摘要:

125 PAPERS READ BEFORE TEE CHEMICAL SOCIETY. 111.-Study of Eydrogea Dioxide md of certain Peroxides-(continued from page 24). By T.FAIRLEY, F.R.S.E. VII. ON SODIUMDIOXIDE. INalcoholic solutions this substance may be precipitated by addition of hydrogen dioxide in a manner closely resembling the precipitation of barium strontium and calcium dioxides by the same reagent from aqueous solutions of their hydrates Thus if to a solution of sodium hydrate containing about 20 per cent. of NaHO we add a solution of hydrogen dioxide containing about 5 per cent. HzOz,and then com-mon alcohol of 80 per cent. in moderate excess there is rapidly- often immediately formed a crystalline precipitate of hydrated sodium peroxide. In this preparation it is better to have excess of alkali rather than of the dioxide.The precipitate should be rapidly sepa- rated from the liquid by filhation through ribbed paper filter or still better a cloth filter as the crystals gradually decompose when suffered to remain in the liquid. The crystals of this sodium peroxide have the beautiful pearly lustre characteristic GI! many hydrated peroxides and consist of sodium dioxide with eight atoms of water of crystallisation. They do not contain any alcohol. They are identical with the crystalline hydrate described by Vernon Hercourt* and obtained by the evaporation of the solution of anhydrous sodium dioxide prepared by heating sodium in a current of oxygen. Thus they lose water by exposure over sulphuric acid in a vacuum; and on exposure to the air for a few days they rapidly lose their brilliancy owing to formation of sodium carbonate from absorption of carbon dioxide and evolution of oxygen.When considerable quantities are operated on crystals may some- times be obtained of considerable magnitude in large mica-like plates. This is observed more especially in cold weather. These plates are transparent flexible and can be split with the knife in the same manner as mica. They may be formed from smaller crystals uniting together in the same way as shown by ice in the process of regola-tion. 4k Chena. Soc. J. xv 207. VOL. XXXI. K FAIRLET ON HYDROGEN DIOXIDE AS showing the influence of various proportions of reagents the following experiments may be quoted :-(I.) On mixing- 10 C.C.NaHO solution (20 per cent.) 4 C.C.H,O , ( 5 per cent.) 20 C.C. alcohol (80 per cent.). an abundant precipitation of the dioxide was obtained. (11.) 10 C.C. of the same NaHO solution 7.5 C.C. , H,O , 22 C.C. , alcohol also gave an abundant precipitate of the dioxide and the precipitatiori appeared to be facilitated by addition of a little more sodium hydrate. (111.) 10 C.C. of the same NaHO solution 20.4 C.C. , HZO 3 60 C.C. , alcohol gave no precipitate but only a slight opalescence.* The further addi- tion of alcohol also failed to give a precipitate which was however immediately obtained on addition of sodium hydrate. These experiments show that while excess of sodium hydrate does not interfere with the precipitation excess of the hydrogen dioxide interferes with or even prevents it.This may be due to the formation of a double peroxide of sodium and hydrogen soluble in alcohol. It is also to be observed that oxygen is much more freely evolved in presence of excess of the hydrogen dioxide. This may arise either from the decomposition of the unstable double peroxide if such be formed or else according to the equation- Na202+ H,O = 0 + 2NaHO. Ry heating this dioxide alone about seven-eighths of the water are given off and all the peroxide oxygen and by heating it with silica or in a current of carbon dioxide all the water and peroxide oxygen are expelled. The latter therefore form convenient processes for the analysis of the dioxide. In the following analyses the oxygen was generally determined in acid solutions by means of decinormal potassium permanganate :-I.0.1 gram required 9 C.C. of permanganate = 0.0072 oxygen corresponding to 7.2 per cent. 11. 0.0705 required 6.35 C.C. permanganate = -00508oxygen corresponding to 7.2 per cent. * On exposing this liquid to cold it deposits a small quantity of fine crystalline needles. These though very different in appearance and form from the crystals obtained by Expts. I and 11 have the 8ame composition. AND CERTAIN PEROXIDES. 111. 0.1135 evaporated with hydrochloric acid gave -0592 gram sodium chloride and required 10.2 C.C. of decinormal silver nitrate corresponding to 27.85 per cent. of NhO. IT. 0.1009 gram decolorised 9.1 C.C.permanganate = 0.00728 oxygen corresponding to 7-21 per cent. V. 0.854 gram deoolorised 77 C.C. permanganate = 0.0616 oxygen corresponding to 7.21 per cent. VI. 0.924 gram decolorised 83.2 C.C. permanganate = 0.06656 oxygen corresponding to 7.21 per cent. VII. 0.2 gram boiled mit'h 10 C.C. normal sulphuric acid neu- tralised 1.8C.C. = 0.0559 sodium oxide corresponding to 27.95 per cent. VIII. 0.3265 gram heated with silica gave 0.2125 gram water corresponding to 65.09 per cent. IX. 0.4157 gram heated in a current of pure dry carbon dioxide gave water 0-2689 gram corresponding to 64.68 per cent .,and sodium carbonate 0.19875 gram corresponding to sodium oxide 27.96 per cent. These results agree with the formula N&0,.8H2O as the following percentages show :-Found.n f I. 11. 111. IV. v. VI. VII. VILI. IX. ' w L+ -Na20 ...... -27.85 -27.95 27.96 0 .......... 7-20 -7.21 - H2O ........ --65.09 64-68 Calculated. Mean found. NazO ...... 63 27.97 ........ 2 7.92 0 .......... 16 7.20 ........ 7.20 8HzO ...... 144 64.83 ........ 64.88 222 100*00 100*00 VIII. ON NEW OXIDESAND COMPOUNDS OF URANIUM. Uvaniurn Tetroxide. On addition of pure dilute hydrogen dioxide to solution of uranic nitrate or acetate a yellowish-white precipitate is formed somewhat lighter in colour than freshly prepared uranic hydrate. In presence of excess of uranium salt the precipitate is very stable and may be dried at 100" C. without losing oxygen. If the hydrogen dioxide is in excess oxygen is evolved during the filtration of the precipitate from the liquid especially if the latter is not quite cold.In no case Ii2 FAIRLEY ON HYDROGEN DIOXIDE has any lower oxide thatl that corresponding to the empirical for-mula U04*been obtained. The presence of excess of salts of sodium potassium barium cal- cium and probably many others prevents the precipitation of uranium by hydrogen dioxide and hence the new oxide is either not obtained at all or slowly and with difficulty by mixing an acid solution of barium dioxide with the solution of a uranic salt A moderate excess of strong hydrochloric nitric or sulphuric acids also delays or prevents the precipitation and sulphuric acid is much more powerful in this respect than any other substance whose action I have observed.The oxide when dried at 100" is a yellowish*white powder soluble especially on heating in strong hgdrochloric acid with evolution of chlorine. A mixture of the oxide with hydrochloric acid readily dis- solves gold. On exposure to heat this oxide if finely divided undergoes a very remarkable decomposition. At a comparatively low temperature much below redness or the softening point of the more readily fusible glass,a red glow passes through the mass oxygen is freely given off and the residue contains a considerable proportion of green oxide of uranium. On treating this oxide with alkaline hydrate one portion of the uranium is precipitated as ordinary uranic hydrate and the other enters into solution to form a alt or new oxygen compound with the alkali.These compounds may be viewed as derived from an acid of uranium analogous to perchromic acid and if so would be similarly named as salts of peruranio acid. The fact of the precipitation of the oxide from acid solutions shows that unless we attribute to hydrogen peroxide the character of an acid. these compounds cannot be regarded as compounds of hydrogen dioxide. I do not however consider this view as untenable OE that account and have borne it in mind throughout the study of this class of compounds. According to this view the salts to be afterwards described are double peroxides. Neither hypochlorites nor permanganates nor ozone in acid neutral or alkaline solutions nor any other oxidising agents which 1 have hitherto examined (with the exception of hydrogen dioxide alkaline peroxides &c.) give any higher oxidation products with uranic salts.Hypochlorites and permanganates in acid liquids decompose this oxide in common with other peroxides. Out of a very large number of experiments the following may be quoted in illustration of the influence of varying proportions of reagents used the completeness of the precipitation of uranium under u = 240. AND CERTAIN PEROXIDES. suitable conditions and the composition as proved by synthesis of the oxide formed. On mixing :-(I.)Uranium acetate solution 100 C.C. containing 4.877 grams UO,. 79 Hydrogen dioxide , 38 C.C. 1.064 , oxygen an abundant precipitate was obtained.The filtrate contained no uranium (as proved by evaporation to dryness sand also by testing with potassium ferrocyanide) but it contained the excess of HaOz and abundance of free acetic acid. (11.) Uranium nitrate solution 90 C.C. containing 1.72 grams UOs. Hydrogen dioxide solution 10 c.c. containing 0.152 gram oxygen. After making up the liquid to 200 C.C. and allowing the precipitate to settle the clear liquid on testing with ferrocyanide showed uranium in solution. I therefore added to the whole bulk 13 C.C. of normal sodium hydrate solution containing 0.32 gram NaHO and after thorough mixing and allowing the precipitate to settle the clear liquid was again tested. It had an acid reaction and showed no uranium by evaporation or on testing with ferrocyanide.After filter- ing and washing the precipitate I observed that 1C.C. of the normal sodium hydrate solution was sufficient to change the reaction of the filtrate from acid to alkaline and that it contained hydrogen dioxide as tested by permanganate equivalent to 0.056 gram oxygen. The precipitate dried at 100' C. weighed 2.034 grams and the formula lJO4,2I3,O requires that it should weigh 2.0293 grams.* The formula also requires that it should contain 0.0956 gram of peroxide oxygen and this experiment gives 0.096 gram. This experiment shows that the precipitation of uranium in nearly neutral solutions is complete and that the oxide precipitated has no acid reaction. (111.) Uranic nitrate solution 50 C.C. containing 0.93 gram UO,.Hydrogen dioxide solution 6 C.C. containing 0.0912 gram oxygen. On making up the solution to 100 C.C. and filtering 25 C.C. of the filtrate required 12-23 C.C. permanganate showing that the excess of hydrogen dioxide in the filtrate contained oxygen amounting to 0.03904 gram. This gives peroxide oxygen contained in the precipi- tate -05216 gram while the formula requires 0.052 nearly. In this experiment nearly the wbde of the uranium was precipitated only a minute portion being kept in solution by the acid set free from the * The equation representing the formation of this oxide may be written :-U0~.2NQ3.6H20+ H202 = UQb2H20 + ZHN03 + 4H20. FAIRLEY ON HYDROGEN DIOXIDE nitrate. To determine this amount another portion of 25 C.C.(one-fourth of the filtrate) evaporated to dryness and ignited gave '009 of residue consisting chiefly of UO, and to determine the acid set free I found that 25 C.C. of the filtrate required 20 C.C. of dscinormal sodium hydrate proving that the total filtrate contained 0.504 gram HN03. The formula UO3.N,O5.6H2O would give 0.407 gram and the examina- tion of the crystalline salt from which the above solution was pre- pared showed that free nitric acid was present the crystals no doubt having been formed in a strongly acid liquid. The free acid contained in the hydrogen peroxide used was very minute corresponding to 1.8 C.C. of decinormal sodium hydrate solution. (IV.) To show that there is practically no decomposition of hydro- gen dioxide in such liquids as the above during the time of an experi- ment I took 2 C.C.of the hydrogen dioxide used in Experiment 3 and 10C.C.of the uranic nitrate solution and after allowing the mixture to stand over four hours titrated with permanganate. There was de- colorised 38 C.C.= -0304 oxygen corresponding to 3.23 per cent. of real dioxide-exactly the percentage found in the dioxide titrated directly. This proves that at ordinary temperatures uranic oxide does not induce decomposition in the same manner as chromic and per- manganic acids acting on hydrogen dioxide. The following analyses have been made of this oxide after drying at loo0 c.:-1. 0.2'79 gram ignited till its weight remained conshnt gave 0.228 gram Uz06,corresponding to 70.07 per cent. of uranium or 84-08 per cent.of FO,. 11. 0.329 gram treated with dilute sulphuric acid and titrated with permanganate decolorised 19-C.C. = -01552 gram oxygen cor- responding to 4.71 per cent. of oxygen. 111. 0.336 gram decolorised 19.7 C.C. permanganate solution = *01576 gram oxygen corresponding to 4.69 per cent IV. 0.336 gram decolorised 20 C.C. permanganate = 0.016 gram oxygen corresponding to 4.76 per cent. V. 0.34 gram decolorised 20 C.C. permanganate = 0,016 gram oxygen corresponding to 4.705 per cent. VI. 0.34 gram of this oxide decomposed by ignition and then dissolved in dilute nitric acid and titrated after addition of ammonia and acetic acid with standard solution of pure sodium phosphate (1C.C. = 0.01858 gram uos = 0.01548 U) reqnired 15.5 C.C.= -2879 UO, corresponding to 70.56 per cent.uranium or 84.67 per cent. UO,. VII. 0.7 gram decolorised 41.3 C.C. permanganate solution = 0.3304 gram oxygen corresponding to 4.72 per cent. of oxygen. AND CERTAIN PEROXIDES. VIII. 0.81 gram decolorised 48 C.C. permanganate = 00384 gram oxygen corresponding to 4.74 per cent. IX. 0.82 gram after decomposition in acid solution by permanga-nate was treated in the flask with granulated zinc and dilute aulphuric acid to reduce the uranium to uranous salt. (The liquid should scarcely cover the zinc and the reduction is finished within 30 minutes more or less according to the pro-portions used. The liquid is then diluted decanted clear or filtered the zinc washed and the washings added to the liquid and the titration proceeded with after addition of dilute sul-phuric acid.) There was decolorised in this case 48 C.C.of decinormal permanganate solution (1C.C. = -0008 gram oxygen = -012 gram uranium) = 0.576 gram uranium corresponding to 70.24 per cent. of uranium or 84.28 of UO,. X. 0.81 gram titrated with permanganate required 48 C.C. perman-ganate = -0384gram oxygen corresponding to 4-74 per cent. After reduction it required 47.5 C.C. permanganate = 0.57 gram uranium corresponding to 70.37 per cent. or 84.44 uo3. These numbers give water by difference as 10.82 per cent. XI. 0.81 gram gave 0.089 gram water corresponding to 10.98 per cent. XII. 0.38 gram gave 0.04 gram water corresponding to 10.32 per cent. The following analyses have been made of the air-dried oxide pre- pared by pressure between folds of filter-paper :-XIII.0.958 decolorised 51 C.C. permanganate = 0.0408 oxygen cor- responding to 4.25 per cent. XIV. 0.2572 heated in a current of dry carbon dioxide gave off 0.05 gram water = 19.44 per cent. and -016 gram oxygen. The residue contained a certain proportion of green manous oxide so that when dissolved in sulphuric acid it reduced 6.25 C.C. of permanganate solution = -005 gram oxygen. Deducting this oxygen from the total given off we have *011gram due to the change of UOa into U03,corresponding to 4.23 per cent. The residue weighed 0.191 gram and adding the above oxygen = 0-196 gram UOs corresponding to 76.20 per cent. These numbers agree with the empirical formulce :-For the oxide dried at 100" C........... UOa. 2H20 And the air-dried oxide.. .............. UOa. 4H,O as the following comparisons show ;- The oxide dried at 100" C. Found. r A . 1 11. 111 IT. v. VI. TII. VIII. IX. x. XI. XII Mean. + + u 84*08 -.-84*67 -84.28 84.44 -84.37 r b 471 4-69 4~76 &705 472 4*74 4-74 I -3 -c 1042 99.86 Tho air-dried oxide. Found. -. /-A u ...* 240 Cralculated. XIII. XIV. Mean. 63'83} 76.60 -76.20 76.20 03 48 12.77 0 .... 16 4.26 4.25 4.23 4.24 4Ha0 .. 72 19-14 -1944 19.M 376 1oo*oo 99.88 AND CERTAIN PEROXIDES. The deoomposition of this oxide by alkaline hydrates and the study af the alkaline-compounds corresponding to it lead to the adoption of EL formula of thrice the molecular weight of the above via.:-U3012.6H20, or UO6.2UO3.6R2O. According to this view it is the uranium-salt of pertmanic acid. Alzhydrous Uranhm Tetroxide. When uranic nitrate solution is added to a mixture of hydyogen dioxide and large excess of sulphuric acid no ppecipitate is obtained. On standing however a suEcient length of time? sometimes after a week sometimes several weeks a precipitate is slowly formed which as yet I have only obtained in very small quantity. It is almost white in colour generally heavy and crystalline and is much more inert than the hydrated oxide previously described. Thus it is diffi- cult to decompose it with permanganate even in presence of large excess of sulphuric acid.On applying heat the permanganate is slowly decolorised. The titration with permanganate is much facili-tated by mixing the oxide in a mortar with a little strong alkaline hydrate solution and then adding excess of snlphuric acid. When carefully dried this oxide gives off no moisture on heating alone. On heating it with hydrochloric acid chlorine is evolved. The analyses of this and the following compound must be regarded as provisional pending attempts to obtain them in larger quantity. I. 0,0602 decolorised 3.95C.C. permanganate = -00316 oxygen or 5.24 per cent. , gave *057UO, or 94.68 per cent. corresponding to 78.94 per cent. of uranium. 11. 0,154decolorised 10 C.C. permanganate = ,008 oxygen or 5.19 per cent. and gave -146 U03or 94.8 per cent.corresponding to 79 per cent. of uranium. These numbers agree with the formula UOO. Found. Calculated. I. 11. Mean. 0 ...... -16 5.26 5.24 5.19 5.21 __I 304 100.00 100~00 Highel. Uraniarn Chides. I have not obtained the oxide U20,in a pure state or free from moisture. I hare however determined the ratio of the uranium to FAIRLEY ON HYDROGEN DIOXIDE the oxygen in precipitates obtained by the slow decomposition of liquids prepared with a view to the isolation of peruranic acid (double peroxide of uranium and hydrogen U OB.rcH,O?) . 5.04 grams (= atom in gram units) of pure crystallised uranic nitrate were dissolved in the smallest possible quantity of water and added gradually to a mixture of 20 C.C.of strong nitric acid of 60 per cent.and 4.5C.C. hydrogen dioxide of 2.4 per cent. The liquid was made up to 75 c.c. and allowed to stand overnight. There was a very slow evolution of oxygen and deposition of a quantity of crystal-line precipitate which was collected and dried on clean bricks. lt was found to be completely soluble on triturating with sodium hydrate solution (20 per cent.) forming a liquid resembling in colour and characters the solution of the red-sodium salt to be afterwards described (p. 139). Different portmiom of the precipitate gave the ratio- UO 0 : *489:-04 -489 :-0408 = 12 1 -489 -039 1 This corresponds to the ratio of uranium to peroxide oxygen = 10 1as required by the formula U20,.xH20. Attempts niadc to isolate the highest of these oxides corresponding to the salts have hitherto been unsuccessful.I shall however con-tinue my efforts by application of very low temperatures for the iso-lation of the solid or liquid body UOs.xH20. The decomposition of acid liquids containing uranic oxide and hydrogen dioxide in the proportions required by the formula UO6 varies considerably according to the temperature the acid used and other circumstances. It appears most apt to proceed to the limit of uranium tetroxide in the case of hydrochloric acid,* and least so in the case of sulphuric acid. Ammonium Perm-ana€e. (Double Peroxide of Uranium and Ammonium.) This salt is precipitated on addition of alcohol to uranic solutions to which hydrogen dioxide and ammonia in excess has been added.On mixing a solution of 2.32 grams of crystallised pure uranic nitrate containing 1.2 gram uranium 10 C.C. of hydrogen dioxide of 3-23 per cent. and then ammonia solution in excess the precipitate at first formed was dissolved.. Oxygen was also evolved though to a less extent than in the preparation of the potassium salt. On addi- f A bottle exploded in my hands in which this mixture had stood overnight. AND CERTAIN PEROXIDES. 135 tion of strong alcohol the greater portion of the uranium was padn- ally precipitated. After standing one hour the precipitate was collected on the filter. Another experiment made by mixing 50 C.C.of uranic nitrate solution containing 0.774 gram of uranium with 10 C.C. of the same hydrogen dioxide and excess of ammonia gave on addition of alcohol and stand- ing for one and a half hours a much less successful result.Excess of hydrogen dioxide therefore interferes with the precipitation of this compound. The salt thus prepared is an orange-yellow precipitate readily soluble in water. In the dry solid state it is less affected by exposure to the air than the corresponding potassium or sodium compounds. It is the only ammonium salt that I have as yet obtained. Its solu-tions are precipitated by sodium and potassium hydrates ordinary manic hydrate being separated and sodium or potassium peruranates remaining in solution. Its solution gives precipitates with the sola- tions of most of the metals. On heating the dry salt it glows like tinder and leaves a residue containing uranic and lower oxides of uranium.The following analyses have been made :-I. *372 gram salt titrated with permanganate required 27.3 C.C. =-0218 gram oxygen correspondiug to 5.86 per cent. 11. 25gram salt ignited gave residue U,O -173 gram = -176 Uos corresponding to 70.4 per cent. DO, or 58.67 per cent. uranium. 111. -24 gram ignited the residue dissolved in nitric acid required after addition of ammonia and acetic acid 9.2 C.C. standard sodium phosphate solution to precipitate the uranium = *01548 X 9.2 gram uranium = -1425 gram corresponding to 59-35 per cent. IV. -41gram dissolved in water required 10.2 C.C. decinormal sulphuric acid = 0.01734 gram NH, corresponding to 4.22 per cent. N.B.-The change of colour of the solution may be used as an index of the end-reaction and corresponds to the tests shown by litmus paper.V. -82 gram distilled with sodium hydrate and the ammonia esti- mated in the distillate required 20 C.C. standard acid = *034NH3 corresponding to 4.15 per cent. ammonia. VI. *205 gram decolorised 15 C.C. permanganate = -012 gram oxygen corresponding to 5.85 per cent. VII. -205 gram decolorised 15 C.C. permanganate = -012gram oxygen corresponding to 5.85 per cent. These results agree with the formula- UOS.U03,(NHI)20 .8H20 = UzOlo.2N€&.8H& FAIRLEY OM HYDROGEN DIOXIDE as the following comparisons show :-Found. -f % Calculated. I.11. IT. 111. v. TI.VII. Uz .... .. 480 58.54 58.67 59-35 * 010.... . . . . 160 19.51 19.55 19.69 t .... 36 4.39 4.47 4.39 8R20.. . .. 144 17.56 Difference 17-31 16.57 820 100.00 100.00 100~00 Peroxide oxygen, * O3 ........ 48 5.85 5-86 5-85 f (N€€3)2.... 34 415 4.22 4-15 The experimental numbers give the ratios- Weight of uranium present oxygen estimated by permanganate 10 :1 = 480 :48. Weight of uranium present :to ammonium 40 :3 = 480 :36 results which agree with the above formula. Regarded as a double peroxide of uranium and ammonium the for-mula of this compound becomes 2U04. (NH4),02.8H20. In this point of view this body may indicate the possible existence of ammo-nium peroxide. Attempts made to isolate this compound bave hitherto failed though I have observed that the smell of a mixture of con-centrated hydrogen peroxide and ammonia is peculiar and I have also obtained a crystalline double peroxide of silver and ammonium.I am therefore not without hopes of success in the isolation of ammonium peroxide. Sodiwm Permanate UOa . 2Naz0. 8H,O. (Double Peroxide of Uranitm and Sdium UO . Na404 8H,O.) This compound is readily obtained by dissolving ordinary uranic hydrate or hydrated uranic tetroxide in sodium hydrate solution by addition of excess of hydrogen dioxide. It is well to use excess of alkaline hydrate so as to avoid the formation of a second salt con- taining more uranium than the above. If strong solutions be used the salt crystallises out in a few hours in the form of yellow needles sometimes grouped in star-like clusters.If more dilute solutions be used the salt may be readily separated in crystalline needles or plates by addition of a little alcohol in which it is much less soluble than sodium peroxide. When freshly prepared this oornpound has a beautiful golden lustre. AND CERTAIN PEROXIDES. 137 On exposure to the air it slowly effloresces with absorption of car-bon dioxide and loss of oxygen. It is however much less affected by exposure to the air than pure sodium peroxide an exposure of days in the one case producing little more effect than that of its many hours in the other. It gives off a proportion of oxygen smonnting to three atoms in the above formula in contact with solutions of acidified permanganate alkaline hypochlorites and other unstable oxygen compounds.It gives precipitates with solutions of most of the metals. These precipitates are dissolved or modified by addition of acetic acid. When heated alone it gives off oxygen gas equal to three atoms in the above formula and about three-fourths of its water amounting to 17 per cent. When heated in a current of carbon dioxide it gives off the same proportion of oxygen and all its water amounting to 24 per cent. The hydrochloric acid solution of tlie ignited salt does not dissolve gold whereas that of the unchanged salt readily does so. The solution of this salt is not completely decomposed by boiling either alone or with addition of ammonia. A solution containing 0.9565 gram boiled with excess of ammonia and the liquid further left overnight to evaporate on the water-bath gave a dry residue which was still entirely soluble in water and on addition of dilute sulphuric acid decolorised 28 C.C.permanganate showing that about one-third of the peroxide oxygen still remained in solution. During the boiling a precipitate of crystalline scales was observed. The following experiments may be quoted relating to the preparation of the salt :-Uranic nitrate solution containing 0.929 gram uranic oxide dis- solved in 50 c.~.of water was mixed with 10 c.~.of hydrogen dioxide of 3.2 per cent. and excess of sodium hydrate solution. A portion of uranic oxide remained undissolved. A solution containing half the above quantity of uranic oxide 0.4645gram was mixed with 10 C.C.of hydrogen dioxide of 3.2 per cent.and 2 C.C. of 10 per cent. sodium hydrate solution added. Per-fect solution of the uranium took place and on addition of alcohol there was precipitated first a red crystalline salt and afterwards the yellow salt. The salt was prepared for analysis by pressure between folds of filter paper. If the filter on which the crystalline precipitate sepa- raked by alcohol has been collected be spread out on a dry brick it is easy to dry the salt rapidly. If the wet precipitate be left on the filter in the ordinary way to drain a considerable proportion of the salt may be lost by re-solution especially in warm weather. FAIRLEY ON HYDROGEN DIOXID E The following analyses have been made :-( I. 0.207 gram salt titrated with permanganats required 20% C.C.= 0.01648 gram. oxygen corresponding to 7.96 .r( per cent. 11. 0.207 gram saltrequiiBed 20.5 C.C. permanganate = 0.0164 gram oxygen corresponding to 7.92 per cent. 111. 0.302 gram salt required 29.9 C.C. perma.iiganate = 0.02392 gram oxygen corresponding to 7-92 per cent. T IV. 0.302 gram salt ignited and dissolvcd in acetic acid re- quired for precipitation of the uranium 7.8 C.C. of sodium phosphate solution = 7% x 0.01858 gram UOs = 0.145 gram U03 corresponding to 47.99 per cent. or 59.99 per cent. of uranium. i V. 0.2 gram salt after two days' exposure to the air de- colorised 19.7 C.C. permanganate = 0.01576 oxygen cor- responding to 7.88 per cent. VI. 0.2 gram salt ignited in a covered porcelain crucible lost 0.0498 gram amounting to 24.9 per cent.VII. 0.35 gram salt ignited lost 0.087 gram corresponding to 24.86 per cent. Experiments VI and VII were made from the same portion of slightly decomposed salt as Experiment V and the residue after ignition in each case effervesced on addition of acetic acid. VIII. 0.2 gram ignited dissolved in dilute hydrochloric acid; the uranium precipitated by ammonium hydrate the fil-trate evaporated and the residue ignited weighed 0.0785 gram consisting of sodium chloride equivalent to 0.0416 gram sodiam oxide or 20.8 per cent. The purity of this residue was ascertained by titration with decinormal silver nitrate solution of which it required 13.2 U.C. This is equivalent to 13.2 x 0.0031 gram NasO = 0.0409 gram NhO or 20.45 per cent.IX. The residue frow Experiment VII dissolved in nitric acid and the uranium precipitated by ammonia gave after ignition 0.163 gram Us08,corresponding to 4'7.45 per cent. UOs or 39.54 per cent. uranium. . r X. 0.9565 decomposed dissolved in hydrochloric acid and precipitated by ammonia gave 0.45 gram U30s corre-sponding to 47.93 per cent. UOs or 39.94 per cent. of" uranium. AND CERTAIN PEROXIDES. 139 XI. 0.2039 gram heated in a current of carbon dioxide gave 0.049 gram water and 11.1C.C. of oxygen gas rednced to standard temperature and pressure. This corresponds to water 24.03 per cent. and oxygen 7.8 per cent. These results agree with the formula U0,.2Na20.8H20 or U08Xa4.8H,O as the following comparisons show :-Found. c > I.IV. 11.VII. Calculated. VIII. IX. 111.X. XI. Mean. 03...... 48 7-95 7.96 7.92 7.92 7.8 7.90 2Na20 .. 124 20.53 20.45 --20.45 8H20... . 144 23.84 (Difference 23.60) -24.03 23-81 604 100.00 100~00 99-95 Red Sodium Peruranate U209.Na,0. 6H2O = UOs.U03.Na20.6H,0 (on the peroxide view 2U04.Na20,.6H,0). This salt is precipitated before the preceding when a minimum quantity of sodium hydrate solution is used. On addition of alcohol it often separates out as a deep red oil slowly becoming crystalline. The following analyses have been made :-I. 0.85 gram salt gave 0.619 Do3,corresponding to 72-82 per cent. UO or 60.68 per cent. uranium. 11. 0.85 gram salt decolorised 65 C.C. permanganate = 0.052 gram oxygen corresponding to 6.11 per cent.111. 0.85 gram salt gave 0.125 NaCl equivalent to 0.0662 Na20 or 7.78 per cent. IV. 0.918 gram salt decomposed by heat and titrated with sodium phosphate solution after dissolving. the residue in acetic acid required 36 C.C. = 36 X 0.01858 UOS = 0.6689 go,,correspond-ing to 72.86 per cent. UO, or 60.72 per cent. uranium. These results agree with the above formula thus :- FAIBLEY ON HYDROGEN DIOXIDE Found. Calculated. I. 11. 111. IT U2 ...... 480 72.82 72.86 0,...... 96 12.09 0 ...... 48 6.05 6.11 Na,O .... 62 '7.81 7-78 6H20... 108 13.60 (Difference.. 13.29) 794 100~00 The ratio of the weights in this salt of the peroxide oxygen and of the uranium is 1:10 as in the case of the ammonium salt.Potassium Perwrmzate, U06.2K20.10H20. (Double peroxide of uranium and potassizm UO4.K4O4.10R,O .) This salt is obtained by adding alcohol to its solution prepared by treating uranic nitrate with potassium hydrate and hydrogen dioxide in excess. It separates as a yellow or orange precipitate which is much more unstable than the corresponding sodium and ammonium compounds rapidly absorbing carbon dioxide when exposed to the air and losing oxygen. It is also readily decomposed by heat giving off water and oxygen. Both the analyses and the formation of the salt show that it con-tains three atoms of peroxide oxygen to one of uranium. The following experiments may be quoted :-25 C.C. of uranic nitrate splution containing 0.387 gram of uranium treated with 10 C.C.of hydrogen dioxide (3.23 per cent.) and potas- sium hydrate (10 per cent.) gave on addition of 25 C.C.of alcohol (80 per cent.) a crystalline precipitate which slowly separated out of the liquid. The salt must be separated as rapidly as possible from the liquid to prevent decomposition and loss of oxygen. The following experiment made before the analysis of the salt is instructive as showing the proportion of peroxide oxygen required for its formation. 78 C.C. of manic nitrate solution containing 1.2 gram of uranium were mixed with excess of pure potassium hydrate solution -10 C.C. of a 20 per cent. solution. Hydrogen dioxide was then slowly run in from a burette into the liquid which was thoroughly shaken after each addition of the dioxide.It was found that to effect complete solution of the uranic hydrate in the alkaline liquid 12 C.C. were required containing 0.24 gram of peroxide oxygen. One atom or 240 parts of uranium would therefore require three atoms or 48 parts of AND CERTAIN PEROXIDES. oxygen from the hydrogen dioxide* to produce the new soluble com-pound. Owing to partial decomposition I have been compelled to reject a large number of analyses made of this salt. The following were made the same day that the salt was prepared :-0.71 gram decolorised 60 C.C. permanganate =0.048gram oxygen corresponding to 6.76 per cent. The same after being reduced by treatment with zinc and sul-phnric acid required 20.5 C.C. permanganate equivalent to 0.295 gram U03,or 41.55 per cent.UO, or 34.61 per cent. uranium. 0.126 gram decolorised 10.8C.C. permanganate = 0.00864 gram oxygen corresponding to 6-87 per cent. The same after reduction required 3.6 C.C. permanganate equi- valent to 0.05184 gram UO, or41.14 per cent. or 34.18 per cent. of uranium. 0.13 gram decolorised 11 C.C. permanganate = 0.0088 gram oxygen corresponding to 6-77 per cent. These results agree with the above formula thus :-Found. Calculated. I. 11. 111. Mean. u ...... 240 O3 .... .. 48 34-07 6-81 uos 41.55 41.14 - 41.29 O3 ...... 48 6.81 6.76 6.87 6.77 6.80 2K,O .... 188.4 26-75 10HZO .. 180 25*c56 704.4 100.00 The water in this formula is given only as that agreeing with the percentage composition of the salt dried by pressure between folds of filter paper.OXIDESOF TUNGSTEN IX. ON HIGHER AND MOLYBDENUM. (Preliminary Notice.) Tungstic dihydrate dissolves readily in solution of hydrogen dioxide even in presence of much free acid forming a liquid comparatively stable in dilute solutions but which in the case of strong acid solu-tions gradually deposits insoluble tungstic oxide. * 1 C.C. of this dioxide titrated at the same time required 25 C.C. permanganate solution and contained therefore -02 gram oxygen. An experiment with similar result was made with sodium hydrate. VOL. XXXI. L 142 FAIRLEY ON HPDROGEN DIOXIDE ETC. The solution evaporated to dryness over sulphuric acid in vacuo gives transparent scales of a greenish-yellow colour perfectly soluble in water.The solution so formed can be analysed by titration with permanganate in acid solutions and as the titration proceeds the in-soluble tungstic hydrate re-appears. The new tungstic oxide appears to form crystalline compounds with alkaline peroxides which however are very unstable and necessitate working at low temperatures. Molybdic trioxide also reacts with hydrogen dioxide to form a com- pound which dissolves in acid solutions to form a yellow or deep orange liquid and which gradually deposits an insoluble molybdic oxide of a yellow colour. The solutions of molybdic trioxide in excess of alkaline hydrate and hydrogen dioxide are exceedingly unstable at ordinary temperatures but appear to give crystalline compounds capable of existing at ice- cold temperatures.1 have therefore postponed the further study of these compounds until the prevalence of very cold weather renders this branch of the subject more accessible. CONTENTS OF THE PAPER. PAGE Past I. Hydrogen Dioxide and Metals ............................ 1-6 History and theories published.. ............................ 1 Recurrent chemical action ................................ 2 Action of metals under various conditions and new solvents for gold silver and platinum.. ............................ 3 (Composition of hydrogen dioxide used. Note to page 3.) Explanation of catalytic action of the metals.. ................ 5 Past II. Hydrogen dioxide and metallic oxides ......................6-8 Theories of the reactions and discussion of the transmutations of energy involved in them.. ............................ 7 Pormation of unstable higher oxides ........................ 7 Past III. Thermo-chemistry of the oxygen molecule .................... 0-22 The energy due to the formation of hydrochloric acid.. ........ 8 Energy due to the formation of water.. ...................... 9 Method of approximating to the energy of the oxygen molecule.. 9 General observations on the energy due to chemical attraction .. 9 The energy due to the formation of H& and 03,&c.. ......... 10-11 The nascent state of elements .............................. 11 Description of methods and apparatus used ..................11-15 Results obtained by others ................................ 15 Experiments with permanganic acid and hydrogen dioxide.. .... 15-17 ,> argentic oxide )) ...... 17-20 bypochlorites *. * .. 21-22 99 >) WRIGHT ON TRE ALKALOIDS OF THE ACONITES. 143 PAGE Part IV . Hydrogen dioxide and chlorine. bromiae. and iodine ........ 23 v'vl' sulpiiidesJJ J) ........................ 24 J> >) J) .. alcohol .......................... 24 Part VII. On sodium dioxide-new method of preparstion. properties. and analyses ........................................ 125-127 Part VIII. On New Oxides and Compourzds of Uranium .............. 12'7-141 Uranium tetroxide preparation. properties and analyses ...... 127-141 Higher uranium oxides ................................133 Ammonium peruranate ................................ 134 Sodium peruranate .................................... 136 Red sodium peruranate ................................ 139 Potassium peruranate ................................ 140 Payt IX. Cn higher oxides of Tungsten and Molybdenum (preliminary notice) .......................................... 141

ISSN:0368-1769    

DOI:10.1039/JS8773100125

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

WRIGHT ON TRE ALKALOIDS OF THE ACONITES. 143 IV.-The Alkaloids of the Aconites. Part I. On the Crystallisable Alkaloi’ds contained in Aconitum ATape71w. By C. R. ALDERWRIGHT, D.Sc. Lond. Lecturer on Chemistry in St. Mary’s Hospital Medical School. INa prelimirtary notice read before the Chemical Society in 1875 aid printed amongst the abstracts in the Chern. SOC.Jouma~[2] xiii 1265 the author and Mr. G. H. Beckett described the first results obtained from the examination of various products extracted by Mr. T. B Groves (Weymouth) fimom Aco@tum ferox and A. NqueZZtcs the mode of extraction adopted being percolation of the ground dry roots with alcohol slightly acidulated with hydrochloric acid evapo- ration to a small bulk of the extract thus obtained precipitation of bases by ammonia and extraction by ether of the alkalo’ids thus pre-cipitated.In this way there was isolated from the A.fwox an alka- loid crystallisable from ether but yielding salts that wholly refused to crystallise drying up to varnishes readily soluble in water appa- rently this substance is the main ingredient in the preparations which have been designated by various chemists “ English aconitine,” “ pseudoaconitine,” “acraconitine,” &c. On analysis this body gave numbers represented by the formula C3,HI9NOl1,the gold salt beiny C36134,NOl,.HGI.AuC13.Further experiments on the “constitution .’ L2 144 WRIGHT ON THE ALKALOIDS OF THE ACONITES. of this substance are in progress and will be described in a subsequent memoir.Very different results however were obtained with A. Napellus. Few substances of high physiological activity have formed the subject of examination by more chemists and pharmacists than this body ; and with few if any have more contradictory results been obtained this want of uniformity in results appears to arise from many causes. In the first place it seems excessively probable that due care in selecting the roots examined was not always exercised so that the roots of different species were probably mixed together there seems from the results obtained by Mr. Groves and the author some reason for supposing that entirely different bases are obtainable from different species. In the next place the mode of extraction employed was in most instances such as must inevitably have caused a large amount of alteration and decomposition of the alkaloids present during the pro..cess of extraction the alcoholic extracts having generally been heated in contact either with a mineral acid or with an alkali or both ; as the active principle of aconite roots is known to be of a highly unstable character the chances of uniform results being obtained by such pro- cesses are very small. Lastly with only one or two exceptions the substances isolated have not been subjected to analysis and absolutely no numerical results have been given by the majority of writers and experimenters. Thus the only numerical values that the author has been able to find recorded prior to 1870 are those of von Planta (AnmaZen der Clzenzie lxxiv 25'7) and that the substance examined by this chemist did not present satisfactory iudications of purity and indeed of authen-ticity is manifest from the circumstance that the material examined was purchased from Merck who had not prepared it himself and that it wits an amorphous powder.No history of its preparation from the root is given but presumably it was extracted by the process of Geiger and Hesse who first discovered the alkalo'idal character of the active principle of A. NapelZus roots ; this process involves heat- ing the alkalojid in ccmtact first with lime and secondly wit?h sul- phuric acid which could hardly fail to bring about considerable alteration in so unstable a body as the active principle is known to be.For these reasons therefore the formula arrived at by von Plan ta vie. C30H47N07, the hydrochloride being C,H4,N07.2HC1 (!) must be regarded as open to grave objection (vide imfra). In 1860 Mr. Groves succeeded in isolating from A. NapeZZw a crystalline alkaloid possessing high physiological activity and forming well crystallised salts (€'harm. J. Trans. [2] viii 121) ; this was exhi- bited in the Exhibition of 1862 (as was also a specimen of a crystal- lised alkaloid obtained by Morson but which was apparently not WRIGHT ON THE ALKALOIDS OF THE ACONITES. 145 derived from A. NapeZZus). Unfortunately Mr. Groves’ product was not analysed at the time but a portion of the nitrate of the sample thus obtained has subsequently been examined by the author and Mr.Beckett the crystals of base regenerated from the nitrate by ammonia and ether gave the following values :-0.2270 gram gave 0.5235 CO and 0.1480 H,O. 0.2975 , , 0.6845 , , 0.195 5 , 0.5795 , of gold salt gave 0.1200 An. Calculated for Calculated for C3&b3NO10. C33I-IGNOI,. Found. Carbon in free base .. 63.89 62.34 62.90 62.75 Hydrogen .......... 7.15 6.97 7.24 7.30 Gold in gold salt .... 20.85 20.50 20.71 From the results detailed below the conclusion is unavoidable that this product either was imperfectly purified or else had been some-what altered and diminished in molecular weight during its extrac- tion; the latter is not at all improbable as the specimen had been purified by conversion into the insoluble mercuric iodide compound and regeneration from this substance.The author has found in the case of the base derived from A.ferox above alluded to that the mer- curic iodide process actually does cause a considerable amount of change of this character. Some years subsequently (1871 and 1872) M. Duquesnel succeeded in isolating from Aconitzwn napellus a well-crystallised base to which he gave the name “aconitine crystallis6e,” to distinguish it from the amorphous preparations met with in commerce under the name of aconitine. Tlie process employed was extraction with alcohol acidu- lated with tal-taric acid evaporation of the extract at temperatures not exceeding 60° precipitation by sodium bicarbonate and crystal- lisation of the precipitate from a mixture of ether and light petroleum spirit (Coinpt.rend. lxxiii 207 ; also Ann. Chint. Plzys. [4] 25 151). &I. Duquesnel gave the following numbers as obtained from this preparation :-Carbon.. .............. 59.96 60.18 Hydrogen. ............. 7.35 7.54 Nitrogen .............. 2.58 2.69 from which he deduced the formula C,,H4,,N0,,. The experiments described below clearly show that this product could not have been pure inasmuch as frequently repeated crystallisation does not suffice to separate completely the crystallisable alkaloid contained in A. N(t-pellus from another amorphous substance of lower molecular weight obtained along with it by M. Duquesnel’s process. 146 WRIGHT ON THE ALKALOIDS OF THE ACONITES. In 1874 wishing to obtain a larger supply of the crystalline base from A.Napellus isolated by him in 1860 Mr. Groves operated on two batches of 1cwt. each of roots purchased as Aconitunz Napellus and presenting the appearance of that species ; whether however there was not a large admixture of some other species or whether the roots examined were of abnormal character from some peculiarity of soil or climate is open to question from the totally unexpected nature of results obtained with these roots. Qn working up the extract obtained by means of alcohol acidulated with hydrochloric acid a well-crystal- lised mass was obtained consisting of the mixed nitrates of two entirely dissimilar bases (Year-book of Pharmacy 1874 507). Of these one when in the free state crystallised readily from ether and has been found by the writer to be identical with the alkaloid obtained in an imperfect,ly pure condition by M.Duquesnel; the other wholly refused to crystallise from ether or any other solvent when in the free state although the varnish-like products obtained on evapora-tion of the solutions of the base readily formed well-ci.ystallised salts on moistening with dilute mineral acids. Curiously enough whilst the former base was highly active physiologically the latter was almost inert half-grain doses being taken internally by Mr. Groves without the production of any marked symptoms. It seems not at all im- probable that the very varying activity exhibited by different com- mercial preparations sold as aconitine " may be at least partly due '6 to the circumstance that the usual modes of preparation of the drug are not calculated to effect any separation of the active alkaloi'd from the inert base should the latter be contained in the roots employed.These products obtained by Mr. Groves have been subjected to careful examination by the author with the following results :-A. ComparativeZy inert Base. Picraconiti?ae.-The sdts of the com- paratively inert base when tasted do not produce the peculiar prickling of the tongue characteristic of aconite roots but simply have a bitter taste ; for which reason it is suggested that the term " picraconitine " may be conveniently employed to designate this base. It was at first thought by Mr. Groves that this substance might be identical with the body isolated by Br o ug h ton from zlconitunz 1LeterophgZZu.m (called atees in India) and termed by him atisine but the numerical values obtained and other circumstances are quite inconsistent with the identity of the two bodies.Thus Broughton found (Medical Press ami! Circular May 27 1874) that atisine melted at 85" formed crys- talline salts only with difficulty and gave a platinum salt pretty readily; from this last the formula C4,H,IN2Q5 was deduced; picm- conitine on the other hand does not fuse at loo" forms crystalline salts with great ease forms a platinum salt so soluble in water that it is only precipitated in very concentrated solutions and cannot be WRIGHT ON THE ALKALOIDS OF THE ACONITES. 147 washed without almost wholly dissohing ; and lastly yields numbers leading to the formula C3,HP5NO10.(1) Crystals of picraconitine hydrochloride prepared by Mr. Grov e s (Zoc. cit.) and purified by several recrystallisations 0-61.90 gram (air- dry) lost at 100" 0.0295 gram. (2) Ditto recrystallised from water 0.4725 gram (air-dry) lost at 100" 0.0230 gram. (3) Ditto again recrystallised from water 0.5260 gram (air-dry) lost at 100" 0.0190 gram. (4) Ditto yet again recrystallised from water 0-91.90 gram (air- dry) lost at 100" 0.0380 gram. Found. Calculated for C31H45NO~~,HC1,1~Hz0. (1.) (2.) (3.) (4.) 4-13 4-77 4.87 3.61 4.13 Specimen (1) 0.2680 gram dried at loo" gave 0.5755 GO and 0.1850 H,O. Specimen (1) 0,4490 gram dried at loo" gave 0.1000 AgC1.Specimen (4) 0.3520 gram dried at loo" gave 0.7555 CO and 0.2400 HZO. Specimen (4) 0.3320 gram dried at loo" gave 0.0750 AgCl. 7 9 77 97 , 0.5050 , , 0.1100 99 , 0.4790 burnt with soda lime gave 0.0735 Pt. Found. Calculated. (1.) (4.) C,l ............ 372 59.29 58-56 58-53 H46 ............ 46 7.33 7-67 7.58 N.............. 14 2.23 -2.18 O, ............ 160 25.49 - c1 ............ 35.5 5-66 5.51 5-59 5.44 Picraconitine precipitated from hydrochloride No. 4 dissolved in ether and obtained as a varnish by spontaneous evaporation not fusible at 100". 02460 gram gave 0.5675 COz and 0.1745 H,O. Calculahed. Found. c31 .......... 3 72 62.95 62.91 H .......... 45 7.61 7.88 N............ 14 2.37 01 ..........160 27.07 C31H45NO1,. ... 591 100??0 Picmconitine aurochloride is precipitated in canary-yellow flakes not 148 WRIGHT ON THE ALKALOIDS OF THE ACONITES. perceptibly crystalline and exceedingly sparingly soluble in water on addition of gold chloride to picraconitine hydrochloride solution. After drying over sulyhuric acid it does not alter at 100”. From hydrochloride (1) 0.6790 gram gave 0.1430 Au = 21.06 per cent. 7 , (2) 0.6995 , ,) 0.1475 , 21.09 , 1.1170 , ,) 0.2380 ) 21-35 , Average. ............. 21.15 Calculated for C31H4,NOlo,HCl,AuCI,. ..... 21.07 It is noteworthy that no indications of the presence of this base were observed by Mr. Groves in his former experiments (1860) nor was any such body obtained in the author’s experiments described below ; the circumstance however that roots purchased as Aconitum NapeZZus were found on this one occasion to yield a crystallised pro- duct (nitrate) of which by far the larger proportion was a substance inert as compared with the active principle of the roots is of great pharmaceutical importance as tending to throw light on the great discrepancies sometimes noticed in the physiological potency of dif- ferent specimens of the drug met with in commerce under the name of “aconitine.” B.Physio2ogically active Base. Aconitine-The base crystallisable from ether and possessing high physiological activity was separated by the author from the mixture of nitrates of this alkaloid and of picraconitine obtained by Mr. Groves (Zoc.cit) by simply dissolving in ether the mixture of bases precipitated from the mixed nitrates by ammonia and leaving the solution to evaporate spontaneously ; in this way a small quantity of crystals was obtained which after two recrys- tallisations from ether gave the following numbers :-Carbon in free base.. ............ 62.90 Hydrogen. ..................... 7.45 Gold in gold salt. ............... 20.32 These numbers agree fairly with those required for the formula C33H45NO11 and are almost identical with those obtained from the crystallised base isolated by Mr. Groves in 1860 (supra). The two products agreed closely in all their characters and moreover they exactly agreed with M. Du quesnel’s description of his “ aconitine crystallis&e.” The experiments which follow clearly demonstrate that each one of these three bodies must have consisted essentially of the Same alkalojd but not in a state of purity; when pure this base (to which it is proposed to restrict the term aconitiize for scientific pur-poses) is indicated by the formula C33H43N0I2.WRIGHT ON THE ALKALOIDS OF THE ACONITES. 149 The imperfectly purified crystalline base obtained from the mixed nitrates as above described did not materially alter in molecular weight by recrystallisation and appeared to be uniform in character ; but on dissolving it in slightly warm dilute hydrochloric (or better hydrobromic acid) and allowing the solution to crystallise a salt was produced from which a base was regenerated by sodium carbonate and ether apparently identical with the original substance but giving somewhat different numbers.On repetition of the process no fur- ther change in the base was produced whence it is evident that aconitine (like eertain other alkaloids e.g. papaverine) has so strong a tendency to adhere to other substances found along with it that simple crystallisation of the free base several times successively is insufficient to purify it completely although conversion into a crystal-lisable salt and recrystallisation of the latter effects a complete sepa- ration The following numbers were obtained with the pure base thus regenerated from the hydrobromide :-0.2845 gram gave 0.5080 CO and 0.1370 H20. Calculated. Found. c33 .......... 396 61.39 61.71 Ha3 ..........43 6.67 6-78 N............ 14 2-17 01,........... 192 29.77 CaH&"la .... 645 100.00 After solution in warm dilute hydrochloric acid crystals of the hy-drochloride were formed ; of these when air-dry 0.5140 gram lost at 100" 0.0390 gram ........ = 7-59 per cent. The formula C33H43N012,HC1,3H30 requires 7.34 ,, 0.4'750 gram of dry salt gave 0,0995 AgCl ,. C1 = 5.18 ,, Calculated for C3,H4,N01,,HC1. ..... C1 = 5.21 , The hydrobromide recrystallised from water gave the following values :-0.4087 gram (air-dry) lost at 100" 0.0250.. .. = 6.11 per cent. Calculated for C3,H4,NOl2,HBr,2+H2O.. = 5.83 , 0.3837 gram of dry salt gave 0.1000 AgBr.. Br = 11.09 , .........= 11.02 ,, Calculated for C33H43N012,HBr On addition of auric chloride to the aqueous solution of phis hydro- chloride pale-yellow amorphous flakes of a gold salt very sparingly soluble in water were thrown down ; after complete drying over sul-phuric acid in the dark these lost no weight at 100" ; in a thin film 150 WRIGHT ON THE ALKALOIDS OF THE ACONITES.however the salt slightly darkened in the light in the course of a day or two at the ordinary temperature. 0.4630 gram of gold salt dried at 100" gave 0.0925 Au gold = 19.98 per cent. Calculated for C33H43NO12,HCI,AuC13 = 19.98 , These numbers clearly show that pure aconitine when regenerated from a crystallised pure salt is expressed by the formula C33H43N012 the difficulty in obtaining tlie base pure by simply recrystallising it from ether is exactly that which is noticed in the case of papavel-ine which as was first pointed out by Hesse and subsequently by the author and Mr.Beckett (this Journal May 1876) cannot be ob- tained pure by simple recrystallisation but is readily purified by con-verting the approximately pure substance into a crystallisable salt (acid oxalate) recrystallising this and regenerating the alkalo'id from the product. With the object of submitting aconiiiine to a thorough chemical investigation 2 cwts. of Acoizitum Napellws roots were worked up by Messrs. Hopkinssand Williams to a condensed extract in ac- cordance with the directions of M. Duquesnel this " tartaric acid pro- cess '' being employed rather than one involving the use of a mineral acid in order to avoid possible decomposition it seems by no means improbable that the amorphous and ill-defined substances described by Hubsc hmann and others under the name of napelline ecolyctine lycoctonine &c.may be really only aconitine or some allied body more or less altered and decomposed during the extraction process. The ground root was percolated by alcohol acidulated with tartaric acid (about 60 gallons of alcohol and 1lb. of tartaric acid being em- ployed altogether) and the extract was evaporated to a small bulk at as low a temperature as possible. About 5 gallons of condensed extract were then obtained which was worked up by the author as follows :-The liquid consisting of a clear brown-red aqueous portion and a dark soft resin was exposed to the air in shallow vessels for a few days to dissipate some of the remaining alcohol and was then diluted with water and filtered from resin ; the aqueous filtrate was agitated with benzoline (light petroleum distillate) whereby some remaining resin was removed and the aqueous liquid was then pre- cipitated by a slight excess of potassium carbonate the filtrate con- tained a base soluble in carbonate of ptassinm which gave a copious precipitate with mercuric iodide dissolved in potassium iodide this precipitate when decomposed by sulphuretted hydrogen finally yielded a small quantity of crystals of aconitine but chiefly consisted of a base which appeared to be wholly non-crystalline and to form non-crystailline salts and much resembling (if indeed not identical with) WRIGHT ON THE ALKALOIDS OF THE ACONITES.151 the non-crystalline base or mixture of bases obtained as described below from the mother-liquors left on recrystallising the potassium carbonate precipitate. The precipitate thrown down by the potassium carbonate was agi-tated with ether and the ethereal solution thus obtained with tartaric acid solution ; the ether thus freed from base was used over again several times finally the whole of the precipitate was thus dissolved with the exception of some humus-like flakes the ether left after agitation with tartaric acid contained in solution a small qnantity of a clear soft yellow resin. The acid tartrate solution thus obtained was systematically worked up in order to discover if more than one crys- talline alkaloid was present; it was first precipitated with sodium carbonate and the precipitate agitated with successive small quanti- ties of ether whereby finally a considerable portion was left undis-solved in the form of snow-white crystalline flakes the ethereal solution thus obtained gave by spontaneous evaporation a copious crop of slightly coloured crystals which were filter-pumped dissolved in benzene and precipitated by addition of benzoline (light petroleum spirit) finally the mother-liquors and drainings of these crystals were evaporated and the residue dissolved in dilute acetic acid whereby a little resin was left undissolved the solution was treated with a little sodium carbonate to throw down colouring matter and remaining resin and the filtrate with excess of sodium carbonate and ether ; this ethereal solution gave successive crops of crystals on spontaneous evaporation with a final syrupy rnother-Jiquor which dried up to a varnish and refused to yield any crystalline salts on solution in acids and spontaneous evaporation it could not therefore have contained any considerable amount of picraconitine this final product gave the following numbers:-Carbon in base ..........66.39 Hydrogen .............. 7.94 Gold in gold salt ........ 23.91 which are not far removed from the numbers found by von Plants (Zoc. cit. supra) and from which he deduced the formula C30B47N0, viz. :-Another sample. Carbon in free base .. 67.81 68.34 67-95 64.83 66.95 Hydrogen ..........8.82 8.90 8-64 8.14 8-59 Nitrogen ............ -3.59 3.31 - L Gold in gold salt .... -22.06 --It can therefore hardly be doubted that the product examined by von Planta consisted mainly of the non-crystalline base (or mixture 152 WRIGHT ON THE ALEALOIDS OF THE ACONITES. of decomposition-products formed during extraction 2) just described. It may be noticed that von Planta’s numbers represent the gold salt as being C3,H,7NOi.HC1.AuC13 + H20 (?),whilst what he regarded as a hydrochloride C3,,H4,NO7.2HC1 must evidently have been formed by an action of the hydrochloric acid different from mere combination. In this way three batches were obtained:- (A.) Left undissolved by ether at first (ether not employed in large quautity).(B.) Crystals deposited from first ethereal solution and purified by benzene and petroleum. (C.) Crystals from mother-liquors. Each one of these batches,. when fractionally crystallised from ether yielded the same numbers in all cases closely approximating to those required for the formula C33H43N0,2, but giving a gold salt containing a little too much gold; when however these approximately pure specimens were converted into hydrobromides and the drained and washed crystals of that salt were treated with sodium carbonate and ether crystals of base were obtained perfectly corresponding with the substance similarly purified from Mr. Groves’ products described above and designated aconitine and giving exactly the numbers required for the above formula.Thus the following numbers were obtained with the substance purified only by crystallimtion from ether :-Specimen No 1. Crystals left undissolved by ether (A) converted into gold salt- 0,8045 gram gave 0.1640 Au. 0.9210 , , 0.1875 , No. 2. (A) treated with ether sufficient to dissolve one-third ; solu-tion crystallised by spontaneous evaporation- 0.2615 gram gave 0.5840 CO and 0.1600 H,O. 0.4825 gram gold salt gave 0.0980 Au. No. 3. Portion of (2) insoluble inether similarly treated crystds from this second ethereal fractional solution- 0.3545 gram gave 0.7880 COaand 0,2200 H,O. 0.2720 , , 0.6060 , 0.1670 , 0.5730 , gold salt gave 0.1165 Au. No. 4. Crystals left undissolved from (3)-0.2830 gram gave 0.6380 CO and 0.1730 H,O.0.2880 , , 0.6475 COz and 0.1800 H,O. 0.6760 , gold salt gave 0.1375 Au. WRIGHT ON THE ALKALOIDS OF THE ACONITES. 153 No. 5. (B) recrystallised from ether-0.2700 gram gave 0.5980 CO and 0.1620 H,O. 0.5630 , gold salt gave 0.1140 Au. No. 6. (C) recrystallised from ether-0.2525 gram gave 0.5705 CO and 0.1520 H,O. 0.5615 , gold salt gave 0.1135 Au. ,I 0.5190 , , 0.1050 , Carbon Hydrogen Gold in in base. in base. gold salt. No. (1).................... -20.38 . .................... -20.36 (2). ................... 60-91 6-79 20.31 (3) .................... 60.62 6.89 20.33 , .................... 60.76 6.82 - (4) .................... 61.48 6.79 20.34 , .................... 61.32 6.94 - (5) ....................60-40 6.6'7 20.25 (6) ....... ............. 61-62 6 69 20.23 20.21 Average .................. 61.02 6-79 20.30 Calculated for C,3H4,N0,2.... 61.39 6-67 19.92 Specimens Nos. 2 3 and 4 (A) were mixed and converted into hy-drobromides as was No. 5 (B) and also No. 6 (C). The recrystallised salts gave the following numbers :-Purified hydrobromide I (from A) 0.3850 gram of air-dry salt lost at 100" 0,0230 = 5.97 per cent. Purified hydrobromide I1 (from B) 1.3800 gram of air-dry salt lost at 100" 0.0820 = 5.94 per cent. Calculated for C,,H4,N012,HBr,2~H,0= 5.83 per cent. I. 0.3620 gram dried at 100" gave 0,0945 AgBr Br = 11.11p. c. 9, 11. 0.5720 , , , , 0.1485 , 11.05 7) Calculated for C33H,3N0,,,HBr = 11-02 , The base regenerated from these three specimens gave these values- Base from hydrobromide 1.-0*2660 gram gave 0.5955 GO and 0.1600 H,O.7 II.-0.24440 0.5500 CO and )) 0.1520 H,O. ,> III.-0*3005 , 0.6800 CO and 0.1850 H20. 154 WRIGHT ON TEE ALKALOIDS OF THE ACONITES. Found. Caleulsted. I. 11. 111. Mean. CS3.......... 396 61.39 61.06 61.47 61.71 61-41 HQ.......... 43 6-67 6-68 6.92 6.84 6.81 N .......... 14 2.17 -- -OI2..-....... 192 29.77 -- C~&&~NOI~ .. 645 100*00 The gold salts gave these values :-From I 0.8445 gram gave 0.1690 Au = 20.01 per cent. yy 11. 0.5725 , , 0.1145 ,) = 20.00 , , 111. 0.6210 , , 0.1240 , = 19.97 , Average 19.99 , = 19-92 ,, Calculated for C33H~NO12,HCl,AuC1~ From these numbers it is clear that the AconiiumNapellus roots examined contained only one base crystallisable from ether ; and that this base when perfectly pure was identical with the crcoyzitine C,H,,N012 previoualy isolated in an approximately pure crystallised state by Groves and subsequently by Duquesnel the different formula arrived at by the latter being due to the imperfect purity of the alkaloid extracted by him.The quantity of crystallised base C33H43N0127isolabed from the 2 cwts. of roots amounted to a little upwards of an ounce the total amount of alkaloids (amorphous products included) being some 2iozs. ; this represents a yield of about 0.03 per cent. of crystallised base and 0.07 per cent. of total bases. M. Duquesnel states that the amount of “aconitine cr~s~allisbe” obtainable from A.hTupeZZw varies from 0.6 gram and even none at all to 4 grams per kilo. i.e. from 0.06 to 0.40 per cent,. It may be noticed in this connection that the values given by Proctor Zinoffski and others as to the amount of alka-loid present in aconite roots simply represent the total alkalo‘icls crystalline and non-crystalline and give no clue as to how much of either kind was present ; inasmuch however as these values differ with the country in which the roots were grown &c. &c. it is extremely probable that the amount of crystalline base C~~H*~OI? will be found to vary according to circumstances. It is proposed to study the chemical relationships and the “constitu-tion” of this alkaloid and the allied bases from A.ferox (pseudoco-nitine C36H43N0,1).The physiological action of aconitine is excessively energetic so much SO as to render working with it a matter of coil-siderable pain and difficulty unless great care be taken in manipula- tion and more especially in avoiding the inhaling of the dust of the WRIGHT ON THE ALKALOIDS OF THE ACONITES. 155 crystals of the base or its salts. A minute fragment too small to be seen if accidentally blown into the eye sets up the most painful irri- tation and lachrymation lasting for hours ; whilst similar particles if inhaled produce great bronchial irritation or profuse sneezing and considerable catarrh or "sore throat," according to the part where they lodge. The following sentences summarise the results obtained as above described from the work of Mr.Groves and the author. 1. AconitumNapellus roots as met with in commerce yield by appro-priate means a highly active well-crystallised alkalo'id (nconitifze) which is represented by the formula C33H4,N0,2 ; the crystallised bodies obtained formerly by Groves (1860) and by Duquesnel (1871) consisted mainly of this base but were not perfectly pure. 2. It has happened in one instance that roots purchased as A.NqeZZw yielded only a small quantity of aconitine and that a large amount of a nearly inert bitter base yielding well crystallised salts (picracowitine) mas also present. The preparations usually met with in pharmacy under the name of "aconitine," or " nitrate of aconitine," must necessarily contain this inert base whenever it was present in the roots employed ; and consequently such pharmaceutical preparations cannot be relied on as of uniform physiological potency.3. Besides aconitiize and picmconitine A. Napellus roots contain another alkalojid (alteration product of aconitine produced during extraction ?) of lower molecular weight and incapable of yielding crystalline salts or of crystallising itself. Commercial "aconitine," when not crystallised is liable to contain this substance as an impur-ity ; thus the body examined by von Planta appears to have almost wholly consisted of this amorphous uncrystallisable substance which is perhaps identical with or may contain the body "napelline," and other analogous substances described by other chemists.4. The physiologically active crystallisable alkalojid of A. NrpeZZus (aconitine) appears to be wholly dissimilar from the crystallisable alkaloi'd of A. ferox (pseudaconitine) although the two are doubtless allied and are similar in many of their properties. The inactive bitter base of A. Napellus (picraconitiilze) is not identical with Broughton's atisine from A. heterophyllum. 5. The use of strong mineral acids and other reagents in the extrac- tion of aconite alkalo'ids from the roots (as in the older processes of Geiger and Hesse of Hottot and Lihgeois &c.) is extremely likely to cause loss of crystallisable aconitine by alteration and decom-position ; and to this cause is to be attributed the statement of chemists who have used such processes that the alknlold of A.Napellus is non- crystalline. Not improbably the "lycoctinine " and "acolyctine " of Hiilschmann from A. Zycoctonum are alteration-products thus HIGHT ON A PROPOSED METHOD OF formed. The tartaric acid process of M. Duquesnel is preferable but in view of the first rough crystals of base thus produced being impure and of the difficulty of separating a mixture of the crystallised salts of aconitine and picraconitine it is desirable that in future the sub- stance employed medicinally should have been prepared and separatled from picraconitine (if present) by extracting the mixed alkaloids from the roots by Duquesnel’s process ; recrystallising the crude aconitine crystals thus obtained from ether or analogous solvents so as to sepa- late picraconitine and the other non-crystalline bodies ; converting into a crystallised salt (for which purpose the hydrobromide is well fitted) ; and finally regenerating the alkaloid (if required in the free state) by sodium carbonate and crystallising from ether ;in this way a perfectly defhite homogeneous substance is obtained possessing in a high degree ‘the physiological powers of aconite root.

ISSN:0368-1769    

DOI:10.1039/JS8773100143

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

156 HIGHT ON A PROPOSED METHOD OF V.-Notes on some Experiments made with a view to ascertaining the Practical Nature of a P,roposed Method of Determining the Mineral Stretzytli of Soils by means of Water-culture. By G. A. HIGHT, Indian Forest Department. THE usnal object of water-culture experimenh is to ascertain what particular salts are congenial or necessary to the growth of any parti- cular plant. When a plant is grown in an artificially prepared solu-tion so that it can obtain it,s nourishment solely from the salts con-tained in that solution the exact effect of any salt upon the growth of the plant can be easily observed by adding that salt to or abstracting it from the solution. In order to ascertain whether any soil will sustain any plaxt the usual plan is to examine chemically the soluble matter in the soil.If the soluble salts correspond to those which have been shown by water-culture or by other means to be suitable to the growth of the plant then the soil is regarded as chemically capable of sustaining the plant. The object of the experiments the results of which are tabulated on page 159 was to combine these two processes. The plant was grown in a watery extract of the soil to be examined and it was thought by observing its development and durations to obtain a practical test of the suitability of the soil for the plant in other words of the strength of the soil. If several soils were tested at one time the results might DETERIUNING THE XINERAL STRENGTH OF SOILS ETC.157 it was believed be referred to me another or to a known artificial solution and expresses in figures. It must be'borne in mind that; nothing further was intended than to find a means for determining the chenzicaZ strength of the soil and that the more important factors-more important at least from a forestal point of view-of moisture situation &c. are not taken into account. In order that the experiments might be exhaustive it would pro-perly speaking be necessary to prepare the solutions with water con-taining carbonic acid as it is well known that many of the nourishing salts (phosphates and carbonates) insoluble in pure water are readily soluble in water containing carbonic acid. But as these experiments were only regarded as preliminary to ascertain the practical value of the method it was considered sufficient to use pure writer.Solut,ions of some of the salts of the organic acids prodwed by the decay of vegetation also dissolve the phosphatas and carbonates ; but to intro-duce these into the solution would complicate matters unnecessarily for it is only proposed to test t'he mineyal strength of the soil m Ihe following soils were tested :-A. Loam from Garko forest. This soil was selected from a spot where the trees were dying off. B. Loamy sand from Kelaya forest taken from inside EL large enclo- sure where the young growth was doing very well. C. Loamy sand from Kirsar forest. D. Loam from Butta forest selected from between two of the largest trees. E. Clay from Ghaz forest mountain soil; taken from a part of the forest where the trees were most dense.All these soils excepting E were first deposited from the River Indus. D,B and E were supposed from the growth of the forest upon them to be rich soils; A and C to be poor ones. It must how-ever be remembered that the growth of the forest is no test for the i,zirLwaZ strength of the soil. Each specimen was taken at a depth of 14 feet from the snrfsce. The proportion of the solutions was 1ounce of soil to each pint of water. The solutions were prepared as follows :-4ounces of very carefully dried and sifted soil were piaced in a porcelain evaporating dish. Oiie pint of distilled water was poured over it. The dish was placed in a sand-bath and the contents slowly raised to a temperature of 212" Fah.They were then allowed to cool and after settling for a short time as much as possible of the muddy water was poured off into a second vessel. Over the remaining soil another pint of distilled water was poured ; this raised to 212" Fah. VOL. xxx1. M HIGHT ON A PROPOSED METHOD OF and decanted as before. On the soil before it dried a third pint of water was poured and decanted off and similarly with a fourth. The decanted liquid was then twice filtered. There resulted 3 pints 6 ounces of solution. Distilled water was then added sufficient to bring the whole up to 4pints. This just more than filled three wine bottles of very opaque glass. All the soils were treated in this way in succession and three bottles filled with the extract from each.They were then numbered and labelled as follows :-8’1Kirsar. 14 Ghaz. 7 9 15 16 Normal 5 Helaya. 11 Bntta. 17 } solution. 6 12 lo} No. 3 was damaged owing to the bottle into which the extract was placed not having been properly cleaned. Seedlings of “Acacia arabica ” were placed in the solutions on July 25th eight days after they had been sown. The seedlings were so selected as to be very nearly equal in development and in weight from amongst a very large number. The more vigorous ones were chosen and great care was observed that they should be entirely free from any damage caused by removal from the soil &c. The stage at which the seedlings had arrived was about as follows :-The cotyledons had just opened out ; the peduncle was scarcely beginning to develope itself ; the root was 2-3 inches in length and the average weight of the plants 0.32 grams.A notch was cut in the cork of each bottle and the seedling was supported by a ball of cotton-wool in such a way that the surface of the solution was at exactly the same point where the surface of the soil had been before. In Nos. 16 and 17 labellcd “normal solution,” was a solution pre- pared artificially by the recipe given in Prof. Johnston’s “How Crops Grow,” p. 155. The solution gave a slightly acid reaction. Every morning the portion of the solution taken up by the plants was replaced with distilled water in order that the roots should always remain at the same depth in the water.Every other morning the plants were carefully taken out dried on a piece of blotting paper and weighed. The weights are noted in the appended register. This was continued until August 20th when the experimenter met with an accident and the plants could no longer be attended to. Fresh distilled water was however poured in every morning ; but they were no longer properly cared for and three or four were destroyed by accident. The remainder however continued to flourish and were all alive at the end of October when some of them were about 8 inches high. A. Loam from Gar-B. Loamy sand from C. Loamy sand froin D. Lomi fivin Buttn E. Clay froin Gliaz ko Forest selected I-Idaya Forest ta-Kirsar Fomst. Forest froiii be-Forest uiount:iin where klie trees ken where the t~v-eentwo of the soil ; tnlicn wlicrcx Norriial Dat c.wcre dying off J0""g growtli was largest trees. the trces were tht. solution. (;llIgust 2-4 Solu-doing vcry well. most dense. tion alkaline). ~. ~~ Erupt. Expt. Expt. Expt. Expt. Expt. Expt. ' Erupt. Expt. EYPl. Expt. Expt. Expt. Expt. Expt. Expt. Expt. n k 1. 2. 3. 4. 5. 6. I. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. --.---Irn1s. Jrms. Xrms. Jmis. Xrms. Jrms. Xrms. Grms. Jrms. frms. Jr111s. hms. fr11 IS. Jrms. Xrms. Jrms. 3rms. July 25 .... -. 0 '37 0.24 0 '36 0.32 0.27 0 '32 0 -34 0 *30 0 -38 0-31 0 '29 0 -30 0.28 0 .29 0 '28 0.35 0.28 , 27.. .. .. 0 -45 0.29 0.34 0.33 0 -33 0 *37 0 *41 0 -36 0.43 0 '36 0 *32 0 -3.5 0.30 0.28 0 '30 0 31) 0.32 ) 29. * * * . . 0 ,48 0 *30 0.25 0.33 0.34 0 '38 0.44 0 '36 0.43 0 36 0.32 0.35 0 *33 0.30 0 *30 0 '4.3 0 *35 ) 31 ...... 0 *52 0 '31 0 *24 0.36 0 '37 0 '42 0 *47 0 .40 0 *45 0.38 0.36 0.38 0 -36 0 *33 0 *31 0 *41 0 .38 Angust 2 I . I. 0 -57 0 *34 0 -26 0 *39 0 -40 0 *45 0 *51 0 '42 0 '43 0 '40 0 -40 0 '41 0 '40 0.36 0.36 0 '45 0 -40 )) 4 I. *. 0 *58 0.36 0 -26 0 *39 0 *41 0 *45 0 -53 0.44 0 *51 0 -41 0.42 0.42 0.42 0 '37 0.35 0.45 0 -40 >amage 6 .... 0 -59 0 *37 0 -19 0 '40 0 -42 0 '46 0.52 0 *36 0 51 0 *41 0 *43 0 *42 0 *42 0 '37 0.37 0.45 0.41 )) Iryinq, , 8 .... 0 *% 0.37 dtn lged 0 *40 0.42 0 *48 0 -50 0 '37 0.51 0 *41 0'%4 ,ccic?ent 0 -42 0 '40 0.36 0 -45 0 *42 )) 10 ..*. 0 .58 0.39 at lirst. 0.40 0 .35 0 *51 0 *51 0.39 0 *52 0 -43 0 *49 *. 0 .43 0 '40 0 '36 0 '47 0 *44 )) 12 ....0 59 0 '35 .. 0.38 0 33 0 *49 0 *50 0 *40 0 *52 0 -45 0 .49 .. 0 '43 0 *4,1 0 *35 0 *4i 0.44 , 14 .. .. 0 -63 0 *40 .. 0.39 0.37 0 -53 0.53 0 *40 0.54 0 ,414 0.5% .. 0.47 0.43 0.35 0 '47 0.49 a. ,) I6 .. *. 0 -6% 0 .43 0 .40 0* 430 0.60 0.56 0 -40 0.55 0 -46 0 56 .. 0 *50 0 *43% 0 *3H 0 *49 0.49 ,) 18 .... 0 *69 0 '46 *. 0 *41 0.45 0 *65 0.58 0 *4i 0.60 0.50 0 '60 .. 0 '53 0 *49 0.41 0.53 0 -53 , 20 ... . 0.68 0 -48 .. 0 -4.2 0 -46 0 %8 0 $0 0 *43 0.63 0 *50 0 '61 0 -52 0 '19 0 41 0.54 0 52 -_--__--a. ---Total piti in 0.31 0.24 -0.17 0 .lo 0 .19 0 *36 0 -26 0.13 0.23 0 .19 0.32 0.12 0 *24 0 *20 0 '13 0.19 0.24 weiglit . . I 6. No. of leaves.. 18 14 13 14 22 18 6 16 9 16 7 I.3 14 11 10 6 . . Length of roots 3& in. .2k in. 2&in. 2'4 111. 74 in. 6 in. 34 in. 6 in. 32 in. 3; in. 10 in. 4 in. 7i in. 3; in. 3 in. 1'2 1ll. 612 in. I

ISSN:0368-1769    

DOI:10.1039/JS8773100156

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. General and Physical Chemistry. On a Case of Work produced by the Electric Current. By R. COLT,ET(PJziZ. Mag. [5] i 469-417).-The total quantitly of energy becoming free in a galvanic cell (a Daniel1 element for in-stance) by the solution of a gram of zinc is a constant quantity inde- pendenti of the time taken in dissolving the zinc. A portion of this energy is manifested under the form of heat in the circuit ; another may appear as mechanical work done by the current. A diieect consequence of the principle of conservation of energy is that this second portion can only exist and increase at the expense of the first their sum being constant. Relying on the laws of Faraday and Joule it can be proved theoretically that any work produced by the current is accompanied by the appearance in the circuit of a new electromotive force opposed to that of the pile.This result has been confirmedin all cases hitherto studied in electro-rna,gnetic motors induction-currents weaken the primary current the separation of the elements of a chemical com-pound is always accompanied by the manifestation of the electro- motive force called polarisation &c. The author says if on the contrary the experiment can be arranged in such a manner as to employ external work to reinforce the primary current the new elec- tromotive force will be of the same sign RS that of the pile as if €or example by the exertion of our arms we were to impress on the clectro-magnetic motor a motion in the opposite direction to that taken by it under the influence of the current.The author's aim has been to apply these principles to a case not hitherto investigated and to confirm by experiment the existence of this force which at present cannot be classified among known electromotive forces but as he thinks must be regarded as a new one. To illustrate his view the author imagines the following experiment the current of a Daniel1 element passes up through a vertical tube filled with a solution of silver nitrate entering and issuing from the liquid by electrodes of silver and traversing a galvanometer. A quantit,y of silver equiva- lent to the zinc in the pile will dissolve at the lower and be deposited at the upper electrode ; this transport of the metal upwards consti- tuting the work done by the current.This work is however accom- panied by work of opposite sign due to the opposite transport of the atoms previously combined with the silver ; this being manifested by a din7inution of concentration of the salt in the immediate vicinity of the negative and of corresponding augmentation near the positive electrode. For most salts (including silver nitrate) this work is found to be less than the transport of the metal ; there are however two iodides zinc and cadmium in which the opposite occurs. Having QENERAL AND PHYSICAL CHZMISTRY. 161 seen that all work produced by the currmt or supplied by external forces serving to reinforce the current is accompanied by the appear- ance of a new electromotive force in the first case the electromotive force designated by the author e will have the opposite sign in the second case.the same sign as that of the pile E. Thus in a colamn of silver nitrate an ascending current will be feebler than a descend- ing one for in a circuit of equal resistance there will be in the first case an electromotive force 3-e in the second B + e ; the inverse will take place with cadmium iodide. The following are given by the author as the final values of the electromotive force for a column of one meter :-Silver nitrate ................ e = 0.000005195 Daniel1 Cadmium iodide .............. e = 0~0000156~0 , The apparatus employed consisted of a glass tube filled with the solution of the electrolyte closed at one extremity communi,cating at the other with an air-pump by means of an india-rubber tube which could be closed by a pinchcock and having the electrodes sealed into two lateral tubes.The tube was suspended through its centre of gravity so that either end might be turned upwards. Tube No. 1 had a length of 1.6 meter and when filled with solution of silver nitrate had a resistance of 774 Siemen's units ; tube No. 2 had a * length of 3.6 meters and a resistance nearly double No. 1. The author gives a series of tables of his results having observed alternately the intensity of the proper current of the tube when ascending and descending through the liquids. The mean results are stated in the following tabular form :-Silver Nitrate.Table I. .... Tube 1 ...... Diff. D -A = 4.1 ) 11. .... , 1 ...... , D -A = 4.5 , 111. .... , 2 ...... , D -A = 6.9 Cadmium Iodide. Table IT..... Tube 2 ...... Diff. A -I)= 6.8 A designates the ascending D the descending current. J. M. T. Electro-chemical Deposition of Aluminium Magnesium. Cadmium Bismuth Antimony and Palladium. By AEX. B ERTRBND (Cornpt. reyacl. lxxxiii t154-857).-;iZ.ls?nir~i.u?n is depo- sited on a copper-plate in granules from aluminium-ammonium chlor- ide. The deposit may be polished. Chlorine is evolved at the positive pole. Alagnesiunz,.-An adherent homogeneous deposit of magnesium may be obtained by electrolysing magnesium-ammonium chloride with a very powerful current. C'aclmium.-A spongy deposit of cadmium is obtained from its chloride to which a iew drops of sulphuric acid have been added.ABSTRACTS OF CHEMICAL PAPERS. Cadmium-ammonium chloride gives a grey non-adherent deposit chlorine being evolved ; a similar deposit was obtained from cadmium- calcium chloride ; cadmium bromide acidulated with weak sulphuric acid gives a coherent mass susceptible of polish. If an iron wire be used as negative and a copper wire as positive electrode the cadmium is deposited in long brilliant needles. A good result is also obhained with acidified cadmium ammonium bromide. Cadmium-ammonium iodide yields a spongy mass. The sulphate gives a coherent deposit capable of receiving a fine polish ;a non-coherent deposit was obtained from the double sulphate of cadmium and ammonium.Bismuth.-Ammonium chloride is the best solution from which to obtain an adherent deposit. The solution should contain 25 to 30 grams per litre and should be cold. With a single Daniell’s cell the deposit takes place slowly and to a small extent; with a Bunsen’s element it is quickly formed and very adherent. When polished it has a shade intermediate between those of antimony and oxidised silver. It is not altered in dry air. A~ztimony separates well from its double chloride with ammonium at ordinary temperatures. The deposit is black and may be advan- tageously used to replace platinum. When deposited from thc chlor- ide by a weak current on a fragment of antimony the metallic layer has very curious explosive properties.Palladiunz may be deposited from a perfectly neutral solution of palladium-ammonium chloride. W. R. Ratio of the Two Specific Heats of a Gas. By C. SIMON (Compt.retid. lxxxiii 726-728) .-The author states that by assum- ing certain hypotheses as to the constitution of gases he is able to deduce for the ratio of the two specific heats the exact value 7.5 or 1.40 the experimental numbers for simple gases being comprised between 1.39 and 1.42. The hypotheses in question are that the molecules of a gas are identical among themselves ; that each consists of four atoms (or smaller molecules) placed at the angles of a regular tetrahedron ; that the atoms thus constituted rotate about their centres of gravity; and that their vibrations are insensible or non-existent.R. R. Application of the Mechanical Theory of Heat to the Study of Volatile Liquids Simple Relations between the Latent Heats Atomic Weights and Tensions of Vapours. By RAOUL P ICT E T (Phil. Mag. [51 i 477489) .-In consequence of an abuse of formulae not translated into ordinary terms expressing the relations connecting the various properties of volatile liquids the author pro- poses in this paper to give some laws representing with sufficient exactness the notions at present held upon this subject. He com-mences by determining the principal factors for the problem. To put the problem in a comprehensible form he supposes a reservoir which may be called A containing any volatile liquid ; a pump B draws off the vapour formed in A at a constant temperature toand tension P and forces it into another reservoir C at a temperature t’ and pressure P’ the liquid passing into the gaseous state in A with GENERAL A4ND PHYSICAL CHEMISTRY.16;s the reverse in C. To complete the cycle the liquid is to be brought back to its initial temperature and a conduit-tube permits the liquid accumulated in C to return into the first reservoir A. In the above operation it mnst be supposed that t' > toand consequently P' > P. For instance taking one kilogram of ether at to = 0" its vapour is drawn off under tension Po and forced into C at a temperature t' = 20 and under pressure P2,, ; then one kilogram of ether is reduced from the temperature 20" to 0" in passing through the junction-tube D the cycle being completed since the ether has returned to 0" under the initial pressure Po.Thus by means of Regnault's numbers and table the two essential elements of the problem can be calculated-(1.) Heat absorbed in A by the return of' the liquid from the temperature A' to to. (2.) The work expended by the pump B to obtain com- pression of the vapour from pressure P,to Pr2*,these two equations being entirely independent of each other one of them giving heat- units the other kilogram-meters. For the mathematical calculations the author adopts the following symbols :-to temperature of refri-geerant A; t' temperature of condenser C ; *&. co-efficient of dila-tation of gases ; Y,maximum tension of the vapour at t' ; T work done by the pump B ; c specific heat of the liquid ; d density of the va'pour at Oo referred to that of air ; 1.293 kilogram-weight of a cubic mewr of air ; 1033.3 kilograms = atmospheric pressure on a square meter; X latent heat of the liquid at to.The author proceeds to work oub the mathematical reasoning by a series of five equations. He then gives a table showing the coincideuce existing between the numbers calculated from their hypotheses and those furnished by experiment. Liquid. Boiling Derirat,ive. 1 I point. 0 Water .......................... 100 533~.9 536 0 -0346 Alcohol. ......................... 78.21 210 214 -05 0,0325 Carbon sulphide .................. Chloroform ...................... Ethyl oxide ......................46 35 60 84 90 *12 60 -73 83 -54 89 -76 61 0*03189 0 *03563 0 -03337 Benzene ........................ 80 92 *9 92 5% 0 '03000 Ethyl chloride .................... Mercury ........................ Sulphurous acid .................. Oil of turpentine. ................. 10 155 350 -10 92 -8 65 -6 71 -6 94.2 92 -1 68 77 94 -5 0 '03779 0 '0261 0 -02049 0,04374 The deviations are slight and may be explained by the anomalies of Nariotte's law and errors of experiment'. From further mathematical reasoning the author concludes that for two temperatures t and t' taken arbitrarily the difference of the internal latent heats multiplied by the atomic weight is a constant number for all liquids and then giyes a table containing numerical verifications of his hypothesis.He tinally draws the following conclusions :-(1.) Cohesion is a constant quantity for all liquids. 164 ABSTRACTS OF CHEMICAL PAPERS. (2.) The derivate of the Naperian logaritlhmof the quotient of the tensions by the temperatures is constant for all liquids at the same pressure and temperature. (3.) The latent heats of all liquids brought to one and the same pressure multiplied by the atomic weight at the same temperature gives a constant product. (4.)For all liquids the difference of the internal latent heats at any two temperatures multiplied by the atomic weight is a constant number. Also on comparing his investigations with Dulong and Petit’s law on specific heats one more relation can be established viz. :-(5.) The latent heats of all liquids are multiples of the specific heats.J. M. T. A pretended Relation between the Mechanical Equivalent of Heat and the Molecular Weights. By J. THOMSEN (De~t. Che7n. Ges. Ber. ix 1355-135‘7) .-This relation which Klingel tried to prove (Pogg. Ann. clviii liiO) is founded on the fact that the number 0.0699 which expresses the difference between the specific heats of air at constant pressure and at constant volume is almost itleiitical with that of the specific gravity of hydrogen. But this agreement is a mere accident as will be easily seen. c. s. Compressibility of Gases at Pressures less than one Atmos-phere. By D. MEKDELEJEFF (Dead. Ohen?. G‘es. and V. HEMILIAN Be)..,ix 1341-1345) .-Hydrogen air carbon dioxide and sulphur dioxide were examined at pressures varying from 650 to 20 mm.and it was found that when the pressure is diminished c123 > 0 instead of being = 0 or the compressibility is less than that required by hyle’s ~ law. The value of -d(P4 increases with a diminution of pressure and is for hydrogen when p 400 mm. = 0.U00002 and when p 120 mm. = 0~000010. Carbon dioxide and sulphur dioxide show at pressures not much below an at,mosphere negative deviations but at lower pressures they become positive. Thus the following values were found for carbon dioxide :-yo= 63 mm. pl = 200mm. p,,’uO= 10000 mm. plv = 10029 mm. po = 190 mm. pl = 64 mm. p2 = 22mrn. povo= 10000 mm. p,vl = 9996 mm. pv2 = 9983 mm. To obtain concordant results it is absolutely necessary that the measurements of pressure volume and absolute temperature be cor-rect within one ten-thousandth.Air shows positive deviations below one atmosphere they then I-Pecome negative until 30 nt,rnospberes when as Katterer has shown they remain positive up to 100 atmospheres. Hydrogen always shows positive deviations at any pressure either high or low. c. s. GENERAL AND PHYSICAL (IHEMISTRY. 165 Determination of Vapour Densities. By J. W. BR~HL (Deut. Chern. Ges. Ber. ix 1368-1376).-The use of steam in determining vapour-densities by Hofmann's method has the great advantage that there is no difficulty in obtaining a uniform temperature because steam possesses a very great capacity for heat and moreover no thermometer is required the temperature of the steam being ascertained from the height of the barometer and read off from Regnault's tables.By increasing Torricelli's vacuum and diminishing the weight of sub- stance the author has succeeded in determining the vapour-densities of bodies boiling at 250" by means of steam. The tube which he used liad a length of 1.5 meter an interior diameter of 18 mm. and was drawn out a little at the open end in order to close it with the finger when filled with mercury. The vacuum thus obtained was 190 C.C. The tube was calculated as follows ; about 820 mm. from the open end a mark was made with a file and the tube filled up to it with mercury which was weighed and thus the capacity of the tube up to the mark found to be 185.513 C.C.The mercury was then put hack and three times 15 C.C. of mercury were added and the increase in height every time determined the mean being 57.467 mm. or 1mm. = 0.261 C.C. The volume of vapour is therefore given by multiplying the distance of the mercury from the mark with 0.261 and adding 18-5.513. After the tube is completely filled with mercury it is inverted in the trough which is kept completely filled in order to avoid differences of level and then surrounded by an outer tube or jacket of about SO mm. of diameter and a length of 950 mm. through which steam is passed until the mercury remains constant; after measuring its height (b) the apparatus is allowed to cool a little and then the substance is introduced and heated until the height (b') is again con- stant.The pressure I3 is then found by the formula :-B= b -b' 1 + 0~000181t The correctness of this equation is proved in the paper to which is added a table containing the experimental numbers and the results of which we abstract the following :-Dimet.hy1-Camphor. Parabromo-I 1 i aniline. benzene. Coumarin* -.--------Calculated .......... 60.39 75 *83 117.66 72 *82 V. d. { Found .............. 61.04 76-65 117 *66 70 '96-71 '85 B.p. ...................... 192" 205O 219" 291" 6 -6'.. .................... 21 *2 18 95 18.4 20-2 Weight of substance. ......... 0 -0214 0 -0205 0.0181 0.017 0,0198 The density of the vapour of coumarin was determined in aniline- vapour. c. s. Chemical Affinity. By H. KOMMRATH (Deut.Chem. Ges. Ber. ix 1392-1325) .-The attraction of silver and chlorine is stronger ABSTRACTS OF CHEMICAL PAPERS. than that of sodium and chlorine. If the compounds thus formed are saturated we must assume that chlorine has a different attractive force for each of the other 62 elements and the number of chemical mole- ~ cular forces would thus be 62 x 63 -1953. But if the affinity of 2 chlorine is always the same sodium chloride is a non-saturated com-pound and the same will be the case with most other compounds. This may be explained by the following hypothesis different atoms possess different quantities of chemical affinity but oniy potentially i.e. the maximum is developed only under certain physical conditions and when they are attracted by a force having the same intensity.If an atom of sodium has the intensity na and chlorine cl we have :-cl > na and sodium chloride still possesses the free force cZ-?za which how- ever is too weak to attract another atom. In each chemical reaction potential energy is therefore converted into actual and consequently if iwo compounds AB and CD decompose each other :-AB + CD = AC + BD we have- nb + cd > ac -i-bd. This hypothesis explains the existence of compounds with water of crystallisation so called molecular compounds &c. c. s. Capillary Affinity. By E. CHEVREUL(Comnpt. rer~d. lxxxiii 682) .-The expression capillary affinity comprehends all the facts presented when a solid body unites with a gas or a liquid or with a solid dissolved in a liquid whilst the solid body maintains its original form ; such an action is the removal of colouring matter from a solu- tion by means of charcoal.The experiments to which this paper has reference concern the action o € massicot on lime-water strontia-water and baryta-water. From the results it appears that if a precipitate A is very bulky in comparison witlh a body B which would not be pre- cipitated if it were alone by the body C which has precipitated A the precipitate may carry down by capillary affinity more or less of the body B. It is necessary in studying actions of this kind to take into conside- ration the causes which may act diversely in the cases where solid bodies are in contact with liquids. C. H. P. The Limits between which Fire-damp can Explode; and some New Properties of Palladium.By J. J. COQUILLION (Comnpt. I-end. lxxxiii 709).-Mixtures of marsh-gas and air in dif- ferent proportions introduced into a cudiometer and fired by the electric spark gave the following results. Marsh-gas 1,air 5. Tlie spark is without effect. Marsh-gas 1 air 6. Explosion occurs only in a succession of shocks. This is the first limit of possible explosion ; the marsh-gas is in excess. ISORGANIC CHJGMSTRY. Marsh-gas 1 and 7 8 or 9 of air give a sharp explosion. A lighted match will burn the gas without producing any explosion. With 12 13 14 15 of air for 1of massh-gas the explosion occurs but grows gradually weaker. With 16 of air the effect is reduced to a series of slight intermitkent commotions. This is the second limit ; the air is in excess. Palladium heated to bright redness by the electric current in a mixture of 2 vols. of oxygen and 1of marsh-gas gives no explosion though the bulk of the gases diminishes in the theoretical proportions. A flame causes a great explosion. C. H. P.

ISSN:0368-1769    

DOI:10.1039/JS8773100160

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

107 Inorganic Chemistry. Note on Ultramarine By A. LEHMANN (Deut. ClLenz. Ges. Ber. ix 1376).-Philipp has stated that blue ultramarine is changed into green on heating it with sodium sulphate and charcoal; this reaction was discovered by the author. c. s. Some Double-salts of Calcium Sulphate. By R. FA s s B E sD E R (Deut. Clzenz. Ges. Bey. ix 1358-1363).-CaS(3r + K,SOc + H30 is best obtained by dissolving so much of potassium sulphate in a satu-ratted solution of calcium sulphate as would saturate the water of the latter in the cold. The salt separates in small silky needles. CaS04 + (NH4),SOa+ H,O is prepared by dissolving 285 grams of ammonium sulphate in sufficient water to get 800 U.C.of solution which is then saturated with calcium sulphatc evaporated to 500-600 c.c.and filtered at 40-50". It seems to form small rhombic prisms and to be isomorphous with the potassium compound. CaSOa + K,S04 + 2KC1 is formed by adding a small excess of potassium sulphate to a solution of calcium sulphate and potassium chloride which has been saturated at 16". Calcium sulphate dissolves pretty freely in nnimoninm chloride and in potassium nitrate. 82 C.C. of a solution of the latter saturated at 15" dissolved at 15.5" 1part and 21" one part of gypsum dissolved in 69 parts. In a saturated solution of magnesixm sulphate gypsum is absolutely insoluble. c. s. Reactions of Gallium. By LECOQ (Compt. DE BOISBAUDRAN rend. lxxxiii 824-825) .-Gallium may be separated from aluminium by taking advantage of the greater solubility of gallium hydroxide in ammonia than aluminium hydroxide.When a mixture of gallium and aluminium chlorides is fractionated with sodium carbonate although the first portions of the precipitate show the lines Ga a 417 and Ga 403.1with greatest intensity yet the separation cannot be thus affected. Sodium carbonate does not precipitate indium till after gallium. If gallium were intermediate in qualities between indium ABSTRACTS OF CHEMICAL PAPERS. and aluminium it should be precipitated after indium and before aluminium or cite versd. Slightly acid sulphate and chloride of gallium are not precipitated by an acid solution of ammonium acetate but neutral salts of gallium become turbid. An excess of ammonium acetate renders the solution clear and it does not again become turbid on boiling at least if not diluted with a large quantity of water.Gallium chloride is very soluble aDd deliquescent ; its solution when concentrated is clear but it turns turbid on dilution ; the precipitate which is doubtless an oxychloride dissolves with diEculty in dilute hydrochloric acid. Hence when it is desired to extract all the gal-lium from an insoluble substance strong hydrochloric acid must be used as solvent. If exactly enough hydrocliloric acid be added to a solution of gal-lium to prevent its turning turbid when diluted the solution grows turbid when heated and becomes clear on cooling. The same is the case with gallium sulphate and its alums. Crystals of gallium chloride have a powerful action on polarised light.Gallium sulphate is not deliquescent. An alum was made by mixing ammonium and gallium sulphates. It crystallises when a particle of alum is placed in the solution. The existence of the alum is thus proved. W. R. Titanium Compounds. By C. FRIE u 6:L and 5. Gu B R I N (A7m Chim,Phys. [5] vii 24-56).-This work was undertaken with the object of ascertaining the true position of titanium amongst the ele- ments the authors doubting the propriety of classifying titanium in the same group with silicon as none of the crystal-forms in which titanic acid occurs resemble in any way that of crystallised silica; nor do the natural titanates resemble the silicates. This research is more particularly connected with the study of the chlorides oxychloride the lower oxides and the nitrides of titanium and the results show that titanium and iron are closely related.1. TITAXIUM RIDES.-DZ'~Z'~LW~AHL CHLO hexchloride Ti2CI6 is best pre- pared by heating a mixture of metallic silver and titanium tetrachloride (in the proportion of one atom of the former to one molecule of the latter) in a sealed tube in a temperature of 180" to 200". 'l'he mass partially dries up and a garnet-red solid remains behind which con- sists evidently of silver chloride and dititanium hexchloride the fol- lowing reaction having taken place 2TiClI + 2Ag = Ti,Cl + 2Ag;Cl. If the amount of silver taken exceeds the proportion given above no dititaninm hexchloride is obtained. This compound is insoluble in carbon disulphide chloroform benzene carbon tetrachloride and tita- nium tetrachloride but dissolves in water forming a rose- coloured solution.On heating a mixture of silver chloride and ditihanium hexchloride obtained by Ebelmen's method (ARLUhirn. Yiiys. [3] xx 386) in a current of dry carbonic acid tetrachloride of titanium distils Over and the silver chloride is reduced to metallic silver. On increas-ing the temperature inverse reactions occur the metallic silver reduc- ing the tetrachloride and the hexchloride thus formed reacting upon tilt silver cliloride. The authors explain this remarkable reaction by INORGANIC CHEMISTRY. 169 pointing to the fact of dititaniurn hexchloride being non-volatile and consequeiitlv not distilling at the same time decomposing in to tetra-chloride and dichloride (TiCl, a coinpound which decomposes water at the ordiiiary temperature and is a reducing agent of the greatest poarer) the latter reducing the silver chlc )ride formed and eventually causing complete conversion into tetrachloride.Zinc exerts a similar action upon titanium tetrachloride only in a lesser degree than silver. The hexchloride absorbs oxygen when in contact with the air being converted into titanic acid and tetrachloride ; heated in a current of hydrogen at the temperature of boiling sulpliur tetrachloride distils over and a black substance remains behind. Tetrachloride is not de- composed at the same temperature. Bromine acts upon the hexchloride more particularly when aided by a gentle heat.On distilling the resulting product excess of bromine first passes over ; then at 160" the greater part distils over the distillate being a colourless liquid which fumes in the air. An analysis of this liquid proved it to have a chemical composition corresponding with the formula TiCI,Br and to be a,titanium chlorobromide as will by seen from the results ob- tained viz. :-Weight of liquid taken for analysis = 0.4168 gram. , TiO obtained = 0.1610 , = 20.97 per cent. of Ti. Theoretical amount = 21.14 per cent Weight of chloride and bromide of silver obtained = 1.2340 per cent. 1.2205 gram of this mixture reduced in a stream of hydrogen gave 0.857 gram of metallic silver; whence C1 + Br = 78.52 per cent. Theoretical amount = 78.86 per cent.Pitanknz DichZoride.-After very numerous and mostly unsatisfac- tory experiments the authors have devised the following process which is divided into two parts viz. (1.) The preparation of hexchloride ; (2.) The conversion of the hexchloride into dichloride ; but in order to eiisure success there must be an entire absence of air and moisture during the conversion of the former into the latter. A tubulated retort of green glass is used and sealed to a green glass tube 40 to 50 centimeters in length and of equal bore to the delivery-tube of the retort. At the end of the former tube is attached a tube bent down- wards. passing into a receiver intended to retair the excess of titanium tetrachloride. The green glass tube is covered with platinum foil for a length of from 20 to 30 centimeters and then placed in a gas com- bustion-furnace; the air which may be present is displaced by a current of perfectly dry and pure hydrogen passing through for several hours.When all the air is displaced the tetrachloride of tita-nium is allowed to How into the retorts from a funnel having the following construction. In a tubulure at the upper part a caoutchouc stopper is inserted perforated with one hole and pttssing through this hole is a glass rod which can be pushed down so as to close the stem of the fuiinel in order to stop the flow of liquid from the funnel or on raising it to allow the liquid to flow out. On the side of the body of the funnel is fused another tubulure which serves for the replenishing of the funnel with tetrachloride ; it is closed with a glass ABSTRACTS OF CHEMICAL PAPERS.stopper. Below the place where the glass rod closes the stem and at one side of it there is a third tubulure which is connected with the hydrogen generatinq apparatus or the carbonic acid apparatus as the case may be. The green glass tube is heated to redness on the part which is covered with platinum foil hydrogen passed through the apparatus and the tetrachloride in the retort heated to boiling when it is observed that fine hexagonal lamell= of hexchloride are de- posited on the cooler portion of the tube and even partially penetrate into the receiver. The process can be continued until a sufficient quantity of hexchloride has been obtained care being taken that the tube is not completely stopped up with deposit by occasionally heating the spot.The apparatus is allowed to cool in a stream of hydrogen and the latter is then replaced by dry carbonic acid gas. The green tube is separated by a file from the retort and its contents pushed into a matrass (previously filled with carbonic acid gas) by means of a thick platinum wire. The matrasv has a lateral tube sealed to it for the exit of the gases whilst the tubulure or mouth of the matrass is closed by a caoutchouc stopper through which a glass tube is inserted reaching to the bottom of the matrass and serving for the delivery of the gases. A current of hydrogen is passed through the apparatus in order to displace the carbonic acid ; it is then placed on a suitable sand-bath surrounded with tiles to prevent any cold draught and heated to dull redness when tetrachloride of titanium is evolved and carried along by the hydrogen.When this evolution ceases the apparatus is allowed to cool in a stream of hydrogen which is after- wards replaced by a stream of carbonic acid gas and the contents of the apparatus are rapidly transferred to a tube filled with carbonic acid gas and sealed up. The titanium dichloride thus formed is a blackish powder which is occasionally in the form of flakes very un- stable in air and in the presence of moisture (with the latter it becomes lighter in colour). Thrown into water it hisses like red-hot iron and dissolves a copious evolution of hydrogen being the result.On the addition of ammonia to this solution a copious black precipi- tate is formed hydrogen being evolved at the same time. The black precipitate gradually changes to blue and eventually to white and on throwing a few drops of water upon the dichloride (taking care not to moisten it completely) sufficient heat is generated to cause it to take fire in the air. On being heated in the air the di-chloride burns like tinder fumes of the tetrachloride being evolved and titanic acid remaining behind. It is insoluble in ether bisulphide of carbon and titanium tetrachloride and on being heated gently with absolute alcohol hydrogen is evolved and a yellowish liquid formed which on the addition of ammonia furnishes a blue-black precipitate.Dry ammonia gas passed over the dichloride at a red-heat gives rise to the formation of a peculiar nitride Ti,N4 hydrogen being set free accord- ing to the following equation 3TiC12 + 4NH3= Ti3N4+ 6HC1 + 6H. Bromine forms with the dichloride a fuming liquid which boils at about 180” and is probably TiCI,Br,. Some difficulty was experienced in obtaining the dichloride perfectly free from oxychloride of tita-nium (Ti202C12) but the authors succeeded eventually in obtaining a pure product . IKORQANIC CHEMISTRY. Ozychloride of Titunium Ti202C12 is met with generally in the pre- paration of titanium dichloride especially when air and moisture have been present. The small reddish-brown lamelle observed by Ebelmeii (Ann. Chim Phys. [3] xx 391) occurring in the preparation of the hexchloride were supposed by him to be a protochloride of titanium but were in reality oxychloride.The authors prefer to prepare it by passing a mixture of hydrogen gas and titanium tetrachloride over titanic acid heated to bright redness. A somewhat larger yield is the result of this process and the oxychloride clothes the sides of the porcelain or glass combustion-tube with soft flocculent crystals which are rectangular plates probably of the rhombic system. The oxy-chloride is not readily attacked by water or by very dilute nitric acid in the cold ; thus it can be separated from the dichloride by dis- solving it in water and filtering but at the same time it is always altered in appearance. The crystals of oxychloride allow a reddish-brown light to pass through them and thev are acted upon by am-monia first beooming black and afterwards white the crystalline form remaining intact.Hydrogen is given off when the crystals are acted upon by ammonia and this fact proves that the oxychloride does not belong to the type of’ Tic& but to that of the hexchloride Ti,Cl,. Titanium oxychloride is tolerably stable in air but eventually becomes paler in colour and changes into titanic acid ; heated in air it burns forming titanic acid and fumes of tetrachloride. The analyses made were not as correct as might be desired but the authors had very little substance at their disposal and they are of opinion that a small quantity of titanic acid was mixed with the oxychloride.The for-mula Ti202C12 corresponds with the following percentage composi- tion :-Ti. c1. 0. 49.26 34.97 15.76 Found.. 50.16 31.07 Xesquioxide of Titnniuna.-It was observed that titanic acid which had been subjected to the action of a mixture of hydrogen and tita- nium dicldoride (as in the preparation of thc oxychloride) was changed into a copper-coloured substance with violet reflections and exhibiting isolated crystals and groups of crystals. The porcelain combustion-tube is generally coated with this substance here and there with beautiful hexagonal plates of the same. This coating or deposit must not be confounded with another one of a deep brass-yellow which occurs at the fore part of the tube and which also exhibits red crystals the latter being the nitride of titanium described further on.The hexagonal crystals are in reality sesquioxide of titanium formed from the reduction of titanic acid by hydrogen and assisted in its crystallisation by titanium dichloride which is also partially reduced by the action of the water formed in the above reactions. Thus the authors obtained pure titanium sesquioxide having a metallic lustre and a reddish-violet colour. The crystals were examined under the inicroscope and found to be isomorphous with the specular iron-ore from Elba as the primary rhombohedron R the scalenohedron +R3(?) modified by the basal terminal plane (a of the authors) were ABSTRACTS OF CHEMICAL P-G'ERS. observed. The characteristic triangular striation was observed on the basal terminal plane caused by its oscillatory combination with an obtuser rhombohedron and its lustre was not so brilliant as that of the two first-mentioned forms.Measurements of the crystals were made by means of a Wollaston's goniometer although the crystals were only $& to && of a millimeter in size and found to agree closely with those of specular-iron and ilrnenite. Long ago G. Rose con-sidered the sesquioxides of iron and titanium to be isomorphous whilst Nosander supposed the combination TiFeO to be isomorphous with Fe,O,. The authors show by their investigations that ilrrienite cannot be regarded as a simple mixture of the two isomorphous com- pounds Ti203 and Fe203,as in that case the angle of FeTiO would be t,he mean of the angles of Ti& and Fe,03 ; it therefore appears more reasonable to admit the existence of three isomorphous compounds viz.Ti203 FeTi03 and Fe,03 which can intermix with each other. This isomorphism helps to explain the varying composition of titanic irons. It is evident from the above-mentioned isomorphism that a closer relation has been established between titanium and iron than was formerly supposed to exist. Titanic hexchloride and ferric hex- chloride crystallise in the hexagoiial system ; a dichloride of titanium exists corresponding with ferrous chloride ; Ti,O dissolves in sul-phuric acid furnishing a salt crystallising in hexagonal lamella? and corresponding exactly with ferric sulphate ; further it will be seen that nitrides are formed of the two elements iinder the very same cir- cumstances.There is also an analogy existing between the spectra of the two elements. Isomorphism also exists in a marked degree between the silicon and titanium compounds of oxygen and chlorine as will be seen from the following table :-Corresponding iron compounds. SiO TiO -Si,C14 TiCl --Ti,O Fe,O Si,CI Ti,Cl Fe,CI -FeO -TiC1 FeC1 Titanium sesquioxide is a copper-red powder with violet refleAtions it exhibits a play of colours corresponding with that observed on specular-iron and is hard enough to scratch glass but not quartz. Specific gravity = 4.601 at 100". Boiling nitric acid does not act upon it but boiling sulphuric acid does so snlphurous acid and titanic acid being formed when the operation is carried out in the presence of air ; if the air be excluded a slight separation of free sulphur takes place owing to reduction.Hydrofluoric acid and nitro-hydrochloric acid dissolve titanium sesquioxide when assisted by a gentle heat ; on heating it with caustic potash hydrogen is evolved. If the sesquioxide be ignited strongly in the air it is converted into titanic acid and this property was made use of in determining the composition of Ti,O,. Weight of sesquioxide taken = 0.6640 gram. Weight of titanic acid obtained = 0.737 gram. Ti = 67.67 per cent. Tlieoretical amount for Ti,03 = 67.56 per cent. If the sesquioxide contain an admixture INORGANIC CHEMISTRY. 173 of nitride the percentage of titanium is higher.On passing a stream of a mixture of dry hydrogen and chlorine gases over tlitanic acid heated to redness in a porcelain tube sesquioxide is not obtained a? might naturally be supposed but a greyish-blue crystalline substance of homogeneous appearance agreeing well with an intermediate oxide of titanium already obtained by Deville by a similar process and to which he assigned the formula Ti3O5. Action of Titanium Dichloride Chlorine and Hydrochloric Acid upi~ Titak irons and on Mixtures of Titanic Acid and Oxide oj. Irou-From the above statements titanate of iron may be considered an intermediate compound between ferric oxide and sesquioxide of tita- nium viz. Ti,O, FeTi03 Ti,O ; the authors therefore considered it highly probable that a chloride existed analogous to titanate of iron and intermediate between ferric hexchloride and titanic hexchloride but they did not succeed in preparing it.When ferrous oxides are acted upon at a red-heat by titanium tetrachloride ferrous chloride and titanic acid are formed. On passing chlorine over titanic iron heated to a dull redness ferric chloride volatilises and crystallises in plates in the cool part of the tube oxygen being evolved and titanic acid remaining behind. The authors propose to separate titanium from iron by this reaction modifying it however by passing a ml.e-fure of chlorine awl hydrochloric acid over the titanic iron as it was found that a perfectly pure white titanic acid was thus obtained. The process is as follows :-The chlorine and hydrochloric acid generating apparatuses are connected by means of a T-piece the free limb being attached to a hard glass combustion-tube drawn out at one end and this extremity connected with an apparatus consisting of three bulhs partially filled with water.From the latter apparatus a long .glasi tube serves to conduct any escaping gas and for the condensation ot traces of ferric chloride. The combustion-tube rests in a channel of platinum foil and is also covered by platinum foil in such a manner that the covering foil can be lifted off from time to time in order to examine the porcelain b3at containing the substance to bc acted upon and under the boaC a little fine sand is placed to prevent it adhering to the soft glass. The combustion-tube is heated for about two hours (the first half hour at a red-heat) when the decomposition is generally completed but it is not complete so long as the titanic acid in the boat has a yellow colour and the heat must not be too great otherwise there will be a slight volatilisation of titanium.The ferric chloride formed is washed carefully out of the combustion-tube bulbs and other tubes and the iron estimated as ferric oxide ; shoultl the latter contain a traceof titanium it is again treated in the manner described above and the residue of titanic acid weighed. As an example of the accuracy of this method the following analysis 0" titanic iron may be cited :-Weight of substance taken.. .. 0.4615 gram. Titanic acid obtained ..... ... 0.2035 , = 44.52 per cent.Ferric oxide obtained . . .. . ... 0.2750 , = 59.58 , 44.52 per cent. of titanic acid combines with 39-08per cent. of ferrods VOL. XXXI. TJ ABSTRACTS OFCHEMMICIAL PAPERS. oxide (equal to 43.42 of ferric oxide) leaving a residue of 16-16of ferric oxide; the result therefore is Ti02. FeO. ~~~03. 4-52 39.08 16.16 = 99.76. Nitrides of Titanium.-Wohler (AWL Chirn. Phys. [31 xxix 175) stated that four nitrides of titanium existed viz. Ti3NZ7 TIN2,Ti5N6 and Ti3N4. The authors have re-studied these compounds and found that only three exist viz. Ti3Nz Ti3N1,and Ti,N,. The first nitride is found in the cupolas of blast-furnaces occurring in cubical crystals ; the second is obtained by heating ammoniacal dichloride of titanium in a current of ammoniacal gas ; the third is obtained by t>he action of ammoniacal gas upon sesquioxide of titanium or titanic acid and is analogous to the sesquioside and to the hexchloride of titanium in composition.Ti2N2.-The authors prepared this compound in the following man- ner :-Perfectly dry ammoniacal gas is passed over one or two porce- lain boats (containing fine powdery titanic acid and sesquioxide of titanium) placed in a combustion-tube care being taken Cyo prevent the admission of air by causing the gas to pass through a column of mercury one or two centimetres in length. The combustion-tube is heated for four or five hours in order to ensure the complete decom- position of the sesyaioxide and titanic acid as the process is slow and must be repeated several times before the nitride is obtained in suffi-cient purity.By examination under the microscope small black specks are here and there discernible in the interior of the grains of the nitride. The specific gravity of Ti2N2 is 5.28 at 18"; it is an amorphous powder or a deposit having a brass-yellow colour and is easily decomposed into titanic acid on being ignited in the air at a high temperature. Ti2N2 can be obtained mixed with carbon on heating titanic acid at a red-heat in a current of cyanogen but no compound resembling the product observed in blast-furnaces is thus obtained. Ti3N4 is easily prepared by Deville and Wiihler's method (Ann. Chin?,. Phys. [3] lii 97). The authors succeeded in obtaining it in reddish-violet crystalline crusts.Under the microscope the crystals appeared to be acute rhombohedrons. On being heated to redness in a current of hydrogen it decomposes easily into Ti2N, and it is fouiid that this occurs with greater facility if dry ammoniacal gas is substi- tuted for t,he hydrogen. In conclusion the authors point out that the titanium cornpounds can be referred to three types of definite compounds corresponding with the chlorides TIC& Ti,Cl, TiCl, and that a remarkable analogy exists between titanium compounds of the second type and ferric compounds. C. A. B. Evolution of Antimony from Stibnite by Nascent Hydrogen. By W x.SKEY (Chenz.News xxxiv 147).-Antirnony or arsenic sulphide placed in hydrochloric acid together with zinc evolves arseniaretted or nntimoniuretted as well as sulphuretted hydrogen.?TT. R. MINERALOGICAL CHEMISTRY. 175 Silicotungstates of Caesi im and Rubidium. By R. GoD E F F R oY (Deut. Chem. Oes. Ber. ix 1363-1367) .-Cmsimh silicofzcngstate $iW120-12C3R, is obtained as a white crystalline precipitate by adding cesium chloride to an aqueous solution of silicotungstk acid. It dis-solves at 26" in 20,000 parts and at 100" in 192-200 parts of water and is insoluble in alcohol and water containing hydrochloric acid but dissolves to some extent in ammonia. Rubidium silicot unystate SiWlz@d2Rbs, is a very similar body but more soluble 1part dissolving at 20" in 145-150 parts and at 100" in 19-20 parts of water and very freely in ammonia ; in alcohol and water containing hydrochloric acid it is insoluble.In conclusion the author gives a table of the solubility of the salts of the alkali-metals from which it appears that while the simple salts of rubidium and cmium are more soluble than those of the other metals the double-salts as well as the silicotungstates borofluorides &c. are less soluble. c. s. and DURASSIER Action of Acids on Iron. By MM.TR~TE (Conapt. rend. lxxxiii 744).-Bars of iron immersed in water acidu- lated with sulphuric acid were found to have been attacked so as to pre-sent the fibres of the metal in ralief; but when nitric acid was added to the liquid the surface of the metal became hollowed into givoves Iia~ing no relation to the directioii of the fibres but following the course taken by the bubbles of gas which were liberated by the action of tlie acids.R. R. Some Changes in the Physical Properties of Steel produced by Tempering. By A. S. K IM B A L L (Chem. News xxxiv 81).-Ex-periments were made upon the behaviour of tempered bars under a transverse strain. when the following results were obtained :-I. The modulus of elasticity decreases as the hardness of the steel increases ; in other words the harder the bar the greater the deflec- tion produced by a given weight. 11. The increase of deflection in a. given time is greater the harder the steel. 111. The immediate set increases with the hardness of the steel. IV. A bar recovers from a temporary set with greater rapidity the harder it is. D. B.

ISSN:0368-1769    

DOI:10.1039/JS8773100167

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

MINERALOGICAL CHEMISTRY Mineral0 gical Chemistry. Some Amerieaa Vanadium Minerals. By F. G E NTH (Chcm. News xsxiv 78-80) .-1. RoscoeZite.-Occurs in small seams 1-20th to 1-10th of an iriclr thick in a decomposed yellowish brownish or greenish rock. The seams are made up of small micaceous scales a quarter of an inch long or smaller and frequently arranged in stellate or fan-shaped groups. The specific gravity of the purest scales was found to be 2.938 ; lustre pearly ;colour dark clove-brown to greenish-N2 ABSTRACTS OF CHEMICAL PAPERS. brown. Before the blow-pipe it fuses to a black glass colouring the flame slightly pink. With phosphorus salt it gives a skeleton of silicic acid a dark yellow bead in the oxidizing flame and an emerald-green bead in the reducing flame.It is only slightly acted upon by acids but readily decomposes when heated in it sealed tube to 180" with dilute sulphuric acid leaving the silicic acid in the form of white pearly scales and yielding a deep bluish-green solution. With sodium carbonate it fuses to a white mass. The vanadium was determined in the mineral by titration with potassium permanganate. After the separation of the other elements the vanadic acid was reduced by hydrosulphuric acid to V204,which after expulsion of the excess of hydrosulphuric acid was re-oxidized to Vz05 by the perman- gannte. No matter whether only a very minute quantity of sulphuric acid is present or a very large excess it was found that the VzOiis completely oxidized into V20,by this process.From the quantity of oxygen required for oxidation in both cases it was found that vana-dium in the mineral is present as V,OI1 = 2V203.V205.The other elements were determined by the usual methods. The finely powdered mineral was dried over sulphuric acid for two days and the different samples gave the following results :-(a)Purest fknles.-One portion was dissolved in sulphuric acid and the quantity and state of oxidation of the vanadium determined also the silicic acid and insoluble impurities; the latter were left behind on dissolving the silicic acid in sodium carbonate. A second portion was decomposed by sodium carbonate and nitrate and a third for the determination of the alkalis by Smith's method. (b.) Another sample not so pure was analysed by fusion.(c.) Still more impure than (h) was analysed by dissolving in dilute sulphuric acid in a sealed tube &c. ; ca is the result of this analysis c@ after deducting 11.45 per cent. of impurities. (d) was decompcsed by dilute hydrofluoric acid; the material for analysis had not been dried over sulphuric acid. (e) was dried over H2S04for several weeks ; a portion decomposed with sulphuric acid gave 5.37 per cent. insoluble silicates 0.23 per cent. of gold and 43.24 per cent. of silicic acid. The VsO, was determined by difference ; a second portion was decomposed by fusion giving the analysis in e. Insoluble silicates quartz gold &c. a. [0.85] 6. - c m. 11.45 __.--- ~ SiO.. ................. 47-69 47-82 43 -46 A1203 ................14.10 12.60 10.52 FeO.. ................ 1.67 3.30 2 -03 MgO ................ CaO. ................. 2.00 trace 2.43 trace 1-74 0.20 NazO (trace Li20)...... K20. ................. 0-19 '7'59 0.33 8'03 0 -30 5.35 VS0ll ................ 22.02 21.36 20 50 Ignition 4.96 5 -13.............. 5 '32 100'22 101 *oo 100-87 I -1 100-00 I I MINERALOGICAL CHEMISTRY. A mineral very similar in composition and perhaps a compact impure variety of roscoelite is found associated with the scales. 2. Psittacinite.-This mineral which was mistaken for a tellurate of lead and copper proved on analysis to be a “hydrous ” vanadate of lead and copper. It occurs in very thin cryptocrystalline coatings sometimes showing a small mammillary or botryo’idal structure also pulverulent.Colour siskin-green (“ psittacinus,” siskin or rather parrot-green) to olive-green ; fuses readily before the blowpipe to a black shining mass and gives with fluxes the reactions of vanadium lead and copper. It is soluble in dilute nitric acid the solution yield- ing on evaporation a deep red mass. It occurs sometimes associated with gold and small quantities of cerussite chalcopyrite and limo- nite upon quartz at several of the mines in Silver Star District Montana and its occurrence in these mines is looked upon as a favourable indication for when it is met with the vein becomes imme- diately or soon after rich in gold. The following are the results of five analyses :-a. b. c. d. e. PbO. .......41.36 50.17 42.89 27.12 42-38 CUO ...... 14.34 16-66 14-72 9.75 15.03 v,o ...... H20.. ...... 14.64 7-42 19.05 - 15.87 Not deter. 9.96 - 15.77 7.25 SiO,. ....... Al,O ...... Fez03 ...... 15-13]1.29 1 2.72 )-deter.J Not 1 7-60 3-83 I 2.19 {0.65 1 0.15J 10.10) 4*84\ J 15-57 4.00 D. B. The Tripolite of Barbadoes. By T. L. PHIPSON (Chem News xxxiv 108).-A most remarkable deposit of tripolite exists in the above-mentioned island where it is mixed with carbonate of lime. Under the microscope it is found to be exceedingly rich in remains of fossil infusoria the forms of which are very well preserved. The silica is hydrated and soluble to a great extent in potash and like tripolite from other localities it constitutes an excellent polishing material. On account of its value in this respect tripolite has many imitations in commerce but it can be recognized at once by analysis and also by the microscope.The following figures give analyses of a Barbadoes sample a Swedish sample and two kinds of imitation tripolite met with in London :-Fe203and SiOz. Al,03. CaCo3. P2O5. Moisture. X*. Barbadoes ...... 71.50 2.32 10.60 0.08 5.66 9.84 = 100 \ v Dagesfors Sweden 78.00 6.15 15.85 = 100 * Combined water and trace of organic matter. ABSTRACTS OF CHEMICAL PAPERS. Imitations- SiOP CaOC02. Fe203,&c. H2O. (1.)(2.) 1.0 84.7 88.4 6.1 5.6 4-8 5.0 = 100*00 4.4= 100~00 A sample of genuine tripolite from the Puy de Dome gave- Si02,87.2; H20,10.0; A120 Fe,O, &c. 2.8. Another sample from Algiers gave- SiOz 80.0; H20,9.0; Al,03 Fe203,CaO &c.10.0. In all cases the silica is mostly soluble in strong boiling alkali. Barbadoes tripolite having been found a bad conductor of heat it has been used with advantage for covering boilers. Boettger men- tions that it will displace the aniline colours from their solution in spirit and fix them so that after awhile the solution filters colourless. D. B. The Crystalline Form of Melinophane. By E. BERTRAND (Conzpt. rend. lxxxiii 71 1).-The form is found to belong to the right prismatic system the crystals observed were truncated pyramids. The angular measurements are given. There is some reason to believe that the planes of separation x-hich are found in the crys- tals and which are practically parallel to the optic axis are not true cleavage planes.C. H. P. The Formation of Meteorites and Volcanic Agency. By G. T s CEIER M A K (PhiZ. Mag. [51 i 497-507) .-It is perhaps by an examination of the external form and internal structure of meteorites rather than by chemical analysis that we shall obtain further informa- tion respecting the origin of these extraordinary bodies. Meteorites reach the earth in the form of angular fragments which exhibit sometimes sharp sometimes rounded edges but possess no con- centric structure even in their interior. The angular nature of their faces is unquestionably due to fracture and the fragment itself to the disruption of large masses of substance ; the rounded edges and their external crust are not original character- istics but can be proved to have been developed by the rapid transit of the meteorite through the atmosphere.An inspection of this crust has shown that during the latter stages of flight disruption OP the meteo- rite itself sometimes takes place. Guided by this examination and by peculiarity of shape Maakelyne succeeded in reconstructing a meteorite from fragments which fell many miles apart. While the crystalline structure of many meteorites indicates that during the formation of their substance considerable intervals of time for tranquil crystallisation at an uniform tempcrature must have elapsed other specimens seem on the contrary to be composed of masses of angular fragments resembling rat her terrestrial breccias or volcanic tuff's.These characters together with the peculiar "slide " of terrestrial rows which is often observable in the structure of MINERALOGICAL CBEMISTRY. 179 mdxorites presuppose that the material of which they consist has been furnished by one or more large masses the formation of which must have occupied a long period of time but unfortunately it does not in any way account for the process of disintegration and disruption of the generating mass Passing over the older theories which attribnted the meteorite to the disrnption by impact of planetary masses the author attempts to shew &hat taking into consideration their fragmentary character and small siee it is more probable that they resulted from a pulverisation brought about by a force acting from within outwards ;in short by an explosion.He points out that as is well known an examination of the surface of the moon shows that it has passed through a stage of volcanic activity much more intense than we have any experieiice of; ~Jiatrecent researches have shown that explosive phenomena and violent cyclonic movements are still noticeable in our coslvicnl system ; and $hat hherefore it is not unmsonable to suppose that other and smaller star-masses may in a similar manner continue fo lose substance by constant projection of fragments into space until at last they them- selves are resolved into small portions and traverse the universe in orbits of the most varied kind. It has been already stated that although many meteorites appear to result from a gradual and tranquil crystallisation the majority on the contrary are made up of minute flakes and splinters and of ronnded granules.These granules which were termed by Rose “ chondra,” pivsent the following features which enable us to recognise their mode of formation. 1. They are imbedded in a matrix consisting of fine or coarse spliknter-like particles. 2. They are invariably larger than these particles. 3. They are always distinct individuals never merging into ezch other or joined together. 4. They are quite spherular when composed of a tough mineral in other cases merely rounded in form. 5. They consist sometimes of one mineral sometimes of several minerals but always of thc same material as the matrix.6. The structure of the interior of the spherule is in no way related to its external form. Precisely similar clznnd~aare met wikh in terrestrial volcanic tuffs and fherefme we are justified in supposing that these meteoric chondra owe their origin to a similar cause. They would therefore be the result of volcanic tsituration and owe their form to a,prolonged explo- sive activity in a volcanic L‘thr~al;,7’ where rock-masses liave been broken up and the tougher particles not pulverised but rounded by continued attrition. A gooddeal more evidence of a similar character is advanced by the author in support of his views of formation ; he alludes to the finding of hydrogen in meteoric iron as proof that permanent gases and perhaps valpours which are the great agents in transmitting volcanic energy have played some part in the formation of these bodies ; and dthough it may ever be impossible to obtain direct evidence of the volcanic activity which is supposed to have hurled these mysterious ABSTRACTS OF CHEMICAL PAPERS.masses of stone and metal into space yet such evidence as the violent gaseous upheavals on the solar surface ; the more feeble action of our terrestrial volcanoes ; and the stupendous eruptive phenomena of which the lunar craters tell the history nevertheless lend powerful support to any theory which assumes that meteorites owe their formation to volcanic agency. J. W. The Pitted Surface of Meteorites By N. ST oRY-MA SEE LY N E Plzil. il.lng.[5] ii 126-131).-1n the Compt. rend. for April 1876 Daubrke offered an explanation of the hollows which characterise the crusted surface of meteorites. This explanation he partly draws from the very singular parallelism between this alveolar surface of meteorites and that presented by the fragments of unburnt gun-powder that fall at some distance from the muzzle of a large piece of ordnance. The author considering that DaubrBe’s explanation is not the most satisfactory way of accounting for phenomena so similar brings forward an opinion of his own. The fragments of powder alluded to are generally about the size of a small nut and often very irregular in form. They present this pecu- liarity that the surface is usually covered with a sort of irregular reticulation composed of hollows which though sometimes isolated and nearly hemispherical more often become confluent while remaining comparatively shallow.This appearance is so strikingly similar to that presented by the black incrusted and indented surface of an ordi-nary meteorite that it naturally leads one to suppose that the resemblance is not accidental but that it is due to a similar cause; more especidly as in each case we have an acoompaniment of deto- nation with enormous velocity and sudden difference of temperature and pressure. There can be no doubt that the fragments of gunpowder are the cores of some of the cubes of powder which owing to the sudden removal of the vast pressure within the gun have not had time to be entirely consumed.Owing to want of perfect homogeneity in com- position the combustion proceeds at the surface of the fragments at different centres of ignition while the depth to which it penetrates depends an the density of the powder and the pressure exerted on it by the surrounding gases. To take the case of‘a meteorite. The heat produced by atmospheric resistance fuses the surface of the stone or iron ;the fused and oxidised material is thrown off as rapidly as it is formed and the heat quickly begins to penetrate towards the interior of the mass. It is then sup- posed that the want of homogeneity in the mass permits the heat to penetrate from the exterior more rapidly in some places than in others so that the sudden expansion due to the almost instantaneous accession of enormous temperature on the surface of the stone tears out small pieces of it flings them away from the swiftly moving mass and thus produces the peculiar pit-like depressions the formation of which is under discussion.It is possible that hhe greater fusibility of some than of other of the ingredients of hhe meteorite may iri certain cases explain some of these indentations ;and again the difference in combustibility of the various MINERALOGICAL CHEiMISTRP. constituents suggests another and at first sight not unlikely cause of the phenomenon. However the author thinks that the latter suggss-tion is not probable since the most readily oxidisable constituents of a meteorite remain invariably unoxidised and he has further noticed that carbonaceous meteorites are not more pitted or even so much SO as meteorites containing no carbon.The view held by Daubrhe is that the hollows are produced on the surface of the meteorite by a sort of boring action effected by the air compressed and fiercely agitated into gyratory motion by the rapidly moving stone. The author observes that if this explanation were correct we shoald without doubt find traces of the rotatory action in a whorl-like distribution or marking of the crust; such markings however are absent and the view is at best rat,her improbable. He considers that the explanation offered above viz. that the pitting is due to difference in the mechanical facility with which the sudden heat penetrates the mass at different points on its surface may be fairly considered as the most probable solution of the question at issue.J. W. Contribution to the History ofthe Old Sulphur Well Harm-gate. By T. E. THORPE (Phil. Mag. [5],ii 50-58).-After a brief historical sketch of the earlier analyses which have been made of the Harrogate waters the author proceeds to detail the results of his own work in connection with the same subject which was executed in 1875. The water when drawn from the well was clear and colourless; smelled strongly of hydrogen sulphide and had a decided alkaline reaction. Having stood a few hours it became turbid from separation of sulphur but after a while it again became clear and acquired a faint yellow tinge. The rate of flow of the spring was calculated at 30 gallons per hour.Its temperature at time of collection was 10" C. but this temperature varies at considerable intervals having been recently as low as 8". Specific gravity at 16.8" = 1011.04. Determination of total Sulrphur.-A known quantity of the water was mixed with bromine immediately after being taken from the spring. After standing the barium sulphate was filtered off and weighed. Determination of Sulphur oxidisable by Iodine Solution.-These deter-minations were made at the well in the usual manner with standard iodine solution and starch. The results were identical with those obtained by the use of bromine as before mentioned and showed that no thiosulphate was present. Determination of the Sulphur as Hydrogeii Sulphide and as Alkaline SuZyhide.-A current of hydrogen gas was passed through the water and the hydrogen sulphide expelled ; the escaping gas was conducted into an ammoniacal solution of' silver nitrate and the resulting silver sulphide collected converted into chloride and weighed.From the weight thus obtained the amount of sulphur present as hydrogen sulphide was calculated. By deducting the free hydrogen sulphide from the total weight of sulphur calculated to represent hydrogen sulphide the amount of combined sulphur was obtained. Carbon oxy- ABSTRACTS OF CHEMICAL PAPERS. sulphide which is said to exist in certain Hungarian sulphur-waters was searched for but with a negative result. The following table exhibits the results in grains per gallon of the principal analyses which have been made of the water of the Old Sulphur Well.We are thus enabled to trace the nature of the changes which the spring has experienced from time to time. Analyst ................ Wept. Xunter. Hof-1 MUS-Davis. Thorpe. mann. pratt. 1 Date .................. 1823. 1830. 1853. 1867. 1872. 18'75. Temp.. ................. -$8.2" F -48 -9' F. Sp. gr. ................. .013 -24 011.13 -1011 -16 ---____-__ -Lime .................. 48.243 46.233 -38.697 Magnesia .............. 23.446 27.392 -23 *S3!) Baryta.. ................ -3.68 -4 -833 Lithia ................. -0 -266 Potash. ................. 33.869 44.165 -6 -063 Ammonia .............. --0 -328 Soda .................. 474.05 470'63 -477 *0B Chlorine ................650.38 654 -90 615 *62 613.77 Bromine ................ irace trace -1.985 Iodine .................. trace truce -0.103 Sulphur ................ 6.353 6.737 6.412 6.536 Carbon dioxide .......... --< 5.403 Silica .................. 0.241 -0 -703 Sulphuric acid .......... 0.101 absent -absent Ptesidue on evaporation.. .. 1095.91 1108 .?8 1046 -56 LO47 013 Free 13s.. .............. 5.31 7-01 -10.16 Free CO,. ............... 22.03 15-55 -40 -10 Total in cubic inches. ..... 36.09 -The most striking alteration is shown in the quantity of potash which is less than one-seventh of the amount observed in 1867. The proportion of bromine however has increased. The amount of bqrinm salt in the water is large and appears to be increasing it is therefore desirable that it should be determined from time to time since the presence of this element in large proportion must undoubtedly exer- cise considerable influence on the therapeutic action of'the water. J. w.

ISSN:0368-1769    

DOI:10.1039/JS8773100175

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS. Or g anic C h e m is t ry. Action of Sulphuryl Chloride on Alcohols. By P. B E H R E sD (Deut. Ohem. Ges. Bey. ix 1334-1338).-When one mol. of alcohol is added drop by drop to one mol. well-cooled sulphuryl chloride a brisk reaction sets in and the chloride of ethylsulphuric acid is formed. ORGANIC CHEMISTRY. 1s3 It is a colourless oily liquid possessing a very pungent smell. But if sulphuryl chloride be added to alcohol ethyl sulphate is formed as well as its chloride and ethyl chloride. By acting on the chloride of ethylsulphuric acid with methyl alto-hol the mixed ether $0 { ;s5, is obtained as a yellowish neutral liquid which water resolves into methyl alcohol and ethylsulphuric acid. Sulphuryl chloride acts very violently on methyl alcohol ; the chlor- ide SO,( OCH,)Cl thus formed resembles the corresponding but is more easily decomposed by water.On acting upon it with methyl alcohol a mixed sulphate is obtained whiclt is ideiitical with that described above yielding with water ethylsulpliuric acid and methyl alcohol. The chloride of butylsulphuric acid when freshly prepared is a colourless liquid which soon tnrns brown and changes into a viscous liquid. The compound obtained by the action of sulphuryl chloride on benzyl alcohol is so unstable that it could not be obtained in a pure state. c. s. Reciprocal Action of Oxalic Acid and the Monatomic Alco-hols. By A. CAHOURS (Cowipt. revd. lxxxiii and E. DEMAR~AY 688).-1t appears from experiment that the reciprocal action of dry oxalic acid and the primary alcohols of the first series gives rise to the formation of oxalic and formic ethers.This occurs also with the primary alcohols of the second series. since allylic alcohol by similar treatment yields a mixture of oxalo-and formi9-allylic ethers. Benzylic alcohol was likewise completely etherified the oxalate formed being solid and ci-ystallisable. It boils at a very high tempe- rature and is changed by ammonia into oxamide while benzylic alco- 1101 is regenerated. Wheii oxalic acid acts upon a mixture of propylic and isopropylic alcohols propylic oxalate is almost exclusively formed and if' this is saponified a mixture of the alcohols rich in normal propylic alcohol is obtained which when again etherified by oxalic acid furnishes nearly pure oxalate of propyl.This affords a method of separating the two alcohols. C. H. P. Limited Oxidation of Essential Oils and Preliminary Re-port on the Ethers. By CH. 1'. KIXGZETT (Clml. Sews xxxiv 127 and 135).-A. Oxidation of Turpentine.-It has already been mentioned that turpentine yields when oxidised in a current of air in presence of aatc:r peroxide of hydrogen together with camphoric acid acetic acid camphor and certain other less defined suhstances the oil itself increasing in density and containing certain oxidised bodies among which is a quantity of camphoric peroxide. The rate at which this oxidation takes place is very slow at first and is indi- cated by the estimation from hour to hour of the peroxide of hydro-gen which is formed ; but when once the oxidation has fairly set in it proceeds more rapidly with increasing production of peroxide of ABSTRACTS OF CHEMICAL PAPERS.hydrogen and the other products the amounts of which are simply limited by that of the turpentine itself. If no fresh turpentine be added to that already in operation there will come a time when the percentage of hydrogen peroxide is at a maximum and then if the blowing be continued after that time it slowly diminishes in fact at about the same rate that it forms. Tf 0x1 the other hand fresh tur- pentine be added the oxidation proceeds as rapidly as ever while there is no limit to the quantity of peroxide formed. The slow rate at which the oxidation of fresh turpentine proceeds the greater rate it attains after the turpentine has been changed and the increase in density of the turpentine is exemplified by tbe following figures :-Grams of H,O in 100 C.C.solution. A. After 37 hours 0.0651 gram H20. 97 >7 58 0.4500 7) 0.864 originally. B. , 24 , the spec. grav. of the oil = 0.880 99 4!4! 79 7 99 = 0.949 By the following determination the increase in the boiling point of' the oil as the oxidation proceeds is illustrated :-Oil after 24 hours' Original oil. oxidation. 10 p.c. at 157" C. at 162" C. 20 , 159 , 165.5 ,, 7 7 79 99 30 , 160 , 168 40 , , 160 . 171 7 77 50 , , 160.5 , ? 174 77 97 ,7 9 7, 60 161 7 181 77 77 99 7, 70 162 7 193 7 97 80 7 164 ,> 7 210 -90 1% 1 77 9 B.Aqztiseptic and Dkinfecting Powers of the Xolution,.-The above-described solution possesses great power as an antiseptic and disin- fectant ; this property is not however entirely dependent upon the peroxide of hydrogen contained but relates also to the camphoric acid and other constituents. White of egg milk and beer are kept fresh for some considerable time. For 35 C.C. of substance from 1.75 to 4C.C. of antiseptic were used From a series of experiments under- taken with the view of ascertaining to which constituents of the solution the antiseptic and disinfecting character is to be ascribed it was found that its power is distributed between the peroxide of hydrogen and camphoric acid but the former of these is able to evolve large quantities of oxygen which in this state is nascent and of a powerful oxidising character.C. Ox?'dntio.nof the Ethers.-Former researches by the author seemed to show that all the members of the terpene family of the formula C,,H16give peroxide of hydrogen by atmospheric oxidation aEd that this property is no doubt related to cymene CI0Hl;,which as obtained ORQANIC CHEMISTRY. 185 from various sources also yields peroxide of hydrogen so that any hydrocarbon containing cymene [paramethyl-propyl-benzene, C6H,(CH,) (C,H7)] as a proximate nucleus would presumably give peroxide of hydrogen under suitable treatment. Thus it was possible to produce a large quantity of peroxide of hydrogen by oxidation in a current of air at 60" in presence of water from menthene GiIOH18, a small quantity of which the author obtained from Dr.Wright. For Wright has by the action of bromine on methenes succeeded in obtaining a terpene from which on further bromination cymene was produced. It was further demonstrated that clove terpene C15H2i by the fact of its failing to give peroxide of hydrogen in oxidation does not contain cymene as a proximate nucleus which fact Wright has supported by showing that clove terpene gives no cymene by the action of bromine. Regarding cymene as a hydrocarbon constituted of proximate nuclei the author was led to consider the possibility of obtaining peroxide of hydrogen by the atmospheric oxidation of suitable compouflds containing methyl propyl &c.And for the obvious reason that the ethers may in a certain sense be considered as oxides of the hydrocarbon radicles of the marsh-gas series the author fixed upon them for his first experiments. Ordinary ethylic ether has long been credited with the power of producing ozone but beyond this at the time the author commenced his investigations the subject was in a stlateof mystery similar to that which surrounded the so-called formation of ozone by the oxidation of essential oils. That is to say nothing was known about it beyond that there had been recognised under these conditions a principle which was mistaken for ozone and of whose production there was no reasonable theory. Ethylic ether gives apparently by atmospheric oxidation acetic ether and certainly peroxide of hydrogen the latter having been ob- tained in estimable amount.The reaction which takes place may be explained as follows :-(1.) The oxidation of ether into acetic ether and water. (2.) The oxidation of acetic ether into the anhydride and that into the peroxide. (3.) The decomposition of the latter with water simultaneously with its formation. The formation of acetic peroxide in the above case is similar to that which takes place in Brodie's method of preparing that body by acting on acetic anhydride with barium peroxide. It appears that ordinary atmospheric oxygen plays the same part in these experiments as the oxFgen of the barium peroxide in Brodie's metLod. This fact would give strength to the author's theory regarding the formation of peroxide of hydrogen from turpentine which may be represented as its oxidation into camphor (corresponding to ether) then the oxida- tion of this body into camphoric anhydride and of the anhydride finally into the peroxide which is slowly decomposed by water.In conclusion it is stated that the above method of experiment will be applied to all the ethers available. Meanwhile the preliminary results in this nen- direction already foreshadow a system of classifi-cat'ion of the terpene derivatives. The production of peroxide of ABSTRACTS OF CHEMTCAL PAPERS. hydrogen from camphoric peroxide and acetic peroxide amounts to a demoristration of the existence of the radicle hydroxyl in these com- pounds and in a certain sense may be considered as the isolation of hydroxyl itself.D. B. Isomeric Sulphine-compounds. By F. K R i? G F R (,Toicm. pr. Chenz. [21 xiv. 1937213).-1. Compounds of DiethzJlmeth?~lsull~~ne. The ethyl sulphide used for this investigation was obtained by treating alcoholic potassium sulphide with ethyl chloride which was prepared by Groves' method. If to one part of zinc chloride only one and a half of alcohol be taken and the mixture heated from the beginning a large quantity of ether is always formed. which is avoided by using at least two parts of alcohol and heating the solution after it has been saturated with hydrochloric acid in the cold.* When equal numbers of molecules of ethyl sulphide and methyl iodide are heated with a little water on a water-bath diethylmethylsulphine iodide is obtained as a reddish-brown syrupy liquid which does not crystallise and when heated gives oE the smell of ethylsulphide.On shaking it with moist silver chloride the corresponding chloride is formed which dries up in a vacuum to a pale syrup. The hydroxide which was obtained by decomposing the iodide with moist silver oxide refuses also to crystallise and is a powerful base ; the nitrate and sul- phate crystallise in a vacuiim in long ddiquescent needles ; the oxalate and picrate could not be obtain0 I in crystals. On adding platinic chloride to a solution of the chloride the com- pound (S(C2H5)zCH3C1),PtC14is obtained as a pale red crystalline powder which is sparingly soluble in cold water and insoluble in alcohol and ether.From hot water it crystallises in cubes octohedrons or tetra-hedrons which on drying crumble to a powder. The salt melts at 214"with decomposition. S(C,H5)zCH3Cl,AuC13is readily soluble in alcohol ether and hot water and crystallises in long pale yellow needles melting with de- composition at 192". S(C,H5),CH$1.6HgC1~ is a thick white crystalline precipitate which is sparingly soluble in cold water alcohol and ether. It crys-tallises from hot water in prisms resembling rock-crystal and melting at 198" without decomposition which takes place only at a higher temperatlure. When a solution of the crude iodide containing hydriodic acid is mixed with a hot solution of mercuric cyanide the smell of carbnmines and hydrocyanic acid is given off and a yellow oil is precipitated which solidifies on cooling and is insoluble in all solvents.Rut when cold solutions are mixed only hydrocyanic acid is evolved and yellow quadratic crystals separate out which are insoluble in alcohol ether * Abstmctor's note.-Eriiger says that this observation agrees with mine inas-much as on preparing amyl chloride I obtained only a small yield but much amyl ether and therefore I considered Groves' method not to be fit for obtaining the homologues of ethyl chloride. This is however a mistake; I obtained only a little ether and a good yield of chloride which was a iiiixture of the primary and secondary ; and for ths reason Groves' method is not adapted for the preparation of the homolgues.ORGhNlC CHEMISTRY. and carbon sulphide and very slightly soluble in water ; on evaporat- ing this solution the compound remains as an amorphous mass. Its formula is S(CzH5)zCH,CN,HgIz and it is formed accoyding to the equation :-S(C2B5)ZCHJ + HI + Hg(CN)z = S(C:H,),C&CN,HgIZ + HCN. It melts at 115" and a few degrees above it decomposes into mer-curic iodide a carbamine and a liquid smelling like ethyl sulphide. When it is treated with hydrogen sulphide in presence of water mercuric sulphide is formed which undergoes the known changes of colour and on continuing the action of the gas becomes at last rd being converted into cinnabar which on heating sublimes as a black mass yielding again a red powder. Analogous compounds of sulphine- cvanides and mercuric iodide give the same reaction while the double mercuric sulphine chlorides give black mercuric sulphide.In order to obtain pure diethylmethylsulphine iodide a mixture of ethyl sulphide and methyl iodide was heated for some days to 120" but the reaction proceeded according to the equation 2S(CzH,)z + SCHJ = S(CH3)J + S(CZH,),I + SCZHJ. When trimethylsulphine iodide is heated with an excess of ethyl iodide to 150" it is hardly changed while on heating triethylsulphine iodide with methyl iodide it is converted into trimethylsulphine iodide. 11. Compoiiztds of Ethylmethyl.szc~~hl:ne.-Eth~lmethylsulphide was obtained by acting with methyl iodide on sodium mercaptide ; it boils at 65-66" and not at 58.8-59*5O as Carius has stated.On heating it with ethyl iodide and a little water the compound SC,H,.CH,. C,H,I is formed which crystallises in a vacuum in long very deli- quescent needles. The corresponding chloride does not crystallise and the nitrate and sulpJhate are as deliquescent as the analogous salts of diethylmethyl-sulphine. (SC,K5.CH3.CzH5C1),PtCl~ is a dark red crystalline precipitate which is insoluble in eCher and alcohol and crystallises from water in appa-rently monoclinic prisms which on drying crumble down to a rose-coloured powder and melt at 186" under decomposition. When it is repeatedly recrystallised or heated for some time wit'h water it is changed into the isomeric diethylmethylsulphine-compound. SC,H5.CH3.C2H5C1.AuC13 is a pale yellow crystalline powder which is readily soluble in hot water alcohol and ether and melts with decomposition at 178".SC2H5.CH3.C2H5C1,2HgC12 is a white crystalline precipitate crystal- lising from hot water in rhombic plates meltinq at 112" ; under water it melts below loo" and does not then crystallise any more. SC2H,.CH3.CzH5CN.Xg12 is an amber-yellow precipitate consisting of apparently monoclinic prisms ; it is insoluble in water alcohol and ether and melts at 98". When more strongly heated it yields mercuric iodide a carbamine and a sulphide. The results of this investigation prove that the sulphine-compounds ABSTRACTS OF CHEMICAL PAPERS. obtained by the combination of methyl iodide with ethyl sulphide are isomeric with those formed by combining ethyl iodide with methyl- ethyl sulphide.As these bodies are so veq stable and when heated are not simply resolved into their components the author does not regard them as so-called molecular compounds and comes therefore to the conclusion that their isomerism is caused by a difference between the four combining units of sulphur. c. s. Combination of Chloral and Acetyl Chloride. By J. CURIE; and A. MILLET (C0312pt. rend. lxxxiii 745-'746).-Chloral and acetyl chloride combine when they are heated together for some time at 100". The product is a liquid heavier than water and insoluble in it and boiling without decomposition at 186". From this body nascent hydrogen removes two atoms of chlorine and a new substance is obtained insoluble in water and boiling at 146" without decomposi- tion.This substa,nce is isomeric with acetate of dichlorinated ethyl which boils at 125" and also with dichloracetate of ethyl which boils with decomposition at 156". When it is warmed with zinc and acetic acid aldehyde is formed. R. R. Action of Potassium Sulphydrate on Chloral Hydrate. By A. MICHAEL(Deut. Ohern. Ges. Ber. ix 126'7).-When potassium sulphydrate is added in small quantity to an aqueous solution of chloral hydrate the liquid becomes turbid from separation of sulphur and after filtration deposits crystals of a compound agreeing in com- position with the formula C,H,C1&302. This substance forms fine transparent colourless rhombohedrons melting with decomposition at 96-97" It possesses a peculiar mereaptan-like odour and dissolves easily in water.It is decomposed by solution in water and by ammo- nia and apparently also by the further action of potassium sulphydrate. The reactions of the body are consistent with the following constitu- tional formula :-CC1 -CH.OH\ CH -CH.O€€/s. J. R. Note on Reboul's Normal Pyrotartaric Acid. By W. DITT-MAR (netit.Chem. Ges. Bey. ix 1339).-The author some years ago obtained deoxyglutanic acid which like its isomeride pyrotartaric acid is not resolved by heat into carbon dioxide and butyric acid and he then pointed out that one of these must be the normal compound. c. s. Ethers of Hydroxamic Acids Ethylhydroxylamine and Methylhydroxylamine. By W. L ossE N and J. Z AN N I (Liebig's Arzuza,Zen,,clxxxii 220-230) .-I3 thylbenzhydroxamic acid was obtained by Eiseler as a'n oily body only.When prepared from pure materials however it crystallises in brilliant tables or prisms which mejt at 33-5-54.5". Ethyl-ether of Eth,ylbe~xh~droxa???;ic Acid.-This body is readily ORGANIC CHEMISTRY. 189 formed by the action of ethyl iodide on ethylbenzhydroxamic acid is dissolved in alcoholic potash N(C7H,O)K(Cz&,)O + CZHJ = N(C,R,O) (C2H5)20 + RI. It is a yellowish highly refractive liquid of agreeable aromatic (idour insoluble in water but easily soluble in alcohol and ether. When dissolved in weak spirit and heated with a little hydrochloric acid it is resolved into ethylhydroxylamine and ethyl benzoate thus N(C7HjO)(C2H5)20 + H20 = N(CZ'H,)H,O + C,H,OZZ.C,HS.The former product combines with the hydrochloric present to form ~thy711ydrozyZa?~z~ne hydrochzoride N(C2H,)H20,HCl a crystalline substance which deliquesces in the air and dissolves easily in absolute alcohol. It is precipitated from its alcoholic solution in large penrly lamin= on addition of ether. When heated it melts and decomposes evolving gas. Its solutions exhibit many of the reactions of hydroxyl-nmine reducing silver mercury and copper salts and also chromic acid in alkaline solution. The chloropZatinate 2[N( C2H,)H20,HIC1]+ PtCl, formed by mixing alcoholic solutions of the hydrochloride and platinum tetrachloride is deposited as a yellow crystalline powder on adding ether to the solution. It dissolves easily in water and absolute alcohol and crystallises therefrom in prisms on evaporation.1CIethyl-eth er of EthjZbenzhydroxamic acid (ben2oay1 methylethyl-hydrox~j 1-1 2 3 (mine) N(C7H,0)(CH,) (C,H,)O is obtained by the action of methyl iodide on ethylbenzhydroxamic acid in alkaline solution in the same manner as the ethyl-ether which it resembles in external characters. When treated with dilute hydrochloric acid it yields methylhydroxyl- amine and ethyl benzoate N(C,H,O) (CH,) (CzH5) 0 + H2O = N( CH,)HzO + C7H5Oz.CzH5. ~~etlzyZhydroxyZni7li,2e hydrochZoride N(CH3)H20.HCl,formed in the reacation just mentioned closely resembles the ethyl-compound. It crystallises from a hot saturated solution in alcohol in flat prisms. The chloroplatinate 2N( CH3)H,0.HC1 + PtCII dissolves very easily in water and alcohol.It is precipitated from its alcoholic solution by ether as a crystalline powder and is deposited from its solutions on evaporakion in large flat orange-red prisms or tables. Ethy1-ether of nlethy1 Benaliyd roxarnic acid (benxoxylethylmethy111y-1 2 3 droxyZa?szirte N(C7H50) (CZH5) (CH,) 0 formed by the action of ethyl iodide on methylbenzhydroxamic acid dissolved in potash is meta-meric not identical with the methyl-ether of ethylbenzhydroxamic acid described above. It is a mobile liquid of agreeable aromatic odour. By decomposition with hydrochloric acid it yields ethyl- hydroxylarnine and methyl benzoate N(C,&O)(C2H,)(CH,)O + H,O = N(C,H,)H,O + C~H~OZCH,. J. Rs. T'OL.XXXI. 0 ABSTRACTS OF CHEMICAL PAPERS. Researches on the Ferrocyanides. By M. WYr or R o F F (412,I. Clhim. Phys. [51 viii 44$-486).-Tliis memoir relates to the insoluble ferrocyanides. They are described in alphabetical order because the variations in the composition of the salts of metals of the same gronp are so great as to defeat any attempt at classification. In the formuh throughout the radicle FeCy is represented by Cfy. Alunu’nim~ ferrocyrcnide A14Cfy3.17H20,is deposited after some time from hot concentrated solutions of yellow prussiate and an aluminium salt when they are mixed as a gelatinous bluish-white precipitate. Jt is slightly soluble in pure water ; on drying it becomes horny and resembles fused silver chloride. Airtiniony ferrocyanide Cfy3Sb4.25H,0 was not prepared by the author who simply quotes Atterberg’s results.Bisvzufhferrocyanide. (A) KBiCfy.4H20; (B) Bi2Cfy.5H,0. (A) was obtained by precipitating yellow prussiate with a moderately acid solution of bismuth nitrate. It occurs as a bulky bright yellow preci- pitate having a greenish tinge and is slightly soluble in pure water. (B) is obtained by precipitating with hydroferrocyanic acid instead of the yellow prussiate. It exactly resembles (A). In (A) the bismuth is triatomic ; in (B) it is only diatomic. Cadmizc7i.2 ferrocyanide K5Cd5Cfy4.H20= 2Cd,Cfy. KCdCfy. K,Cfy. H,O.-Whatever may be the proportions of the cadmium salt relative to the yellow prussiate employed the composition of the ferrocyanide shown b!-the above formula remains unaltered.When cadmiurn ferricyanide is dissolved in concentrated ammonia fine red crystals are deposited after some days. They are absolutely insoluble in water but dissolve in ammonia. Their composition is (FeCy,),Cd,.2(NH4),0. It is probable that the ammonia replaces water as in the silver ferrocyanide. Cerii~mferrocyanides. (A) KCeCfy.4H20 ; (R) Ce4Cfy,.30H,0. These €orniult~are written upon the hypothesis of the triatomicity of the metal ; if the metal be considered as diatomic the formultr would be Ce3K2Cfy2 and Ce,Cfy respectively. The same may be said of the metals lanthanum didymium erbium and yttrium whose ferrocyanides offer a great analogy to those of cerium. B’eri*uc~/n?zidwof CohaZt.-( A.) Co,Cfy.K,Cfy ; deep violet.(B.) SCo2Cfy.CoRCfy.K4Cfy.14H,0 = K5C05Cfy4; pinkish-grey. (C.> Co2Cfy.7H,O ; emerald-green. (D.) Co7Cfya.22H20 = 2Co,Cfy. Co3Cfy,; greenish-grey. These salts with tho exception of (B) resemble in properties and composition the corresponding salts of nickel. (A) aiid (U) are obtained by the yellow prussiate ; (C) and (Dj by hydroferrocyanic acid ;(B) and (D) with an excess of the cobalt salt. (H) is insoluble only in presence of an excess of the yellow prussiate. The others are completely insoluble in water. They are readily decomposed by alkalis. (C) and (D) are readily transformed into (A) when heated with a solution of yellow prussiate. Copp~i. fp mm/anl‘de.s.-(A) Cu,Cfy.lOH,O Hatchet’s brown. (B), E,Cu,Cfj.K4Cfy.12H,0 deep brown ; crystallised.(C) RCuCfy.H,O red-brown. Hatchett’s brown is soluble in yellow prussiate ;the solution on eva- BRQANTC CHEMISTRY. poration deposits crystals which have the composition K3Cu2Cfy. 6HZO. Didymium ferrocyucnide DHCfy.2H,0b Erbium feworynnide ErKCfy.4H20.-This salt has been described by ClBve and Hoeglund but was not prepared by the author. Iron 3’errocynnide.s.-The cyanides of iron generally regarded as simple when acted upon by alkalies eliminate iron and form ferro- or ferricyanides for which reason the author regards them as doiible cyanides containing t,he radicle Cfy (FeCy,). The formula for iron percyanide would thus be FeCfy and for the protoeyanide if it exists FezCfy. The equation 2FeCfy + 6KHO = 2K3FeCy6 + Fez03+ 3H20 illustrates the action of potash on the percyanide; and in fact the ferricyanide produced may always be found although it rapidly changes bo ferrocyanide in contact with the alkali.In the reaction given to explain the formation of iron percyanide- SR,Cfy + 8NH4C1f Aq = Fe2Cg,.3H20+ GNH4Cy+ 8KC1+ 2NHb 2 molecules of ammonia are evolved but under certain conditions they attach themselves to the percyanide giving (NH,),FeCfy a body which is so stable that it can be decomposed only by fusion into potash. This formula is parallel wjhh that of Williamson’s ferrocyanide of potassium and iron obtained by the action of weak sulphuric acid on potassium ferrocyanide ;or as is here shown by precipitating potassium ferrocyanide with a ferrous salt ; but Williamson’s formula is regarded by the author as inexact the correct formula being 3Fe,Cfy.2K4Cfy.This body is very unstable and is soluble in water but not so in water containing ammonium chloride. When thoroughly shaken with ammonia though not decomposed it becomes violet, and on standing for some time returns to white. This experiment may be repeatetl several times. By treating the white salt with nitric acid. Williamson obtained A violet-blue salt which he described as ferricyanide of iron and potassium but the analyses here given lead to the formula K4Fe,Cfy5 = 2Fe3Cfy2,K4Cfy;the reaction is shown by the equation- 3Fe2Cfy.2%Cfy + 4HN03= 2Fe3Cfy2.K4Cfy+ 4KN03 The inverse reaction is easily effected for by heating the violet salt with excess of yellow prussiate the white salt is formed and potassium ferricynnide set free.Ferric salts yield with potassium ferrocyanide two different corn-pounds according to the proportions employed namely soluble blue K6Fe6CfyG, and Prnssian blue E’e,Cfy6. The fbrmer has been generally viewed as a double ferrocyanide of iron and potassium. It is now shown to be really a ferricyanide having the composition Fe3Cfy, its production by the reaction between potassium ferrocyanide and feri*i(a chloride being completed only on the application of heat. It may he produced equally from a ferrous salt and potassium ferricyanide. If 02 192 ABSTRACTS OF CHEMICAL PAPERS. soluble blue be precipitated and then washed with a solution of potassium chloride the wash-waters will contaiii potassium ferricyanide which is a proof not only that the soluble blue is a ferricyanide but that it is formed of two distinct ferricyanides which may be separated without destroying the compound or affecting its solubility and its formula ought really to be written 2Fe,Cfyz,2K3Cfyz.Various metallic salts react upon soluble blue ; they do not yield the corresponding ferricyanides lout variable compounds belonging to it tdally different type. The reaction is complete only on heating though all metallic salts precipitate the blue even in the cold. The following salts of the series were obtained. They all resemble Prussian blue save the zinc-salt which is pals green and the lead-salt which is yellowish-white :-Zn4FeCfy2 -KzMnFe2Cfy2 Cd,FezCfy2 -PbFe,Cfy2 -Cu4FeCfy? CrFe2Cfyz -K2NiFezCfyz-K4CuFeCfy2 (precipitated cold).Salts of mercury and silver partially decompose the soluble blue. When washed with n weak acid those of the above salts which contain 1 atom of iron outside the radicle lose 1atom of the metal joined to the iron ; those which contain 2 atoms of iron without the ‘radicle may lose 1 atom of metal and 1atom of iron. The following were obtained :-Zn3FeCfy2 Cd2FezCfyz Pb3FeCfy,. The lead salt was the only one of which the aspect changed by the treatment; it became bluish. The salts are insoluble and yield nothing more on further treatment with acid. Their constitution may be explained (with the exception of that of the lead salt which from the fact that it changes colour by treatment wikh acid may be mixed with oxide of iron in which case it would be Pb4FeCfy, and would be covered by the general rule) upon the following which appears to be the only tangible hypothesis.It is supposed that by the action of metallic salts upon soluble blue a new ferrocyanogen radicle is formed FeCfy = (Fe3C1,),and that this radicle can combine with G or 8 atoms of hydrogen to form the hypothetical acids H6(FeCy2) and H8(FeCfy-z) ; the formuls of the metallic salts then present nothing abnormal ; they become Zn4(FeCfy,) ; PeCd,(FeCfyz) ; KzMn(FeCfyz) CrFe(FeCfy) &c. The soluble blue prepared by ammonium ferrocyanide is more stable and more soluble than that yielded by the potassium salt; it may be dried without sensibly decomposing and is not precipitated by alcohol.Its composition is (NH4),B”e,Cfy6.9H,O. The ferrocyanides of the alkaline earths always yield an insoluble blue. Przcssian bZue has the constant composition Fe4Cfy3 but the amount of combined water varies ; the blue prepared with ferric chloride gave 8H,O ; with ferric sulphate 4H,O ; with the nitrate 9H,O. Prussian blue is completely soluble in hot concentrated hydrochloric acid and is reprecipitated unchanged on the addition of water. Efforts were made to crystallise it from the hydrochloric acid solution but failed ; both it and the soluble blue appear to be perfect colloids. ORQANIC CHEMISTRY. 193 French blxe Fe3Cfy2 is obtained pure by precipitating soluble blue with an excess of ferric chloride ;it is stable.When treated with weak hydrochloric acid or dissolved in the concentrated acid and reprecipi- tated by water it is converted into Yrussian blue. Ferrocyanide of Lanthanum KLaCfy.4Hz0.-For general remarks see Cerium. FevrocyaiGde of Lead,Pb2Cfy.3Hz0.-It may be prepared either with yellow prussiate or hydroferrocyanic acid. It loses all its water at loo" and is.absolutely insoluble in water acids or ammonia. E'errocyanides of _Wungnnese.-( A.) 5Mn2Cfy,4KaCfy,4H20; rose-white. (B.) Mn2Cfy.7H20; brownish-white. (A) is prepared by precipitating yellow prussiate with a manganese salt. Its composition is constant whichever reagent is in excess. (B) obtained by precipitating hydroferrocyanic acid with a man-ganese salt.Fewocyaizides of Molybde~zum.-( A.) Mo,Cfy.K,Cfy.40H20 ;very dark brown. (B.) Mo4Cfy.20H20; paler brown. (C.) MozCfy8Hz0; yellowish-brown. (U.) MozC'fy14Hz0;clear brown. (A) is obtained by precipitating yellow prussiate with acidulated ammonium molybdate which must be in great excess since the precipitate is soluble in the yellow prussiate. The formula given by Atterberg for the salt prepared in the same way viz. K,Cfy (MOO~)~(M~O,);~OH~O, was derived it is thought from an error of calculation. (B) is obtained by precipitating yellow prussiate by molybdenum chloride or any salt of molybdenum. (C) is obtained by Precipitating hydroferroeyanic aaid by an excess of ammonium molybdate. (D) is obtained by precipitating the molybdate by excess of hydro- ferrocyanic acid.It is very saluble in water from which alcohol pre- cipitates it. All these salts are but slightly stable except (C). They are soluble in aruionia which clecpmposes them but they are reprecipitated by acids (C) separating in the state of (D). Ferrocyunides of Nickel. -(A.) Ni,Cfy,&Cfy,SH,O rose-grey. (B.) K,Ni,C€y,,K,Cfy,l~~?O ; clear green. (C.) Ni2Cfy,14H20 or llHzO ; dark brown or greenish-grey. (D.) Nj7Cfyc,4iHi,0= 2Ni2Cfy,Ni3Cfy,.47H,0 ; dirty green. (A) and (B) are obtained with the yellow prussiate the latter when this salt is in excess; (C) and (D) by hydroferrocyanic acid the former with excess of nickel. (C) has 14H20,when precipitated from cold solutions and 11H20,when the solutions are hot.E'ewocytr;nides clf'iViiobiim.-(A.) 1<Nb&fy2.67H,0. (B.) K2Nb12Cfj-. 39H,O. These bodies are probably mixtures of the ferrocyanides with nic,bic acid. Niobate of potassium is not precipitated by yellow prussiate save in the presence of a large quantity of hydrochloric or sulphuric acid while themselves precipitate niobic acid. Both form brown precipitates which may be dried without decomposition. Atterberg has given the formula Cfy,(NbO),K,.lOH,O but his figures calculate out better as K,NbCfy.4Hz0 or K5Nb,Cfy3.12Hz0. 194 ABSTRACTS OF CHEMICAL PAPERS. 8ilver Ferrocyanides.-(A,) Ag4Cfy.H20. (B.) Ag4Cfy.(NHa),0. (A) was prepared by reacting with yellow prussiate or hydroferro-cyanic acid on excess of silver nitrate.It is white but rapidly becomes blue in the air ; should be washed with boiling water and dried over sulphuric acid. (B) was prepared by treating (A) with ammonia. It is white but much less stable than (A). The ammonia was estimated in this as in a811 the other ferrocyanides by treatment with potash and absorbing the evolved gas in a standard solution of sulphuric wid. Ti11 Perrocyawides. -(A.) Sn5Cfyz.18+H20 deep grey. (B.) Sn2Cfy.4Hz0;white. (C.) Sn9Cfy4.25H,0 ; bluish-white. (A) is prepared by precipitating yellow pruseiate by stannic chloride. (B) by stannous chloride. (C) by precipitating potassium ferricyanide with stannous chloride. Stannic chloride is without action on potassium ferricyantde. These salts are rather unstable ; insoluble in water and acids slightly soluble in ammonia.Atterberg has .described a salt of the formula lOCfySn.&Cfy. 230H,O but the numbers he obtained correspond equally with KSn3Cfy3.68H20. Atterberg's formula assumes tin to be tetrakomic but the salts (A) and (B) above would remain unexplained. They were prepared several times and found to be of constant composition. Ferrocy urziclesof Titanium-(A.) K,Ti,Cfyz. 11HzO. (B.) 11Cfy2Ti2. K4Cfy,43H,0. (C.) Ti7Cfy2,25Hz0. They were obtained by precipitating yellow prussiate with oxychlo- ride of titanium (A) with an excess of the former ; (B) with slight excess ; and (C) with great excess of the latter. (A) is soluble in the yellow pmssiate and separates with difficulty as a gelatinous precipi- tate.(C) is probably a mixture of the ferrocyanide with titanic oxide or acid. IFtrrocyades of Funptem-(A.) K2W,Cfy.20Hz0. (B.) KWzCfy. ?&O I The former is obtained with an excess of yellow prussiate the latter with excess of ammonium tungstate. They are soluble in water and reprecipitated by acids and probably consist of mixtures of the ferro- cyanides with tungstic acid. Ferrocyanides of Uranium.-(A.) 3U2Cfy.&Cfy.12H20. (B.) UCfy.10H20. Both brown. (Aj is formed by precipitating yellow prussiate with excess of uraniuni nitrate; (B) by precipitating it with excess of the green uranium salt. In a vacuiim they dry without decomposition. Ferrocyalzides of Vanadium K,,VCfy6.-The Yanadates and the salts of vanadium oxide pecipitate the yellow prussiate; the precipitates being clear green very bulky and somewhat soluble in water.The formula is regarded by the author as doubtful on accouiit of the &ai-culty of' obtaining an exact estimation of vanadium. Perrocyanide qf Yttriu,m KYCfy2H20.-A white powder prepared with yellow prussiate and yttrium nitrate. It has been described by Clbe and Hoeglund. (See Erbium.) Fermcyccnitles OJ* Zim.-( A.) 3Zn2Cfy.K4Cfy.12H20. (B.) Zn,Cfy,. ORGANIC CHEMISTRY. 195 4H,O. Both white and absolutely insoluble in water. (A) was pre- pared from yellow prnssiate and any salt of zinc ; (B) with hydro-ferrocyanic acid and any salt of zinc regardless of proportions in either case. (B) may also be formed by treating zinc f'erricyanide with ammonia.ri 1he salts of mercury chromium .gold and platinum and acetate of irou modified by heat do not precipitate the yellow prussiate. C. H. P. Pseudosulphocyanogen (CNSH). By W. R. H. (Chenz. News xxxiv SO). -By treating sulphocyanates more especially the alkaline salts with chlorine bromine or iodine a yellow body insoluble in water is produced which was supposed to be the radicle szsZphocyatLoger~ but was found on analysis to contain a small and somewhat variable amount of hydrogen not removable by excess of chlorine hence it was called ysrudos~~lLocya,Log~n. From some experimellts made to obtain this substance in the pure state it appears that the hydrogen is not the only element which varies in its amount in differently prepared specimens.Considerable differences in the corn- position of the product are obtained with slight variations of tern-perature and strength of the sulpocyanate solutions. NH,SCy solu- tion absorbs chlorine rapidly with rise of temperature. When the vessel is kept cool (10-15" C.) and the chlorine not used in excess a light yellow precipitate is produced which after washing with hot water in which it is slightly soluble appears to undergo a decomposi-tion. A considerable amount of hydrocyanic acid is given off from the substance when suspended in the solution which has been submitted to the action of chlorine. No hydrocyanic acid is given off after washing and drying at 100". Pseudosulphocyanogen may possibly be utilised as a water or oil colour ; it may be obtained of several yellow shades and is exceedingly permanent.It is not altered by the action of light or when ground up moist with nitrate of lead bismuth or silver or with silver sulphide. It requires high temperatures for its decomposition. When it is mixed wet with solid silver nitrite and exposed to sunlight a blackening occurs due only to intermixed reduced silver. From analysis the formula CNHS was obtained but the tripled formula C,H,N3S3 agrees better with the product of its decomposition by heat viz. mellone. D. B. The Compounds of Pthalic Acid with the Phenols. Part I. By A. BAEYER (Liebig's A,malen clxxxiii 1-74).-(1.) Ir'luoresceiw. This compound is obtained by heating a mixture of 5 parts of phthalic anhydride and 7 parts of resorcin to 195-'200" until a solid mass is formed :-CBHA03 + 2C,H,O3 = C,,H,,O + 2HzO.The residue is boiled with water and the undissolved portion washed with alcohol which dissolves resinous bye-products. The crude fluorescein is dissolved in dilute soda precipitated with dilute sulphuric acid and extracted with ether. On adding a listle absolute ABSTRACTS OF CHEMICAL PAPERS. alcohol to this solution and distilling off the ether fluorescein crys- tallises in grains or crusts. The crude fluorescein may also be purified by boiling it with a quantity of dilute soda which is insufficient to dissolve the whole or by adding calcium chloride to its alkaline solu- tion filtering off the dark brown precipitate and adding sodium phosphate which produces a brown precipitate of calcium phosphate.The liquid is then again filtered and the pure compound precipitated from the filtrate by an acid. Fluorescein is an amorphous yellow flocculent precipitate which on standing heating or drying becomes crystalline and consists of C20H,,0,+ H,O. From alcohol it crystallises in dark red anhydrous grains and from wood-spirit in yellow prisms which probably contain methyl alcohol. It is almost insoluble in cold water and dissolves sparingly in hot water with a yellow colour ; in presence of acids it is more freely soluble. When freshly precipitated it dissolves readily in alcohol ether &c. but in the crystallised state only slowly ant1 after continued boiling. In hot acetic acid it is readily soluble but nearly insoluble in benzene toluene and chloroform.The ethereal solution is pale yellow and not fluorescent while the yellowish-red alcoholic solution shows a green fluorescence. It may be heated to 280" without any change and begins to decompose at 290". Fluorescein dyes silk and wool yellow but does not combine with mordants . Fluorescein is a very weak acid dissolving in strong alkalis with a dark red colour. This solution is not fluorescent but changes on dilution to yellowish-red and yellow and then exhibits a spiendici yellowish-green fluorescence like that of uranium glass and even if so much water is added that the liquid appears colourless in transmitted light it shows in reflected light a green tinge like the colour of some Alpine lakes.The concentrated solution allows only the red and yellow rajs to pass while when dilute it gives an absorption-spectrum with a broad dark band in the green. When alcoholic ammonia is added to a solution of fluorescein in ether a reddish-yellow Precipitate is foimed which loses ammonia on boiling or drying. In lime- and baryta- water fluorescein dissolves with a reddish-yellow colour ; its alkaline solution is not precipitated by magnesii;lm salts while alum produces a reddish-yellow precipitate which en further addition of alum becomes yellow and then consists of pure fluorescein. The salts of some other heavy metals behave in a similar way; the lead and silver salts are mole stable and form reddish precipitates .The striking colouring properties of fluorescein afford the means of detecting even traces of resorcin in presence of other phenols. It is only necessary to heat the substance with an excess of phthalic anhy- dride to near the boiling point of the latter. If the melt remains colourless neither resorcin nor pyrogallol or phloroglucin is present but if it has a yellowish-red colour these substances may be present. In the latter case the residue is dissolved in dilute soda the smallest trace of resorcin then becoming apparent by the fluorescence of the solution while pyrogallol yields a blue and phloroglucin a yellow liquid which are not fluorescent. If a large proportion of pyrogallol ORGANIC CHEMISTRY. should interfere with the reaction a solution of potassium perman- ganate is carefully added which destroys the gallein at once but acts only slow13 on the fluorescein.I>iacetyZ-$uorescein Cz0H1005(C2H30)2, is formed by heating fluocescein with four or five times its weight of acetic anhydride to 140°,until on mixing a small quantity with alcohol yellow cryst,als separate out which are insoluble in ammonia. The whole is now treated in the same way in order to convert the anhydride into the acetic ether. The crystals are dissolved in acetic acid and the solution poured into several volumes of alcohol when the pure compourid crystallises in colourless needles melting at ZOO". It dissolves but sparingly in alcohol and wood spirit but readily in acetic acid and hot acetone while it is insoluble in ether benzene and chloroform.It is decom- posed into fluorescein and acetic acid by boiling alkalis and rapidly in slcohoiic solution ; the same decomposition is produced by concentrated sulphuric acid and hot hydrochloric acid. Dibe?zxoyI-~ui)rescei.12,C20H1005( C,H,O), is obtained by heating fluo-rescein with benzoyl chloride for an hour to 140". The dark brown residue is boiled with water and crystallised from acetone. It forms colourless crystals melting at 215" dissolves sparingly in alcohol wood-gpirit and ether but readily in hot acetone. Alcoholic potash and concentrated sulphuric acid resolve it into its components. ~~onethyZ-~zcorescei.n, C2,H,,0,(C,H,) .-To prepare this compound potash-solution is saturated with fluorescein the liquid evaporated to dryness and the residue heated for 2-3 hours to 120' with more than 9 mol.of ethyl bromide and ten times its weight of alcohol. The solu- tion thus obtained is diluted with water and treated with sodium car-bonate to remove unaltered fluorescein. The monethyl-compound is then extracted with ether the solution evaporated the residue dissolved in alcohol and the solution concentrated. On heating the syrupy residue with ether nionethyl-fluorescein crystallises in pale yellow needles melting at 155-136". It is readily soluble in alcohol wood-spirit chloroform and benzene and separates from these solvents as a syrupy mass miscible with ether and crystallising therefrom in needles which are but sparingly soluble in the pure solvent.When water is added to a hot alcoholic solution it becomes milky on cooling and deposits tarbid yellow crystals. The cornpound is insoluble in diiute alkalis which on heating decompose it. Concentrated sulphuric acid dissolves the ether with a greenish-yellow colour arid a light green fluorescence which disappears 011 adding water ; on neutralising this solution the unaltered compound is precipitated. DiethyZ-flimrescein C20H1005(C2H5)2, is not formed by the action of ethyl bromide on the potassium-compound and only sparingly when the silver-compound is heated with ethyl bromide and ten times its quantity of alcohol. The reddish-brown solution thus formed is con-centrated and precipitated with water the precipitate is treated with sodium carbonate to dissolve unaltered fluorescein and the insoluble portion dissolved in ether which is then evaporated and the residue crystallised from alcohol from which it separa,tes in pale yellow plates.The compound is sparingly soluble in ether and alcohol ; the alcoholic solution shows a vivid yellow fluorescence. It is not changed by dilute 298 ABSTRACTS OF CREMICAL PAPERS. alkalis but concentrated solutions and sulphuric acid decompose it into alcohol arid fluorescein. FZuoresceirz chloride C20H1003C12, is easily obtained by heating one mol. of fluorescein with two mols. of phosphorus pentachloride for 1-2 hours to 100". The product is successively treated with boiling water a warm solution of sodium carbonate and boiling alcohol.On dissolving the residue in hot toluene and adding alcohol the chloride crptallises out and is purified by repeating this operation. It)form8 colourless prisms melting at 252" and dissolving readily in hot benzene toluene and chloroform and sparingly in alcohol ether acetic acid and chloroform. It is not changed by aqueous or alcoholic potash while on fusing it with potash it is completely destroyed ; but on heating it with slaked lime and a little water to 230" for some hour& it is again converted into fluorescein. Cold concentrated sulphuric acid dissolves it without alteration but on boiling the solution decom- position takes place and on adding water dark red flakes are precipi- tated dissolving in ether with a wine-red colour. When the chloride is heated wit)h an excess of fuming hydriodic acid to 150" for 5-6 hours the compound CPOHlz03ClP is formed crystallising from alcohol ether and acetic acid in small rhombohedra1 plates melting at 229-250".It dissolves in dilute but not in con-centrated alkalis and contains probably in the place of the two carbonyl groups CO the groups CH.OH. The foregoing results prove that fluorescein contains two hydroxyls and its constitution and formation are explained by the following equa- tion :-0 c6H.( ::>o + 2C6H4 = C6H4{CO.C,H,jOII + 2HZO. {OH OH co.C,H,-OH It is therefore the anhydride of resorcin-phthalein,-The latter compound appears to be formed by the action of strong alkalis on fluorescein for on boiling the latter with an excess of soda the liquid when sufficiently concentrated becomes dark violet and crystals of the same colour separate out.On adding water the solution first becomes red then assumes a dingy colour and on standing or more quickly on heating it assumes t'he colour of an alkaline solution of fluorescein which is precipitated on adding an acid. When alcohol is added to the violet solut'ion it becomes intensely violet arid t>hen gives an absorption-spectrum having a dark band between the blue and green and another betweeri t'he green and red. Jf an acid be added to the violet alkaline solution a yellow precipitate is formed dissolving in ether with a yellow colour and on then adding an alkali the latter becomes again violet. These reactions show that resorcin-phthalein is a stable body in presence of acids or strong alkalis but that in a weak alkaline solution it soon changes again into its anhydride.When fluorescein is boiled down with an excess of caustic soda the violet colour changes into a brownish-yellow. On dissolving the melt 111 water and adding an acid a milky liquid is formed from which ORGANIC CHEMISTRY. 19! crystals soon separate. They were purified by crystallisation from dilute alcohol and in this manner large yellowish striated crystals were ob- tained having the formula C1,H,,O + H20,and losing their water at 100". They melt at about 200° but decompose even below this tem- perature when heated for some time. They dissolve sparingly in hot water very freely in alcohol and ether and form with alkalis a yellow solution which gives with silver nitrate a yellowish-white precipitate ; on heating it metallic silver is formed.When the substance is heated with resorcin it yields fluorescein which is also formed by heating the substance alone phthalic anhydride subliming at the same the- These reactions show that the body is ,~Lonoresorcin-~ht~~aleili CJ& { ~~~~~3~0H)2' On heating it more strongly with soda it is resolvLd into resorcin and phthalic acid which is further deconiposed into carbon dioxide and benzoic acid. When fluorescein is heated with soda-lye and zin-dust the solution becomes colourless. On adding an acid and shaking with ether jhoresciu is dissolved and remains on evaporation as a colourless varnish.It forms an alkaline colouriess solution which absorbs oxygen while oxidising agents convert it quickly into fluorescein. Fluorescein dissolves in concentrated sulphuric acid with a dark red colour a compound of the two bodies king formed which is ob- tained pure by heating 2 mols. of resorcin and one of phthalic anhydride with an equal weight of sulphuric acid to 100" for 5-6 hours. The melt is wasbed with cold water and crystallised from wood-spirit at a low temperature. In this manner yellowish-red prisms are obtained Laving the empirical formula C,,H,,O + SO, and melting at 140-130". They are decomposed by recrystallisation become turbid in damp air and are resolved by warm water or alkalis into their com- ponents. When fluorescein is boiled with sulphuric acid for some time t.esorcirL-coeruZein is formed which is precipitated by water in dark red flakes.It dissolves in alkalis with a greenish-blue and in ether with a reddish-violet colour and is also soluble in water the concentrated sulution being red and the dilute splendid reddish-violet. It is reduced in an alkaline solution by zinc-dust and the red liquid thus formed again becomes blue on exposure to the air. Di,litr.o-~uo.resceilz,C,oH,o(N02)205,is obtained but not quite pure by dissolving fluorescein in 20 parts of sulphuric acid and adding to the solution at 0" two parts of fuming nitric acild. It is an amorphous yellow powder dissolving in pocash with a brown dour which on henting changes to red and blue. On heating it with aceticanhydride the compound C,,H,(N0,j203(OCOCH3)2 is formed crystallisirig from alcohol in pale yellow needles.The same oompound is formed by acting with nitric acid on a solution of acetylfluorescein in sulphuric acid but not by dissolving it in cold nitric acid while on heating tetranit rofluorescein is formed. When dinitrofluorescein or better its acetyl-compound is boiled for ABSTRACTS OF CHEMICAL PAPERS. five minutes with 20 times its weight of a lye containing 15 per cent. of alkali the liquid changes to red and then blue. Acids pxoduce a yellow precipitate crystallGng from ether-alcohol in glistening red crystals consisting of C,,H,,(NO,),O,. This compound dissolFes in alkalis with a blue colonr which on dilution first changes inCo violet and then again into blue.In its absorption-spectrum the yellow is completely cut off and it shows a faint band between the blue and green. The potassium salt of this dinitro-jluoresoein hydwta appears to be formed by acting with alcoholic potash on dinitro-fluoresceh a blue crystalline body separating out which is soluble in water. Hydrochloric acid and tin reduce dinitro-fluorescein in an alcoholic solution diarnido-fluorescein being probably formed. Its hyd~ochloride crystallises in greenish-grey needles and dissolves in alkalis with iL cherry-red colour. With nitrous acid it yields a body crystallising in yellow needles and dissolving in alkalis with a light reddish-brown colonr and a strong dark green fluorescence. T~trrcrL.llro-fl.uorescein,C20H,(N0,)40,,is formed by adding an excess of fuming nitric acid to about 5 grams of fluorescein ; a violent reac- tion soon sets in and after all is dissolved the compound is precipitated with water washed with water and a little alcohol and dissolved in 50 parts of boiling glacial acetic acid.On cooling the compound separates in colourless warty crystals. It is sparingly soluble in alcohol with a yellowish-red colour and a faint yellowish-green fluorescence. The addition of a little mineral acid changes the colour into a pale reddish-vklei while on adding more the liquid becomes colourless. In alkalis it dissolves with a yellowish-red colour and in boiling water with a red colonr. It dyes on wool an intense and fast orange.Dilute boiling alkalis do not change it but concentrated alkalis change the colour to brown and then to a pale yellow. Tin arid hydrochloric acid reduce tetranitrofluorescein to an aniido- compound dissolving in alkalis with a splendid bluish-violet colour. In ammonium sulphide it dissolves with a brownish-red colour which changes to violet oil heating. Acids produce a brown precipitate crystallising from ether in brown needles and dyeing on silk a dingy violet. MorLobrom~~uorescei52 is farmed by suspending fluorescein in 4 parts of glacial acetic acid and adding the required quantity of bromine mixed with 4 parts of acetic acid. The compound is a yellowish-red amorphous body which could not be obtained in crystals and is changed by boiling acebic anhydride into a sticky mass.The alkaline solution has a reddish colour and faint green fluorescence. Dibrorvlo$uoresceirt is formed by iising 2 mol. of bromine. It forms compact reddish-brown needles with a deep green reflection melting at 260-270" and dissolving sparingly in acetic acid alcohol and acetic ether. Its alkaline solution is reddish-yellow and shows a faint yellowish-green fluorescence. On boiling the liquid changes into violet anti blue and the fluorescence into a dark green. On boiling it with acetic anhydride the diacetyl-compound is formed crystallising in colourless needles which become red at 180°,and melt at 208-210". TetrabroraoJuoresceilz or Eosiiz CzoH8Br,O5.-This beautiful body ORGANIC CHEMISTRY. which is now manufactured on the large scale and has been introduced into commerce by H.Caro as a dye-stuff is formed by mixing fluores- cein with 4 parts of acetic acid and adding the required quantity of bromine which is diluted with four times its weight of acetic acid. It is also formed by adding bromine to a mixture of fluorescein and alcohol. It is purified by converbing it into the pure potassium salt and decomposing it by a mineral acid. An amorphous reddish-yellow precipitate is thus obtained which is dried and dissolved in twenty times its weight of absolute alcohol which is then distilled off until crystals begin to separate; or the potassium salt is decomposed by dilute sulphuric acid and the liquid shaken with ether. The amor- phous eosin is much more freely soluble than the crystals ; the alcoholic solution is reddish-yellow and not fluorescent; it is but sparingly soluble in acetic acid and almost iiisoluble in water chloroform and benzene.The crystals obtained from alcohol consist of CzoH8Br405 + C2H60,the alcohol being given off at 100". If to a boiling alcoholic solution water is added until it becomes turbid and theu a little hydro- chloric acid the liquid on boiling becomes clear again and dull flesh- coloured cryst,als separate out consisting of the pure compound. Nosin is a bibasic acid ; its salts are decomposed by mineral acids but only imperfectly by acetic acid. The potassium saZt Cz0H6Br405Kz + 6H20 occurs in commerce as " soluble eosin," and forms brown indistinct prismatic crystals with a blue and yellowish-green reflection.To obtain it in well-defined crptals 100 parts are dissolved in 50 parts of water and after addi- tion of 100 parts of alcohol and filtering the solution deposits on standing splendid large plates which in transmitted light appear red and show the above reflection. They form a red powder and belong to the triclinic system being combinations of 00 P 00 P 03 co P 03. They contain 5 mol. of water. On dissolving them in dilute alcohol small Tecldish-brown crystals with a greenish-yellow reflection crystal- lise on cooling which appear to contain 1mol. of alcohol. When the aqueous solution is quickly dried the salt separates as a varnish having a yellowish-green metallic lustre. It dissolves in 2 parts of water.The concentrated solution is dark yellowish-red and in a thin layer pale pink. -4dilute solution is yellowish-red and exhibits a st,roiig greenish-yellow fluorescence which is also seen when the solu-tion is very weak. Its absorption-spectrum has a broad dark band in the green. Its alcoholic solution exhibits similar colours but a stronger fluorescence. The absorption-spectrum is destroyed by mineral acids but not by acetic acid. A dilute aqueous solution con- taining 1part in lEi0 gives the following reactions :-It is not changed by magnesium sulphate. Calcium and barium chloride give crystals on quickly boiling down the liquid while cad- mium sulphate deposits crystals in 12 hours and nickel snlphate after weeks. Mercuric chloride gives at once a crystalline precipitate and on standing a mixture of red and yellow crystals.Red amorphous precipitates are formed by salts of silver and lead and reddish-brown by copper salts while alum zinc sulphate stannous chloride cobalt nitrate ferric and ferrous chloride maiiganese sulphate and bismuth nitrate give amorphous reddish-yellaw precipitates. 202 ARSTRACTS OF CHEMICAL PAPERS. The fimrnoniurn saZt CzoHfiBrdO,(NHd),, is obtained in small red needles when a solution of tetrabromofluorescein in alcoholic ammonia is concezztrnted they give off some ammonia on drying. The 7inlizcrn sidt C,,,H6Br405Ba+ 2H20 is prepared by mixing a solution of 2 parts of the potassium salt with a solution of 1part of barium chloride in such a proportion that 60 parts of water are pre- sent.On boiling crystals separate ont of which more are obtained on evaporating the mother-liquor after cooling they form small rhombic plates with a green reflection ; the aqueous solution is yellowish-red and shows a green fluorescence. The cupric salt C,,H,Brd05Ca + +H,O forms small yellowish-red needles with a faint green lustre ; it is more freely soluble than the barium salt. The cadmiwm salt is deposited from a dilute solution in very glisten- ing small six-sided plates having a brilliant greenish-yellow lustre ; at 100" ih loses water and becomes pen. The silver salt C20E6Br405Ag2 a dark red precipitate which is is insoluble in salt-solutions but dissolves in pure water and alcohol and on heating it with the latter to 150" and leaving the solution to cool it crystallises in microscopic indistinct) prisms which are almost black.The precipitated salt becomes green when dried in a vacuum. The lead salt C2,HfiBrd05(PbOH)2, is obtained as a red precipitate when the potassium salt is mixed with lead acetate while the nitrate produces a similar precipitate which is not quite pure CzoH,Br40,Ph. Red M~nethyl-~c:trabron2ofuorescein, or Erythrin C20H6Br,0,{ OCzH, is formed when the potassium salt of eosin is heated to 140-150" for 4-5 hours with 15 parts of alcohol and a quantity of potassium ethyl- sdphate which would be sufficient to form the neutral ether. On cooling the tubes contain a gelatinous mass mixed with large crystals which on adding water remain undissolved while the unrhanged potassium salt of erythrin dissolves.The crystals which consist of the potassium-compound 9f eosin are dissolved in alcohol of 50 per cent. and the solution mixed with acetic acid. If it! be concentrated erythrin separates as an amorphous precipitate but from a dilute solution it crystallises on evaporation in red needles with a beetle-green lustre. Erytbrin is also formed but not so readily by the act,ion of ethyl bromide on the potassium salt of eosin. Erythrin dissolves slowly but freely in alcohol with a reddish-yellow colour and more readily in chloroform and acetic acid. From the first two solvents it separaies in warty crystals but when its solution in a mixture of acetic acid and alcohol is diluted with water distinct crys- tals iire obtained.When erythrin is heated with snlphnric acid to 150" it is again converted into eosin. The potassium salt C6H,Hrp05(C,H,)K + HzO is very sparingly soluble in wbter and absolute alcohol but readily in hot dilute alcohol of 50 per cent. The concentrated solution is yellowish-red the dilute pale pink with R yellowish-green fluorescence ; its absorption-spectrum is alinost the same as that of eosin. The salt called in commerce "insoluble eosin," dyes silk and wool like eosin but the shades are more inclined to violet. The crystals appear to be rhombohedrons. ORGANIC CHEMISTRY. 203 They have a strong beetle-green lustre and yield a pink powder. Silver nitrate precipitates the solution ; the precipitate is amorphous red in reflected light and beautiful violet in transmitted light; on heating or standing it becomes crystalline and in the dry state it has a beetle-green lustre and appears in transmitted light intensely blue.The lead salt is EL similar precipitate. CotourlessMonet7~yl-tetrabromo~11,orescein.-Tl~isisomeride of erythrin is formed together with the diethyl-compound when the silver salt of eosin is heated with an excess of ethyl iodide or bromide and twenty times its weight of alcohol to 100" for 3-4 hours. To separate the two ethers the product is repeatedly exhausted with boiling alcohol in which the monethyl-ether is more readily soluble and crystallises on cooling in yellow needles. As soon as the red crystals of the diethyl-ether appear the treatment with alcohol is stopped and the yellow crystals boiled with a solution of potash in alcohol of ,50 per cent.which dissolves chiefly the monethyl-compound. The solution is then mixed with more dilute alcohol and acetic acid and the ether which separates out is again treated in the same way and is thus obtained in colourless needles. It is sparing!y soluble in boiling alcohol and a little more freely in glacial acetic acid ; its very pale solution is coloured light yellow by alkalis and gives yellowish- white precipitates with silver nitrate and lead acetate. It dissolves but sparingly in carbonates and dilute alkalis. The existence of two isomeric monethyl-compounds shows that the two hydroxyls occupy different positions.Dieth,yZ-fetrnhromqflzro?.mceiiz C,,H,Br,O,( C2H,), is obtained not only as described above but also by heating the silver salt of the red mon- ethyl-ether with ethyl iodide. To isolate itl from the residue from the preparation of the white monethyl-ether this residue is exhausted with chloroform and the crystals after boiling with dilute alcoholic potash are recrystallised from chloroform. It forms small but mell- defined crystak which appear to be rhombohedrons and dissdve very sparingly in alcohol and ether with a yellowish colour and freely in ch1orofoi.m and glacial acetic acid wibh a reddish-yellow colour. Aqueous alkalis do not decompose it on boiling but alcoholic potash as well as hot sulphurjc acid converts it into eosin. i~ono?~aet?L?JZ-tetrubrom~~uurescein or MefhyZerytkrix C,nH7Br40,(CH,) is sparingly soluble in alcohol more freely in chloroform it crystal-lises in red needles 'having a beetle-green lustre.AcetyZ-tetrnbron7n~uoreseein is formed by heating eosin with three times its weight of acetic anhydride to 140". It forms colourless needles dissolving sparingly in alcohol acetone wood-spirit and acetic ether and inore freely in hot benzene and chloroform. On heating it becomes red at 180° but melts only at 278". '1'et,-abromo~uorescei.nchloride C20H6Bi*403C12, is obtained by heating tetrabromofluorescein with phosphorus pentachloride for an hour to 100". The product after being well boiled with water and a dilute alkali is dissolved in seventy times its weight of concentrated sulphu- ric acid at 150" filtered through asbestos and then mixed with 3 volumes of alcohol.The liquid is then heated to the boiling point and water added until crystals begin to separate out. It forms colour- ABSTRACTS OF CHEMICAL PAPERS. less needles which melt and sublime without decomposition ; its only solvent is concentrated sulphuric acid which decomposes it only at the boiling point,. When tetrabromofluorescein is heated with concentrated potash on a water-bath the liquid soon assumes a blue colour and shows when diluted a very strong dark-green fluorescence. The dilute solution turns red in contact with the air but the conceiit]rated remains blue. Mineral acids produce a pale reddish-yellow precipitate of the hydrate CZ0H,Br4O5+ H20 which has undoubtedly a constitution analogous to that of the dinitro-compound.When the solution is heated on a wateT-bath the blue solution changes into dark yellow. This change takes place more quickly if the potassium-salt is heated with twenty times its weight of soda of 50 per cent. Mineral acids precipitate from the solution- Dibromomonoresorcin-pl2thaleir, CO.C6HB1.,(OH)2 C6H4{ CO,H lising in small colourless rhombic plates which melt at 218-220". It is almost insoluble in water and dissolves in alkalis and alcohol with a yellow colour. On fusing it with resorcin dibromofluorescein seems to be formed and when it is heated with phenol and sulphuric acid to 120" a body is formed dissolving in alkalis with a red colour.The acid liquid from which the preceding compound has been pre- cipitated contains dibrornoresorcin CeH,Brz(OH), which is shaken out with ether. It crystallises from warm water in colourless needles melting at 92-93' ; t,he aqueous solution gives with ferric chlor- ide first a violet colour which soon changes into an indistinct dirty green. Water and sodium-amalgam or zinc-dust and soda reduce tetrq- bromofluorescein to fluorescein and when the tetrabromo-compound is boiled for five minutes with twenty times its weight of concentrated sulphuric acid h~ptabronzoc~i-~leilz is formed which by C40H13Br7010 adding water is precipitated as a dark violet mass and during wash- ing begins to dissolve with a blue colour. On dissolving it in dilute potash and adding alcoholic potash a dark-blue precipitate of the potassium-salt is obtained which yields with acids the pure coerulein readily soluble in acetone from which it crystallises in stpeel-blue needles.The absorption-spectrum of the dilute solution shows a faint broad band in the green and the dilute alkaline solution which has a greenish-blue colour gives an absorption-band in the red. Dibromod7:72itl.qpiLoresceirt C20H6Br,(N0,)20,,is formed by the action of nitric acid on dibromofluorescein and by treating dinitrofluorescein with bromine. It is also obtained by dissolving 1 mol. of the tetra- nitro-compound in boiliug acetic acid and adding 2 mols. of bromine. It crystallises in compact yellow needles which are very sparingly soluble in alcohol and acetic acid and dissolve in alkalis with a yellow-ish-red colonr becoming pale pink on the addition of much water.It is not fluorescent but gives an absorption-spect;rum resembling that of eosin. The acetyl-compound forms colourless needles melting at 250° but changing to violet at 210". Some of the derivatives of fluorescein have already been described by Fischer (this Journal 1875 p. 159). ORGANIC CHEMISTRY. 11. Omin-phathaleilz by E. Fischer.-This homologue of fluoresoin is formed by heating phthalic anhydride with orcin and is best obtained by heating 3 parts of phthalic anhydride 5 parts of distilled orcin with 5 parts of sulphuric acid for two hours to 135" ; if the temperature be kept at 100-120" bye-products are formed and sulphur-dioxide is evolved.The brown melt is washed with water dissolved in dilute potash boiled and then the phthalein is precipitated by acetic acid. It is purified by crystallising from acetone and is thus obtained in groups of needles. It is insoluble in water ether benzene and toluene and readily soluble in alcohol wood-spirit acetone and acetic acid. In alkalis it dissolves with an intense dark-red colour without fluorescence when pure. With mineral acids it forms red compounds which are soluble in water ; on heating it with sulphuric acid a ccmulein is formed which after drying is almost black and dissolves in ammonia with a dark-red colour. Diacety Zorcin-ph'thazein crystallises from alcohol in silky needles having a faint bluish lustre and melting at 219-220".Orcin-phthalein crystadlises from hot acetic acid in short prisms which when heated with the acid €or some time become yellowish- red rnoizncetyl-o~ci~c-pktha~ei.n being formed which is obtained pure by heatiny the substances to 150". When orcin-ph thalein is heated with hydrochloric acid and alcohol the compound C,2H,,05+ HC1 is formed which on evaporating the alcohol separates in dark red flakes. On heating it or boiling it with water it loses the acid but it dissolves in alcohol wood-spirit and acetone without decomposition. Tet1.abro.lnorcin-phthaZei.12,C2,HI2Br4O5, is obtained by adding bro- mine to a boiling solution of the phthalsin in acetic acid. It is a pale yellow crystalline powder nearly insoluble in most solvents but some- what more soluble in a mixture of acetone and carbon sulphide.Its almost black alkaline solution becomes dark-brown on dilutlion and shows a blackish-green fluorescence. As the formation of phthalic acid from tetranitrofluorescein shows that the substitution has taken place in the resorcin-residues it appears most likely that the same is the case with tetrabromorcin- phthalein which is not decomposed by boiling alkalis and must therefore have the following constitution :-,cH, /CO-CBr,-OH GH*\CO-CBr,\OH>o . CH3 When the phthalein is brominated in presence of alcohol penta-bro~noi.cirt-phthaZeilzis formed which can be distinguished from the tetra-compound only by analysis. Orcii?phtkalinis obtained by heating the phthalein with dilute soda and zinc-dust ; potash acts but slowly and with difficulty.On addiiig dilute sulphuric acid to the colourless solution white flakes are formed which when pure do not absorb oxygen. The dry compound can be boiled with hydrochloric acid without change but if the acid be added VOL. XXXI. P ABSTRACTS OF CHEMICAL PAPERS. to the boiling alkaline solution the red compound of the acid with the phthalein is formed. The phthalein is sparingly soluble in water but readily in most other solvents and does not crystallise. The diacetyl-conzpouncl C22H160,( C,H,O) forms small cubical crystals melting at 211". The constitution of this body is probably \CH c. s. Terephthalic Aldehyde. By E. GRTMAUX (Cowpt. rend. lxxxiii.825-82 7).-The only three dialdehydes known are glyoxal succinic aldehyde and phthalic aldehyde. The author has prepared terephthalic aldehyde by a method discovered by himself and Lauth viz. by oxidising the chloride of the acid radicle with dilute nitric acid or with lead nitrate. The tollylene chloride was boiled with 20 parts of water and some lead nitrate till red fumes no longer appeared. The liquid was then distilled after addition of water and the aldehyde was carried over by the water-vapour. It has the formula C8H60,;it forms delicate white needles and melts at 114-115". It dissolves in ether and in alcohol sparingly in cold water and in about 60 times its weight of boiling water. It forms a compound with sodium disulphide which cannot be separated from its solution.When treated with potassium cyanide it appears to be polymerised forming a reddish-bro wn substance yellow and amorphous when dry insoluble in water and in ether soluble in boiling alcohol and in alkalis but not in their carbonates and melting at 170-174". It is analogous to benzoin. The aldehyde was proved to be terephthalic by oxidation. The mixture of chlorides from which the tollylene chloride had been separitted by freezing was oxidisable with difficulty with lead nitrate ; the product of the oxidation appeared to be isophthalic aldehyde. It melted at 88". W. R. a-Cresylsulphuric Acid. By E. BAUMANN (Deut. Chem. Ges. Bey. ix 1389-1392).-Horses' urine contains besides phenyl-sulphuric acid also a cresylsulphuric acid forming a potassium salt which is less soluble in water and alcohol than the phenyl-sulpbate.It is not coloured by ferric chloride but on heating it to 150-160" it seems to be changed into a cresolsulphonate which is coloured blue by the ferric salt. The corresponding cresol (Xt&leZer's taurylic acid) is identical with Engelhardt's and Latschinoff's a-cresol. It yields with bromine an unstable substitution-product or a mixture of such. c. s. New Mode of Formation of Azobenzene. By R. ANSCH~~TZ and G. SCHULTZ (Deut. Ckewt. Ges. Rer. ix 1398-1408).-Glaser found that by the action of sodium on parabromaniline benzidine is formed. On repeating this experiment the principal product was found to consist of azobenzene no benzidine being formed.C. S. ORGANIC CHESUSTRY. Haloiid-Derivatives of the Nitrotoluenes. By C. WAC H E N-DORFF (Deut. Chern. Ges. Ber. ix 1345-1347).-When the different nitrotoluenes are treated with chlorine or bromine above loo" the substitution takes place in the side chain. Thus on heating parani- trotoluene with bromine to 125-130" pa!ranitrobenx?yZ bromide is formed crystallising from hot alcohol in silky needles and from cold alcohol in thin plates melting at 99-100". It prodnces a burning pain on the skin and violently attacks the eyes and mucous membranes of the nose. By using more bromine paranitro5enzyZene dibromide is obtained crystallising from hot alcohol in needles or plates melting at 82-82-5". When chlorine is passed into paranitrotoluene at 185-190" para-nitrobenzyl chloride is formed which has already been described by Heilstein and Geitner and by Grimaux.A more highly-substituted product could not be obtained and if nitrotoluene is treated witlt is antimony perchloride ?netnchloro-pct?.cc.nitrotoZ~e~~e formed crys-tsllising from hot alcohol in long glistening pointed prisms melting at 64-65". Ib is freely soluble in alcohol ether and glacial acetic acid and sparingly in hot water from which it crystallises in small needles. On oxidation it yields Hubner's nitrometachlorobenzoic aLcid. By acting with bromine on metanitrotoluene metnnitrobempl bromide is formed crystallising from hot alcohol in small needles or plates melting at 57-58" and by using more bromine metanitro- benzylene dibromide is obtained in microscopic needles melting at 101-102 ".The author formerly described the corresponding ortho-compounds ; but the orthonitro-toluene which he then used contained the para- compound. Perfectly pure orthonitrotoluene yields only dibromortho-?LitrotoZueize,which separates in compact plates. On recrystailisatiou from hot alcohol they change into small white needles melting at 235-226". It is readily soluble in aqueous alkalis and reprecipitated by acids in flakes. c. s. Two New Modifications of Dichloronaphthalene. By P. T. CLEVE(BUZZ.Xoc. Chi'rn. [21 xxii 244-245).-The following table gives a view of all the dichloronaphthalenes rediscovered since Lament's time. Name. Melting point. Discoverer. r% 35-36" Faust and Saame.8 68" ?> Y 107" Atterberg. 6 114" ClAve & 135" 7 The two latter were prepared from the two disulphonic acids recently cliscovered by Ebert and Merz by the action of phosphoric chloride. The &chloride is soluble in alcohol and forms large lam in^. The e-chloride crystallises in prisms and is sparingly soluble. W. R. P2 ABSTRACTS OF CHEMICAL PAPERS. Nitro-and Amido-naphthylsulphonicAcids and their DerL vatives. (Part 11.) By P. T. CL~VE, Rzc77. SOC.Chim. [Z] xxvi 241-244) .-Napldhionic acid, C,,H,NH,. S03H,was prepared both by Piria's method (acting on nitronaphthalene with ammonium bisul- phite) and by Schaal and Schmidt's (acting on naphthylamine with sulphnric acid) and it mas proved that both these processes give the same acid.By the action of nitrous acid it is converted into dinzo->H, naphthionic acid CIoH6 C6 a yellowish crystalline powder which detonates by percussion or by Heat and evolves nitrogen when heated with water. Excess of nitrous acid converts it into dinitro- naphthol CloH,(N02)20H,owing to the action of the nitric acid formed on the oxynaphthylsulphonic acid resulting from the decom- position of the diazo-acid. The melting point of the dinitro-naphthol was found to be 130". A dioxynaphthalene cannot be prepared from diazo-naphthionic acid by the action of caustic potash. A dichloronaphthaZene crystallising in prisms and in colourless needles and melting at 67.5" was obtained by converting the diazo- acid into chloronaphthylsnlphonic acid by heating it with hydro-chloric acid and distilling the potash salt with phosphoric chloride.The product has the formula C,,H6C1.S02.C1 and when redistilled with phosphoric chloride gives the dichloronaphthalene. It corre-sponds with that obtained by Faust and Saame and called by them P-dic72lorona~hthalene,also with that obtained by Atterberg of Upsala by acting on a-nitronaphthol with phosphoric chloride. This shows that naphthionic acid belongs to the same series as a-nitronaphthalene which contains the groups NO and OH in the same benzene ring and next each other. The following bodies have doubtless an analogous structure :-Melting point. P-Dichloronaphthalene. ......... Nitrochloronaphthalene ........ Hydronaphthoquinone.......... Naphthoic a.cid giving ........ Naphthoic anhydride .......... Naphthoquinone .............. a-Naphtholsulphonic acid ...... a-Carbonaphthalic acid ........ Naphthionic acid .............. a-Nitrosonaphthol of Fuchs .... a-Amidonaphthol.............. a-Nitronnphth 01 .............. a-Nitronaph thylamine ........ Diamidonaphthalene of Lieber-mann and Dittler. ........... . 68" 85 176 125 CloH6C&. Ci,H,(NOZ)Cl.Cl,H,( OH),.CloH,O,. Nitracetonaphthalide and its de- rivatives .................. C10H6(~02)~~~2~3~. W. R. ORGANIC CHEMISTRY. Note on some New Derivatives of Anthracene. By W. H. P E RK IN (Chern. News xxxiv 145).-Anthracene dibromide crystal- lising in flat oblique prisms which turn yellow and opaque at the ordinary temperature with evolution of liydrobromic acid is prepared by treating anthracene with a solution of bromine in carbon disulphide.It dissolves with difficulty in carbon disulphide alcohol and ether. When the dibromide is heated the monobcomide is formed ; it may also be prepared by acting with the theoretical amount of bromine dissolved in carbon disulphide on anthracene. It melts at 1.00" ; dis-solves in benzene and carbon disulphide also in alcohol and glacial acetic acid ; crystallises in long needles and combines with picric acid. The dichloride separates out as a white precipitate on passing chlorine into a one per cent. solution of anthracene cooled to 0". It is very unstable. It dissolves sparingly in alcohol ether benzene acetic acid and carbon disulphide.On fusing it monochloranthracene is formed. This compound crystallises from alcohol in golden-yellow flat needles and melts at 103"; dissolves easily in ether benzene carbon disulphide and alcohol and moderately in acetic acid. Its compound wlth picric acid crystnllises in beautiful scarlet needles. W. R. Simultaneous Formation of two Trioxyanthraquinones and Synthesis of a New Isomeride of Purpurin. By A. Ros EX-STIEHL (Cornpt. rend. lxxxiii 827-830).-Schutzenberger in making approximate analyses of commercial purpurin mentions as one of its constituents a yellow substance dyeing yellow with alumina AS a mordant. The author during his researches on the colouring matters of madder amassed several grams of this substance. As it is an isomeride of purpurin C,J&O, he gives it the name of a-pzcrpurin.It is obtained by boiling pseudopurpurin with boiling water whereupon water is absorbed and oxygen evolved ; and hydrated purpurin and the new body are formed. It was separated from the purpurin by oxidising the latter with potassium permangmate or by exposing its alkaline solution to air. Any remaining purpurin is removed as a lake with iron. The yield of the new substance is very small. It is a light orange-coloured powder which begins to melt at 180° and sub- limes with partial decomposition. It is more easily soluble in water than the other madder dyes and dissolves easily in alcohol acetic acid benzene and chloroform. It is soluble in strong sulphuric acid and is reprecipitated by water.With alkalis it gives red compounds intermediate in colour between purpurin and purpuroxanthin. The lime and baryta lakes are sparingly solable in boiling water ; it dis-solves in a hot solution of alum and is deposited on cooling. With alumina mordants it gives an orange colour three or four of Chev-reul's tables; it is saturated only in presence of an equivalent of calcium acetate. This dye does not resist the operations of soaping and clearing ;it gives no colour with iron mordants. It has the following relations to the oxyanthraquinones tetraoxy-anthraquinone or pseudopurpurin CI,H4(OH)402,when heated with water to 100" loses an atom of oxygen and gives rise to two trioxy- ABSTRACTS OF CHEXICAL PAPERS. quinones CI4H,(OH),O2,one giving ft red and the other an orange colour with alumina.These two when reduced in alkaline solution give a single dioxyanthraquinone CI4H,(OH),Q2 Schutzenberger's purpuroxanthin. The latter when oxidised in hot solution gives a purpiirin which dyes red ; in cold solution a pnrpurin dyeing orange. All these substances exist in madder as glycosidcs. e-Purpurin when treated with phosphorus in alkaline solution loses an atom of oxygen and is cohverted into a dioxyanthraquinone pur-puroxanthin ; when boiled with an alkali it undergoes molecular transformation into purpurin. e-Purpurin can be synthetically pre- pared ; by oxidising alizarin purpurin is formed ; from purpurin its isomeride can be prepared ; by reduction purpuroxanthin is formed ; and the latter when oxidised yields a-purpurin.W. R. Action of Quicklime on Phenanthrenequinone. By R. AN-RCH~TZand G. SCHULTZ (Deut. Chew. Ges. Bey. ix 1400-1403).-When phenanthrenequinone is distilled with common soda-lime it yields as chief product diphenyl as Grabe has already shown. On using a soda-lime sold as prepared from sodium no diphenyl was formed but (1) fluorene ; (2) a red body of high boiling point which also accompanies the diphenyl ; (3) a white compound melting at 150". When only quicklime is used the products consist of diphenyl ketone melting at 83-84' and fluorene. c. s. Nitrophenanthrenequinone. By R. ANSCHU TR and G. SCHULTZ (Deuf. Chern. Ges. Ber. ix 1404).-This compound is ob-tained by boiling the quinone with a mixture of common and fuming nitric acid; it forms golden yellow plates melting at 257" and is almost insoluble in alcohol and sparingly soluble in glacial acetic acid.On distilling it with soda-linie a volatile base is formed. c. s. Herapathite and similar Acid Periodides. By S. M. JOR-ENSEN EN (J. p.Chenz. [el xiv 213-268).-The first section of this paper consists of an historical introduction ; the second treats of the methods of analysis employed by the author ; and the third gives an account of the bodies prepared and examined. A. QUININE Coiwouxr?s.-Quinine forms many compounds similar to herapathite and they may be divided into two series. One to which herapathite proper belongs contains three molecules of sul-phuric acid to four of quinine ; the other one molecnle of acid to two of quinine.The first series consists of tolerably stable compounds while the salts of the other series are prone to decomposition with formation of compounds belonging to the first series. 1st Herapcathite 4.C20H24N,02.3SH204.2HI,14 + rcH,Q is best pre-pared by dissolving neutral quinine sulphate in the calculated quantity of snlphuric acid warming with alcohol up to boiling mixing with the calculated quantity of hydriodic acid and iodine the first in aqueous the second in alcoholic solution and allowing the whole to cool slowly. ORGANIC GEEEXISTRY. 211 Herapathite is found to contain unaltered quinine and one-third of the iodine is present as hydriodic acid. 2nd Sulphato.periodid e of Quinine 8C20H2,N202.6HzS0*.4HI,110.-There are several methods of obtaining this compound. One is to dissolve one molecule of neutral quinine sulphate with two molecules of sulphuric acid in alcohol and to add to the solution heated to boiling one atom of iodine dissolved in alcohol. The crystals of' this salt have a metallic lustre and are of an olive-grey colour between the grass-green of herapathite and the bronze-yellow of the next com- pound. They are more soluble in warm than in cold alcohol but not so soluble as herapathite. 3rd Sulphato-periodide of Qnciniwe 4Cz0H2~N~0~.3HzSO~.2HI.T6 + 2H20.-This compound may be formed by addition of 1part of iodine to 3s parts of herapathite in alcoholic solution. It crystallises in long flat needles or in plates of the same form as herapathite.It is of a bronze-yellow colour and is less soluble than herapathite in hot alcohol. On recrystallisation it is decomposed into iodine and the previous compound. 4th Xulphato-periodide of Quinine 8CzoH,,XzOz.6H,S0,.4HI.I,,+ 4H20.-Formed in the attempt to produce the 7th compound (see below) from the calculated quantities of quinine sulphate hydriodic acid and iodine. Bronze-yellow brownish needles with fine metallic lustre. It is isomorphons with the previous compound. 5th Su7pkato-perioclide of Quinine 2C~0Hz4NzOz.H2S 0,.2HI.1,.-Obtained by mixing an almost cold solution of one molecule of neutral quinine sulphate in alcohol with two atoms of iodine dissolved in hot alcohol and allowing the mixture to stand for two hours.It consists of long red brilliant needles which in air become changed into a black glassy mass 6th Sulphato-periodide of Quinine 2 C2,H2,N202. H2S0,.2HI.II.-T he calculated quantity of neutral quinine snlphate hydriodic acid and iodine is dissolved in hot alcohol and the solution is mixed with so mucli hydriodic acid that nothing crystallises out on cooling. On cautious addi tion of water olive-green laminae separate. This com- pound is more soluble in hot than in cold alcohol but cannot be crystallised from this solvent. Berapathite is deposited 011 cooling. 7t h Xzdphnto-periodide of Quini?~e,2C2,H2,N,0,.H2. SO,. 2HI.18.-May be obtained in several ways-for instance by mixing a hot alcoholic solu- tion of herapathite with a large quantity of solution of iodine diluting somewhat with water and allowing the mixture to stand.This coin-pound forms brilliant black needles and laminae with a greenish reflec- tion. If washed with too strong a solution of alcohol the crystals resemble potassium permanganate in appearance. They cannot be recrystallised for although slowly soluble in alcohol another compound not yet accurately examined separates on cooling. In addition to the two classes of salts above described- 4Qu.3HzS0+2HI.In 2QU.H2SOA.2HI.I, a third seems to exist of the composition 3Qu.2H2S04.2HI.I,. The salts of this series have not yet been examined with suEcient accuracy ABSTRACTS OF UHEMICAL PAPERS. to settle their formula^! with certainty but the author's results are as follows :-NO.1. 3C,oH2~N,0,.ZH,S04.ZHI.T, (?).-This compound corsists of groups of fine needles which are blue by transmitted light when in thin layers. It is obtained during the recrystallisation of the next substance. No. 2. 3C3,H,N202.2H,SOi. ZHI.I,.H,O (?).-Consists of olive-grey lamine which separate from a hot alcoholic solution of' acid sulphate of quinine on addition of varying quantities of solution of iodine. No. 3. 3C,oH?4N,02.2H,S04.2H1.1, (?).-Obtained only once in a pure state from one molecule of neutral snlphate of quinine two mole- cules of normal sulphuric acid and 200 C.C. of an old solution of iodine containing 16.8 grams of free iodine. All attempts to repro- duce this body with a freshly-prepared solution of iodine failed.It consists of olive-green needles with metallic lustre which polarise light in exactly the opposite direction to herapathite. B. COMPOUNDS OF MErrHPL-QUININE.-1St Xulphato-periodide of Methyl-yuinine 2C,oH,4N,0,( CH3)I,HzS04.1d.-This compound is ob-tained by slowly cooling a mixture of the theoretical quantities of methyl-quinine iodide and sulphuric acid with about four-fifths of the calculated quantity of iodine in alcoholic solution at a temperature of about 60". It consists of reddish-brown needles often several centi- meters in length which are easily soluble in hot alcohol. 2nd Xulphato-p eriodide of &.!let hy1-quinine 2C,,H,4N 0,(CH,)I. H2S@i.P6.-1SiIost easily prepared by slowly cooling a mixture of methyl-quinine iodide sulphuric acid and iodine (in the calculated quantities from a hot alcoholic solution.It consists of very fine brilliant brown laminae soluble with difficulty even in hot alcohol. 3rd Xu& hato-pe riodide of Methy1-quinine 4C20H2iN,0,(CH,) I. 2112S04.T,4.-Prepared by warming an alcoholic solution of No. 1 to 60" and adding an alcoholic solution of four atoms of iodine of the same temperature. It consists of brilliant almost black lamine which must be filtered off from the still warm solution and washed with alcohol at about 60". The temperature must be kept down or else the product consists chiefly of No. 2. It is soluble with difficulty in hot alcohol. 4th Szclphate-periodide of il/lethyZ-quinine 4C20H,~N,0,( CH3)I. 2H,S@4.1,,.-Obtained by mixing a hot alcoholic solution of No.1 with a large excess of a cold solution of iodine. It consists of long thin almost black needles with a greenish metallic lustre. The ergs- tals dissolve with difficulty in hot alcohol. Compounds containing four molecules of methyl-quinine to three of sulphuric acid could not be obtained. 0. COMPOUXD QuINrnlE-METHYL-QUININE.-An attempt was made OF to prepare herapathite with methyl-quinine in place of hydriodic acid by mixing the calculated quantities of methyl-quinine iodide quinine sulphate and iodine in hot alcoholic solution. The result was a com-pound of herapathite with No. 1sulphato-periodide of methyl-quinine and water. This body crystallises in dark chocolate-brown masses which appear under the microscope as carmine-red intertwined hairs.The water is given off at 100 . The compound dissolves with some difficulty in hot alcohol. G. 1'.A. ORGASIC CHEMISTRY. 213 Oxidation of Cholic Acid with Potassium Dichromate and Sulphuric Acid. By H. TAPPEINER (Zeitschr. fiir Biologie xii 60-74).-Cholic acid was prepared from bile by boiling with baryta- water was recrystallised till perfectly white and pure and was then oxidised in portions of a gram by a mixture of 10 grams potas- sium dichromate 15 sulphuric acid and as much water as occupied three times the volume of the acid the whole being gently heat'ed in a sand-bath an inverted condenser being attached to the flask. After 6-10 hours white masses floated on the surface of the liquid and also an oily film which solidified on cooling.On filtering and distil- ling the filtrate acetic acid passed over and traces of a solid acid were left in the retort. The solid substance left on the filter dissolved readily in alkalis and was reprecipitated by acids. The precipitate was washed and suspended in water. On distilling the whole oily drops passed over solidifying to white crusts on cooling. This took place so slowly however that distillation for a month was necessary to effect the complete expulsion of the volatile acid. The white crusts thus obtained melted at 33-44" and gave a barium salt containing 20.43 per cent. Ba agreeing with a mixture of stearate and palmitate. The non-volatile residue dissolved perfectly in alcohol and crystal- lised therefrom in needles which did not melt at 250" but melted with decomposition at a higher temperature.It formed a barium salt soluble in water and by this means a more convenient mode of sepa-rating the volatile acid was obtained a5 the barium salt of the volatile acid is insoluble in water. When kept for a long time at 150' it slightly browned. On analysis of the acid and its barium salt num- the barium salt bers were obtained leading to the formula C40H,,01z being Ba,( CMH55012)2, i.e. the acid being pentabasic. The silver salt is a white non-crys talline curdy precipitate of' analogous composition C4oH55Ag5012. Laiger quantities of cholic acid were treated and the volatile and non-volatile acids separated as barium salts.On repeatedly crystal- lising the volatile acid from alcohol the melting point rose and finally a body was obtained melting at 67" and giviiig numbers agree- ing with the formula C22H4203.Another acid was also isolated (by fractional precipitation as barium salt) agreeing with the formula C,5H3002, and melting at 54". Hence it appears that there is some reason for assigning a connection between bile and fatty acids. The aqueous chromic liquid from which these acids had separated in the solid form yielded on evaporation a small quantity of crystalline scales. These consisted of an acid melting at 196-198" and giving numbers agreeing with the formula Cdl€€58022,the silver salt being C:41H48Ag10022, and the barium salt C41H48Ba5022. [The analytical num- bers agree better with (CB1HB9022)2Ba9].C. R. A. W. The Fluorescent Body in Atropa Belladonna. By R. PAsS-BE N D ER (Deut. Chem. Ges. Ber. ix 1357-1358) .-This body which is contained in all parts of the plant is distingnished by its strong fluorescence and stability as shown by the following experiment. Two unripe berries were crushed with a little water the mass dried on EL water-bath the residue exhausted with alcohol the solution again ABSTRACTS OF CHEMICAL PAPERS. evaporated and the remainder dissolved in water. The filtered solu-tion was shsken at a gentle heat with animal charcoal which takes up the compound. On then digesting it with alcohol and a little ammonia a liquid is obtained showing a beautiful blue fluorescence even if very dilute.The solution may be evaporated repeatedly with- out the compound losing its fluorescence which reappears on the addi- tion of ammonia. c. s. Styrax. By J. H. VAN’T HOFF(Deut. Clhem. Ges. Bey. ix 1339-1341).-In reply to Berthelot the author maintains the correctness of his former observations on styrolene and cinnamene (this Journal 1876 ii 703). c. s. Note on Litmus. By H. W. MITCHELL(Chenz. News xxiv 140-141) .-Wartha has separated four organic bodies from litmus. The first is obtained by treating commercial litmus with alcohol of about 90 per cent. filtering cold and boiling the clear tincture ; whereupon indigo is precipitated as a fine powder according to the author. The second body is obtained by evaporating the violet-red mother liquor ; it is a beautiful red or from many varieties green fluorescent sub- stance iiidifferent to acids.The litmus residue left after treatment with alcohol is digested with distilled water for 24 hours after which the deep-coloured solution is evaporated on the water-bath and the residuary extract is treated several times with absolute alcohol cou- taining a little glacial acetic acid and again evaporated until it forms a brown powdery mass. This mass is now exhausted with absolute alcoliol and acetic acid whereby a large quantity of a scarlet-red body is dissolved which resembles orcein and becomes purple-red in place of blue with ammonia. The portion of the brown powder irisoluble in the acidified alcoholic solution consists of litmus colouring matter in a very pure form so pure in fact that by means of it the carbonated alkaline earths contained in spring-waters may be titrated with as great delicacy as by the use of cochineal tincture which is far from being the case with crude litmus.To get this substance perfectly pure it is first washed with absolute alcohol then dissolved in a small quantity of water and thrown into a large excess of alcohol and the flocculent purple precipitate is collected and again thoroughly washed with alcohol. In repeating the above experiments the author confirrris Wartha’s results in every particulai. save as regmds the indigo which could not be obtained by boiling the alcoholic tincture. The fluorescent body above mentioned is violet or purple and gives a solution in alcohol of a similar colour which shows a beautiful green fluorescence with sunlight and with the spectroscope gives a very characteristic absorption-band in the green together with an almost total absorption of the violet end of the spectrum.It is soluble in water amplic alcohol and common ether very soluble in alcohol but is insoluble in carbon bisulphide chloroform petroleum naphtha and turpentine. The solutions both in amylic alcohol and in ether exhibit a beautiful fluorescence but the ethereal solution shows the absorption-band in the green only very faintly. The body which resembles orcein shows a very faint fluorescence ; its alcoholic solution PHYSIOLOGICAL CHEMISTRY gives a spectrum in which the absorption is characteristic and quite distinct from that of the last; it is slightly soluble in water very soluble in alcohol but seems to be insoluble in ether chloroform carbon disulphide and petroleum naphtha The pure litmus colour-ing matter is insoluble in alcohol ether chloroform bisulphide of carbon and petroleum naphtha very soluble in water.It turns blue with ammonia and yields in alkaline solutions a beautiful violet-lake with alumina one of a pale violet colour with stannous acetate and deep blue lakes with calcium and barium. The residue left after extracting the pure litmus dissolves to some extent in hydrochloric acid. The residue insoluble in hydrochloric acid consists mostly of fine sand but yields some colouring matter to strong ammonic hydrate.About 25 grams of the pure colouring matter 15 grams of the body like orcein and 10 grams of the fluore-sceut body were obtained per ounce of litmus. D. B.

ISSN:0368-1769    

DOI:10.1039/JS8773100182

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

PHYSIOLOGICAL CHEMISTRY. Ph y s i01 o gi c a1 Chemistry. Quantitative Analyses of Blood. By G.BUNGE (Zeitschr(ft f. Biologie. xii. 191-216).-The following are analyses of the blood of pigs horses. and oxen :-I.-De$brinated Pig's Blood . Per 1.000 parts of blood.corpuscles . Per 1.000 parts of serum. Water .................. 632.1 Water .................. 919.6 Solid constituents .......... 367-9 Solid constituents .......... 80.4 Hzemoglobin ............ 261.0 Albumin ................ 67.7 Albumin ................ 86.1 Other organic substances .... 5.0 Other organic substances .... 12.0 Inorganic substances ........ 7.7 Inorganic substances ........ 8.9 Potash .................. 0.2'73 Potash .................. 5.343 Soda ....................4'272 Magnesia ................ 0.158 Lime.................... 0.136 Chlorine ................ 1504 Magnesia ................ 0.038 Phosphoric acid ............ 2.067 Oxide of iron .............. 0.011 Chlorine ................ 3.611 Phosphoric acid ............ 0.188 11.-DeJibrinated Horse's Blood . Per 1.000 parts of blood.corpusc1es . Per 1.000 parts of serum. Water .................. 608-9 Water .................. 896.6 Solid constituents .......... 391.1 Solid const.ituents ............ 103.4 Potash .................. 4-92 Potash .................. 0-27 Chlorine.................. 1.93 Soda .................... 4.43 Chlorine.................. 3.75 ABSTRACTS OF CHEMICAL PAPERS. 111.-DeJibrinated Ox-blood. Per 1,000 parts of blood-corpuscles.Per 1,000 parts of serum. Water .................. 599.9 Water .................. 91313 Solid constituents .......... 400.1 Solid constituents .......... 86‘7 Hemoglobin ............ 280.5 Albumin ................ 73.2 Albumin ................ 10’7.3 Other organic substances .... 5-6 Other organic substances .... 7.5 Inorganic substances ........ 7.9 Inorganic substances ........ 4.8 Potash .................. 0.254 Potash .................. 0.74’7 Soda.. .................. 4351 Soda .................... 2.093 Lime.. .................. 0.126 Magnesia ................ 0017 Maqnesi ................ 0.045 Chlorine ................ 1.635 Oxide of iron ............ 0.011 Phosphoric acid ............ 0.703 Chlorine ................3.717 Phosphoi-i: acid ............ 0.266 H. H. B. S. Can Inorganic Constituents be withdrawn from the Bones by the introduction of Lactic Acid into the Intestines? By E. HEI s s (Zeitschrijtf.Biologic xii 151-169).-The decrease in the amount of the inorganic constituents of the bones which is known to take place during the progress of certain diseases has been referred by some to defective nourishment but by others to the solvent action of an accumulation of acid in the body. This latter view is supported by Marchand (Jour.f.prakt. Ckem. xxvii 93) who states that the urine of a child suffering from rachitis was found to contain more than the normal amount of phosphate of lime in addition to considerable quantities of lactic acid and that its bones subsequently proved to be deficient in lime-salts but to contain an excess of organic matter.He consequently attributes this disease to a solution of bone-earth by lactic acid derived from the fermentation of carbohydrates in the intestines and induced by a diseased state of the mucous membrane of the stomach so that according to his views rachitis proceeds in the first instance from a disordered state of the digestive organs. Beneke however believes this solution and secretion of phosphate of lime to be brought about principally by oxalic acid though this seems very improbable ; and it has moreover been asserted by Buchheim and Piotrowky that oxalic acid is without influence upon the excretion of lime. Researches on the origin of bone-diseases have also been made by Heitzmann who asserts that rachitis and osteomalacia were produced in certain animals to which he had administered lactic acid by sub- cutaneous injection or by mixture with the food.Since however he gave no analysis of the diseased bones to prove a diminution in mineral constituents and as his results also for other reasons did not seem to be conclusive the author was induced to re-investigate the subject. For this purpose a small spaniel dog 18 months old and weighing 4,701 grams was fed daily with food containing lactic acid in quan-tities at first of 1-2 grams but afterwards increased to 4-6 grams and finally to 7-9 grams. In order that its dung and urine might be collected without loss it was kept during the whole time the experiment lasted in a confined space from which it was only removed from time PHYSIOTA3GICAL CHEMISTRY.217 to time to be weighed. At the expiration of 308 days it was bled to death through an opening made in the carotid artery. Throughout the whole time the animal had never shown any symptoms of disease and Professor Bollinqer who made a careful post-mortem examination failed to discover the least signs of rachitis or osteomalacia. In order however to ascertain whether the lact!ic acid had withdrawn any mineral constituents from the body the different 'parts were separately weighed and submitted to analysis ; but in every case the results obtained were perfectly normal showing no deficiency whatever in the alkaline earths.Lastly the total amount of lime and magnesia contained in the food consumed was found to be precisely the same as that excreted in the dung and urine thus proving conclusively that none could have been withdrawn by the lactic acid. The question then remains as to what became of the lactic acid. The author believes it must have been decomposed on passing tbrough the dog's body since no appreciable quantity could be detected in the urine. €3. H. B. S. Researches on the Formation of Hippuric Acid in the Organisms of Herbivorous Animals supplied with different kinds of Fodder. By H. WEISKE(Zeitschr{ft f. Bidogie xii 241-265) .-Two fully-grown wethers of equal age and similar breed received each 21hs. of meadow hay daily. Their urine was at the same time carefully collected and examined and the figures thus obtained give the following mean results for each animal per day :-~~~~ ~ Consumption 1Quantity of Hippuric of water.urine. '1'. p' acid. 1 I 1 1 No. I..... 1143 grams. 520 C.C. 1-060 9 -11grams. 15 *45 grams. -No. 11.. .. 820 C.C. 1.043 9-80grams. 116.07 grams. 1 I I 1 The mean daily product'ion of hippuric acid was therefore 15-76 grams-a quantity which closely approximates to that found by Hofmeister. Animal No. 1then received in addition 15 grams of common salt with the following result :-Description of Consumption Quantity Spec. Nitrogen. H;ziF food. of water. ofurine. grav. .->_____c_---~~ 1684 grams 864 C.C. 1*0549.42grams 16'09grams I The addition of salt to the food was therefore followed by an increase in the consumption of water and in the volume of urine as well as to a slight extent in tbe quantity of nitrogen and hippuric acid.This result is just the reverse of that obtained by Grouven who states that with cattle the addition of salt to the food caused a very 218 ABSTRACTS OF CHEMIC4L PAPERS. considerable decrease in the quantity of hippuric acid secreted with the urine. (Physiolo!y. Chena. F/~tterungsve?..suche. Berlin 1864). Experiments were next made with mixtures of hay with wheat beans and potatoes respectively in the proportion of one part of dried hay to one part of the dried substance of tlhe other ingredient. The experiments extended in each case over four days aad gave the follow- ing mean results :-I Hippuric Description of food.Consumption Quantity of Sp. gr. of water. urine. acid. -__-----1lb. meadow-hay . . 1293 grams 1 *039 6 *32grams + 1 lb. wheat . . . . . . } 1 lb. meadow-hay . . 1660 , 1.054 4.67 ), +llb. beans .. .. . . } I 1 lb. meadow-hay . . + 41bs. potatoes. . . . } 963 > 1 -051 2-84 , This admixture of easily digestible foods with the hay must there- fore have diminished the secretion of hippuric acid since it has been previously shown that 1lb. of hay will produce about 8 grams. The effect of dosing with salicylic acid and benzoic acid was then tried the precaution being taken of feeding with hay alone for one day on changing from one acid to the other. The results were as follows :-Urine.Description of Consump-Ill Date. food. tion of vat er. March grams. e .c. 13. to 14 2 lbs. hay. -8201.043 9.80 16-07 15 to 1’7 2 lbs. hay + 5 1 grams salicylic 1188 761 1 *053 9.34 15 -41 acid. 18 to 19 2 lbs. hsy + 10 grams salicylic 868 642 1.059110 5% 14 -23 1 acid. ~ 20 .... 2 lbs. hay + 15 grams salicylic 1520 1257 1 *033;11‘43 I8-7E 1 acid. 21 .... 2 lbs. hay. 1875 690 1 *047 10 *’77 16 *05 22 to 24 2 lbs. hay + 5 1 grams benzoic 1423 663 1 *O4710 ‘44 25 *11 acid. 25 to 2’7 2 lbs. hay + 10 } grams benzoic 1490 831 1 -04810 -89 31 ‘74 acid. 28 to 30 2 lbs. hay + 15 1 grams benzoic 1503 873 1 -051 11 -09 36 -4s acid. March 31 to April 3 2 lbs. hay. 1620 865 1*0449 -92 16 -0C PHYSIOLOGIICAL CHEMISTRY.These figures show that wben a small dose of salicylic acid is admin-istered a portion only is secreted as salicyluric acid but that this portion is always greater than that wliich passes into the urine un- changed. This was also noticed by Bertagini who swalloxed 0.85 grams of salicylic acid per hour for two days and found in his urine unchanged salicylic acid as well as salicyluric acid. It is interesting to notice the extreme regularity with which the hippnric acid was secreted ; thus the average per day was :-From 11th to 14th March. . On feeding with hay alone 16-07’ grams. , 15th , 20th , ... hay + sa-Y? licylic acid . . . . . . . . . . 16.14 ,’ On the 21st March . . . . . . On feeding with hay alone 16.05 , FromSlst March to 3rdApril ,) 2 16.00 ,) Kletzinsky’s supposition that the hippuric acid is formed at the expense of urea is confuted by these experiments for it will be seen that the increase of hippuric or salicyluric acid was nearly always accompanied by a corresponding increase of nitrogen tlie only excep- tion being on the administering of 5 grams of sulphuric acid from 15th to 17th March.Separate experiments were made with peas linseed wheat and oats respectively bnt no hippuric acid could be separated from the urine in any of these cases although the liquid was allowed to stand fcr 48 hours. The same negative result was obtained on feeding with unpeeled potatoes as well as with pea and bean straw but the straw of cereals behaves difTerently in this respect.Animal No. 1was fed for seven days upon wheat-straw and afterwards for the same length of time uDon oat-straw with the following results :-L Con-Urine. sum^^' Average per Description of day. food. water. Quantity. Sp. gr. Kitrogen. Hippuric acid. -ll I-I---June. grams. C.C. From 14 to 16 1lb. wheat straw. 133’7 2 *EJl ,) 21 to 23 141b. oat straw. 1160 3 *24 So that almost precisely the same quantity of hippuric acid was produced by the consumption of 1 Ib. of either wheat or oat straw. These results disclose a remarkable relation between the amount of nitrogen and hippuric acid found in tlle urine after the assimilation of hay and straw. Thus sheep No. 1 when fed exclusively upon hay secreted in 24 hours 9-11grams nitrogen to 15.45 grams hippuric acid ; consequently at the same ratio the amount of hippuric acid secreted for 1.95 gram nitrogen should be 3.31 grams and 3-24 grams was actually found.The urine remained always distinctly alkaline whereas Henneberg ABSTRACTS OF CHEMICAL PAPERS. and Stohmann found that the urine of cattle gave under similar con- ditions an acid reaction. If hay is soaked for 24 hours in a cold dilute (1.25 per cent.) solu- tion of sulphuric acid or potash and afterwards well washed and dried its property of forming hippuric acid on passiiig through the body becomes quite changed. This will be seen from the following experinients :-Urine. Date. Description of Consumption food. of water. [_ 13 ....I} Quantity.Sp. gr Hippuric acid. ----____-Sept. 10 .... Hay treated 1200 grams. 1232 C.C. 1‘009 -1580 1250 , 1.005 -)) )) 11 .... with sulphu- { )) ) 12 .... ric acid. 690 7) 733 )) 1.017 -690 1.016 Y7 ------._-.__-740 )) -_--Sept. 26 ,... 1030 grams. 552 )) 1,021 2.62 grams. 1030 ) 513 ,) 1.023 3’02 , 810 7 440 )) 1-02? 4.66 ) )) 1090 )) 398 1.034 3-05 ,) Mean .. . . . . 1 ,. .. I 990 grams. I 476 C.C. I 1.026 3.60 grams. I This complete disappearance of hippuric acid from the urine after the assimilatior of hay that has been treated with snlphuric acid com- pletely refutes Meissner and Shepard’s theory ascribing its origin to the cuticular substance since this is neither destroyed by a solution of sulphuric! acid nor of potash of the aboi-e strength.Hofmeister who made similar experiments found that treat,ment of hay with boiling water did not interfere with its property of forming hippuric acid but that this was completely destroyed by treatment with boiling water alcohol and boiling solution of potash of 3 per cent. It may therefore be assumed that trhe substance which causes its forniation is insoluble in boiling water partially soluble in solution of potash (1.2.5 per cent.) and completely soluble in dilute sulphuric acid (1.25 per cent.) as well as in boiling alcohol and solution of potash of 3 per cent. H. H. B. S. Alleged Power of Glycerin to replace Sugar. By C. U s TIM ow IT sc H (PJliige~’sArcRiv. f. PhysioZogie xiii 453-460) .-Glycerin pure or diluted with water was introduced into dogs or rabbits either through the jugular vein or by means of a fistula into the stomach the animal being meanwhile narcotised with morphia.To augment the excretion of urine warm beer was in some experi- ments introduced into the stomach. This exerts no influence upon the action of the glycerin. The urine was collected both before and after the introduction of glycerin. The original urine from the dog generally showed a re-ducing action on the cupric salt but that from the rabbit never. Within 4 to 15 minutes after the introduction of the glycerin a PHYSIOLOCnICAL CHEMISTRY. 221 remarkable acceleration in the excretion of urine takes place the urine being as clear as water. When the rate of excretion reaches its maximum there is a gradual coloration of the urine first to straw- yellow then slowly to red and finally to blood-red the coloration being independent of the quantity of glycerin injected.The secretion of urine attains in some cases a maximitm of 3 C.C. per minute. The results of experiments made upon the urine after elimination of albumin and filtration through animal charcoal lead to the following conclusions :-1. Glycerin acts as a diuretic. 2. This action may be considered as due either to the hygroscopic property of glycerin or as dependent upon the dilution of the blood. 3. The presence of hemoglobin in the urine streiigthens the second supposition whilst separate investigations show a loss of corpuscles from the blood.4.That the reducing power of the urine is referable to the presence of a product of decomposition of the glycerin. Ei. That the reducing body is not sugar. 6. The action of glycerin is the same both upon healthy and upon diabetic animals. F. J. L. On the Influence which the tying of the Ductus Chole- dochus exerts upon the amount of Glycogen in the Liver. By E. KULZ (Pflugey’s Archiu. f,PhysioZoyie xiii 460-andE. FRERICHS 468).-Wickha8m Legg found that if the ductus choledochus of a cat were tied no sugar was found in the urine within five or six days after puncture whilst without tying glycosuria commenced within an hour after puncture. Subsequently v. Wittich found that this tying of the ductus choledochns diminished the quantity of glycogen in the liver and caused sugar to appear in the urine.This diminution he considered due either to the rapid conversion of glycogen into sugar and extrac- tion by the blood which would account for the sugar in the urine or from the liver not producing any more glycogen beyond what existed at the time of tying. To prove which of t-hese suppositions holds good experiments have been made upon guinea-pigs and rabbits which show that the ligature of this duct considerably lessens the amount of glycogen in the liver whilst at the same time no sugar can be detected in the urine. Experiments were nest performed upon rabbits which had been starved for six days and then fed with cane-sugar solution through the mouth. The results obtained confirmed the previous ones.These experiments as also the observation of Tegg prove v. Wittich’s second supposition to be correct. F. J. L. Occurrence of Nuclein in Human Brain. By R. v. JAKSCH (P’zcger’s Archizt.f.PhysioZogie xiii 469-474).-A substance has been obtained from human brain which is analogous physically and chemi- cally to the nuclein of Miescher. The white substance of the brain contains but a small quantity of nuclein compared with that in the grey whilst the total amount obtained from the brain of a boy aged VOL. xxxr. Q ABSTRACTS OF CHEMICAL PAPERS. 16 was 3 grams. The nuclein which is probably not absolutely free from impurity gave on analysis :-No. 1. No. 2. Phosphmus ........ 2.08 1.71 Nitrogen .......... 13-12 13-15 Carbon............ 50.60 50.50 Hydrogen ......... 7.40 7-80 F. J. I;. Chemistry of the Crystalline Lens. By M. LAPTSCHINSKY (Pjuyer'sArchiv. f.Physiologic xiii 631-633) .-The existing analyses of the crystalline lens not being sufficiently complete further analyses have been made the eyes of oxen having been taken for the purpose and those methods of analysis employed which are given in Hoppe-Seyley's Hnd7;oolc ?f Pliysiological Chemical Analysis. Of fonr analyses the average result obtained was :-Albumin 34.93 per cent. ; Lecithin -23; Cholesterin -22 ; Fat *29 ; Soluble salts -53; Insol. salts -29. The quantity of globulin found was 24.62 per cent'. ; therefore the amount of soluble albumin was abont 11.0per cent. A globulin-substance was isolated which in its actions resembled vitellin but was marked by its great purity whereas the vitellin obtained from the yolk of a hen's egg is mixed with considerable quantities of lecithin and nuclein.The quantity of lecithin found was inconsideralole. The cholesterin varied greatly in quantity. Fat is r:ot so considerable as is generally supposed the lecithin cholesterin and fat together being generally less than 1per cent. The ssh of the soluble salts gave an alkaline reaction effervesced with acids and contained phosphoric acid chlorine sulphuric acid potash and soda. F. J. L. The Fermentation of Urine; in reference to a communica-tion by Pasteur. By H. CH. BASTIAN (Comyt. rei~l.,lxxxiii 362). -This paper maintains that urine and many other organic acid liquids are capable of the spontaneous production of bacteria. Such liquids in which the germs of bacteria had been killed by heating would remain sterile at 2.5" but at 50" would spontaneously produce the bacteria. Tyndall entirely disagrees with the author and coincides with the views of Pasteur. C. H. P.

ISSN:0368-1769    

DOI:10.1039/JS8773100215

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Absorption of free Nitrogen by the Proximate Principles of Vegetables under the influence of Atmospheric Electricity. By M. BERTHELOT (Compt. rend. lxxxiii 677-682).-By some previous experiments detailed in the Compt. wnd. lxxxii 1253 it mas shown that free nitrogen is directly absorbed by organic sub- stances under the influence of the electric current. The absorption occnrs with pure dry nitrogen and the hydrocarbons oxygen being absolutely excluded with lignin or with moist dextrin and it also VEGETABLE PHYSIOLOGY AND AGRICULTURE. 223 takes place if air be substituted for pure nitrogen. In those experi- ments the electricity was developed of enormous tensions by a large Ruhmkorff coil the conditions being therefore comparable to the tensions produced between the clouds and the ground during a thunder-storm and the application of the results to vegetation was legitimate for fhose exceptional conditions.The present series of experiments show that the fixation of the nitrogen occurs equally under the influence of the far weaker electric tensions which are incessantly produced in the ail.. The apparatus employed consisted of two glass tubes one within the other the interior surface of the inner one being coated with a leaf of silver or platinum and connected by a platinum wire passing through bot'h tubes with a conductor electrolysed by the atmosphere. A sheet of tin-foil is rolled round the outer tube and is connected with the ground.The space separating the edge of the tin-foil from the platinum wire is coated with shellac. Into the annular space between the two tubes is introduced the matter to be operated upon such as strips of moist filter-paper or a little strong solution of dextrin and then that space is filled with nitrogen. The difference of electric tension between the two armatures is the difference of the potential between the ground and a layer of air two meters above it. In some of the apparatus the inner tube was dispensed with the inner arms'-ture being in contact with the organic substances acted upon. The experiments lasted about two months the average electric tension being about that of 3& elements Daniell the absolute value having oscillated between + 60 to -180 Daniell.In every case without exception whether the tubes were open or hermetically closed the nitrogen was fixed by the organic substance forming a nitrogenous compound which was decomposed by soda-lime with evolution of ammonia. No indication of the formation of nitric acid by the electric current of this feeble tension was found. C. H. P. The Metamorphoses of the Groups COOH CH.OH CH, and CH, in the Living Plant. By A. STUTZER (Deut. Chem. Ges. Ber. ix 1395-1397).-When young growing plants of Bmssica rapa are placed in air containing no carbon dioxide they continue to grow if they are fed with calcium oxalate or tartrate. But if any carbon dioxide that may be formed by the decomposition of these acids be I-emoved by caustic soda only those fed with tartaric acid con-tinue to live ; they may also be fed with glycerin or with ferric sue- cinate which however does not act so favourably as the tartrate.From the results it is concluded that the carboxyl-group can be assi-milated by plants only after it has been oxidised to carbon dioxide. while alcoholic groups (or methene) are taken up directly. C. S. Action of Boric Acid and of Borates on Vegetation. EJ-F IrG. PELIGOT (Con@. ?.end. lxxxiii 688).-Even very sniall qnan-tities of boric acid either free or in combination are fatal to plants. It is suggested that they may also be delcterious to animals and if so the foods preserved by means of borax,such as fresh meats received from Q2 ABSTRACTS OF CHEMICAL PAPERS.Buenos Ayres even though washed before use might be injurious to the persons eating them. This question is being investigated. C. H. P. Organic Constituents of BarleyandMaIt. By G. KEHNEMANN (Dezct. C'hern. Ges. Ber. ix 1385-1388) .-The sinistrin which the author has discovered in bar Ley disappears almost completely during germination but is always contained in wort and beer as malt contains broken and not germinated grains. Sinistrin is sparingly soluble in hot water and separates on cooling as a turbidity ;its solution is lano-rotatory while that of the sugar in barley which is crystalline and does not reduce Fehling's solution is dextro-rotatory. On account of the large quantity of sinistrin in fresh barley its infusion is left-handed while that of malt is right-handed.Barley contains also a soluble proteid and one which coagulates. c. s. Vegetation of Maize commenced in am Atmosphere Free from Carbonic Anhydride. By M. BOUSSINGAULT (Ann. Chi?,(. Phys. [S] viii 433-443).-In a bottle of 10 litres' capacity contain- ing air deprived of carbonic anhydride and a layer of silicious sand which had been washed ignited and then moistened with boiled dis- tilled water two grains of maize weighing together 0.846 gram were sown. Two other grains from the same source were analysed and from the results the composition of the two which were sown was calculated. After 45 clear days the two which were sown had deve- loped into plants the stalks of which were 24 centimeters high and each had three well-formed leaves and a fourth just forming.At this stage this portion of the experiment was stopped. Of the grains. nothing but the empty skins remained the starch albumin and fat which had filled the cells had been modified or burnt by a sort of respiratory combustion and on one of the products viz. carbonic anhy- dride the leaves provided with chlorophyll had acted in order to re-instate the carbon in the body of the organism which they create with the assistance of light. This clearly establishes the chemical composition of the harvest with regard to the cornposition of the seeds. The plants which weighed 0.6894 gram when dried were ana- lysed; ihe results are compared with the composition of the dried grains thus :-Carbon.Hydrogen. Oxygen. Nitrogen. Ash. Brains.. .. 0.7428 0.3303 0.04'73 0.3404 09114 0.0134 Plants ,.,. -0.3046 ---0.0114 0.0138 0.6894 0.0487 0.3109 --u__-Differences -0.0534 -0.025'7 + 0.0014 0'0295 -0'0000 + 0*0004 During the vegetation there was therefore a,loss of matter ; the loss in carbon must have remained as carbonic anhydride in the bottle. The experiment clearly demonstrates that a seed placed in a sterile soil surmounted by a sterile atmosphere develops at first in germi-nating a fertile that is to say a carboniferous atmosphere in the midst of which the leaves by the aid of light produce chlorophyll and nfter-wards amylaceous and saccharine substances. It has been established VEGETABLE PHYSIOLOGY AND AGRICULTURE.225 by the observations of eminent physiologists that leaves containing granules of chlorophyll when exposed to light in presence of carbonic! anhydride and water give rise to the formation of starch sugar and similar bodies at the same time evolving oxygen. The presence or absence of green protoplasma establishes therefore two orders of cellules ; those which introduce matter into the organism and those which do not but in which t.he principles formed by the action of the chlorophyll and light as well as the albumino’ids undergo great modification whether by oxidation or by the intervention of diastatic ferments. The changes effected in the vegetable cells which are without chlorophyll may even occur in the epidermic cells and in the fluids of the animal kingdom.These substances apparently proceed from the principles formed in the leaf and in a cellule without chlorophyll ; in an animal cellule saccharose may become invert sugar starch a fatty body &c.; but these cellules cannot create either of those substances creation being understood to mean the faculty of introducing into the economy things which vegetate or which breathe inert elements taken from the air water or earth. This principle has been announced by 31. Dumas and the author thus “Animals do not create ; they simply transform the principles elaborated by plants.” The inferior order of plants which do exist without chlorophyll or light do not possess the power of dissociating carbonic anhydride ; they draw their carbon from other more highly-organised bodies ; either living or dead which had been thus highly organised by the action of chlorophyll and light.C. H. P. Analysis of the Ash of the Ground Pea (Arachis Hypogaea) as cultivated in Virginia. By W I L L I A 31 S.B 1%ow N (C’hem.Neios xxxiv 147-149).-1ii lOU parts of pure ash excluding ferric oxide which the author6 believe to be an accidental impurity there were found :-Root. Stem. Leaves. Hmk. Seed. K,O .......... 23.043 25.902 15.880 37.395 37.134 Na2O ........ 18.816 3.063 2.897 3.763 3.342 CaO ........ 28.180 43.440 53.71‘2 20.145 3.749 xgo ........ 8.706 13-296 4.844 13.506 14.262 P,Os ........ 3.684 1.590 4.679 5.0ti2 29.102 s03 .......... 13.015 10.613 15-235 17.749 11.742 c1 ..........1.162 1.501 2.533 0.486 0.346 Si02 ........ 3.705 0.933 0.791 2.003 0.401 100.261 100.338 100.571 100.109 100.078 Deduct 0 equi-valent to Cl.. 0.261 0.338 0-571 0,109 0.078 ---~--100~000 L00*000 100~000 100~000 100*000 In t.he dried plant the ash is as follows:-Root,. Stem. Leaves. Husk. Seed. 11.830 13.298 i-747 2.586 1.818 Oil = 47.34 per cent. Nitrogen = 3.415 per cent. W. R. ABSTRACTS OF CHEMICAL PAPERS. Comparstive Analysis of Roots of Vines. By M. BOUTIN (C'ompt. Tend. lxxxiii 735-740) .-The author finds that in American vines which have resisted the attacks of the phylloxera a resinous principle exists in the roots especially in their bark and that it is present in about double the proportion in which it occurs in the French vines.He believes that the resisting power of the American vines is due to this resinous body. The puncture made by the insect is cica- trized by the exudation of the resinous matter when this is present in sufficient quantity and the escape of the nutritive juices of the plant is thus prevented. The nodosities which the insect causes do in fact disappear after a time and a root-fibre is sent out from the spot where the bark h%sbeen wounded. R. R. Alcoholic Fermentation. By A. FITZ(Deut. Chem. Qes. Ber. ix 1352-1355) .-Pure 4Jucor mcemosus grows in a solution of milk-sugar wit'hout producing fermentation or inverting the sugar ; but on in- verting it by an acid the fungus acts as ferment. Mucor racenzosm does also not produce fermentation in a solution of inulin but readily ill levulose prepared from it.When JIuco~r/xce?nosu.sis added to must of different percentage of glucose fermentation easily sets in at 25-30' but ceases as soon as 2.5 per cent. of alcohol is formed while the action of Jfucor nauceclo ceases when the liquid contains 0.5 per cent. c. s. Fermentation of Glycerin. By A. FITZ(Deut. Chem Ges. Ber. ix. 134s-1352) .-Redtenbacher found that when a mixture of glycerin water and yeast ferments it yields acetic and propionic acids and Berthelot obtained alcohol by fermenting a solution of glycerin with chalk and casein. The author obtained quite different results by using a mixture of 2000 water 100 glycerin 1potassium phosphate 0.5 magnesium sul- phate 2 German pepsin and 20 chalk to which was added a t'race of a schizomyceta which will be described in a future communication. At a temperature of 40" the liquid soon begins to ferment carbon dioxide and hydrogen being given off and the fermentation is finished in ten days. The solution then contains .nornatcZ b?LtyZ nlcohd and 1~0rnzaZ butyric acid besides a little ethyl alcohol and a bigher acid probably caproic. 100 parts of glycerin yielded 7.7 pure butyl alcohol and 12.3 anhydrous calcium butyrate. c. s.

ISSN:0368-1769    

DOI:10.1039/JS8773100222

出版商:RSC    

年代:1877

数据来源: RSC

摘要:

226 ABSTRACTS OF CHEMICAL PAPERS. An a 1yti c a1 C h em i str y. Several Me€hods of Chemical Analysis. By H. PELLET (BUZZ. Soc. Cl~inz.[el xxii 246-261).-1st. Estimation oj' Chloriwe imprese,Lce qf Phoqhoric Acid by Silver Nitrate and Potassium CYluomate.-The liquid in which chlorine is to be estimated is rendered neritral with calcium carbonate after acidifiuation with nitric acid. The determination is ANALYTICAL CHEMISTRY. then conducted as usual potassium chromate being used as indicator. Organic substances such as sugar need not be removed. A correction must be made owing to the solubility of silver chromate by adding a few drops of potassium chromate to a quantity of distilled water equal in volume to that in which the silver has been estimated and adding silver nitrate till a reddish colour is produced.2nd. Esti?nntiorL of Ammonia in Salts of Ammonium-10 grams. of the ammonium salt are weighed out and dissolved in 30 or 40 C.C. of water. After solution a few decigrams of pure calcium carbonate are added. The liquid is made up to 100 C.C. and filtered. Tlie standard soda is prepared so that 50 C.C. correspond to 0.3 gram of nitrogen and to 30 C.C.of dilute sulphuric acid also representing 0.3 gram of nitrogen. The soda is added in excess and the solution is boiled till all ammonia is expelled. The excess of soda is then estimated with the stardard acid. 3rd. EstiTiaation of Lend Barium aml Bismuth with Potassium Dichro-?nate.-The author’s process differs from that of Mohr by the addition of an excess of bichrome and by the estimation of the unreduced por- tion with salts of iron and potassium permanganate.He uses this method to avoid the removal of drops for the purpose of ascertaining the end of the reaction and also because the usual test for excess of bichrome with silver nitrate does not give trustworthy results for barium chromate reacts on silver nitrate when they are left long in contact. 4th. Estimation of soluble Sulphates with Standard Solutions.-The sulphuric acid is precipitated with excess of barium chloride ; the excess of barium chloride is precipitated with excess of potas-sium dichromate; and finally the excess of the latter salt is de-termined by addition of excess of a ferrous salt and titration with permanganate.The precautions to be observed are the solutions must be neutral ; if they are acid calcium carbonate is used to neu-tralise t’hem. If calcium sulphate is present in solution the calcium is precipitated as oxalate and the excess of oxalic acid thrown down with calcium carbonate. If nitric acid is present its quantity is esti-mated with a ferrous salt and permanganate and deducted from the final amount of permanganata required. If the liquid contains phos- phoric acid a few drops of calciuni chloride are added after neutralisa- tion with calcium carbonate. 5th. Estimatiom of the total Nitrogen in iWanwes Soils and various products oj’ Sugar Works.-The essential characteris tic of the process is to mix the organic substance if necessary with an excess of starch or sugar in order to reduce the nitrogen existing as nitric acid or as nitro-compounds to nitrogen when the analysis is made by combus-tion with soda-lime.The author got good results in analgsing nitro- stearic acid by this process. 6th. Applicrdiorb of Pelouze’s Process to the estimation of small quantities of iZTitric Acid-Four white glass flasks each capable of containing about 250 c.c. are taken. Introduce into No. 130 C.C.of hydrochloric acid into Nos. 2 3 and 4 30 C.C. of hydrochloric acid + 1C.C. of a solution of ammonio-ferrous sulphate contairiing 2 grams per litre and 50 C.C.of hydrochloric acid. Boil all four. Nos. %,3,and 4 are slightly colourecl ABSTRACTS OF CHEMICAL PAPERS. owing to oxidationof the iron salt.No. 2 is approximately decolorised by adding a few drops of a solution of stannous chloride containing about 1gram per litre and 50 C.C. of hydrochloric acid (to be kept under a layer of olive oil). The same volume is added to Nos. 3 and 4 2 C.C. of a solution of potassium nitrate 0.001 gram = 1.000534 gram of nitric acid are added to No. 3 and to No. 4,1,5 or 16 C.C.of the liquid to be tested. The four flasks are kept boiling for about a quarter of an hour. The volume of the liquid ought not to exceed a few cubic centimeters. An excess of hydrochloric acid is disadvan- tageous. To the first flask 100 C.C. of distilled water are added and potassium permanganate (0.1 gram per litre) is added till the liquid acquires a rose colour. This amount has to be subtracted from that added to the other flasks.The second third and fourth flasks are also diluted with 100 C.C. of water and permanganate is added t'ill a coloration is apparent. By comparison between the third and fourth the amount of nitric acid is calculated. This method gives vcrg accu-rate results provided no substances oxidisable by nitric acid are present. W. R. On the use of Platinum in the Ultimate Analysis of Carbon Compounds. By F. KOPFER(Deut. Chem. Ges. Bey. jx 13i7-1385).-This method has been described by the author on page 660 of' the last volume. He has now simplified it but the paper can be under- stood only by the help of drawings. c. s. Estimation of Nitrogen Tetroxide in Organic Substances. Chemical Composition of various Gun-cottons &c.-By P.and H. PELLET CHAMPION (Compt. Ted. lxxxiii 707). Organic substances which contain nitrogen tetroxide are completely reduced under certain conditions by ferrous salts. When the substance to be examined is not carried off by the vapour of water the apparatus described by F. Jean (BUZZ. SOC.Chitlz. 1876 ii 10) may be employed. A flask of 250 C.C. capacity is fitted with a caoutchouc stopper through which pass two tubes one leading to a pneumatic trough the other a funnel-tiibe drawn to a point is provided with a tap. The portion of this tube between the tap and the point is filled with distilled water. About 0.5 gram of the sub-stance is introduced into the flask with about 50 C.C. of water and a few grams of iron-ammonia-alum ; the flask is closed and the contents boiled until all the air is removed.The point of the delivery-tube is placed under a graduated bell-jar and the funnel filled with a mix-ture of sulphuric and hydrochloric acids which is allowed to flow slowly into the flask. The sulphuric acid is simply to assist in the decomposition of the nitro-body. When about 50 C.C. of the mixed acids have been introduced the tap is closed and the boiling continued PO long as gas is evoIved. Subsequently the volume of the gas is read off,and the nitrogen calculated from the formula for the decomposition of nitrates. For substances such as nitroglycerin which are volatile in the vapour of water the following method is adopted. The strength of a solution of potassium permanganate is determined AKALYTlCAL CHEMISTRY.by means of ferrous sulphate which has been heated to boiling and decolorised by stannous chloride after acidification with hydr.ochloric acid. A measured bulk of the iron solution is then placed in a flask decolorised as before and cooled in a current of carbonic anhydride or after covering its surface with some petroleum oil. About 0.5 grani of the substance is then introduced and the flask heated on a water- bath. When the substance is completely decomposed the liquid is heated to boiling to remove nitric oxide and titrated with the per-manganate. Abel's compressed gun-cotton Russian collodion and gun-cotton prepared by the authors were all found to have a composition corre- sponding with the pentn-nitrocellulose of Peloaze and not the tri- nitrocellulose of Abel.A sample of gun-paper contained only two equivalents of nitrogen tetroxicle. C. H. P. General Method of Analysis of Vegetable Tissues. By E. FRE MY (Con@. red. lxxxiii ll:36).-Up to the prescnt Lime but little interest has been taken in the chemical study of vegetable tissues and no general method such as is used in mineral analysis has been applied to their separation and estimation. The following bodies have been distinguished in the principal tissues of vegetables celZuZose bodies (cellulose paracellulose meta-cellulose) uasculose cutose yectme calcium peetate ?iitrogenous suh-stances and various mineral compounds. Cellulose Bodies.-In this class are included those bodies which dis-solve without coloration in bihydrated sulphuric acid ( SOAH,+ H,O), producing dextrin and sugar which are not sensibly altered by alka- line solutions and resist for a long time the action of strong oxi- disers.The author has dist'ingnished by means of the ammonio-cupric reagent three varieties of cellulose. (I.) CeUulose which dissolves immediately in the cupric reagent and forms a large part of cotton and of the utricular tissue of certain fruits. (2.) ParacelZuZose which does not dissolve in the cuprio reagent until alfter the action of acids ; it forms the utricular tissue of certain roots and the epidermis of leaves. (3.) Zetacellulose (fungin) .-Insoluble in the cupric reagent even after the action of acids ; it is found chiefly in agarics and lichens.In the analysis of vegetable tissue the first variety of cellulose is determined directly by means of the cupric reagent ; the second in the same after being submitted to the action of acids and the third is dissolved in bihydrated sulphuric acid. When it is not required to distinguish these three bodies the whole may be dissolved in the sul- phuric acid. VascuZose.-This substance constitutes the larger part of the ducts and spiral vessels ; it generally accompanies cellulose in vegetables but dsers completely from it in composition and properties. It con-tains more carbon and less hydrogen than cellulose ; and it is vasculose which cements the fibres and cells together. It may be said to form the heavy part of woody tissue ; it abounds ABSTRACTS OF CHEMICAL PAPERS.in hard wood and in the stony concretions of pears; the shells of nuts and the stones of apricots contain more than half their weight of vasculose. Vasculose is insoluble in sulphuric acid and in the ammonio-cupric reagent also in alkalis under ordinary circumstances but when heated with alkalis under pressure it dissolves easily ; it also dissolves in oxidising agents. Vasculose can be separated from cellulose by sulphuric acid or by the cupric reagent; but if it is intended to weigh the cellulose the vasculose must be dissolved in dilute nitric acid. Cutose constitutes the fine transparent membrane which covers the exposed parts of vegetables. Cutose is insoluble in sulphuric acid but dissolves in dilute soh- tions of the carbonates of potassium and sodium ; with nitric acid it produces suberic acid.It is separated from cellulose by the cupric reagent and from vasculose by potash at the ordinary pressure. Pectose is insoluble in water but is rendered soluble and transformed into pectin by dilute acids. It occurs in the utricular tissues of fruits and roots and is estimated by heating with dilute hydrochloric acid dissolving in water and precipitating with alcohol. CuZciutra pectnte forms part of the membrane which binds the cells together. It is estimated by treatment with dilute hydrochloric acid which liberates pectic acid in the insoiuble state ; this is dissolved in potash and reprecipitated by an acid.The nitrogenous bodies and the haorganic constituents are determined in the usual way. The following is a summary of the method of analysis. Cold dilute hydrochloric acid decomposes the calcium pectate setting free the pectic acid which is weighed as alkaline pectate. Boiling dilute hydrochloric acid chauges the pectose into pectin which is precipitated with alcohol. The ammonio-cupric reagent dissolves the cellulose. Hot hydro- chloric acid renders paracellulose soluble in the cupric reagent. Sulphuric acid (bihydrated) dissolves the cellulose bodies. Hot dilute potash dissolves the cutose. Potash under pressure dissolves vasculose. Dilute nitric acid renders vasculose soluble in alkaline solutions. c. w. w. Proximate Composition QfCoal-gas.By W. D ITTMAB (Cl~e~z. Neu;s xxxiv 145).-In a late memoir “ Sur le Gas d’Eclairage,” pub- lished by Bert’helot and abstracted in this Joarnal (1876 ii 183) he gave an analysis of the coal-gas of Paris showing it to contain 3 to 3.5 per cent. of benzene 0.1 of acetylene 0.1 to 0.2 of ethene and 0.02 of propene and other hydrocarbons the remainder consisting of diluent non-luminous gases. Unless the Paris gas has an exceptional constitution this analysis throws discredit on all former analysts. Berthelot in fact accuses them of manipulating the figures they ob- tained in eudiometric determinations so as to fit the hypothesis that the real illuminating principle of gas is ethene. The author disproves this accnsation by adducing an analysis of gas by Bunsen and shows ANALYTICAL CHEMISTRY.231 that what he states to be ethene could not have contained more than 17 per cent. of benzene. The author made a series of experiments on Glasgow coal-gas with the view of ascertaining how far his analyses would tally wi%h those of the Paris gas of Berthelot. The gas was passed first through a long column of nitric acid of 1.5 specific gravity and its illuminating power compared with that of the original gas. The gas was feebly luminous hence it was inferred that oletines were not absent in an exceptional degree. To reassure himself on this point the author prepared mixtures of ethene with hydrogen and on testing their illuminating powers he found that a mixture of 3 volumes of hydrogen to 1volume of ethene was sufficient to reduce its luminosity to that of marsh-gas and a 10 per cent.ethene flame gave no more light than that of a Bnnsen lamp ; but a 3 per cent. benzene flame was sufficiently lumi- nous. This argues in favour of Berthelot's theory. Yet considering the process of purification to which coal-gas is subjected very little benzene. can remain in the gas for a 6 per cent. mixture of benzene vapour with hydrogen after being shaken with water was found to have the proportion of benzene reduced to 2. The author failed in his attempts to separate benzene from olefines. Nitric acid of 1.4 or 1.5 sp. gr. is not the proper means of separation for it acts on ethene as well as on benzene. Non-vulcanised india- rubber gave the best result.A trial was accordingly made to separate these hydrocarbons from each other by its use ; the gas after being dried over calcium chloride was passed over a coil of sheet india- rubber and condensed in bromine. The resulting bromide boiled below the boiling point of propene bromide (142'). The percentage of bromine was 83.52 hence assuming the formula of the bromide as ClrH2.Brz,the result is :-With alcoholic potash more than half the bromine was removed showing that it did not consist of monobromobenzene but of bromides of the olefines. The author therefore disputes the accuracy of Berthe- lot's statement. w. R. Detection of Alum in Bread and Flour. By J. A. WANKLYF (A?mLyst 1876 14).-9s flour contains gluten-a substance con-taining about 1 per cent.of sulphur-snlphuric acid always appears in the ash of flour and bread. Sulphuric acid added in the form of alum may probably he found in the cold aqueous extract of the flour ; before determining the amount of sulphuric acid the soluble gluten must be coagulated and removed. M. M. P. M. Estimation of Colour in Water. By C. A.. CAMERON (Chem. News xxxiv 77).-Although it has been proposed to use solutions of caramel instead of standard solutions of ammonia for the purpose of comparison in " Nesslerising " water the author does not recommend the use of'the former solution as even when it contains much alcohol it becomes turbid and useless after a time and soon changes its hue. ABSTRACTS OF CHEMICAL PAPERS. To those who prefer caramel soliitions the use of coloured discs of the following description would be more favourable.Fill a Nessler tube with distilled water and place it over a disc so coloured that on look- ing down through the column of water it may by the reflected light from the disc have the colour of a solution of say 0.005 gr. of ammonia per gallon of water mixed with the usual 4 per cent. of Nessler's solution. A dozen discs would be sufficient but in using them the Nessler's soliition should be always of exactly the same corn- position. 11. B. Anthracene Testing. By J. T. B K oWN (Chem. News,xxxiv 136). -In applying the anthraquinone test to commercial samples of anthra- cene various minor difficulties occw one of which is that damp samples are apt to lose moisture during the time occupied in reducing them to a sufficient degree of fineness to allow the small quantity of I gram to be a correct sample of the bulk while another and more serious difficulty is the uncertainty caused by the occasional occurrence of accidental impurities in the quantity weighed out.To obviate these difficulties the author proposes the following modification of the test :-50 grams of the crude anthracene are weighed out and 250 C.C. of petroleum spirit measured out; the anthracene is triturated in a mortar with a sufficient quantity of the spirit to form a thin cream which is poured into a weighed filter (retaining any grit or sand) and washed with the remainder of the spirit. The residue having been drained the filter is carefully folded pressed between bibulous paper dried at about 60-80" and weighed.The contents of the filter are crushed to a fine powder one gram of which is weighed out and treated by the ordinary anthraquinone test. D. B. Note by the Abstractor.-The above-mentioned modification is of but little importance with regard to the commercial mode of testing anthracene as the temperature at which trituration takes place and the density of the spirit used materially influence the results obtained besides which petroleum spirit does not remove hydrocarbons of a boiling point approaching near that of anthracene. D. I3. An Abnormal Sample of New Milk. By J. PATTINSOX (Analyst 1876 47-50).-The milk was obtained from a roan cow pronounced to be in good health; no salt was given as such in the food the farm was situated not far from the sea.The following are the results :-Milk from roan Milk from white Arerage milk from cow. cow iiew roan. 8 cows in stable. Water ............ 9rj.15 86.80 87.54 Fat. ............. 3.00 5-71 3.53 Casein ............ 2.00 3-05> 3*9i}9.4y 3.15 8.93 Milk sugar. ....... 3*90} = 6.85 4.65 Ash .............. 0.95 0.87 0.73 100.00 100.00 100~00 Chlorine in ash. ... 0.27 0.14 0-13 Equal to sodium chloride ........ 0.44 0.23 0.21 M. M. P. 11. ANALYTICAL CHEMISTRY. 233 Analysis of Butter. By J. MUTER(Analyst 1876 7-14).-Pure butter always contains a notable amount of fatty acids other than palmitic olecic and their congeners.The author's process is as follows:-(1.) Water is estimated by drying 100 grams over a low gas-flame at 110" till effervescence ceases and the curd and salt sink to the bottom leaving the butter-fat perfectly clear. (2.) The melted fat is poured off into a beaker the residue decanted on to a weighed filter washed with petroleum-spirit dpied and weighed as curd and ash. (3.) The filter is ignited the ash is reported as salt. (4.) The fat poured off in (2) is filtered-if not perfectly clear-and brought into a specific gravity bottle fitted with a thermometer stopper the bottle is placed in water maintained at 39.5" (103" F.) the fat being itself at 35" (95' F.) when it is transferred to the bottle the water surrounding the battle is allowed to cool until it reaches 37.7" (looo F.) when the bottle is withdrawn from the hot water dried and weighed.This experiment is repeated three times. The quantity of water at 37.7" (100" F.) which the bottle contains has been already determined. The specific gravity of the fat at 3'7.7"is then obtained referred to waler at the same temperature. (5.) About 10 grams of the fat at 37.7" are weighed into a clean dry 800-900 cb.c. flask ; 0.3 gram caustic potash and 60 cb.c. rectified spirit are added. The flask is placed in boiling water and maintained at this temperature until no turbidity ensues when water is added. 500 or 600 cb.c. of water is added and heating continued until the whole of the alcohol is evaporated. The contents of the flask are made up to about 400 cb.c.with nearly boiling water; a cork carrying a tube 2 feet long is placed in the mouth of the flask ; and 5 grams of strong sulphuric acid is poured down the tube followed by a little Tvater. The flask is agitated with a circular motion until the fatty acids rise as a clear stratum which by cooling to 3" or 4O solidifies to a cake. The cork is removed a piece of cambric is fastened over the niouth of the flask and the liquid is decanted (without breaking the cake) into a litre flask. After washing with a little cold water 300-400 cb.c. of warm water are added the cork of the tube is inserted and the whole is heated to about 75" the contents being agitated until the fat forms an emulsion with the water ; the contents are then cooled the water decanted through cambric and this process is repeated until the washings are perfectly free from acid.The flask is now dried until the fats are fused when they are poured into a platinum basin and weighed. Any fat adhering to the flask is dis- solved in a little ether which is evaporated in a small weighedbeaker; the cambric is also if necessary exhausted with ether. The filtrate is made up to 1litre ; the total free acid is estimated in a portion by stan-dard soda and calculated as HzSOs; 100 cb.c. are precipitated by barium chloride and from this total H,SO is calculated. Another portion is evaporated to dryness ; the residue is heated in a covered pla- tinnm dish till fumes cease ; a fragment of ammonium carbonate is added ; and the whole again heated.The K2S0,so found is calculated to H2S04,which is noted as combined sulphuric acid. From these data the free sulphuric is obtained which deducted from total free acidity gives free acid other than sulphuric in solution this is calcu-lated to butyric acid. ABSTRACTS OF CHEMlCAL PAPERS. The author adopts 88 per cent. of fattyinsoluble acids as a standard for calculation if associated with at least 6.3 per cent. of soluble acids. but would not consider a butter adulterated if it showed less than 89.5 per cent. insoluble and 5 per cent. soluble fatty acids. There is an invariable relationship existing between specific gravity at 100" F. and of most of acids. M. M. P. M. Detection of Colouring Matters in Wine. By A. DUPRI? (AnnZyst 3 876 26) .-This paper describes a method €or detecting the presence of the colouring-matters of logwood brazil-wood and cochi- neal in wine.These substances dialyse ; the colouring-matter of pure red wines does not. (Certain artificial colouring-matters-rhatany- root for instance-do not dialyse.) If the dialysake obtained from a red wine is yellow or brownish-yellow it is to be examined chemically and optically. Logwood and Brazil-wood alter SO much with age that the only safe method is to keep a tincture of known age for comparison. The ammoniacal solution of cochineal colouring-matter yields these well -marked absorption-bands. M. M. P. M. Detection of Fuchsine in Wine. By E. BOUILHON (COW@. rend. Ixxxiii 858-859) .-Instead of using potash or ammonia the author employs baryta to liberate the rosaniline of the fuchs' ,me some-times used in fraudulent coloration of wines.500 cb.c. are evapo- rated in a basin to about 125 cb.c. the Beat is removed and 20 grams of barium hydrate are added. The mixture is shaken allowed to cool and filtered and the filtrate is made up to 125 cb.c. with distilled ivater. A few crystals of baryta must now be added to make sure that all the colouring-matter of the wine is precipithted. It is then shaken with 50 or 60 cb.c. of ether ; the layer of ether is decanted into a basin ; one drop of acetic acid of 8",and three or four drops of water are added ; and a small piece of white silk. If an appreciable amount of fuchsine is present the silk assumes a pink colour immediately; if not the ether must be allowed to evaporate ; the few drops of water remaining are evaporated nearly to dryness; and the silk is again dipped in the liquid. This process allows the detection of one hun- dred millionth part of fushsine in wine. W. R.

ISSN:0368-1769    

DOI:10.1039/JS8773100226

出版商:RSC    

年代:1877

数据来源: RSC