摘要:

I r is well known that when glyccrin subjccted to tlie ordinary atmo- bplieric prcssure is heatcd so inucli as to cause eballition it is more or less rapidly ciccouiposed ; and t h t almost the whole of the glyceriil opcmtcd on may be clecoinposecl by repeated distillation. This decom- position may Iione\-cr bc entirely prevented by a reduction of the prcssnre in tlie apparatus cmplopcd to 12-50 mm. T'he boiling-point of glycerin was determined by effecting the dis- tillation in a long-necked flask having a supplementwy neck athclied :Lt right angles to tlie principal one. In the principal neck the thermo- meter was fixed by tlie aid of a caoutchouc cork while the smaller neck was connected in a siiniliir manner with a two-necked receirer. The glycerin togetlier wit11 3 fe:v fragments of tobacco-pipe (this latter being required to prevent the bumping mliich 17-ould otherwise occur) being placed in tlie retort-flask tlic receivcr was connected with a Sprengel's mercurial pnmp and a manometer tlie caoutchouc joints beiiig made air-tight mitli glycerin in the usual way.Unless the glyccrin dibtilled liad been dehycliated by prerious distillation ;,I a. vncunni the first portion of the distillate consisted principally of water ; :tftcrwards wlieii the glycerin in a pure state came over the tempera- ture indicated by the thermometer was 179.5" C. At this time the pressure on tlie liqiiid was 12 5 mm. a pressure nearly corresponding to tlie tension of aqncons val'our at the temperature of the receiver. A cleteimination of the cu~bcn and hydrogen in the glycerh distilled :LS above mas made tlie oxidant emploj-ed being copper oxide followed by 0xJ-g"" gas. Bound. T1iex-y. - I. -4281 grm. substaiice gam %lOi! grm. COz and .3-139 grni. H20. I. 38.9 - 8.9 O3 48 C3 36 11,. . 8 39.1 6.7 52.2 - - 100.0 92 Under a prcsmre of 50 nim. glycerin distils without change a t about 210" C. Glycerin dehydrated by distillation absorbs water from the atmo- byhere to the extent of about 50 per cent. of its weight. The amount absorbed is as might be expected rery variable.

ISSN:0368-1769    

DOI:10.1039/JS8712400084

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

85 By EDWARD M.D. DIVERS THE Handbooks give us no information on this subject. PQligotis I believe the only chemist who has written anything about it. In his well-known memoir on Hyponitric and Nitrous Acids,” he states that he tried to prepare nitrous anhydride by distilling silver nitrite and that he obtained instead nitrosonitric anhydride the nitrite being con- vertedinto nitrate bythe first portions of the anhydride disengaged by the heat. Having need for the purposes of another investigation to be familiar with the action of heat on this salt I examined it with the results now to be described. The products of this action consist principally of silver nitrate reguline silver and oxides of nitrogen. But the relative proportions of the quantities of these substances to each other and as a conse-quence of this the composition also of the gaseous matter vary con- siderably in different experiments.When silver nitrite is heated in a crucible or watch-glass over a lamp its decomposition becomes first evident by its turning grey where in contact with the hot crucible and by its giving off red fumes. The mass very soon enters into a state of semi-fusion and intumescence and then becomes solid again and of a whitish-grey in some parts and greenish-yellow in others red fumes still being produced but much less copiously than during the intumescence. Lastly on continuing the heat the yellow portions of the mass slowly change to grey like the rest with formation of a small quantity more of red fumes.Pro-longation of the heat beyond this point causes the glass or porcelain to be attacked; but as the entire greying of the mass has been found to be a sign that nothing or almost nothing remains but silver nitrate and free silver it is here unnecessary to pursue beyond this point the changes which take place. As there is found to be a material difference in the loss of weight sustained in different experiments it might naturally be supposed at first that this is due to a decomposition of the silver nitrate formed; but that it is not so is shown firstly by the fact that longer heating at about the same temperature causes very little more loss ; secondly that the temperature does not appear to be so high as that required for the free decomposition of silver nitrate ; and thirdly that the loss sus-tained bears no direct relation to the degree of heat employed.* Sur l’acide hypoazotique et mr l’acide azoteur. bn.de Chimie et de Phys. [S] vol. ii (18411),p. 58. VOL. XXIV. I DIVERS ON THE ACTION OF HEAT When the nitrite in an open dish is heated in an oven at any tem- perature between about 85" on the one side and 140"C. on the other it loses its sensible characters almost imperceptibly becoming whitish- grey and non-crystalline without fusion or any apparent change in bulk. The change which takes place in the nitrite when it is heated in an open vessel in either of the above ways does not generally differ very much in its results from that represented. by the equation- as the following experiments show :-I.1.005 grm. was moderately heated over the lamp in a crucible so as to effect rapid decomposition. When this seemed complete the lamp was removed. During the heating a little metallic fume escaped along with the oxides of nitrogen. The lid of the crucible was raised once or twice during the heating and again afterwards and the red fumes allowed to disperse. The contents of the crucible were washed with water and the residue dried weighed and proved to be reguline silver by its losing only three-tenths of a milligramme on ignition. Before washing out the residue weighed -849grm. and after washing out and ignition ,426 grm. By deducting the reguline silver obtained from the total silver in the original salt the soluble matter was shown to have contained a little unchanged nitrite.The ratio of the reguline silver to the volatile matter is nearly that of Agz N203. 11. 1.219 grm. of the nitrite was heated in an open match-glass over the lamp till all the yellow portions of the mass had just become grey. The mass was weighed washed out with water dried and weighed again. It was then ignited and found to have lost only half a milligramme by the operation. There was material loss by the con- siderable spirting and throwing off of metallic fume which occurred during the intumescence and therefore the silver in the matter after- wards dissolved out by water was determined as chloride. The soluble matter contained a very little nitrite as wa's shown by its action on potassium permanganate imperfectly estimated by this reagent to be about .01 grm.Before washing out the residue weighed 1.012 grm. and after washing out and ignition *528 grm. The matter dissolved out by water gave -408 grm. silver chloride = -307 grm. silver. Deducting %he total silver found in the residue after the application of heat from that in the nitrite used the amount of loss by spirting &c. was determined and found =; -027 grm. nitrite. In calculating the percentage relations of the products of the decomposition thk quantity therefore of nitrite was deducted from the quantity taken for the ex- OX SILVER NITRITE. periment and dgo froin the loss caused by heat. The ratio of the reguline silver to the vdatile matter is nearly that of A@ :N20s.In another experimenb just Like the last the gross loss by heat was in the same proportion to the nitrite used as in the last experiment. This experiment was not pursued further. 111. -535 grm. of nitrite was heated in an oven for nearly forty hours at a temperature of about 98" and was found by repeated weighings to be losing weight during all this time. It mas then maintaiped for twelve hours longer at a temperature of 110"-125" an$ lost only *0002 grm. more. The loss by heat = -080 grm. What was left was washed out with water dried and reweighed. The residue was not ignited but other experiments to be described prove that it was metallic silver. It weighed -237 grm. The ratio of this residual silver to the loss sustained by heat is closely that of Ag2 :NzQ3.The silver nitrite employed far these experiments and the others recorded in this paper was carefully prepared and some of it ascer-tained to contain '70.06 per cent. silver estimated BS chloride. The theoretical quantity is '70.13 The percentage numbers for the preceding experiments and those for the equation to which they are referred are these :-Calc. I. 11. 111. Volatile .,. . . . 16.45 15.5 15.1 15.0 Reguline silver 46.75 42.4 4.3 442.2 Soluble .... . . 36.80 42.1 40.6 40.8 100.00 When instead of employing an open crucible or dish for heating the nitrite over the lamp a closely-covered one is used so that the gaseous and fixed products of decomposition may be kept for a time in contact the loss of weight experienced by the mass is less and the amount of nitrate formed is greater.The ultimate change effected in this way approaches though not closely to that expressed by the equation- 2NOzAg = NO + Ag + NOqAg. The following experiments a,re adduced in support of this stab ment :-I\-. -301 grm. was heated in a watch-glass covered by another. It gave *%O grm. gmes and ,261 grm. metallic silver the rest being soluble. The ratio of the metallic silver to the gaseous matter is about the mean of those of Ag :NO and Ag2 Nz03. V. a768 grm.was heated in the same way but not quite so fully m I2 DIVERS ON THE ACTION OF HEAT in the last experiment. It gave *077grm. gases and -265 grm. metallic silver the rest being soluble and found to contain some nitrite.The ratio of' the silver to the gaseous matter is nearly that of Ag :NO. VI. 1.022 grm. was heated till the watch-glass began to be acted on by the nitrate produced. The gases expelled = *118grm. and the metallic silver left = ~379grm. The ratio of the silver to the gaseous matter approaches that of Ag NO. VII. 1.218 grm. was heated in a covered watch-glass immediately after the heating of the same weight of nitrite in an open watch-glass in the experiment marked 11,over the same gas flame and at t,he same height from it ; so that this experiment and Experiment 11,are parallel ones and serve to show strikingly the effects of covering the nitrite during heating. The process was also carried just to the same point as regarded the appearance of the mass.The only difference was that the glass being covered less heat was lost by radiation and the change was therefore sooner completed. As in the other case the soluble matter contained a very little nitrite. The loss by heat in- cluding a little metallic fume = -151 grm. and the weight of the metallic silver = -468 grm. The ratio of the silver to the gaseous matter is nearlythe meanof Ag :NO and Agz N,O,. For the sake of comparison the percentage numbers of these experi- ments and those calculated for the equation to which they are referred are added- Calc. IV. v. VI. VII. Volatile .... .. . . 9.74 13.3 10.0 11.6 12.4 Reguline silver .. 35.06 41.5 34.6 37.1 38.4 Soluble ........ 55.19 45.2 55.4 51.3 49.2 100.00 The indication of these numbers is rendered more evidenh by corn-paring them with those of the first table.But more conclusive evidence can be brought forward that the effect of keeping the gases given off in contact with the undecomposed nitrite remaining is to cause nitric oxide alone to be lost. This has been obtained by so heating the nitrite in a vessel nearly closed as to decompose it only very gradually. VIII. ,4433 grm. of the nitrite was placed in a small tube and the empty portion of the tube filled up by a glass rod barely small enough to be pushed into it. After 12 hours a.t about go" it weighed -4431 grm. ; after 12 hours more at 95"-99" it weighed -4437 grm. ; after 12 hours more at 115"-135" ,446 grm. ; after 14 hours more at about 134",it weighed ,450" grm.; after again 14 hours mostly at 136" -453 grm. ; and after 14 hours more when the heating was discontinued -454Agrm. There was therefore instead of a loss a material gain in ON SILVER NITRITE. weight = *0111grm. Faintly reddish gas was first detected in the tube at 115". At 134"the crystals began to shrink and fuse together and this occurred first near the stopper of the tube and only very slowly proceeded backwards to the end of the tube. It would not therefore be right to conclude that silver nitrite fuses at this tempera- ture the fusion apparently taking place only in the nitrite after it had become mixed with nitrate. During the heating the mass scarcely altered in colour. The explanation of the gain iiz weight is of course evident.The nitrite decomposing and evolving nitric peroxide or at any rate a nitrogen oxide this becomes reduced to nitric oxide if not already such by oxidizing unchanged nitrite; the nitric oxide then serves as a carrier of atmospheric oxygen to the nitrite as it is known to do to other substances. The extent to which atmospheric oxygen was thus fixed in the preceding experiment is more fully shown by the examination which was made of the contents of the tube. These were treated with water and found to contain ,0216 grm. of metallic silver which therefore as nitrite had been in combination with ,0092 grm. gaseous matter. This loss being balanced against the oxygen absorbed its weight must evidently be added to the observed gain in weight to obtain the actual amount of oxygen absorbed by the rest of the nitrite.The total oxygen absorbed is therefore equal to .0203 grm. Of this about -017 grm. must have been derived from the air the rest coming from the decomposed nitrite thus :-NOzAg=Ag + NO + 0. I have calculated that not very much less than half the uit'rite was converted into nitrate in this experiment. This experiment is sufficient to establish that hot nitrite reduces the higher oxides of nitrogen to nitric oxide so that we have proof that the tendency under one set of circumstances is to convert nitrite into the ultimate products metallic silver nitric oxide and silver nitrate according to the equation already given. But it is quite clear that nitric oxide and the silver nitrate are secondary products of the action of heat.This can however be shown in another way to be undoubtedly the case as in the following experiments. JX 2.098 grms. were heated in a dish in an oven for 72 liours at a temperature of about 98" in a moist atmosphere obtained by keeping a dish of water in the oven. The loss in this experiment = -441grm. and the residual mass by washing out with water and re-ignition yielded 1.157 grm. of silver. The soluble matter contained a little nitrite. X. -794 grm. was heated for about 95 hours in an atmosphere of steam at a temperature rising from 98" to 140". The residue weighed *58@grm. This experiment was not pursned further. These two 90 DIVERS ON THE ACTION OF HEAT ON SILVER NITRITE experiments are sufficient to establish the fact that under a given set of conditions namely free exposure in a moist atmosphere silver nitrite tends to yield only metallic silver and nitrogen peroxide thus :-NOaAg =Ag +NOz as the percentage numbem of the above experiments and those for this equation will show when compared with those already given :-Calc.I. 11. Volatile .,,.. 29* 87 2114 27.0 I -Fixed .......... 70.13 100.00 The conclusion then from all these experiments is that like other silver salts the nitrite splits up under the influence of heat into metallic silver and the acid radical or its components and that silver nitrate nitric oxide and perhaps nitrous anhydride are formed only by secondary reactions. With regird to nitrous anhydride the experi- ments which have been here given to prove that the gases evolved are either nitrous anhydride or its equivalent furnish no proof that they actually include this body.On decomposing the nitrite by heat over the lamp until fusion and intumescence have just ceased the mass is of a greenish-yellow as I have already mentioned. If the mass be then washed with water it will be found that though much of this coloured matter consists of or contains nitrite the colour of the mass is partly due to a small quantity of bright-yellow matter that is left after thorough washing along with the silver. This matter is unaffected by light soluble in ammouia insoluble in water and decomposed by boiling in water. I have not examined it but its probable composition is I think indicated by some experiments of quite a different character from the present an account of which however I am obliged to reserve for another paper about to be published on an essentially different subject.The fusio2 which occurs in the mass of heated nitrite so soon as it has undergone some oxidation suggests that the nitrate formed com-bines with the nitrite to form a nitrite-nitrate or hyponitrate. The point at which this fusioii occurs is far below that at which silver nitrate fuses. In Experiment VIII the nitrate formed is calculated to have been in nearly the proportion of one atom to one atom of the andecomposed nitriltl,. I ti is therefore not impyoloable that a11 unstable nitrito-nitrate exiStF The President ir.quired in what way Dr.Divers had ascerbdined that the solid residue contained no argentic oxide ? GILL'S EXAMINATION $TO. Dr. Divers replied that the washed residue had the appearance of metallic silver and that after weighing it he had srtbjected it to strong ignition and then weighed it again; there was only a difference of a few tenths of a mgm. between the two weighings. Dr. Odling asked what the evidences were for assuming the exist- ence of a silver nitiito-nitrate ? The existence of such a compound would necessitate a modification of the views at present entertained on the constitution of salts. Dr. Divers said that his supposition rests on the circumstance that the nitrite began to fuse at about 134" after partial decomposition.Since the melting point of silver nitrate is much above that degree he attributes it to a compound of the nitrit,e and the nitrate having like some alloys a lower melting point than either of its components. But on the whole he considers the combination only a loose one. Dr. 0dling observed that the circumstance which Dr. D ivers had mentioned was only an instance of what occurred in some oibcr cases of mixture of two salts for it is well known that such mixturns fnse at some lower degree of temperature than either of the salts separately. Dr. Divers agreed with Dr. Odling that the evidence for the exist- ence of a nitrito-nitrate is but a slender one. In Experiment VIII however when complete fusion of the mass had taken place the pro- portion of the nitrate formed to that of the nitrite left undecomposed was that of one atom to one atom.He himself however found it hard to admit the existence of a silver hyponitrate silver being univalent. It stood differently with lead which is a bivalent metal. Dr. Armstrong remarked in support of the existence of the new salt that Prof. Wislicenus had in a recent publication stated some reasons for viewing silver as a bivalent elemen:. Dr. Mills asked what proof there was that the g. 3 evolved in some of the experiments really was nitrous acid and not a mk'ure of nitric oxide and oxygen? Dr. Di-Fers did not intend to insist upon the former view; he quite admitted the possibility of the gas being such a mixture or one of nitric oxide and nitric peroxide.

ISSN:0368-1769    

DOI:10.1039/JS8712400085

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

GILL'S EXAMI"ATION $TO. By C. HAUGHTON GILL. THOSE engaged in the examination of low sugars and molasses have frequently had to complain of obtaining quite unintelligible results. It GILL'S EXAMINATION OF GLUCOSE-is well known that the solution of the sugary body is decolorised and clarified by the addition of basic lead acetate before submitting it to optical examination-but I find that the power of invert sugar to rotate a ray of polarised light is so greatly altered by the presence of this reagent that the results obtained by the so-called polarisation of syrups containing much invert sugar are worthless when clarification has been effected in the ordinary way. The alteration of rotatory power of pure invert sugar by basic lead acetate is shown by the following experiments :-15 c.c.of a so'tution of invert sugar o~~~~~~~~$$e~~} read -28,25 at 240 c. made up to 60 C.C. by water tube of 20 c.m. 15 C.C. of the same solution with c I). water:and 2 C.C. of saturated solu- .. ) -24.7 at 24' C. tion of basic lead acetate to 50 C.C. 15 C.C. of the same solution with I. a. .I basic acetate solution alone to , + 57 at 25" C. 50 C.C. These results have been confirmed by many other observations. The alteration producing this reversal of rotatory power takes place only on the Zevulose of the liquid-the dextrose suffers no change of optical properties. A solution of pure dextrose prepared from invert sugar and reading 60.3 made up to 2 vols. by strong solution of basic 1read 30.5.lead acetate. A solution of nearly pure levulose prepared by Dubrunfant's method and reading -44 at 20"C. made up to 2 vols. by I , + 6 at 20' 0. solution of basic lead acetate. The maximum alteration of rotatory power caused in this way seems to be equal to that which would be caused by converting all the levu- lose into an equal weight of dextrose. This reaction also affords a means of detecting the levulose in presence of an excess of dextrose. The alteration of the rotatory power of levulose is not permanent. On removal of the lead or on acidifying the liquid the original rotatory power is restored. The alteration is not due to the alkalinity of the led solution as regards alkalinity alone for weak soda or ammonia produces no such change till it begins to decompose and destroy the sugar.It is probable that a soluble lead compound of levulose possessed of dextro-rotatory power is formed. Now when a sugar solution containing invert sugar is clarified by basic lead acetate the invert sugar loses in part or in whole its levoro-htory power and the first direct reading is too high. When the liquid * The readings of this instrument 2* x loo = angular degrees. CONTAINING SUGARS. is acidified and inverted by heat the original invert sugar has its true levorotatory power restored and added to that of the invert sugar proceeding from the cane-sugar thus producing a greater “difference” in the readings than that due to the cane-sugar alone and consequently leading to too high R result.The remedy for this difficulty is-to remove the lead and acidify the liquid before making the first reading. For this purpose I prefer to use a strong solution of sulphur dioxide which possesses the advantages of removing t’he lead and bleaching the liquid at the same time while it is incapable of inverting cane-sugar in the cold even in twenty-four hours. The decolorising effect is so great that even the worst treacles give liquids of a pale straw colour when thus treated and moreover (C * inversion ” can afterwards be performed wit’hout any fear of spoiling the colour ; whereas by the ordinary method the liquid frequently becomes too red to allow of optical examination. Another error also arises from the use of the lead-salt as a clarifier for those sugar solutions in which glucose is to be estimated by the use of Fehling’s copper solution.The presence of lead here leads to a result much to9 low since it also becomes partly reduced and thereby necessitates the use of a greater volume of the saccharine solution which is called on to reduce lead as well as the known amount of copper. Sulphur dioxide serves to remove the lead while excess of t>he reagent exerts no other action on the copper solution than that of facilitating the subsidence of the cuprous oxide. As illustrating the extent of the error which may be introduced by the presence of lead the following experiment selected from many others may be taken. Solutions of invert sugar of the sBme strength used in each case.Volume required to precipitate cuprous oxide from 10 C.C. of Fehling’s liquid. 1. Free from foreign bodies .,,...,,,.,. .. .,.. . . 10 C.C. 2. Containing 10 per cent. of its volume of solution of} 17 c,c. basic lead acetate. ......,.... ....,.... .... To utilize these observations the practica,l course of analysis of a low sugar or molasses becomes Weigh off double normal quantity ;dissolve treat with excess of basic acetate and make up to 100 C.C. ; filter ; measure off 50 C.C. of filtrate ; make up to 100 c.c. by solution of sulphuric dioxide ; and filter again. This solution will have the usual degree of concentration and can be proceeded with as if prepared in the ordinary manner from good sugm.

ISSN:0368-1769    

DOI:10.1039/JS8712400091

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS. ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. Physical Chemistrg. Researches 0th the Spec$c Heck Demitits am1 Expamions of some Liquids. By C. MARIGNAC.* PARTI.-SPECIFICHEATS.The specific heat of aqueous solutions is estimated as follows. A large sized mercurial thermometer with a spirally coiled tube for a reservoir is heated in an oven to a few degrees above the point required. On being taken out it is brought near to the calorimeter in which it is immersed the instant the mercury in the stem has fallen to the desired point. The calorimeter contains the liquid the specific heat of whish is to be estimated and the quantity of liquid employed is regulated so that the intro-duction of the heated thermometer produces in every experiment sensibly the same elevation of temperature.Under like atmospheric conditions all exterior disturbing causes thus influence the temperature of the calorimeter to the same extent in every experiment and have no influence on the result. All corrections may therefore be dispensed with. To ensure these like conditions the experiments performed on each solution are made to alternate with the parallel experiments on water and are thus strictly comparable with these latter. The quan- tities of liquids used am inversely proportional to their specific heats. For saline solutions a silvered brass calorimeter is employed; for strongly acid liquids a thin glass vessel is substituted. The specific heat of more volatile liquids is estimated by enclosing them in a thin glass bulb containiiig a small bEt sensitive thermometer and employing this bulb instead of the large mercurial thermometer as the source of heat In these cases the calorimeter of course always contains the same amount of water and the quantity of liquid nsed in the bulb is so adjusted that it has always the same capacity for heat and therefore produces the same elevation in the temperature of the calorimeter.The experiments as in the previous case being compara- tive all corrections for loss by radiation &c. are here also dispensed with Different experiments made by the foregoing methods with one and the same liquid give extremely concordant results. In what follows C stands for the nioleculw heat of tlre various liquids employed 1% for the number of moiecules of wiiter to one molecule of the substance dissolved.SuZplmric acid H20.,SO + ndq.-The acid employed had been purified by dist,illation and brought to tho monohydrate by repeated * Phil. Mag. [4] xli 134. PHYSICAL CHEMISTRY. congelation. Experiments made by tlic first method lead to the follow-ing empiricai formula for the calculation of C :-334.8 2882 7262 C = 18%+ 8.58 +-__ + -. n rb2 TL3 The formula is inapplicable to solutions containing less than 5 mole- cules of water. The specific heat of the monohydrate was found to be 0.3315 for temperatures between 16" and 20". Some experiments made by the second methoh on mixtures with less than 5 molecules of water gave the following results for the specific heat between 20" and 56" :-Specific heat.Noleculsr hat. Monohydrate .................. 0.3363 33 With 1molecule of x-at;r ........ 0.4411 51.2 79 ?Y 77 3 ........ 0.5056 76-8 77 77 7) 5 ........ 0.5833 109.7 These results agree well with those of the first series and also confirm the curious fact established by Pfaund lei- that the first equivalent of water added to monohydrated sulphuric acid increases the molecular heat by a quantity precisely equal to that of the water added while fbr every further dilution there is a considerable loss of molecular heat. Sodium suZphate Na,O.SO + 1~ hq.-Experiments on solutions with 50 100 and 200 iimlccules or T>atcr respectively lead to the followine formula for C : " 4094 98000 C = 1%-16.34 + -~ TL I? -The formula becomes inaccurate in the case of weaker solutions.For solutions containing more than 200 molecules of water the specific heat is less than that of the water alone; the specific heat is always diminished by the addition of water. Sod~u~.lt-lLycl~,oge1L sulplintc %} Q.SO + ?L Aq.-The empirical for-mula for C is 1292 ll500 c = 18,b 4-11.65 + --5"L 2 A comparisonof the molecular heats of solutions of sdphate ofsodium bisulphate and of sulphuric acid of corresponding strengths shows that the molecular heat of bisulphate solutions is always above the mean of the molecular heats of the neutral sulphate and of sulphuric acid. Thc mixing of these two substances produces a lowering of temperature.HydrochZo& mid HC1 +n Aq.-In this case C = 1% -28.39 + 1.10 I 268 n n2 The specific heat of hydrochloric acid solutions even of the most concentrated is always less than that of the water itself which they contain. ABSTRACTS OF CHEMICAL PAPERS. Sodium Chhide NaCl + 12 Aq.-The formula is C = 18u -20.45 + 481 2100 -_. 1L 722 Addition of water to a solution of chloride of sodium always occasions a diminution of the molecular specific heat. A solution containing about 18 molecules of water has the same molecnlar heat as the water which it contains ; in more dilute solutions the molecular heat is less than that of the water contained in them. Szcgar C12,H2201, + 1% Aq.-The experiments lead to the conclusion that the molecular heat of sugar in the liquid state is 147 and its specific heat 0,430.The molecular heat of any solution of sugar will then be the sum of the molecalarhents of the water and the sugar they coiit ain . Soliitions in Sulyhiile of C~ir-bov Specific heat of snlpliide of cai*ti.b011. . . . . . .. 0.238 Molecular heat . . .,. . . . ,..... :... . 18.1 Solutions of the following substances in sdphide of carbon were examined namely sulpl~u~, phosphoi-us bromine and iodhe. The experiments show that the diminution of specific heat resulting from solution or from dilution is either not observable at all or is sliglit (sulphur and phosphorus). The molecular heat of these solutions above all never becomes inferior to that of the solvent alone.Geizeral Obse~~ations.-According to Kopp and R'egnault the molecular heat of a compound and of an alloy is always nearly equal to the SLIM of the molecular heats of its constituents. As regards aqueous solutions it appears however that while solutions of sugar and ammonia are in conformity with Kopp and Regnault's approxi- mate law the molecular heat of mixtures of alcohol and water is always above the sum of the molecular heats of its constituents. In the case of most salirie solutions 011 the other band A diminution of molecular heat tnkes place. If all solutions behaved in a similar manner this anomaly might be simply due to the difference in physical condition between the solid and the liquid state; but as various solutions behave very differently it must be due to a chemical cause.Thus we may assume that every change of temperature involves a change in the chemical constitution of the solution such chemical work being either a source of absorption or of disengagement of heat. This of necessity augments or diminishes that which must be transmitted to the solution to change its temperature and consequently the heat alters its appa-rent specific heat. Pfaund le r who has previously" expressed this same idea has more recently? even proposed the study ofthe specific * 3.pi'. Chem. vo1. ci p. 507. + Zeitschr. f. Chemie [2] vi p. 66. PHYSICAL CHEMISTRY. heats of solutions and their elements as a means of determining the degree of dissociation produced in them by heat.It appears useful to enunciate or recall these theoretic ideas at the present time even though it may be difficult to explain the opposite effects observed in mixtures of alcohol and of sulphuric acid with water by this hypothesis of a change in the chemical constitution of the solution according to temperature A. D. On the Spectra of Carbon. By W. MARSHALL D,Sc.* WATTS THISpaper is the sequel to one which appeared in the “ Philosophical Magazine,” for October 1869. The author gives the readings of the lines obtained by passing the spark from an induction coil through carbonic acid or carbonic oxide a Leyden jar being included in the circuit. These readings he converts into wave-lengths by means of an interpolation curve founded on the observation of twenty lines whose wave-lengths are given in An g str om’s map.s. w. On the Examination of the Bessemer Flame with Qoloured Glasses ad with the Spectroscope. By J. M. SILLIMAN.? PROFESSOR 81LLIMAN treats his subject under two headings-lst the examination of the Bessemer flame with coloured glasses ; and 2nd with the spectroscope. The results of the first part are confirmatory with slight variations of Rowan’s observations. The author in his experiments used three coloured glasses two light yellow and one blue through which the sunlight appeared of %I deep purplish-blue tint. In the second part after narrating the work done by Roscoe and Lielegg the writer describes his own instrument and the order observed in his work. The instrument is provided with a single equiangular prism and a reflected scale.In the course of his experi- ments he made the important observation that a mwement of the eye before the eye-glass occasioned a similar movement of the lines of the spectrum along the scale on which their position could be made to differ more than half a degree. To obviate it however the position of the eye before every reading was adjusted SO as to bring the sodium line always on 50”. He has failed to find some of the lines given by Lielegg but has detected others not given by him. The lines of which Professor Silliman gives readings are thirty-three in number :-1st Period 23&,35 50 135. 2nd Period 23+ 35 43 44 a&, 45&,46 4’74 484 50 52 53 56 564 6lQ 62 62+ 63 65 66+ 67$ 70 72 120 135.* Phil. Mag. [4] xli 12. t. Phil. Mag. [4] xli 1. ABSTRACTS OF CHEMICAL PAPERS. 3rd period 23$ 35 43 4A 443 454 46 47& 484 50 514 52 53 56 564 57 61$ 62 624 63 65 66* 67 67+ 70 72 100 102 103 105 108 135. Amongst the dark bands the most intense were- &-46 51-55 56-58 62-64& others at 33-344 36&,37& 38&,40 68 7.2. The author discusses at some length the theory adopted by Wed-ding that the aboence of the spectrum at the beginning and end of the blow is due to the small quantities of the bodies volatilized and inclines to consider that in the ease of the manganese spectrum the lack of sufficient flame may accouut for its sudden disappearance at the termi- nation of a blow. In conclusion the author suggests the use of more delicate instruments and augurs much good to the science of spectrum analysis by careful observations of the Bessemer flame.S. W. 018 the Exarnimtion of the BCessemey Flame Iruitli Colowred Glasses aid PARKEX.* un'th the SpectroscoTe. By J. SPEAR THEcombination of coloured glasses used by Mr. Parker in his in-vestigation consisted of one light cobalt-blue and one amber coloured. He does not approve of a deep blue glass as the flame under such cir- cumstances merely shows varying shades of crimson. With regard to the utility of using coloured glasses the author considers that they me of advantage to the inexperienced and tend to preserve the eyes but that the skilled workman is able to detect the change with surprising accuracy with the naked eye.In his spectroscopic examination Mi*. Parker made use of a direct vision instrument of five prisms. The spectrum obtained by him does not vary from that obtained by other investigators. The presence of an absorption-band is considered by him as merely owing to the effect of contrast. He thinks that the first group of green lines and the prominent red group cannot be referred to manganese. He has obsemed the most promiqent bright lines especially the two green groups when the metal is poured out of the converter into the ingot- mould a large flame appearing simultaneously. The writer thinks the spectrum in this case " is caused by the graphite with which the moulds are lined to fill up any cracks or cremces. and thus facilitate their ready separation from the ingots and must therefore be due to the combus- tion of carbon by the air carried down with the stream of metal at an intense white heat."? 8.w. * Chem. News xxiii 25. .t. Observations on the two preceding papers hsve been published by Dr. W.M. Watts (Chem. News xxiii 49). PHYSICAL CHEMISTRY. On the Electmnotive Fowe on Contact of Di'eyent Metals. By E. EDLUND.* INzt previous paper the author has shown that if a voltaic current tra- verses an electromotor in the same direction as the current produced by the electromotor itself an amount of heat is absorbed in the electromotor which is proportional to the electromotive force multiplied by the intensity of the current. If the current is in the opposite direction a quantity of heat is produced which is proportional to the same product.For the same intensity of current the quantikies of heat absorbed or produced in various electromotors are therefore proportional to the electromotive forces. If then a current is traversing a conducting wire consisting of two different metals there must be an alteration of temperature at the place of junction because there exists at that place an electromotive force. Now experiment has shown that heating or cooling occurs at the place of contact between two metals when a voltaic current traverses it and that this alteration of heat is as theory requires proportional to the intensity of the current. Hence the measurement of the quantities of heat absorbed or produced by the voltaic current gives a determination of the magnitude of the electro- motive forces produced by the contact of the metals.Now the quantities of heat produced by the passage of the current are of two sorts. Firstly heat is produced owing to the voltaic resist- ance of the wire in quantity proportional to the square of the intensity of the current ; while secondly an amount of heat proportional to the intensity of the current is either absorbed or produced at the point of contact of the two wires. Now let s be the intensity of the current and vz and R two constants then s2m will be the heating effect due to the voltaic resistance and A s77 the heating or cooling due to the action at the point of contact of the two metals.Further suppose the index to have moved A + a divisions with the current passing in one direction and A + a' division with the current passing in the opposite directions. We shall have Sam & sn = A + a s2m SIL = A + a' and 2s12 = ci -a'. The difference between the two stationary positions of the &leg when the current passes in opposite directions is thus a measure of the heat produced or absorbed at the point of contact of the two metals. Experiments made on this principle gave the following electromotive series Bismuth argentan (German silver) platinum copper and iron -silver and zinc being undecided. The relative numerical values are :-* Phil. Mag. [4] xli 18. ABSTRACTS OF CHEMICAL PAPERS. 100 Bismuth-copper ................141.3 Argentan-copper ................ 15.57 Platinum-copper ................ 7.37 Copper-iron .................... 17.83 Experiments were next undertaken in order to ascertain the thermo- electric relations of these combinations. The results when calculated for a difference of temperature of 10" and a conductivity =100 yielded the following deflections of the magnetometer :-Bismuth-copper the deflection ........ 92.27 Argent an-copper ........ 23.18 l? Platinum-copper ,> ........ 8.23 Zinc-copper ........ 0.90 ?I Silver-copper 9 ........ 0.63 Copper-iron ........ 24.93 97 The thermoelectric series of these metals is therefore the following Bismuth argentan platinum zinc silver copper and iron. In the former series the position of silver and zinc could not be determined owing to the slight effect produced by their combination with copper ; the other metals are however in the same order in both series.If the numbers in both series be calculated so as to be equivalent for one of the combinations-copper-iron for example,-we obtain-Thermoelectric Electromotive series. series. Bismuth-copper.. .... 92.27 197.6 Argentan-copper .... 23.18 81.77 Platinum-copper .... 8.23 10.30 Zinc-copper ........ 0.90 - Silver-copper........ 0.63 - Copper-iron ........ 24.93 24-93 The combination bismuth-copper was once more examined in regard to its thermoelectric and electromotive forces ; the results agreeing substantially with the above. It will thus be seen that although the number for the combinations argentan-copper and platinum-copper are nearly equal in both series yet as shown by the combination bismuth- copper the electromotive and thermoelectric forces are not proportional to one another.According to Seebeck thesemetals have the following order in the electric tension series :-silver platinum copper iron bismuth and zinc. There is thus no similarity between this series and the other two ;and hence it is highly probable that the electrical tension does not depend exclusively 011 the contact between the two metals but on the layer of gas or water which is condensed on their surfaces. On the other haQd the metals which in contact with each other produce the PHYSTCAL CHEMISTRY. greateah electromotive form also produoe the most powerful thermo- electric current when the place of contact is heated; but these thermo-electrical currents are not in all combinations proportional to the corresponding electromotive forces.A. D. On some Hydro- and Themno-electric Forces reduced to the Siemens’ Unit Resistance and weber’s unit of Current. By T. KOHLRAUSCH and M. A. AMMA”.* THEelectromotive forces me expressed accordingto Ohm’s law o =wi; where the resistance w is expressed in Siemens’sunits the intensity i in the magnetic unit of Weber. The electromotive forces thus measured qre given as Siemens-Weber. Hydro-eZectric circuits measured by tangent compass- 1. Grove’s element (sulphuric a,cid 1.06 sp. gr. zinc freshly mal-gamated) = 19.98.Siemens-Weber. 2. Daniell’s element (sulphuric acid and zinc as above) =11.71 Siemens- Weber. 3. Copper-zinc elemen4 (sulphuric acid and zinc as above) = 1082. Siemens- Weber. Thernm-electric circuits measured by Poggendorffs compensation method. The metals were hmd-drawn wires of about 1millim. diameter one junction having a temperature of about 16” C. the other one of to higher the eloctrornotive force e (in Siemens-Weber) is found. For German silver and copper- e = 0*0001549t+ 0*000000291t2. For copper and iron-e =0*0000969t+ 0~0000000149t2. F0r German silver and iron-e = 0.0002476t + 0~000000196ta. The values of e thus caclulated agree very closely with those found by direct observation. A. R. Polarization of Metallic 8zcrfaces in Aqueous Solutions a mew 2MetTLoc-j of obtaining Elwtricity from Mechanical Force afid certain relations between Electrostatic Induction and the decompositiow of Water.” By C.3’. VARLEY.~ THZauthor describes an apparatus by which he obtains electrio currents from polarized surfaces of mercury ; by a mechanical arrangement he ahm fhe rehkive amount of the polarized surfaces of the elements of # Phil. Mag. [4] xli 15’7. + Proc. Roy. SOC. xix 243. VOL. XXIV. K ABSTRACTS OF CHEMICAL PAPERS. the battery and by such change obtains electrical currents. Thesecond part of the paper refers to the electrostatic capacity of platinum plates in dilute acid and water. C. G. '(On a constant form of Daniell's Battery." By Sir WILLIAM THOMSON.* THEauthor employs the following form of element.:-The ce!l is of glass ; in form cylindrical or rectangular with a flat bottom. The depth may be 10 centimetres or more where perma- nence and ease of management are of more importance than very small internal resistance. A disk of thin sheet copper is placed at the bottom of the trough; to this is soldered or riveted a copper wire insulated with gutta-percha passing up vertically through the liquid ; and with this the zinc of another element can be connected. A grating of zinc to which is attached a suitable electrode is supported in the upper part of the jar. A glass tube (the charging tube) a centimetre or more in internal diameter expanded to a funnel at the top is supported so as to rest with its lower open end about one centimetre above the copper.A glass siphon with cotton-wick core or a capillary glass tube is placed so as to draw liquid gradually from a level about a centimetre and a half above the copper and to discharge the same at a level slightly higher than the upper surface of the zinc grating. The jar is then filled with semi-satnrated solution of zinc snlphate. To put the cell in action finely broken crgstals of copper sulphate are placed in the funnel at the top of the charging tube. The liquid stratum below the aperture of the tube thus becomes saturated with copper sulphate. The cell is now ready for use and may be kept so by occasionally pouring in fresh water or water onequarter saturated with zinc sulphate at the top of the cell to replace the liquid removed by the siphon from near the bottom.The author recommends the use of specific gravity bulbs kept floating in the liquid to show with precision whether the liquid added from time to time should be pure water or water more or less saturated with zinc sulphate. The best results are obtained when the liquid in contact with the zinc is a little less than half saturated with zinc sulphate. The siphon extractor mast be arranged to carry off all the water of crystallisation of the copper sulphate decomposed in the cell and enough of water besides to mrry away as much zinc sulphate as is formed in the use of the battery. C. G. * Proc. Roy. Soc. xix 253. INORCIANIU CHEMISTRY. On Solutims for Electrodeposition of Copper and Brass.By W. H. WALE”+. A SOLUTION containing one pound of cupric sulphate and one pound of sulphuric acid to the gallon of water deposits the metal in a solid compact mass with a somewhat botryoidal surface. The addition of 1 ounce of zinc sulphate (as recommended by Napier) annuls this botryo’idal form and renders the deposit tough compact and even. From a solution containing a greater proportion of zinc sulphate the metal is deposited in tufts of needles standing at right angles to the surface of the metal. Ordinary electro-brassing solutions show the same peculiarity’in even a more marked degree and this makes it im-possible to produce a good deposit of more than 0.01 to 0.03 inch in thickness. This form of deposit is owing chiefly to a copious evolution of hydrogen taking place during its formation.However the author has found that by employing a solution containing both the oxides an2 the cyanides of the constituent metals together with some neutral ammonium tartrate this evolution of hydrogen may usually be avoided or should it nevertheless take place to a slight extent it may be entirely stopped by the addition of some cupric ammonide. Such a solution yields brass of a uniform character and the deposit which may be obtained of any thickness desired is tough and has a compact even texture. aS there is no evolution of hydrogen no electric force is wasted and perfect results may be obtained with a single Wollas- ton’s or Smee’s cell. A D.

ISSN:0368-1769    

DOI:10.1039/JS8712400094

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

INORCIANIU CHEMISTRY. Inorganic Chemistry. Om th6 AcG~ of Water on Iron wd of Hydrogert on Oxide of Irorl. By H. SAINTE-CLAIRE DEV1LLE.t THEfollowing researches into the action which water-vapour exerts upon iron have been carried out on the same plan as that by which the author has established that the progressive decomposition of a gaseous substance is characterized by a dissociation-tension which like the tension of a vapour can be measured in millimetres of mercury. Perfectly pure iron was subjected to the action of water-vaponr of known tension and temperature the iron itself being also maintained at * Phil. Mag. [4] xli 41. t Ann. Ch. Pharm. clvii 71 from Comptes Rendus lxx 1105 1201 and hi 30. K2 1M ABSTRACT8 OF UHEMICAL PAPERS.a constant temperature throughout an experiment which in different experirngmts could be varied between 150" C. and abcmt 1600". The apparatus employed consisted of a pomelain tube containing the iron and communicating at oqe end freely with a glass tube-retort contain- ing water to furnish the vapour asd at the other with a maBometer. By meam of Q lateral tubs at the upper part of the manometer the interior of the apparatus could be placed in commqniga+ion with a Geissler's oy Sprengel's pump and by another arraagemen+ iicould be filled whq required with gwe hydrogen or other gas The iron employed was paroua and obhstine4 brreducipg the red oxide with hydrogen. The oxide employed ww af necessity the magnetic oxide which was obtained by the action of strnm on reduced iron.The glass retprt-tube was kept either in ice or in water of constant temperature flowing from the Paris ~G~LG, the temperature being main-tained always lower than that of the air inorder th& condensation of aqueous vapour might not occur in any other part of the apparatus. For all temperatures to which the iron mas exposed below 300" an oil-or a mercury-bath heated by a gas-flame pmvided with Schlosing's regulator was used. For the constant temperatures 360",&0" 860° and 1040" the vapours of boiling mercury sqlphur cadmium and zinc were respectively employed. The mdxnium was heated ina mercury-bottle to which near its neck was fitted a gun-barrel serving to con-dense and return the cadmium to the bottle while another iron tube passed through the bottle within which the porcelain tube WPPSplaced.The zinc was heated in a black-lead crucible such as is used in the manufacture of steel through the body of which an earthen tube passed to receive the porcelain tube and to the lid of which was attached another upright earthen tube to condense and return the zinc to the crucible. The iron bottle or the crucible was placed in a furnace heated by petroleum and the temperature of v\hich was kept constant by graduated stop-cocks to regulate the supply of oil. Lastly for all temperatures above 1040" the porcelain tube was exposed to the direct regulated flame of the petroleum and by this means Bhe tempwakm at which iron melhs was reached which is below that at whioh a thick refractory porcelain tube softens.The following remlks have been obtained :-(l.) On.mbjeating a;ny quantity of iron to the action of water-vaponr the iron continues to oxidize until at a fixed temperature the tension of the liberated hydrcl-gen becomes constant in value. (2.) The point of maximum temiun for a given temperature b&g been reached the withdrawal of smeof the gas so as to diminish the pressure is rapidly followed by a restoration of the tension caused by the decompsitioxl by the iron of a new qmtity of water which evaporates from the retort; or the pressure bekg IN0 RGANIO CHEMISTRY. increased by sending some hydrogen into the apparatus the pressure rapidly returns to its original amount by a reduction of some oxide of iron by the hydrogen with formation of water which condenses in the retort.(3.) The point of niaximum tension for a given temperature of the iron having been reached the space in which the moist hydrogen is enclosed can be brought to any desired temperature without the tension of the gas changing-provided that is that the temperature is not so low as to cause any water to condense. For example when heat is ap- plied to the apparatus the tension of the gas is preserved by some of the hydrogen condensing on the oxide of iron. (4.) When the tension of the Faker-vapour is maintained constant and equal to 4.6 mm. corres-ponding to a temperature of 0" and the temperature of the iron is made different in different experiments the tension of the hydrogen is found to be less as the temperature of the iron is higher.At a temperature of 200" the tension of the moist hydrogen = 100 mm. ; at 260" it is 68.8 mm.; at 360" 45 mm. ; at 440" 30.4 mm. ; at 860° 17.7 mm.; at lOM" 13.5 mm. ; and at the melting point of iron 9.7 mm. The lower the temperature of-the iron the more slowly does the tension reach its maximum or-if the tension of the gas has been raised beyond the maximum for the temperature of the iron-the more slowly does it sink to this. (5.) When the tension of the water-vapour is maintained con- stant and at the maximum corresponding to some other temperature than that of O" it is found that (a;) the higher the tension of the water- vapour the higher is the tension of the hydrogen the temperature of the iron remaining oonstant; (b) an increase in the tension of the water-vapour causes more than a proportionate increase in the ten- sion of the hydrogen; and (c) the difference of the increase of the respective tensions becomes less and less as the temperature of the iron is made higher thus with the iron at 200° the increase (supposed to be uniform) of the tension of the hydrogen corresponding to an increase of 1 mm.in that of the water-vapour is 29.8 mm. while with the iron at about 1600" it is only 0.56 mm. (6.) All the laws as to the form+ tion of hydrogen by heating together a small quantity of water and a large quantity of iron hold good just the same and with the same constants for given temperatures when a small quantity of hydrogen is allowed to act on a large quantity of oxide of iron.The most perfect analogy exisks between khe phenomena which form the subject of this memoir and those of hygrometry the iron at a given temperature comporting itself like water and the hydrogen as the vapour evolved from it as a consideration of the results recorded under (I) (2) and (3) will at once show the principle involved in (3) having a manifest analagy with the principle of Watt. From (5 0) it may be assumed that at a sufficiently high temperature of the iron the increase in the tension of the hydrogen would = 0 ;in this case the tension of ABSTRACTS OF CHICMIGAL PAPERS. the hydrogen would only be added to that of the water-vapour as if it were an indifferent gas and the hygrometric law relating to a mixture of gases and vapours would still find its application to the phenomena here investigated.The phenomena of combination decomposition dis- solution and passage to the solid liquid or gaseous state being all attended with a disengagement or an absorption of latent heat have no doubt a common cause. Berthollet’s hypothesis as to the injhence of mass does not serve to explain the phenomena of the action of iron upon water-vapour ;for lstly the tension of the hydrogen is quite independent of the quantity of iron ; and 2ndly as the masses or relative weights of the hydrogen and the water-vapour are respectively proportional to their tensions it is evident from (5 b) that the proportion between the weights of the gaseous substances entering into a reaction does not affect its results.From (4) it most unexpectedlyappears that the higher the tempera- ture of the iron the smaller is the quantity of water which it decom-poses or in the figurative language of chemistry the less is the a5nity it shows for the oxygen of water. Not only is this the case but as again unexpectedly appears from (5 c) it is at the lowest tempera- tures of the iron that the tension of the hydrogen most rapidly increases when the tension of the water-vapour increases. The following facts are incidentally communicated in the memoir :-(1.) Iron is distinctly though slowly attacked by steam at 150°,which may perhaps account for the singular erosion by distilled water of the iron of the boilers of steam vessels.(2.) The oxide of iron obtained by acting on iron by water-vapour at a temperature of 440°,and removing the hydrogen as fast as it is produced has a composition corresponding to Fe405; it is amorphous black magnetic but not polar scarcely attacked by concentrated hot or cold nitrio or sulphuric acid ; it is readily soluble in cold hydrochloric acid without sensible evolution of hydrogen and forms a deep-brown solution yielding a black precipitate with potash. (3.) By the action of steam on spongy platinum mixed with potassium cyanide at a dull red heat much hydrogen is disengaged and among other products a large quantity of potassium platinocyanide is formed E.D. On the Condition of Carbon and Silicon in Iron and Steel. By G.J. SNELUS.~ THE author after quoting the views held by Berzelius Karsten and Rammelsberg Von Mayrhofer and others who have assumed the existence of definite chemical compounds of iron and carbon in the # Journal of the Iron and Steel Institute Feb. 1871 p. 28. INORGANIC CHEMISTRY. formulae published by them proceeds to describe his own investiga-tions. He employs the following mechanical means to obtain the graphitic substance. By means of a penknife he was able to remove the graphitic scales from slowly-cooled Bessemer pig. -0345 grm. of the material thus obtained was heated in a current of oxygen and yielded- Residue 0.0015 grm. (consisting of sand with a mere trace of FeOs) COZ 0.104 gm. = 0.0283 C. By means of a magnet the author separated as far as possible the iron from the graphite in finely po,wdered pig-iron.0.1045 grm. of this graphite after combustion gave a residue weighing 0.012 grm. (containing 0.008 grm. Fe203 and 0.004 grm. sand &c.). The CO formed weighed 0.2505 grm. = 0.0955 grm. C. Lastly 0.1415 grm. kish purified with hydrochloric and hydrofluoric acid yielded 0.518 grm. CO F= 0,14154 grm C. and left no weighable residue. In all these cases the author concludes that the graphite scales thus removed contained no iron the small quantities found in the analyses being due to accident. Advantage was also taken of the great friability of graphite. Borings from grey Bessemer pig were sifted through a fine silk sieve. Pig containing 3.008 per cent.gave in the fine dust 7 605 and another sample containing 4.071 per cent. yielded in the dust 9.288. By avail-ing himself of the lesser density of graphite and levigating the finely- sifted borings the author obtained the following results :-Originalpig. Siftings. Levigatedpowder. (1) Bessemer pig ...... Combined carbon 3.igo0.2 7.790.17 21.274 - ...... forge pig. iG*phi”eCombined carbon (2) Middlesborough 2.6500.35 7.0150.30 41.329 - “ These results clearly show that in grey pig-iron the carbon exists in two states and that the free or graphitic carbon can be more or less separated by mechanical means while the so-called ‘combined carbon’ decreases in the separated portions in the same ratio as the reeidual iron.” Finally the author holds that the absorption of carbon by iron is rather a case of solution than of definite chemical combination.SiZicon.-This element invariably occurs in pig-iron and even in steel and wrought iron the author has never found it entirely absent. In good Bessemer and in tool steel it rarely exceeds two or three parts in 10,000 of iron. By employing the methods quoted above the author obtained the following results :- ABSTRACTS OF CKElMIUAL PAPERS. Amozcnt of silicon per cent. im-1. 2. 3. Original Fine Let.igatd Pig-eiftings. powder, West Cumberland Bessemer pig .. 2.419 2.380 -Dowlais Bessemer pig.. ...,.,..,. 3.849 3.639 3.158 Middlesborough pig. .... . . ....... 1.815 1.610 1.219 Here the silicon unlike the graphite does not increase in the .finer portions but diminishes.It remains with the iron just as the ''combined " carbon does. Hence the author concludes that the silicon is in combination or in solution in the iron and is never-except perhaps in an exceptional case-found in the free state. 6. G. A. BELL.* The Compositiorb of the liierric Iodates. By CHICHEBTER THE author describes some experiments undertaken to facilitate the preparation of a ferric iodate to be used as a substitute for ferrous iodide. The compound Fe2O3.2IzO5,8H20 formed by precipitating a solution of iron alum by an excess of potassium or sodium iodate has been used with success in medicine ; but appears to alter by exposure to air. A compound which has the advantages of being anhydrous perfectly stable tasteless and odourless is obtained as a fine yellow precipitate by heating a solution in 5 or 6 parts water of ferrous iodide obtained in the usual manner from 2 parts iodine with 2 parts potassium chlorate dissolved in a little hot water and 1* parts strong nitric acid.The formula Fe2o3,3I,o5 or Fe(103)3 expresses its composition. It con-tains 9.64 per cent. Fe and 65.57 per cent. I ; the crystallised ferrous iodide of the Pharmacopceia containing about 15 per cent. Fe and 67 per cent. I. It is scarcely soluble in cold water and but slightly so in strong nitric acid. The use of but small quantities of nitric acid in the above oxidising mixture produces compounds less rich in iodic acid ; one of a deep red colour appears to contain Fee03,1205 dried at 100" C.; it decomposes however during was-.These basic mixtures are converted into the triiodate by digestion with warm dilute nitric acid. W. €3. D. Om NickeZ Chomate and Ammonio-Nickel Chromate. By E. A. SCHMIDT.? NrcKEL chromate having the formula 3Ni0.Cr03+6H20 (Fk.esenins Zeitschr. f.Chemie. [2] VI. 30) is formed only when the precipitate is * Pharm. Journ. Trans [S] I,624. -f Zeitschrift fir Chemie [a] vii 31,from Ann. Ch Pharm. clpi 19. INORGANIU GHEMISTRY. thrown down in presence of excess of nickel-salt as for instance on mixing boiling solutions of 2 mol. of nickel sulphate and 1 mol. of potassium chromate. When on the other hand the chromate is in excess precipitates containing less nickel are thrown down under otherwise similar conditions with 2 mol.potassium chromate and 1 mol. nickel salphate the aathor obtaked the salt 5Ni0.2CrOsf 12H20,ttnd with 4 mol. of the chromate to 1 mol. of nickel sulphate the salt 2Ni0.Cr03 +6H20. No salt containing less nickel €ham the last wm obtained; on the contrary by employing 10 or 12 mol. potassium chroma,te to 1 mol nickel aulphate precipitatek were throwh down the composition of which lay bst*een 5Ni0.2Cdl3 end 2Ni0.03. When basic hickel chromate still moi& iS triturated to a thin pulp with arnmoaia and gaseous ammonia is passed in till the brown colour completely disappears innmonio-nickel chromte is deposited in the form of a yellowiBh-green crystalline powder. Further quantities of the same salt are obtsbined by placing a few crystals bf neutral ammonium chromate in the mother-liquor.Large and well- formed prismatic crystals are produced when the ammoniacal solution is covered with a layer of alcohol ; they are yellowish-green diohroic by transmitted light and undergo decomposition in the air and more rapidly on warming giving off ammonia. Malaguti and Sarzean assign to this salt the formula Ni0.CrOs.3NH3+4H20 ; but the author found the salt to be anhydrous and to have the composition expresaed by the formula Ni0.CrOs.3NH3. J. R. (3ry the Atkalhe Reaction of Silver Oxide and Xilver Nitrate. By A. VOGEL.+ THEolder statements of the alkalinity of silver oxide are confirmed by Dr. Vogel who obtained the oxide by adding lime-water to a solu-tion of silver nitrate which was distinctly acid ; the silver nitrate was kept in excess.The liquid from which the oxide was removed had still a feebly acid reaction. Carefully washed the damp silver oxide gave distinct indications of alkalinity with litmus- and turmeric-paper Several samples of commercial lunar caustic showed an alkaline reaction with litmus-paper but Dr. Vogel thinks that the lunar caustic may be regarded to some extent as a bash salt inasmuch rn a solution of crystallised silver nitrate lost its acid reaction by boiling with silver foil or silver oxide and became alkaline. W. H. D. * N. Repert. Pharm. xx 93

ISSN:0368-1769    

DOI:10.1039/JS8712400103

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

110 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. On the Chemical Composition and Microscopic Constitzctiom of certain PHILLIPS.* Cornish Rocks. By J. ARTHUR ‘‘ KILLAS ” is the name applied by Cornish miners to all sedimentary cleavable rocks. Their geological age has not been determined beyond that they belong to the palaeozoic era and it is believed that they are of Devonian age. They enclose five large and several smaller “islands ” of granite and are as well as the granite itself traversed by dykes of granitic and porphyritic rock called ehans by trap dykes by copper and tin lodes and by various cross-courses including Jlucans or fissures filled with clay. Typical killas is a grey bluish-grey or greenish-grey clay-slate and when weathered is brownish-yellow or buff.It is usually exceedingly fissile with the planes much contorted but is often more compact near its junction with the granite. The sections examined in the microscope by “a low power ” were magnified 60 or by a “high power ” about 400 linear. I. Killas from Polgooth Mine adit level sp. gr. = 2.60. This is a very soft slate of a light-grey colour marked in places with a darker shade or yellow tinge. By transmitted light under a low power thin sections exhibit no structure but appear as a milky-white mass enclosing moss- like semi-crystalline markings of a brownish-green and traversed by fissures filled by crystalline transparent quartz. With a high power it is found to be composed of an aggregate of minute granules intimately blended together without definite outlines and to enclose some grains of oxide of iron and apparently fragments of hornblende and some patches of a chloritic mineral.11. Killas from Polgooth Mime 80.fathoms level sp. gr. = 2.74. This specimen much harder than the above is of a grey colour strongly marked with reddish-brown. Here the microscope detected no difference excepting that the grains of oxide of iron were larger but less numerous and that there were fewer of what appeared to be broken crystals of a hornblendic mineral. The granular fragments are larger and more distinct their larger surfaces being nearly parallel with the planes of cleavage of the slate. The chloritic mineral is again very abundant and peculiar markings were observed about its margin.111. Killas from Polgooth Mine 100fathoms level sp. gr. = 2.73. At this depth it is much harder than that found at shallower levels is of a greenish-grey slightly streaked and spotted with yellow. The sections resemble those from the 80 fathoms level but contain no horn-blende and fewer chloritic patches. IV. Killas from Polmear Mir~e,40fathoms below the surface sp. gr. = 2-68. This clay slate is much contorted dividing readily in curved Phil. Nag. [4] xli 87. MINERALOGICAL CHEMISTRY. laminm with glossy surfaces bearing wavy lines resembling minute ripple marks. It is of a medium grey and slightly yellow in places. Its sections resemble those of the Polgoobh specimens. Granules of quartz are disseminated through the finely-grained matrix which derives its greenish tint from chlorite,and which is minutely divided by a system of markings made up of pairs of parallel lines,each about I 2, th of an inch long and F& th of an inch apart.V. Slate from “ Sanctzcaries ” near St. Bustell sp. gr. = 2.52. This is light grey and buff in colour and appears to be weathered. It divides with difficulty into lamine the surfaces being without polish. It is divided by headings variously coloured apparently by infiltration of water containing oxide of iron. VI. Killas from Dolcoath Mine 215fathom level sp. gr. = 2.71. This rock is exceedingly hard the cleavage imperfect and its prevailing colour dark-grey. Freshly fractured surfaces exhibit numerous minute brilliant indistinct crystals probably of some hornblendic mineral.With a low power its sections appear to be made up of transparent angular particles giving co1oUz.s with polarised light ; the greenish patches disseminated through the mass are probably chlorite. With a high power are seen black grains of magnetite and titaniferous iron and fanlike aggregations of transparent acicular crystals often diverging from a particle of oxide of iron. Similar crystals also cross each other in all directions and are probably hornblende or schorl. Mechanically embedded are rounded fragments of mica and of a semi-translucent minerd not sufficiently opaque for oxide of iron. VII. Killas from Botallack Pennsance surface near lode sp. gr. = 2.95. This is a very hard dark greenish-grey rock containing minute crystals of pyrites ; its cleavage being to a great extent obliterated by metamorphism it breaks into roughly tabular masses whose planes approximate to those of original cleavage.The low power shows an amorphous base often green due probably to chlorite and enclosing transparent crystals and crystalline patches often fringed with acicular crystals which give brilliant colours with polarised light. With a high power long slender crystals probably of apatite and minute triclinic crystals possibly of axinite are seen. VIII. Rock from Botallack 130fathoms sp. gr. = 2.82. A very dark green specimen with traces of lighter shade and no cleavage is slightly magnetic and encloses in places minute crystals of pyrites. The grains of iron oxide are more numerous than in specimens obtained nearer the surface.It contains fewer long crystals than the surface rock and is traversed by minute veins of quartz enclosing transparent acicular crystals probably of hornblende. From its physical consti- tution and the large amount of magnesia it contains it may be regarded as an impure serpentine. IX. bb Best roofing slate,” DelaboEe sp. gr. = 2.81. Whilst under a low ABSTRACTS OF CHESXIGAL PAPERS. power this date shows no distinct structure bat is thickly dotted with dark pots with a high power numerous clusters about &th of an inch in diameter of reddish-brown crystals appear. These result from the agpgation of several hexagonal plates of according to Mr Sorby’s examination more or less altered specular iron.The matrix is moreover) traversed in all directions but especially in planes parallel to the cleavage by long transparent crystals that are brilliantly coloured by polarised light. Both brown and white crystals have been formed in sit%. X. DiorzXe “ Saqctuaries,” St. Mewan. sp. gr. = 2.97. This rock is of a dark green colour verging on black is exceedingly hard and tough distinctly crystalline and magnetic. These sections exhibit nnmistak- able evidence of extensive alteration. The felspat does not generally present any distinctive characteristics although in a few instances the parallel striping peculiar to triclinic varieties was observed The rock also contains semi-transparent yellowish-brown crystals probably hornblende a green mineral of fibrous structure which is believed to be a variety of hornblende many black grains of oxide of iron some well-defined hexagonal crystals probably apatite and an abundance of a green chloritic mineral.This diorite has probably undergone much a1teration. XI “ Greenstone,” Blowing-House Hill Bt. AustelZ sp. gr. = 2.89. This stone is very similar to the “ Sanctuaries ” rock but is of a some- what duller aspect and is divided by a series of oblique cross headings,which impart to it a tendency to divide into rhomboidal masses; it is also less decidedly crystalline and exhibits a grain resembling that of some varieties of metamorphosed schist. The sections shew a compact felspathic matrix enclosing B few indistinct crystals of felspar together with large quantities of the greenish chloritic mineral observed in the St.Mewan diorite from which the greenstone differs but little in composition. The greenish mineral is arranged in approximately parallel bands and patches many of the latter appearing to be partially decomposed horhblende crystals and though retaining at their cehtre to a certain extent their original structure and colour have at the edges been transformed into chlorite or an allied mineral. The rock also conthins tmny black grains of oxide of iron and some hexagonal crystals probably of apatite. It is believed to be an altered clay-slate. XII Serpentinous rock Mennheniot sp. gr.=2*77. This is a moderately hard stone of a dark green colour has a somewhat crystalline fracture and schistose structure and is slightly magnetic.It occurs more or less intermixed with clay-slate and beds of unaltered slate are fomd interstratified with it. It exhibits numerous resinous headings many of which are coated with asbestos with fissures containing calcite. MINERALOGICAL CHIENISTRY. 113 Rmiform concretions of sapanite are frequently found in a clay app;L. rently resulting from the decomposition of the principal rock. The microsoope show-s a highly metamorphosed rock consisting of an amorphous matrix porphyritically enclosing yellowish-brown or green patches with indistinct crystalline forms evidently pseudomorphs with many grains of magnetite and crystals of what is probably schiller-gpar or diallage.XIII. Beypentine Lizard,sp. gr. = 2.99. The specimen is of a very dark green colour in places verging on black and thickly spotted with red ; it has a ooarsely granular structure is without my indication of foliation and eneloses imperfectly develaped cry staltls. XIV. Orthoclase,“ Glass nili’ne,’’ Roche sp. gr. = 2.55. This yellowish- white felspar occurs in granite containing considerable quantities of schorl and is traversed by reins of milky quartz enclosing tourmaline and cassiterite. Prof. Miller of Cambridge examined it crystallo-graphically and pronounced it to be a mono-clinic felspar. The following table exhibits the mean results of the analyses of these rocks :-H20. Si02. Ti02. PaO,. A1203 Fe203. FeO. Mn304. CaO. MgO. 1120.~~~ I. 408 60.42 -0.21 d0.83E 8.17 1-89 041 1.71 trace. 0.77 1-55 11. 3.63 63.10 trace. trace. 20.15 3.61 2.955 trace. 1-27 trace. 0.95 3-18 111. 3.265 60.915 trace. -20.78 13.415 4.92 trace. 1-62 -0-93 9-08 PQ8S IV. 6.58 49.265 trace. -18.00 12-68 8.56 082 2.13 trace. 0*56E 0.745 V. 6.16 53.30 trace. trace. 21-72 6.015 428 -trace 075 2-92 4195 VI. 1.15 67-315 0.13 -20-841 2-883 1.66 -2085 trace. 0.59 3-37 iulphur. VII. 3.125 40.21 015 0.66 2401 4\21 11-29 trace. 41@ 6-58 1.67 3-53 VIII. 11.09 32.98 trace. trace. 1673 ?a25 13.71 twe. 4-90 11-52 0.73 0.625 IX. 4.61 58-30 0.23 trace. 21-59 7-055 257 -039E 1.091 2.45 1.135 M~0.p X. 0.80 47.56 trace. 011 17.16 13.06 . 9.30 trace. 411 tram. 2-30 5.45 XI. 1.00 47.505 trace. tram.17.00 11.75 10.71 0.41 6-28 trace. 2.89 2.545 cr203 XII. 1056 38-70 trace. trace. 1’7.59 15.04 4-56 0.14 498 6-00 trace. 0845 XIII. 15.52 3@72 -2.991 1.905 5.07 0.08 trace 3L56; 0.32 0.765 and 0.29NiC XIV. 0.665 65.165 -19.08 0.50 -1.622 trace. 10.37 2-40 X likewise contains traces of sulphur ;XI1 and XIII traces of an oxide of manganese. In the estimation of silica in the foregoing apalyses the following method was adopted. The fused mixture after treatment with hydro- chloric acid was evaporated to dryness and siZica (a) removed in the usual manner. The filtrate was evaporated to dryness and a small additional quantity of silica (b) separated From this filtrate iron and ABSTRACTS OF CHEMICAL PAPERS aluminium were precipitated as basic acetates and collected.This pre- cipitate was dissolved in hydrochloric acid a few drops of nitric acid were added and after cooling the bases were reprecipitated by ammonia washed dried ignited and weighed. This precipitate was dissolved in hydrochloric acid and a third portion of silica (c) obtained by filtra-tion. W. F. (‘New Mineral” from Buwnah.” By D. WALDIE. THEauthor publishes the results of an analysis of a “mineral,’’ the physical characters of which he failed to notice and the locality of whose occurrence in Burmah he did not determine. The percentage numbers are-Copper .............. 17.000 Silver................ 0.096 Iron ............... 36.470 Antimony ............ 1.150 Arsenic .............. 32.700 Sulphur.............. 1.360 Earthy matter ........ 0.560 89.336 The deficiency of over ten and a half per cent. is supposed to ariee from loss of arsenic during the analysis. The silver is equal to 31i ounces troy to the ton. A second sample subsequently received from the same source has a laminated structure and uneven fracture is somewhat cellular and of a steel-grey colour with a purplish tint and metallic lustre; it is rather redder than mispickel. Minute specks of brownish-green matter were occasionally seen particularly near the lamellae. It gives no streak on paper a dark-grey one on porcelain has a hardness =5.5 and a sp. gr.from 7.3 to 7.4. Its composition is :-Soluble in hydrochloric acid :-Copper oxide.. .... 1.21 Iron protoxide ....1.97 Lead oxide ...... 1-89 Arsenious acid .... 1.12 7 6.19 Insofuble in hydrochloric acid Copper.. .......... 12-13 Iron.. ............ 42.12 Arsenic .......... 38.45 Antimony ........ 0-54 Earthy matter.. .... 0.12 -93-36 99.55 * Chemical News xxiii 4. PUBLISHED IN BRITISH AND FOREIGN JOURNALS. 115 The constituents approximate to two equivalents of arsenic six of iron and one of copper. The author named this substance O'Rileyife. W. F. Supposed Native Copper. By H. BOWMAN." THE specimen was found in a cargo of copper pyrites from the Tharsis mines in Spain. It weighed 215 lbs. and has a sp. gr. of 8.4. The colour varies in different parts from copper-red to almost white with a hackly fracture. The interior is full of cavities above shot size ; the outer surface has no adherent matrix.Its composition is :-Copper............ 84.80 Iron .............. 5.54 Zinc.. ............ trace Nickel ........... 0.28 Cobalt ............ 0.14 Antimony ........ 0.50 Arsenic .......... 7.10 Sulphur .......... 0.75 Oxygen .......... 0.41 -99.50 In three samples the percentages of iron were 4.8,5.4 and 8.1. Zircons.-A. H. Chnrcht examined some rounded pebbles each weighing about 2 grs. which came from Mudgee New South Wales and identified them as zircons. The specific gravity of the Mudgee stones was 4.704. They resembled the stones obtained from Expailly in Anvergne. w. v. #ahn/ite from Nine Hill Frunklin Furmce New Jersey. By G.J. BRUSH.$ THEMine Hill mineral differs from the gahnite of other localities in the frequent occurrence of the cubic plane. These planes are often the largest giving the crystals the form of cubes with truncated dodecahedra1 edges and only small octohedral planes. There are also minute planes of the trapezohedron 2-2 truncating the edges of the dodecahedron ; others of the trigonal-trisoctahedron 3 j and sometimes * Chemical News xxiii 19. t Chem. News,xfi 78. $ Amer. Journnl of Scienoe [S] i 28. ABSTRACTS OP CHEMICAL PAPERS. two planes betwem the cubie and octahedral which qpem Go belong to the forms 4-4and 8-8. These surfaces rounded and feeblylustrous blend in a curved surface and do not admit of accurate measurement. The inclinations on a cubic plane are for 4-4 160" 30'; for 8-8 170" 30'.The crystals vary in diameter from 4th to 16 inch are blackish green their fragments being olive-green and have a hard-ness = 7.5 and a specific gravity = 4.89 -4-91. Two analyses gave as a mean result :-Oxygen ratios. Alumina ............ 49.78 28'20) 25.77 Ferric oxide ........ 8.58 2-57 Zhc oxide.. ........ 39.63 Manganous oxide .... 1.13 Magnesia .......... 0.13 0.05 I Silica .............. 0.57 99.81 This gives the ratio of oxygen of R and R ae 1 3.17. By assum- ing 1.56 per cent. of the ferric oxide to be present as the lower oxide the ratio is exactly 1to 3. This variety of grthnite is richer in zinc than any heretofore examined. It occum in association with black mica apatite calcite and a brownish variety of chrysolite which con-tains zinc.w.P. Qrl the Mineral Constitueds of Neteorites. By N. STORY-MASKELYNE.* THE Bredemback meteorite.-This metmemite fbund at Breitenbach in Bohemia bears B great resemblance to the siderolite of Rittersgriin in Saxony. It is a spongy metallic mass the hollows of the iron being filled by a mixture of crystalline minerals. These are a bronzite with the formula Mg$ Fe+Si03 orthorhombic in its crystalline form. The crystallography of this minepal was investigated by von Lang and has been published in Pogg. Ann. cxxxix 315. Secondly a mineral composed of silica having the specific gravity Of quartz after fusion and crystallised in the orthorhambic system. The elements of the orgstal are-n :b :c = 1.7437 :1 3.3120 ad the anglm-100 101 = 27" 46' 100 110 =60" 10' 110 101= 63" 19' * Proc.Roy. Society xix 266. ORGANIC CHEMISTRY. The optic axes lie in a plane parallel to the plane 0.10 the first mean line being the normal to the plane 100. They are widely sepa- rated and present in air an apparent angle of 107". This mineral is beyond question orthorhombic and as the tridymite of von Rath is hexagonal in its symmetry the mineral of the Breitenbach siderolite will be a trimorphic form of silica. Its specific gravity was found to be 2.245 that of tridymite being 2.295 to 2.3 and that of quartz 2.65. The analysis of the mined by distillation of the silica as silicic fluoride and subsequent determination as potassium fluosilicate gave 97.43 per cent.of silica the remainder being oxide of iron and lime. A second analysis gave 99.21 per cent. silica and 0.79 residue.. The nickeliferous iron the chief constituent of this meteorite is an alloy of the formula FeloNi and contains a trace of copper. In addition to the above minerals the iron encloses occasional well developed octn- hedrons of chromite troilite and a small amount of schreibersite The XhaZka Meteorite.-Haidinger held this stone to be made up of a mineral which he termed piddingtonite and which according to von Hauer might be a compound of bisilicate and trisilicate of iron and magnesium. The latter acid silicate however no more forms a constituent of this meteorite than does the other acid silicate shepardite as Dr.Laurence Smith has shown enter into the com-position of the Bishopsville meteorite. Haidinger's view that the Shalka stone though apparently made up of two silicates a grey and a mottled variety is nevertheless composed of a single mineral species varying in colour is now confirmed by analysis. It is found to be a bronzite of the formula Mg%Fe+SiOs ;in association with it are distinct crystals of chromite. Rammelsberg who has recently published the results of his examination of this meteorite in Pogg. Ann. cxlii 275 finds in it a bronzite associated with 12 per cent. of olivine. It is probable that the meteorite varies in composition in different parts and that Rammelsberg analysed that portion in which an olivinous ingredient occurred in appreciable preponderance. On treating the mottled variety with hydrochloric and sulphuric acids it was noticed that the action was in each case confined to that of a solvent. W. F.

ISSN:0368-1769    

DOI:10.1039/JS8712400110

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

ORGANIC CHEMISTRY. Organic Chemistry. On Pyrene. By C.GRAEBE.~ LIEBERNANN and the author described some time ago a mix-ture of solid hydrocarbons derived from coal-tar and having a higher boiling point than anthracene. From this mixture a hydro-* Zeitschr. f. Chem. [Z],rii 22 from Deut. Chem. Ges. Ber. iii 738. VOL. XXIV. r 11s ABSTRACTS OF CHEMICAL PAPERS. carbon ascertained by Liebermann to be chrpene C,,H,, can be separated by sulphide of carbon in which it is nearly inso-luble. From the soluble portion the iiuthor has separated a hydro- carbon Cl6Hl0,which he calls yyi-ene. The sulphide of carbon having been distilled off the residue is repeatedly treated wit'h boiling alcohol used each time in quantity insufficient to dissolve the whole mass.In this way several crTstallisations of hydrocarbons are obtained the melting point of which varies hetween 80" and 160". After several cl*ystallisations from alcohol they are dissolved in boiling alcohol and treated with their own weight of picric acid in the same solvent. A quantity of ~cc7crystals at once separates which increases as the liquid cools. This is crystallised from alcohol ixntil the melting point of the hydrocarbon bccomes constant. The picric acid compound is then decomposed by ammonia whereby the pyrene is separated. It crystillises from alcohol in plates dissolves slightly in cold alcohol pretty freely in hot alcohol and very easily in benzol ether and sulphide of carbon. It fuses at 142",and like anthracene distils at a high temperature.Tts red crystalline compound with picric acid is very distinctive and is the only cornpound of a hydrocarbon with picric acid besides the corresponding one of naphtha,lene which is formed immediately on mixing together the alcoholic solutions saturated at the ordinary temperature of its two constituents. It is more stable than the anthracene compound. Pyrene is readily acted on by nitric xcicl even of sp. gr. 1.2 diluted with six times its volume ofwater being converted into nitropyrene. In solution in glacial acetic acid pyrene is but very slightly attacked when boiled with chromic acid. Heated with a mixture of potassium chromate and sulphuric acid diluted with an equal bulk of water it is converted into ppene-quinone. With bromine it yieldb two different derivatives accordingly as it is acted on in the dry state or in solution in sulphide of carbon in the first case giving dibyomojyrene dibyomide and in the second tribromopyrenc.Heated with hydriodic acid to 180"-200" in sealed tubes pyrene takes up hydrogen becoming CI6Hl2and CIsH,,. Concentrated sulphuric acid heated with pyrene converts it into a sulpho-acid . Pyrene-puinone CI6H8(O2)",is obtained as a red powder slightly soluble in alcohol ether benzol and sulphide of carbon pretty freely in hot acetic acid and very soluble in nitrobenzol. It sublimes in red needles but most of it is decomposed. It resembles chrysoquinone in appearance but is turned brown instead of blue by cold sulphuric acid. Powdered zinc reduces it to pyrene again; boiled with powdered zinc and dilute potash it dissolves with red coloiir and separates again on * exposure to the air.Ppene is different from Glaser's diacetenylphenyl E. D. ORGANIC CHEMISTRY. OILTetrn~lI~eiz?~I-efhz~le?-te, cc Defivative of Beiwoize. By ARNa BEH R.* THEauthor prepares benzone by distilling dry calcium benzoate wit7~-out addition of Eime and in this way obtains 40 per cent. of the theoretical amount. When benzone is heated to 180"in a sealed tube for 12 to 18 hours with excess of phosphorus pentachloride a chlo-rinated compound is formed in which the oxygen of the benzone is displaced by two atoms of chlorine (CGH,),CO + PCL = (CsH,),CCl + PC1,O. On attempting to distil the yellow liquid thus formed it is found that as soon as the phosphorus oxychloride has passed over the liquid begins to turn brown and evolve hydrochloric acid.The temperature rises rapidly to near the boiling-point of benzone whilst only a small quantity of chorinated oil distils ad the conteats of the i.eto3d become brown and pasty and carbonize when further heated. The author endeavoured to remove chlopides of phosphorus by means of water but without success and was therefore under the necessity of operating with a mixture of the chlorihated compouild pcith ben2one. The compound is extremely active at once attacking alcoholic ammonia dry ammonia silver acetate dissolved in glacial acetic acid and other substances. Finely divided silver obtained by peducing the freshly precipitated chloride with zinc completely depiives it of chlorine.The action requires to be moderated by cooling so that the temperature shall not rise above 200° as otherwise the compound is decomposed and hydrochloric acid set free. On distilling the product from a retort of hard glass benzone passes over first followed at a very high temperature by the hydrocarbon which solidifies in the neck of the retort. It dissolves very sparingly in alcohol and ether but easily in hot benzol from which it is deposited in pointed crystals as the solution cools. It is purified by precipitating the saturated benzol solution with a large quantity of alcohol and then forms a white crystalline powder. halyses of the body agree with the formula cZ6fI20. After having been melted together it melts at 221" (uncorr.).By the action of bromine it yields the compound C36H17Br6, and forms substitution-compounds with concentrated sulphuric and fuming nit& acids. -J. R. On Dibrom obenzene. by VI c ToR MXP ER.+ PUREcrptallised dibromobenzene methyl iodide and sodium were found to act upon one another only after standing for some hours and when the ice surrounding the flask had melted. The action then * Zeitsehr. t.Chem. [el vii 25. Zeitschr. f. Chem. [Z],rii 26. L2 ABSTRACTS OF CHEJlICAL PAPERS. proceeded quite quietly n large quantity of hydrocarbons being formed of which the greater portion boiled at 135-140". This body when oxidized with potassium chromate and sulphuric acid yielded terephthalic acid,which was found on careful examination to contain no trace of isophthalic acid.Moreover when a mixture of the hydro- carbons was oxidized completely by distilling off the portion unacted upon after every 8 or 10 hours' boiling and oxidising afresh the terephthalic acid formed in abundance was free from any trace of isophthalic acid. Hence the position of the bromine-atoms in crystal- lised dibromobenzene is 1 4. On a Sulphotolzcene derived from Bromosulphotoluene. By H. HUEBNER, and F. C. G. MUELLER.* INa former communication the authors have described a sulphobromo-toluolic acid the salts of which crystallise most beautifully and could therefore be obtained in a state of perfect purity. It was to be expected that by replacing the bromine with hydrogen a chemically pure sulpho- toluolic acid would be obtained,? To effect this sodium amalgam was added to an aqueous solution of the sodium salt.After six days all the bromine was present as sodium bromide from which the sodium salt of the new acid could not be separated by crystallisation as like all the other salts it is very soluble in water and alcohol. To isolate the acid the liquid was neutralized with sulphuric acid concentrated by evaporation and evaporated to dryness after separation of Glauber's salt; the residue was treated with phosphorus pentachloride ; and the chloride of the sulpho-acid after being well washed was heated with water in a sealed tube to 130" for some hours. The content of the tube were then boiled down in a flask until the temperature rose to llOo and thick fumes of hydrochloric acid escaped and a strong current of air was then blown through by which all the remaining hydrochloric acid was expelled.On cooling the sulpho-acid solidified to a brown crystalline mass. The salts of this acid are very soluble in water and alcohol whilst those of the brominated acid are much less soluble ; it is remarkable that the corresponding salts in the two series contain the same amount of water of crystallisation. The following were prepared :-(C613[1.CH3S03)2Ba + 2 aq. is an indistinctly crystalline powder. (c6H4.CH3s03)2,Ca does not crystallise from an aqueoua solution. When a concentrated alcoholic solution is heated the salt separates in small shining plates,which dissolve again on cooling.(C6H1. CH3S03)zPb * Zeitschr. f. Chem. [2] vii 14. t On acting upon toluene with sulphuric acid two isomeric sulpho-acids ape always formed the separation of which is difficult-C. S. ORGANIC CHEMISTRY. 121 -+ 2 aq. crystallises from the aqueous solution in thin plates which are grouped in rosettes. From a concentrated alcoholic solution it is pre- cipitated by addition of ether in small shining plates. From a solu-tion inabsolute alcohol it crystallises inlong needles. Cs&.CH3SO3Na + f aq. crystallises from absolute alcohol in large shining plates. C6H4.CH3S@3K + 4aq. is less soluble inabsolute alcohol than the other salts and crystallises from this solution in brilliant plates which resemble naphthalene and when formed very slowly are grouped together in beautiful rosettes .By acting on this last salt with phosphorus pentachloride the pure sulphochloride C&&.CHsS02C1 was obtained as a faint yellow trans- parent liquid having a penetrating smell. By treatment with tin and hydrochloric acid it was converted into the corresponding sulphydrate C6&. CH3SH a colourless and strongly refractive liquid which has a powerfid odour and is very caustic destroying the akin. It forms mercaptides with metals. Toluene bisui@hide (C6Ha.CH3)2S2, is obtained by boiling the sulphy- drate for some days with dilute nitric acid. It is a yellowish oil which boils with partial decomposition at about 150". By boiling the chloride with aqueous ammonia the amide C& CH,S02NH2is produced.To isolate it the liquid is evaporated to dryness and the residue exhausted with ether. From the boiling aqueous solution it separates in small feathery crystals ; once it was obtained in large plates. It is very readily soluble in alcohol ether and aqueous ammonia. The pure compound melts at 90-91". The authors believe that their acid is identical with the so-called metasulpho-toluolic acid which has been investigated by Barth Engelhardt and Latschinoff and by A. Wolkoa. They hope to settle this question definitively by further researches. c. s. On some Dewkativss of Isobutylic Alcohol. By K. REIMER.* THEisobutylic alcohol employed by the author was prepared from fusel-oil by Gamer and Pinner's process and boiled at 108".The butyl bromide obtained from it by the action of bromine and phosphorus boiled at 87"-88". The bromide heated to 150" with alcoholic am- monia yielded the three butylamines which were difficult to separate. After approximate separation of the three bodies by fractional distilla- tion the portion having the lowest boiling-point when mixed with ethyl-oxalate yielded at once the crystalline and easily purified dibzi-tylommide C202N(CaH,),NH, fromwhich monobuty lamine C4H,.H2N boiling at 62"-65" (70°,Wurtz) was obtained by boiling with potas- sium hydrate. The portion of the crude butyl-bases boiling between * Zeitsclir. f. Chem. [2] Tii 26 from Deut. Chem. Ges. Ber. iii '756. 122 ABSTRACTS OF CHEfilICfi PAPERS.110"and 130' was digested for some days with ethyl oxalate and thus Jrielded eth2/kd-ibzctyZoxamate C,02.N(CaHg)s.0C2H5, which gave clihzc-tglamine (C4H,),HN,boiling at 120"-122" when boiled with potas- &urn hydrate. The fraction of the butyl-bases having the highest boiling-point was digested with butyl bromide until the base liberated by soda-ley boiled between 177" and 180". The product consisted almost entirely of tribzitylainiize (CiHg),N. All these amines yield exceedingly beautiful platinum-salts. It is remarkable that all attempts to prepare a tetrabutylammonium-compound have failed. Tributylamine beated with butyl bromide under pressure yields tri-butylamine hydrobromate and butylene. ButyZ suZphocyanate CS.NCaH,,obtained from butylamine boils at 161"-163" and forms with ammonia a fine crystalline sulphuretted urea (CS)(CaHS)H3N2 melting at 90"-91".The isomeric sulphocyanate obtained by the action of butyl sulphate on potassium sulphocyamte boils at 174"-176". Butylamine is likewise formed on heating salts of butylsulpburio acid with ammonia 2C4HJCSOa + 4H3N = &SO* + (&N)$O4 + 2CaHl1N. The yield however falls far short of the theoretical amount and the reaction cannot be recommended for the prepairation of butylamine. J. R. On Some transformations of Phmol. By L. BARTIT.* PHENOL is easily attacked by fused caustic potash hydrogen being abundantly evolved. The hsion has to be stopped as soon as the mass assumes the consistence of a syrup. It contains now besides non-attacked phenol salicylic acid and oxybenzoic acid a new compound C12H1002, which the author calls diphenol.To isolate this body the fused mass is dissolved in water an excess of sulphuric acid is added and the liquid is shaken up with ether which dissolves all the products formed. The acids are removed by shaking the solution with aqueous ammonium carbonate and after evaporating the ether the residue is subjected to fractional distillation to separate the phenol from diphenol which boils at 340"-350". By dissolving it in a solution of sodium carbonate again exhausting with ether and distilling it is obtained pure. It is a very viscous oily liquid which after standing for some tilse deposits crystals. It has a faint aromatic odour; water disgolves a small quantity; the solution gives a blue colorrttion with fe;r$c chloride.It is soluble ia alcohol ether caustic potash and less in ammonia. It ig acted upm bF nitric mid sulphuric acid and pbsspbrorw pentachloride ; the produots thus formed were not obtained in the pure state. * Zeilschr. f. Chein [2],Tii 18 from Am Ch Phanli. ch 9. ORGANIC CHEXISTRY. 123 By heating it with caustic potash and methyl iodidc in presence of alcohol to 120"-130" dia&oZ CIIHlaO,was formed which was extracted from the products of the reaction with ether. It is a rather mobile liquid boiling between 310"-320" and having an aromatic odour. On standing a crystalline powder separates out from it consisting of microscopic octohedrons which melt at 146".They have the same com-position as dianisol and are either the pure compound or an isomeride. The liquid dianisol gives with bromine an amorphous substitution- product and with nitric acid an indistinctly crystalline nitro-compound ; the crystallised dianisol yields also an amorphous bromine-compound but the nitro-compound crystsllises in densely interwoven needles. The author in all his experiments recovered a little more than one-half of the phenol; of diphenol he obtained 12-15 per cent. and of the acids scarcely 1 per cent. He has convinced himself that all these products are really derived from phenol and not from an admixture by using the non-attacked phenol over and over again and by employing pure phenol obtained by distilling oxybenzoic acid with caustic lime.The author believes that the constitution of diphenol is expressed by the formula { ~ ~ ~ ' Each molecule $~* of phenol loses one atom of hydrogen and the two monad groups thus formed combine with each other. The formatiom of the two isomeric acids he explains by assuming that a phenol-residue C6H40H,unites with COOH resulting from the more complete oxidation of snothelv molecule of phenol. c. s. Of&the Actiou of Pheuol 012 Anzmo&LL. By 11. BEETHELOT.+ E RT H E L 0T on putting the reaction C6H60+ NH = C6H7N+ Hzo to the test by heating phenol which was saturated with gaseous am- monia when in the fused state to 280" for 24 hours obtained but a mere trace of aniline using a solution of chloride of lime as a test.Heating to 360" did not increase the quantity of aniline to any appreciable extent. Phenol heated for several hours to 360" ~ith ammonium chloride or iodide gave no trace of aniline. C'onversely aniline gave no trace of phenol when heated for 20 1iourb with 10 parts of water to 310'. W. €1. D. On Pheiaylic Ether and Diplmzylerw Oxide. By W. HOF~~IEISTER.~~ ha already stated in a preliminary notice a mixture of phenol and diazobenzene-sulphuric acid evolves nitrogen even in the cold and more freely when gently warmed; and a thick oily liquid is formed which contains a body having an aromatic odour. On treating the * Ann. Ch. Pharm. clvii 109. t Zeitschr. f. Chem. [2] vii 24 frofii Deut. Cheiu. Ges. Ber. iii 747. ABSTRACTS OF CHEMICAL PAPERS.mixture with excess of soda-ley and distilling the portion insoluble therein from a retort in a current of steam there passes over a pale- yellow oil which sinks in water and when purified by repeated recti- fication solidifies completely in a cooling niixture to a mass of colour-less long needles. The analysis of this body agrees exactly witb the composition of phenylic ether CsH,N,HSO$ + CGHSOH = (C6H5),O + SHzOr + Nz. Phenylic ether forms a colourless solid mass having an agreeable aromatic odour. It melts at 28" and boils at 248". The slightest admixture of a foreign compound prevents its solidifying. It is in-soluble in water but mixes with ether in all proportions. It is not affected by distillation with phosphorus pentachloride but is attacked by a mixture of the pentachloride and oxychloride when heated to 220" in a sealed tube for 10 hours.On opening the tube hydrochloric acid escapes and on distillation there pass over first a large quantity of phosphorus trichloride followed by the oxychloricie added and lastly at 260-280" a colourless chlorinated oil. Monocldorobenzene is not formed in this reaction. Phenylic ether is not reduced when its vapour is passed over zinc-filings heated in a combustion-tube. It is not attacked by hydriodic acid when heated therewith to 250" for 10 hours nor by prolonged heating with n mixture of chromic acid and glacial acetic acid. Pheizyloxide-clisulp23uricacid. Concentrated sulphuric acid does not act upon phenylic ether in the cold but when warmed in the water- bath gradually dissolves it ancl on diluting the product with water a perfectly clear solution is obtained.The barium-salt prepared in the usual manner crystallises from its solution in small warty masses ; when purified by recrystallisation it has the composition C~,HBO(SOs),Ba. It dissolves easily in water alcohol and ether. The free acid was obtained by decomposing the lead-salt with hydrogen sulphide and concentrating as a syrupy liquid which after standing for some time in a desiccator deposited tolerably large hard colourless deliquescent crystals easily soluble in alcohol but insoluble in ether. Di$henylene Ora'de.-The author further examined the phenylic ether described by Lesimple (Aim.Ch. P7zarnz. 138,375). This body crystal- lises readily from alc'ohol in fine colourless laminte having an agreeable aromatic odour and the composition C,,H80.These crystals agreed perfectly in external characters and in melting-point with the body described by Lesimple. The compound is not acted upon when its vapour is passed over red-hot zinc filings. It is attacked by phosphorus pentachloride at 220" in a sealed tube a chloi-inated body being formed which cyystallises from alcohol and melts at 92". J. R. ORGANIC CHE1\IISTRY. O~L the Actiwt of Siclphuric Acid OYL Orgnitic CI)loricles contniiLiiig 0:cygew. By A. OPPENHEIM.* (1.) nlosaochlo?.72ycll.i?t of GZyco7 C2H4.0H.C1 behaves just like ethyl chloride C2H5Cl evolving hydrochloric acid and forming the acid C2H4.0H.S04H already obtained from glycol and sulphuric acid and described under the name of sulphoglycollic acid by Maxwell Simpson.(2.) Epichlorhyd~i~a,C3H5C10 unites with sulphuric acid to form a thick oil CH20H.CHSOaH.CHzC1 much heat being pro-duced ;potash removes the sulphuric acid from it. (3.) Bmtzoyl chloride is acted on much more energetically by sulphuric acid than by water hydrochloric acid escaping in torrents without the mixture becoming sensibly warm. When an excess of sulphuric acid is used the new compound crystallises out in prisms. As soon as it is brought in contact with water much benzoic acid separates. The crystals placed on a porous tile in a vacuum become opaque amorphous and com-pletely soluble in water without separation of benzoic acid.By adding the sulphuric acid to an excess of benzoyl chloride heating and distil- ling off the excess in a current of carbonic acid a fused hard hygro- scopic mass remains which like the preceding product is completely soluble in water and consists of sulphohenzoic acid which in this way can be easily obtained and in large quantity. (4.)AcetyZ chZoride gives with sulphuric acid only hydrochloric and acetic acids. (5.) Ch7oropht72aZic acid gives with two molecules of sulphuric acid an oily body which by distillation yields at 280" a rapidly solidifying crystalline mass breaking up with water into sulphuric and phthalic acids. (6. ) Moiaochloy-and tyichior-acetic acids may be boiled with sulpharic acid without saffering any change.E. D. On the Acids obtuined by the OaidatioIt of Feriitentntioit Butylz'c Alcolzol. By E. ERLEN1IEYEX.j" THE oxidising action exerted on fermentation butylic alcohol by potassium chromate and sulphuric acid appears to take place in two stages. In one case where heat mas not applied isobutyric acid was the result. By heating the mixture the isobutyric acid can be made to break up completely into carbon dioxide and acetic acid. In a quantitative experiment 98.4 parts C02 were obtained per 100 parts isobutyric acid; in another case 100.4 C02. The equation C4H80 + o6= 2C02 + 2H20 + C2H402 requires 100 GO2 per 100 parts iso-butpic acid. Normal butyric acid according to Veiel does not yield acids of the series containing less carbon than itself W. H.D. -Zeitschr. f. Chem. [Z],vii 21 from Deut. Chem. Ges. Ber. iii 735. t 3.Repert. Pharm. xs 86. 126 ABSTRACTS OF CHEJIICAL PBPERS. & the O&dcction of Isobzctyric Acid. By A. POPOFF." THEobservations of Chapman Morkownikoff and Buttlerow on the oxidation of some oxy-acids and the hypotheses to which they have given rise lead to the conclusion that in such oxidations the carbon atoms first attacked are those which are already partly combined with oxygen. For example-RRH \I/ RR C + 0,= + GOa + H,O. COZH co Now there exist iso-acids (properly para-iso-acids) of the fatty series possessing a constitution exactly analogous to that of the oxy-acids but containing hydrogen in the place of hydroxyl. It was to be expected that these bodies would behave towards oxidising agents in the same way as the oxy-acids.The correctness of this supposition has been codkned by experiment in the case of isobzctyic acid. Isobutyric acid prepared by $1or ko wnikof f's process is scarcely attacked by a mixture of potassium dichromate and dilute sulphuric acid a very small quantity of carbon dioxide being formed after boiling for 24 hours. But when excess of isobutyric acid is heated to 140"-150" with an aqueous solution of chromic acid for 18 or 20 hours a quantity of carbon dioxide escapes on opening the tube after cooling. On submitting the contents of the tube to distillation and neutralising the distillate with potash to remove free isobutyric acid and the acetic acid which might possibly be formed an oily layer is obtained which boils at 55"-60" and possesses all the properties of cccetone.Hence we have- CH,CH,H CH3CH.j \I/ c + 0 = + CO? + H,O. COzH co It is to be assumed therefore that all iso-acids of t'he above form yield by oxidation the corresponding ketones the carbon-atom which is in combination with carboxyl and with the smallest quantity of hydrogen being first attacked. J. R. On the &fe?.ertt Valerie Acids. By E. E RLE h IIIE YE R.+ Ix connection with this subject the author calls in question the value of the behaviour of a body towards polarisecl light in determining 6 Zeitschr. f. Chem. [2] vii 4. t N.Repert. Pharin. xx 88. ORGANIC CHEMISTRY. chemical identity. He considers it possible that in liquids as in solids chemically identical molecules may act on polarised light when they are arranged in smaller or larger groups but may produce no effect when they exist as single molecules.His experiments with different valeric acids may be thus summed up :-(1.) Valerie acid from valerian root is optically inactive and chemi- callyidentical with the acid from inactive amylic alcohol and that from isobutyl cyanide. The three acids give the same barium salt which is easily crystallisable. (2,) The acid from active amyl alcohol and that obtained by oxidising leucine (prepared from albuminous substances) are optically active and have a somewhat higher specific gravity and lower boiling point than the inactive acid ; their barium salt dries up to an amorphous glass.(3.) The optically active acid when heated with some drops of sul-phuric acid to 200" is converted with partial carbonisation into an acid which optically is quite inactive but which possesses the other properties of the active acid its barium salt also drying up to an amor- phous glass. From his experiments Erlenmeyer infers that the active acid differs in constitution from the inactive acid; he thinks it will prove to be trimethyl-acetic acid 01%methj1-ethyl-acetic acid. W. H. D. Om the action of Ammoilia upon a-Chloqwopionic and P-Iodopropionic acid. By W. HEINTZ.* WHENn-chlorpropionic acid is boiled with aqueous ammonia a large quantity of lactic acid is formed besides alanine. Alcoholic ammonia acts very slowly upon a-chlorpropionic acid ; to accelerate the reac- tion a little strong aqueous ammonia was added.Besides alaiaine and ethyl-lactic acid a certain quantity of lactic acid mas obtained probably formed by the presence of the water. CaZcium ethyZ-lactate dried in the air has the composition (C5H903)2Ca+ 2H20; the salt which was analysed by Wurtz had been dried at 100". When a-chlorpropioiiic acid is heated with alcohol a-chlorpro- pionic ether is formed but no ethyl-lactic acid. By treating 6-iodopropionic acid with ammonia an isomeride of alanine which the author calls ethylene-Zactamic acid and etlzylene-dizactamic (diparalactamic acid) are formed.? The latter compound corresponds to diglycollamic acid. * Zeitschp. f. Chem. [Z],vii 19 from Ann.Ch. Phaym. chi 25. .t. This compound mould be better called paralactantic or /3-amidopropionicacid -42. s. 128 ABSTRACTS OF CHEMICAL PAPERS. To effect the separation of the two acids the solution was repeatedly boiled down with lead oxide as long as ammonia was given off. On exhausting the residue with water basic lead iodide was left behind ; from the solution a lead salt of dilactamic acid was precipitated in colourless needles by addition of alcohol. This salt was dissolved in water and converted into acid dilnctnnznte of Zeud by passing carbonic acid through the solution. This last salt crystallises from a hot alco- holic solution in very small and thin plates. A better method of separation is to conrert the two acids into the silver-salts.To effect this the iodine and ammonia are removed as described and the lead is precipitated from the solution by sulphuretted hydrogen. By adding silver-oxide to the filtrate as long as silver dilactamide is formed-a salt which is almost insoluble in water-and passing sulphuretted hydrogen through the filtrate a solution of ethylene-lactamic acid is obtained. This solution when evaporated leaves the acid as a syrupy liquid which by agitation with ether and repeated boiling of the residue with alcohol is converted into a solid mass. The acid is readily soluble in water but nearly insoluble in absolute alcohol. It crystallises in transparent prisms belonging probably to the monoclinic system. On heating it to 170" it turns brown and sublimes very slowly in feathery needles ; at a higher tem- perature it is completely decomposed leaving a very difficultly combusti- ble charcoal.It has zU sweetish taste; the faint acid reaction of its concentrated solution is probably due to the presence of a little d&c- tanlic acid. It combines with bases as well as with acids. The copper salt (C,H,NOz)zCu + 5H20 which is much more soluble in water thax the corresponding alanine compound crystallises in large dark-blue rhombic prisms. With silver-nitrate the acid forms the compound C,H,NOZ.AgNO3, in colonrless needles which deflagrate on heating. Dilncfa?nic mid C,H,,NOI which was obtained by decomposing the lead or silver-salt with sulphuretted hydrogen remains on evaporation as a thick colourless syrup gradually solidifying on standing to a radiate crystalline mass.Once by adding a particle of the solid acid to a concentrated solution the author obtained distinct crystals Con- sisting of shining plates or flat needles. If to the solution saturated with ammonia, silver-nitrate is added a precipitate of silver dilactcr,?nnte C6HSNOdAgz is obtained. On adding more silver-nitrate to the filtrate whilst warm the compound CsH,oNzO,Agz + 1iHZO separates on cooling in colourless crystals. When ammonia is added to its solution silver dilactamate is precipitated. The author did not succeed in obtaining corresponding lead and copper salts; neither was he able to prepare a crystalked nitrate of this acid. By using alcoholic ammonia the sane compounds were formed as ivith aqnecm m-mioiiia.__-c. 8. On wine Pmclucfs obtnirml fro!n Asp& Acid. By E UC:E :;I S c H A AL.+ INACTIVE aspartic acid has been obtained artificially from the ammonium salts of malic malcic and fumaric acids ; but this acid has not yet been transformed into asparagine. To effect this the author prepared the acid silver salt of aspartic acid (which be obtained from asparagine) and heated it gently in the water-bath with ethyl iodide and a little alcohol. A reaction set rapidly in iodide of silver and monethyl aspartate being formed. The latter compound is a crystalline substance which after evaporating the alcohol and excess of ethyl iodide was dissolved out with ether. When this monethyl compound C,H { NH is treated with ::::H strong aqueous ammonia it is easily converted into asparagine pos- sessing all the properties of the natural product.When dry hydrochloric acid gas is passed over asparagine for three days and the temperature is gradually raised to 180° a white hard mass is formed. The same product is obtained by boiling asparagine with strong hydrochloric acid and heating the dried mass in a current of carbon dioxide first to 120" and afterwards to 200". The body thus obtained is a mixture of two compounds ; one which is sparingly soluble in cold water can be extracted by boiling water ; it has the composition C1,HI4N4O,,and is formed according to the equation-4C4HTNOA = C,&€JT40 + ?H,O. The residue insolnble in water is CaH2,N,Oli formed according to the equation-SC,H,XO = C&f3Z,NgO, + 15H20.Both the soluble and the insolnble compound take up water when boiled with ammonia or baryta-water and are converted into iizactke aspartic acid. c. s. On the Sulpho-acids of O?.thobl.oi.lzotol.e~~e. By E. WROBLEVS KY.? ITwas shown in a former paper (Zeitschr. vi 329) that in the action of bromine on orthobromotoluene the substituted bromine does 7zof * Ann. Ch. Pharm. clvii 24. .5 Zeitschr. f. Chem. [2],vii 6. ABSTRACTS OF CHEMICAL PAPERS. occupy the pam-position and it became of interest to ascertain which position would be occupied by other bodies in orthobromotoluene. With this object the author has investigated its behaviour with fuming sulphuric acid.The fuming acid must be added gradually to the bromotoluene the mixture being kept cool at first and the combination finally aided by warmmg in a water-bath. On saturating the product with baryta, three barium salts (a p y) separable with tolerable facility by fractional crystallisation are obtained. The &salt is most abundant the u-salt less so (about 25 per cent.) while the proportion of y-salt is very small (3 per cent .). The a-barium- salt (C7H6BrS03)zBa+ H,O crgstallises in small prisms. 1,000 parts of water at 19" dissolve 5.28 parts of the salt. The n-potassiunz-salt crystallises in fine prisms. When melted with potassium hydrate it evolves a large quantity of hydrogen the fused mass readily yields a considerable quantity of salicylic acid melting at 155".Hence this acid is orthobromotoluerLe-metas~lp~ur~c acid. The barium-salt of the @-acid (C7H6BrS03)%Ba +3Hzo crystallises in fine shining laminae. 1,000 parts of water at 190" dissolve 14.52 parts of the salt. The 6-Zead-sdt (C7H6BrS03)2Pb + 3H20 and the 6-calcium-salt (C7H6BrS03)2Ca+ 5Hz0,form large prismatic crystals. The 6-potassium-salt crystallises in large shining lamina. When fused with potassium hydrate this salt likewise yields a considerable quantity of saZicylic acid ; consequently this acid is also an orthobrornotoluene-metnszclphuric acid. The barium salt of the y-acid (C7H6BrS03)zBa+5Hz0,crystallises in needles. 1,000 parts of water at 19" dissolve 32.48 parts of the salt. A8 this acid is formed in very small proportion only but little of it could be converted into potassium-salt and fused with potassium hydrate.The very small quantity of oxy-acid thus obtained did not colour ferric chloride and was therefore oxybenzoic or paraoxy-benzoic acip. A nitro-compound of p-orthob.1.omotoluene-metasu~huric acid is readily obtained by the action of nitric acid on the &acid. One nitro-acid only appears to be formed. The bn~iurnz-salt [C7H5Br(NOz)S03],Ba + 7Hz0 crystallises in needles soluble in water. The lead-salt [C7H5Br(N02) X0,)d'b + 3Hz0 forms fine prismatic crystals easily soluble in boiling water. The caZcium-saZt [C7H,Br(NO2) SO3I2Ca + 9Hz0 crystallises from alcohol in large prisms very easily soluble in alcohol and water.J R. ORGANIC CHEMISTRY. On Szclpliobe~axoicAcid. By ADOR and OPPENHKIM.* THEauthors point out t,hat the barium salt of the sulphobenzoic acid described by Carius and Kammerer (Ann. Ch. Phai-m. cxxxi 153) readily shows supersaturation and does not differ in solubility from the salt previously investigated by Be hling. The sulphobenzoic acid from benzoyl chloride and sulphuric acid gives like the ordinary sulphobenzoic acid when fused with sodium forniate isophthalic acid (melting point 275") and with potash oxybenzoic acid (melting point 182"). W. H. D. On StcJphosndek Acid. By R.MEs s E L.? FUMARIC acid combines directly with neutral potassium sulphite forming acid the potassium salt of szcZphof~~~~Cc (B. Credner),$ and ac-cording to Messel its isomeride iiialeic acid behaves similarly.On heat- ing maleic acid for eome hours with a solution of potassium sulphite in a retort connected with an upright condenser and then allowitlg the liquid to stand large colourless crystals were obtained which gave on analysis numbers agreeing with the formula C4H4K2S07+ 2 aq. The neutral potassium salt C4H3K,SO7 + aq. is prepared by neutralising a solution of the above salt with potassium carbonate. On adding lead acetate to a solution of the acid salt a yellowish-white heavy precipitate is thrown down which becomes crystalline on boiling. On decomposing this with hydrogen sulphide an acid potassium salt of the formula CJ&KS07 is obtained. The neutral lead-salt may be prepared from this last-named salt by precipitation with lead acetate.On the addition of a barium salt to a solution of any of the above the neutral barium salt is precipitated as a white powder. By the action of calcium car- bonate on sulphomaleic acid a non-crystalline calcium salt probably of the composition C4H4CaS07 is obtained and this by neutralization with calcium hydrate yields the neutral salt. The silver salt C4H3Ag,S07is prepared from the acid potassium salt containing only 1at. potassium by neutralizing with ammonia and precipitating with silver-nitrate ; it is a heavy precipitate slightly soluble in cold readily soluble in hot water. The free acid is obtained by decomposing the ailver-salt with hydrogen sulphide. On heating sulphomaleic acid or its salts to fusion with potassium hydrate it is decomposed into ficmaric acid and sulphite.Messel has also examined for the purpose of comparison the barium calcium and silver-salts of suZphosucciwic acid prepared by Fehling's method and finds them in all respeds identical with those of sdpho-* Zeitschr. f. Chem. [Z] vii 22 from Dent. Chem. Ges. Ber. 1870 '738. I. Ann. Ch. Pharm. clvii 15. 5 Inaugural-Dissertation ; Tiibingen 1869. ABSTRACTS OF CHEMICAL PAPERS. nialeic acid. Sulphosucciiiic acid also yields fuinnric acid on fusion with potassium hydi-ate but this is perhaps not a primary product of decomposition but results from the malic acid first formed. From the absolute identity of the silver-salts he concludes that the three acids sulphofumaric sulphomaleic and sulphosuccinic are identical and not isomeric and are represented by the constitutional formula COOH-CH~-CHSO~OH-COOH.H. E. A. THEauthor says it appears that the non-saturated carbon-compounds in which two carbon atoms are connected by two combining powers,? unite directly with the alkaline biszckhites. He investigated the sulpho- acids obtained by this reaction from the three isomeric bodies itaconic mesucoi& and citracolzic acids. The result of this somewhat incomplete research is that the three r CO.OH isomeric acids yield one and the same snlpho-acid C,H SO,H ,which CO.C)H he calls sulpho-pydurtaric acid as he does not doubt that the same body will be obtained by the action of fuming sulphuric acid upon pyrotartaric acid.To prepare the acid he boiled a moderately concentrated solution containing one of these acids and neutml potassium sulphite in a retort connected with a reversed condenser for four to five hours. The potassium-salt of the new acid thus obtained is an amorphous mass. The barium- and lead-salts are slimy precipitates which are most difficult to wash. The only salt which was obtained in a pure state and analysed was the calcium-salt a crystalline precipitate obtained by adding calcium chloride to a solution of the potassium-salt ; it is moderately soluble in boiling water and can easily be obtained pure by recrystallisation. Dried in the air it has the composition (C5H10S207)2Ch + 7H20; at 100" the salt loses 5 molecules of water another at 160" and the last at 180"; above 190" it begins to decompose.To obtain the free acid &om this salt oxalic acid cannot be used as it does not produce complete decomposition ; it was therefore treated with sulphuric acid and dilute alcohol. On evaporating the alcoholic * Ann.Ch.Pharm. clvii 34. + The termnon-saturated implies that these compounds contain carbon-atoms with free combining powers. Most clicmists however are now of opinion that in these compounds two carbon-atoms are linked together by more than one unit of corn-bining capacity. Kekul6 calls such bodies "Wasserstoffarmere Verbindungen." It woiild be desirable to have an eqiiivaleij t English term .-C. S. ORGANIC CHEMISTRY. solution the acid remained in indistinct crystals.It is very soluble in water; the small quantity produced prevented the author from obtaining it free from sulphuric acid and the acid calcium salt. The acid potassium and ammonium salts form warty crystals readily soluble in water. The neutral potassium salt is not precipitated by iron copper mercury or zinc salts. On boiling the potassium salt with a little water and an excess of caustic potash down to a crumbling mass potassium sulphite and the potassium salt of a new acid are formed by replacement of the monad group SOsH,by hydroxyl. To obtain the free acid the fused mass was decomposed by dilute sulphuric acid ; the solution concentrated by evapomtion and the residue shaken with alcohol ; the alcoholic solu- tion boiled down ; the residue treated with barium carbonate ; and the barium salt thus obtained which is very soluble in water was decom-posed by sulphuric acid.The acid forms small hard crystals readily soluble in water sparingly in alcohol and ether. The silver-salt contains 59.5 per cent. of silver COOAg which agrees with the formula C3H5 OH . { COOAg The acid has the composition and all the properties of ozypyrotartaric acid which Maxwell Simpson obtained by the action of caustic potash upon dicyanhydrin CsH5 OH. The author leaves it however, { : undecided whether those two bodies are identical or not as he did not determine the melting-point of his acid. Simpson's acid melts at 133". c. s. Actiom of Bromine on Acetic Aldehyde. By W.HAARMANN." BYthe regulated action of bromine on aldehyde a compound is formed which crystallises in long needles soluble in ether alcohol and water. This body possesses a penetrating tear-exciting odour and exhibits the composition of dibromaldehyde C2H2Br20. It instantly reduces silver-nitrate to the metallic state. The above formula is further sup- ported by the fact that under slightly altered conditions bromine acting on aldehyde produces dibromacetic acid. J. R. Action of Cyank Acid O?L Acrolein. By F.MELMS.~ ACROLEIN absorbs cyanic acid with avidity the same phenomena being observed as in the corresponding experiment with acetic aldehyde On * Zeitschr. f. Chem. [Z] vii 27,from Deut. Chem. Gee. Ber. iii 768. t Zeitschr. f Chem. [2] vii 27 from Deut.Chem Gee. Ber. iii 759. VOL. XXIT'. w ABSTRACTS OF CHEMICAL PAPERS. treating the product of the action with hot hydrochloric acid the trigenic- acid of the ally1 series crystalliscs from the liquid as it cools in colourless needles which dissolve with some difficulty in water. The ammonium-salt of the acid gives a white amorphous precipitate with silver-ni hate. J. R. Cfo~zvwsionof Chloral into Aldehyde by i;!ccmc Xzcbstitution. By J. PE?LSONXE.~ THEauthor obtained aldehyde by adding zinc to a solution of chloral hydrate acidulated with hydrochloric or sulphuric acid In an experi- ment in which the action was moderated by adding the acid gradually and in small quantities only to the zino and chloral sufficient aldehyde was obtained to prepare the ammonia compound and render its identity certain.At the same time polymers of aldehyde are formed in par- ticular paraldehyde. By passing ammonia gas into a well cooled vessel containing small quantities of anhydrous chloral trichloraldehyde-ammonia C,HCl30.NH3 is obtained very similar in its properties to aldehyde- ammonia. When ammonia is passed not so slowly into quantities of chloral greater than 2 or 3 grms. the liquid even when well cooled becomes heated and besides the trichloraldehyde-ammonia chloroform and formamide C&NO are produced owing to secondary reaction thus C2HC1,O + NH3 = CHCl3 + CR3NO. W. H. D. The Quality of Chloral Hydrate. By 13. H. PAUL.? THISpaper contains the results of an examination of several commercial preparations of chloral.Twelve samples from various sources repre- senting the chloral hydrate now supplied in the market were analysed by heating with ammonia in tubes to about 40" C. for three or four hours. The volume of the chloroform produced by the action of the alkali is measured and the percentage by weight obtained by calculn- tion 1.497 being taken as the sp. gr. of chloroform. The following are the results obtained :-* Ann. Ch.Pharm. clvii 113. .F Pharm. Joiirii. Trans. [3] i 621. ORGANIC CHEMISTRY I35 No. of Sample. 1 White amorphous dry lumps .......................... 2 Hard transparent fragments of crystals .................. 3 TlLin translucent crplalline cake ........................4 Wl&c opaque cake appaiwitly not quite d~y eapccially at one surface.. ...................................... 5 Very small cl.yrstals aggrcgated into trn1ducci1t IuI~I~ ~5 it11 a slightly moist appearance.. ........................ 6 White semitranslucent cnke with sliglitly moi -t zppearnnce .t Translucent crystalline cake consisting of small scals ciystdq moist and greasy to the tonch.. ...................... 8 Large tabular crystals like chlorate of potash ............ 9 Translucent lumps consisting of scaly crystals -lightly m0i.t to the touch ...................................... 10 Small acicular crystals apparently breaking up into ecnles when rubbed in the hand slightly nioisl to the touc.11.. .. 11 White opaque lumps resembling efliorescecl earboixte or ammonia xith dibtiiict crystalline fimture h~zn 1 t .IIIC~ at the interior and greasy to the touch................ 12 Chloral alcoholate .................................... Pure chloral alcoholate ................................ Pure chloral hydrate .................................. Two other samples examined by Dr. Versmaim had the following properties :-I I Crystals ...... Boiling point = 96” to 97’ C.. Pcint of re-solidification =49’C. 9’1 -4 Cake ........ Sp. gr. at 49” C. = 1.61...... Both samples are pure chloral hydrate which have by exposure attrzcted some moisture. The absence of alcohol was proved by the non-forma-tion of iodoforrn after decomposition by ammonia and separztion of chloroform.Dr. Paul rcgmds as the pu.tc,~fcim of chloyii hyclmic tht which presents commonly the appearsiice of ordinary alum broken into fmg-rnents about the size of grains of paradise the fragments being perkily transparent free from powdcr only slightly odorous dry to the hand and not becoming moist by exposure. The definite necdle-r,liq~cd crystals like ammonium oxalate soivetiiiies met with are he l~licvcs. characteristic of the alcoholate. V. IT.D. LIBSTRACTS OF CHEMICAL PAPERS. Actio?t of Ch,Zor*i?ieon IIyrli.ocynnic Acid i.n Alcoholic Xolution. By C. BISCHOFF.~ TIIF:author found that when chlorine acts upon mercuric cyanide the compound C8HIiC1,N20a as observed by Stenhouse is invariably pro- duced but when an alcoholic-mlution of hydrocyanic acid is employed a compound having the €ormrtla C,H1,C1N2O4 is formed in most cases.The properties of the new body closely resemble those of the compound already known. It crystallises in white silky needles which are dis- tinctly softer than the crystals of Stenhouse's body. Its melting point is 147". The compouiid dissolves easily in ether and alcohol and also in warm nitric acid from which it is precipitated by water. It is insoluble in hydrochloric acid. Sulphuric acid dissolves it with evolution of lieat forming a yellow solution. When this solution is heated the compound is broken up alcohol and carbon dioxide being eliminated with simultaneous formation of ammonium sulphate and sulphur dioxide. Soda-ley and baryta-water likewise resolve the body into alcohol carbon dioxide and ammonia.When heated with hydro-chloric acid in sealed tubes it yields carbon dioxide ethyl chloride and ammonium chloride. All these decompositions are accompanied by partial carbonisation. By the action of alcoholic ammonia a viscid ~ellomish-brown base is formccl which absorbs carbon dioxide from the air ;its composition of which has not yet been determined. J. R. 01~u New Class of Cyanic Ethers. By A. W. HOFMANN.~ AN examination of the body obtained by the action of phosphorus-bases on phenyl cyanate has shown that it is not identical with either phenyl cyanuratc or phenyl isocyanurate. The cyanurate obtained €rom triphenylmelamine melts at 260" ; the isocyanurate derived from phenol melts at 224' ; whilst the melting-point of the new compound is 175".This body differs also in its other properties from the cyanmates previously known. Similar reactions to that occurring with phenyl cyanate take place under the same conditions with methyl and ethyl cyanates. Ethyl cyanate is converted slowly at ordinary temperatures more rapidly at the temperature of boiling water under pressure into a viscid liquid which afterwards solidifies to a crys- talline mass. Methyl cyanate placed in contact with a drop of tri-ethylphosphine is inshntly converted into a crystalline mass with considerable evolution of heat. The body obtained from ethyl cyanate melts at 95" and is probably identical with the ethyl cyanurate already >k Zeitschr. f. Cliein.[Z] vii 27 from Deut. Chem. Ges. Ber. iii '160. t Zcitqrlir f. Clicm. C21 Tii 29 from Dent. Chm. Gcs. Ber iii 765. ORGANIC CHEMISTRY. 137 known. The melting point of ordinary methyl cyanurate is 175"; that of methyl isocyanurate is 132";the new compound melts at 98'. Phenyl cyanate. New compound. Phenzl cyanurate. On a New Mode of forming Isonitriles. By A. W. HOFMANN.~ ALLYL sulphocyanate and 7 molecule of triethylphosphine yield as is known a urea containing both nitrogen and phosphorus. This body when heated is resolved into triethylphosphine sulphide a,nd the isonitrile of the ally1 series [CS.C3H,.(CJ3,)3]NP = (C,Hj),PS + C3Hj.CN. The sulphocyanates of methyl ethyl and amyl behave in exactly the same manner. On mixing together the phosphorus-base and the sulpho- cyanate a rise of temperature takes place and the odour disappears evidently owing to the formation of a compound analogous to the urea mentioned above.When the mixture is further heated under pi*essure magnificent crystals of triethylphosphine sulphide are deposited on cooling whilst at the same time the pungent odouy of the isonitrile of the series reveals itself. J. R. On a reaction of Chloyoform. By A. W. HOFSIBRN.? TOdetect small quantities of chloroform especially in presence of ethereal compounds closely allied to it and possessing siiiiilar pro-perties advantage may be taken of its behaviour with the mona-mines in presence of alcohol and sodium hydrate. The odour of isonitriles thereby produced is an infallible sign of the presence of chloroform.The experiment is performed by adding the liquid to be tested to a mixture of aniline-any other primary monamine fatty or aromatic serves equally well-and alcoholic soda. If chloroform is present a violent reaction takes place either immediately or on warm-ing gently and the peculiar-smelling vapour of the isonitrile is evolved. Bromoforrn and iodoform of course behave like chloroform thc reaction occurs moreover with all bodies capable of yielding chloro- form bromoform or iodoform by the action of alkalis. For example on adding a solution of chloral in aniline to alcoholic potash the %eitsclir. f. Chem. [2],vii 29 from Dcnt Chcin. Gi.3. E<i*,iii 7G5. -f Zeitschr. f. Chem. [Z] vii 30 from Deut.Chem. Ges. Eer iii 7fY10 ABSTRACTS OF CHEIIICAL PAPERS. vnpoui* of an isonitrile is immediately evolved in abundance. ChZor-( tl~yZi/lc~z~, treaicd with alcoho!:c potash and aniline yields no isonitrilc :tad is i1ille~cEo~c easily clistiiiguish ecl fro? chloroform. The reaciion 1ici.c xcomniended is FO clelicnte that one part of cli!oroforin dissolved to CiOW part nC :l7z slay be detected with certainty. in S~VV TirE oiily inember of this class whicli has hitherto been obtained but oii1~-imperfectly Ftudicd is p!wiiylic cyanate. The author's researches oil tlie mustard oils led him to a simple process for the preparation of this aid other aroniatic cyamtes. In a former paper he drew attention to tlie facility with whicli the mustard-oils combine with a molecule of :Jcohol forming half-sulphurcttcd nretlisnes which when distilled a1one or better with phosplioric anhydride again split up into their coniponents th us-Taking the results of t!:e, ;experiments into consideration it was to be expected that plienylic cyniiate would be formed on distilling phenyl- nrelhnne with pliosphoric anhydride.Plicn :-iv.etlin,ne.; 01% phenyl-mi-bnmio ethers had already been obtaiilccl bj? iicatiiig the piieiiylic cyaiiate with methyl- ethyl- or aniyl-nlc~,lid, mid siiice then ethyl-plieilyl urethane has been carefully stndicci hy Wilm ~iidVis chin who prepared it by acting upon nuiiiiic \ 1 th chloro-carbonic cihm 2 Tlic author 'has repeated the experiments of these gentlemen and confirms tlieii- results with the exception of the statement that this cther volatilizes without deconiposition ; he finds that on distillation some of it always splits tip ilito pheiiylic cyanate and alcohol This decompodion becomes complete if the urethane is heated with i~?~ph~i~;~ ;Inliycli-ide tlie alcohol rem2.iiis behind and pure phenylic Proc.Rot-. SOC..xix 108. 0RGANICI CHEMISTRY. cyanate distils over as a colourless liquid having a great refractive power and boiling at 163" (not as he formerly stated at 178"). It has a very pungent smell and its vapour excites a copious flow of tears. The behaviour of this body with other substances bas already besii described in the author's former papers. With water it yield. cnrbonic acid and diphenylguanidine ; it combines with alcohol the urethane being reproduced ; and with ammonia and the compound ammonias it forms an inconceivable number of ureas.But the most characteristic reaction which it exhibits is that on dipping a glass rod moistened with briethyl phosphine into a large quantity of the cyanate it becomes very hot in a few moments and solidifies to a mass of beau-tiful crystals being transformed into a polymeric cyanurate. Tolylwrethasze 0,is obtained by the action of chloro-carbonic ether upon toluidine; the reaction is so violent that it is advisable to conduct it in presence of ether. When the solution filtered from the toluidine hydrocblorate is evaporated it leaves the tolyl- urethane as an aromatic oil which when cooled by a freezing mixture solidifies with difficulty.It is insoluble in water; from alcohol it crystallises in long prisms melting at 32". On distilling it with phosphoric anhydride toZyZ cyanate N passes over a colour- C7H7 co 1 less liquid boiling at 185" and showing in all its properties the greatest resemblance to the phenylic compound ; triethylphosphine acts on it however more slowlg. The reaction of xylidine with chlorocarbonic ether is more sluggish than that with aniline; q7ylzkvethccne c0(c8H9&7g} 0,crystallises in fine neeedles which melt at 58". Xylyl Cyanate c-,}N is a colourless highly refractive liquid boiling st about 2W and possessing only a feeble odour ; it exhibits reactions similar to those of the other aromatic cyanates but they often require days to be completed.Naphthy lure thane C0(C10H7)m 0 obtained by treating naph- C2H5 I tlq-lamine with chlorocarbonic ether crystdises from alcohol in needles which melt at 79". Nap11thy1 cya7 La te c,g} N is a colourless not very mobile liquid boiling at about 269"-270". At the ordinary temperature it is almost odourless but its vapour has the pmgent smell peculiar to the cyanic ethers. With water nlcohols and ammonias it gives the characteristic rmctions of t'hat class of bodies and acts with incomparably greater 9 rnickce 2nd precision than the xrlyl cvwpnnnd This ib pnrticc- ABSTRACTS OF CHFXICAL PAPERS. larly shown in the action of triethylphosphine which causes the oyanate of the naphthyl series to solidify almost instantaneously.c s. On the Action qf Acetic acid 01% Phenyl Su@hocya?aate. By A. W. Ho F M AN N.* WHENa mixture of the two bodies is heated to 130"-140" for some hours under pressure carbon dioxide and hydrogen sulphide escape on opening the tube and the liquid when poured out solidifies to a mass of splendid crystals which are obtained in a state of perfect purity by recrystallising them once from alcohol. The body (phenyl- diacetamide) resembles acetanilide in its properties. It melts at 111" (?). When heated with alkalis it yields as might be expected aniline and acetate On a Reaction of Cyanuric Acid. By A. W. HOFMANN.~ CYANURIC acid if present in the free state and in any considerable quantity is most readily detected by heating the highly dried substance in a short narrow tube.The smell of the vapour of cyanic acid thereby evolved is so characteristic that there is little room for doubt as to presence or absence o-f the acid. To detect the acid when in solution however and present in extremely small quantity only ad-vantage may be taken of the sparing solubility of sodium cyanurate in hot concentrated soda-ley. The liquid to be tested is placed in a watch-glass mixed with strong soda-ley and warmed for a moment over a pointed flame. If cyanuric acid is present splendid delicate needles of the sodium-salt at once make their appearance spreading from the point at which the flame is applied and disappearing again as the liquid cools provided the solution is not too strong.The formula of sodium cyanurate is Na3C3N303. J. R. Zeitschr. f. Chem. [a] vii 31,from Deut. Chem. Ges. Ber. iii 770. 1. Zeitschr. f. Chem. [Z],vii 31 from Deut. Chem. Ges. Ber. iii 769. ORGANIC CHEMISTRY. Dizcg)Losis of Primmy Secondary and Tertiary Anhzes. By A. W. HOFMANN.* ITis a well-known fact that the primary amines alone arecapable of yielding the isonitriles with chloroform and potash-ley. This reaction being of extraordinary delicacy and the odour of the isonitriles being quite unmistakable though it varies to some extent with different radicals the presence of a primary amine may be distinguished without the slightest daculty. It is only necessary to dissolve a few centi- grammes of the base in alcohol and mix the solution with alcoholic potash or soda in a test-tube and having added a few drops of chlo-roform to warm gently.If a primary amine is present a violent reaction occurs and vapours of isonitrile recognisable by their simul- taneous effect upon the nose and the tongue are at once evolved. If in this experiment the characteristic odour of isonitrile is not perceived the question remains whether the base under examination is a secondary or a tertiary amine. In this case the formation of sulpho-cyanates may be taken advantage of. It has been proved by experi-ment that both primary and secondary amines yield sulphocyanates analogous to mustard-oil the peculiar odour of which is easily recognisable. The experiment is made by dissolving a few centi- grammes of the base in alcohol mixing the solution with about an equal volume of carbon bisulphide and evaporating 8 part of the alcohol.The residual liquid is then heated with an alcoholic solution of mercuric chloride. If a primary or secondary amine is present the irritating odour of the sulphocyanate of the series is at once perceived. Unfortunately this reaction is not quite general. The first reaction described above is common to all primary amines whether belonging to the fatty or to the aromatic series ; but in the case of the secondary bases the formation of sulphocyanates takes place only with amines of the fatty series or with mixed amines. To distinguish between secondary and tertiary aromatic amines which do not yield sulphocyanate recourse must be had to the old method of treatment with methyl iodide &c.J. R. On Ethylene-bases. By A. W. H0FMANN.t A MIXTURE of ethylene bromide and alcoholic ammonia deposited on standing for some montjhs considerable qnantities of a white compound which when treated with water mas found t,o consist of a mixture of ammonium bromide with an amorphous body nearly insoluble in de Zeitschr. f. Chem. [a],vii 29 from Deut. Chem. Ges. Ber. iii 76’7. -i-Zeitschr. f. Chem. 1121 vii 28 from Dent. Clic~.Ge.3. Ber. iii 7’62. ABSTRACTS OF CHEMICAL PAPERS. water alcohol and ether. This peculiar substance was shown by mialysis to be a mixture of salts of tetrethyZe.l.L~-tria.1.iLine, with 1,2 and 3 molecules of hydrobrornic acid (C,H,),HN,.HBr (C2H4)iHN3.2HBr md (C,H,)IHN3.3PIBr.On prolonged boiling with ammonia the hydrobromic acid is removed and corresponding hydrates resembling the salts in being amorphous nnc! uncrystalkible are formed. From these hydrates the otlicr salts of Ghe bases may be obtained. J. 1%. 072 Akdehyde-gree?a. By A. W. HOFXANN." CRTJDE aldehyde-green in the pasty state still contains sodium sulphate and acetate. It is freed from these and all other mineral substances by washing with warm water and then leaves no incombustible residue when burnt on platinum foil. Many attempts were made to crystallise the body thus purified or to convert it into a crystalline compouiid but without success. The washed green was therefore dissolved in alcohol and the solution precipitated by ether this process being repeated several times to ensure as pure a product as possible.The fine green amorphous mass was found to contain sulphur. When dried in a vacuum it has the composition represented by the formula C27&7N3 szo. J. R. Oia the Actioit of Cyunoyert 011. AmliYae. By A. W. HCJFMANN.~-TOGETHER with aniline cyanide there is formed a red crystalline mass which when purified by suitsble means yields finc red crystals of a mono-acid bnse having the fmlnla CZ1H17N5, and yielding with hydro- chloric acid tlic crystalline salt C,lHl,N5.KC1. This bocly may be Yegarded as a modified ti~iplic~~l-guaniL~i-e on this vie17 may be and Pepresented by the formula G[N3.H2(CGH5)3] .2CM. When heated with weak spirit (best under pressme) the base is resolved in% diphenyl- pambanic acid with climinntion of animonia and amline @/_N3.Hz(CGH5)3].2@/N +3H,Q =CQ.C,O,.Wz(CJ&) +2H3N +C,H,N.013 lyjiling ;he alcoho!ic a~lntioilOF ~Lc 1:; YC Tt.-ithconcentrated hydro- ch )ric acid for some time the Giphcnylparabmic also decompoeed !a iL; and ultimately ammonia aniline cnrboii clioxicle and oxalic xcicl art' produced. '4 &it dx.f. Cl~m.[21 Yii 28 fi-oni Deut. Cl~cin.Gc,. Eer. iii '763. t Zeitsclir. f. Ch~i.[3! rii 28 froin Deut. Clieiii. Geq. Be.. . iii 764. ORGANIC CHEMISTRY 143 By A. W. HOFNAXN? Action of C$miogen OH ~~~)l~enylgun~~~~~~~~. AX alcoholic solution of triplienylgnanidine absorbs large quantities of cyanogen ; after standing so:ne time the sn-tnrtlted- solntion deposits yello..~~isli-T~rlijte crystals wll..ich may be purified by rccrFstAlise tion.This body has the same composition as that formed by the ecticii of cyanogen on aniline namely C,,H,,N5 but cIiEers from it in colom. cr-jmtallineform solubility aid more especially in its b~hnviczr.wit! acids. In contact with hydrochloric acid it asmmes a deep -j-ellovris;h-red colour evidently due to the formation of a salt which however cannot be isolated the red body being speedily resolved wit'li elimina- tion of mirnonia into a ciptalline yellow compound which must be regarded as oxaZyZtqphenyZguaiLicliiz C.C20,.N3(CGH5)formed accord-3 ing to the equatioa C21H17N5 + 2H20 = C21H,,N302 + 2H3N. This compound when boiled with alcohol and hydrochloric acid yields aniline and diphenylparabanic acid the latter body being dtb-ately resolved into aniline oxalic acid and carbon dioxide.J. R. XptlLesis of ,%&.titdl-(J flvrwXhws. By E. E it^^ EXEY E R.? THEauthor in contiimation of a previous experiment in which he obt:> ined hydrochloride of guanidine by heating ammonium chloride in alcoholic solution with cyanainide has obtained sdts of phenSl- tolyl- and methSl-guaiiidine by tlie action of tlie hydrochlorides of phenyl-amine toluidine and metliy1an:ine on cyanamide. Fll ine methylgnanidine tlius obtained does not appear to differ per-ceptibly in its own properties or those of its salts from the description given of methyluramine obtained by oxidising creatine cii' creatinine.The platino-chloride however said by Senarmont to crystallise in rhombohedrons by Dessaignes in flattened prisms was obtained in hendyohedrons belonging to the monoclinic system. The author pro-poses to prepare methylguanidine by Dessaignes' method and submit the t.m platin0 chlorides to H. v. Kobe11 for comparison. w. El-.ID. EJIJ 1) thcsis of Allitslciids.$ SCHIFF has succeeded in producing by synthesis a product which possesses +he chcu,acter;stic pyoperties of the active principle of 4 Zeitscliy. f. Chem. C2] \ii 28 froiL3Dwt. Chem. Geq. Ber. iii 761. p K. Repeft. Ph2mi. ss,85. t Phrrm. J. Trans. [3] i 605. ABSTRACTS OF CHEMICAL PAPERS. hemlock (Coniuzcm maculatum) . When alcoholic ammonia acts upon butyraldehyde at a temperature not above 100"C.two bases are pro-duced one of which dibutyraldine is represented by the following formula C~HI~NO = 2C4HBO + NH -HZO. Dibutymldine. Butyraldehyde. By the dry distillation of dibutyraldine there is obtained amongst other products a final one which has the composition of the alkaloid in question CBH17NO = HZO + CeHJT. Dibutyrald ine. Conine. J. B. On the Oxidation-prodwcts qf Picoliize. By JAMES D EWAR.* THEpicoline used in this investigation boiled between 130" and 140"; analyses of t'he platinum salts of portions boiling between those tem- peratures showed the fractions to be substantially picoliue with a possible trace of lutidine. As is well known picoline is not acted upon by nitric or chromic acid even at high temperatures; of other oxidizing agents permanganic acid or its potassium salt seems to be the most powerful.The oxidation was performed in a large flask which was connected with a reversed Liebig's condenser; for one operation the author took 150 grms. of potassic permanganate 16 litres of water and 25 grms. of picoline. The mixture was heated to the boiling point when a violent reaction set in necessitating the removal of the source of external heat ; the reduction of the perman- ganate was completed in half an hour. The products of the reaction are ammonia probably a small quantity of pyridine carbonic nitric acetic oxalic! and a complex of new acids amongst which dicarbo-pyyidenic acid C,H,N predominates ; C""" this body after several recrystallisations from water was obtained in colourless plates resembling naphthalene.It is a bibasic acid; the neutral ammonium salt is extlremly soluble in water ; the acid salt is less soluble and crystallises in fine silky needles. The mercury copper cadmium and zinc salts are also readily soluble. The barium and calcium salts which are also soluble were obtained in minute prismatic needles by adding the respective chlorides to a solution of the neutral sodium or ammonium salt. The silver salt uf this acid is specially characteristic ; it is ob5ained as a u-hite gelatinous precipitate which is insoluble in boiling water and is not visibly affected by exposure to light. * C'iiem. News sxiii SF. ORGANIC CHEMISTRY.On heating dicarbo-pyridenic acid it melts at about 210" C. frothing up and evolving a small quantity of carbonic anhydride and emitting the characteristic smell of the bases of the pyridine series. When heated with soda lime the acid is decomposed and a basic substance is obtained which is most probably pyridine. Besides dicarbo-pyridenic acid there are acids having a higher mole- cular weight formed by the oxidation of picoline which have not been studied yet as the quantities which the author had at his disposal were only small. The author considers pyridime C5H5N,the lowest member of this series of bases as the nucleus from which all the other members are derived ; just as all aromatic compounds are derivatives of benzol. Pyridine would thus be benzene in which nitrogen functions in place of the triad group (CH)"'.* We thus have the following rational formula :-Pyridine.Methyl-pyridine oi*picoline. Dicarbo -pyridenic acid. C5H5N CSHAN.CHs CO2H C5H3N{ C02H. Dicarbo-pyridenic acid bears therefore the same relation to pyridine that phtalic acid does to benzene and its formation from picoline i~ quite analogous to the formation of phthalic acid by the action of oxidising agents upon benzene as shown by Carius. c. s. 0%Acridine. By GRAEBE and CAR0.t INpurifying large quantities of anthracene a small quantity of a basic substance (acridine) accompanies the crude hydrocarbon To prepare it crude anthracene before it has been treated with solvents is boiled with dilute sulphuric acid and acid potassium chromate added to the filtered solution.An almost insoluble precipitate at once forms soluble in a lmge quantity of boiling .water. By several crystdisations acri- diiie is obtained in beautiful orange-yellow needles or prisms from which ammonia liberates the base. By washing with a little cold water and crystallising from hot water the base CI2H,N can be easily obtained pure. Pure acridine is colourless crystallises in plates volatilizes with aqueous vapour melts and begins to subhe in plates at 107" and distils unchanged at 360". It is readily soluble in alcohol and in ether. It acts energetically even in very dilute solution on the sensitive parts of the skin and on the mucous mem- brane. Its powder inspired even in the smallest quantity causes The same view has already been expressed by Iiocrner.-C.S. + Ann. Ch. PEmm. clvii 159. ABSTRACTS OF CHEMICAL PAPERS. sneezing. Tlie salts of zcridine are all yellow or orange-yellow although the pure base is coloariess. They ciytallise very readily but nevertheless have not RS yet yielcled perfectly constant numbers on analysis. Very dilute solutions appearing coloudess by transmitted light exhibit a niagynificent blue colour by reflected light which passes into green the more concentrated the solutioa is made and disappears almost completely when the solution is of a deep yellow colotu. by transmitted light. E. D. Decosyositiox of C@eidine By Bc:riz~s,zHydmte. By F. RO~ENGARTEN 2nd. A. STRECKER.* SOME years ago Strecker-f showed that by the action of barium hydrate on caffeine a new base was obtained which he termed cqfeidhe.Its for-mation is explained by the equation- At the same time methylamine and ammoniawere given off and the mother-liquors contained substances the nature of which was not de- termined. Otto Schultzeii$ has since communicated that the final products of the action of barium hydrate on caEeidine are-besides barium carbonate iiiethylarninc and ammonia-barium formate and a crystailine body of the composition C,HiNO2. This latter formed crystalline halts wi$h hydrochloric and sulphuric acids bnt no double cornponnds with platinum chloride or gold chloridc and €rom this he concluded that it was neither sarcosine nor alanine but the alaninc corresponding to pa~nlncticacid ; against which view however is the fact noticed by himself khat when treated with nitrous acid it docs not yield pnmkctic acid but a nitroso-compound the calcium salt of which is represented by the formula [C3B,(NO)NO2] Ca + aq.Rosengarten and Streeker have re-examined this reaction and find that in the maill Schultxen is correct. They were able however to obtain both platinurn and gold sdts of the crystalline compound C,H7NO2 (niethylamidacetic acid) and find that thew salts are identical both in composition and propei-ties with those prcpared from ordinary sarcosine. Both sarcosine prepared fi-om crcatine and that from caffeine we93 found to dissolve cupric oxidc on )soiling,-well formed blue rborribic crystals separating out as the liquid cooled ; their compcsition is indi- cated by the formula C3H6C~iN02 + aq.Finally the sarcosine froin caffeine was coiiverted into creatine by mixing its aqueous solutioii wit12 Aim. Cb. Pham:. clvii 1. ~ + Ihid CXTiiil 360. i’ Zcicsciir. f. Ciiem. [2],iii 611 ORGANIC CHEMISTKT. a concentrated solution of cyanamide with add-itioii of n sinall quantity of ammonia. The crcatine obiained was icientical with ordinary creatine. Rosengarten aild Strecker note that while Volhard (C’lism. CentruZbZntt 1869 364) obtained only 20 pts. of creatine from 100 pts. sarcosine they by observing the conditions followed by one of them (Strecker Jahresb. fib Chemie 1861 530) in the preparation of glyco-cyamine obtained a yield of 130 per cent.of recrystallised creatine. It is evident that the action of nitrous acid as observed by Schultzen is a further proof of the identity of the body C,H,NO with sarcosine when it is considered that those compounds which contain the NH group are by the action of nitrous acid in general converted into O~J-compounds whereas those in which methylamine NCH,H, is present yield ?zit.r*oso-compounda :-A.NH2 + NOzH = A.OH + OH + PJ A.NHCH3 + NOzH = A.N(CH3) NO + HZO. The equation representing the decomposition of caffeine is the follow-ing :-CJ31JY,O + 6HZO = 2CO2 + 2NCH5 + NHs + CH,O, + CsHTNOz. Creatine similarly treated yields sarcosine carbonic acid and ammonia but both methylamine and formic acid are wanting.H. E. A. Om Acetop~eric~i?te-Coiri~~oz~r.lds. By R. KEAUY.” A mmum of 1 mol. chloracetic acid with 2 mols. aqueous pipedine mas allowed to stand several days the excess of piperidine distilled of? the residae shaken with silver oxide and the filtrate freed from silver by hydrogen sulphide then boiled so long as piperidine passed over and fina.lly evaporated to crystallisation. The product was then recrystal- lised from alcohol. The reaction may be represented as ~O~~OT.FTS :-2(@5HloHN) + Cl.CH,.COOE + HOE = HO.C5H,,.HN.CH,.COOH + CjH,,.H,N.Cl. The compound C,NH,,O, ncetopiperidizmz hydroxide forms colourless crystals belonging to the rhombic system which by careful heating may be sublimed unchanged ; it is readily soluble in water less soluble in alcohol.By the action of cupric oxide on its aqueous solution a copper salt is obtained crystallising in blue plates which contain 4mols. H,O. The dry salt has the composition CU(O.C~NH~~O), and is therefore an acetopiperidine and not a derivative of acetopiperidium hydroxide * Ann. Ch. Pharm. clvii 66. ABSTRACTS OF CHEMICAL PAPERS. Acetopiperidizm chloride C1.C5Hlo HN.CH2.COOH is obtained by evaporating a solution of the hydroxide in hydrochloric acid. By mix-ing concentrated solutions of gold chloride and the above chloride an aurochloride is precipitat,ed of the probable composition- 3(IICl.AuC13) .4C,NH1,02. A barium double salt which may perhaps consist of C7NHI30,.BaCl was also prepared. H. E. A. On S't.1.ycli?kine-oxeth~lb'unqozcnds.By R. MESSEL.* R. MEss EL has prepared compounds of strychnine and quinine with ethylene hydroxychloride (C2H40HCl). The strychnine derivative- C21H22N202+ C2H,0HC1 = C23H2TN203C1-is readily soluble in water from which it crystallises in white glistening tufts containing 1mol. H'O. Ammonia produces ?LO precipitate in its solutions ; potassium dichromate and concentrated sulphuric acid give a fine violet colour which disappears after long standing. With platinum chloride it forms an orange-coloured crystalline double salt 2C23H2,N203C1.PtC14.-The sulphocyanate iodide nitrate sulphate and hydrate were all obtained by double decomposition from the chloride. A freshly prepared solu-tion of the free base is without action on litmus paper and entirely tasteless; its salts have at first a sweetish and afterwards a sharp bitter taste.With regard to the physiological action of the chloride middle-sized frogs were killed by 3 to 4 mgrm. subcutaneously injected and even much smaller doses caused total paralysis of the motor nerves lasting for hows and even days while the muscles contracted power- fully on direct irritation. H. E. A. Decomposition of Morphine Acetate iit Solution. By JOHN M. MAISCH.~ ATTENTION is directed to the decomposition which a solution of this salt is apt to undergo on keeping for some time. A solution of 8 grains of the acetate in + oz. of distilled water which had been set aside for several months had deposited a considerable quantity of brown matter and from the liquid which was of a pale brownish colour a single crystal had separated reaching from the surface of the liquid diagonally through the solution to the bottom of the vial.The crystal (which was alkaline and contained neither acetic carbonic nor any mineral acid) proved to be pure morphine. The liquid was neutral to test-paper but appeared still to contain a small quantity of acetate of morphine in solution. W. H. D. * Ann. Ch. Pharm. clvii '1. -f Pharm. Journ Trans. [3] I 664. ORGANIC CHEMISTRS. On the Preparation and Composition of Eyo.scyanzi.ne. By H. H o EH N and E. REICHARDT.* THEprincipal novelty in the method of preparation consists in prccipi-tating the impure alcoholic solution of sulphste of hyoscyamine with tannin.The tannin compound being not insoluble in alcohol a certain quantity is found in the liquid in which the precipitation is effected. The authors recommend the removal of the fatty oil from the henbane seeds (in which it exists to the extent of 26 per cent.) by means of ether. They give 0.0453 per cent. as the amount of hyoscyamine in henbane seeds. To the description of appearance and behaviour towards re-agents already given by Geiger and Hesse may be added the melting point go" of hyoscyamine its formation of precipitates with mercuric chloride platinic chloride and auric chloride ;. the gold precipitate appears to decompose after a time with formation of hyoscinic acid. The alkaloid gave on analysis as mean numbers 67.6 C. 9.0 H. 5.1 N.which lead to the formula C15H23N03. The hydrochloride plattinochloride and sulphate were analysed with results expressed by the formula C1;H2,NO3.HC1 + 2H20,2(C15H23N03.HC1).PtC14 and 2(C15Hz3N03)2H2SOa + 2H20,respectively. By boiling for several hours with saturated solution of baryta hyos- cyamine breaks up into an acid and an amine called by the authors hyoscinic acid and hyoscine.-Hyoscinic acid is described as crystallising in long glistening needles which melt at 104°-1050 and smell something like benxoic acid. The acid gave on analysis 65.1 per cent. C. 6.45 per cent. H. its barium salt 30.3 per cent. BaO and 3.25 per cent. H20; results expressed by Bn(CSH,0& + 2H20. Phloretic acid is an isomer of hyoscinic acid but appears to be bibasic and does not melt below 128" to 130" C.Hyoscinic acid appears rather to resemble atropic acid ClaHsOd obtained by Kraut in an analogous manner from atropine. Hyoscine was obtained as an oily liquid of strongly alkaline reac- tion which crystallised by standing over sulphuric acid As the whole quantity obtained did not exceed 0.3 grm. little was done beyond analysing the chloride and platino-chloride. C6H14NCI,and 2(C6Hl3N,HCI) .PtC14 express the composition of t'hese substances giving for hyoscine the formula C6HnN. The breaking up of hyoscyamine may be represented thus :-C~~H~~NOS = CsH1003 + Cd313N. In an actual experiment 0.9 p.hyosyrtmine gave when boiled with Ann. Ch.Pharm. clvii 98. GOT,. XXIV K ABSTRACTS OF CHEMICAL PAPERS.baryta about 0.5 grm. acid and 0.3 grm. of base. The above equation would require 0.56 grm. and 0.34 grm. respectively. W. H. D. and On Chlorncetccmicleand Iodacetamide. By N. MENSCHUTKIN M. 5E RM o LA JE w.* MonochZoraceta~nide C2H,C10.NH,. This body is prepared by cautiously mixing 1volume of pure chloracetic ether? (boiling below 147") with 2+ volumes of concentrated ammonia without shaking the mixture. After standing for 24 hours the ethereal layer becomes con- verted into a solid crystalline mass which is purified by recrystallisa- tion from the smallest possible quantity of water the mother-liquor yielding a brown product nearly free from amide when evaporated. The product crystallises in thick prisms easily soluble in alcohol and water especially when boiling.It melts at 119.5" and soliaes at about 116"; sublimes very easily even at the temperature of the water- bath in broad large needles ; and distils in very small quantity appa- rently undecomposed. Alkalis and baryta-watcr readily evolve ammonia on warming The ?nerczcry-comn~ou.1zcl (C,H,ClO.HN),Hg,. is formed by adding precipitated mercuric oxide to an aqueous solution of chloracetamide so long as the colo~ changes to white then adding a large quantity of water boiling filtering and exhausting the residue with boiling water. The air-dried compound does not lose weight over oil of vitriol but begins to decompose at 100". The compound is deposited from solution in fine needles or in warty masses made up of small needles.It dis-solves with great difEculty in boiling water and is nearly insoluble in cold water. When it is heated to 170" a violent reaction occurs; chlora- cetamide sublimes and mercury and carbon are left behind. The silver-compound cannot be obtained on account of its instability. Iodacetamide is obtained by treating an alcoholic solution of chlora- cetamide with solid potassium iodide for a day at the ordinary tempera- ture with frequent agitation and then evaporating the alcoholic solu- tion. The amide crystallises from water in which it is easily soluble in fine colourless opaque prisms. When heated it melts turns yellow and decomposes evolving fumes of iodine * Zeitschrift fur Cheruie [Z] vii 5. J. R. f' Chloracetic ether is best prepared by distilling from a water-bath an alcoholic solution of chlomcetic acid saturated with hydrochloric acid.Tile ether boils at 142"-14P the last portions however dist,illing only above 150". ORGANIC CHEMISTRY. 151 On some Compourtds of Aldehydes with Amides. By Dr. LUDWIG MEDICUS.~ when two molecules of benzamide and one molecule of oenanthol are heated together for four or five hours ; as soon as the benzamide is fused the reaction begins and water is given off. The residue was dissolved in boiling alcohol and on cooling the new compound separated in white crystalline flakes. It is insoluble in water and sparingly soluble in ether. When carefully heated it melts at 128'; it is perfectly neutral and not acted upon by caustic potash even on boiling.Cold hydrochloric acid does not affect it but the boiliag acid acts upon it water being taken up and benzamide and oenanthol being reproduced. Oenanthyliderte-d~~o?aobronzo-nitrd~ is formed by the action of nitrobenzamide upon oenanthol and has the greatest resemblance to the preceding compound. It forms small white needles not soluble in water sparingly soluble in ether readily in hot alcohol. It melts at 170" if carefully heated ; decomposes when heated quickly ; caustic potash bas no action upon it ; boiling hydrochloric acid decompmes it. By treating it with an alcoholic solutioD of ammoninm sulphide an amido-oompound is formed which was not obtained in the pure state. BenxyZidene-oxamide C202< zE>C7H6. Oil of bitter almonds does not act upon oxamide but oxamethane does the reaction hkes place in two stages; first the oxamethane splits up into oxalic ether and oxamide and the latter in the nascent state acts upon the aldehyde thus :-(1) (21 The reaction takes place at 150" and is finished after four or five hours.To obtain the compound in the pure state the residne is first exhausted with ether to dissolve the greater part of the oil of bitter almonds which is still present then treated with boiling alcohol which leaves oxamide behind. The solution is evaporated and the regidue treated with a mixture of alcohol and ether which lemoves oil of bitter almonds and oxamethane. The residue consists of benzyli- dene-oxamide which is easily obtained pure by crystallisation from hot X Ann.Ch.Pharm. clvii 44. N2 ABSTRACTS OF CHEMICAL PAPERS. water. It forms brittle and shining plates containing Q mol. water of crystallisation which they lose at 100". It is also readily soluble in alcohol sparingly in ether and crystallises from these solutions in silky needles. It is easily decomposed by boiling with caustic potash oil of bitter almonds potassium oxalate and ammonia being formed. Boiling hydrochloric acid attacks it but slowly. When heated it begins to decompose above 200" and at a higher temperature it melts and undergoes complete decomposition. c. s. Poisonous pdnciple of the l'utzc Plant (Coriaria ruscifolia). By W. SKEY.* THEpoisonous principle of this plant does not appear to be of the nature of an alkaloid.By treating the ground seeds repeatedly with alcohol a greenish-red coloured substance was obtained which when acted upon by ether was separated into two parts one a green oil soluble therein ; the other a resinous substance quite insoluble in that menstruum. The oil given to a cat after a 12 ~OWS'fast in a dose of about 5 minims produced vomiting and convulsions from which however the animal gradually recovered. As the symptoms agreed generally with those exhibited by cattle and sheep when poisoned by the Tutu plant the author infers that this oil constitutes or at least contains the poisonous principle of the plant. The oil appears to be a non-drying fixed oil and to contain an acid peculiar to itself and quite distinct from the ordinary fatty acids ; to this acid the author is inclined to ascribe the poisonous effects of the oil.Should this view prove to be correct the matter would assume a peculiar interest as affording another instance in which a non-nitro-genous oily body affects the system like a neurotic poison. J. B. On Curczmtin the Colouring itfatter of TzwmeTic. By F. U. DAUBE.~ THE substance hitherto described as the colouring matter of turmeric is a mixture of different resins with the pure compound which the author has succeeded in obtaining in the crystalline state by the following simple process :-A strong current of steam was passed over coarsely powdered turmeric to remove the essential oil and the residue was washed with hot water as long as colouring matter was extracted then dried and treated with boiling benzol.On cooling crude curcumin separatcd in crystalline crusts which were pressed between filtered paper and dissolved in cold alcohol a small quantity * Pharm. Journ. Trans. [3] I,568. f-N.Repert. Pharm. xs 36 from Deutsh. Chem. Ges. Ber. iii No. 11. ORGANIC CHEMISTRY. of a yellow body being left behind. To the filtrate a solution of neutral lead acetate was added and then so much basic acetate that the solu- tion just showed a faint acid reaction. The brick-red precipitate after being washed mas suspended in water and decomposed by sulphuretted hydrogen. From the precipitate the curcumin mas extracted with boiling alcohol and the solution allowed to evaporate very slowly Pure curcumin crystallises in shining prisms apparently belonging to the orthorhombic system which by transmitted light appear of a hock or amber colour and by reflected light are orange-red.The alcoholic solution is fluorescent like tincture of turmeric ; the spec- trum of the reflected light does not show any alteration from the red end to F but the blue violet and ultra-violet portions are replaced by a greyish green band in which the lines H 5 M N &c. are distinctly visible. By analysing this modified spectrum with a prism it was found to contain very little red and the blue end had nearly disappeared. This secondary spectrum agrees Yery nearly with that of uranium glass. Curcumin begins to melt at 165" and is completely decomposed at a higher temperature.It is very readily soluble in alcohol and ether but ihese solvents cannot be used for extracting it from turmeric as they also dissolve resinous matters. In benzol it is very little soluble (1part in 2,000 parts) but as the resins are quite insoluble in this liquid it has to be used to obtain the pure compound. It is also a little soluble in concentrated mineral acids which however act on it. In alkalis it dissolves with a bright reddish-brown colour ; acids pre- cipitate from this solution the original substance ; calcium- and barium- salts produce reddish-brown precipitates. The lead-compound which has a bright red colour is soluble in acetic acid and is slowly decom- posed by carbonic acid. The composition of curcumin is CloHlo03.The analyses of the lead-compound did not give concordant results but they make the formula C20H,8PbOs probable.Hot dilute nitric acid oxidizes curcumin to oxalic acid. Sodium amalgam decolorises the alcoholic solution completely. The colour reactions of pure curcumin are much purer than those of turmeric solu-tion. The author employed curcumin-paper prepared with Swedish filter-paper which was fiee from lime. Alkalis change the yellow into a brownish-red which after drying assumes a violet tinge ; dilute acids restore the original yellow. A solution of boric acid produces a pure orange which appears only after drying ; if' the paper had been pre- viously dipped in a dilute acid the coloration became darker as dilute acids alone produce a blackish tinge after drying.The orange colour is not changed by diluted acids but dilute alkalies convert it into a blue which soon changes into R dirty grey. By acting on curcumin with boric acid and concentrated sulphuric acid E. Schlwnberger ABSTRACTS OF CHEMICAL PAPERS. obtained a substance which he called rosocyaaia as its solution has the colour of a rosaniline salt and its metallic compounds are blue. The author bas repeated these experiments with pure curcumin and has obtained the @&me results but his investigation is not quite finished. c. s. Cmt$mtiows to the Knowledge of Argemone Mexicaiza.* THEfirsf section of this paper contains an interesting historical account of the plant and its migration by Fluckiger who also objects to some statements of Charbonnier on the purgative action of the oil obtained from the seeds of the Argemone.Fliickiger did not find its action as a purgative so powerful as that of castor oil. The oil was examined for volatile acids by 0. Frijlich. 3$ lbs. of oil were saponified with soda-ley the solid soap was salted Out and the aqueous liquid treated with sulphuric acid and dis- tilled. The distillate was neutralised with soda evaporated down decomposed by sulphuric acid and repeatedly shakeD up with ether. The ethereal solution gave about 1 grm. of a liquid boiling above 100". This went over between 140" and 240". About 6 grm. of it liquid boiling between 160"-190" was obtained from it. It gave ' on analysis 55.8 per cent.C. and 9.4 per cent. H. A mixture of butyric and valeric acids would give numbers approaching these. The portion coming over above 190"became solid on cooling. It showed the melting point (12OO) and several other properties of benzoic acid but there was not enough for analysis. The aqueous liquid exhausted with ether appeared to contain acetic acid. W. H. D. Fluorescence of Peppwmiizt Oil. By FLUC KIGE R .t FLUCKIGER states that 50 to 70 drops of peppermint oil shaken with one drop of nitric acid sp. gr. 1.2 become faintly yellowish brownish and after an hour or two exhibit a beautiful blue violet or greenish blue colour; by reflected light the liquid is of a copper colour and not transparent. The reaction may be hastened by the application of heat or by adding a larger proportion of acid.All the samples of oil examined exhibited this behaviour the colour varying however with different specimens ; nevertheless although this reaction is perfectly characteristic of peppermint oil it appears not capable of being applied as a trye test since an admixture of 5 per cent. of oil of tur-pentine for instqaoe did not prevent the appearance of the blue or green colour. H. E. A. * Arch. Pharm. [Z] cxlv. 51. f Pharm. J.Trans. [S] i 682.

ISSN:0368-1769    

DOI:10.1039/JS8712400117

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. Analytical Chemistry. Electrv-thermic Methods of Aizalyllsis ard Synthesis. By E. MULDER and F. C. E. von EMBDEN.~ PO%many experiments such as the combustion of carbon or sulphur the reduction of carbon dioxide by carbon &c. a simpler arrangement than that previously described by the authors may be adopted. If it is desired to burn carbon in oxygen for instance a large test- tube or a flask is partially filled with the gas over the mercurial trough the volume being marked by means of a caoutchouc ring. Into this vessel is introduced a copper wire carrying at its upper end a small dish made of clay through the bottom of which it passes. To the extremity of the wire is attached one end of a fine platinum wire which is wound round a fragment of charcoal and connected by its other end to a copper wire passing through the dish and dipping into the mercury in the vessel.The copper wire carrying the dish is insu-lated by a glass tube bent into the form of an inverted siphon with very unequal limbs the longer limb reaching above the level of the mercury in the tube or flask while the shorter projects above the sur-face of the mercury in the trough. This tube becomes partly filled with mercury in the act of introducing it with its contained copper wire into the vessel of gas. The apparatus being thus arranged one pole of a battery (two Grove’s elelvents are quite suficient) is dipped into the mercury in the trough and the other into that in the glass tube where- upon the platinum wire becomes red-hot and the charcoal is kindled.Another method applicable however to fewer experiments consists in the use of a float which may be made of clay. To burn sulphur in oxygen for example a copper wire passes through the float being secured underneath and carrying above a small dish of copper or clay on which is a fragment of sulphur fused to a platinum wire one end of which passes through a hole in the dish and i8 fastened beneath the other end being connected with an insulated copper wire passing through the dish and float and secured to bAh. The vesscl being partly filled with oxygen and the height marked with a caoutchouc ring the float is introdnced and rises to the surface of the mercury. One pole of the battery is connected with the mercury in the trough the other with the insulated wire; the platinum wire then becomes red-hot and the sulphur burns quietly.J. R. * Beitschrift fur Chemie [2] vii 1. ABSTRACTS OF CHEMICAL PAPERS. A Method of QzicLm5fntiveAnalysis cmcl Synthesis. By E. MULDER." THEprinciple of thianiethod will be made clear by an example. A?anlysis of gaseous Hydmpz Cldode 6y meaws of iyon A graduated glass tube closed at one end is partially filled with the gas over the mercurial trough and the volnine read off in the usual manner. Two copper wires one of which is insulated by glass are then introduced into the tube. One of these mires is coiled into a flat spiral at top ; the other carries at its extremity a kind of brush formed of a number of ihort pieces of iron wire of different lengths secured to it by means of platinum wire.One pole of a battery of three Grove's elements being connected with the mercuryin the trough and the other with the insu-lated copper wire the apparatus is adjusted with the hand so that the ends of the iron wires are brought into contact with the copper coil whereupon the iron begins to glow and ferrous chloride is formed. When the volume of the gas ceases to contract the wires are removed and the volumes of theresidual hydrogen is read off. It is :obvious that one of the wires may be of platinum passing through the top of the tube the other which need not then be insu-lated passing up through the mercury as before. This principle modified to suit particular c:tses is applicable to the analysis of compound gases and vapours such as hydrogen chloride hydrogen sulphide or water-vapour by means of iron copper &c.; or of mixtures of gases such as oxygen and nitrogen by means of copper (method of analysing air).It is applicable further to the combination of gases as hydrogen and oxygen and of solid elements as iron carbon sulphur &c. It may also be employed to effect the combustion of carbon iron and other solids in nitrogen protoxide nitrogen dioxide &c. ; or of gases by means of partially oxidized iron or copper wire lead-chromate and other solid compounds of oxygen ; or of vapours such am alcohol-vapour (method of organic analysis). Lastly it is appli- cable to experiments on the dissociation of gases and vapours such as ammonia or water-vapour by platinum palladium &c.This method of experimenting is extremely well suited for lectures the apparatus being simple and t'he manipulation easy J. R. On some Sources of Error in Tolumetrk Analysis. By R.R.TAT LOCK.? THE object of the author is to point out cert'ain sources of error in volumetric analysis and to indicate how they niay be avoided. Reference is made to the contradictory statements of various experi- ++ Zeitxhrift fur Chemic [2] rii 2. t Cliern. News xxiii 13. ANALYTICAL CHEDIISTRY 157 mentalists respecting the change of volume that takes place on mixing saline solutions with water. From the fact that the specific gravity of a mixture of a saline liquid and water is greater than its calculated mean and from direct experiments it is inferred that contraction does as a rule take place on admixture of a saline liquid with watsr.Strong solutions were found to contract proportionately far more thail weak ones. Two sources of error are specially mentioned-the one arising from this contraction and the other from tlie fact that vessels do not deliver in a given time corresponding volumes of water and saline solution but rather less of t'he latter the exact amount depending to some extent upon the sp. gr. of the solution. The first named source of error may be obviated (1) by using as weak soluticns as possible and (2) by mixing the saline liquids thoroughly with the water before making quite up to the required bulk.The error caused by the adhesion of it saline liquid to the delivering vessel may be obviated by graduating it in terms of the particular solution to be employed. A. T. On the P.recipitation of Slrzall Quantities of Phosplzo& Acid by nzeuns of Ammonium Xolybdate together with a few Renzarks on the Yellow Prec+itate containii2g Silico-molybdic Acid. By E. R I cH TE R s.* AMMONIUM molybdate deservedly enjoys the reputation of being an extremely delicate reagent for phosphoric acid. Its sensitiveness depends however upon well-defined conditions which must be strictly complied with if small quantities of phosphoric acid have to be deter- mined. Among these is the absence of free hyd.rochloric acid in anything like large quantities whilst nitric and snlphuric acids do not interfere with the accurate precipitation of phosphoric acid within the usual limits of quantitative analysis.It is otherwise however in the case of earthy minerals &c. the solution of which usually contains extremely minute traces of phos- phoric acid together with much free acid and a large amount of salts (nitrates and sulphates). A large excess of ammonium molybdate has to be employed in order to counteract the solvent power of distilled water on the free acid as well as on the salts. The sulphates and nitrates of the light metals especially of the metals forming the strongest bases are found to retard the separation of the precipitate and require therefore the largest amount of ammonium molybdate. A 5 per cent.solution of the ammonium sulphate acidulated with &lute nitric acid on the other hand acts rather favourably. Nitrates in general appear to assist the precipitation. Ammonium nitrate was especially observed to accelerate the formation of the yellow precipitate Dingl. po'lyt J cicix 183. 158 ABSTRACTS OF CHEMICAL PAPERS. in a most extraordinary manner and from very dilute solutions the precipitation being accomplished also by a much smaller quantity of ammonium mol ybdat e. Standard solutions containing respectively- (I) *002grm. and (11) -010 grni. of phosphoric acid per litre ;also solutions. (I11and IV) containing the same amounts of phosphoric acid dissolved however in ammonium nitrate (100 grms. per litre) were prepared.10 C.C. of solutioiis I and 11,to which 0.3 C.C. of a solution of ammonium molybdate had been added remained perfectly clear on standing for several hours in a waim place. Solution 111 gave a precipitate on standing at the ordinary temperature for twelve hours; solution IT,after stancling for 30 minutzs only. The pre- cipitation was complete after 20 hours and the further addition of several cubic centimetres of ammonium lzlolybdate to the clear filtrate produced no further precipitate even on heating for 24 hours. On warming solution 111 a precipitate was produced after the lapse of one hour and on adding a further quantity of ammonium molybdsic (about 2 C.C. for every 10 C.C. of solution) the sensitiveness of the reaction in the presence of the ammonium nitrate became practically unbounded.The extent to which ammonium nitrate counteracts the solubility of the phospho-molybdate precipitate in solutions of the sulphates and nitrates of the alkalis and alkaline earths as far as they are soluble (concentration 1in 10 or if less soluble saturated solutions) was next ascertained and it was found that ammonium nitrate assists the pre- cipitation in a like ratio. Solutions containing much nitric acid required only about one-third the amount of the reagent in the presence of ammonium nitrate. Richters proposes to conduct the determination of very small quan-tities of phosphoric acid in the presence of large quantities of nitrates and sulphates as follows :-The acid solution is diluted with water so as to leave about 1grm.of the salt in 10 c.c. or if much ammonium sulphate be present 1grm. in 20 C.C. The solution is rendered slightly ammoniacal and then once inore acid (nitric acid). If IG sufficient amount of ammonium nitrate be not already formed in this manner an equal volume of a 20 per cent. solution of this salt is added and the solution heated to 50" C. after the ammonii-un molybdate has been added. On adding aminonin to n tlioro.ilghlyacid (nitric) solution a certain amount of ammonium nitrate is formed (which may be readily estimated if the strength of the ammonia solution be known) and should be taken into account in diluting the solution to the above strength. The separation of the yellow precipitate is both rapid and complete in fact instantaneous from solutions which contain only _-o,A of the weight of the original salts.AXALYTICAL CHEMISTRY. Richters proposes to employ a slightly acidified 15 per cent. solu-tion of ammonium nitrate in the place of ammonium molybdate for washing the yellow precipitate or else a nitrate solution mixed with a few cubic centimetres of the ammonium molybdate. The precipitate obtained from the phosphate solutions containing much ammonium nitrate is distinguished by a somewhat brighter yellow colour. Richter s remarks lastly on the yellow precipitate produced by ammonium molybdate from solutions containing silicic acid which is but slowly soluble in cold dilute ammonia with separation of flakes of silicic hydrate and not unfrequently accompanies the magnesia11 precipitate to which it gives its flaky appearance.w. v. Estimation of Xu@ltur in Cast IYO~.By W. H. ELLIOTT.:* THIS method depends on the evolution of the sulphur as sulphuretted hydrogen the absorption of the latter in solution of pure soda (pre- pared from sodium) and the determination of the sulphuretted hydrogen in the acidified soda-solution by means of standard solution of iodine. w. v. Estimation of P?tosp?~o~us is5 ovde Pig-I~on,Steel nzzcl iVa7leccble Iron. By F. KESSLER.? THI~ method is based upon the precipitation of the iron in the state of ferrous chloride by potassium ferrocysliiide FeCl + K4FeCy6= Fe"K2PeCy6+ 2KC1 and the separation of the phosphoric acid from the filtrate in the form of ammonio-magnesic phosphate.As the pro- cess involves filtration from a bulky precipitate-an operation known to every chemist as being among the most tedious-the author proposes to collect only the first haIf of the filtrate for precipitation with magnesia mixture. Assuming an iron to contain 1per cent. of phos-phorus in order to obtain a precipitate of magnesium pyroplzosphate amounting to ,100 grni. 2.793 grms. of crude iron mould hare to be operated upon; or as only half the bulk of the filtrate is to be employed the quantity of the metal would have to be doubled. This quantity of metal (5.6 grms.) after solution in acid requires no less than 42 grms. of crystallised potassium ferrocyanide. The ensuing pre- cipitate weighing at least 34 grms.exclusively of chemically combined water it became necessary to make a correction for bulk. 11grms. of soft iron wire were dissolved in hydrochloric acid and the solution diluted to 500 C.C. 84 grms. of crystallised potassic ferrocyanide were dissolved in water and the solution likewise made up to 500 C.C. The specific 8 Chemical News xxiii 61. -f Chemical News xxiii 76. 160 ABSTRACTS OF CHEMICAL PAPERS. gravity of the iron solution was found to be 1.055 that of the ferro-cyanide solution 1.093. 250 C.C. of each solution were mixed and the bulk of the mixed solutions was then found to be equal to 505 C.C. The filtered liquid had a specific gravity of 1.033 hence the bulk of the liquid was calculated as follows :-250 (1.055 + 1.093) -34 = 503 grms.503 and 50s --=18 C.C. 1.033 In order therefore to work only with 250 c.c.-one-half the filtrate- the liquid containing the precipitate has t'o be first madeup to 518 C.C. This quantity may be varied according to the purity of the metal from 517.5 to 518.5 C.C. Previous to dissolving the iron in acid it should be suitably commi- nuted; crude pig-iron for instance should be broken up in a steel mortar and passed through a sieve the meshes of which are 0.5 mm. apart. 5.6 grms. of the metal are then treated in a corered porcelain vessel with 60 C.C. of nitric acid sp. gr. 1.2;the solution is evaporated to dryness ; and the residue strongly ignited (best in a muffle) to bright redness first in the porcelain vessel next in a platinum crucible in order to oxidize the carbon.It is then dissolved in 35 C.C. of hydro- chloric acid sp. gr. 1.19 with the aid of a gentle heat. A residue of silica is left. The acid solution so obtained is washed into a flask without being previously filtered and diluted to about 200 C.C. A current of sulphuretted hydrogen is next passed in order to reduce the ferric to ferrous salt a method of reduction which Kessler prefers to the reduction by means of an alkaline sulphite. 200 C.C. of a solution of potassium ferrocyanide (strength 210 grms. of the crystallised salt per litre) &re next added and the bulk of the liquid made up to exactly 518 C.C. The precipitate is filtered OR. Prom 20-30 C.C. of the first portion of the filtrate usually pass through turbid andmay be rejected.250 C.C. of the clear filtrate are collected in a graduated flask and precipitated in the usual way by adding in a beaker 10 C.C. of magnesia mixture (strength 200 grms. ofmagnesium sulphate per litre). Kessler observes that the precipitate is always covered with a greyish flocculent substance which he removes by throwing the precipitate and the body just referred to on a small filter and washing with ammonia of sp. gr. 0.98. He next dissolves the precipitate which adheres to the sides of the beaker and also the portion contained on the filter in nitric acid of sp. gr. 1.035 when a bluish coloured insoluble cyanogen-compound is left behind. The phosphate is reprecipitated by means of ammonia collected on a small filter and washed with ammonia of sp.gr. 98,until on testing no more chlorine is detected. It is then dricd ignited and weighed as magne- ANALYTICAL CHEMISTRS. lG1 sium pyrophosphaie *lo0grms. of which salt correspond to 1per cent. (or more correctly to 09975 per cent.) of phosphorus. The author states that he found the method correct in every respect and suitable for all practical purposes and that he prefers it to the molybdic acid method for the estimation of phosphorus in crude pig-iron steel and malleable iron. w. v. Estimation of Zinc in Galvanized Iron. By THOMAS T.P. BRUCE WARREN.* THEzinc in galvanized iron exists in two states; firstly part of the zinc forms an alloy with the iron; and secondly to this alloy a greater or lesser quantity of zinc adheres mechanically.Only the part of zinc forming the alloy is necessary for the protection of the iron. This combined zinc cannot be removed from t,he iron by mercury but is nevertheless capable of uniting with a definite proportion of that metal '7 parts of this combined zinc taking up 11parts of mercury. On heat-ing the iron the mercury is again volatilised. On the other hand all the uncombined zinc can be removed by means of mercury. Let then a piece of galvanized iron be taken weighed cleaned with dilute sul- phuric acid and ipmersed for from 4 to 8 hours in mercury ; it will be found that part of the zinc has been removed part has remained on the wire together with the mercury absorbed. The piece is next taken out of the mercury well rubbed with chamois leather and again weighed after which it is heated iU EL non-oxidizing flame and the weight once more taken.The difference between the first and third weighings will be the uncombined zinc while the difference between the second and third weighings when multiplied by 7 and divided by 11,gives the combined zinc. This process moreover reveals all imperfections in the zinc coating since no mercury adheres firmly to such places. A. D. On a Mode of distinguiskimg the Deposit from Reimh's Pyocess from ST. CLAIRGRAY.? Salts of Mercuyy. By JAMES THE coated slip of copper is rubbed with a flat piece of pure gold. If the deposit on the copper contaius mercury the gold becomes marked with a clear white shining crust which is removable by nit,ric acid.C. H. 0. a Pllil. Mag. [4] xli 132. -f-Chem. News xxxiii 73. ABSTRACTS OF CHEMICAL PAPERS. Estimatiol of U7-ei-r by means of Soditcnz Hypobromite. By G. HUFNER.* HYPOCHLORITES, as is well known decompose ammonia compounds with evolution of nitrogen and Woh1er.f. based upon this reaction R method for determining the amount of ammonia in guano. It consists in measuring the nitrogen which a weighed quantity of guano yields when treated with a solution of bleaching powder the amount of ammonia being calculated €i*om the volume of nitrogen which is given Off. Urea is ached upon in a similar manner it is converted by the hypochlorous acid into free nitrogen water and carbonic anhydride 1 grm. of urea corresponding to 370 C.C.of nitrogen (at 0" C.and 760 m.m. pressure). E. W. Davy$ described in 1854 a method-afterwards somewhat modified by Leconte-by which he effected (although imperfectly) the decomposition of the urea and the collection and measurement of the nitrogen in a graduated cylinder over a saturated solution of com-mon salt. W. Knop proposed to employ instead of sodium hypochlorite a. solution of barium or sodium hypobromite an oxidizing agent which is at once more effective and more stable and a solution of which is readily prepared when required. The preparation of sodium or barium hypobromite is described by Rnop fj as follows 600 grms. of barium hydrate are placed in two litres of water and are shaken up with 100 C.C.of bromine. On adding a solution of 300 grms. of barium hydrate in one litre of water (prepared by dissolving the hydrate iii warm water) the bromine disappears and a golden-yellow solution is obtained which probably contains barium bromate and bromide as well as bromite and hypobromite. Sodium hypobromite is obtained by dissolving 100 grms. of sodium hydrate in 250 C.C. of water and leaving the solution to cool before adding 25 C.C. of bromine. 50 C.C. of this solution diluted with 200 C.C. of water suffice to liberate 130 to 150 C.C. of nitrogen from a solution of sal-ammonaic. The instrument devised by Knop-known under the name of agonteter-renders it possible to determine urea rapidly and readily and to complete within 15 to 20 minutes several determinations with sufficient accuracy.Hiifner now proposes to modify Knop's method so as to employ * J. pr. Chern. [2] iii 1. f-Prakt. Uebuiigen in der Chem. Analyse Boettiiigen 1853. 5 Phil. Mag. [4] iii 385. § Freseilius Zeiisch. f Aaalyt. Cliein ix 2 p. 225 ANALYTICAL CHEMISTRY. 163 a gentle heat in order to complete the re-action securing at the same time the advantage of not having to mix the urea solution and the oxidizing agent before the gas can be collected On heating the hypo- bromite solution oxygen is however evolved as well and the mixed gases (nitrogen and oxygen) are therefore collected in a gradnated cylinder. A urea solution is placed in the lower part of a mixing apparatus shut off from the part containing the concentrated hypo- bromite solution by means of a wide-bore glass stop-cock.A glass cup from 4 to 5 c.m. in depth is fitted to iis neck by means of a caoutchouc ring over the open end of the mixing vessel which reaches somewhat above it and delivers the evolved gases into the mouth of the inverted measuring cylinder which is about 30 c.m. long and 2 c.m. wide. The lower part of the mixing apparatus below the glass stop-cock has a diameter of 1.5 c.m. and holds about 10-11 C.C. of urea solution. The bore of the glass stop-cock should not be less than 7-8 mm. The upper portion of the mixing vessel is large enough to hold about 100C.C. of sodium hypobromite diluted with its own bulk of distilled water. The glass cup is filled with a saturated solution of common salt over which the measuring cylinder filled with distilled water is inverted and fitted into its position.On opening the glass stop-cock the specifically heavier hypobromite solution mixes rapidly with the urea solution and a brisk evolution of gas ensues. The Pecomposition is assisted towards the end by plunging the lower part of the mixing vessel into hot water. A small quantity of oxygen has to be deter- mined in the usual way by transferring the gases over mercury and absorption with pyrogallic acid. The published experiments approximate closely to the theoretical percentage of nitrogen in urea. The author adds in conclusion some speculations on the composition and constitutional formulze of other nitrogenous bodies such as hippuric acid ethylamine aniline coniiine nicotine asparagine uric acid creatine and others for which we must refer to the original paper.w. v. Detection of Alcohol in Chloroform and Chloral Hydrate. By HAGER. HAGER has carefully examined* the method for the detection of ethylic alcohol described by (A. Lieben Ann. Oh. Pharm. Xzqy. viii 2) based on the formation of iodoform and finds it extremely delicate and capable of detecting of alcohol in a liquid after about one day’s standing. He uses the following reagents 1. A solution of potassium iodide in 5 to 6 times its weight of water supersaturated with iodine ; * Pharm. J. Trans. [S] i 683. ABSTRACTS OF CHEMICAL PAPERS. 2. A ten per cent. solution of potassium hydrate. To detect alcohol in cl~lorofo~w2,2 vols.of the latter are shaken up with 5 to 10 vols. of water of about 50" C. ; the liquid is then poured on a filter previously saturated with water; to the filtrate are added 5 or 6 drops of thc potash 'solution and the whole is heated to about 50" C. ;the iodidc solution is then added drop by drop with gentle agitation until the colour of the liquid remains brown and finally it is cayefully decolorised by the addition of potassium hydrate and set aside to deposit. After 12 to 24 hours the sediment is examincd 1i11derthe microscope and t'lie iodoform crystals recognised by their star-shaped form. The presence of alcohol or rather of chloral alcoholate in c7doi.d kydrate may be detected in a similar manner. Schering (ibid.) calls attention to other distinctions between chloral hydrate and alcoholate :-the former when warmed with twice its vol.of water dissolves but the latter melts without solution and solidifies again on cooling. Siilphuric acid remains colourless when warmed with the hydrate whereas it turns brown with the alcoholate. No reaction or only a very slight one ensues on warming the hydrate with nitric acid sp. gr. 1.2; the alcoholate is violently attacked and nitrous €umes are evolved in abundance. H. E. A. Eznmindion of F1ou.r. By W. DANCKWOETT.* THEauthor has endeavoured to ascertain approximately the amount of wheat-flour present in what was declared and taxed as rye-flour. The amount of residue (gluten) left after washing out the starch and soluble matter from different mixtures of wheat and rye-flour was determined ; mixing the flour with weli washed wheat-bran appears to facilitate the drying of the residue.The bag in which the sample is put the flour and bran employed are all thoroughly dried in the water- oven; as is also the gluten left by the washing. 10 grms. rye-flour mixed with 1grm. wheat-bran placed in a bag of silk bolting-cloth of a certain fineness and washed with distilled water until the water was no longer milky gave after subtracting the weight of the bag and bran a residue of 0*5-0.8 per cent. ; pure wheat-flour similarly treated gave 7.0-8*0 per cent. residue ; mixtures of 3 p. rye- with 1p. wheat-flour 1.0to 2.0 per cent. ; mixtures of equal weights of rye and wheat- flour gave 3.0to 3.5 per cent.residue. These numbers were the mean of several experiments. The suspected flour similarly treated gave in seven experiments a residue varying from 1.0-2.2 per cent. This would be given by a mixture of 70-75 per cent. rye-flour with 25-30 per cent. whea,t-flour. * Arch. Pharm. [2] xx 47. ANALYTICAL CHIZMTSTRY. Microscopical examination of mixtures of the two flours gave very doubtful results. W. H. D. Analysis of 17lilk.* By J. A. WANKLYN. THE“British Medical Journal” reports the following result of an analysis of the contents of a tin of Newnham’s condensed milk. Water ............ 19.0 Casein ............ 10.0 Ash .............. 2.0 Fat ............. Milk-sugar ........ 69.0 Cane-sugar ........There appeared to be about as much fat as casein. From this analysis it follows that one pound of the condensed milk contains the solid constituents of from three to four pounds of Gesh milk. In the course of an examination of milk undertaken for the “Milk Journal,” the observation was made that there is a source of inaccu-racy in the ordinary methods of examining milk hitherto quite unsus- pected. It mas found that the exact molecular condition of the casein influenced the specific gravity of the milk in other words that samples of milk of the same strength varied in specific gravity according to the molecular condition of the casein. The followmg examples are given to show how this may cause a want of correspondence between the specific gravity of milk and the amount of its solid contents.The speaimens of milk had been kept in corked bottles for four days. Per cent. of SP. gr. solids dried Per cent. at 60 9. at 212”F of mh. Sample A .... 1*0004 11.34 0.94 B... 0.9960 10.48 0.75 ,7 79 C.. .. 1.0184 8.92 0.66 To be of any value at all the specific gravity must be taken while the milk is very fresh for when milk is kept for two or three days even in a closed vessel the density falls in a very remarkable manner. It is therefore proposed in judging of the strength of milk to adhere to the method of evaporating to dryness in the water-bath and weigh- ing the residue. J. B. * Pharm. Journ.‘Trans. [3] I,605. VOL. XXIV. 0

ISSN:0368-1769    

DOI:10.1039/JS8712400155

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

ABSTRACTS OF CHEMICAL PAPERS. Technical Chemistry. Prepamtiom of Hydrogen Gas.* THE Journal of the Society of Arts states that M.M. Tessi6 du Motay and Marechal have lately discovered a new and economical method of producing hydrogen gas. The process consists in heating the hydrates of the alkalies and alkaline earths with coke coal charcoal &c. to a red heat whereupon carbonic acid and hydrogen are given off abundantly ; and as the decomposed hydrates especially that of lime can be used indefinitely by simply remoistening them with water the method is very economical. In this operation the hydrogen gas is generated without any special production of steam and may thus be produced without any other generating apparatus than the retorts themselves ; and as these retorts are not exposed to the direct action of the steam they are not subject to any interior deterioration.This process it is said in conjunction with the method of obtaining cheap oxygen from the manganates of soda discovered by the same chemists is likely to create a revolution in many industries and especially in metallurgy. 3. B. On the Application of certaiw Fluorine-compounds for the Preparation of Frosted @lassfor Photographic Purposes. By E. S I E Gw ART.? IN place of aqueous hydrofluoric acid for etching glass the author recommends a solution of eight parts of an alkaline fluoride dissolved in 100 of water and mixed just before using with one part oil of vitriol. Before immersion in this bath the glass requires to be cleaned in another made with potassium dichromate and sulphuric acid to remove all traces of organic matter from its surface.A few hours at ordinary temperatures suffice to produce a fine glistening frost. The reat of the paper contains details concerning the preparation and use of etching-wax for producing patterns and figures. C. H. G. On the Constitution of Ultmrnarine. By W. STEIN. DOESultramarine as a whole constitute a chemical compound and in what state of combination does the sulphur exist therein ? Examining the latter point the author rejects the idea of the sulphur * Pharm. Trans. [S] I 566. t Dingl. Polyt. J. csix 222. $ Journ. pr. Chem. [23 iii 39. TECHNICAL CHEMISTRY. 167 existing either as hyposulphite sulphide or polysulpliide of sodium and while admitting the presence of sodic sulphite in most samples of ultra-marine considers its presence accidental the essential sulphur consti- tuent being aluminium sulphide.He finds that aluminium sulphide exists in two forms as a crystalline colourless (yellow) mass and as an amorphous black powder. The black modification arises when the body is formed at comparatively low temperatures or when the presence of foreign matter between the particles prevents them fusing together. He considers that this last condition obtains in the ultramarine manu- facture and that the characteristic blue colour of the body is due not to its chemical composition but to its mechanical structure-that it owes its colour indeed to the same causes which give a blue tint to a mixture of lamp-black and milk &c.He therefore concludes that ultramarine (blue) consists of a white (ground) mass with which black aluminium sulphide is mingled in a state of molecular division. White ultramarine he regards as the blue compound the colour of which is compensated by the orange-red of sodium sulphide present with it and the green pigment as arising from the conversion (partial ?) of the orange-red sodium sulphide into sodium bisulphide whereby yellow and blue occurring together give rise to green. C. H. G. The Efects of Cold Zcyon t7~eStrength of Ivon. By W. BROCKRANK.* THE bars of pig-iron employed were made from a mixture of four pig- irons of the highest class added to some good scrap-iron so as to insure a sounder and more regular casting; all the bars were cast from one ladle.The testing machine used was a powerful lever or st,eel-yard the bars having a three-foot bearing. The results showed a gradual and considerable decrease of strength in the bars with the in- crease of cold below the freezing point. They also lost their elasticity in a similar degree. Tension. Tension. .-'P At 20'. At 80". /At 20". At 80". ' 2142 lbs. 2142 lbs. 16$ twists. 1G twists. 2114 , 2058 , 15.& , 14i 99 2114 , 2086 , 9 ,? 13Q 9 a 9, 2142 , 2086 , 14 ?> 144 2114 , 2128 , 16 , 124 9 2114 , 2086 , IS!? ,9 Wi 99 -Total.. 12640 , 12586 , -90 9 834 , $7 Average 2123.3 2097.6 15 13.9 ,) * Chem. News xxiii 62. 168 ABSTRACTS OF CHEMIOAL PAPERS.Mr. Brockbank refers to the general experience of ironfounderq and cites instances of breakages of castings during frosty weather showing that the strength of cast iron is very materially lessened by severe cold. Experiments were also made to test the effect of frost upon the tensile strength of wrought iron. The methods used by Kirkaldy viz. torsion and gradual tensile strain did not give a true result as the iron tested worse when warm than when frozen. The simple test of the striker's hammer was then resorted to and a number of experiments was described showing "short ') crystalline fracture in the iron without any appearance of fibre whilst the same iron,-a strip of boiler plate,-after being slightly.warmed to " dispel the frost," was exceedingly tough and fibrous showing a good fibrous fracture.Rails in course of manufacture for East Indian railways at the Dar-lington Iron Company's Works failed to pass the required test in frosty weather whereas at ordinary temperatures a failure was a very rare occurrence. Rails were heated to 120" F. others were tested at the temperature of 26" F. The following table shows the results :-Test of East Indian Railway Rails,82 lbs. per yard November 29 1869 tested by a Falli.iLg Weight of 2,000 lbs.; Cewhes of Support 3 feet 6 inches apart. Number of Height Permanent Tempera-Remarks. blows. of falls. set. ture. ft. in. Firat blow.. .. 50 7-16th .. Second , . . .. 50 3-4th~. . .. 120" Not broken. Third , .... 70 *.*.1 5 0 13-lGth~ .. 1 Do. Ditto. First )) .. . . 50 3-8th~... . Second ,) .... Third 70 .,.. ) ,... .. .. ,) First 50 34th~.. . . Second , ,... 50 13-16ths .. Do. Ditto. Third ,) .... 70 .. .. First ,) ,... 50 34th~.,. Second , .... 50 743th~..,. Do Ditto. Third , .... 70 .. .. First , . . .. 50 Second , .... 50 .... 26" Broke with 2nd blow. First , .... 50 3-8ths.. , Do. Passed test. Second , .. .. 50 5-8th~.. . . } First , .... 50 Second , .... 50 ..t. Do. Broke with 2nd blow. First .... 50 Second , .... 50 Do. Ditto. First , ,... 50 Broke .. . Do. Broke with 1st blow. First ) ,... 50 Do. Broke with 2nd blow. Second ,) .... 60 TECHNICAL CHEMISTRY. All the experiments adduced prove that iron becomes much weaker both in its cast and wrought state under the influence of low tempera- tures.It loses its toughness becomes quite brittle under sudden impact and changes its structure &om fibrous to crystalline. W.V. On the Production of Alloys of Iron and Manganese and on their Appli-cation to the JIawufactzcre of Steel. By P. ROIIN.* THEauthor after referring to Heath’s patent in 1839 for the employ- ment of manganese in the manufacture of steel and to the use of late years of the Spiegeleisen of Rhenish Prussia and other ferro- manganese alloys in the Bessemer Siemens-Martin and other pro- cesses proceeds to describe the process of Henderson of Glasgow. This process which has been at work for some time at the Phamix Foundry Glasgow consists in reducing upon the open hearth of a Siemens’ furnace a mixture of carbonate of manganese and oxide of iron in presence of excess of carbon by means of st neutral or reducing flame.The furnace bottom is of ground coke consolidated and baked up to form a crucible on a large scale. The charge of finely ground oxides mixed with powdered charcoal or coke is heated to redness for several hours. It thus becomes converted into a metallic sponge which contains the reduced metals from both oxides and is then run down to a regulus by raising the temperature to a full white heat. The quantity of manganese in the alloy depends chiefly upon the high temperature obtained at this latter stage of the process hence the necessity of employing a Siemens’ furnace by which a high reducing tempera- ture can readily be obtained.Though considerable loss occurs owing to the action of the silica in the ores used upon the manganese yet with proper selection of mate-rials an average of 20 per cent. to 30 per cent. of manganese is obtained in the alloy. An ordinary-sized furnace worked by one man can produce 15 cwt. of ferro-manganese every 24 hours. The cost by this process the author states to be about S7 perton for alloy containing 20 to 25 per cent. of manganese ; this is exclusive of royalties the amount of which per ton the author does not state. The author concludes by pointing out, that not only will the manufacture of these ferro-manganese alloys prove a profitable accessory to every Bessemer steel works in the country but that it will also make these works independent of the fluctuations and uncertainties of the foreign SUDDlY.C. G. * Journal of the Iron and Eltee1 Institute Feb. 1871,70. ABSTRACTS OF CHEMICAL PAPERS. Ohserrations on the Manufacture of Vermilion. By M. ALs BE EG.* IN manufacturing vermilion by Martin's process two stages are to be observed first the formation of the amorphous black sulphide and second the conversion of this into the crystalline red modification by the successive solution of the black sulphide by the alkaline sulphide present and its deposition in the red form. The crystals of red sul- phide so obtained are rhombohedrons approaching a cube. They are doubtless the primitive rhombohedrons observed on the native crystals R on R 92" 36'.The solubility of sulphide of mercury in alkaline sulphides constitutes a source of loss of from 5 to 8 per cent. of the mercury employed in this process. C. H. G. Black Lz1sti.e Colozhr for Sthgchr-paper. 'By Dr. KIELMEYl3R.t 8 lbs. ordinary glue 16 lbs. water 1lb. potato starch 5& lbs. water 521bs. Campechy extract of 6" Baume 1lb. 2 oz. green vitriol 8%lbs. brown glycerin ; all boiled together and stirred when cold. Paper once painted with this mixture acquires when dry a fine bright black surface remains supple and does not exhibit a tendency to get sticky. If it be desired to render the paint thicker or thinner the starch and the glue must be increased or diminished in the same proportion or the lustre will be spoiled.C. H. G. ('Sucrnte of Hydrocurbo?zate of Liwe " applied to the purijication of flugar-cnne Juice. By BOWINand LOISEAU (Chem. News xxiii 19). Preparcrtion of yzLic32ly-7~a?.deizi72Ycolauyecl Cements. By R BOETTGER. WHENfinely-pulverized chalk is stirred into a solution of soda-water glass of 33" B. until the mixture becomes thick and plastic a cement is obtained which will harden in between six and eight'hours possessing an extraordinary durabi:ity and alike applicable for domestic and industrial purposes. If any of the following substances be employed besides chalk diffcrently-coloured cements of the same general character are obtained. 1. Finely pulverized or better still levigated stibnite (grey antimony or blnck sulphide of antimony) will produce a dark cement which after buroishing with an agate will present a metallic appearance.* Chein. Kcws xsxiii 73. t Dingl. Polyt. J. cscix 233. 1 Pharin J. Trans. [2] iii 19. TECHNICAL CREMIXTRY. 171 2. Pulverized cast-iron a grey cement. 3. Zinc-dust (so-called zinc-grey) an exceedingly hard grey cement which after burnishing will exhibit the white and brilliant appearance of metallic zinc. This cement may be employed with advantage in mend-ing ornaments and vessels of zinc sticking alike well to metals stone and wood. 4. Carbonate of copper a light green cement. 5. Sesquioxide of chromium a dark green cement. 6. Thenard’s blue (cobalt blue) a blue cement.7. Minium an orange-coloured cement. 8. Vermilion a splendid red cement. 9. Carmine-red a violet cement. On a curious property of Gun-cotton. By L. BLECKRODE.~ A FLAME may be applied to gun-cotton which has been previously wett,ed with carbon bisulphide without explosion taking place Only the latter substance takes fire immediately the gun-cotton remaining apparently intact amidst the burning bisulphide presenting almost the aspect of a mass of snow slowly melting away. Ether alcohol and benzol may be employed with the game result. The author considers this slow corn- bustion which takes place when the cotton is moistened with carbon bi- sulphide or any other volatile liquid to be a most direct and satisfactory proof in favour of the conclusion to which Professor Abel was led by his researches viz.that if the gases resulting from the first action of heat on gun-cotton upon its ignition in open air are impeded from completely enveloping the burning extremity of the gun-cotton twist their ignition is prevented ; and as it is the comparatively high temperature produced by their combustion which effects the rapid combustion of the gun-cotton the momentary extinction of the gases and the continuous extraction of heat by them as they escape from the point of corn- bustion renders it impossible for the cotton to continue to burn other- wise than in a slow and imperfect manner undergoing a transformation similar in character to destructive distillation. A piece of phos-phorus placed in the moistened mass of gun-cotton is melted and even boils during the combustion but does not burn as it is pre-vented from contact with the oxygen till all the gun-cotton has disap- peared.He suggests that gun-cotton should be preserved under carbon disulphide or benzol by which the danger in case of fire is eliminated. Should the liquid become ignited the cotton will be only slowly destroyed. H. E. A. Phil. Mag. [4],xvi 39. ABSTRACTS OP CHEMICAL PAPERS. Om the recovery of Ta~fctr~c and Oxalic Acids from the Residues of the Lb Discharge ” Process and on Eau de Labarrape as a substitute for Chloride of Lime in dischargi?zg Turkey Red. By ARMAND Mu LLER.~ WHENcloth which is in parts impregnated with one or both of the above-named acids is passed through the discharge vat which con-tains chloride of lime with a greater or lesser excess of lime a well- known decomposition takes place and the acids are converted into their calcium salts which being insoluble settle together with the excess of undissolved lime at the bottom of the vat.If the slimy deposit so prodriced be allowed to remain in the working vat for some weeks with frequent agitation it becomes continually richer in the salts and poorer in free lime till it attains even such it percentage of the former as 65.5 per cent. calcium tartrate and 18 per cent. calcium oxalate. From this mixture washed and somewhat diluted with water the acids are liberated by addition of a previously determined quantity of sulphuric acid of 1.568 sp.gr.,and after stirring and boiling with as much more water as is equal to the weight of the original deposit the liquid is separated from the calcium sulphate by help of a centrifugal machine. Any excess of sulphuric acid contained in the liquid is removed by boiling with barium tartrate. This method is still better when chloride of soda (eau de Labarraque) is employed in the discharging vat in place of the chloride of lime As the tartrate of soda remains in solutioii it is only necessary to add from time to time a sufficient quantity of chloride of lime solution to precipitate all the tartaric acid as a lime salt and to restore the original working strength of the vat. In this case the precipitate will contain no calcium hydrate or carbonate and consequently a great saving of sulphuric acid will be effected. A further advantage is found to follow the use of the soda solution namely that the whites are whiter and the reds are less injured than when the chloride of lime is employed. C. H. G. * Chem. Centr. 1871 134.

ISSN:0368-1769    

DOI:10.1039/JS8712400166

出版商:RSC    

年代:1871

数据来源: RSC

摘要:

PAPERS READ BEFORE THE CHEMICAL SOCIETY. XIV.-Comntuit.ication s from the Laboyatory o,f the Lodo~aITLstitlctiolz. No. I.-Oiz the Formation of fhdpho-ncids. By HENRY E. AEMXTROSC:. (Preliminary Notice.) OCCUPIED with an investigation into the constitution of sulphuric acid the views on which are as is well known even at the present moment extremely conflicting my attention was soon drawn to the body dis- covered by Prof. Williamson viz. chZor7ydric szdp7~de (sulpliuric chlorhydrate sulphuric oxychloride) SO,HOCl and particularly by a somewhat remarkable reaction noticed by Karl Knapp,* who found that the chief product of its action on benzene was szdphoLmzide,-sulplLobenxo7ic "chlot*ide and szdp7~obenzolic,ricid being likewise formed biit in relatively very small quantity :-2C,H + S02.H0.C1 = C6H5}S02 + OH? + HCI.CGH5 CCHG + SO,.HO.Cl = SO2.CGH5.Cl + OH,. CCH + S02.HO.Cl = SOz.CsH5.HO + HCl. It mas presumable that sulphobenzolic acid m-ould be the main pro-duct ; the reverse was actually the case. This led me to commence a series of experiments to determine if possible the conditions under which the one or the other of the above reactions takes place and to arrive at a general expression €or the action of chlorhydric sulphate on organic bodies. Acfioiz of SO2.HO.Cl on Bvomobenxene C,HsBr Monobromobenzene,1eq. diluted with carbonic d-isulphide was mixed with the chloride 1eq. ; moderate reaction took place hydrochloric acid being evolved in quantity. After warming on the water-bath for a short time the carbonic disulphide was distilled off and the product mixed with water.A brownish semi-solid mass then separated out and mas removed by filtration ; the filtrate was neutralised by baryta- water and heated to boiling whilst a current of carbonic anh$ride n-cs passed inio it to remove excess of baryta. On cooling LZ difficu!tly soluble barium salt crystallised out in magnificent white iriclesccnt plates which were pressed and dried between bibulous papcr and analy sed. Q Zeitdiri€t fur Chemie 1869 41. TOT,. XYIV. P 174 ARMSTRONG ON THE 1.4032 grm. lost ,035 grin. on drying at 100" = 8.6 per cent. OH ,4444 grm. dry salt gave el723 grm. BaSOA = 22.5 per cent. Ba. These numbers correspond well with the formula (C6H4BrSOa),Ba C 3 aq.which requires 8.1 per cent. OH2,and 22.6 per cent. Ba. The portion insoluble in water was washed with cold alcohol to free it from adhering bromobenzene and then dissolved in hot alcohol ; on cooling it cryktallised in fine long white glistening needles which after pressing and drying at looo were analysed with the followiq results :--4271 grm. gave .607 grm. CO,and 9974 grm. OH = 38.7 per ceut. C. and 2.5 per cent. H. The formula g:g$:S O,-dibromosulphobenzid~~e~~ires 38.3 per cent. C. and 2.1 per cent. H. When dry this body forms white dky needles soluble in hot clifficultly soluble in cold alcohol It melts at 168" and solidifies again at 149". The action on bromobenzene is therefore somewhat different to that on benzene.Brornosulphobenzolic acid is the main product the yield of dibromosulphobenzide not exceeding 20 per cent. Bromosnlphoben-zolic chloride was formed if at all in but very small quantity. Whether the bromosulphobenzolic acid thus obtainecl is icleiitical with that prepared by the action of concentrated sulphuric acid on hrniiiobenzcne I cannot state not having compared them directly. A cf;on of SO,.HO.Cl on X'a'trobeizxew CbH5N02. The two bodies were mixed its before in the proportion of 1eq. of each but without the addition of carbonic disdphide. In this case the action was cxtremely sluggish and it was only after long-continued warming that thc evolution of hydrochloric acid ceased. On mixing with water a small quantity of a black tarry niass remained which may possib7y contain dinitrosulpliobenzide.The solution was converted into the barium salt but as this was exceedingly impure it was dissolved together with a quantity of baric hydrate and the solution saturated with hydrogen sulphide. After boiling the solution the barium was carefidly precipitated by sulphuric acid and the filtrate evaporated to crystallisation. By this means the very impure nit8rosulphobenzolic acid first formed was reduced to the amido-acid which could more easily be purified. According to Schmitt,* by the action of concentrated sulphuric acid * Ann. Ch. Fl~~rm., cxx 163. FORMATION OP SULPHO-ACIDS. on nitrobenzene and reduction of the product to the amido-acid an amido- sulphobenzolic acid is obtained isomeric with sulphanilic acid prepared from concentrated sulphuric acid and amidobenzene (aniline).His acid crystallises with 1$ mol. aq. ; sulphanilic acid with 1mol. only. My pro-duct I believe is not sulphanilic acid being much too soluble in water and crystallising differently ; but on the other hand it crysta,llises with only 1mol. aq. :-1.2555grm. lost ,1153 grm. = 9.1 per cent. OH,. C,HkNH2.HS03 + ztq. requires 9.4 per cent. so that until it has been compared directly with Schmitt's acid it is impossible to say with certainty whether by the action of sulphuric acid and of chlorhydric sulphate on nitrobenzene the same or isomeric snlph o-acids are produced. Action of S0,.HO.C1 01t NitPO~J7~efzol U6HIN02.H0. Nitrophenol (the volatile modification melting point 45")1ey.sus-pended in carbonic disulphide was mixed with 1eq. of the chloride immediate action took place and large quantities of hydrochloric acid were evolved. After distilling of€ the carbonic disnlphide the pro-duct was em5rely soluble in water. The excesR of sulphuric acid was removed by lead carbonate the excess of lead by hydrogen sulphide and the solntion was then nen-tralised with potassic carbonate and evaporated to crystallisatioii. In this way the very characteristic yellow needles of the rZQiotassic nitro- p?~ei1olsuZp7~nte + 2 aq. were obtained and from a CGH~NO~.OK.SO~K solution of this salt on the addition of acetic acid the tufts of light-yellow needles of potassic ~zit~oj~?~e~~obz~~7i~te,SOsK. CGH3NOZ.0H.Very remarkable is the action of the chloride on the non-volatile modification of nitrophenol. According to Kekul6 whereas the volatile modification is readily converted into the sulpho-acid by the action of concentrated sulphuric acid it is not possible to prepare a sulphoacid from the isomeric non-volatile modification. The same nitro-acid was prepared by Kolbe and Gauhe by nitration of para-phenolsulphonic acid ; they could not howevei- obtain a nitro-acid by thc action of nitric acid on metaphenolsulphonic acid. I had hoped to obtain such an acid by the action of SO2.HO.C1 but it is not so. TVhen these substances are mixed in equivalent proportions with the addition of carboiiic disnlphide immediate action takes place and large quantities of hydrochloric acid are evolved.On the addition of water an oil separated which dissolved almost entirely in hot miter but from the solutioii on cooling the characteristic long white neec1le.s of nitrophenol crystallised out ; tht?filtrate contained only sulplluric ticid and traces of nitrophenol. P2 176 HOW ON A WATER FROM THE COAL NXASURES The sulpho-acid if formed (and it seems to me beyond doubt that it is) in the first instance is evident,ly decomposed by water into nitro- phenol and sulphuric acid. It may perhaps be possible to isolate it by appropriate treatment. Actioyz of SQ2.H0.C1on Naphthaleize. 1eq. naphthalene dissolved in carbonic disulphide was acted on by 1eq. chlorhydric sulphate ; violent action took place accompanied by evolution of hydrochloric acid.The reaction was terminated after dis- tilling off the carbonic disulphide by heating €or some time at 100". Tlie residue remaining after treatment of the product with water consisted almost entirely of naphthalene since it m.as volafilised on boiling with water. The naphthalene compound analogous to sulphobenzide is therefore not formed in any appreciable quantity. From the aqueoLis solution a barium salt was obtained containing 24.4 per cent. of bnrium. Baric sulphonaphthalate requires 24.7. To decide if possible whether both the CL and /3 modifications of sulphonaphthalic acid were formed the calcium salt was prepared and a determination of the water of crystallisation made. The P-salt is anhydrous mhereas the a-salt crystallises with 2 mols.aq. correspond- ing to 7.3per cent ;my salt contained 3.6 per cent. and Ibelieve there- fore was a mixture of the two isc;meric salts. In all probability the a-acid first formed is converted by subsequent heating into P-acid. The anhydrous calcium salt contained 8.8 per cent. Ca ; required 8 per cent. By the action of 2 mols. S02.K0.C1on 111101. naphthalene a disuh?lio-acid is formed. The conclusion to be drawn €romthe above few experiments is it seeiiis to me that; the normalaction so to speak of chlorhydric sulphate is to form a ~z@ho-ncid,the chlorine of the chloride removing hydrogen fi-ollz the body acted upon and replacing it by the group SOJH; it is only under certain conditions that both C1 and HO are removed from the chloridc and a compound analogous to sulphobenzide is formed. What these conditions are I hop to establish by a further more extended series of experimeniR.

ISSN:0368-1769    

DOI:10.1039/JS8712400173

出版商:RSC    

年代:1871

数据来源: RSC