phosphorus is removed in the form of azophosphate of iron while the remaining one-third combines with oxygen. There is certainly not as much nitrogen found in the form of ammonia as in the azophosphate; but when it is borne in mind that the whole of the ammonia is never obtained by the process followed I conceive the experiment lends its full weight of evidence to the view given above of the formation of azophos-phoric acid. A second portion of acid was likewise analyzed by boiling with iron-salt and subsequent fusion with potash. 0.463 grm. of the crystals dried in uacuo yielded 0*414grm. of azophosphate of iron 0.440 grm. of ammonio-chloride of platinum and 0.148 grm.of phosphoric acid. If the whole amounts found of the two elements-phosphorus and nitrogen-be reckoned to 100 parts we have AND ITS PRODUCTS OF IDECOMPOSITION~ I. 11. Phosphorus . . . 39-36 $8.01 Nitrogen . . . . 9.27 ll*OS which indicates at least 8 atoms of water. Reasons will presently be assigned for believing this acid to be tribasic. The formula 3 "0,P3N 0,,5 HO would require Phosphorus . 96 40.67 Nitrogen . . . . 28 11-86 . 40 16.95 Oxygen . Water . . . . 72 30-51 -. 236 100~00 This view of the constitution of the acid itself simplifies our cou-ception of the reaction by which azophosphoric acid is produced It will be 23 HO. P,Nz05. 5 HO + 3 (MO,SO,) + S HO = 3 MO. P NO,. 5 HO + PO + NH + 8 SO, As this crystalline acid is analogous to azophosphoric acid but differs from it in the same manner as the latter differs from phos- phoric acid namely by the addition of PN I shall designate it-Deut-azophosphoric Acid.Deutaxophosphate of baryta-This salt has been already described it varies in composition. In the experiment which afforded the series of analyses Nos 4 to 7 the base increased in amount and even- tually a salt was obtained having very nearly the composition 3 BaO P,N,O, 3 HO. Calculated. Found. VI. VIL Baryta . 230 5463 53.2 55.0 Phosphorus . 96 22.80 22.4 17.0 Nitrogen. 28 6.65 5*O 5*4 Hydrogen 3 0.71 0.7-0-8 I) Oxygen . 64 15*20 421 100*00 This baryta-salt like the azophosphate is decomposed by heat turning black and evolving at the same time aqueous vapour ammonia and free oxygen which has arisen from the decomposition of water to supply the hydrogen which has entered into combination 360 DR.ULADSTONE ON CHLOROPHOSPHURET OF NITROGEN with part of the nitrogen. Thus in the two analyses just recorded the loss in weight caused by heating the salt coincided very nearly with that which was calculated from the amounts of ammonia and water given off Decomposed Theoretical Actual Water. Nitrogen. water. loss. loss. Exp. VI. 0.0065 -+ 0.0045+ 0.001 x 9 = 0020 0.023 Exp. VII. 0.0055 + 0*0033+ 0*0007x 9 = 0.015 0.015 Deutazophosphate of Ammonia.-In the decomposition of chloro- phosphuret of nitrogen by an alcoholic solution of ammonia we obtain this salt mixed with chloride of ammonium.Now the amount of chloride of ammonium produced from a known weight of the chlorophosphuret can be easily calculated. If therefore we sub-tract the amount of it from the weight of the dry salts we obtain the weight of the deutazophosphate which has been formed. During the investigation of azophosphoric acid the decomposition of the original chlorophosphuret of nitrogen was thrice performed quantitatively. Excess of ammonia was employed and the resulting salts were dried in a water-bath. Exp. I. 0.2135 grm. of P N C1 yielded 0.387 grm. of ammo-niacal salts. Exp. 11. 0.2553 J J 0.469 9 J J9 Exp. 111. 0.7035 > 1.2505 , JY Now 0.2135 grm. of P N C1 consists of 0*088 P3N, and 0.11255 C1 which would produce 0.1895 NH C1; and this number sub- tracted from 0.387 leaves 0.1975 as the amount of deutazophos- phate of ammonia.Therefore Exp. I. 0.088 grm. of P3 N yields 0.1975 grm of am- monia-salt. Similarly Exp. 11. 0.105 , 9 0.2425 , , and Exp. 111. 0.2894 , ,> 0.6264 , , These numbers are in the ratio of- Exp. I. Exp. 11. Exp. 111. 100 100 100 224.4 230.9 216.4 So large an increase of weight tends to show that at least three equivalents of oxide of ammonium have combined with the deutazo- phosphoric acid. A formula deduced from such slight grounds is of 361 AND ITS PRODUCTS OF DECOMPOSITION. course problematical and the variations in the three results (mainly attributable to the very deliquescent character of the salt) are beyond the range of a single equivalent of water; yet if we suppose the ammonia-salt to have a composition similar to that of the baryta- salt namely 3 NH 0.P3 N 0,. 3 HO the increase upon the original P3 N would be as- 100 216.9 a number coincident with the lowest and most trustworthy result afforded by experiment. If ammonia be added to a strong solution of the pure acid a mass of crystals immediately separates; upon the application of heat this crystalline precipitate redissolves and there remains a neutral salt which may be evaporated to a syrup without crystallizing. If this neutral substance be dissolved in a small quantity of water the addition of strong ammonia will again cause the precipitation of a crystalline salt.Deutazophosphate of ammonia is very deliquescent in damp air ;when heated per.se it swells up greatly and evolves am- moniacal gas whilst azophosphoric acid is found among the products in the fixed residue. Deutazophosphate of Silver.-A portion of the flocculent diffi- cultly soluble silver-salt rneutioned at the commencement of this paper was found to contain only 53.2 per cent of oxide of silver,- which is much less than a composition similar to that of the baryta- salt would require. Deutazophosphoric acid is capable of forming white flocculent salts with the earths,-baryta strontia lime and magnesia and with oxide of lead; but I have not succeeded in preparing salts of this acid containing such metals as iron copper or zinc either by double decomposition or by presenting the freshly precipitated oxide to a solution of the acid itself.AMMONIO-AZOPHOSPHATE OF IRON. An examination of this substance was nndertaken principally in the hope that it would throw some light upon the function of those atoms of water which form a constituent of the azophosphates and deutazophosphates and which cannot be driven off at least from the former without destroying the salt itself. It was stated in my previous paper that azophosphate of iron is wholly soluble in ammonia but that the compound thus formed is decomposed on evaporation in a water-bath. If however the drying be conducted at the ordinary temperature in vacuo over SUL 362 DR. GLADSTONE ON CHLOROPHOSPHURET OF NITROGEN phuric acid a deep-red mass is obtained covering the bottom of the vessel like a varnish and splitting up as it becomes perfectly de- siccated.This substance dissolves completely in cold water giving a red solution neutral to test-paper. 0.2253 grm. of this substance dried in vacuo decomposed by dilute hydrochloric acid yielded 0.1645 grm of azophosphate of iron (Fe 0,. P NO,. 5HO) and 0.120 grm. of chloride of ammonium. Now 0.120 grm. of chloride of ammonium is equivalent to 0.0583 grm of oxide of ammonium and such an amount it is which must be added to the 0.1645 grm. of azophosphate in order to approximate the original weight of the salt 0.2253 grm. 0.1645+0*0583=0*2228. Or if these numbers be reckoned to 100 parts we have 73.0 Azophosphate of iron Fe 0,.P NO,. 5HO . Oxide of ammonium NH 0 . . . 25.8 -98.8 This agrees most nearly with the numbers deduced from the formula Fe 0,. 3NH4 0. P NO,. 6HO. namely Azophosphate of iron . 243 75.70 Oxide of ammonium . . 78 24-30 7- 321 100*00 This experiment appears to indicate that the 5 atoms of combined water are not either wholly or partially basic but are nevertheless intimately connected with the compound itself yet as 1atom can be driven off from the iron-salt by heat and as the azophosphate of baryta contains but 2 atoms of water the hydrogen cannot be con- sidered as an integral part of the formula of the acid. Applying the phosphoric-acid theory of Messrs. Fleitmann and Henneberg to the expression of the azophosphate of iron we shall have the formulae 2Fe 03+2(P NO,.5HO) and 1+P NO,. 5HO. Fe2 3NH 0 j '3 AROMATIC LIQUID. It has already been stated that chlorophosphuret of nitrogen is decomposed under the influence of alcohol giving rise to hydro- AND ITS PRODUCTS OF DECOMPOSITION. chloric acid and a liquid body having an aromatic odour and not miscible with water. This last substance is readily soluble in alcohol and in the essential oils. It has usually a slight yellow tinge but I have obtained it nearly colourless. It appears incapable of being distilled without change. A portion subjected to a temperature gradually increasing was decomposed at a little above 100° C.; a light colourless and highly volatile liquid came over ;and afterwards a heavy oleaginous body of a very pungent odour which was not miscible with the former.The aromatic liquid in question is not attacked by aqueous solutions of potash nitric acid or sulphuric acid; but it is instantly decomposed by an alcoholic solution of potash with the formation of salts which are perfectly soluble in water and which when fused with an excess of the alkali yield ammoniacal gas whilst phosphoric acid remains in the fixed residue. The solution of the salts obtained by this decomposition of the liquid by means of any alkali when properly neutralized affords a baryta-salt resembling the deutazophosphate of baryta just described ;if mixed with a solution of sulphate of sesquioxide of iron it gives no precipi-tate at first; but on boiling it yields the characteristic white flocculi of azophosphate of iron The aromatic liquid then contains deutazophosphoric acid.A portion of the liquid under examination was purified from ad-hering acid and water first by carbonate of soda and afterwards by standing over dry chloride of calcium. It was-then introduced into a small glass bulb and burnt with chromate of lead as in the usual combustion-process for organic compounds. In consequence of the liquid becoming carbonized in the bulb the combustion was worthless as a quantitative experiment; but it proved that the substance con- tained a large percentage of carbon and hydrogen; and if the mode of its formation be considered I think there can be little doubt that the aromatic liquid iu question is deutazophosphoricether.From the reactions which have formed the subject of this paper it appears that the so-called “chlorophosphuret of nitrogen” is a body analogous in constitution to pentachloride of phosphorus. It exhibits little or no tendency to combine with any other substance without itself undergoing decomposition; but it is resolved by as- sumption of the elements of water into hydrochloric acid and another acid-a compound of the electro-positive portion with five equivalentg of oxygen. PC15+5HO=P0,+SHCI and P N C1 =t 5 HO =P N O,+5HCl. 363 DR. GLADSTONE ON CHLOROPHOSPHURET OF NTTROGEN The reaction by which it is formed when ammonia and penta- chloride of phosphorus are brought together cannot be distinctly traced.It is evidently a by-product-a result in all probability of the action of the newly-formed compounds of phosphorus and nitrogen upon the pentachloride. It is not found amongst the pro- ducts of decomposition when pentabromide of phosphorus is heated with chloride of ammonium. It was to be expected that a substance might exist presenting a composition intermediate between that of pentachloride of phos-phorus PCI, and chlorophosphuret of nitrogen P N CI,-in fact P NCI,--and which should give azophosphoric acid Pz NO, when decomposed by water ;but no such compound has yet been observed. Liebig and Wohler mention a substance given off in the prepa- ration of chlorophosphuret of nitrogen which has a peculiar and distinct odour I have remarked the same but only I believe when the chloride of phosphorus has not been thoroughly saturated with chlorine.The two acids with which this investigation has made us ac-quainted may be considered as the second and third terms of a series commencing with ordinary phosphoric acid and bearing a marked resemblance to it both in their tribasic character and in their general properties. They differ in composition from phosphoric acid in containing its elements PO conjugated with PN or 2PN; and thus present another instance of that law of which we have so many examples in organic chemistry that the addition of any number of atoms of a certain increment will only modify the particular pro- perties of a body not affect its general character. Phosphoric acid .PO, Azophosphoric acid . . Pz N 0,or (PN) PO Deutazophosphoric acid . P3 N 0 or (2PN) PO,. The general resemblance between these three acids and at the same time the gradual departure from the primitive type which the more compound acids present may be well exhibited in a tabular form PHOSPHORIC ACID. AZOPHOSPHORIC ACID. Hydrated acid is stable. Hydrated acid is stable. >> , deliquescent. J9 , deliquescent. ,I , glacial. , amorphous. 1) Tribasic. Tribasic. Forms soluble salts with alkalis. Forms soluble salts with alkalis. , insoluble salts with earths. , insoluble salts with earths. , flocculent and white salts , flocculent and white salts with earths. with earths , insoluble salts with metals. , insoluble salts with metals., flocculent and mostly white , flocculent and mostly white salts with metals. salts with metals. Fe 0,salt insoluble in weak acida. Fe 0,salt insoluble in dilute acids. , , white. , $ white. DEUTAZOPHOSPHORIC ACID. Hydrated acid is stable. 1 , deliquescent. ,I , crystalline. Tribasic Forms soluble salts with alkalis. , slightly sol. salts with earths , flocculent and white salts with earths. 366 DR. GLADSTONE ON CHLOROPHOSPHURET OF NITROGEN &c. Note.-Since writing the above my attention has been drawn to a paragraph at the conclusion of a paper on Organic Combinations by M. Laur ent in the lCComptes Rendus” of the French Academy for September 9th 1850. He there remarks that the formulz assigned by me to ‘‘Chlorophosphuret of Nitrogen” and Azophosphoric acid” are quite inadmissible.He gives moreover the following as the reactions which ought to take placc in their formation C15 Ph + H3N =C12PhN+ H3C13 and 2 C12 PhN+6 H20=P206H6N+4 C1H+H3N or according to our notation P C1 + NR,= PNCI + 3 HCl and 2 PNCl,+ 12 HO=P NH Ola+ NH3+4 HCI ; and thizs he considers my ‘I azophosphoric acid” as ‘‘ pyrophosphamic acid.” In the October number of the Comptes Rendus” of Messrs. Laurent and Gerhardt these views somewhat enlarged are put forth in full detail. Yet as these eminent chemists admit in their editorial remarks that fresh experiments are necessary to verify their corrections I have little doubt that the statements contained in the present paper will satisfy them that the reactions expressed by their formulz do not really take place.Dec 2 1850. ROBERTPORRETT, EsQ. Treasurer in the Chair. The following presents were announced <‘ Memoir on the Explosiveness of Nitre,” by Robert Hare M.D. presented by the Author. ‘‘Pharmaceutical Journal for December 2’ presented by the Edit or. “Quarterly Journal of the Geological Society for September,” (No. 24 Vol. 6.j presented by the Society. “ ofversigt af Kongl. Vertenskaps- Akademiens Forhandlingar :” Sjette Argangen 1849. “Kongl. Vetenskaps-Akademiens Handlingar for ar 1848 :” presented by the Royal Stockholm Aaadeiny. An Introduction to the Atomic Theory,” by Charles Dau-beny M.D. F.R.S. presented by the Author.

ISSN:1743-6893    

DOI:10.1039/QJ8510300353

出版商:RSC    

年代:1851

数据来源: RSC

摘要:

MR. HERAPATH ANALYSIS OF SUGAR FECULENCIES 367 XXXL-On a Cement for stopping the cavities of Teeth. BY T.J. HERAPATH, F.C.S. A good cement for stopping the cavities of carious teeth has long been a great desideratum to dentists because unfortunately almost all those now known possess some disadvantage or other. Even the copper-amalgam hitherto the one most preferred by the members of this profession and of which the analysis and mode of preparation have been recently described by M. Pettenkofer,* is apt to communicate a very unpleasant metallic taste to the food find soon becomes discoloured in consequence of the formation of a thin film of black sulphuret of copper. But in the course of the last few months another succedaneum the invention of an American gentleman has been brought into notice; and this would appear to * Ann.Ch. Pharm. June 1849. MR. HERAPATH ON A CEMENT possess every requisite that could be desired. The substance referred to is an alloy of tin and cadmium. 'When combined with a small quantity of mercury it becomes soft and semi-fluid and may then be easily pressed into the cavity of the decayed tooth where it soon solidifies into a hard tenacious crystalline amalgam thus preventing the access of air to the interior of the tooth and rendering the organ fit for the purposes of mastication. Being at the same time of a dull white colour similar in appearance to frosted silver and not liable to become tarnished close scrutiny is required in order to detect its presence.The great advantage of this latter property need not be pointed out. When about to be employed the alloy in fine powder is mixed up by the operator in the palm of his hand with from two and a half to three times its weight of mercury or such a quantity as will suffice to render it perfectly soft when it is immediately pressed into the cavity in the enamel the latter having been previously cleansed and dried by the ordinary method. The alloy above-described as may be naturally supposed is readily acted upon by acids even by the diluted vegetable acids which gradually dissolve out the cadmiurn. But as the salts of cadmiumdo not appear to produce any injurious action upon the system unless taken in large quantity of course no ill effects need be expected to result from this circumstance.This metallic combination of tin and cadmium presents us with another interesting example of the effects of crystallization and amorphism on the physical properties of bodies. As in the case of the copper-amalgam before adverted to the specific gravity does not appear to vary 111 the transition from the amorphous to the crystal- lized condition as the amalgam when hard occupies very nearly if not exactly the same space that it does when soft and fluid. In conclusion I may observe it has been found that the pro-portion of the cadmium may be considerably reduced without altering the physical properties of the compound. A mixture of 5 parts of cadmium and 7 to 8 of tin is the best and has been found to answer remarkably well.A quantity of the cement in qiiestion was placed in my hands some time since by a friend who wished to learn the nature of its com-ponents. Upon subjecting it to analysis it was found to consist of tin and cadmium in the following proportions 8.90 grs. gave 3.962grs. of Sn02and 6.629 grs. of CdO. 10800 , , 4.460 , of Sn02 , 7.429 , of CdO. 10*00 , , 4.630 , of Sn02 , 7422 , of CdO. FOR STOPPING DECAYED TEETH. It would therefore appear to be coinposed of I. 11. Irr. Mean. Tin . . . 34.899 34-960 34.980 34.946 Cadmium . 65.061 65.010 64.950 65.007 and must therefore be considered as an alloy of these two metals in the proportion of one atom of the former to two of the latter. The best mode of preparing it I find to be as follows :-Melt a quantity of bees’-wax in a pipkin over the fire and then throw in the cadmium; by these means the loss of cadmium which would other- wise result from oxidation is avoided.So soon as the metal is completely fused add the tin in small pieces till a perfectly homo- geneous alloy is formed. This can be afterwards granulated in the usual manner or by introducing it into a wooden or iron box and shaking it up rapidly while it still remains in the fluid state. Since the above was written I have analysed another and some-what similar cement which was stated by theinventor to be composed of platinum and tin. A quantitative examination however proved it to possess the following composition in 100 parts Silver . . 73.188 Tin . . . 21-127 Zinc . slight traces Platinum with very slight traces of gold . 5.685 100*000

ISSN:1743-6893    

DOI:10.1039/QJ851030367b

出版商:RSC    

年代:1851

数据来源: RSC

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FOR STOPPING DECAYED TEETH. XXX1I.-On the Chemical Constitution and Nature of Organic Radicals. BY H. KOLBE.,PH,D. F.C.S. Do compound radicals exist in organic combinations exercising therein the functions of simple elements and combining like the latter with oxygen sulphur chlorine &c. in certain atomic pro- portions to form oxides (acids) sulphides and chlorides ? Do these compound radicals consist of unaZterabZe groups of atoms or can the substitution of their hydrogen by chlorine bromine hypo- nitric acid &c. be effected unaccompanied by the distiirbance of chemical equilibrium ? YOL III,-NO. XII. BB 370 DR. KOLBE ON THE CHEMICAL Is it at variance with the principles of the electro-chemical theory that elements of such different chemical properties as hydrogen and chlorine should displace each other ; and that oxygen chlorine and similar bodies of decidedly electro-negative character should rank among the constituents of organic radicals ? The above questions first set on foot by the discovery of chloracetic acid have been answered in various ways and most decidedly and minutely by Berzelius in the correspondence that lasted for some years between himself and Dumas These interesting discussions were unfortunately interrupted by the death of the first-named chemist with- out any understanding or approximation of views being effected so that the opinions of chemists are to this day widely at variance with regard to the above points.Berzelius and with him the greater number of German chemists have as is well known adhered to their opinion of the existence of compound radicals the correctness of which they have considered as proved by the successful isolation and the chemical properties of cyanogen and cacodyl.In addition to this Berzelius obstinately defended the principle against all attacks made by adherents to the theory of substitution that organic radicals were unalterable groups of atoms; that substitution could not be effected in them without a thorough alteration of their chemical constitution least of all the substitution of hydrogen by bodies of such prominently electro-negative properties as chlorine bromine oxygen &c. ; and that the assumption of organic radicals containing oxygen or chlorine was in contradiction to the principles of the electro-chernicat theory.On the other hand Dumas without distinctly stating whether indeed he assumes the existence of organic radicals has maintained the principle that compounds containing an equal number of equiva-lents arranged in a like manner are possessed of the same funda- mental properties and that the function exercised by an element in organic combination is not dependent upon its original properties but rather upon the position which it occupies in the compound. Both chemists agree in the opinion that the assumption of a replace- ment of the positive hydrogen by the negative chlorine in a compound radical is at variance with the electro-chemical theory because according to this theory the nature of a compound cannot be consi- dered as independent of the chemical nature of its constituents.This accordance of opinion with respect to the latter point has been most probably the principal reason why the question as to the immutability of organic radicals has not been made the subject of investigation to the degree that it merits. CONSTITUTION AND NATURE OF ORGANIC RADICALS. 371 It may be considered as beyond all doubt that the theory of radicals in its present state no longer suffices to furnish proper explanations of the innumerable metamorphoses resulting from so-called substi- tution and that by a continued adherence to the unchangeability of compound radicals the secure foundation resulting from the theory of radicals becomes continually weakened.We are indeed at the present moment almost forced by facts to assume that organic radicals are alterable groups of atoms in which chlorine bromine hyponitric acid &c. may enter in the place of hydrogen the molecular grouping of their atoms remaining unchanged and secondary radicals being thus produced which are possessed in part of properties similar to those of the primary ones. Instead of at once discussing the question whether and how far this mode of viewing may be made to accord with the electro-chemical theory I will endeavour in the following pages to apply this hypothesis to a series of organic combinations arid more particularly to those the comportment and metamorphoses of which it has been most difficult to explain by the theory of radicals as it now stands The difficulty of bringing the behaviour of acetic acid with chlorine and its reproduction from chloracetic acid to accord with the assump- tion of an unalterable acetyl-radical of the formula C H, first led Bereelius to construct the hypothesis that acetic acid and chlora- cetic acid might be conjugated oxalic acids the one containing methyl and the other sesquichloride of carbon as adjuncts and that the conversion of acetic into chloracetic acid was solely due to a me-tamorphosis of the adjunct while the oxalic acid itself remained unaltered.Whatever may be the opinion entertained as to the value of this hypo- thesis it cannot be denied that the pre-existence of methyl in acetic acid has received a high degree of probability from facts most of which were only subsequently discovered Independent of the analogy existing between acetic and chloracetic acid on the one hand and between methylo-hyposulphuric acid and sesqui-chlorocarboh yposulphuric acid on the other to which I have already referred in a previous paper,* the conversion of acetate of ammonia into cyanide of methyl and the reproduction of acetic acid from the latter as also the decomposition of acetic acid by the galvanic current into methyl and carbonic acid can scarcely be satisfactorily interpreted otherwise than by the assumption of the existence of methyl as a component part gf acetic acid.* Ann Ch. Pharm. d. LIV 148 ff; Chem. SOC. Mem. 11 360. BB2 372 DR.KOLBE ON THE CHEMICAL It has not as yet been attempted to extend the above hypothesis to the remaining combinations of acetyl which if acetic acid were methyloxalic acid must evidently have a composition corresponding to this view. The result of such an attempt would be the necessity of assuming the existence in aldehyde acetylous acid chloride of acetyl &c. of the partly hypothetical bodies C,O C 0 and C C1 coupled with methyl. We should likewise be forced to assume that in .the terchloride of acetyl (the so-called dichlorinated chloride of ethyl) which according to Regnault may be converted by continuous boiling with alcoholic potassa into acetic acid and chloride of potas- sium the sesquichloride of carbon considered as combined therein with methyl must differ considerably in its properties from the same substance when uncombined as the latter cannot be converted by similar treatment into the corresponding oxygen-compound oxalic acid ;moreover a further extension of the hypothesis to the remaining compounds allied to acetic acid-for example to the other mem-bers of the series (C H,) o, as also to benzoic acid and its homo- logues &c.would show that instead of viewing them as oxides of compound radicals as hitherto we must consider them all as conju- gate oxalic acids and finally that of all the radicals which are partly really isolated there would be few or none remaining. Even caco- dylic acid if the replacement of a portion of its hydrogen by chlorine be accomplished as there is little doubt it will must no longer be considered as an oxygen-compound of cacodyl but perhaps as arse- nious acid conjugated with two equivalents of methyl.If however we adhere less strictly to the immutability of organic radicals another hypothesis very nearly allied to the former of the chemical constitution of acetic acid and the acetyl-compounds in general presents itself possessing the advantages of the former without sharing its defects namely that an acetyl-radical really exists in the acetyl-compounds ;that it must not however 6e consi- dered as a group of four equivalents of carbon and three equivalents of hydrogen the four carbon equivalents of which possess equal func- tions but that it should rather be viewed as a compound of two epui-valeuts of carbon and methyl as the adjunct Acetyl = (C H,)T, in which the C presents the exclusive point of action for the powers of ujlinity of oxygen chlorine &c.According to this view the composition of the acetyl-compounds with which we are as yet acquainted would be expressed by the fol- lowing rational formulz CONSTITUTION AND NATURE OF ORGANIC RADICALS. 373 Subacetylous acid . . . HO . (C H,)-C, 0 (aldehyde). Acetylous acid . . . . ('2 H3)nc2, Acetylic acid HO (C H3)^C,, '2 0, . . . . . (acetic acid). (&her hydro- { Terchloride of acetyl. . . (C H3) ^C2 Cl chlorique-bichlorurd) . Dinoxamide of acetyl . . (C H3)^C2>{ $Ho (acetamide). Oxydichloride of acetyl Oxydisulphide of acetyl .Oxysdphochloride of acetyl (C H3)-C2 (&her chloro- I c1 sulfuri). The assumption of this conjugate acetyl-radical in aldehyde and acetic acid renders it evidently necessary that the interpretation hitherto given to the process of acetification should be slightly modi- fied. The action of the oxygen on the alcohol effects probably at first the splitting of ethyl into methyl and the carbo-hydrogen C H2 the elimination of which from organic compounds belongs to the most common phenomena. At the moment of its liberation it under-goes a further decomposition; as the hydrogen becomes oxidised the two equivalents of carbon immediately reunite with the methyl forming the conjugate acetyl-radical (C2H3)-Cg with which the oxygen of the oxide of ethyl remains combined (C H5)0 .H0+2 O=HO (C HJ-C, 0+2 HO L.-v-.-J L-v-Alcohol. Aldehyde. The conversion of aldehyde into acetic acid by the direct assimila- tion of two equivalents of oxygen HO . (C H,)^C, 0+2 O=HO (C H,)^C, 0 L-TA LPTL Aldehyde. Acetic acid. must be considered as of old as a pure process of oxidation. It appears to me that all other relations of acetic acid to different compounds may be explained in an equally satisfactory manner by assuming it to be composed according to the above rational formula. Its formation from cyanide of methyl by boiling with potassa (C H3) C N + KO +3 HO=KO . (C H3)-C, 0 + N H3 L-v-J Cyanide of methyl. Acetate o€ potassa. DR. KOLBE ON THE CHEMICAL the decomposition of acetate of ammonia by distillation with phos- phoric acid into cyanide of methyl and water NH 0 .(C H3)^C2,03 + n PO = (C H,) C2N + 4 HO +n PO L.-v-J --A Acetate of ammonia. Cyanide of methyl. the decomposition of an aqueous solution of acetate of potassa at the oxygen-pole of the galvanic current into methyl and carbonic acid KO (C H3)^C2,0 + O= C2 H3+ KO CO,+ CO L-v-J Ly-’ Acetate of potassa. Methyl. the conversion of acetic acid by heating its lime-salt with hydrate of lime into carbonic acid and marsh-gas (hydride of methyl) CaO . (C2 H,)^C, O,+HO . CaO=H (C HJ+2 (CaO . CO,) -v-3 + Acetate of lime. Marsh-gas. and finally the formation of oxide of cacodyl by the distillation of acetate of potassa with arsenious acid 2 [KO .(C2H3)^C,,0,] +As 03=(C,H3)2As,0+2(K0,C02) + 2C0 L-v--3 Acetate of potassa. Oxide of cacodyl. All these decompositions are most simply and naturally expressed by the above equations. I consider it at present impossible to explain the formation of acetone from acetic acid as we are as yet quite in the dark with regard to its rational composition and indeed have not even established its empirical formula with certainty. The opinion defended with so much warmth by the adherents to the theory of substitution that the so-called dichlorinated oxide of ethyl still possessed the constitution of oxide of ethyl does now scarcely need any refutation. Not only do the close relations borne by this compound to acetic acid into which it is converted by lengthened contact with water almost preclude a doubt of its belonging to the acetyl-series but it is of itself more than probable that the oxide of ethyl would undergo a similar metamorphosis by the action of chlorine as with oxygen.The action of chlorine on oxide of ethyl likewise appears to consist in the first instance of a splitting of the ethyl-group into methyl and C H, which is followed by the immediate decomposition of the latter carbo-hydrogen and the formation of (C H3)-C, together with hydrochloric acid ; this radical remaining in combination with the oxygen of the oxide of ethyl assi- -. CONSTITUTION AND NATURE OF ORGANIC RADICALS. 375 milates in addition two equivalents of free chlorine and thus becomes (C2 H3)-C2,{ g12, i.e. oxydichloride of acetyl according to the following equation C4H50 + 4C1= (C HJC2,{ g12+ 2 HCl U Lv-2 Oxide of ethyl. Oxydichloride of acetyl. The same mode of viewing may be applied with facility ta the decomposition of this acetyl-compound by water or alkalis into acetic and hydrochloric acids -2 Oxydichloride of acetyl. L-and its conversion into oxybisulphide of acetyl (&her bisulfuk) and oxysulphochloride of acetyl (&her chlorosulfur6) by the action of hy drosulphuric acid Oxydichloride of acetyl. Oxybisulphideof acetyl. and L-L-v+ Oxydichloride of acetyl. Oxysulphochlonde of acetyl. To these acetyl-combinations must still be added the dinoxamide of acetyl (C2H,)"C2 { $H the formation of which from acetate of oxide of ethyl and ammonia is explained by the following equation Acetate of oxide of ethyl.Acetamide. Alcohol. It can scarcely admit of adoubt that the product of decomposition of chlorideof ethyl corresponding to the dichlorinated oxide of ethyl namely the so-called dichlorinated chloride of ethyl possesses a con-stitution siinilar to that of the former and is therefore the true DR. KOLBE ON THE CHEMICAL terchloride of acetyl,* (C H,)^C, Cl, although it exchanges its chlorine for oxygen with much greater difiiculty and requires long continued boiling with alcoholic potassa for its complete coiiversion into acetic acid. By the action of chlorine on ether there is formed according to Malaguti in addition to the dichlorinated oxide of ethyl a second body the so-called semi-chlorinated ether which M alaguti did not succeed in separating and purifying respecting the existence of which however his experiments leave no doubt.This substance corresponds with the chloride of aldehyde discovered by Regnault in so far that both may from their empirical composition be considered as ethyl- compounds the former as the oxide of ethyl the latter as the chloride * The substance originally named chloride of acetyl is the gaseous body (C H Cl) formed by the treatment of the oil of olefiant gas with alcoholic solution of potassa. The product obtained by the action of pentachloride of antimony on this gas isomeric with the dichlorinated chloride of ethyl has been named by Berzelius superchloride of acetyl; to the dichlorinated chloride of ethyl itself he has given the name super-chloride of paracetyl.It might appear from this that the superchloride of acetyl of Berzelius obtained from the oil of oletiant gas was the true terchloride of acetyl corresponding to acetic acid while the so-called superchloride of paracetyl obtained from chloride of ethyl was only an isomeric compound not really belonging to the acetyl-series If it be considered however that the latter substance permits the replacement of its chlorine by oxygen thus passing over into acetic acid while the former cannot be directly converted into acetic acid or any other member of the acetyl- series there can be no doubt whatever that the dichlorinated oxide of ethyl (super- chloride of paracetyl) is the true acetyl-compound namely the terchloride of acetyl (C H,)^C, c1,.The gas obtained by the action of alcoholic potassa upon olefiant gas the so-called chloride of acetyl appears to me to belong as little to the acetyl-series as the so-called superchloride of acetyl. The isomerism of its supposed radical with acetyl may however be easily explained if we consider it as hitherto to be a body (C H3) homologous to aflyl (C H5) for which I propose the name of vinyl as suggestive of its origin (comp. Iiadwbrterbuch der Chemie Bd. v. p. 548 ff). The olefiant gas may be considered as the hydrogen-compound of this radical or as hydride of vinyl consisting of + volume of vinyl-vapour and + volume of hydrogen which corresponds perfectly with the observed specific gravity assuming a condensation of 2 vols.carbon-vapour and 3 vols. hydrogen to 1 volume in vinyl 2 vols. carbon-vapour . . . 1.658. 3 , hydrogen . . . . . 0.207. 1vol. vinyl gas . . . . . 1.865. , vinyl gas . . . . . 0933. $. , hydrogen . . . . . 0.034. 1vol. hydride of vinyl . . . 0.967. Assuming with Liebig the oil of olefiant gas to be a combination of hydrochloric acid with the chloride of the radical vinyl and admitting the possibility of a substitution of CONSTTTUTION AND NATURE OF ORUANIC RADICALS. 377 in each of which one equivalent of hydrogen is replaced by one of chlorine (C {:()O semichlorinated ether (C4{:f)C1 chloride of aldehyde. As long however as this view is unsupported by facts I consider it much more probable that these compounds possess a composition corresponding to the hydrochlorates of oxide of vinyl and of chloride of vinyl (comp.note p. 376) being thereforecombinations of hydro-chloric acid with oxide of acetyl (in the semichlorinated ether) and chloride of acetyl (in the chloride of aldehyde) (C H,)-C, 0 .H C1 semichlorinated ether (C H3)-C2 C1. I1 C1 chloride of aldehyde. the hydrogen in vinyl itself by chlorine the composition of the substances derived from olefiant gas may be best expressed by the following rational formulse Vinyl = C H,. Hydride of vinyl . . (C H,)H olefiant gas. ~~~~'~~~~fc~lO:} (C H,) C1 H C1 chloride of elayl (Berzelins). Chloride of vinyl . . (C H3) C1 chloride of acetyl (Berzelius).Hydrochlorate of chlo- ride of ch~orovinyl *} (c {F{>C~ Chloride of chlorovi-}(c4{ 3)Cl H ~1 superchloride of acetyl (Berzelius). nyl ..... chloride of formyl (Berzelius). Hydrochlorate of chlo- H GI ride of &chlorovinyl.} (c {Z&)C~ superchloride offormy1 (Berzelius). ''* Hydrochlorate of chlo-ride of trichlorovinyl. }('4 "3) c12 ide of vinyl Hydrochlorate ,Of .Ox-} (C H3) 0,H C1 oxychloride of elayl (Berzelius). ~:fT:)(C,~~ H H3) Br H~Br bromide ~of elayl (Berzelius). ~ ~ Hydriodate of iodide 1(C H3) I H I of vinyl . . . .J iodide of elayl (Berzelius). Iodide of vinyl . . (C H,)I iodide of acetyl (Berzelius). The conversion of the substance mentioned under the name of hydrochlorate of chlo-ride of trichlorovinyl and discovered by Pierre (Ann.Ch. Phys. [S] XXI. 439) into the so-called protochloride of carbon (C CI, or C Cl,) by boiling with alcoholic potassa is probably accompanied by an alteration in the arrangement of the elements (C C1,) C1 to (C C13)-C, C1 (chloride of trichloracetyl) the latter formula expressing the rational composition of protochloride of carbon as I shall presently endeavour to show. The sulphur-compounds of vinyl require e more careful examination than they have hitherto beeii subjected to. The sulphides of elayl described by Lowig and Weidmann were doubtless impure substances containing an admixture of sulphur. It might be interesting to examine the behaviour of chloride of vinyl with sulphocyanide of potassium as a sulphocyanide of vinyl (C H3) Cy S, coifesponding to oil of mustad (C H5) Cy S, might possibly be produced under these circumstances.DR. KOLBE ON THE CHEMICAL By this assumption the formation of semi-chlorinated ether from oxide of ethyl C H 0 $2 C1=(C2 H,)^C, 0.H C1+ H Cl < 2 L7-7--Oxide of ethyl. Semichlorinated ether. its conversion into oxybichloride of acetyl (bichlorinated oxide of ethyl) by treatment with chlorine Y -J L-yL Semichlorinated ether. Oxybichloride of acetyl. and its decomposition by water into aldehyde and hydrochIoric acid. (C HJ-C, 0 H Cl+ HO=HO . (C,H,)^C, 0 + H C1 L-v-L-v-3 Semichlorinated ether. Aldehyde. may be explained in a simple and perfectly satisfactory manner It may be regarded as self-evident that a hypothesis constructed upon the constitution of acetic acid or any other member of the series of fatty acids must likewise admit of application to the remaining members of that series.If therefore we consider acetic acid as the oxide of the conjugate radical (C H3)-C, it follows naturally that we must assume the existence of conjugate radicals analogous to acetyl in propionic valeric margaric formic acids &c. Indeed in an attentive examination of these compounds I have not met with any fact that was in contradiction with the above hypothesis; and I believe that I do not err in expressing the conviction that the compartment of the fatty acids from formic acid up to melissic acid and their manifold relations to other compounds may be better interpreted by the above hypothesis than by any one of the former views.The decomposition of valeric acid by the galvanic current into butyl (C H,) and carbonic acid and its formation from cyanide of butyl (C H,) C N (valeronitril) are particularly well adapted to support this opinion. The relation of stearic to margaric acid and its bibasic nature may be easily explained without our being obliged to adopt the assertion made by Laurent and Gerhardt that both these acids possess the same composition and saturating capacity and are only two isomeric modifications if we view stearic acid as a double acid composed of two different oxides of margaryl (C 32 €13JnC2 namely H 0 (C32 H,)-C, 0 + H 0 (C32 H3,)’’C2 O,-~S CONSTITUTION AND NATURE OF ORGANTC RADICALS.379 I shall presently endeavour to establish the view that in s similar manner sulphobenzoic and sulphacetic acids are double acids and owe their bibasic property to this circumstance. According to the above hypothesis the composition of the fatty acids would be expressed by the following rational formula Formic acid Acetic acid. Propionic acid. Butyric acid. Valerie acid. Caproic acid. Enanthylic acid. Caprylic acid. Pelargonic acid. Caprinic acid Ricinostearic acid (margaritic acid) Laurostearic acid (pichurimo-stearic acid). Cocinic acid. Myristic acid. Benic acid. Bthalic acid. Margaric acid. Stearic acid. Bassic acid. Behenic acid. Cerotic acid. Melissic acid. A glance at the above table will show that the radicals of the fatty acids contain as adjuncts the radicals of the alcohoIs of which however we are as yet acquainted with onIy a few namely methyl ethyl amyl cetyl and cerotyl.The important discovery made by Dumas that the ammonia-salts of acetic propiouic valeric and other acids may in accordance with the deportment of formiate of ammonia be converted by distillation with phosphoric acid for instance into the cyanogen-compounds of the adjuncts of these acids -for instance cyanide of methyl cyanide of ethyl cyanide of propyl and cyanide of butyl-furnishes us with the prospect of obtaining by this method the whole series of alcohols that arc DR. KOLBE ON THE CHEMiCAL 380 still wanting provided we are successful in converting the cyanides into other combinations of the alcohol-radicals The experiments hitherto made on this subject have however given no results.Among the radicals of the fatty acids formyl H-C stands to a certain extent isolated it being the only one in which the adjunct contains no carbon. As however its compounds bear the greatest resemblance to those of acetyl this would appear to indicate that the nature of the adjuncts of conjugate radicals exercises comparatively little influence over the chemical character of their compounds. The composition of those formyl-compounds of which the consti- tution is established with tolerable certainty may be expressed by the following rational formulze Formylic acid . .. . HO .HnC3 0 Formic acid. Terchloride of forrnyl . . HT, Cl Chloroform. Terbromide of formyl . H-C, Br Bromoform. Teriodide of formyl . H^C2 I Iodoform. Tersulphide of formyl . Sulphoform. Dichloriodide of formyl Chloriodoform. Dibromoiodide of formyl Bromiodoform. Diodocyanide of formyl Formyl-aci-bichlo-ride (Be r z elius). Oxydichloride of formyl (Ether methylique bichlorure'). The analogy of hydrated oxide of methyl to hydrated oxide of ethyl warrants the supposition that the former in its oxidation and conversion into formic acid undergoes a decomposition similar to that of the latter in its transformation into acetic acid; namely that the elimination of C H from the composition of methyl precedes the production of formic acid from methyl-alcohol (C2 H3) 0.HO+4 O=HO -' . HnC, O,+2 HO v Hydrated oxide of methyl. Formylic acid In the same manner the rational formula HnC2 { f or (32 &chlorinated oxide of methyl is based upon the supposition that when two equivalents of chlorine enter oxide of methyl in the place of two of hydrogen it undergoes a metamorphosis correspond- CONSTITUTION AND NATURE OF ORGANIC RADICALS. 381 ing to the conversion of oxide of ethyl into oxydichloride of acetyl namely (C H3) 0+4 Cl=H^C,,{ +2 H C1 + -7-f Oxide of methyl. Oxydichlonde of formyl. Unfortunately the chemical deportment of dichlorinated oxide of mythyl has been too little studied to admit of the deduction of any argument therefrom for or against the above view ; it can only be supposed from its analogy with dichlorinated oxide of ethyl (oxy- dichloride of acetyl) that alcoholic potassa would convert it into formic acid and hydrochloric acid HT, { -i-3 KO =KO.H-C, 0,+ Z KCl + Oxydichloride of formyl. Formiate of potassa. The view that the so-called perchlorinated ether the penta-chlorinated oxide of ethyl no longer possessed the constitution of oxide of ethyl was already defended in opposition to the older theory of substitution by Malaguti in his excellent researches on the chlorinated ethers. Moreover if we consider it established that chlorine like oxygen is capable of converting oxide of ethyl into an acetyl-compound the pentachlorinated ether cannot really be a direct product of decomposition and much less a substitution-product of oxide of ethyl but must rather be considered as a derivative of oxydichloride of acetyl.Indeed its most intimate relation to the acetyl-compounds may be inferred from its chemical comportment and that of its products of decomposition chloracetic acid the so-called chloraldehyde &c. Even the fact that perchlorinated ether chloracetic acid chloraldehyde chloroxethose &c. may be almost directly converted into acetic acid and the latter again into chlora- cetic acid renders it more than probable that all these bodies have a similar chemical constitution. It becomes most clearly perceptible in the study of these com-pounds into what a labyrinth of hypotheses and to what very improbable assumptions we are forced if we forsake on the one hand the theory of radicals and adhere on the other to the immu- tability of organic radicals.It is certainly quite as difficult to agree with the hypotheses of Laurent and Dumas as to adopt the views taken by Berzeliu s* of the constitution of perchlorinated * Lehrbuch 5th Edit. Vol. V. 788-825. '- 382 DR. KOLBE ON THE CHEMICAL ether and its derivatives and of the substitution-products of the ethers in general. I will endeavour to interpret these phenomena of substitution from the point of view above adopted and to base the following considera- tions upon the hypothesis that a substitution of chlorine for hydrogen takes place in the acetyl-radical without dissolving the complex atom three new secondary radicals being produced thereby which contain in the place of one two or three equivalents of hydrogen a propor-tionate number of equivalents of chlorine and which are gifted with properties similar to those of acetyl itself.For the better indication of their relations to the latter I will assign to them the names- chloracetyl dichloracetyl trichloracetyl and express their rational composition by the following formulze Acetyl . (C H,)^C Chloracetyl . . (C { ;f)-'2 Dichloracetyl (C2{ E1a)-'2 Trichloracetyl (C CI,)-C2 Of the various combinations of these three secondary acetyl-radicals those of trichloracetyl have been by far the most accurately studied; I will therefore first submit them to examination.EIydrated oxide of trichloracetyl HO.(C C13)-C2 0 Chloral. Trichloracetylic acid . . . HO.(C C13)-C2 0 Chloracetic acid. Oxide of trichloracetyl . . (C C13)1C2 0 Chloroxethose. Chloride of trichloracetyl . . (C Cl,) C, C1 Chlorethose(ch1or.ofcarbon). Oxydichloride of trichloracetyl . (C CI3)-C2 Chloride of chloroxethose { g, Oxydibromide of trichloracetyl . (C ClJ-C, Bromide of chloroxethose. { ir2 Dinoxychloride of trichloracetyl . (C C13)-C2 Chloraldehyde. { Ef Dinoxamide of trichloracetyl . (C Cl,)-C, Chloracetamide. { 2H Dinoxyphosphamide of trichloracetyl (C C13)"C, { O2 Chloracetyphide. PH Cblorodibromideof trichloracetyl (C Cl,)-C, { g Bromide of chlorethose. We may easily perceive that those of the trichloracetyl-compounds above-mentioned which are also represented in the acetyl-series differ in various points in their properties and chemical comportment from the corresponding members of the latter series.The acetyl has evidently undergone no unimportant modifications by the exchange of its hydrogen for chlorine. In these instances as in the substi- tution-products of aniline the chlorine to however great an extent it CONSTITUTION AND NATURE OF ORGANIC RADICALS. 383 appears to have lost its specific properties imparts some portion of its chemical character to the combination in which it has entered the place of the hydrogen. This influence is rendered very distinctly evident in chloraniline and trichloraniline by the weakening of the basic properties of the aniline; in the compounds of trichloracetyl it is not so obvious although it is always rendered to a certain extent perceptible by a modification of the original affinities of acetyl.It should therefore not appear surprising that chloracetic acid when boiled for instance with potassa deviates somewhat in its com-portment from its analogue acetic acid or that oxydichloride of trichloracetyl (perchlorinated ether) the analogue of oxydichloride of acetyl (dichlorinated oxide of ethyl) should be decomposed with much greater difliculty by similar treatment with potassa than the latter. It is worthy of note that the conversion of the chlorides (oxychlorides) of acetyl and trichloracetyl into the corresponding acids is effected with greater ease in proportion to the number of atoms of oxygen that the compound contains.While the terchloride of acetyl which coiitains no oxygen is but very slowly converted into acetic acid by boiling with alcoholic potassa the oxydichloride of acetyl is converted into that acid with the greatest ease by the mere action of water; and doubtless the dinoxychloride of acetyl which is as yet unknown but the production of which may be expected with tolerable certainty to result from the treatment of concentrated acetic acid with pentachloride of phosphorus will be a liquid much more easily decomposed by water. On the other hand dinoxychloride of tri-chloracetyl (chloraldeh yde) is equally distinguished from the oxydi- chloride of trichloracetyl by the facility with which it is converted into chloracetic acid.-M alagut i* has left it undecided whether the small quantity of formic acid which he detected in the fluid after continuous boiling of perchlorinated ether with alcoholic potassa owed its production to the action of the potassa on the alcohol or to the conversion of perchlorinated ether into cloracetic acid (C C13)-C3 { +3KO =KO (C C13)-C2 0,+2 KCl.v Perchlorinated ether. Chloracetate of potassa. The simultaneous deposition of chloride of potassium gives at any rate a greater probability to the latter view. The accompanying equations will show that by the assumption of -2 * Ann. Ch. Phys. [S] XVI 19. 384 DB. KOLBE ON THE CHEMICAL a trichloracctyl the most simple and natural explanations are furnished 1.Of the decomposition of chloracetic acid into terchloride of forrnyl and carbonic acid by boiling with potassa HO (C ClJ-C, 0 + 2 KO = HT, C1 + 2 (KO CO,) L-v--J 7 Chloracetic acid. Chloride of formyl. 2. Of the formation of chloracetamide by the action of ammonia on chloracetate of oxide of ethyl -v-d L-v-.-J Lv-d Chloracetic ether. Chloracetamide. Alcohol. 3. Of the conversion of chloracetate of ammonia by phosphoric acid into the substance termed by its discoverers Dumas Malaguti and Leblanc chloracetonitrile and which is probably a cyanogen- compound (C Cl,) . C N NH 0 (C CI3)-C2 O,+ nPO,= (C CI,)^C N -t4 HO nPO L-v-& L-v--' Chloracetate of ammonia. Chloracetonitrile. 4. Of the reproduction of' chloracetic acid and ammonia from chloracetonitrile by boiling with potassa (C C13)"C2 N + KO + 3 KO = KO .(C CI,)"C, 0 + NH,. Lv-d L-.-vp2 Chloracetonitrile. Chloracetate of potassa. 5. Of the transformation of perchlorinated ether at a temperature of 300°C. into sesquichloride of carbon and dinoxychloride of tri-chloracetyl (chloraldehyde) L-WU -yy-' L7-Perchlorinated ether. Sesquichloride Chloraldehyde. of carbon. 6. Of the metamorphosis which the latter body undergoes when heated with concentrated sulphuric acid 0 0 (C C13)"C2 { c1+ HO . SO,= (C,C 1,)^C2 { ci -t HC1+ SO -L-Y---J Perchlorinated ether. Chloraldehyde. 7. Of the decomposition of chloraldehyde by water into chloracetic acid and hydrochloric acid CONSTITUTION AND NATURE OF ORGANIC RADICALS.385 (c c13)_c, { Ef + 2 HO = HO. (C Cl)-C, 0 +-HCl. L-v-J L---v-a Chloraldehyde. Chloracetic acid. 8. By alcohol into chloracetic ether and hydrochloric acid (C Cl,) C, { 4+ (C HJO. HO=C H 0. (C CI,)-C, 0,+ HCI. LFV-d \-Chloraldehyde. Alcohol. L,-v--) Chloracetic ether. 9. By ammonia into chloracetamide (C C13)nC2,{ Ef + 2NH = (C Cl,) C, { $H + NH,Cl 2 c-v-2 L-v-J ChIoraldehy de. Chloracetamide. 10. By terphosphide of hydrogen into chloracetyphide (C C13)-C2 { gf + PH3= (C2 C13)-C2 { pH+ HCl. L-v-3 L-v-”J Chloraldehy de. Chloracetyphide. and finally the formation of chloraldehyde by a simple change in the arrangement of the elemeots of the so-called perchloracetic ether effected by passing the vapour of the latter through a dull red- hot tube L v------d L-v-J Perchloracetic ether.Cloraldehyde. Chloraldehyde exhibits in its behaviour a remarkable similarity to the so-called chloride of benzoyl (CI4 H 0 Cl). The reason of this analogy between two such heterogeneous compounds may be easily arrived at if the benzoyl-radical (free from oxygen} be viewed as a conjugate radical like acetyl and trichloracetyl having the rational formula (C12 HJC,. All three radicals possess in common the term C, forming the real point of attack for the powers of affinity of the negative elements while the adjuncts alone are different. Here then the subordinate part played by the adjuncts compared with that of the body with which they are conjugated and their comparatively slight influence over the chemical nature of the compounds of conju- gate radicals is again most strikingly exhibited.The above similarity is however not merely confined to chlorobenzoyl and chloraldehyde it exists equally between benzoic acid and chloracetic acid benzamide and chloracetamide benionitrile and chloracetonitrile and will doubt-VOL. IJI.-NO* XII. cc DR KOLBE ON THE CHEMICAL less extend to the sulphide of benzoyl and cyanide of benzoyl and the terms corresponding in the trichloracetyl series with which we are yet acquainted. The analogy of these compounds is best rendered evident by the following comparison of their rational formuh '-G2 H5)^C ('2 c13)-c2 Benzoyl. Trichloracetyl.-U v + Benzoic acid. Chloracetic acid. -Chlorobenzoyl. Chloraldehyd. -v Benzamide. C hloracetamide. PI2 H5)'c2 N (C Cl3)* c2 N - Chloracetronitrile. Benzonitrile. The difference between the behaviour of oxydichloride of trichlor-acetyl (perchlorinated ether) with sulphide of potassium and that of the corresponding member of the acetyl series (the oxydichloride of acetyl) is worthy of remark. Whilst the latter when treated with hydrosulphuric acid exchanges 1 or 2 equivalents of chlorine for sulphur the former undergoes a simple reduction by treatment with an alcoholic solution of sulphide of potassium and is con-verted into the oily compound called by Malaguti chloroxethose (C2 CI3)-C2 0 (oxide of trichloracetyl) sulphur and chloride of potassium being separated.0 (C2 C13)-C2 { c1 + 2 KS= (C C13)-C2 0+ 2 KC1+S v2-Perchlorinated ether. Chloroxethose. The mode of formation of chloroxethose together with its property when brought into contact with chlorine (or bromine) of combining directly with two equivalents of these elements and thus being reconverted into perchlorinated ether (or the corresponding bromine- 0 compound (C C13)-C2 { Br LONSTITUTIQM AND NATURE OF ORGANIC RADICALS. 387 -v Chloroxe t ho se. Perchlorinated ether. as also its comportment with chlorine in the presence of water whereby it is partially converted into chloracetic acid (C C13)"C2 0+2 Cli-3 HO=HO. (C ClJ-C, 0,+2 H C1 T L-v-3 Chloroxethose. Chloracetic acid. are in perfect accordance with the view expressed by the above formula namely that chloroxethose is the oxide of trichloracetyl.The above considerations lead to the conjecture by no means unfounded that the chloride of carbon C C1 (Malaguti's chloride of chlorethose) which in its comportment exhibits so remarkable an analogy with oxide of trichloracetyl is the chlorine-compound of the same radical corresponding to this oxide namely chloride of trichloracetyl (C CI3)-C2 Cl. We may perhaps even go farther and regard the sesquichloride of carbon obtained from this chloride of trichloracetyl by direct assimilation of chlorine as the higher chlorine- eompound of the same radical namely as terchloride of trichloracetyl (C C13)-C2 Cl, or at least assume the existence of two isomeric coin-pounds C C1 (sesquichloride of carbon trichloromethyl) and (C ClJnC2 Cl (terchloride of trichloracetyl).The principal objection against the assumption that the chloride of carbon produced by the combination of chloride of trichloracetyl with chlorine is the terchloride of the latter radical lies in the circum- stance that we have not yet succeeded in replacing by oxygen the three equivalents of chlorine considered as combined with trichloracetyl. Alcoholic solution of potassa is certainly not quite without action upon it as after continuous boiling chloride of potassium is depo- sited the liquid becoming brown ;neither chloracetic acid terchloride of formyl nor formic acid can however be found among the products of decomposition.It is possible that in this experiment the terchlo- ride of trichloracetyl gives off two equivalents of chlorine to the potassium without any replacement ensuing the oxygen of the latter attacking the alcohol and oxidizing it to aldehyde; this would also account for the brown colour assumed by the alcoholic potassa- solution. It must however be borne in mind that terchloride of acetyl too is only attacked with difficulty by boiling alcoholic potassa md that the action of the latter is likewise obstinately withstood by the oxydichloride of trichloracetyl. On the other hand the conjecture that the so-called chloride and sesquichloride of carbon are chlorine- cc 2 388 DR. HOLBE ON THE CHEMICAL compounds of trichloracetyl is supported by a vast number of facts.The formation of the chloride of trichloracetyl from the so-called chloride of carbon by passing thevapours of the latter through a red- hot tube 4 c c1 = (C C1Jnc2 c1+4 c1 c-y-J Perchloride of Chloride of trichloro-carbon. acetyl. may be coupled with many similar examples in which compounds poor in carbon yield by the action of a high temperature less volatile substances richer in carbon as for instance the formation of naphthalin benzol &c. The solid chloride obtained together with the chloride of trichloracetyl doubtless owes its production to the further action of the large quantity of liberated chlorine upon the liquid chloride and must therefore be considered as a secondary product of decomposition of the dichloride of carbon.The remarkable similarity exhibited between the so-called sesqui- chloride of carbon and the oxydichloride of trichloracetyl (perchlo- rinated ether) in their outward appearance as also in their behaviour with hydrosulphate of potassium a point to which attention was first called by M alagut i finds a surprisingly simple explanation in the assumption of the rational formulE (C C13)'-C2 Cl, for the first named body. A simple comparison of the rational formulae of these two substances 0 (C cl,) -C2 { c12oxydichloride of trichloracetyl (C Cl,) 712 Cli terchloride of trichloracetyl (sesquichloride of carb.) and of the corresponding members of the trichloracetyl-series that are poorer in chlorine namely of oxide of trichloracetyl and chloride of trichloracetyl (C C13)-C2 0 oxide of trichloracetyl (chloroxethose M alaguti) (C Cl,) C, Cl chloride of trichloracetyl (chlorethose M alaguti) is only needed to account for the concordant behaviour of the two former compounds with hydrosulphate of sulphide of potassium and of the two latter with chlorine and bromine and particularly to explain the remarkable relations of the two latter to chloracetic acid.With regard to the tran;sformation of chloride of trichloracetyl into chloracetic acid by exposure to the action of chlorine in the presence of water under the influence of solar light it is partly due to the decomposition of water into hydrochloric acid and oxygen and partly CONSTITUTION AND NATURE OF ORGANIC RADICALS.389 to the power possessed by chloride of trichloracetyl of combining with oxygen directly as it does with chlorine at least when the former is in the nascent state. Dinoxychloride of trichloracetyl (chloraldehyde) is next formed and this being readily decomposed by water is con- verted into chloracetylic acid. (C C13)”C2 C1+ 2 HO + 2 C1= (C C13)T2,{ Ef -f-2 H C1 -y-d Lp-d Chloride of tnchloracetyl. Dinoxychloride of trichloracetyl. (c,c13)-c2,{ 8+ 2 NO= HO . (c ci,)-c, 0 + H ci L-7-V Dinoxychloride of Trichloracetyl. trichloracety1. The conversion of the greater part of the chloride of trichloracetyl into terchloride of trichloracetyl in the above process is doubtless owing to the slowness with which the oxygen is liberated from water by the chlorine.If a similar condensation of the elements be assumed in trichlora- cetyl as in acetyl one volume of trichloracetyl containing therefore two volumes of carbon-vapour and three volumes of chlorine ; 2 vol. carbon-vapour . . . 1.658 3 , chlorine . . . . 7.846 1 vol. trichloracetyl . . . 9.004 and if the chloride of trichloracetyl and terchloride of trichloracetyl be regarded as containing according to the usual modes of conden-sation half a volume of trichloracetyl combined respectively with half a volume or one and a half volume of chlorine the calculation of the specific gravities of these bodies in the gaseous form will furnish numbers corresponding very closely with the observed vapour densities of the so-called protochloride of carbon = 5.82 and sesqui- chloride of carbon = 8.157 4 vol.trichloracetyl . . . . . . 4.502 8 , chlorine . . . . . . . . . 1.224 1 vol. chloride of trichloracetyl . . . 5.726 4 vol. trichloracetyl . . . . . . 4502 -$ , chlorine . . . * . . . . . 3.672 1 vol. terchloride of trichloracetyl . 8.174 DH. KOLBE ON THE CHEMICAL It is worth mentioning here that the decomposition of oxydichloride of trichloracetyl into two equivalents of sesquichloride of carbon and one equivalent of dinoxychloride of trichloracetyl at a temperature of 300° C. may be even more simply expressed by the following equa- tion than by the mode of viewing adopted at page 384 Oxydichloride of trichloracetyl. Terchlonde of trichloracetyl.trichloracetyl. According to the view expressed in this equation the metamor- phosis of oxydichloride of trichloracetyl into terchloride and dinoxy- chloride would be due to a simple transposition of the negative elements combined with the radical. The remaining modes of formation of the chloride of trichlor- acetyl for instance by the action of chlorine on chloride of ethyl and hydrochlorate of cloride of vinyl (oil of olefiant gas) appear to me to accord likewise with the above assumption; in the first case the terchloride of trichloracetyl is not formed as a direct product of decomposition of chloride of ethyl but as a substitution-product of the terchloride of acetyl into which the chloride of ethyl is first con- verted; in the second case the formation of the terchloride is evi- dently preceded by that of the chloride of trichloracetyl which may again be viewed as a product of decomposition of the hydrochlorate of chloride of trichlorovinyl (C C1,)Cl.HCI lately discovered by Pierre from which it is probably produced in consequence of the separation of the apparently but loosely combined hydrochloric acid by the transposition of the elements from (C,Cl,) Cl into (C,C13)-C2 C1. (Compare the note page 376.) In speaking some time back of the chemical constitution of alde- hyde and chloral,* I advanced the assumption that they might be conjugate combinations of formylous acid respectively with methyl and sesquichloride of carbon C H,. C HO aldehyde. C Cl,. C HO chloral.According to this view by which the close relations of these two compounds is very well expressed and a satisfactory interpretation given of the decomposition of chloral by alkalies into terchloride of * Ann. Chem. Phaim. LIV 184. CONSTITUTION AND NATURE OF ORGANIC RADICALS 391 formyl and formic acid the oxidation in the conversion of aldehyde into acetic and of chloral into chloracetic acid would extend to the common constituent formylous acid which would be transformed into conjugate oxalic acid with formation of water. If however the readiness with which the elimination of hydrogen-equivalents pro- ceeds at least in aldehyde be taken into consideration it must appear strange that the action of chlorine should confine itself solely to the hydrogen of the adjunct and that the formylous acid so readily acted upon by oxygen should remain unaltered.This difficulty is imme- diately overruled by assuming with Liebig the pre-existence of a basic atom of water in chloral as well as in aldehyde and by viewing the former as hydrated oxide of acetyl and the latter as hydrated oxide of trichloracetyl HO. (C H,)^C, 0 aldehyde. HO. (C C13)-C2 0 chloral. The formation of chloracetic acid in the oxidation of chloral by means of fuming nitric acid would then be as in the conversion of aldehyde into acetic acid the result of the direct assumption of two equivalents of oxygen HO .(C C13)-C2 O+Z O=HO. (C C13)"C2 0 c-v-3 L-v-3 Chloral. Chloracetic acid. This hypothesis likewise furnishes a proper explanation of the decomposition of chloral by solution of potassa into formic acid and terchloride of formyl as is shown by the following equation HO.( C CI,)^C,+ KO. HO =KO. H-C, O,-i-HT, Cl Chloral.T Formiate of Terchloride of potassa. formyl. With regard to the interesting metamorphosis which hydrate of chloral undergoes by treatment with sulphuric acid other expressions may be easily given of the composition of chloralide accounting equally well for its formation and chemical comportment as the formula 2C HCl .3 C 0 constructed by Stadeler,* which it is difficult to bring into accordance with the above view of the constitution of chloral It might with equal justice be considered as a combination of two equivalents of oxide of trichloracetyl with one equivalent of hydrate of formic acid =2 [(C C1 .C, O)] +HO .H-C, 0,,or as a double * Ann Ch.Yharm. LXI 104. DR. KOLBE ON THE CHEMICAL compound of chloral and formiate of the oxide of trichloracetyl =NO. (C C13)'T2 0 + (C HJ-C, 0. H-C, 0,. It is left for future researches to decide which of these formulz can claim the advantage or which view of the rational composition of chloralide is the correct one. It has already been stated that we are as yet only acquainted with a few compounds of the intermediate secondary acetyl-radicals pre-ceding trichloracetyl namely chloracetyl (C {%)^C, and dichlo- racetyl (C { CH1,)-Cd. One of the most interesting is the acid of chloracetyl corresponding to that of trichloracetyl namely chlora- cetylic acid HC).(C2{ :i)^C, 0,,which Leblanc* prepared by the action of dry chlorine-gas on concentrated acetic acid in diffused daylight . cf -C2 O,+HCl NO. (C H,)-C, 03+2Cl=HO. (c( ("> L-v--3 L--.-\.---.-J Acetic acid. Chloracetylic acid. We must also include among these bodies the two substitution- products of terchloride of acetyl described by Regnaul t,f and resulting together with chloride of acetyl from the decomposition of the so-called chloride of aldehyde (first substitution-product of chloride of ethyl) namely the terchloride of chloracetyl(C ,{c"12> ^C 3 Cl, (trichlorinated chloride of ethyl) and terchloride of dichloracetyl (Cz{tl)-C2 C1 (tetrachlorinated chloride of ethyl.) The substi- tution-products corresponding to oxydichloride of acetyl namely the oxydichlorides of chloracetyl and dichloracetyl have not yet been obtained.The vapour-densities of terchloride of acetyl (= 4*530),of ter- chloride of chloracetyl (= 5*799) of terchloride of dichloracetyl (= 6*983) and terchloride of trichloracetyl (= 8*157),as deter-mined by Regnault are in perfect accordance with the above assumption if we consider 8 vol. of each of the radicals of these bodies combined with Q vol. of chlorine to form 1 volume accord- ing to the usual mode of condensation. Acetyl (C H3)-C,. Tercbloride of acetyl (C H3)^C, C&. 2 vols. carbon vapour. . 1.658 Q vol. acetyl gas . . . . 0.932 3 , hydrogen . . 0.207 Q , chlorine . . . . 3.604 1 vol. acetyl . . . . 1.865 1 vol.terchloride of acetyl. 4.536 * Ann. Chim. Phgs. [3] LXXI,353. (found . 4.530) + Ibid X. 212. CONSTXTUTION AND NATURE OF ORGANLC RADICALS 393 Chloracetyl (C { Ef}-Ce. Terchloride of chloracetyl (C L c1)-C,0,C13 2 vols. carbon-vapour. . 1.658 Q vol. chloracetyl-gas . . 2.123 2 , hydrogen . . . 0.138 +j-, chlorine . . . . 3.672 1 vol. chlorine . . . 2,449 1 vol. chloracetyl . . . 4.247 1 voI. terchloride of chlor- acetyl . . . . . . 5.795 (found . 5.799) Dichloracetyl(C { tf)-C2 Chloride of dichloracetyl (C { F1)-C2 C 2 vols. carbon-vapour . 1.658 vol. dichloracetyl-gas . . 3.314 1 , hydrogen . . . 0.069 3 , chlorine . . . 3.672 2 , chlorine . . . 4.898 1 vol. dichloracetyl . . 6-628 1vol. chlor. of dichloracetyl 6986 (found .6.983) Trichloracetyl (C C13)-CT Chloride of trichloracetyl (C Cl,)-C, Clg 2 vols. carbon-vapour 1.658 4 vol. trichloracetyl-gas . 4.502 3 , chlorine . . 7.346 + , chlorine . . . + 3.672 1 vol. trichloracetyl . . 9*004 1 vol. chlor. of trichloracetyl 8.174 (found . 8.157) The metamorphoses which chloride of ethyl undergoes consecu-tively by the action of chlorine may be exhibited by the following forrnulze of the resulting products of decomposition Protochloride of ethyl . . . . (C H5) C1 . . &her hydrochlorique bydrochlor. Hydrochlorate of protochloride of acetyl (C H3)-C, C1 HCI { monochlorurk. { ether hydrochlor. Terchloride of acetyl . . . . (C HJ-C, C13 bichlorur6. Terchloride of chloracetyl . . trichlorurk. Terchloride of dichloracetyl .. . (C { t()-C2 C1 { &her hydrochlor. quadrichlorurk. Terchloride of trichloracetyl . perchlorurk. It still remains for us to discuss the chemical constitution of those bodies which are produced by substitution from the combinations of the other radicals homologous with acetyl. With regard to chlorobutyric and chlorovaleric acid as also to nitropropionic acid the assumption of the conjugate radicals (C H5)-C2 (C H,)-C, and (C H,)-C in propionic butyric and valeric acids and the analogy of these substances with acetic acid scarcely admit any other explanation of the above processes of substitution than that the 394 DR. KOLBE ON THE CHEMICAL hydrogen in the adjuncts of these radicals is substituted by chlorine hyponitric acid &c.new secondary radicals being thus produced which still possess the constitution of the primary radicals. Hence the cornposition of nitropropionic chlorobutyric and chlorovaleric acids is expressed by the following rational formulz. HO .(c4( Eb4)-C2 0 Nitropropionic acid. HO ,(C iH ) cc -C2 0 Dichlorobutyric acid. HO . (C cf4 -C2 0 Quadrichlorobutyric acid. {H ) NO.(C cl' -C2 0 Dichlorovaleric acid. {" ) HO C {li5)-C2 0 Quadrichlorovaleric acid. ( c, It is much more difficult to explain satisfactorily the metamorphoses which the formyl-compounds undergo by the action of chlorine. Although I do not dispute the existence of a secondary formyl- radical of the composition Cl-C, but am on the contrary convinced of its existence in chlorinated formiate of oxide of ethyl and of oxide of methyl yet the assumption of its existence in the substitution-products of the simple formyl-compounds for instance in chlorinated chloride of formyl oxydichloride of formyl &c.appears to me exceedingly bold and improbable. Even the behaviour of hydrated formic acid with chlorine by which it is converted not into cbloro- formic (HO .Cl-C, 03),but into hydrochloric and carbonic acids unmistakeably indicates the action of aenities different from those exerted in compounds the radicals of which contain a carbo-hydrogen as adjunct. Terchloride of formyl undergoes an analogous decomposition being split up as is well known into two equivalents of perchloride of carbon by the action of chlorine H-C, C1 +2Cl= 2 C C1 + H C1 + w Terchloride of formyl.Perchloride of carbon. It would at any rate be difficult to deduce from the chemical comportment of perchloride of carbon any argument in favour of that substance being terchloride of chloroformyl (C1-C % C1,) or chloride of trichloromethyl (C Cl, Cl) or of its possessing any other rational formula.-The chlorinated oxydichloride of formyl (the final product of the action of chlorine on oxide of methyl having the empirical formula C C1 0),has been unfortunately too little studied to afford by its comportment any conclusion as to its constitution. It may perhaps CONSTITUTION AND NATURE OF ORGANIC RADICALS. 395 be a simple combination of perchloride of carbon with chloro-carbonic acid having the rational formula C Cl, Cn gl* This pro- duct appears at any rate no longer to possess the constitution of oxide of methyl nor of oxybichloride of formyl; at least the observation made by Regnault that the condensation of the so-called oxide of perchloro-methyl in the gaseous form is only half as great as that of the compound from which it is directly derived appears to indicate that the conversion of oxydichloride of formyl (dichlorinated oxide of methyl) into oxide of perchloromethyl is accompanied by a change in the relative position of the atoms.It is at present impossible to decide whether the final product of the action of chlorine on sulphide of methyl is analogous in compo- sition to the foregoing substance or whether its composition may be S expressed by the rational formula C C1,.C { cl Malapti,* in his admirable researches on the chlorinated ethers was the first to advance and support with powerful arguments the view that the various compound chlorinated ethers examined by him (in which all the hydrogen was substihted by chlorine) contain no perchlorinated ether in the form in which it is known in the isolated state (oxydichloride of trichloracetyl) but that they more probably have the same constitution as the normal ethers of which they are the derivatives. The composition of perchloracetic ether would then be expressed by the rational formula (C Cl,) 0 (C C1JnC2 0,. If it were assumed on the other hand that the oxide of ethyl in acetic ether in its conversion into perchloracetic ether underwent the same metamorphosis as it does in the free state namely that it was converted thereby into oxydichloride of trichloracetyl the perchloracetic ether would then have to be viewed as trichlo-racetate of oxydichloride of trichloracetyl = 0 { Cl,.Irrespective of the argumenis maintained by Malaguti against the existence of perchlorinated ether as it is known in the free state in perchloracetic ether it appears to me in itself but slightly pro- bable that in a metamorphosis so completely altering the molecular arrangement of atoms as for instance in the conversion of carbonate of oxide of ethyl (C H5) 0 CO, into carbonate of oxydichloride of * Ann Chein Phys. [3] XVI 4. 396 DE. KOLBE ON THE CHEMICAL trichloracetyl (C C13)-C2.{El CO, the two members-carbonic 2' acid and oxydichloride of trichloracetyl should remain combined. The objection may be raised here that it is still enigmatical why the action of chlorine on oxide of ethyl combined with acids produces no change in the molecular arrangement of the atoms while free oxide of ethyl under similar circumstances immediately passes into an acetyl-compound; this may be answered by re-ferring to the many cases in which a compound owes its existence olely to its combination with another body or even to the mere presence of such a substance. Carbamic acid cyanic acid and many others are well known to exist only in combination with bases; they split up on the moment of their liberation into simpler groups of atoms.We know likewise that the addition of a few drops of solution of potassa to the neutral aqueous solution of a large quantity of sulphovinate of potassa is sufficient to prevent perfectly the easy decomposition of that substance by boiling. If moreover the view be adopted without hesitation that in hyposulphobenzolic and napthalic acids the hyposulphuric acid assumed as existing therein acquires a stability perfectly foreign to it when in the free state by the assimilation of the adjunct it is certainly not less justifiable to assume that the elements of oxide of ethyl in compound ethers are held together with a greater force by their combination with acids than is the case with free oxide of ethyl so that the original grouping of atoms remains the same even if chlorine be replaced for all the hydrogen-equivalents of a compound ether.The property possessed by so many binary compounds of gaining increased stability by their combination with a third body may be compared to the action of a powerful magnet on two weaker ones which alone have not power sufficient to support each other but to which this power is imparted on the approach of a more powerful magnet. It must not however be considered strange that we have not as yet succeeded and perhaps never shall be successful in converting the chlorinated compound ethers into the normal ethers by a process similar to that by which chloracetic acid is reconverted into acetic acid and chloraniline into aniline. The attachment of their con-stituents the chlorinated acid and the chlorinated oxide of ethyl appears weakened to such a degree by the entrance of chlorine in the place of hydrogen that a comparatively slight impulse such as is imparted by the action of heat alkalis alcohol &c.is required to effect an essential change in the molecular arrangement of their atoms. All the endeavours to reproduce the original compounds CONSTTTUTION AND NATURE OF ORGANIC RADICALS. 397 from the chlorinated ethers have met with no result and it is probable that the slight stability of the latter compounds will always present an insurmountable obstacle to the success of such experiments. The highly interesting and numerous metamorphoses of chlorinated compound ethers for the knowledge of which we are principally indebted to Malaguti and Cahours furnish undoubtedly the most appropriate means of deciding the question of the rational composition of the latter substances.We will therefore examine the explanation furnished of these phenomena by the above mode of viewing. The metamorphoses of the various chlorinated ethers containing chlorinated oxide of ethyl by potassa ammonia alcohol methyl- alcohol &c. exhibit a remarkable analogy in the circumstance that the resulting products of decomposition are the same as would be furnished by a combination or a mixture of the particular (chlori- nated) acid with dinoxychloride of trichloracetyl (chloraldehyde). It may hence be assumed with tolerable certainty that the contact of these substances with the above agents always effects in the first instance their separatisn into the two groups of atoms composing them namely into chlorinated oxide of ethyl and the chlorinateh acid.It appears however that a chlorinated oxide of ethyl cannot exist as such but exhibits a tendency to pass over into the metameric compound oxydichloride of trichloracetyl (C Cl)-C 2 {O while the c1 acids separated from chlorinated oxide of ethyl (with the exception of carbonic acid) cannot exist in the anhydrous state. It is therefore probable that at the moment of separation an exchange is effected of one equivalent of oxygen for one of chlorine in the chlori- nated oxide of ethyl while it undergoes the above metamorphosis; whereby there is formed on the one hand an oxychloride correspond- ing to the hypothetically anhydrous acid or a direct product of decomposition produced by a transposition of the atoms and on the other hand dinoxychloride of trichloracetyl.This metamorphosis may be best understood by means of the following general equation in which Ac represents the acid-radical Indeed the term (C cl,) C { (312 (the so-called chloraldehyde) is found to be a constant product of decomposition by heat of all com- 398 DR. KOLBE ON THE CHEiMICAL pound ethers containing chlorinated oxide of ethyl accompanied by a compound corresponding in composition to the formula Ac '2 {Cl Or at least by a direct product of decomposition of the latter. The chlori- nated ethers of oxide of methyl undergo a perfectly analogous meta- morphosis with the only difference that in this case chlorocarbonic acid is formed instead of (C ClJ-C, {gf (C Cl,) 0.Ac 0,=2 C{ 0 Cl+Ac{ gf The above rationale holds good likewise with respect to the con-version of perchloracetic ether into two equivalents of the dinoxy- chloride of trichloracetyl (chloraldehyde) having the same composition as the former by the passage of its vapours through a red-hot tube L 7-) =(C2 C13)^C {02 Perchloracetic ether. 2' c1 Chloraldeh yde. the decomposition of chlorinated formiate of oxide of ethyl into chloraldehyde and chloracarbonic acid L-v-' Perchloroformic ether. Lyp---J Chloraldehyde. that of perchloroxalic ether into chloraldehyde chlorocarbonic acid and carbonic oxide (the two latter being doubtless products of decomposi- tion of C {3(still unknown) L-77-2 Perchloroxalic ether.v Chloi aldehyde. as also with the decomposition of the perchlorinated acetate of oxide of methyl isomeric with perchloroforrnic ether into chlorocarbonic acid and chloraldehyde CONSTITUTION AND NATURE OF ORGANIC RADICALS. 399 2 v L v Chlorinated acetate of oxide of methyl. C hloraldehyde. of chlorinated formiate of oxide of methyl into four equivalents of the isomeric compound chlorocarbonic acid L-v-3 u Chlorinated formiate of Chlorocarbonic oxide of methyl. acid. and of the chlorinated oxalate of oxide of methyl into chlorocarbonic acid and carbonic oxide Chlorinated oxalate of oxide of methyl.The metamorphosis of perchlorocarbonic ether by exposure to heat into chloraldehyde sesquichloride of carbon and carbonic acid = (cs c1,) 0 .C02 = (c c13)ncp{ L-v-d Chlorocarbonic ether. h-v-J Cblorafdehyde. exhibits a slight deviation from the above which is evidently based partly upon the property of carbonic acid of existing in the anhy- drous state and partly upon its volatility. The latter is probably the principal cause why the carbonic acid at the moment that it should exchange an equivalent of oxygen for an equivalent of chlorine with the intermediate product oxydichloride of trichloracetyl (C,Cl3)T2,ig12(which is undergoing transposition) evades this metamorphosis SO that the latter substance alone undergoes a further change; and thus we obtain instead of chloraldehyde and chlo- rocarbonic acid carbonic acid and the products of decomposition of oxydichloride of tricbloracetyl namely chloraldehyde and sesqui- chloride of carbon.400 DR. KOLBE ON THE CHEMICAL We find in accordance with the above assumptions that perchlora- cetic ether (C GI,) 0 . (C C1,JnC, 0 = 2 (C2 Cl,)"C, {4) behaves with potassa ammonia and alcohol exactly like dinoxychloride of trichloracetyl (chloraldehyde) ;potassa forming with it trichlorace-tate of potassa and chloride of potassium ;ammonia dinoxamide of trichloracetyl (chloracetamide) and chloride of ammonium ;alcohoI trichloracetate of oxide of ethyl and hydrochloric acid.-In like manner chlorinated formiate of oxide of ethyl and the metameric acetate of oxide of methyl behave with these reagents like a mixture of chlorocarbonic acid and chloraldehyde (compare their metamorphoses at a high temperature p.399). Solution of potassa converts them nto trichloracetate and carbonate of potassa and chloride of potas-sium ; ammonia into chloracetamide and chloride of ammonium (and doubtless into carbamide or its products of decomposition) ; alcohol into trichloracetate and oxychlorocarbonate of oxide of ethyl and hydrochloric acid ; methyl-alcohol into the corresponding methyl- ethers.-Chlorinated carbonate of oxide of ethyl which is converted by potassa into chloride of potassium carbonate and formiate of potassa (the latter being evidently a product of decomposition of the previously formed trichloracetate of potassa) ;by ammonia into chlo- ride of ammonium chloracetamide (and probably carbamide and car- bamate of ammonia) and which furnishes with alcohol trichloracetate and carbonate of oxide of ethyl besides hydrochloric acid resembles in these metamorphoses an instable compound of chloraldehyde and 0 0 chlorocarbonic acid (C Cl,) 0 .GO = (C ClJ-C, { cF + C { ci or a compound of oxydichloride of trichloracetyl with carbonic acid (C Cl,) 0 CO = (C ClJT, {gl .CO, if we may assume that 2 oxydichloride of trichloracetyl at the moment of its formation can pass over with the elements of water into trichloracetylic and hydro- chloric acids analogously to the dinoxychloride of trichloracety1.-The chlorinated oxalate of oxide of ethyl which yields with potassa trichloracetate and oxalate of potassa and chloride of potassium ; with ammonia chloracetamide chloride of amrnoniurn and pro-bably oxamide ; with alcohol trichloracetate and oxalate of oxide of ethyl together with hydrochloric acid and chloride of ethyl comports itself like a compound of chloraldehyde with a hypothetical oxalo-dinoxychloride corresponding to oxa-{2, mide C, which may be presumed to be decomposed by ammonia into chloride of ammonium and oxamide.In the decompo- CONSTITUTION AND NATURE OF ORGANIC! RADICSLS. 401 sitiou of chlorinated oxalate of oxide of ethyl by alcohol Malaguti obscrvcd besides the formation of oxalic ether and chloracetic ether the production of the body C Cl 0 (Cbloroxethide M) correspond-ing in composition to the formula (C Cl,) 0.2 C 0 (?). In the same manner the decomposition of chlorinated oxalate of methyl by potassa into chloride of potassium oxalate and carbonate of potassa,-by alcohol into hydrochloric acid oxalate and chlorocar- bonate of oxide of ethyl,-and by ammonia into chloride of ammonia and carbamide (and doubtless oxamide) corresponds perfectly with the comportment of a compound of chlorocarbonic acid with the above-mentioned hypothetical oxalo-dinoxychloricle. It might be expected from the analogy of chlorinated formiatc of oxide of ethyl with the other compound chlorinated ethers that it would comport itself with the above reagents like chlorocarbonic acid into which it is converted by the action of a high temperature 0 (C Cl,) 0.ClnC2 0 = 4C { cl* The formation of oxychlocarbonate' of oxide of ethyl and hydrochloric acid by treatment of the chlorinated ether with alcohol is likewise in accordance with this supposition; instead however of yielding chloride of ammonium and carbamide by treatment with ammonia it is stated by Cahours to yield dinox- amide of trichloracetyl (chloracetamide) . Although the percentage-composition obtained by Cahours for the latter compound agrees exactly with that of chloracetamide I cannot refrain from doubting the above statement and presuming that it must be based upon some error. Additional weight is given to this supposition by the fact that in endeavouring to construct the formula of chloracetarnide from that of the Chlorinated formiate of oxide of methyl there remain two atoms of oxygen of the use of which no account can be rendered as will be seen from the following equation (C Cl,) 0.Cl-C, 0,+2 NH = (C CI3)-C2,{ $-Ha+N H,Cl+20 3 L-v-/ I-v-Chlorinated formiate of Chloracetamide.oxide of methyl. It is very desirable that Cahours should repeat this experiment and remove the doubts on the subject. 1 shall refrain from making any observations on chlorosuccinic ether and its complicated decompositions described by 31alagu ti as it is my belief that the metamorphoses which free succinic acid under- goes by the action of chlorine must be first examined and determined VOL.111.-NO XII. Dn DR. KOLBE ON THE CHEMfCAL before we can furnish any account of the rational composition of chlorosuccinic ether or of its products of decomposition. The perfect similarity exhibited by chlorinated acetate of oxide of methyl and chlorinated formate of oxide of ethyl as far as our present knowledge of them extends has induced most chemists to consider them as identical. While the most different views exist respecting the manner in which the elements are grouped in these two compounds their supposed identity has been employed as an argument against the assertion that compound clorinated ethers still possess the constitution of the normal ethers. I myself am far from concluding that because the chlorinated ethers which have hitherto been more carefully examined exhibit an analogy with those from which they have been produced,-the molecular arrangement of the atoms arid of the proximate constituents must likewise remain unaltered in the action of chlorine on all other compound ethers; on the contrary I consider it more than probable that ethers of complex composition such as chlorinated amylic-ether valerianic or even niargaric ethers cease to possess the constitution of the original ethers long before the whole of the hydrogen is replaced by chlorine.Perhaps even the chlorinated succinic ether belongs to this class as its complex composition and metamorphoses lead to the assumption that the exchange of its hydrogen for chlorine is followed by a far more intricate decomposition.The identity of chlorinated formiate of oxide of ethyl and chlorinated acetate of oxide of methyl even if it were established could therefore not serve absolutely to determine our views concerning the nature of other chlorinated ethers. But I am not of opinion that the two latter compounds have the same chemical constitution and are really identical because they are alike in their comportment. If we view these two others as composed according to the rational formuh (C CI,) 0 .Cl-C ,-O3 chlorinated formiate of oxide of ethyl (C C13) 0 (c C1,) C ,O3 chlorinated acetate of oxide of methyl and consider at the same time that their proximate constituents- (C Cl,) OandClnC2,0 on the one hand (C2CI3) 0,and(C2 Cl,)"C,O on the other-are held together with but feeble affinity-if we bear in mind moreover that as no one of these adjuncts exists in the uncom- bined state at the moment that their chemical equilibrium is disturbed by the influence of any agent their further decomposition must be preceded by a transposition of their atoms after the following manner -\-,,-A L-v-J Chlorinated formiate of oxide Chloraldehyde.Chlorocarbonic of ethyl. acid. CONSTITUTION AND NATURE OF ORGANIC RADICALS. 403 L-v--d I-v-d -Chlorinated acetate of oxide of methyl. Chloraldehyde. Chlorocarbonic acid. (these metamorphoses being produced in reality by the action of a high temperature) ;-if all these circumstances be duly considered it will be easily understood why these two bodies exhibit a similar comportment or at any rate yield the same products of decomposition with such agents as are capable of effecting this disturbance in the chemical equilibrium of their constituents Their correspondence besides in specific gravity boiling-point &c.must least of all excite surprise as even the two normal ethers from which they are produced exhibit a perfect similarity in these respects. Acetate of oxide of methyl and formiate of oxide of ethyl are well known to differ only in their behaviour when boiled with alkalis; they evidently owe this mark of distinction to the greater stability of their consti- tuents without which they would probably be likewise considered as identical. I feel convinced that by a careful investigation and com- parison of these two chlorinated ethers for instance with regard to their refractive power or to their behaviour with such bodies as do not effect their decomposition their relative solubilities in ether benzol and so on some slight varieties will be discovered between them which will lead to a proof of their dissimilarity by experimental means.If the compound ethers which have been the subject of our con- sideration in which all the hydrogen is replaced by chlorine still possess the constitution of the original substances it follows neces- sarily that the molecular arrangement of the atoms in the intermediate products must likewise be the same. The dichlorinated acetic ether which is decomposed by water and potassa into acetic and hydro- chloric acids corresponds therefore in composition to the formula (C { 3)0.(C2 H,)^C, 0,. Its conversion into these products is probably preceded as with perchloracetic ether by a separa-H tion of the two members and as (C fCf) 0 cannot exist in the 2 free state by a transposition of these atoms to (C H3)-C2 { c12 (oxydichloride of acetyl). The trichlorinated acetate of oxide of ethyl produced by a continuation of the process of substitution is either H acetate of oxide of trichlorethyl (C,( cf) 0. (C H3)-C2 0, or 2 DD2 404 DR KOLBE ON THE ORGANIC RADICALS. monochloracetate of oxide of dichlorethyl The deliquescent potassa-salt-containing chlorine obtained therefrom according to Leblanc by treatment with solution of potassa is probably monochloracetate of potassa mixed with acetate of potassa ; and the oily body simultaneously deposited is possibly a secondary product of decomposition produced from monochloracetic acid in a manner similar to the formation of trichloride of formyl from trichloracetic acid.By the distillation of trichloracetic acid with alcohol containing sulphuric acid as also by the treatment of dinoxychloride of trichlor- acetyl with alcohol an ether isomeric with the above compound is produced namely trichloracetate of oxide of ethyl differing greatly in its behaviour from the former and particularly in the circumstance that it yields alcohol again by treatment with boiling potassa. A comparison of their rational formulae will suffice to account for their isomerism (C {*3) 0.(C ,{,H,2)^C, 0 trichlorinated acetic ether.a CI (C H5) 0. (C ClJ-C, 0 trichloracetic ether Among the intermediate substitution-products of compound ethers in which only a portion of the hydrogen is replaced by chlorine and which have generally speaking been less carefully studied the dichlo- rinated acetate of oxide of methyl and the dichlorinated formiate of oxide of ethyl are particularly distinguished not merely by being iso- meric like the final products above-mentioned but also by correspond- ing in their cheniical comportment without however being identical. If they be coiisidered as composed according to the rational formulz (C,{ $2 0 .(C H,)-C, 0 dichlorinated acetate of oxide of methyl 0 .H-C, 0 dichlorinated formiate of oxide of ethyl (c4{2) the decomposition of both by potassa into acetic formic and hydrochlo- ric acids admits of a ready explanation. In the first compound the decomposition is probably preceded by the transposition of H (C,{ c,J 0 into H-C, { 0 (oxydichloride of formyl) and in the c], second case by the metamorphosis of (C c1, ''3{ { ) 0into (C H,)^C, 0 c1, (oxydichloride of acetyl) . The formic acid is therefore prodcced in the first case from the basic member and in the second case from the acid member of the dichlorinated ethers j on the other hand the MR. BRODlE ON THE ALCOHOL RADICALS. acetic acid produced in this reaction from the dichlorinated formiate of oxide of ethyl must be considered as a product of decomposition of the member (C4{ H cl”,’ 0 while it is pre-existing as such in the dichlorinated acetate of oxide of methyl.(To be concluded ila the next Jozsmal.)

ISSN:1743-6893    

DOI:10.1039/QJ8510300369

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年代:1851

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MR. BRODIE ON THE ALCOHOL RADICALS. Dec. 16 1850. WILLIAMALLANMILLER,M.D. V.P. in the Chair. Henry Medlock Esq. and James Simpson Esq. were elected Fellows of the Society. The following Presents were announced Journal of the Franklin Institute,” Vol. XX. No. 4 October 1850; from the Society. ‘c Proceedings of the Philosophical Society of Glasgow,” Vol. 111 No. 4; from the Society. ‘‘ Recueil des Actes des Serinces Publiques de l’Acad6mie Imperiale des Sciences de St. P&ersbourg tenues le28 De’cembre 1847 et le 19 Dkcembre 1848.” XXXII1.-Observutions on the Constitution of the Alcohol-Radicals and on the formation of Ethyl. BY B. C. BRODIE,F.R.S. (SECRETARY OF THE CHEMICAL SOCIETY.) On the occasion of the remarks of Dr. Hofinann on Dr.Frank-land’s second paper on the Organic Radicals I made to the Society some observations on the theoretical constitution of those bodies. New facts have since been brought to light which strongly confirm the view which I then gave; and as the concluding remarks of Dr. Frankland’s last paper have again brought this question before the Society I take the opportunity of here making a memorandum of them. Dr. Frankland pointed out various and in my opinion indis- putable analogies between these hydrocarbons and hydrogen ; and representing hydrochloric acid by the symbol HCl the chloride of ethyl as C H C1 and the isolated element hydrogen as H he con- 406 MR. BRODIP sistently gave the formula C H as that of the isolated ethyl. This formula however involved the singular anomaly that the atom of the gaseous ethyl occupied only half the space of the atom of all other hydrocarbons.Gerhardt with whose chemical ideas this anomaly was incon- sistent gave a theory of these bodies which doubled their formula.* On his view methyl was a homologue of marsh-gas. The consti- tution of the two substances being thus expressed Marsh-gas . C H,= C H,+ H or C H,= CH,+H Methyl . . . C H,=2C H,+H or C H,=ZCH,+H This view however not only doubled the formula of these bodies but entirely set aside all their importance as radicals from the point of view of Frankland. Gerhardt considered himself further as justified in this by the absence of any remarkable chemical properties by which these bodies were to be distinguished from other hydro- carbons.Hofmann in an elaborate and indeed most convincing argu- ment confirmed the necessity of doubling these formulze; but at the same time he considered that the modeof the formation of the bodies appeared to be certainly in favour of the lower formula.? “Hy-driodic acid and zinc,” says he ‘‘yield iodide of zinc and hydrogen ; in the same manner it would appear the iodide of an alcohol radical gives rise to the formation of iodide of zinc and the alcohol-radical.” The perfect analogy of these reactions I admit; but I deny the inference as to the formula. If we represent the formation of the hydrogen Zn+IH=ZnI+H we must it is true in consistency represent the formation of the radical ethyl in a similar manner Zn + IC H =ZnI -!-C H ;but the formation of the hydrogen may also be represented thus in which case the analogous formation of the ethyl is given by the expression That this or some other similar expression which equally involves * Corupt.Rend. Trav. Chim. 1849 19 and 1850 12. -/-Chem. SOC Qu.3. 111 128. ON THE BLCOHOL R-IDICALS. the hypothesis that the formation of the isolated element is a chemical synthesis of the particles of the combined element is the only rational expression of this reaction is not an arbitrary assumption to meet the present case but proved by a great variety of phenomena. I have elsewhere* fully discussed that general law of chemical action of which this is I believe but a particular example and I shall confine my remarks now to the present instance.When zinc acts on the iodide of ethyl in the presence of water the reaction according to Frankland is thus expressed (I Cj~j~lo) =ZnI ZnO +C H5 TI this may be taken as the type of the other changes; for substituting in the change iodide of ethyl for water we have the formation of ethyl or substituting water for the iodide of ethyl we have the formation of the hydrogen thus (gfzH,o)=2 ZnO+H a reaction which truly takes place at high temperatures. The view which I have given shows the relation between these phe- nomena and that they are all expressions of one and the same law of chemical action whereas otherwise at least two hypotheses and two different forms of chemical change are required to explain them.It is to me truly remarkable that Frankland who maintains so strongly the analogy between the iodide of ethyl and water and the ethyl and hydrogen yet denies the possibility of the substitution of these bodies for each other in this series of chemical changes. There is a remarkable case of the formation of hydrogen to which I have referred in the paper before alludedto,t which I believe can only be accounted for on the view I have given. This is the decom- position of the hydruret of copper Cu H by hydrochloric acid. The substance itself and the reaction were discovered by Wurtz. Hy-drochloric acid which does not act upon copper decomposes this body thus Cu H +HCl= Cu C1+ H,. This I regard as (what is called) a siniple case of double decoiiipo- * Phil.Trans. 185O,II 789. t Phil. Trans. 1850 11 79%. 408 MR. BRODIE sition. The formation of the hydrogen being the correlative fact to the formation of protochloride of copper. The oxidation of alcohols by hydrate of potash is likewise a case in point. The hydrogen in this experiment comes partly from the alcohol and partly from the hydrate of the alkali thus Alcohol. Acetic acid. I regard the formation of the hydrogen as a chemical synthesis as truly as that of the acetic acid. The decomposition of water by the zinc-methyl is perfectly analogous to the formation of hydrogen by the decomposition of the hydruret of copper. Thus Zn C H,+ HO=ZnO+C H H and in the oxidation of acetic acid by the hydrate of potash and the formation of marsh-gas or the hydride of methyl the inethyl conibincs with the hydrogen of the hydrate of potash in the same way as the hydrogen of the alcohol in the other experiment thus Acetic acid.Hydride of Carbonic acid. methvl. we can therefore with one of these bodies effect the same kind of chemical changes as with the other. These considerations induced me to try the experiment whether the zinc-ethyl would not decompose the iodide of ethyl with the formation of iodide of zinc and ethyl Zinc-ethyl. Ethyl. as the copper-hydrogen decomposes the hydrochloric acid with the formation of protochloride of copper and hydrogen. This experi- ment was wanting to complete the series of analogies for although Frankland* had shown the presence of zinc-ethyl or some body containing this compound among the products of the reaction of zinc upon the iodide of ethyl yet he Bad not shown that it took any part in the change; and indeed as it was a constant product of the decomposition as also was olefiant gas and hydride of ethyl when once formed,it might never be decomposed.With this view I prepared il tube according to the directions of Fpnkland containing * Chern. Stc. Qn. J. TI 298. ON THE ALCOHOL RADICALS. iodide of ethyl with a great excess of zinc and exposed it for some hours to a temperature of 140° to 150° C, at which temperature I had ascertained that a considerable proportion of zinc-ethyl was formed. I broke the end of the tube allowed the gas formed to escape and then introduced a fresh portion of iodide of ethyl and re-sealed the capillary opening.The zinc was still in excess. The tube was now exposed for some hours to a temperature of 100° C in a water-bath. On re-opening the tube a certain quantity although small of gas was evolved showing that action had evidently taken place. This might be the result of the action of the zinc-ethyl on the iodide of ethyl but it vds also possible that even at ZOOo the excess of zinc had acted on the iodide for the residue still contained a large portion of zinc-ethyl effervescing strongly with water; I now repeated this experiment with the difference only that I at once placed the tube in the water bath. After several hours' action the iodide of ethyl had disappeared the zinc was covered with a crystal- line crust and on opening the tube under water a small quantity of gas was given 05and the residue contained a large quantity of zinc-ethyl.Hence it is plain that even at looozinc acts upon the iodide of ethyl. The question now was whether the zinc-ethyl thus formed could be decomposed by the iodide at a higher temperature. My first experiments were quite unsuccessful I took a small quantity of zinc and a very large quantity of the iodide of ethyl and exposed the sealed tube for several hours to a temperature of looo. It was then transferred unopened to an oil bath and kept for several hours at a temperature of about 160° C. At the end of this time a much larger quantity of gas was given off than at 100'; but the residue still effervesced strongly with water nor could I at all succeed even when very small portions of zinc were used in entirely getting rid of the zinc-ethyl.The substance however which had been exposed to the higher temperature had undergone a great alteration in appearance the tube being full of white crystals. The zinc-ethyl also from the quantity of gas evolved had been undoubtedly acted upon although partially. It occurred to me that the reason of the cessation of the action was that the zinc-ethyl or other substance formed in the experiment was not sufliciently soluble in the surrounding fluid and that the action would be different in a different medium. Frankland* had already found that the zinc-ethyl was soluble in ether; ether therefore ap- peared to be a suitable solvent.I therefore repeated these experiments still with a great excess of the iodide of ethyl but with the addition of * Chem SOC.Qu. J. 111,293. 410 MR. BRODIE about twice its bulk of pure ether. The experiment succeeded per-fectly. At loooC, the zinc disappears with the formation of only a trace of gas and a large quantity of the zinc-ethyl. A small quan- tity of solid matter remains in the tube but no zinc. A tube which had thus been exposed for several hours to 100Qwas now heated to 170°in an oil-bath. A large quantity of white crystals were deposited and on opening the tube under water a considerable quantity of gas was evolved and the residue contained not a trace of zinc-ethyl neither the fluid nor the solid matter effervescing with water.On ether alone at this temperature zinc has not the slightest action. In the experiments of Frankland there are two ways in which zinc decomposes the iodide of ethyl the one in which the two particles of ethyl combine and ethyl is formed the other in which one of these particles decomposes the other with the formation of hydride of ethyl C H H and olefiant gas or the hydride of acetyle C4 H3 H. This latter decomposition we may conceive to take place by the division of the hydrogen within the body thus (I '4 '30HZn Zn HnC H5 I ) =C H,-H +C H,"H 4-2IZn. Frankland had indeed already ascertained the presence of ethyl in the gas produced by the action of zinc upon the iodide of ethyl and ether at a high temperature; but yet it seemed to me of importance to prove that the decomposition had not taken place entirely in this latter manner.For it was possible that the reaction of the zinc-ethyl on the iodide of ethyl might differ from that of the zinc and that the constant formation of the hydride of ethyl and olefiant gas might be owing to this very reaction. I therefore dried the gas and treated it with anhydrous sulphuric acid and manganese after the method of Frankland and conducted the experi- ment with the precautions which he recommends. After the necessary corrections for temperature and pressure an experiment of this nature gave the following results Total bulk of the gas 39.78;gas after the absorptioa by SO, 33.54; gas after the absorption by alcohol 4-53 This givesas the constitution of the gas allowing the gas unabsorbed by sulphuric acid to be a mixture of ethyl and the hydride of ethyl Elayl .6.24 Ethyl and hydride of ethyl . 29.01 Nitrogen . 4-53 -39-78 ON THE ALCOHOL RADICALS. 411 It was plain therefore that only a very small portion of the iodide of ethyl had been decomposed in this other manner. In Frankland's experiment (without ether) the ratio of the gas absorbed by alcohol to the elayl was as 100:28.6; in this experiment it is as 100:21.5. Circumstances have as yet prevented me from com-pleting the analysis of this gas ;but this experiment together with those of Frankland I consider conclusive as to the nature of the reaction.The next step in these experiments should be the decomposition of the iodide of methyl or of amyl by the zinc-ethyl in which case the formation of a compound hydrocarbon might be anticipated of the formula C H,. C H, or C H,. C H, ethyl-methyl and ethyl- amyl.* Ethyl stands to hydride of ethyl in the same rela-tion as ether to alcohol and would be to these hydrocarbons as ordinary ether to the compound ethers discovered by Williamson.? The parallel series being complete thus H H Hydrogen . H 10,water C H H Hydride of ethyl . C z5 }02Alcohol. C H C,H Ethyl C H C,H '4 '5 CIOH, Ethyl-methyl (unknown) Ethyl-amY1 (unknown) * -Ethylate of Amylate of c4 H5 } 0 methyl,c H3z0g:l} 02 ethyl. * D r. Hofmann has communicated to me that he has actually tried this experiment with the iodide of amyl but without success.The same causes however which prevent the reaction with iodide of ethyl would here doubtless operate with yet greater force the iodide of amyl being decomposed by zinc only with very great difficulty. It is probable that if the iodide of amyl were mixed with ether the decomposition would be greatly facilitated. I can hardly doubt that at any rate the methyl-compound would be readily obtained. .t. Phil. Mag. XXXVII 350.

ISSN:1743-6893    

DOI:10.1039/QJ8510300405

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年代:1851

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摘要:

CATALOGUE OF BOOKS PRESENTED BY J. J. GRIFFIN ESQ. J 0URN AS S. ANNALESde Chimie et de Physique tomes 70 71 72. Paris 1839. BERZELIUS’S Jahresbericht uber die Fortschritte der physischen Wissenschaften Band 1 to 10. Tiibinqen,1821-31. 1 Jahrgang read 1821 6 Jahrgang read 1826 2 ? , 1822 7 9 , 1827 3 9 , 1823 8 ,? , 1828 4 ?? ,? 1824 9 ? , 1829 It 5 17 , 1825 10 , 1830 POGGENDORFF (J. C.) Annalen der Physik und Cheniie Band 37 38 39. Leipig 1836. -Erganzung Band 1 Stuck 1. Ib. 1842. SCHWEIGGER (Dr. J. C. S.) Journal fur Chemie und Physik. Band 1 2 3 Niimberg 1811. 9 4 5 6 , 1812. J? 7 8 9 ?t 1813* WORKS ON GENERAL CHEXISTRY. BEAUME’SManual of Chemistry translated by Dr. John Aikin 8vo. Warrington,1778. BERKENHART’Y (Dr.John) First Lines of Philosophical Chemistry 8vo. London 1788. GLAUBER’S(John Rudolph) Works. Three Parts folio. 16. 1689. CATALOQUE OF BOOKS PRESENTED BY J. J. GRIFFIN ESQ. 413 GREEN’S Text-book of Chemical Philosophy 8vo. (Dr. Jacob). PhiZude@hica,1829. HENRY’S (Dr. Wm.) Elements of Experimental Chemistry 6th Edition 2 vols. 8vo. London 1810. HEPSON’S(Dr. C. R,) General System of Chemistry chiefly from the German of Wieglieb 4to. Ib. 1789. LEMERY’S(Dr. Nicholas) Course of Chemistry translated from the 11th French Edition. Ib. 1720. LEWIS’S(Dr. Wm.) Philosophical Commerce of Arts 4to. 16. 1765. -Elaboratory Laid Open 8vo. 16. 1758. -Course of Practical Chemistry 8vo. Ib. 1746. MACQUER’S(M.) Elements of Chemistry translated by Andrew Reid 4th Edition 2 vols.8vo. I6. 1787. REID’S (Dr. D. B.) Text-book for Students of Chemistry 8vo. Edinburgh 1835. Elements of Practical Chemistry 2nd Edition 8vo. 16. 1831. SHAW’S(Dr. Peter) New Method of Chemistry Vol. 11. containing the processes or operations of the art 4to. London 1741. THOMSON’S (Dr. Thomas) System of Chemistry 4 vols. 8vo. Edinburgh 1802. --6th Edition 4 vols. 8170. London 1820. WORLER’S (Dr. F.) Grundriss der Chemie. Unorganische Theil 2te Auflage 8vo. Berlin 1933. WORKS ON SPECIAL SUBJECTS IN CHEMISTRY. BERGMANN’S (Sir T.) Physical and Chemical Essays translated by Dr. Edmund Cullen 2 vols. 8vo. London 1788. Essays Physical and Chemical 8v0. I&.179 1. (T.) Dissertation on Elective Attractions translated by Dr.Beddoes 8vo. Ib. 1785. BERTHOLLET’S (C.L.) Researches into the Laws of Chemical Affinity translated by Dr. M. Farrell 8vo. 16. 1804. BLACK’S(Dr. Joseph) Experiments upon Magnesia Alba Quick-lime and other alka- line substances. To which is annexed an Essay on the cold produced by evapo- rating fluids by Dr. William Cullen 12mo. Edinburgh 1782. --Another Copy said on the title-page to be extracted from Essays and Observations Physical and Literary read before a Society in Edinburgh Anno 1755 12mo. Ib. 1796. BOYLE’S (Hon. Robert) Experiments on Colours 8vo. London 1670. BROWNRIGG’S (Dr. Wm.) Art of making Common Salt 810. 16. 1748. CHENEVIX’S (Richard) Remarks upon Chemical Nomenclature 8170. Ib. 1802. CRAWFORD’S (Dr. A,) Experiments and Observations on Animal Heat and the Inflam- mation of Combustible Bodies 2nd Edition 8vo.16.1788. DAGUERRE, Des ProckdBs de DaguerrCotype et du Diorama 8vo. Paris 1839. DALTON’S (Dr. John) New System of Chemical Philosophy Part I 8vo. Munchester. 1808. 414 CATALOGUE OF BOOKS DAUBENY’S (Dr. Charles) Introauction to the Atomic Theory 8vo. Oxford,1831. DUNDONALD (Earl of) 011the Intimate Connection that exists between Agriculture and Chemistry 4to. London 1795 FRENCH’S (Dr. John) Art of Distillation Calcination and Sublimation ;as also the London Distiller 4to. Tb. 1664. FULHAME’S (Mrs.) Essay on Combustion with a View to a New Art of Dyeing and Painting 8vo. I&.1794. GARAYE(Grafen von) Chymia Hydraulica oder Neu Entdeckte Handgriffe Saltz aus- zuziehen 12mo.Frankfurt 1749. HOLLUNDER’S (Chr. F.) Beitrage zur Farbe-Chemie und Chemischen Farben-Kunde 8vo Leipzig 1827. HUME’S(G. L.) Essay on Chemical Attractions 8vo. Cambridge 1835. KOPP (Herrnann) Ueber die Modification der Mittlern Eigenschaft 8vo. Frankfurt 1841. LESLIE(Sir John) On the Relation of Air to Heat and Moisture 8vo. Zdinburgh. SCHEELE’S (C. W.) Chemical Observations and Experiments on Air and Fire translated by Dr. J. Forster with Additions by Kirwan and Priestley 8vo. London 1780. STAHLII(Georgii Ernesti) Experimenta Observationes Animadvertiones CCC Numero Chymicz et Physic% 8vo. Berolini 1731. WILLIAMS(MI. C.) On the Combustion of Coal and the Prevention of Smoke 8vo. Liverpool 1840.WORKS ON PHARMACY AND MEDICAL CHEMISTRY. GMELIN (Jo. Fr.) Apparatus Medicaminum. Part 11,Regnum Minerale 8vo. GottingQ 1796. LEWIS’S (Dr. Wm.) Experimental History of the Materia Mediea 4th Edition edited by Dr. John Aikin 2 vols. 8vo. London 1791. MAUGHAM’S (Wm.) London Manual of Medical Chemistry 18mo. Ib. 1831. MITSCHERLICH’S (Dr. C. G.) Lehrbuch der Arzneimittellehre 8vo. Berlin,1837. PARIS’S(Dr. J. A.) Elements of Medical Chemistry 8170. London 1825. PHARMACOPCEIA of the United States of America. By authority of the National Medical Convention held at Washington A.D. 1830. 8vo. PhiEade@hia 1831. TROMMSDORFF’S (John B,) Handbuch der Pharmaceutischen Waarenkunde 8VO. Erfurt 1806. ALC EE MY. DIGBY(Sir Kinelm) Of Bodies and of Man’s Soul ; Of the Powder of Sympathy and of the Vegetation of Plants 4to.London 1669. -On the Cure of Wounds by the Powder of Sympathy 3rd Edition 18mo. Ib. 1660. HELVETIUS(Dr. J. F.) The Golden Calf which the World Adores and Desires 18mo. Ib. 1670. PRESENTED BY J. J. GRIFFIN ESQ. WORKS ON GLASS. BASTENAIRE-DANDENART (F.) L’Art de la Vitrification ou Trait6 Ql6mentaire de la Fabrication du Verre 8vo. Paris 1825. BLANCOURT’S (H.) Art of Glass showing how to make all sorts of Glass Crystal and Enamel; also the Painting of Glass &c. 8vo. London 1699. NERI (Antonio) The Art of Glass wherein are shown the ways to make and colour Glass Pastes Enamels &c. &c. 8vo. London 1662. BdET ALLURGY* GELLERT’S (C.E.) Metallurgic Chemistry translated from the German 8vo.London 1776. HENCKEL’S (J. F.) Pyritologia or a History of the Pyrites the principal Body in the Mineral Kingdom 8vo. I&.1757. SCHINDLER (M.) L’hrt d’Essayer les Mines et les MQtaux traduit par Geoffroy 8vo. Paris 1759. VAUGHAN (Henry) Of Coin and Coinage. WORKS ON BLEACHING-. BERTHOLLET, See Works on Dyeing. BLACHETTE (L. J.) Trait6 Thdorique et Pratique du Blanchiment 8vo. Paris 1827. CURANDAU (F. R.) Trait6 du Blanchissage & la Vapeur 8vo. Ib. 1806. HOME’S (Dr. Francis) Experiments on Bleaching 8vo. Edinburgh 1756. N.B.-The earliest work on Bleaching. LE-NORMAND (L. Seb.) Manuel Pratique de 1’Art du Dkgraisseur 3rd Edition 121x10-Paris 1826. O’REILLY(R.) Essai sur le Blanchiment 8vo.I&.1801. PAJOT-DES-CHARMES, L’Art du Blanchiment 8vo. I&.1798. RENNIE’S (Professor) Papers on the Art of Bleaching contained in the “ Glasgow Me- chanics’ Magazine,” 8vo. GZasgow 1824. STRATINGH (Professor) Ueber die Bereitung und die Anwendung des Chlors 8vo. Ikmenau 1829. ART OF DYEING. BANCROFT’S (Dr. E.) Experimental Researches concerning the Philosophy of Permanent Colours 8vo. vol. 1. London 1794. 2 ~01s.8170. 16. 1813. 416 CATALOGUE OF BOOKS BERGNES L’Art du Teinturier 12mo. Paris. 1827. BERTHOLLET (C. L et A. Be) filbments de 1’Art de la Teinture avec une Description du Blanchiment par l’acide Muriatique oxigknk 2nd Edition 2 tomes 8vo. lb. 1804. BUCHOZ (J. P.) Trait6 des Plantes propres ii la Teinture 8vo.16. 1799. CHAPTAL (M. J. A.) L’Art de la Teinture du Coton en Rouge 8vo. 18. 1807. -Principes Chimiques sur 1’Art du Teinturier-Dkgraisseur 8~0. 16. 1808. CHUBB (W. P.) On Dyeing and Scouring 8vo. London 1830. DAMPOURNEY, Proc&dCs et Exp6riences SIX les Teintures solides des vkgetaux indighes 8170. Paris 1792. HAIGH’S (James) Dyer’s Assistant in the Art of Dyeing Wool 12mo. London 1800. HOMAPEL(M.) ,Cours Thkorique et Pratique sur 1’Art de la Teinture en Laine Soie Fil Coton &c. 3Eme Edition 8vo. Paris 1818. MACQUER(M.) Art de la Teinture en Soie folio. Ib. 1763. PACKER’S (Thomas) Dyer’s Guide 12mo. Londola 1816. PILEUR D’APLIGNY,L’Art de la Teinture des Fils et Etoffes de Coton 12mo. Paris 1801. PBRNER(M.) Instructions sur 1’Art de la Teinture et particulihrement sur la Teinture des Laines 8vo.Jb. 1791. (Wp.) TUCKER’S Family Dyer and Scourer 12mo. London 1822. VINCARD(huguste) L’Art du Teinturier Coloriste sur Laine Soie Fil et Coton 8vo. Paris 1820. VITALIS(J. B.) Manuel du Teinturier sur Fil et sur Coton Filk 8vo. Xouen 1810. WHOLE ART OF DYEING translated from the German 8vo. London 1705. WORKS ON CALICO PRINTING. B-L’Art de peindre et d’imprirner les Toiles en grand et en petit Teint 8vo. Paris 1800. COOPER’S (Thomas) Practical Treatise on Dyeing and Calico Printing. PhitadeBhia 1815. DELORMER’S (M.) L’Art de faire l’Indienne 12mo. Paris 1773. KREISIG(C. F.) Der Zeugdruck und die damit verbundene Bleicherei und Farberei 3 Binde 8vo.Berlin 1834-37. O’BRIEN’S (Charles) British Manufacturer’s Companion a Treatise on Calico Printing in all its Branches 12mo. LondGn 1791. VITALIS (J. B.) Cours blkmentaire de Teinture sur Laine Soie Lin Chanvre et Cotqn et sur 1’Art d’imprimer les Toiles 2de Edition. 8vo. Rouen 1827. WORKS ON MINERALOGY AND GEOLOGY. CRONSTEDT’S (A. F.) Essay towards a System of Mineralogy translated by Eugestrom with a Treatise on a Pocket Laboratory Revised by E. M. Da Costa 8vo. London 1770. PRESENTED BY J. J GRIFFIN ESQ. KIDD (Dr. J.) On the Theory of the Earth 8vo. Oxford 1815. KIRWAN’S (Richard) Elements of Mineralogy 2nd Edition 2 vols. 8vo. London 1794. LEONHARD’S(Karl Casar von) Taschenbuch fur die gesammte Mineralogie mit Hinsicht auf die neuesten Entdeckungen 8vo.Frankfurt 1807-1 824. Band 1 1807. Band 7 1813. Band 13 1819. , 2 1808. , 8 1814. ,? 14 1820. , 3 1809. , 9 1815. , 15 1821. , 4 1810. , 10 1816. , 16 1822. , 5 1811. , 11 1817. , 17 1823. , 6 1812. , 12 1818. , 18 1824. REPERTORIUM (General Index to the above for the Years 1807 to 1816.18. 1811-1817)0 ROSE’S (Gustav) Elemente der Krystallographie 2te Auflage 8vo. BerZin 1838. SCHMEISSER’S (J. G.) System of Mineralogy formed chiefly on the plan of Cronstedt 2 vols. 8vo. London 1795. WORKS ON’ELECTRICXTY. BECCARIA’S (Father Giambatista) Treatise upon Artificial Electricity and on the Elec- tricity of the Atmosphere ; translated from the Italian 8vo. London 1776. CARPUE’S(J. C.) Introduction to Electricity and Galvanism 8vo.18. 1803. DESAGULIER’S (D. J. T.) Dissertation concerning Electricity 8vo. 16. 1742 FRANKLIN’S (Benjamin) New Experiments and Observations on Electricity made at Philadelphia 2nd Edition 4to. 16. 1754. FREKE’S (John) Essay to show the Cause of Electricity 2nd Edition 8vo. 18. 1746. LOVETT’S (R.) Philosophical Essays in Three Parts 8vo. Worcester 1766. -Electrical Philosopher containing a New System of Physics 8vo. 18. 1774. -The Subtil Medium proved 8vo. London 1756. -Newton’s Ether Realized and Electricity made useful 8vo. 18. 1758. -ReFiewers Reviewed and Electricity made useful in Medicinal Intentions. 8vo. Worcester 1760. MAHON’S (Charles Viscount) Principles of Electricity 4to. London 1799. MARTIN’S (Benjamin) Essay on Electricity 8vo.1b. 1746. NAIRNE’S Description and Use of the Patent Electrical Machine 8vo. 18 1787. NOLLET’S (AbbE J. A.) Versuch einer Abhandlung von der Electricitat der Korper 8170. Erfurt 1749. INQUIRY PHILOSOPHICAL into the Properties of Electricity 8vo. London 1786. PRIESTLCY’S (Dr. Joseph) History and Present State of Electricity with Original Experiments 5th Edition 4to. I& 1794. RACKSTRAW’S (B.) Observations and Experiments on Electricity 8vo. 18. 1748. TURNER’S(R.) Electricology ; or a Discourse upon Electricity 8vo. Worcester 1746. WATSON’S (Wm.) Experiments to illustrate Electricity 2nd Edition 8vo. London 1746. WILKINSON’S (C. H.) Elements of Galvanism in Theory and Practice 2 vols. 8vo. 18. 1804. WILSON’S (Benj.) Treatise on Electricity 2nd Edition.16. 1752. VOL. 111.-NO. XII. EE 418 CATALOGUE OF BOOKS PRESENTED BY J. J. GRIFFIN ESQ. ELECTRICA VARIA ANDREAS GORDON Versuch einer Erklkung der Electricitat. Erfurt 1745. Du FAY,Yon der Electricitlt der Kiirper. 16. 1745. KRATZENSTEIN (C. G.) Von dem Nutzen dcr Electricitat in der Arzneinissenschaft. HalEe 1145. -Von den1 Aufsteigen der Dunste und Darnpfe. 16.1744. ROSENBERG, (A. G.) Von den Ursachen der Electricitat. Breslau 1745. WORKS ON PHYSICS. GILBERTI(Gulielmi) Tractatus de Riagnete 4to. Sedmi 1628. N.B.-The$rst published work on Magnetism. HAUKSBEE’S (Francis) Course of Mechanical Optical Hydrostatical and Pneumatical Experiments to be performed by him; the Explanatory Lectures read by Wni.Whiston MA. 4to. -(F.R.S.) Physico-mechanical Experimeuts on various subjects 8vo. Londofi 1719. IIELLARY (Dr. Wm.) On the Nature and Laws of Motion of Fire 8\70. 16. 1760. NICHOLSON’S (Wm.) Introduction to Natural Philosophy 2 vols. 8vo. Id. 1787. BUCEIER-KUNDE, POLPTECHNISCHE 8vo. Niimzberg 1829. WINKLER’S (J. €1.) Elements of Natural Philosophy delineated 2 vols. 8vo. London 1757.

ISSN:1743-6893    

DOI:10.1039/QJ8510300412

出版商:RSC    

年代:1851

数据来源: RSC

摘要:

TITLES OF CHEMICAL PAPERS JN BRITISH AND FOREIGN JOURNALS PUBLISHED IN THE YEAR 1850. A. Acids.-On the separation of certain acids of the series (CH). 0, by J.Liebig. Ann. Ch. Pharm Ixxi 3; Chem. SOC.Qu. J. iii 74. Acid Acetic.-Preparation of acetic acid on the large scale by A. Beringer. Ann. Ch. Pharm. lxxiv 345. .. .. Manufacture of acetic acid.-Pharm. J. x 31. .. . . Manufacture of the acetates of lime soda and lead.-Idem. 31. .. . . On the preparation of acetate of lead by means of pyroligneous acid by M. Schnedermaniz. Rev. Sci. xxxix 156. *. .. On the simultaneous action of heat and alkaline bases on the acids homologous with acetic acid by A. Cahours. Compt+ rend. xxxi 142. .. .. On the manufacture of pyrolygneous acid pyroxylic spirit or wood naphtha and the commercial acetates of lime soda and lead and of acetic acid.Pharm. J. x 69 135 196 300 Aconitic.-On the acid of the equisetum$uviutiZe and on certain aconitates by Jf. Bctusse. Compt. rend. xxxi 387. Arsenious.-Observations on arsenious acid realgar and orpiment by Hnusmnnn. Ann. Ch. Pharm. lxxiv is$. .. .. On some of the salts of arsenious acid by J Xteen. Idem 218. .. .. On the action of arsenious acid upon albumen by J. B Ed-wards. Chem. SOC.Qu. J. iii 14. .. .. Combination of arsenious acid with albumen by Mr. Kela-dall. Pharm. J. is. 526. Aspartic.-Formation of aspartic acid from bimalate of ammonia * by M. Dessaignes. Compt. rend. xxs. 324 ; Chem. SOC.Qu. J. iii 187. *. .. On the formation of aspartic acid from malic acid by J Wo/& Ann.Ch. Pharm. Ixxv 293. Bisulpham y1ic.-On the identity of bisulphamylic and hyposulphamylic acids by J.Donson. Chem. SOC.Qu J. iii 158. Bisulyhethy1ic.-On the identity of bisulyhethylic with hyposulphethylic acid and of bisulphimethylic with hyposulphamethylic acid by Sh. Muspmtt Chem. Soc. Qu. J. iii 18. Boracic.-On certain properties of boracic acid and on the quantitative estimation thereof by H. Rose. Pogg. Ann. Ixxx 262 ;Chem Gaz. 1850 381. EE 2 TITLES OF CHEMICAL PAPERS Acid Bromobenzoic.-On anhydrous bromobenzoic acid by M. Mdler. Compt. rend. xxx 325. Butyric.-Formation of succinicacid by the oxidation of butyric acid by M. Dessaignes. Compt. rend. xxx 56 ; also J. Pharm. [37] xvii 139.Carbolic.-On creosote and carbolic acid by Gorup-Besanez. Pharm. J. is 392. Caproic.-Contributions towards the history of caproic and enanthylic acids by J. Brazier and G. Gosslcth. Chem. SOC.Quar. J. iii 210. Ch1oric.-On the preparation of chlorate of potash on the large scale by F. C. Culvert. Chem. SOC. Qu. J. iii 106. .. Combustion experiments with chlorate of potash by A. Yogel. Ann. Ch. Pharm. Ixxiv 114. Chromic.-Mode of detecting chromates.-Rev. Sci. xxxix 198. .. On two new salts of chromic acid by A. Duncan. Phil. Mag. xxxvi 109. .. On the bichromate of ammonia and some of its double salts by R. Richmond and J. Abel. Chem. Soe. Qu. J. iii 199. Chrysammic.-Note on dulcose and on bromobenzoic and chrysammic acid by A Laurent.Compt. rend. xxx 339. .. .. On chrysammic acid by A. Lazcrent. Cornpt rend trav. chim. vi 163. Citric.-Citrate of quinine and iron by MY,Barber. Pharm. J. ix 338. Cuminic.-On the passage of cuminic acid through the animal system by A. W. Hofmann Chem. SOC. Qu. J. iii 181. Cyanic.-On the compounds produced from cyanic acid and ether by Dr. Limpricht. Ann. Ch. Pharm. lxsiv 208. Fatty.-On Chinese vegetable tallow and the fatty acid contained in it by J. B.v. Bork. J. pr. Chem. xix 395. Ferritungs tic.-On the ferritungstic and ferrimanganitungstic acids by A. 14aurent. Compt. rend. xxx 692. Fumaric.-Easy method of preparing fumaric acid by H7.DeZfls. Gallic.-On tannic gallic and metagallic acids by J. Mulder. J. pr. Chem.xlviii 90; Chem. Gaz. 18.50 41. Hippuric.-On the presence of hippuric acid in ox-blood by F. Verdeib and C. Dolfuss. Ann Ch. Pharm. lxsiv 214. .f On hippuric acid and the products of its oxidation by peroxide of lead by H. Schwarz. Idem. lxxv 190. .. Occurrence of hippuric acid in the blood.-J. pr. Chem. 1 34. Hydroeyanic.-Otr the compound of bichloride of titanium with hydro- cyanic acid by F. Woliler. Ann Ch. Pharm. lxxiii 226. .. .. On the preparation of anhydrous hydrocyanic acid by F. Wohlw. Idem. 218 ;Pharm. J. x 300. Hydrofluosi1icic.-On the use of hydrofluosilicic acid in quantitative am- lysis by H. Rose. Pogg. Ann. lxxx 403. Hydrosu1phuric.-On the products of the decomposition of hydrosul-phuric and sulphurous acid in water :by AWM.Sobrero and Selmi.Ann. Ch. Phys [3] xxviii 210. H ypoch1orous.-On hypochlorous acid and the chlorides of sulphur by 3. &fillon. Idem. xxix 506. Hyposul pham e th yli c.-vide Acid Bisulphethylic. IN BRITISH AND FOREIGN JOURNALS 421 Acid H yp osulpham ylic.-vide Acid Bisulphamylic. Hypos ul phe thy1ic.- Vide Acid Bisulphethylic. 1odic.-On anhydrous and crystallized iodic acid by V. Jucquelnin. Compt. rend. xxxi 624 .. On the various known methods of preparing iodic acid by T.A. JucqueZuin. Ann. Ch. Phys. [3] xxx 332. .. Mode of detecting iodate of potash in iodide of potassium.-Rev. Sci. xxxix 33. Lactic.-& the artificial formation of lactic acid by A. Strecker. Ann. Ch'. Pharm. lxxv 27. . Action of nascent chlorine on lactic acid by M.Stadeler. Rev. sci. xxxviii 232. Metacetic.-Method of obtaining metacetic acid in large quantities by F. KeZZer. Ann. Ch. Pharm. lxxiii 205 ; Chem. SOC.Qu. J. iii 190. Metaphosphoric.-On the various modifications of metaphosphoric acid by Th. Fleitmann. Chem. Gaz. 1850 91. .. .. On the different modifications of metaphosphoric acid.-J. pr. Chem. xxix 224. Nitric,-On anhydrous nitric acid by M. Deville. Ann. Ch. Phys. [3] xxviii 241. . Action of nitric acid on iodide of potassium by Dr. Vogel. Pharm. J. ix 391. On a qualitative test for nitric acid by J. Higgin. Chem. Gaz. a. 1850 249. .. Mode of concentrating commercial nitric acid.-Rev. Sci. xxxix. 191. . . Action of nitric acid on the organic alkaloids by T.Anderson Chem.Gaz. 1850 363. Nitrohippuric.-On the formation of nitrohippuric acid in the animal economy by C. Bertugnini. Compt. rend. xxxi 490. 0xalic.-On the quantitative estimation of oxalic acid and the mode of separating it from phosphoric acid by H. Rose. Pogg. Ann. lxxx 649. .. On the properties of oxalate of lime by A. Reynoso. J. pr. Chem. xlix 5 11. .. On the probable nan-existence of oxalate of potash and soda by C. Rummelsberg. Pogg. Ann lxxix 562. 0enanthylic.-Contributions towards the history of caproic and cenan- thylic acids by J. Brazier and G. Gosslelh. Chem. SOC. Qu. J. iii 210. Pe1argonic.-Researches on pelargonic acid by A. Cukours. Chem. Soc. Qu. J. iii. 240. Phosphoric.-On some new modifications of phosphoric acid by T.FZeit-rnann.Pogg. Ann. Ixxviii 233 338. .. ,. On the qualitative and quantitative determination of phos-phoric acid by Leconte. J. pr. Chem. xlix 380. .. . On some salts of phosphoric acid by 0.J? Kiihn. Chem. Gax. 1850 28 and 50. .. ,. Separation of phosphoric acid from alumina by N.Rose. Idem. 19. .. .. On the proportion of phosphoric acid in some natural waters by A. Volcker. Idem. 346. TITLES OF CHEMICAL PAPERS Acid Phosphoric.-On the separation of oxalic from phosphoric acid by H. Rose. Pogg. Ann. lxxx 649. .. .. Process for preparing biphosphate of lime for manure by M. Gill. Rev. Sci. xssix 197. Pyroliyn eous.-Manufacture of pyroligneous acid.-Pharm. J. x 3 1. Race rnic.-On the specific properties of the two acids which constitute racemic acid by L.Pasteur.Ann Ch. Phys. [3] xsviii 56. t. Detail of experiments made by the Commission of the Aca- demy of Sciences to verify the relations established by M. Pasteur between the rotatory actions of these two acids and that of crystal-lized tartaric acid by M. Biot. Ann. Ch. Phys. [3j xxviii 99. .. Note on Pasteur's memoir on racemic acid.4. pr. Chem. 1 129. On the racemate of potash and soda by IT,Delfs. Pogg. Ann. lxxx 493. Succinic.-Formation of succinic acid by the oxidation of butyric acid by M. Dessuignes. Compt. rend. xxx 50 ; Chem. SOC. Qu. J. iii 186. .. New researches on the formation of succinic acid by fernien- tation by 1l.I. Dessuiynes. Compt. rend. xxxi 432. .. On the occurrence of succinic acid in the human body by W.Heintz. Pogg. Ann. lxxx 114. .. Succinic acid from the residue of Sp. ATtheris nitrosi by J. Reich. Pharm. J. x 310. Sulphamy1ic.-On sulphamylic acid and some of its salts by A. Kektd6. Ann. Ch. Pharm. lxsv 275. Su1phocarbamic.-On the compounds of sulphocarbatriic acid by I& Debus. Ann. Pharm. lxxiii 26. Su1phocarbonic.-On certain decomposition products of bioxysulpho-carbonate of ethyl by H. Debus. Ann. Ch. Pharm. lxxv. 12 I. Su1phuric.-On the hydrates of sulphiiric acid by N. Jucqueluin. Compt. rend xxxi 624 ; Ann. Ch. Phys. [3] xxx 343. .. Concentration of sulphuric acid by MY. Rodw. Pharm. J. ix 390. Sulphurous.-On the products of the decomposition of hydrosulphuric and sulphurous acid in presence of water by AWi?.Sobrero and Xelmi. Ann. Ch. Phys. [3] xxviii 215. .. On the earthy alkaline sulphites and particularly on bisulphite of lime by MM. M2ne and Yinchon. Compt. rend. xxx 711. Tartaric.-On the molecular condition of tartaric acid which has been fused by heat with or without loss of its substance by M. Biot. Ann. Ch. Phys. xxix 35 341. Thionic.-Note on the thionic acids by &IN,Fordos and Ge'lis. Ann. Ch. Phys. [3] xxviii 451. Titanic.-On the preparation of pure titanic acid by F. Wohler. Ann. Ch. Pharm. lxxiv 212. Uric.-Simplified method of obtaining uric acid from serpents' excrements by W. lkZ#s. Pogg. Ann. lxxx 310. Valerie.-On the action of heat on valeric acid by A. ?V. H~finwna. Chem. SOC. Qu. J.iii 121. XM BRITISH AND FOREIGN JOURNALS. Ace tone.-Test for distinguishing acetone from pyroxylic spirit :by M. Scanlan. Pharm. J. ix 455. Acorns.-Analysis of acorns with some remarks on the occurrence of milk- sugar in seeds by H. Braconnot. J. pr. Chem. xxix 232. Air.-On the composition of the atmosphere at Moscow during the cholera time by N. Laskowsky. Ann. Ch. Pharm. lxxv 176. -On the chemical composition of atmospheric air :by Jf. Lttwy. Compt. rend. xxxi 725. A1anine.-On the direct preparation of ethylamine and on alanine by A. Strecker. J. pr. Chem. 1 56. Albite.-On a granular Albite associated with Corundum and on the Indianite of Bournon by B. Sillimun,jun. Phil. Mag. xxxv 484. Albumen.-On the action of arsenious acid upon albumen by J.B. Edwards. Chem. SOC. Qu. J. iii 14. -Combination of arsenious acid with albumen by LW~. KendaEE. Pharm. J.ix 526 2'. by:the albumen of eggs ofthe freezing onObservations-BelE. Phil. 'Trans. 1850 i 221. -Observations on the freezing of the albumen of eggs :by J. Paget. Chem. Gaz. 1850 277. -On the alkaline reaction of the albumen of eggs by Barreswil. J. pr. Chem. I 134. -On sugar in the albumen of eggs by Barrttswil. Idem. A1buminose.-On the presence of albuminose in the blood by Me Mialhff-Compt. rend. xxx 745. A1coholates.-Contributions to the history of the alcoholates and of nitrate of magnesia by A. Chadyeu. J. pr. Chem. xlix 107. Alkalis.-On the separation of the alkalis from magnesia and on the analysis of alkaliferous minerals by Elrelrnen.Ann. Ch. Phys. [3] 324. Alkaloids.-On the constitution of certain alkaloids by H. Wertheim. Ann. Ch. Pharm. lxxiii 208 -On the nitrogenated principles of vegetables as the sources of artificial alkaloids by J. Stenhouse. Phil. Trans. 1850 i 47; Absh.. Chem. SOC. Qu. J. iii. Allantoic Liquid -Note on the amniotic and allantoic liquids by J. Stas. Compt. rend. xxxi 629. Aloes.-On the watery extract of aloes by F. L. FFinckler. Pharm. J. x 310. A11oy.-On a natural alloy of silver and copper from Chili :by Ft*.Field. Chein. Soc. Qu J. iii 29 -On alloys considered with regard to their chemical composition by fW.Levol. J. Pharm [3] xvii 11 1. Almonds.-On some new combinations of the essence of bitter almonds by A.Laurent and Ch. GPrRardt. Compt. rend. xxx,401 ; also Compt. rend. trav. chim. vi 113. Alumina.-Preparation of a crystalline nitrate of alumina of unusual con-stitution by the Prince of Salm-Horstrnar. J. pr.Chem. xlix 208. -On the impure pyrolignite of alumina as a mordant for red colours by 2'. C. Culvert. Pharm. J. x 305. Amalgams.-On some amalgams by J. P. Joirle. Chem. Gaz. 1850 339. Amalgam.-On the amalgam of cadmium ant1 tin by Prof. Yarrentrapp. Ann. Ch. Pharm. lxxiii 256. TITLES OF CHEMICAL PAPERS Amalgam.-On the amalgam of copper by M. Pettenkofer. Rev.Sci. xxxix,58. Ammonia.-On the bichromate of ammonia and some of its double salts by 11. Richmond and J. Abel. Chem. SOC.Qu. J. iii 199. -Description of an ammonia-meter by J.Grifin. Idem. 206. -On the assimilation of the nitrogen of the air by plants and on the influence of ammonia on vegetation by M rille. Compt. rend. xxxi. 578. -On certain new compounds of ammonia with the ferrocyanides and par- titularly with the ferrocyanide of nickel by A. Reynaso. Compt. rend. xxx 409 ; Ann Ch. Phys. [3] xxx 252. -On the compounds of ammonia by A. Laurerzi. Compt. rend. trav. chim. vi 201. -On the quantity of ammonia in the atmosphere by Prof. Horsford. Ann. Ch. Pharm. lxxiv 243. -On the quantity of ammonia contained in the liquid condensed from coal- gas by &I. Malenfant. J. Pharm. xviii 131. -Researches on the quantity of ammonia contained in the urine by &I.Boussingault. Ann. Ch. Phys [3] xxix 472. -On the formation of ammonia by contact of porous bodies with air and sulphuretted hydrogen gas by Muldw. J. pr. Chem. 1 431. -On the trapezohedral crystals of sal-ammoniac by C. F. Naumann. J. pr. Chem. 1 11. -On the ammoniacal compounds of platinum by Ch. Gerhardt. Compt. rend. trav chim. vi 273. Amniotic Liquid.-Analysis of the amniotic liquid of the human female by J. Regnauld. Compt. rend. xxxi 218. -Note on the amniotic and allantoic liquids by J. Stcls. Idem. 629. Amy1.-Researches on the organic radicals-Part ii amyl by E. Frankland. Chem. SOC. Qu. J. iii 33 Analysis Mineral,-On the use of hydrogen in mineral analysis by L. E. Rivot. Ann. Ch. Phys. [3] XXY 188. Andersonite.-On the colours exhibited on the surface and in the mass of Andersonite a compound of iodine and codeine by W.Haidiitger.Pog. Ann. lxxx 553. Angraecum.-On the odoriferous principle of Angrmum frugrans by M. Gobley. Chem. Gaz. 1850 307. Aniline.-On the decomposition of aniline by nitrous acid by T. S. Hunt. Idem. 21. Animal Economy.-On the action exerted on the living animal economy by substances which preserve dead animal matters by E. Robin. Rev. sci. xxuviii 18. -Kingdom.-Notice of observations on the adjustment of the relations between the animal and vegetable kingdoms by which the vital func- tions of both are permanently maintained by R Warington Chem. SOC.Qu. J. iii 52. -Substances.-Contributions to the doctrine of the identity of the sul- phurous and nitrogenous animal and vegetable substances by F.Keller. Ann. Ch. Pharm. 72 24 ; Chem. Gaz. 1850 121. ** .. On the certain new processes and agents for the preser- ~ationof animal and vegetable substances. by E. Robin. Compt. rend. xni 720. IN BRITISIf AND FOREIUN JOURNALS. Anisole.-Researches on anisole and phenetole by A. Cahours. Ann. Ch. Pharm. Ixxiv 298. Antimony.-On the quantitative determination of antimony by H. Rose. J. pr. Chem. xix 222. -On stibethyl a new organic radical containing antimony by C‘. Lowig and E. Schweizer. Ann. Ch. Pharm. lxxv 315. -Separation of antimony from arsenic by M. Ullgren. J. Pharm. xvii 55. -Behaviour of antimony with chloride of sulphur by F. Wohbr.Ann. Ch. Pharm lxxiii 374. -On the chlorosulphide of antimony by S. Cloez. Ann. Ch. Phys. [3] xxx 374. Aphanite.-On the Aphanite of St. Bresson (Vosges) by A. Delesse. Ann. Min xvi 367. Apiine.-On apiine by A. Planta and W. Wallace. Ann. Ch. Pharm. lxxiv 262. Aridium-On aridium probably a new metal by M. Ullgren. Chem. Gaz. 1850 289. Aris to1ochia.-Constituents of Arisfolochia clemcstitis by F. L. Winckler. Idem 135. Arsenic.-Observations on arsenious acid realgar and orpiment by Huus-mann. Pogg. Ann. lxrix 308. -On some of the salts of arsenious acid by J. Stein. Ann. Ch. Pharm Ixxiv 218. -On the state in which arsenic and manganese occur in the deposit of the boiiing spring at Wiesbaden by R.Fresenius. Idem kxv 172.-Quantity of arsenic in the calcareous deposit of the Carlsbad waters by 3’. Wolder. Idem. lxxiii 217. -Separation of antimony from arsenic :by M. UZZgren. J. Pharm. [3] xvii 55. -On certain compounds of arsenic by P. Kotschowbey. J. pr. Chem. xlix 182. -Action of arsenic on chloride of sulphur by F. Wohler. Ann. Ch. Pharm. lxxiii 374. -Use of sulphide of arsenic as a depilatory by 2’. Boudet. Pharm. J. x 193. Arteries.-Chemical composition of the coats of arteries by H.S,Sckultze. Chem. Gaz. 1850 135. Ar tichoke.-On the constituents and use of the Jerusalem artichoke (Xelian-thus tuberosw) by MM. Payen Poinsot,and Ferez. J. Pharm. xvi 434. Asafetida.-Researches on the oil of asafetida by H. HZasiwetz. Ann. Ch. Pharm lxxi 23 ;J.Pharm. [a] xvii 234. Ashes.-On the composition of the ashes of the cactus by fi,Field. Chem. SOC.Qu. J. iii 57. -Analysis of the ash of the white and yellow of the eggs of poultry by 2%. Poleck. Pogg. Ann. lxxix 155. I_ Ash-analyses by J. Porter. Sill. J. ix 29. -Analysis of the ash of millet-seed by R. Wildenstein. J. pr. Chem. xlix 152. -Analysis of the ashes of blood by G. Roser. Ann. Ch. Pharm lxxiii 334. TITLES OF CHEMICAL PAPERS Ashes.-Fundamental experiments on the determination of the inorganic con-stituents of organic bodies by A. Strecker. Idem. Ixuiii 339. -Analysis of the ashes of the Spanish potato (Convolvulus batatas) and of the eddoes (Arum esculentzm Linn. Colocusia esculenta Schott) by T.J. Herapath.Chem. SOC. Qu. J.iii 193. Atomic Volume.-On the isomorphism and atomic volume of certain mine- rals by J.D. Dam. Sill. J. [2] ix 220. -On the atomic volumes of bodies by M. Arogadro. Ann. Ch. Phys. L3] xxk 218. Atomic Weights.-Connection between the atomic weights and physical and chemical properties of barium strontium calcium and magnesium and some of their compounds by E. N. Horsford. Sill. J. [2] ix 176. -Table of atomic weights.-Idem. '227. Atropine.-Preparation of atropine by means of chloroform by JX. Rabourdin. Ann. Ch. Phys [3] xxx 311. B. Balsam.-On Peru and Tolu balsams by M. Guibourt. J. Pharm. xvii 81. Bark.-Analysis of the barks of Bkamnus frangula and R. ruthurticu by M. Binswanger. Buch. Repert. 1849 No. 11 ; Pharm. J.is. 535. -On Calisaya bark by H. A. Weddell. Pharm. J. ix 428. Beer.-Examination of beer by M. FucJm Rev. Sci. xsxiy 7. -Examination of certain kinds of Wiesbaden beer with reference to their proportion of alcohol and extractive matter &c. by G. EngeZma?in. J. pr. Chem. I 133. Beetroot.-Experiments on the manufacture of sugar from beetroot by Fr. KGJiZmam. Compt. rend. xxx 341. Beet,-Analysis of the syrup of beet sugar used for feeding cattle by Puyen Poinsot and Brunet. J. pr. Chem. 1,204. Benzine.-On the sulphuric and nitric compounds of benzine and naphthaline by A. Laurcnt. Compt. rend. xuxi 537. Bile.-On the presence of bile in the blood by C.Ender1in. Ann. Ch. Pharm. lxxv 167. -On human bile by C. Endediw. Idem. 162. 7 On a peculiar transformation of os-bile by C.EnderSn.Idem. 154. Bi1ine.-On biline by C. Enderlin. Idem. 166. Bismuth.-On the salts of bismuth by Mr. Edwards. Pharm. J. iu 461. Black Earth.-On the black earth (Schumrzerde) of Southern Russia by E. Schmidt. J. pr. Chem. xlix 133. Bleaching.-Improvement in the bleaching of linen by Mr. Mwcer. Rev. Sci. xxxix 107. Blood.-Researches on the composition of the blood.-Compt. rend. xxxi 289. -Analysis of the ashes of blood by G. Roser. Ann. Ch. Phartn. lyyvi 334. -On the presence of albuminose in the blood by M. iTIiaZh6. Compt. rend. xxx 745. -On the presence of carbonates in the blood :by Prof.Il!FuZder. Chem. Gaz 1850 348. --On the quantity of potash in the blood by C. Etderlin. Ann. Ch. Pharm IXYV 150.IN BRITISH AND FOREIGN JOURNALS. Blood.-On the methods of analyzing blood by Gorup-Besunez. J. pr Chem. 1 346. -Analysis of chyle and of blood by E. Millon. Idem. 30. -On the presence of urea and hippuric acid in ox-blood by F. Yerdeit and C. DotZf~s. -4nn. Ch. Pharm. lxxiv 214. -Note on the presence of caseine in the blood of the human female during the period of lactation by N. GuiZlot and 2’. Leblunc. Compt. rend. xxxi 520. Boilers.-On the incrustation which forms in the boilers of stearn-engines :by J. Duvy. Chem. Gaz. 1850 343. .__ Fresh water in marine boilers by Z-. Frank. Inst. J. xix 13. -On the use of the alkaline carbonates for preventing incrustations in boilers by A. Anderson. Chem. SO~. Qu. J. iii 13.Boiling point s.-On the relations between chemical composition boiling point and specific volume by H. Kopp. Chem. SOC. Qu. J. iii 10.1. Borax.-Contributions to the chemistry of borax by E. Schweitzer. Chern. Gaz. 1850 281. -New method of analyzing borax.-Idem 284. -Reaction of borax on turmeric ; by Dr. Voyd ju12. Pharm. J. ix 441. Qu. J. iii. Boron.-On the nitride of boron by F. Wohler. Chem. SO~. Bread.-On Adulterations of flour and bread by Donny and Mareskn. J pr. Chem. xlis 260. -On bread by 2’. KeZZer. Bucfin. Repert. 1850 336. Bromine.-On the existence of alkaline bromides and iodides in plants of the order OsciZlnriace~,living in the thermal waters of Das (De‘parteilient de Landes) by V.Meyruc. Compt rend. xxx 475. -On the presence of bromine in the ammoniacal liquid obtained in the preparation of coal-gas by M.Mhe. Idem. 612. -Decomposition of bromide of potassium in the dry way by F. Schonbein. Chem. Gaz. 1S50 168. -On the action of chlorine and bromine on propylene ethylene and their homologues by A. Culiours. Compt. rend. xxxi 291. Bron z e.-Analysis of certain gold-coloured bronze antiquities found at Dowrir near Parsonstown by -Ur. Donovan. Chem. Gaz. 1850 176. -Analysis of two antique bronzes of the Gallo+Roman period by 31,SuZ-vetat. Ann. Ch. Phys. [3] xxx 361. Bronzing.-On the bronzing of plaster figures by L. EZsner. Idem. 388. C. Cactus.-On the composition of the ashes of the cactus by l? Field. Chem. SOC. Qu. J. iii 57. Cadmium.-On the amalgam of cadmium and tin by Prof.Yurrenirapp. Ann. Ch. Pharm. Ixsiij 256. Caffeine.-On certain decomposition.products of caffeine by P.Rochleder. Idern. 56. -Action of potash on caEcine by A. Wurtz. Compt. rend. xxx 9. Calcium.-On the equivalent of calcium by 0. Erdmunn and R. &!archand. J. pr. Chem. I 237. Calico-printing.-On Broquelte’s process for calico-printing by UurremiZ. Idem. 314. TITLES OF CHEMICAL PAPERS Ca1isaya.-Calisaya bark by H. A. Weddell. Pharm. J. is 428. Camelina Sativa.-On common gold of Plensure by J. Rym. Idem. x 144. Cantharidine.-On cantharidine and its preparations by D. Ottinger. Idem. 431. Caout chouc.-Vulcanized caoutchouc and gutta percha.-J. Pharm. [3] xvii. 205. Curara.-Researches on the Curara poison by MM Pelouze and C.Bernard. Compt. rend. xxxi 532 Car bon.-On some deoxidizing effects of carbon by F. Schb’nbein. Pogg. Ann. lxxviii. 521 ; Chem. Gaz. 1850 101. Carbonic Oxide.-Action of carbonic oxide gas on the corn-worm by G. Barruel. J. pr. Chem. xlix 448. -On some new facts relating to the properties of carbonic oxide gas by F. Lebtunc. Compt rend. xxx 483. Caseine.-Action of potash upon caseine by A. Wurtz. J. pr. Chem. xlix 406. -On the presence of caseine and the variations of its properties in the blood of man and other animals by N. Gaittot and 5’. Leblanc. Compt. rend. xxxi 578. -R-ote on the presence of caseine in the blood of the human female during the period of lactation by $7. Guillot and P. Leblanc.Idem. xxxi 250. Cathartine.-On cathartine by f? S. WinckZer. Chem. Gaz. 1850 232 Cellular Tissue,-On the composition of the walls of the cells of plants by Mitscherlich. Ann. Ch. Pharm. lxxv 305. Cellulose.-On a product of the action of nitric acid upon cellulose. J. Pharm. [3] xvii 158 ; also Sill. J. [2] ix 20. Cereals,-On the adulteration of cereals and on the relative quantity of inorganic constituents in them by Louyet. J pr. Chem. xlix 252. -On the quantity of water contained in the cereal crops of the harvest of 1850 by E. MiZlon. Compt. rend. xxxi 745. Cerebral Matter.-Examination of cerebral matter comparatively with the different organs and products of the animal economy by M. Orflu. J. Pharm. [3] xviii 186. Chlorides.-On certain compounds of metallic chlorides with chloride of cyanogen and hydrocyanic acid by L.Elein Ann. Ch. Pharm. Ixxiv. 85. -Decomposition of chlorides in the dry way by P,Schb’nbein. Chem. Gaz. 1850 168. Chlorine.-On the action of chlorine on metallic chlorides in presence of alkaline chlorides by MM. Sobrero and Selmi. Ann. Ch. Phys. [3] xxix 161, -On a new compound of chlorine sulphur and oxygen by E. MiZZon. Idem. 23’7. -On the action of chlorine and bromine on propylene ethylene and sub- stances homologous with them by A. Cahours. Compt. rend. =xi 291. Chloroform.-Preparation of Chloroform.-Rev. Sci. sxxix 61. -Purification of chloroform by J Abraham Pharm J s 24. IN BRITISH AND FOREIGN JOURNALS. Chloroform.-Test for the presence of chloroform by Dr.Snow. Chern. Gas. 1850 231. -On the use of oxygen as a remedy for accidents in the inhalation of chloroform and for asphyxia by M. Durey. Compt. rend. xxx 524. -Note on Dr. Gregory's process for preparing pure chloroform by Prof. Christison. Chem. Gaz. 1850 371 ;Pharm. J. x 253. Cholera.-On the saline constituents of the evacuations of cholera patients by L. Giiterbock. Pogg. Ann. lxxix 323. -On the respiration and temperature of cholera patients.-J. pr. Chem. 1 35. -Perspiration in cholera.-Idem. 34. Cho1esterine.-On the quantity of water in cholesterine and on the dis- tillation-products of that substance by W. Heintz. Pogg. Ann. Ixxix 524. Cho1estrophane.-Notice concerning cholestrophane by Fr.Rochleder. Ann. Ch. Pharm. lxxiii 123. Chromium.-On the equivalent of chromium and on certain hydrates of chromic oxide :by J. Lefort. Idem. lxxv 106. Cinchonine.-New process for determining the sulphate of cinchonine which exists in the sulphate of quinine of commerce by 0. Henry. Chem. Gaz. 1850 16. Cinnabar.-On a new and very rapid decomposition of cinnabar :by R. BoZZey. Ann. Ch. Pharm. lxxv 239. Cobal t,-Preparation of pure nickel and cobalt on the large scale.-Rev. Sci. xxxix 202. -On the densities of nickel and cobalt by M. Rammehberg. Idem. xxxviii 1 1 1. Cochlearia.-On the constituents of the dry herb of Cocldearia oficinalk by F. L. Winckler. Chem. Gaz. 1850 293. Codeine.-On the constitution of codeine and its products of decomposition Anderson.2'.by Trans. Roy. SOC. Edin. xx 1 57 ; Compt. rend. trav. chim. vi 321. -On a compound of codeine and iodine by T. Anderson. Chem. Gaz. 1850 367. Cohesion.-Influence of magnetism on the cohesion of liquids by C. €?runner julp. Pogg. Ann. Ixxix 141. Co1ocynthine.-By W. Bastick. Pharm. J. x 239. Co1our.-On complementary colours by M. Illaumend. Compt. rend. XXX. 209. Colouring matter.-On the red colouring matters of madder by A. Strecker. Chem. SOC.Qu. J. iii 243. -On the precipitation of the colouring matter of sugar by a metallic oxide by H. Wurbwton. Idem. 55. -On the colouring matter of rhubarb both native and foreign and its application in the arts and in pharmacy :by M. Guyot. J. Pharm. [3 J xvii 5.-On Erythrose the colouring matter of rhubarb by M. Meurin. Idem. 179. I__ Examination of a new yellow colouring matter by W. Stein. 1850,R. TITLES OF CHEMICAL PAPERS Colouring Matter.--On the action of sal-aqmoniac in the oxidation of colouring matters by copper-salts by C. li’occhlin and E. Mathieu Plessy. Bull. Soc. Ind. de Mulhouse xxii 311. Report on the same by H. Schlumberger. Idem 324. -On the colouring matter of the hlorinda citrifolia by 7’.Anderson. -On a new method of fixing colours upon tissues :by C. Bropuette. Chem. Gaz. 1850 354. -On the colouring matter of sandal-wood by A. Weyermann and E. Hajdy. Ann. Ch Pharm. Ixxiv 226. -Improvements in the manufacture of orchil and cudbear-Chem Gaz.1850 209. -Red colour for paper-hangings.-Idem. 200. -Wongshy a new yellow dye by W.Stein Yharm. J. ix 541 Concretion.-Chemical examination of a concretion found in the paunch of a milch-cow (at Monte Video) by M. LenobEe. J. Pharm. [3] xvii 199. Copper.-On the presence of copper in sea-water by MM. Malaguti Uurocher and Sarzeaud. Ann Ch. Phye. [3] xxviii 129. -On the equivalent of copper and on some of its salts :by C. B Xuh.Ann. Ch. Pharm. lxxiii 80 -On a natural alloy of silver and copper from Chili by Fr. Field. Chem. See. Qu. J iii 19. -On copper containing phosphorus by J. Percy Chem Gaz. 3850 1. -On the corrosive action of sea-water on some varieties of copper. by W. James. Idem. 4 -Method of separating silver from cupreous solutions :by M.Bolley. Idem. 116. -Salts of peroxide [protoxide ?] of copper by 3.Schonbeiiz. Idem. 268. -On the decomposition of sulphate of copper and organic substances by H. S. Evans. Pharm. J. Y. 7. Cotton.-On a peculiar kind of cotton fibre which cannot be dyed by W. Cram. J. pr. Chetn. 1 122. Creatine,-a constituent of the flesh of the cetacea :by 8.Price Chem. SOC. Qu. J. iii. 229. Creosote.-On creosote and carbolic acid by Dr. Gorup-Besanez. Pharm. J. iu. 392. Crystalline Form.-New researches on the relations which may exist between crystalline form chemical composition and the phenomenon of cir-cular polarization by L. Pasteur. Compt. rend. xxxi 450. -Report on the above by M. Biot. Idem. 601.-On a reniarkable analogy of form between certain sulphur-salts and oxygen- salts by G. Rose. J. pr. Chem. xlis 155. -On a cause of variation in the angles of crystals by J. Nick$&. Compt. rend. xxx 530 ;Compt. rend. trav. chim. vi 193. -Correction of Rudberg’s determination of the axial angles of biaxial crys- tals by 3.Wilde. Pogg. Ann. lxxx 225. -On the crystalline form of Beudantite by H. J. Brooke. Phil. Mag. sxxvii 349. -On the pseudomorphoses of Mica in the form of Felspar 2nd on the normal growth of Felspar with Albite by G. Rose. l’ogg. Ann. lxxx 1’21. IN BRITISH AND FOREIQN JOURNALS. 431 Crystalline Form.-On the crystalline forms of certain rhombohedra1 metals by G. Bose. J. pr. Chem. xlix 155. -On the rhombohedra1 crystals of sal-ammoniac -by Naumann.J. pr. Chem. 1 309. -On the crystalline form of certain organic substances :by H. Dauber. Ann. Ch. Pharin. lxxiv 200. Cyanides.-On the composition of certain double cyanides by C. Gerhardt. Compt. rend. trav. chim. vi 145. -On the composition of the precipitate formed by subacetate of lead in soluble cyanides by E. Erlenmeyer. J. pr. Chem. xlviii 356; J. Pharm. [3] xvii 238. Cyanogen.-On the compounds of cyanogen with sulphuretted hydrogen :by A. Lauretit. Compt. rend. xxs 618 ; Compt. rend. trav. chim. vi 373. -Estimation of cyanogen by C. Heisch. Compt. rend. trav. chim. vi 225. -On the iodide of cyanogen by C. Herzog. Chem. Gal;. 1850 230. D. Daturine,-found in the urine of persons poisoned with stranionium by R.Aldun. Ann. Ch. Pharm. lxxiv 223. Density.-Observations on the volume and density of liquid and gaseous bodies by J. A. Groshuns. Pogg. Ann. lxxx 296 -On an improved specific gravity bottle by J. Abraham. Pharm. J. x 125. Diabetes.-On the amount of nitrogen in the faxes of diabetic patients by D. CumnpzleJf. Chem. Gaz 1850 155. -On the composition of the faeces of man in health and on diabetes mellitus by J. Percy. Idem. 122. Diamonds.-Artificial production of diamonds by AW. Despretz. Pharm. J. x. 41. Diamond.-On a peculiar change produced in the diamond. when under the influence of the voltaic arc by J. P. Gussiot. Chem. Gaz. 1850 338. -Oxidation of graphite and diamond in the humid way by €2.E. Rogers and W.R. Rogers. 6. pr Chem. 1.4 i 1. Diffusion.-On the application of liquid diffusion to produce decompositions by T.Gmllam. Chern. SOC. Qu. J. iii 60. -On the diffusion of liquids.-Phil. Trans. 1850 i 1 ; also Ann. Ch. Phys. [3] xxix 197 ; ahstr. Chem. SOC. Qu. J. iii 25. Diniorphis m.-On isomorphism dimorphism polymerism and heteromerism by Dr. u. KoltelE. J. pr. Chem. xlix 469. Diphene.-On the nitrogenous compounds of the diphene series by Lawent and Gerhurdt. Ann. Ch. Pharm. lxxv 67. Disinfection.-On a disinfecting compound by 111. Herpin. Chem. Gaz. 1S.50 50. Dropsy.-Examination of the liquid from a case of ovarian dropsy by T. J. Herapalh. Idem. 88. Dulcine.-Memoir on dulcine by V. Jacqueluin. Compt. rend.xxxi 625. TITLES OF CHEMICAL PAPERS Du1cose.-On dulcose a homologue of grape sugar by A. Laurent. Compt. rend. xxx 41. -Note on dulcose and on bromobenzoic and chrysammic acid by A. Lau- rent. Idem. 339. -Note upon dulcose by A. Laurent. Idem. 694. E. Earth.-On the solubility of different earths in eau sucrek by W. Rumsay. Rev. Sci. xxuviii 115. Eddoes.-Analysis of the ashes of the eddoes (Arum esculentum,Linn. Colocasin esculenta Schott) by T. J. Heraputk. Chem. SOC.Qu. J. iii. 193. Eggs.-Analysis of the ash of the white and yolk of the eggs of poultry by 2%. Poleck. Pogg Ann. Ixxix 155. -Observations on the freezing of the albumen of eggs by T. Bell. Phil. Trans. 1850 i 221 ; also by J. Puget. Chem. Gaz.1850 271. -On sugar in the albumen of eggs by Barreswil J.pr. Chem. 1 134. -On the alkaline reaction of the albumen of eggs by Barreswil. Idem. 134. -Emulsive substance in the yolk of eggs by Barreswil. Idem. 137. -Acid in eggs by Barreswil. Idem. 134. -Chemical examination of the eggs of the carp by M. Gobley. J. Pharm. xvii 401 ; xviii 107. Elastic Fluids.-Influence of the known laws of motion on the expansion of elastic fluids by €3. W.Blake. Sill. J. [2] ix. 334. Electrici ty.-Comparative researches in voltaic and statical electricity by M. MJne. Compt. rend. xxxi 427. -On the transmission of electricity through insulating bodies solid and gaseous by Ch. Mntteucci. Ann. Ch. Phys. [S] xxviii 385. -On the superficial conductibility of crystallized bodies for electricity of tension by H.de Senarmod Idem. 257. -On the relation between the electrical conducting power of sulphuric acid and its temperature and degree of concentration by E. Becker. Ann. Ch. Pharm. Ixxv 94. -On the relation between the electrical resistance of certain liquids and their temperature by 0.B. Xiihn. Idem. lxxiii 1. -Development of electricity in the cooling of heated metals in liquids by 2'. C. Henrici. Pogg. Ann. Ixxix 170,473. -Current in an insulatedand unclosedvoltaic circuit by Guillemin. Idem. 333. -Experiments on the electricity of a plate of zinc biiried in the earth by E. Lewis. Sill. J. [Z] ix 1. -On the application of carbon deposited in gas retorts as the negative plate in the nitric acid battery by C.L Dresser. Phil. Mag. xxuvii 219. -On gas-batteries by G. Own%. Pogg. Ann. lxxix 576. I_- Note on the chemical phenomena and the light of the voltaic battery with two liquids :by C. Lfespretz. Compt. rend. xu 418. -On the source of the electromotive power in Daniell's battery by R. IcbliZ-ruusch Pogg. Ann. lxxix 177. -_. On the variations in the strength of the current produced by heating or agitating the electrodes by V.Beetz. Idem. 98. -Communications relating to galvanism by F. C. Henrici. Idem. 568. IN BRITISH AND FOREIGN JOURNALS. 433 Electricity.-Mode of protecting electrical machines from dampness.-€'harm. J. x 42. -On the useful effects of the galvanic batteries most generally employed by M.Ward. Rev. Sci. xxxix 34. -Batteries used in gilding and silvering. Idem. 46. -New experiments on the voltaic arc by Ch. Nutteucci. Compt. rend. xxx 201. v Experiments on carbon and on the length of the voltaic arc by C. DesprPtz. Idem. 367. -On the electromotive force of gases by W. Beetz. Phil. Mag. xxxvi 81. -On the electric properties of crystallized bodies by G. Wiedemuan. Ann. Ch Phys. L3] xxix 229. -On the electricities of steam by Reuben Phillips. Phil. Mag. xxxvi 503. I-On the electricity of condensation by R. PhiZZips. Idem. 303. -On the escape of friction-electricity from bent wires-the electrical brush by J. Lowe. Pogg lxxix 576. --On the laws of electro-magnetism by J. Miiller. Ann. Ch. Pharm. lxxv 247.-On the magnetization of iron by the electric current by Buf and Zurn-miner. Idem. 83. -Electro-physiological researches by C. Nutfeucci. Phil. Trans. 1850 i 257. -Researches on the causes of the development of electricity in vegetation by M. Becquerel. Compt. rend. xxxi 633. -On the electricity of flame and the electric currents thereby produced :by T.Henkel. P~gg.Ann. lxxxi 213. -On the constant appearance of light at the negative pole of the voltaic pile by the AbbkMoigno. Idem. 318. Emery.-On emery and the minerals associated with it by J. L. Smith. Phil. Mag. xxxvi 396. Endosmose.-On certain phenomena of capillarity which may serve to explain the effect of endosmose by P. Coulier Compt. rend. xxx 711. Equisetum.-On the acid of the Equisetum ftziviatile and on certain aconitates by M.Baup. Idem. xxxi 387 ; Ann. Ch. Phys. [3] 312. Ergot.-On Secale cornutunt and its fixed Oils by Dr. Bertrand. Pharm. J. x 133. -On ergotine and extract of ergot by Dr. IqeahohZ. Idem. 132. Erythrose.-On erythrose the colouring matter of rhubarb by M. Meurin. J. Pharm. [3] xvii 179. Ether.-On the preparation of various kinds of ether by means of potash and different natural balsams by E A. Schurling. Ann. Ch. Pharm. lxxiv 230. -On the compounds produced from cyanic acid and ether by Dr. Limpricht. Idem. 208. Ethers.-On the carbanilic ethers of alcohol and methylene by G. ChanceL Compt. rend. XXX '751. Ether Amy1ic.-Extract from a letter from X. Malagut%' to M. Dumas. J.pr. Chem. xlix 291. Etherification.-Theory of etherification by A. T.Villiamson. Phil. Mag. xxxvii 350; Compt. rend. trav. chim. vi 354.-Remarks on the preceding by C. Gerhardt. Idem. vi 361. VOL 111.-NO. XII FF TITLES OF CHEMICAL PAPERS Etherification.-On the theory of etherification and a new class of ethers by G. Chancel. Compt. rend. trav. chim. vi 369; Compt. rend. xxxi 521. -Observations on etherification by T. Gruham. Chem. SOC. Qu. J. iii 24; also Ann. Ch. Pharm. lxxv 196.-Remarks on the preceding Ann. Ch. Pharm. lxxv 115. -Note on Mr. Graham's Memoir on etherification by N. Buignet. J. Pharm. xviii 130. Ethyl.-On the antimonide of ethyl by C. Liiwig and E. Schweizer. J. pr. Chem. xli 385. Ethy1amine.-On the direct preparation of ethylamine and alanine by A.Strecker. Idem. 1 56. -On a new mode of formation of ethylamine by A. Strecker. Ann. Ch. Pharm. lxxv 46. Ethylene.-On the action of cblorine and bromine on prophylene ethylene and their homologues by A. Cahours. Compt. rend. xxxi 291. Eudiometry.-By R. F. Narchand. J. pr. Chem. xlix 449. Evaporation.-Apparatus for evaporating and drying and for preparing dis- tilled water in analytical laboratories by R. Presenius. Idem. 1 130. Explosion.-On the explosions of burning fluids by 3.Horsford. Chem. Gaz. 1850 48. F. Faeces.-On the composition of the fwes of man in health and in diabetes mellitus by J. Percy. Chem. Gaz. 1850 102 and 122. -Amount of nitrogen in the faxes of diabetic patients by D.Campbell. Idem. 155. Faham.-On the odoriferous principle of Faham leaves by M. Gobley J. Pharm. (3) xvii 348. Fat.-Estimation of tRe fatty matter in a muscle which has been converted into fat by M. Liebig,jula. Rev. Sc. xxxviii 107. -On the composition of shea-butter and vegetable fat by MH. Thomson and Wood. Idem. 234. Fecul a,-Examination of sugar and fecu1a.-Idem. xxxix 1. Ferrocyanides.-On certain new compounds of ammonia with the ferrocya- nides and particularly with the ferrocyanide of nickel I by A. Reynoso. Ann. Ch. Phys. [S] xxx 252. Ferrocyanide.-Process for obtaining ferrocyanide of potassium and urea by Dr. Brand. Rev. Sci. xxxviii 418. Fibrin.-On the fibrin of muscular flesh by J. Liebig. Ann. Ch. Pharm. lxxiii 125.-On the diminution of the amount of fibrin by agitation of the blood by N. Calvi. Compt. rend. xxx 30. Flour.-On the principal adulterations of flour and bread by N Donny. J. pr. Chem. xlix 240. -Modes of discovering adulterations of flour by Martens. Idem. 1 363. Fluorine.-On the quantitative determination of fluorine by H. Rose. Pogg. Ann. lxxix 112 ;J. pr. Chem. xlix 309. -Onthe presence of fluorine in blood and milk by G. Wilson. Chem. Gaz. 1850 366. IN BRITISH AND FOREIQN JOURNALS Frigorific Mixtures.-On a peculiar reaction which takes place in forming a frigorific mixture with Glauber’s salt and hydrochloric acid by R. BoZZey. Ann. Ch Pharm. lxxv 239. G. Garlic.-On the essential oils of garlic and mustard by A. Laurent.Compt. rend. xxx 126. Gas.-Description of an apparatus for regulating the heat produced by a gas- burner by A. Kip. Phil. Mag. xxxvi 483. -Remarks on the preceding by W.K. Westly. Chem. Gaz. 1850,239. -On the purification of coal-gas by Mr. Laming. Idem 218. -On the use of coal-gas in chemical experiments by 0. B. liriihn. Ann. Ch. Pharm. lxxiv 115. -Preparation of gas from resin and use of the residues :by Mr. Robertson. Rev. Sci. xxxix 16. -On the ‘(Hydrocarbon,” or resin and water gas by A. Fyfe. Pharm. J. x 131. Gases.-On a safe and simple method of demonstrating the liquefaction of gases and particularly of carbonic acid gas :by X.BertheZot. Compt. rend. xxx 666 ;Ann. Ch. Phys. [a] xxx 237. -On the electromotive force of gases by W.Beetz.Phil. Mag. xxxvi 8 I. -Detail of some experiments on the gases generated in a sewer by N. ScanZan and A.Anderson. Chem. SOC. Qu. J. iii 13. Gasometer.-On a new and simplified gasometer by W.Bel& Pogg. Ann lxxix 428. Ge1atine.-On the composition of gelatine :by T.S. Hunt. Compt. rend. trav. chim. vi 317. Gilding.-Report by M. Ebelmen on a new process for gilding on porcelain by M. Grenou. Bull. SOC.Ind. 1850 38. Githagine.-Ongithagine by E. A. ScharZing. Ann. Ch. Pharm. lxxiv. 351. Glycocol1.-On the artificial formation of lactic acid and on a new substance homologous with glycocoll by A. Strecker. Idem. lxxv 27. Gold.-Observations on sulphide of gold and determination of the atomic weight of gold by a new method by A.Leuol. Ann. Ch. Phys. [33 xxx 355. -Extraction of gold from the copper ores of Chessy and Sain-Bel by HM. Allaist and Bartenbach. Chem. Gaz. ’1850 17. -Analysis of Californian gold :by F. OswoZd. Idem. 23. -On the occurrence of gold in Sarawak by C. Grant. Idem 71. -On an auriferous limestone from La Grave (Hautes-Alpes) by M hey-mar& Ann. Min. xvi 379. -Analysis of different specimens of Californian gold by M. Riuot. Idem. 127. -Experiments on the extraction of gold and silver from their ores in the wet way by J. Percy. Phil Mag. xxxvi 1. -Analysis of certain compounds of gold and silver by A. Levol. J. pr. Chem. xlix 171. -__. Comparative examination of the auriferous sands of California New Gra- nada and the Ural by M.Bufrdnoy. Ann. Min. xvi 111. -On the refining of gold by Dr. Philipp. Chem. Gaz. 1850. 386. FF~ TITLES OF CHEMICAL PAPERS Grain.-On the composition of various kinds of grain by E. Yeligot. Ann. Ch. Phys. [3] xxix 5. Graphite.-Oxidation of graphite and diamond in the humid way by R. E. Rogers and W R. Rogers. J. pr. Chem. 1 4 11. -_I Analysis of artificialgraphite by 3’. Frightson. Chem. Gaz. 1850,27. GuaXcuru.-Chemicalexamination of aroot which grows in the Eastern Repub- lic of Uruguay (Monte Video) and called by the Indians gua’icuru :by M. Lenoble. J. Pharm. [3] xvii 200. Gun- cotton.-Its explosive properties and application to fire-arms-different cases of its spontaneous combustion-the temperature at which it inflames.-Rev.Sci. xxxviii 17’5. -Method of silvering glass by means of gun-cotton by M. WohL J. Pharm [3] xvii 141. -Spontaneous decomposition of gun-cotton by T.€I Pharm. Fustin. J. ix 405. -Temperature at which gun-cotton explodes.-Chem. Gaz. 1850,80. Gunpowder.-On a new gunpowder the base of which is the prussiate of potash by M. A%gendre. Compt. rend. XXY 179. Gutta percha.-Vulcanized caoutchouc and gutta percha. J. Pharm. [3] xvii 305. -New kind of gutta percha.-Rev. Sci. xxxix 13. H. Halogens.-On the compounds of the halogens with phosphorus by J. H. Gladstone. J. pr. Chem. xlix 40. Heat,-On the measurement of temperatures by thermo-electric currents :by I’ Regnault. Phil. Mag. xxxvi 409. -Report on the development of heat in chemical combination by T Andrews.J. pr. Chem. 1 469; Phil. Mag. xxxvi 51. -On the development of heat by the substitution of one metal for another by T.Andrew. Pogg. Ann. lxxxi 73. -On the influence of elements on the boiling point (third memoir) by H. Schroder. Idem Ixxix 34. -Observations on freezing and boiling points by J. A. G-roshans. Idem. lxxix 390. -On the mechanical action of heat especially in gases and vapours by M. Rankine. Trans. Roy. SOC.Edinb. xx 1 147. -On the mechanical equivalent of heat by J. P. Joarle. Phil. Trans. 1850 i 61 ; abst. Chem. Soc. Qu. J. iii 316. -On the mechanical theory of heat by H. Rankine. Pogg. Ann. lxxxi 172. -On the expansion of mercury by heat by H. Militzer. Idem lxxx 55. -On the latent heat of water by C.C. Person. Ann. Ch. Pbys. [3] xxx 73 ; Compt. rend. xxx 256. -Specific heat of water at different temperatures by T. Regnnutt Pogg Ann. lxxix 24 I. -On the specific heat of saline solutions and on the quantity of heat ren-dered latent on solution by C. Person. Compt. rend. xxxi 566. -_. On a new process of heating and illumination by means of pure hydrogen by 0.Henrgl,jun. J. Pharm. [3] xvii 105. IN BRITISH AND POREION JOURNALS. Heat.-On the thermic properties of the tourmaline by H. de Senarmont. Ann. Ch. Phys. [3] xxviii 279. He1enine.-Easy mode of preparing helenine by W. Delfs. Pogg. Ann. kxx 440. Hemlock.-On extract of hemlock by W.Archer. Pharm. J. x. 265. Heteromerism.-On isomorphism dimorphism polymerism and hetero- merism :by Dr v.Kobell. J. pr. Chem. xlix 469. Honey.-On the composition of honey and on certain properties of sugar by E. Soubeirun. Idem. 65. Horse.-On the inorganic constituents of the flesh the coagulum and the serum of the horse :by R. Wiber. Pogg. Ann. lxxxi 91. Humus.-Chemical analysis of humus and on the function of manure in the nutrition of plants by M. Soubeiran. J. Pharm. xviii 5. Hydraulic mortar.-On certain lime-stones of Basse-Bretagne and their conversion into fat limes and hydraulic mortars :by M. Hobliti. Compt. rend. xxx 354. Hydrogen.-On the combustion of hydrogen in oxygen chlorine bromine and iodine by M. Bussy. J. Pharm. [3] xvii 20 ; Pharm. J. ix 441. -On the use of hydrogen in mineral analysis by L. E. Rivut.Ann. Ch. Phys. [3] xxx 188. -Carburet ted.-On a spontaneous and continuous eruption of carburet-ted hydrogen gas by Mr. Howard. J. Pharm. [@Ixvii 136. -Process for obtaining carburetted hydrogen by J. 3’. Cuwaillon. Pharrn. J. ix 441. Hyraceum.-On hyraceum (the dried urine of the Hyrux capensis). -J. Pharm [3] xvii 138. I. Ice-plant.-On the watery secretion of the leaves and stems of the ice-plant (~~se~~~an~he~~urn crystallinurn) by A. Yolcker. Phil. Mag. xxxvi 377. Illumination.-On a new process of heating and illumination by means of pure hydrogen by 0. Henry jun. J. Pharm [3] xvii 105. -Description of various improvements by M.Pauwels in the system of illumination by hydrogen gas.-Bull Soc. Ind. 1849 568. Incombustibility.-On the momentary incombustibility of living organic tissues andon the physical constitution of bodies in the spheroidal state by N.Boutigny. Ann. Ch. Phys. [3] xxviii 158. Incrustation.-On the incrustation which forms in the boilers of steam-engines by J. Duwy. Chem. Gaz. 1850 343. -Remarks on the use of the alkaline carbonates for preventing incrus- tation in steam-boilers by A. Anderbon. Chem. SOC. Qu J. iii 13. Indigo.-On a new indigometric process by R Bolley. Ann. Ch. Pharm. Ixxv 242. Iodine.-Existence of iodine in fresh-water plants by A. Chatin. Compt. rend. xxx 352 467 xxxi 280; Ann. Ch. Pharm. lxxv. 61 ; J. Pharm. [S] xvii 418 xviii 241 ;also by J. Personne. Compt. rend XXX 478. -On the existence of alkaline iodides and bromides in the plants of the order Oscillariacece living in the thermal waters of Dax (Ddpartement de Landes) by ??Miyrac.Compt. rend. xxx 457. 438 TITLES OF CHEMICAL PAPEBS Iodine.-On a inode of obtaining iodine on thelarge scale from certain species of sea-weed by G. K~mp. Chem. GaZ."1850 250. -On the existence of iodine in land-plants by Prof. Feehling. Ann. Ch. Pharm. lxxv 67. 7 On the extraction of iodine from plants and from the products of the distillation of coal by H. Bussy. Compt. rend. xxx 537. I-On the existence of iodine in beet-root by N. Lamy. J. Pharm. xviii 33. -_. On the presence of iodine in aluminous schists.-Chem. Gaz. 1850 46. -New experimental researches on the use of pure nitric acid in conjunction with gelatinous starch to discover the presence of iodine in mineral waters s by M.Cusecca. Compt. rend. xxx 821. -Solubility of iodine in cod-liver oil by Fleischman. Pharm. J. ix 541. -On the presence of iodide of cyanogen in commercial iodine by T,&lo-bach. Arch. Pharm. lx 34 ; Chem. Gaz. 1850 159. -Decomposition of iodide of potassium in the dry way by F. SchGnbein. Chem. Gaz. 1850 166. -New modes of preparing iodide of starch by Dr. QuesneviEle. Rev. Sci. xxxsiii 42 1. -On the definite compounds of iodine and phosphorus :by B. Corenwinder. Compt. rend. xxxi 172. -Impurities and alterations of iodine by Dr. Herzoz. Pharm. J. x 31 1. -On tincture of iodine by M. Gopel. Idem 79. -On the presence of iodine in fresh waters and in land plants by M.Mar-ehund. Compt. rend. xxxi 495. Iron.-On the chemical equivalent of iron by E Muumenk. Idem. 589 ;Ann. Ch. Phys. [3] xxx. 380. -On the iron-ore of Florange (Moselle) by J. Lovallois Ann. Min. xvi. 241. -On smelting magnetic iron-ores by H. Fairburn. J. Frank. Inst. xix 125. -Analytical investigation of cast-iron by Mr. Frightson. Idem. 141. -Analysis of meteoric iron by C. Reichenbach. Pogg. Ann. lxxxix 498. _-Analyses of soft iron obtained by cementation of cast-iron also of cold- short and red-short iron by W.A. Hiller. J. pr. Chem. I 431. -Analysis of a specimen of hot red-short and cold-short bar-iron by Dr. Rubach. Ann. Ch. Pharm. lxxiv 360. -_. Analysis of several native carbonates of iron from the coal-pit on the Ruhr by Schnabel.Pogg. Ann. lxxx 441 _.-On a new method for the determination of iron in clay-band and black- band ironstone by F.Peaty. Chem. Gaz. 1850 330. -On the amount of nitrogen in pig-iron and steel by R. F. Marchand. J. pr. Chem. xlix 351. -On the amount of carbon and sulphur in certain kinds of iron by A. Bachner sen. Ann. Ch. Pharm. lxxiii 215. -On the residue left in the solution of cast-iron by J. Hull. Idem. Ixxiv 112. -On a new method of separating iron from its compounds by J. A. Pou-mnr2de. Compt. rend. xxix 518 ; Chem. Gaz 1850 136. IN BRITISH AND FOREIGN JOURNALS. 439 Iron.-Process for glazing cast-ironvessels byMr.Kenrick. Rev. Sci.xxxix 108. -Compounds of sesquioxide of iron by 3’. XchonbPin. Chem. Gaz. 1850 167.-On the nitrates of iron and some other nitrates by J. H.Ordway. Sill. J. 12) ix 30. -Protection of iron from oxidation by W. Rankin. Frank. Inst. J. xlix 209. -How to preserve protosulphate of iron from oxidation by M. Ruspini. Chem.Gaz 1850 293. -Mode of facilitating the amalgamation of iron by M. Bollger. Rev. Sci. xxxix 110. -On the zinking and tinning of wrought and cast iron by M. Sorel. Idem. 111. Isinglass.-On the adulteration of isinglass by I! Redwood. Pharm. J. ix 506; x 26. Isom orphism.-On isomorphism dimorphism polymerism and heterome- rism by Dr. v. Kobell. J. pr. Chem. xlix 469. -Note on heteronomic isomorphism by J.Dana. Sill. J. [2] ix 407. -On the cause of the isomorphism of dissimilar compounds by C. Ramrnels-berg.Pogg. Ann. lxxx 449 ; lxxxi 1. -General remarks on polymeric isomorphism by Th. Scheerer. J. pr. Chem. 1 449. -On the isomorphism and atomic volume of some minerals by J. D. Dana. Sill. J. [2] ix 220. K. Kermes.-On the use of kermes as an antidote for strychnine and nux vomica by H. Thorel. J. Pharm. [3] xvii 185. -Report on the memoir of M. Thorel by HM.Gobley and Bouchardut. Idem 190. L. Lead.-On the presence of lead in sea-water by MM. Nalaguti Durocher and Sarzeuud. Ann. Ch. Phys. r3) xxviii 129. __.-Extraction of metallic lead from the sulphate by M. Schnedermunn. Rev. sci. xxxix 193. -Preparation of sugar of lead with pyroligneous acid by F. Schnedermann. Pharm. J. x 36. .__-Action of water on leaden pipes and method of estimating small quan- tities of lead by Mr.Horford. Rev. Sc. xxxix 105. -On nitride of lead oxide by H. Blei. J. pr. Chem. 1 380. -Process for making lead-plaster by W. BnrtEett. Pharm. J ix 457. -On spongy lead by H. BoEley. Chem. Gaz. 1850 216. -On sulphite and sulphate of lead by E. La&. Pharm. J. x 248. -Poisonous effects of sulphate of lead by C. Flundin. Idem. 191. -On the poisonous qualities of sulphate of lead by Drs. Gregovy and Christison. Idem. 251 ; also by E. Greaves. Idem. x 265 -On the use of lead in the manufacture of sugar. Improved method of extracting tin lead &c. Idem. 177 243. from their ores. Idem. 74. 440 TITLES OF CHEMICAL PAPERS Leucine -On the composition of leucine by A. Strecker. Ann.Ch Pharm. lxxii 92 -Note on the composition of leucine by M. iWulder. J. Pharm. 133 Xvii 490. -Reply to the above by N. Gerhardt. Idem. xvii 134 ; also Compt. rend. trav chim. -Remarks on the constitution of leucine with critical observations on the late researches of M. Wurtz by T.S. Hunt. Sill. J. ix 63. Lime.-Preparation of hisulphite of lime by MM. M&neand Pinchon. Pharm. J. x 41. -On the separation of the lime contained in the defecated juice of the beet- root.-Rev. Sci. xxxviii 115. -On the separation of lime by A. Reynoso. Chem. Gaz. 1850 38 -_. On the properties of oxalate of lime by A. Reynoso. J. pr' Chem. xlix 51 I. Liquids.-On the diffusion of liquids by T Graham. Phil. Trans. 1850,i 1 ; also Ann. Ch Phys. [S] xxix 197 ;abstr.Chem. SOC. Qu. J. iii. -Researches on the physical properties of liquids and particularly on their dilatation by J. I. Pierre. Compt. rend. xxxi 378. Liquids.-On certain phenomena of the forced dilatation of liquids by M. BPrtheZot. Ann. Ch. Phys. [3] xxx 237. -Note on the effect of pressure in lowering the freezing-point of liquids by R. Clausius. Pogg. Ann. lxxxi 168. Lobeline a volatile organic base from Lobelia inpata by ?T.Baslick. Pharm. J. x 270. Madder.-On the red colouring matter of madder by J. Wolf and A. Strecker. Ann. Ch. Pharm. lxxv 1. Chem. Soc. Qu J. 243. Magnesia.-Contributions to the history of the alcoholates and of nitrate of magnesia by A. Chodnew. J. pr. Chem. xlix 107. -Fibrous hydrate of magnesia. -Phil.Mag. xxxvi 552. -On the separation of the alkalis from magnesia by iM. Ehelmen. Ann. Ch. Phys. [3] xxx 334. Magnesium.-On the equivalent of magnesium by Marchand and Xchewer. J. pr. Chem. 1 385. Magnetism.-Influence of magnetism on the cohesion of liquids by C. Branner jun. Pogg. Ann. lxxix 141. Manganese.-On the state in which arsenic and manganese occur in the incrustation of the boiling spring at Wiesbaden by R.Fresenius. Ann. Ch Pharm. lxxv 172. Mannite.-On the atomic weight of mannite by M. Knop. J.pr.Chem. xlviii 362 ; J. Pharm. [31 xvii 239. -On certain compounds of mannite by Knop. Ann. Ch. Pharm. lxxiv 347. -On the production of mannite by the Aconitum Napellus by I and H. Smith. Pharm. J. x 124. Manure.-On the influence which the nitrogen in manure exerts upon the amount of proteine in the crop by E.John J. pr. Chem. 1 57. IN BRITISEI AND FOREIGN JOURNALS. 441 Manure.-on the function of manure in the nutritiotl of plants by M. Sou-beirait. J. Pharm. xviii 5. -On the disinfection of manures and on the means of rendering useful the mother-liquors of salt springs :by Ch. Calloud. Idem. xvii 28. -Extract from a report on the disinfection of an establishment for the pre- paration of animal manure by R.Duparc. Idem. 39,. Mariotte's Law. -On the interpretation of Mariotte's law by E. I? Hunt. Sill. J. (2) ix 412. Meconium.-on the detection of spots produced by meconium (in chemico- legal investigations) by R. Presenius. Ann. Ch.Pharm. lxxv 116. Mellom-On certain decomposition products of mellonide of potassium by 7.t Hennebery.Idem. lxuiii 228. -On the Composition of mellon and the mellonides :by Ch. Cerhardt. Compt. rend. xxx 3 18. Membrane.-On the chemical composition of arterial membranes by M. SchuZtze. Rev. Sci. xxxix 201. Mercury.-On the expansion of mercury by heat by H. Militzrr. Pogg. Ann. lxxx 55. -On the oxychlorides of mercury by C. Roncher. J. pr. Chem. xlix 363. -On the mode of action of the grey salts of mercury and mercurial vapours by F. Yon Barensprung. Idem. 1 21. -On the distillation of mercury by means of high-pressure steam by M. Yiolette. Compt. rend. xxxi 546. Mesitilo1e.-On the composition of mesitilole by A. Cahaurs. Chem. SOC. Qu. J. iii 17.Metals.-Method by which all the metals contained in a suspected substance may be obtained by one operation (in chernico-legal investigations) by M. Gaultier de CEaubry. J. Pharm. [3] xvii 125. -On the crystalline forms of certain rhombohedra1 metals by #. Rose. J. pr. Chem. xlix 158. -On Aridium probably a new metal by M. Ullgren. Chem. Gaz. 1850 289. Mildew.-On the cause and preventives of mildew in paper and parchments by A. Gyde. Tdem. 259. Millet.-Analysis of the ash of millet-seed by R. Fildensfeii~. J. pr. Chem. xlix 152. Minerals.-Experiments on the artificial formation in the humid way of cer- tain mineral species which may have been produced in thermal springs under the combined influence of heat and pressure by H.de Senar-moat. Ann.Ch. Phys. [3] xxx 129. -Researches on the artificial production of certain crystalline mineral species particularly of stannic oxide titanic oxide and quartz by A. Duubre'e. Ann. Min. xvi 129 ; Compt. rend. xxx 383. -Analysis of several minerals by W. Fisher. Sill. J. [3] ix 83. -On the galvanic relations and conducting power of minerals as a mode of distinction by Prof. Kobell. J. pr. Chem. 1,76. -On the hardness of minerals and a new mode of determining it by R. Franz. Pogg. Ann. lxxx 37. -Examination of certain minerals (Deckenite Yellow Lead-ore and Arse- niate of Lead from Azulaques) by C. Bergemann. Idem. 393. TITLES OF CHEMICAL PAPERS Minerals.-Description and analysis of several American minerals by B.Sillimun. J. pr. Chem. xlix 195. -Investigation of North American minerals (Nemalite Orthite Black oxide of Copper) by C Rammehberg. Pogg. Ann. lxxx 284. -New minerals from Norway described by P. H. Weibye and analysed by N. J. Berlin K. A. Sjogren and J. B. von Borck. Idem. lxxix 299. -On the metalic minerals of the Upper Rhine by Jl,Furiet Bull. SOC. Ind. 1850 207. -On some minerals recently investigated by M. Hermann by J. D. Dana. Sill. J. [21 ix,408. Minerals Aegyrine by A. Breithuupt. Pogg. Ann. lxxx 314. Albite.-On a granular Albite associated with corundum by B. Silliman,jun. Phil. Nag. xxxv 484. Algerite,-a new mineral species :by R. Crossley. Idem. xxxvii 179. Allani te.-On the occurrence of Allanite at Schmiedefeld in the Thuringer Wald by H.Credener. Pogg. Ann. lxxix 144. Araoxene.-On Araoxene a new vanadiate of lead and zinc by Fr. V. Kohell. J. pr. Chem. 1 496. Arkansite.-On the identity of Arkansite and Brookite by R.Hermann. Idem. 200 Beudantite.-On the composition of Beudantite :by J. Percy. Phil. Mag. xxxvii 161. .. . . On the crystalline form of Beudantite by H. J. Brooke. Phil. Mag. xxxvii 349. Brogniardtite.-Notice on Brogniardtite a new mineral species by M. Damour. Ann. Min. xvi 227. Brookite.-On crystals of Brookite from the Ural Mountains by N.V. Kokscharow. Pogg. Ann. lxxix 454. .. On the identity of Arkansite and Brookite by R. Hermann. J. pr. Chem. 1 200. Calamine.-On the geological position of Calamine ores :by J.Delamine. Compt. rend. xxx 765. Carmine-spar,-a new mineral belonging to the order of arseniates by F-Sundberger. Pogg. Ann. lxxx 391. Castor.-On Castor and its relations to Petalite by 0. Roue. Idem. lxxix 162. Diaspore.-Note on the crystals of Diaspore from Gumuch-dagh near Ephesus :by M. DufrLnoy. Compt. rend. xxxi 185. Diorite.-On the Diorite of Pont-Jean (Vosges) by M. Delesse. Compt. rend. xxx 176 ; Ann. Min. xvi 367. Dolomite.-Contributions to the history of the formation of Dolomite by G. Forchhammer. J. pr. Chem. xlix 52. Analysisof Dolomite from the upper strata of the Muschel- kalk near Saarbriicken by R. Wi'ldenstein. Idem. 154. .. From the Altenberg :by K. Monheim. Idem. 318. Enargite,-a new mineral belonging to the order of Glances :by A.Breit-haqt and C. F. Plnttner Pogg. Ann. lxxx 383. Euphotide.-On the Euphotide of Odern by M. Delesse. Compt. rend. xxx 148 ;Ann. Min. xvi 367. IN BRITISH AND FOREIGN JOURNALS. Minerals Euphotide.-On the Euphotide of Mont Genbvre by M. Delesse. Ann. Min. xvi 233. Fe1spar.-On the Felspar of the Zircon-syenite of Southern Norway by C. G. Gmelin. Pogg. Ann. lxxxi 3I 8. Franco1ite.-On Francolite a supposed new mineral by T. H. Henry. Phil. Mag. sxxvi 134. Gold.-On the minerals of the auriferous districts of Wicklow :by W. Mallet. Idem. xxxvii 392. . . On an auriferous limestone from La Grave (Hautes-Alpes) :by M. heymurd. Ann. Min. xvi 379. .. Comparative examination of the auriferous sands of California New Granada and the Ural :by M.Dufr4noy. Idem. 1 1I. Halloysite from the Altenberg near Aachen by K. Monhein. J. pr. Chem. xlix 318. Hydrargy1ite.-On Hydrargylite from Brazil by 2%. w. KobeEE. Idem. 1 493. Hyposk1erite.-On the Hyposklerite of Arendal by C. RamnaeZsbm*g. Pogg. Ann. lxxix 305. 1docrase.-On Manganese-idocrase by Wrebsky. Idem. lxxix 166. Indianite -On a granular Albite associated with Corundum and on the Indianite of Bournon by B. SilEiman,jun. Phil. Mag. xxxv. 484. Iron.-On the Iron-ore of Florange (Moselle) by J. LevaZEois. Ann. Min. xvi 241. .. Analysis of several native carbonates of iron from the coal-pit on the Ruhr :by Sciinabel. Pogg. Ann. lxxx 441. Iron spathic.-Green spathic iron from the Altenberg by K.Nonheim. J. vr. Chem. xlix 318. Kapnite.-Zinc-iron-spar (Kapnite) from the Altenberg by K. Monhek. Idem. xlix 319. Lancasterite a new American mineral by B. Sillimun. Sill. J. fa] is 216. Leuchtenbergite by A. Breithaupt. Pogg. Ann. lxxx 577. Lett somite.-Chemical examination of Lettsomite (Velvet ore) by J. Percy. Phil. Mag. xxxvi 100. Lime -stone.-On certain limestones of Basse-Bretagne and their con- version into fat limes and hydraulic mortars :by M.. HobEin. Compt. rend. xxx 354. .. On an auriferous lime-stone from La Grave (Hautes-Alpes) by M. Gueyrnurd. Ann. Min. xvi 379. Mic a.-On the chemical composition of Cupreous Mica (Kupferglimmer) from the Andreasberg by C. Rammelsberg. Pogg;. Ann. lxxix 465. Misy.-Analysis of Misy from the Rammelsberg near Goslar :by Dr.List.Ann. Ch. Pharm lxxiv 339. Muschel kalk from the neighbourhood of Saarbriicken.-J. pr. Chem. xlk 382. Nema1ite.-Phil. Mag. xxxvi 552. Nephe1ine.-On the Nepheline rock of the Lobauberg by Dr. Hkide-prien. J. dr. Chem. 1 500. Nontronit e from the Andreasberg.-Idem. xlix 382. TITLES OF CHEMICAL PAPBRS Minerals Pegmatite.-On the Pegmatite of the Vosges by M. Delesse. Ann. Ch. Phys. [3] xxviii 124 ;Ann. Min. xvi 97. Pecto1ite.-Analyses of Pectolite and Stellite and proposed union of these two species by J. D. Vhitney. Phil. Mag xxxvi 553. Percy1ite.-On Percylite a mineral not hitherto described by H. J. Brooke; with chemical examination by J. Percy. Idem xxxvi 131. Picroli te.-Analysis of Picrolite from Reichelstein in Silesia by Dv.List. Ann. Ch. Pharm. lxxiv 241. Porph yry.-On the quartziferous Porphyry and Euphotide of Mont-GenBvre by A. IJeZesse. Ann. Min. xvi 233. .. On the Porphyry of Schirmeck by R. Delesse. Idem. 367. Pumice.-On a bed of pumice-stone near Marburg :by H. Hessel. Pogg. Ann. lxxix 3 19. Pyromorphite from the Buschbachberg.-J. pr. Chem. xlix 381. Schists.-Facts and observations relating to the history of bituminous schists by M. Delahuye. Rev. Sci. xxxviii 1 49 97 225 321 337. Serpentine.-On the mineralogical and chemical constitution of the Ser- pentine of the Vosges by M. DeZesse. Compt. rend. xxxi 210. Silver.-On a natural alloy of silver and copper from Chili by F Field. Chem. SOC.Qu. J. iii 29. Stel1ite.-Analyses of Pectolite and Stellite and proposed union of these two species :by J D. k8hitney. Phil. Mag. xxxvi 553. Talcspar.-On Talcspar :by A. Breithaupt. Pogg. Ann. lxxx 313. Tourmaline.-On the composition of Tourmaline compared with that of Mica and Felspar and on the cause of the isomorphism of dissimilar compounds -by C. RamrneZsberg. Pogg. Ann. lxxx 449 ; lxxxi 1. .. On the crystalline system of the Tourmaline by A. Sey-meric. Compt. rend. xxx 707. .. On the thermal properties of theTourmaline by H. de Se-narmont. Pogg. Ann. lxxx 175. Vario1ite.-On the Variolite of Durance by M. Delesse. Compt. rend. xxx 741. Velvet Ore.-Chemical examination of Lettsomite (Velvet ore); by John Percy. Phil. Mag. xxxvi 100.Vo sges.-On the mineralogical and chemical constitution of the rocks of the Vosges by M. Delesue. Ann. Min. xvi 97. .. On the Pegmatite of the Vosges.-Ann. Min. xvi 97; Ann Ch. Phys (3) xxviii 124. Willemite from the Buschbachberg near Stolberg by K. Honheim. J. pr. Chem. xlix 320. Wolfram.-On the chemical composition of Wolfram by R. Schneider. J. pr. Chem. xlix 321. .. On the crystalline forms of Wolfram :by M Descloiseazm. Ann. Ch. Phys (3) xxviii 163. Zinc-spar.-J. pr. Chem. xlix 381. IN BRITISH AND FOREIGN JOUBNALS. Minerals Zinc-iron-spar (Kapnite) from the Altenberg by K. Xonheim. J. pr. Chem. xlix 319. ManganesQ-sinc-spar from the Herrenberg near Riom.-Idem. 382. Zinc.-Siliceous zinc-ore from the Altenberg and from Rezbanya in Hungary by X.Noniieim. Idem. Miniurn.-On the composition of minium by NuZder. Idem. 1 438. -Researches on minium by !? Jacquelain. Compt. rend. xxxi 626. Morinda.-On the colouring matter of the Morindu citrifolia by T. An-dersola. Morphine.-On the preparation of morphine by charcoal by M Diesel. Chem. Gaz. 1850,406. Mortar.-Hydraulicity and solidification of mortar.-Rev. Sci. xxxk 348. -Hyd rau1ic.-On certain limestones of Basse-Bretagne and their conver- sion into fat limes and hydraulic mortars by M. HobZin Compt. rend xxx 354. Mud.-On the mud of the Nile by Lajonchbe Puyen and Poinsot. J. pr. Chem. 1 201. Muscular Flesh.-On the fibrin of muscular flesh by J. Liebig. Ann. Ch. Pharm. lxxiii 125 ; Chem. SOC.Qu. J. iii 188. Mustard.-On the essential oils of garlic and mustard by A. Laureat. Compt. rend. xxx 126. Myroxocarpine,-a new cryatalline substance from white balsam by J. Stenhouse. Pharm. J. x 290. Myrtle.-Examination of the berries of Myrtus communis by E. Riegel. Chem. Gaz. 1850 275. N. Naphthaline.-On the sulphuric and nitric compounds of benzine and naptha- line by A. Laurent. Compt. rend. xxxi 537. Nickel.-On the densities of nickel and cobalt by M. Rammelsberg. Rev. Sci. xxxiii 11 1. -Preparation of pure nickel and cobalt on the large scale.-Idem. xxxix 202. -On certain compounds of ammonia with the ferrocyanide and ferricyanide of nickel by A. Reynoso. Compt. rend. xxx 409. Nicotine.-On some new salts of nicotine by J.Bodeker jun. Ann. Ch Pharm. lxxiii 372. Nitrates.-On the nitrates of iron and some other nitrates by J. M. Ordwq. Sill. J. [2] ix 30. Nitre.-On the formation of nitre on walls &c. by M. Mmigcautt. Compt. rend. xxxi 286. Nitrogen.-On the assimilation of the nitrogen of the air by plants and on the influence of ammonia on vegetation by H. YiZZe. Idem. 578. -On the percentage of nitrogen as an index to the nutritive value of food by A. Volcker. Chem. Gaz. 1850 337. TITLES OF CHEMICAL PAPERS Nitrogen.-% the sulphide of nitrogen by Fordos and Gelis. Compt. rend. xxxi 702. -On the influence which the nitrogen in manure exerts upon the amount of proteine in the crops by E.John. J. pr. Chem. 1 57. -On the amount of nitrogen which birds assimilate from their food by J.L Lassaigne. Chem. Gaz. 1850 216. -On the presence of nitrogen in cast-iron and steel by R. F.Marchand. J. pr. Chem. lxix 351. -On the chlorophosphuret of nitrogen and its products of decomposition by J. H. Gladstone. Part I. Chem. SOC.Qu. f. iii 135 ;Part 11. Idem. iii 354. Nitro harm alid in e.-On some compounds of nitroharmalidine :byJ. Fritzsche. Chem. Gaz. 1850 65. Nitromannite.-On nitromannite :by A. Strecker. Ann. Ch. Pharm+ lxxiii 59. Nitronaphthaline.-On some new products obtained by the action of sul-phite of nitronaphthaline by R. Piria. Compt. rend. xxxi 408. Nitroprussides.-On the nitroprussides a new class of salts by Lyon Play-fuir. Phil. Mag wxvi 197 271,348 ;also Ann.Ch. Pharm. lxxiv 317. -On the chemical formula of the nitroprussides by J. Xi$. Ann. Ch. Pharm. lxxi 340. Nutrition.-On the nutrition of plants by GoMagnus. J. pr. Chem. 1 65. -On the percentage of nitrogen as an index to the nutritive value of food by A. Yolcker. 1850 337. -On the influence of an augmentation of the saline matter on the food upon the proportion of nitrogen contained in the perspiration and in the urine by M. Barral. Chem. Gaz. 1850,47. -On the diet of the Belgian miners by H. Charpentier. Compt. rend. xxx 826. 0. Oils,-On the oils produced by the action of sulphuric acid on different vege- tables by J. Stenhouse. Ann. Ch. Pharm. lxxiv 278 ; Chem. Gaz. 1850 319. -On the behaviour of certain fixed oils with bichromate of potash and sul- phuric acid by G.Arzbiicher. Ann Ch. Pharm. lxxiii 199. -On the essential oils of garlic and mustard :by A. Aaurent. Compt. rend. xxx 126. On the light oils obtained in the distillation of wood by A. Cuhours Idem. 319. -On the oil of Croton tiylium by M. hibourt. J. Pharm. t3] xvii 181. -On the oil of asafcetida by H. Hlasiwetz. Ann. Ch. Pharrn. lxxi 23 ; J. Pharm [3] xvii 234. -On the essential oils of mustard and bitter almonds by A. Laurent. Compt rend. trav. chim. vi 8. -On the essential oil of bitter almonds by C. G. Jfitscherlich. Chem. Gaz. 1850 288. -On the volatile oxidation-products of oil of turpentine obtained by the action of nitric acid by F. C.Schneider. Ann. Ch. Pharm. lxxv 101. -Action of chloride of sulphur on oils -Rev. Sci. xxxix 13. IN BRITISH AND FOREIGN JOURNALS. Oils -On the alcohol-test of the purity of castor and croton oils by J. Pereira. Pharm. J. ix 499. -On Secule carnuturn and its fixed oils by Dr. Bertrand. Idem x 133. Opium,-Tests for opium by G. Reich.-Idem. x. 36. -Process for estimating the quality of opium by M. de Try. Idem. 77. __. On the variable strength and quality of opium by M. ChevalZier. Idem. 78. Organic Alkaloids.-Preliminary notice on the action of nitric acid on organic alkaloids by T.Anderson. Ann. Ch. Pharm. lxxv 80. Analysis.-Gas furnace for combustions in organic analysis by L. S. Beale. Pharm. J. ix. Bases.-Researches on the constitution of the volatile organic bases :by A.W. Hofmann. Phil. Trans. 1850,1 93; absir. Chem. SOC.Qu. J. iii 279. . . Researches on the volatile organic bases :by A. IT.Hofmann.-No. viii. On the behaviour of aniline and the alcohol-bases with nitrous acid.-Chem. Soc. Qu. J. iii 231. .. Investigations on the composition of certain natural organic bases by A. Planta. Ann. Ch. Pharm. lxxiv 245. I. On some new salts of organic bases by G. W. Elderhorst. Idem. 77. Radic ah-Researches on the organic radicals Part. 11 Amyl. by E. Frankland. Chem. SOC.Qu. J. iii %).-Part iii. On the action of solar light on iodide of ethyl.-Idem. iii 321 .. Note on the action of heat on valeric acid with some remarks on the formulae of the alcohol radicals by A.W.Hofmann. Idem. 121. .. observations on the preceding by C Gerhardt. Compt. rend. trav. chim. vi 233. .. On the nature and chemical constitution of the organic radi- cals by H. Kolbe. Ann. Ch. Ph. lxxv 211 ;Chem. SOC. Qu. J ii. 369. .. Observations on the constitution of the alcohol-radicals and on the formation of ethyl :by B. C. Brodie. Chem. SOC.Qu. J. iii 405. .. On Stibethyl a new organic radical containing antimony :by C.Liiwig and E. Sehweizer. Idem. 315. Organic Substances.-On the crystalline forms of certain organic sub-stances by H. Datiber. Ann. Ch. Pharm. lxxiv 200. .. On various organic compounds by A. Luurent. Compt. rend. xxxi 349. .. On the physiological action of similarly constituted organic substances :by J. Schlossberger.Ann. Ch. Pharm. lxxiii 212. .. On the action of a mixture of glucose and sulphuric acid on organic substances by M. Schultze. Idem. lxxi 266 ;abstr. J. Pharm. [3] xvii 145 ;also Chem. Gaz. 1850 98. .. Fundamental experiments on the determination of the inor- ganic constituents of organic bodies by A. Strecker. Ann. Ch. Pharm. lxxiii 339. .. On the inorganic constituents of organic substances in gene= ral and of hens’ eggs in particular :by H. Rose. Pogg. Ann. lxxix 398. .. On the quantitative determination of the inorganic consti- tuents of organic substances :by H. Rose. Idem. lxxx 94 0ryiment.-Observations on arsenious acid realgar and orpiment :by Huus-mann. Ann Ch. Pharm. lxxiv 188. TITLES OF CHEMICAL PAPERS Oxygen.-On a new compound of chlorine sulphur and oxygen :by E.MiL Zon. Ann. Ch. Phys. [3] xxix 237. -Apparatus for preparing oxygen by M. iYunch. J. Pharm. 133 xvii 202. -Impurity in oxygen gas from chlorate of potash :by Dr. Ybgel. Chem. Gaz. 1850 17. -On passive and active oxygen by A. Buchner. Buchn. Repert. ix 234 ; Pharm. J. ix 532. Ozone.-By M. Schunbein Phil. Mag. xxxvi 398 ; Cornpt. rend. xxx 13. -On the nature of ozone :by Dr. Osann. J. pr. Chem. 1 209. -Observations on ozone and black phosphorus :by G. Osann. Chem. Gas. 1850 15. -Communication relative to Schonbein’s experiments on ozone by M. Becquerel. Compt. rend. xxx 13. -Atomic weight of ozone :by G. Osartn. Chem. Gaz. 1850 25. Pancreatic Juice.-Facts relating to the history of the pancreatic juice by J.L. Lassaigne. Compt. rend. zxxi 745. Papaverine.-On papaverine by G. Merrk. Ann. Ch. Pharm. lxxiii 50. Peat.-Application of Irish peat in the formation of various products.-Rev. Sci. xxxviii 112. Pheneto1.-Researches on anisole and phenetole by A. Cuhours. Ann. Ch. Pharm. Ixxiv 298. Phenides.-On the phenides a new class of organic compounds :by Laurent and Gerhardt. Idem. lxxv 75. Ph1oridzine.-By Gush Rose. Idem. Ixxiv 178. I__ On the chemical constitution of phloridzine by A. Strecker. Idem. 184. Phosphorus.-On the luminosity of phosphorus :by R. F. Marchand. J. pr. Chem. 1,1. -Action of sulphur on the pentachloride of phosphorus by J. H. Gladstone. Chern. SOC.Qu. J. iii 5. On the compounds of the halogens with phosphorus by J.H. Glad-stone. J. pr. Chem. xlix 40. -On the definite compounds of iodine and phosphorus :by B. Corenzainder. Ann. Ch. Phys. xxx 242. -On a new allatropic state of phosphorus by A. Schrotter. Pogg. Ann. Ixxxi 276. -On the nature of amorphous phosphorus by A Schrb’fter. Compt. rend. xxxi 138. -Further contribution to the knowledge of the nature of amorphous phos- phorus Pogg Ann. Ixxxi 299. -Metallic alloys containing phosphorus.-Rev Sci. xxxix 298. Photography.-Photography on paper by M. BEanquart Evrurd. Idem. 305 328. -Photography on ge1atine.-Idem. 307. -On an accelerating process in photography by J. Hiddleton. Phil. Mag. xxxvii 178. -Photographic images on paper obtained by means of an albuminized plate &c, by A.H.de Molurd. Compt. rend. xxxi 208. IN BRITISH AND FOREIGN JOURNALS. Photography.-Note on photography on glass and on some new facts :by NiepcQde St. Victor. Compt. rend. xxxi 245. -Additional communications relating to photography on paper by F. Bonsipes. Idem. 726. -Note on a new process for obtaining photographic images on a plate of silver by Ntepce' de St. Victor. Idem. 498. -On paper by 3f. Gatel. Idem. 497. Physiology.-Various facts of chemistry applied to physiology by M. Bnr-reswil. J. Pharm. [3] xxii 113. -On the physiological action of analogously constituted chemical com-pounds by J. Schlossberger. Chem. Soc. Qu. J. iii 179. Plants.-On the growth of plants in abnormal atmospheres by J.H. Gladstone and G. Glndstoize. Chem. Gaz. '18.50 342. Platinum.-On the action of ammonia on chloroplatinate of ammonium by C. Gerhardt and A. Laurent. Ann. Ch. Pharm lxxiii 223 ;Compt. rend. trav. chim. vi 273. -Researches on the ammoniacal compounds of platinum :by C. GerJiardt. Compt. rend. xxxi 241 ; also Compt. rend. trav. chim. vi 273. -Substitute for spongy platinum in spirit-lamps by JL Tagner. Rev. Sci. xxxix 110. Polarization Circular.-On the manifestation of molecular rotatory power in solids by M. Biof. Ann. Ch. Phys [3] xxviii 215 351. -Detail of experiments made by the Commission of the Academy of Sciences to verify the relations established by M. Pasteiir between the rotatory actions of dextroracemic and leveracemic acid and that of crystallized tartaric acid.-Idem.99. -On the rotatory power imparted by heat to essence of turpentine and saccharine solutions :by 3fiX. Provostaye and Dcssains. Compt. rend. xyxi 621 ;Ann. Ch. Phys. xxx 267. __)-General determination of the law of variation of the rotatory power in ternary systems of liquids when a body possessing the rotatory power is placed in contact with two inactive bodies which have no chemical action on each other by df. Biot. Ann. Ch. Phys. [3] xxix 430. -New researches on the relations which may exist between crystalline form chemical composition and the phenomenon of circular polari- zation by L.Pustcvr Compt. rend. xxxi 489. Polarized Light.-Experirnental researches to determine whether water near its point of maximum density or its freezing point exerts any action on polarized light :by 3f.Biot. Cornpt. rend. xxx 281; Pogg. Ann. lxxx 370. -On a new polariscope by H. de Seizarmont. Ann. Ch. Phys [3] xxviii 279. -On the application of colonred polarized light in microscopical investiga- tions.-J. pr. Chem xlix 490. Polymeris m.-On isomorphism polymerism and heteromerism by Ur. v. .&ohell. Idem. 469. Poppy.-Analysis of the seed of the white poppy.-Ann. Ch. Phys. [3] xxxii 4'10;Pharm. J. ix 543. Porcelain -On the red colours used in painting on porcelain by M Xaluefat Rev. Sci. xxxix 17. VOL. 111.-NO. XII. GG TITLES OF CIIhMIChL PAPERS Porcelain.-Researches on the composition of the materials used in China for the manufacture and decoration of porcelain (Part I.) by ,iM.Ebelmen and Salve‘tat. Compt. rend. xxxi 743. Potash.-On the quality of potash removed from the soil by the cultivation of the vine by :tl;Vorrssinpult. Ann. Ch. Phys. [3] xxx 369. -On the racemate of potash and soda by V.DeZ#s. Yogg. Ann. lxxxi 276. Potasso-gypsite.-On potasso-gypsite a double sulphate of lime and potash by J.A. Phillips. Chem SOC. Qu. J. iii 348. Pot ato.-Analysis of the ashes of the Spanish potato (Coizvoluulus bututas) by T. J. Herapath. Chem. SOC. Qu. J. iii 193. Precipitates.-Intermitting siphon for washing precipitates by JCI.Bloch. Bull. SOCInd. 1850 39. Propy1ene.-On propylene a new hydrocarbon of the series C,. €1,. by J. P?. Reyt,olds. Chem. SOC. Qu. J. iii 111. I_ On the action of chlorine and bromine on propylene ethylene and their homologues by A.Cahours. Comp. rend. xxxi 111. Proteine.-On the composition of proteine-compounds by T.S.Hunt. Compt. rend. trav. chim. ri 317. -On a reagent for protejne-compounds by E. ;7.li’Zlon. Ann. Ch. Phys. [3] xxix 507. Psoralea Glandu1osa.-On the tea-plant of Paraguay by LW.LenobZe. J. Pharm. xviii 199. Putrefac t i on.-influence of lime onthe putrefactive process.-€'harm. J.x 27. -On the putrefaction of alimentary conserves and the causes which may produce it by X.iloride. Compt. rend. xxxi 5 19. Pyrog1ycerine.-On pyroglycerine by H. Sobrero. Phil. Mag. xxxvii 394. Pyroxylic Spiri t.-Test for distinguishing acetone from pyroxylic spirit by -21,Scnnlun.Pharm. J. ix. 455. Q. Quinine -On the action of certain re-agents upon quinine by Dr. Togel juiz. Ann. Ch. Pharm. lxxiii 221 ; Chem. SOC.Qu. J. iii 191. -Citrate of quinine and iron by Mr. Barber. Pharrn. J. ix 338. Quinoidine.-On quinoidine by R. Lelmunn and E’. Yolland. Idem. 42. Quinquina.-Note on the yellow quinquina at present found in commerce by M. Bre‘ton. J. Pharm. [3] xvii 93. -Note on the preparation of syrup and extract of quinquina by F. Boudet. Igem. [3] xvii 192. R. Realgar.-Observations on arsenious acid realgar and orpiment by Huusmu~zn. Ann.Ch. Pharm. lxxiv 188. Reduction.-On some phenomena of reduction and on a new method of se-parating iron from its compounds by J. A. Poumarkde. Compt. rend. xxix 518 ; Chem. Gaz.1850 136. Resin,-On the resin of the Norway spruce fir by D. Hunbury. Pharm. J. ix. Respiration.-Researches on respiration by L. Dayer. Ann. Ch. Phys. [3] xxviii 5. -On the products formed from sugar by respiratory ovidation -by ..lPial/d. Compt. rend. xxx 7 15. IN BRITISH AND FOREIGN JOURSALS. 45 1 Rhuharb,-Colouring matter obtainable from the deposit in tincture of rhu-barb by J. Cobb. Pharm. J. ix. 529. -On erythrose the colouring matter of rhubarb :by N. Mearin. J. Pharm. [3] xvii 179. -_. On the colouring matter of rhubarb both native and foreign and its application in the arts and in pharmacy by M. Garot. Idem. [3] xvii 5. Rock.-On the mineralogical and chemical constitution of rocks by M. DeZesst.. Ann. Min. xvi 97 233 367.Hoot.-Chemical examination of a root which grows in the Eastern Republic of Uruguay(Monte Video) and is called by the Indians G-uai’cnru by M Lenoble. J. Pharm. [31 xvii 200. S. Saccharimeter.-Note on a new compensator for the saccharimeter by J. Dubosq and N.SoleiZ. Compt. rend. xxxi 248. Sainfoin.-On the influence which various saline substances may exert on the produce of sainfoin by Ikidore Pierre. Idem. 547. Sal-ammoniac.-On the rhombohedra1 crystals of sal-ammoniac by Naumnnn. J. pr. Chem. 1 309. Salt.-Chemical analysis of the Krankenheiler salt byR.Fresenius. Idem.xlix 146. -I Notice respecting the Krankenheiler salt by A. Barth. Idem. 313. Salts.-On a remarkable analogy of form between certaiti sulphur-salts and oxygen-salts by G.Rose. Idem. 155. -On salts of the oxides R,0 by A. Laurent. Compt. rend. xxx 673. I-On the action of bases upon salts and particularly upon the arsenites by A. Reynoso. Idem. xxxj 68. Salt-springs.-On the useful application of the mother-liquorsof salt-springs by Ch. Calloud. J. Pharm. [3] xvii 28. Sandal-wood.-On the colonring matter of sandal-wood :by A. Weyermanit andT. HufeZy. Ann. Ch. Pharm. lxxiv 226. Saponine.-Researches on saponine by F.Ze BE@‘. Compt. rend. xxxi 654. Scil1itine.-Note on scillitine :by L 3’.Bley. Chem. Gaz. 1950 276. Silver.-On the presence of lead copper and silver in sea-water and on the existence of the last-mentioned metal in plants and in organized beings by NM. MaZnguti Durocher and Sarzeaud. Ann.Ch. Phys. [S] xxviii 129. -Researches on the association of silver with metallic minerals and on the processes to be followed for its extraction by MM. MaZaguti and Durocher. Ann Min. xvii 5 245 461. -On a natural alloy of silver and copper from Chili by Fr. FieEd. Chern. SOC.Qu. J. iii 29. -Experiments on the extraction of gold and silver from their ores TJY the wet way :by John Percy. Phil Mag. xxxvi 1. -Analysis of certain compounds of gold and silver by A. Levol. J. pr. Chem. xlix 171. -Method of separating silver from cupreous solutions by M. Roll~y. Chem Gaz. 1850,116. GGa TITLES OJ? CHEMICAL PAPERS Silver.-Method of silvering glass by means of gun-cotton by M.Wold. J. Pharm [S] xvii 141. -Chemical and therapeutical considerations on the salts of silver by M.Delioux:. Compt. rend. xxxi 725. Siphon.-Intermitting siphon for washing precipitates by M. BEoch. Bull. SOC.Ind. 1850,39. Soap.-Use of Iceland moss in soap-making by M. Chastelain. Rev. Sci. xxxix 297. Soda.-On the products of the soda manufacture by Mr. Brown. Idem. 145. -On the reducing action of soda in blowpipe experiments by R.Fugner. J. pr. Chem xlix 191. _1 On the racemate of potash and soda by ?T.DPZ~S. Pogg. Ann. lxxxi 276. Solutions Saline.-On the supersaturation of saline solutions :by H. Lowel. Cornpt. rend. xsx 163 ;Ann. Ch. Phys. [3] xxix 62. Spheroidal State.-On the force which retains bodies in the spherdidal state beyond the range of their sphere of chemical and physical activity by 3f.Boutigiiy Compt.rend. xxxi 279. -Report on the preceding by 3f.Babinet. Idem. 509. -On the spheroidal state and on the incombustibility of the human body by J. Lcyynl. Compt rend. xxx 415. -On the momentary incombustibility of living organic tissues and on the physical constitution of bodies in the spheroidal state by iW. Boutigny. Ann. Ch. Phys. [S] xxviii 158. -Observations upon M. Bontigny’s recent experiment by Prof. Plucker. Phil. Mag. xxxvi 137. __. Experiments on liquids in the spheroydal state by M. Legal Compt. rend. xxx 182. -New experiments on Leidenfrost’s phenomenon :by J. Schnauss. Pogg. Ann. Ixxix 432. -Various facts relating to the spheroYda1 state :by M. A~thur. Compt. rend. xxxi 589. Starch.-On the quantity of starch contained in different plants.-Rev.Sci xxxviii 140. -On a new substance isomeric with starch by J. Gottlieb. Ann. Ch. Pharm. lxxv 5 1. Steam-engine.-On the incrustation which forms in the boilers of steam- engines :by J. Davy. Chem. Gaz. 1850 343. Stearine.-On the melting point of stearine from mutton suet :by 7T.Heintz. Idem. 68. Stibethy 1.-On stibethy1,a new organic radical containing antimony by Lowig and Schweizpr. J. pr. Chem. xlix 385 ;Ann. Ch. Pharm lxxv 315 4 Chem Gaz. 1850,377. Stramonium,-Daturine found in the urine of persons poisoned with stramo- nium by R.AZZan. Ann. Ch. Pharm. lxxiv 223. Strontia.-Crystalline form of sulphate of strontia by M. Hugard. Compt. rend. xxx 387. -Crystallographic examination of sulphate of strontia and description of several new forms of that substance by M.Dufre‘noy. Idem. xxxi 169. IN BRITISH AND FOREIGN JOURNALS. Strychnine.-On the use of kermes as an antidote for strychnine and nux vomica :by M. Thorel. J. Pharm. [3] xvii 185. -Report on the memoir of M Thorel by MM. Gobley and Bouchardut. Idem. 190. -On the detection of strychnine :by A. K Brieger. Chem. Gaz. 1850 408. Styracine.-On styracine by J. Wolf. Ann. Ch. Pharm. lxxv 297. -On the composition of styracine by A. Strecker. Idem. lxxiv 112. Sugar.-On sugar and the sugar manufacture by M. Rousseau. Compt. rend. xxxi 3. -Report on the preceding by M. Payen. Idem. xxxi 539. -Rev. Sci. xxxix 1, -Qiiantitative determination of sugar and starch by means of sulphate Examination of sugar and fecula.of copper :by H. FehZing. Chem. Gaz. 1850,93. -On the products formed from sugar by respiratory oxidation by M Mialh&* Compt. rend. xxx 745. -Examination of the crystals of sugar which occur in the flowers of the Rhododendron ponticam by B. Sthumer. Ann. Ch. Pharm. lix 151; Chem. Caz 1850,7. -On the use of lead in the manufacture of sugar.-Pharm. J. 177 245. -On the presence of sugar of milk in the cotyledons of plants by H. Braconnot. Chem. Gaz. 1850 87. -On a new kind of sugar obtained from muscular flesh :by Prof. Scherer. Ann. Ch. Pharm. lxxiii 322. -On Dulcose a homologue of grape-sugar :by A. Laurent. Compt. rend. xxx 41. -On sugar in the albumen of eggs :by Baweswil.J. pr. Chem. 1,134. -On a new re-agent for detecting the presence of sugar in certain liquids by jlif; i?huumen&. Compt. rend. xxx 314. -On the employment of acetate of lead and sulphurous acid for purifying sugar :by Drs Sccfleel’n,Gregory and Christison. Chem. Gaz. 1850,340. -Improvements in the refining of sugar by A. Steinkamp. Rev. Sci. xxxix 14. -On the precipitation of the colouring matter of sugar by a metallic oxide by H. Farburton. Chem. SOC.Qu. J. iii 53. -Use of acetate of lead in purifying sugar by J. G. Jfiranda. Pharm. J. ix 390. -Use of acetate of alumina in refining sugar.-Idem. 334. -Improvements in sugar by B-. J. Frank. Inst. ix 132. -Experiments on the manufacture of sugar from beetroot :by Fr.KuhZmunn. Compt. rend. xxx 341. -Analysis of the refuse of crude beet-sugar used in feeding cattle by .&EX Payert Poin.sot and Brunet. J. Pharm. [3] xvii 48. -Observations on the sugar manufacture by Burrestoil. J,pr. Chem. 1 269. -On themanufacture of beet-sugar by iff. HurewuZd. Rev. Sci. xxxix 15. -On the manufacture of beet-sugar without the use of animal charcoal by Dr. Liidersdorf. Chem. Gaz. 1850 316. -Analysis of sugar feculencies by T. J. Herapnfh. Chem Soc. Qu. J. iii 367. TITLES OF CHEMICAL PAPERS. sulphur.-Onanew compound of chlorine sulphur and oxygen by E. XilZo/i. Ann. Ch.Phys. [3] xxix 237. -On the acids of sulphur by J. Furdos and A. G&s. J. pr. Chem.1 83. -On the sulphide of nitrogen by Furdos and Ge‘Eis. Compt. rend. xxxi 702. -On hypochlorous acid and the chlorides of sulphur :by E. .&%?on. Ann. Ch. Phys. [3] xxix 506. -On the action of sulphur on the pentachloride of phosphorus by J. H. Gludstoae. Chem. Soc. Qu. J. iii 5. -Behaviour of arsenic antimony and tin with chloride of sulphur :by F. Wohler. Ann. Ch. Pharm. lxxiii 374. Sulphuretted Hydrogen.-On the removal of sulphuretted hydrogen from solutions in quantitative analysis :by H. Rose. Chem. Gaz. 1850 27. Tamarind.-On the action of volatile acids on the fruit of the Tamarind by Gorup-Besunez. Rev. Sci. xxxviii 233. l’an t a1 u m.-Examination of the composition of tantalum-ores by R. Hermann. J. pr. Chem. 1 184. Teeth.-On a cement for stopping the cavities of teeth by T.J.Heruputh. Chem. SOC. Qu. J. iii 367. Theine.-Method of preparing theine by *H.Heinsius. Chem. Gaz. 1850 119 ; J. pr. Chem. xlix 317. ‘I’hermometer.-Relation between the graduation of the Centigrade and Fahrenheit thermometers by ilL; D’Abbudie. Pharm. J. x 254. Tin.-On the amalgam of cadmium and tin by Prof. Yurrentrup. Ann. Ch. Pharin. lxxiii 256. -Analysis of the tin of the Banca mines.-J. Pharm. [3l xvii 51. -Behaviour of tin with chloride of sulphur by F. WohZer. Ann. Ch. Pharm. lxxiii 374. -On a new method for the quantitative determination of tin :by C. M2ne. Chem. Gaz 1850 365. Titanium.-On the nature of metallic titanum by F. W$hZe)*. Ann. Ch. Pharm. lxsiii 34 ; Ann. Ch. Phys.[3] xxviii 382. -On cyanide of titanic chloride by 3’.Wohler. Ann. Ch. Pharm. lxxiii 219; Pogg. Ann. lxxix 327. __. On a compound of titanic chloride with hydrocyanic acid by F. FWzler. Ann. Ch. Pharm. lxxiii 226. __. Observations on the titaniferous veins of the Alps :by A. Duubre‘e. Ann. Min. xvi 1‘29 -On the preparation of pure titanic acid by F. ?#%Met-. Chem. Gaz. 1850 72 ;Ann. Ch. Pharm. lxxiv 212. -Improved method of extracting tin lead &c. from their ores.-Pharm. J. x 74. -On the two modifications of oxide of tin by C. JViZtstein. Buchn. Repert. x 313. -On the cyanogen-compounds of titanium by El. IYdhler. Chem. SOC. Qu. J. iii 177. ‘~‘oluidi by W.1Yilson. Idem. 154. nc.-i~ctionofchlorideofcyano~~n~ntolui~~ine. Ih' BRITISH AND FOREIGN JOURNALS.Tungsten.-On the amidogen-compounds of tungsten :by F. WohZev. Chem. Gaz. 1850. 161. -On the atomic weight of tungsten with analyses of wolfram :by B. Schnei-der. J. pr. Chem. xlix 231 ;1 152. ri 1 urmeric.-Reaction of borax on turmeric by Dr. Voyet,jun. Pharm. J. ix 441. Tyrosine.-On a decomposition-product of tyrosine by A. Strecker. Ann. Ch. Pharm. lxxiii 70. U. Urea.-Process for obtaining urea and ferrocyanide of potassium by Dr.Brund. Rev. Sci. xxxviii 418. -On the presence of urea and hippuric acid in ox-blood :by F. VwdeiZ and C. Dollfus Ann. Ch. lxxiv 214. Urine.-Occurrence of crystallized ammonia-magnesian phosphate in the urine on the day that magnesia had been taken as a purgative :by M.Garat. J. Pharm. [3] xvii 89. -On the so-called chylous urine :by H. Bence Jones. 'Phil. Mag. xxxvii 302. -Daturine found in the urine of persons poisoned by stramonium by R. Allan. Ann. Ch Pharm. lxxiv 223. I_ Researches on the quantity of ammonia contained in urine by M. Boussin-gauEt. Ann. Ch. Phys. [3] xxix 472. V. Vanadium.-On Araoxene a new vanadicate of lead and zinc by Fr. 21. KoobeZl. J. pr. Chem. 1 496. Vapours.-On an equation between the temperature and maximum elasticity of vapours by FF. Rankin. J. Frank. Inst. xlis 121 181. Vegetable Kingdom.-vide Animal Kingdom. Substances.-Contributions to the doctrine of the identity of the sul- phurous and nitrogenous animal and vegetable substances by F. Keller. Ann. Ch. Pharm.Ixxii 24 ; Chem. Gaz. 1850 121. Vegetation.-Researches on vegetation :by MAW.CEoez and Gratiolet. Compt. rend. xxxi 626. Vine.-On the quantity of potash removed from the soil by the cultivation of the vine by iM.Boussinynult. Ann. Ch. Phys. [3] xxx 369. Vitrification.-Influence of boracic acid on vitrification :by M. Mues. J. Frank. Inst. xix 140; Compt. rend. Oct. 22 1849. Vivionit e.-Formation of vivionite in the animal economy.-Rev Sci. xxxviii 68. Volcanic Rocks.-On the volcanic rocks of the coal-basin of Commentry (Allier) and on the transformation of the coal in contact with one of them into coke by C. i7lnrtcns. Compt. rend. xxxi 656. Volume Specif ic.-On the relations between chemical composition boiling- point and specific volume by H.Kopp. Chem. SOC.Qu. J. iii. 104. W. Water.-The effect of pressure in lowering the freezing-point of water experi- mentally demonstrated by ?K Thomson. Phil. Mag. xxxviii 123. 456 TITLES OF CHEMICAL PAPERS Water.-On the latent heat of water by C. C. Person. Ann. Ch. Phys. [3] xxx 73. -Note on the boiling of water at different heights by A%. Fisse. Idem. xxv& 118. -Observations on the preceding note by V.Regnuult. Idem. 123. -Experimental researches to determine whether water near its point of maximum density or near its freezing-point exerts any action on polarized light by $1.Birt. Compt. rend. xxx 281. -Fresh water in marine boilers by 2-. J. Frank. Inst. xix 131. -On the preservation of water by M. PeriEet. Idem. 140.-Apparatus for evaporating and drying and for preparing distilled water for analytical laboratories by R. Fresenius J. pr Chem. 1 130. Waters Mineral.-Analysis of an aluminous water by T. Beesley. Pharm. J. ix. 452. -On the action of the soap-test on water containing a salt of magnesia only and likewise upon water containing a salt of magnesia and a salt of lime by D. Campbell. Phil. Mag. xxxvii 171. -Analysis of the water of the Mediterranean by J. UsigZio. Phil. Mag. xxxvi 404, -Analysis of Astrop Wells and Sutton Bog mineral waters by T. Beesley. Pharm. J. x 293. -On the air and water in towns and the action of poroiis strata on water and organic matter by R. A. Smith. Idem. 149. -Analysis of a spring at the Orrell Colliery by J S.JIusprizft. Idem. 59. -Analyses of mineral waters,-J. p. Chem. Ud. 1. Medicinal spring at Sternberg p. 49; mineral water of Niederltronn p. 49; l’hames water p. 50 ; Thames water at Greenwich p. 50 ; Mineral spring in the neighbourhood of Bristol p. 51 ; Water from the Elampstead Water-Works Company p. 51; Sea-water from the Gulf of Suez p. 51. -Examination of the mineral waters of Bagnares-de-Luchon :by 2M. Filhol. J. Pharm. [3] xviii 177. -Contamination of drinking water with lead.-Idem. 60. -Chemical examination of the waters of some of the mineral springs of Canada by T.S. Hmt. Sill. J. [2) ix 266. -Artesian well at Casset Dept. de 1’Allier by M. Bertrund. Compt. rend. xxxi 173. -Examinationof the mineral waters of Cransac by C.Blondeau. Idem. 313 -On the natural ferro-magnesian mineral waters of Cransac by 0. Henry. J. Pharm. [3] xvii 161. -The Ferdinandsbrunnen at Marienbad.-Pogg. Ann. lxxx 317’. -Chemical analysis of the water of Neiderbronn (Lower Rhine) by M. Kosmann. J. Pharm. xvii 43. -Observations on the waters of the town and arrondissement of Rheims by E. Il.iuumen4. Compt. rend. xxxi 270. -Analysis of the mineral water of St. Vilaine St Auboin (Loiret) by M. Poumurdde. Rev. Sei. xxxviii 21. -Analysis of deep well-water from Messrs. Holt’s brewery Ratcliffe by J. Mitchell. Chem. Soc. Qu. J. iii 1. -On alterations iu well-water . by C Bloizdeuit Compt. rend. xxx 48 1 IN BRITISH AND FOBEIGN JOURNALS. 45 7 Waters M inera1.-Artificial imitation of mineral waters.- Rev.Sci. xxxix 29. -Hepatic waters.-Idem. 31. Wax.-On the microscopical examination of wax with reference to the detec- tion of that substance in animals and plants by F. Dujadn. Compt. rend. xxx 172. Wheat.-Gluten and starch in wheat by H.Rau Ann Ch. Pharm. lxxiv 108. Wine.-On wine by 3'. L. Winckler. Pharm. 3. x 134. Wood.-On the light oils obtained in the distillation of wood by A. Cahours. Compt. rend. xxx 319; Chem. SOC.Qu. J. iii 183. -An account of experiments 'on the saturation of growing wood with anti- septic chemical solutions by A. Geyde. Chem. Gaz. 1850 258. Wood-s pir it.-manu fact ure of wood .spirit.-Pharm. J. x 30. Wool.-Improvement in the method of removing grease from wool by M9..Mercer. Rev. Sci. xxxix 107. X. Xanthates.-On the action of ammonia on the products of the oxidation of xanthates by iodine by H. Debus. Ann. Ch Pharm. lxxii 1 ; also Chem. Gaz. 1850,143. Xanthic oxide.-On a substance analogous to xanthic oxide occurring in the animal organism by Prcf Scherer. Ann. Ch. Pharm. lxxiii 32s. 2. Zinc.-On the geological position of calamine ores by J. Belanone. Compt rend. xxx 765. -Oxide of zinc by M,Sorel. Idem. x 39. 7 Oxide of zinc as a pigment by M. Chpvalier. Idem. ix 531. -Mutual action of sulphate of magnesia and sulphate of zinc :by M. SchGuf-fez. Phil. Mag. xxxvi 479. -On the innocuous nature of preparations of zinc used in the arts by AW. Sorel. Compt. rend. xxx 743. -Comparative experiments on the effects of oxide of zinc and of sulphate and carbonate of lead on the animal economy :by C.FZandilz. Compt. rend. xxx 510. -Poisonous effects from zinc by MM. Bouvier Lnndouzy arid Mauriwnd. Chem. Gaz. 1850 361 ;also by C. PZartdin. Pharm. J. x 192.

ISSN:1743-6893    

DOI:10.1039/QJ8510300419

出版商:RSC    

年代:1851

数据来源: RSC