摘要:

THE JOURNAL OF THE CHEMICAL SOCIETY LONDON WARREN DE LA RUE P€€.D. W. ODLING M.R. F.R.S. F.R.S. J. STENHOUSE LL.D. F.R.S. THOMAS GRAHAM F.R.S. .Yc-".A -.-b ""-% L y1 "\ NEW SERIES VOL. 111. (Entire Series Vol. XVIII.) . --~ ~~ ~ ?_?. LONDON HI:PPOLYTE BAILLT$JRE 219 REGENT STREET. lStl5. LONDON PRINTED BY HARRISON AND SONS aT. MARTIN'S LANE. CONTENTS OF THE EIGHTEENTH VOLUME. PAOB The Action of Ammonia on SulphochIoride of Phosphorus. By J. H. Glad-stone. Ph.D. F.R.S. and J. D. Holmes Esq. .. . . . . ............ ... . 1 Note on the Artificid Formation of Pyridine from Naphthalene. By W. H. Perkin.. ............ .. .. ,. ,...,.,... ....... .. .. ....... . ...... 9 Researches on the T‘acuum. By Hermann Sprcngcl P1i.D..... . ....... 9 On a New React.ion for the Production of Anhydrides and Eihera. By John Broughton B. Sc. Chemical Assistant Royal Institution .... ..,..... 21 Laboratory Memoranda. By Robert Warington Junr. Assistant to Pro- fessor of Chemistry R. A. ColleAe Cirencester .. ... . . ........... .... 27 Note on the Boiling Points of Isomeric Ethers of thc Formula C’rrHSl102.ByJ. Alfred Wanklyn.. ...... -.. ,...........................,... 30 Note on the Action of Chloropicriu and Chloroform on Acetate of Potash. ByHenry Rassett ... . . ...... . . .............. .. .. ,...,. ,......... 31 On Microscopical Researches in Relation to Pharmacy. By Henry Deane F.L.S and Henry B. Rrady F.L.S................... .. ......,. .. 34 On the Oxidation of India liubber.By John Spiller F.C S. . . .,. .. ,. 44 On a Dense Brine from Saltsprings Nova Scotia. By Prof. Horn D.C.L. University of King’s Collego Windsor N.S. ,..... . . ,... . . . . . . . . ..,. 46 On t!ie most Volatile Constituent,s of American Petroleum. By Edmund Ronalds Ph.D. .. . .... ,. ...... . ,...... ........... ...... .. .... 54 On the Action of Chlorine upon drseuious Acid. By Charles L. Bloxam. 62 On a Crystallised Hydrate of Phenylic Alcohol. By F. Crace Calvert F.K.H. F.CS. .....,.... . ....................,. ,..... .. .... .. .. 66 On the Action of Silicate and Carbonate of Soda an Cotton Fibre. ByF. Crace Calvert F.R.S. P.C.S. .. .... .. .. .. .... .. .. .. ..,....... 70 On Borne Hydrated Cupric Oxychlorides from Cornwali. By -4. H.Church M.A. Professor of Chemistry R. A. College Cirencester . . ..... . .. . .. . 77 On some Hydrated Cupric Oxgsulphates from Cornwali. By A. H. Church 83 On Vapour-Densities. 13y J. Alfred Wanklyn .. .... . ... .. ... . ,.,.,.. 89 Note on a New Brornine-Dcrivative of Camphor. By W. H. Perkin .,..... 92 On the Action of Hydrosulphate of iiminouia upon freshly precipitsted Sul- phide of Copper. By Charles L. Bloxam . ... . . . .. ............ .. 94 Notes upon the General Routine of Qualitative Analysis for Metals. ByCiftrlcs 1,. Bloxam.. .. .. .,.. .. ... ........ .. ............ ..... 97 en the Periodides of some of the Organic Bases. By William A. Tilden Demonstrator of Chemistry in the Laboratory of the Pharmaceutical Society 99 On Phosphitle of 3Iagnesium.By Thomas P. Blunt . .... . . .... ,.... . 106 On the Specific Refractive Energy of E,J. 11 Crla.c\stone 1’h.q. P.1 s. . . iernents and their Compounds. .... . . .... .. .. . . ,. .. .. .... ,. . .? 108 1v CONTENTS. PSGB Observations on some Points in the Analysis of Potable Raters. By Professor W. A. Xiller M.D. LL.D. Pres. Chem. Soc.; Trcau. and V.P.R S.. .. . 117 Researches on Acids of the Acrylic Ser.!es.-No. 1. Transformation of the Lactic into the Acrylic Series of Acids. By E. Frankland P.R.S. and B. F. Duppa Esq. ...... . . ..... . ........ . . .. ...... . . .. . . ........ 133 On Lecture Illustrations. Uyv A. W.Hofmann.. .... . . . . . . . ....... . .... 166 On the Action of Nascent Hydrogen on Azodinaphthyldiamine. By W.H.Perkin.. ..... . ,..... . . ..,..... ... .. .. . ......... . .. ,...,..... 173 On a Mode of Measuring the Relative Sensitiveness of Phcttographic Papers. By Arthur M'Dougall BSc.. ... . ..... ...,.... . . ........ ..... . . . 183 On some Compounds and Derivatives of Gtlyoxylic Acid. By Henry Debus Ph.D. F.R.S. .. .................. ...... .. .. .................... 193 On the presence of Mangmese in Oolite and Lias. By Robert Warington Junr. Assistaut to Professor of Chemistry Royal Agricutural College Cirencester . ... . . . . . .. .. . ,. . . . . . ...,..,.. . . .... . .. .,. .. 206 Table for the Calculation of direct Nitrogen Determinations. By Jas. T. Brown .............. .. ........ ..,... .. ........ ........ ....,. .. 210 Notes on a Cornish Mineral of the dtacamite Group.By A. H. Church.. . . 212 Notes on a Ferric Hydrate from Cornwall. By A. I€. Church .... . .. . .,,. 214 Analyses of some Bronzes found in Great Britain. By A. H. Church .. .. 215 The Estimation of Indigotin or the Blue Colouring Matter of Indigo. ByClemens Ullgren . . ,...,....* .,.. . ..... . .. . ,...... . .. . . . .... 217 On the Qualitative Analysis of Substances Insoluble in Water and Acids. ByCharles L. Bloxam.. ,.......,,..... .... .. .. .................. 226 On the Theory of Isomeric Compounds. By Dr A. Crum Brown ,.. . . .. 230 On the Action of Light upon Sulphide of Lead and its bearing upon the Pre-servation of Paintings in Pictiire Galleries. By Dr. David S. Price F.C.S.. ... . . .. ,.,.. . . ...,. .. ,.. . ..... . . ...,...... . ..,....... 245 Notes on the Compounds of Copper and Phosphorus. By F. A. Abel F.R.S.. 249 cester. ,... ... . , ,.. . ...... . ...... ... . ... . ..... . ...... . ...... 259 On a new Series of Bodies in which Kitrogcn is substituted for Hydrogen. Peter Griesa .... .... ...... . .... . . ... . . . . ..... . .,....... . ,.By Chemical Researches on some new and rare Cornish Minerals. By A. €1. Church M,A, Professor of Chemistry Royal Agricultural College Ciren- .. 268 On the Decay of Gutta-percha and Caoutchouc. By Professor William Allen Killer F.R.S. .. . . . . ,.............. ... . ....... . ,., .. 2'13 On the Absorption of Vapours by Charcoal. By J oh n Hunter M.A. ..,. 285 On Caprylic and CEnanthylic Alcohols. By Ernest T. Chapman ....... 290 On a New C!ass of Organic Compounds in which Hydrogen is replaced by Nitrogen. By Peter Qriess .. ..,.,.. . ............ .. .. .. . . ...... 298 Qn Nitro-compounds (Part 11). ?Vith Remarks on Isomerism. By Edmund J. Mills I).Sc. F.C.S. ..,... .. ................ ....... .. .. ...... 319 On the Synthesis of Tribasic Acids. By Maxwell Simpson M.D. F.R.S . 331 On an Bmmoniacal Deposit formed in the process of Drying Blood By John A. H Newlands F.C.S. .... ........................ ..,. ........ 340

ISSN:0368-1769    

DOI:10.1039/JS86518FP001

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

9 111.-Researches on the Vacuum. By HERMANN Ph.D. SPRENGEL 1. The Instruments. THE methods hitherto proposed for producing a vacuum may be divided into two classes the mechanical and the chemical. A gas wliich fills a space may either be removed mechanically or it may be converted by taking asvantage of its chemical or physical properties into a non-gaseous tensionless body. As however our atmosphere from its general presence is for the most part the only gas which has to be considered when a vacuum is to be formed and as the reduction of its consti-tuents to the non-gaseous form is attended with peculiar diffi- culties I am inclined to consider that all practical methods of producing a vacuum may be regarded as mechanical. Atmo-spheric air may in fact be expelled from a space firstly by a solid * Chem.SOC.J. vol. ix p. 1. SPRENGEL’S RESEARCHES ON THE VACUUM. body secondly by a liquid and thirdly by a gas which afterwards takes either a liquid or a solid form. Perfect vacua have hitherto been obtained only by this last method but with such attending difficulties that it appeared to me highly desirable to improve the other two which afford greater facilities of working. The dis- placement of a gas by means of a solid or a liquid body is effected by instruments commonly called air-pumps. The exhausting syringe of Otto von Guericke with its piston is the type of one class of these instruments while Toricelli’s baro- meter with its column of mercury is the type of the other class.The invention of the common air-pump was a consequence of Toricelli’s vacuum and it is partly due to this that the degree of exhaustion attained by it has been up to the present day com- pared with Toricelli’s vacuum as the standard of perfection. Hence it has followed that physicists have from time to time attempted to use Toricelli’s vacuum as a receiver or in other words to fill receivers with mercury and attach tubes to them as long as those of barometers through which the mercury was allowed to run off All so-called mercurial air-pumps are based upon this principle and differ very little from the famous experi- ment which Toricelli made 220 years ago. This however is not the only way in which the case may be viewed. If the top of a barometer were knocked off the air would enter and the mercury would sink or what is the same the mercury would sink and draw in the air.If however the experiment be so arranged as to allow air to enter together with the mercury and in such a manner that the supply of air shall be limited while that of mercury is unlimited the air will be carried away and a vacuum produced. It is upon this principle that I have constructed a pneumatic machine of which Fig. 1. represents the simplest form. cd is a glass tube longer than a barometer open at both ends and in which mercury is allowed to fall down supplied by the funnel A with which the tube is connected at c. The lower end d of this tube dips into a small glass bulb B into which it is fixed by means of a cork.This glass bulb has a spout at its side situated a few millimetres higher than the lower end of the tube c d. The first portions of mercury which run down will consequently close the tube and form a safeguard against the air which might enter from below if the equilibrium should be dis- turbed. The upper part of cd branches off at x into a lateral SPRENGEL’S RESEARCHES ON THE VACUUM. tube to which the receiver R is affixed. As soon as the FIG. 1 stop-cock at c is opened and A the mercury allowed to run down the exhaustion begins and the whole length of the tube from x to d is seen to be filled with cylinders of mer- C cury and air having a down-ward motion. Air and mer- I! cury escape through the spout of the bulb B which is above the basin H where the mer- cury is collected.This has to be poured back froin time to time into the funnel A to pass through the tube again and again until the exhaus- tion is completed. As the exhaustion is progressing it will be noticed that the en- closed air between the mer- d cury cylinders becomes less and less until the lower part of c d presents the aspect of a continuous column of mer- cury about 30 inches high. Towards this stage of the operation a considerable noise begins to be heard similar to that of a shaken water-hammer and common to all liquids shaken iii a vacuum. The operation may be considered completed wben the column of mercury does not enclose ariy air and when a drop of mercury falls upon the top of this column without enclosing the slightest air-bubble.The height of this column now corresponds exactly with the height of the column of mercury in the baro-meter; or what is the same it represents a barometer whose Toricellian vacuum is the receiver R. Fig. 2 represents the actual instrument with which I am in the habit of working. The funnel A supported by a wooden stand serves as the reservoir for the mercury. By means of the tube z y 3 it is connected with the tube c d which I call the SPRENBEL’S RESEARCHES ON THE VACUUM. “fall tube,” so that the mercury will run down as soon as the clamp z is opened which compresses a caoutchouc tube inserted FIG. 2. P there. The tube xp leads to the receiver which is to be exhaust ‘ed and is in connection with two tubes one of which is attached to SPRENGEL’S RESEARCHES ON THE VACUUM.the common exhausting syringe S while the other serving as a gunge dips into a glass of mercury containing a barometer. When the instrument is at work the rising of the mercury in this guage will consequently show the degree of exhaustion. The exhausting syringe is merely attached as an auxiliary to accelerate the operation because the fall-tube for a reason to be presently mentioned must he of a thin calibre. The greater portion of air is more quickly removed by the syringe and after this has been done as much as possible and the connection between the receiver and the syringe has been broken off by compressing an inserted caoutchouc tube with the clamp i the remainder of the air is carried off by the runniirg mercury.The bulb B and the basin H are exactly as in Fig. 1. The instrument is about 6 feet high so that the mercury collected iii the basin H cm easily be poured back into the funnel A. The use of a pump would facilitate the raising of the mercury and prevent the admixture of air. This latter inconvenience may however be pretty well overcome by gently pouring the mercury on a glass plate floating on the sur- face of that in the funnel. Should a few air-bubbles attach them- selves to the side of the funnel it may be best to remove them by means of a wire or a glass-rod though they are not perhaps of much consequence as they are not observed to pass along with the mercury.The connections between the glass tubes are made of well-fitting black vulcanised caoutchouc tubing sold under the name of “French tubing.” This is free from metallic oxides which mder the tubing porous. Besides this all these joints are bound with coils of copper wire which is easily accomplished with a pair of pliers. Moreaver the space between the inside of the caoutchouc tubing and the outside of the glass tubing is filled with a resinous cement made of fused caoutchouc To prevent this substance soiling the interior of the instrumeut I first after having put the instrument together tie the caoutchouc joint with the copper wire and then turn back the end of the caoutchouc tubing over the coil coat the inside of the end with the cement and turn it back again into its proper position.From this it is obvious that the fused caoutchouc can only penetrate as far as the copper wire coil. The conuection of the funnel with the tube x y o is made by means of a perforated caoutchouc cork. (These corks are easily made from a flat block of caoutchouc cut out with a sharp Mohr’s cork-borer well lubricated with oil). When the instrument has been put together in this manner it is ready for SPRENGEL'S RESEARCHES ON THE VACUUM. use. At first the mercury is allowed to enter the fall-tube in such quantities as to raise the mercury in the guage as quickly as possible. When however the operation approaches its comple- tion which is shown by the rattling noise it will be found useful to lessen the supply of mercury and to let it fall down drop by drop on the column of mercury in the lower part of the fall-tube and to proceed in this way till the exhaustion is completed.I am not able to give any definite statement as to the quantity of mer-cury to be employed as it is obvious that a small quantity say an ounce or two is c%pable of exhausting a receiver of an indefinite size if this mercury is only made to pass the fall-tube often enough; but I may remark that I have found 10 to 15 lbs. of mercury a convenient quantity to work with. In my endeavours to find out how to construct the instrument in order to exhaust a receiver with the greatest economy of time and mercury I have not met with satisfactory results. There of course exists a certain relation between the amount of air to be exhausted the quantity of mercury to be employed and the time of the operation.In order to make the instrument act at all the supply of mercurymust be at least so large that the fall-tube may become closed i. e. the running mercury may form drops of a cylindrical shape breaking off the communication bet.ween the receiver and the external air. As the supply of mercury is in- creased the rapidity with which the air is carried off also increases. But this soon reaches its limit as should the mercury he admitted too rapidly into the fall-tube it gains the preponde- rance and closes the aperture at x. The most favourable condi. tions under which the instrument might be used are those where the mercury is made to fall down drop by drop enclosing between every two drops as large a portion of' air as possible.Volume may be increased by extension either in height or in breadth. If the fall-tube be lengthened the bulk of the enclosed air will be increased and the time required to produce exhaustion will be shortened without increasing the weight of mercury employed. But as it is inconvenient to have the instrument higher than the height of a man I attempted to increase the second dimension Gz. the width of the tubes. I soon found however that it was difficult if not impossible to close tubes of more than R certain width by single drops. In order to clase a wide tube with a cylinder of mercury (or any other liquid) the mercury (or this other liquid) must run in freely and not in drops for the simple SPRENGEL’S RESEARCHES ON THE VACUUM.reason that drops cannot be formed of the diameter of the calibre of the tube. The size of the drops depends upon the specific attraction of the molecules of the liquid the form and surface of the vessel from which the liquid drops the attraction existing between the liquid and the vessel and the resistance offered by the greater or less density of the air through which the drop falls. I have not been able to form in a vacuum drops of mercury larger than about 3 millimetres in diameter. Having failed in the use of a wide fall-tube I endeavoured to effect my object by the use of several small fall-tubes. Here how- ever another obstacle offered itself.It is exceedingly difficult to regulate the flow of mercury so evenly that exactly the same quantity shall run down in each separate fall-tube and I have found in practice that unless the flow of mercury can be so regu-lated simultaneous action cannot be ohtained in the fall-tubes. From these experiments I have found myself unable to produce a vacuum as quickly as with a common exhaustiirg syringe unless by the employment of inconveniently large quantities of mercury at a time. If speed is required I think the fall-tube should have the addition of the exhausting syringe which will take away more quickly the larger quantity of air and leave to the running mercury only the task of completing the exhaustion. By such a combination however the instrument loses much of its simplicity and offers by its numerous joints a far greater chance of leakage.For this reason where time is no object it will be preferable even to do without the gauge and to use the instrument in its simplest form as represented in Fig. 1. The operator will soon learn from observation of the way in which the drops fall down when the exhaustion is completed. Without the auxiliary air-pump the ex-haustion of a receiver of the capacity of about half a litre will take from 20 minutes to half an hour. Though this may appear to be a long time I have no doubt this method will be found after all the quickest and simplest for producing a vacuum as irearly perfect as I have been able to produce. The slowness of the action is obviously due to the smallness of the bore of the fall-tube.As soon as the calibre of this fmbe is increased the time of the operation rapidly decreases for the contents of two cylinders of the same height are to each other as the squares of their radii and the time of the operation ought to decrease in the inverse ratio. The proper size of the bore of the fall-tube is 2+ to 22 millimetres. As soon as I exceeded this SPRENGEL’S RESEARCHES ON THE VACUUM. limit I invariably found the vacua less perfect. It is not difficult with thesewider tubes to raise the mercury in the gauge to the height of the barometric pressure minus 1 or even 4 millimetre; but I have iiot been able to obtain with them vacua so near perfection as I have been enabled to obtain by the use of fall-tubes of 2$ millimetres calibre.The explanation of this fact must be sought for in the size of the drops which as it appears to me must in fall- ing down exercise a certain pressure against the side of the tube thereby preventing the denser air underneath the drop from finding its way again to the part of the tube above the drop where the air is more rarefied. I have not obtained better vacua by the use of fall-tubes of a calibre less than 29 millimetres. Before I proceeded to test the efficiency of the instrument I directed my whole attention to the construction of air-tight joints ; in this however I did not succeed. It is a well-known fact that barometers become inaccurate in time as air finds its way into the Toricellian vacuum between the glass and the mercury enclosed in it.The vacuum in my instrument is of course exposed to the same sources of imperfection. (To offer *a greater resistance to the air which might enter from the funnel I have given to the tube zyo the form of a U tube.) Leakage however happens in a far less degree from this cause than from the imperfection of the caoutchouc joints. Among the numerous modifications I have tried I con-sider the one which I have before described as the most practicable. With this joint the mercury in the gauge does not sink more than about + millirnetre in 24 hours. Williamson and Russell,* in constructing their admirable apparatus for the analysis of gases have met with the same difficulty and I am able to corroborate their statements.The porosity of solid bodies is astonishing and one is almost compelled to think that glass vessels are the only ones impenetrable to gases. The following degrees of exhaustion have been made with cold mercury which had merely been filtered through paper to free it from visible impurities but which had neither been dried nor freed from air by special means. I havk worked with heated mercury (100 to 15OoC.) but have not noticed much difference in the perfection of the vacua. Even if some slight advantage could be obtained by it its use would be objectionable prac- tically speaking from the risk of endangering the health of the * Chem. SOC.J. [Z] ii 238. SPRENGEL’S RESEARCHES ON THE VACUUM. operator.When the mercury is heated and allowed to run down quickly the instrument is at the same time converted into a sort of electric machine In the dark flashes of electric discharge are seeu to light up the exhausted tubes and sparks may be drawn at intervals from the basin in which the mercury collects as from an electrophorus. The fall-tube invariably becomes soiled after some time by some impurity in the mercury and particularly after the employment of heated mercury. I attribute this to the oxidation of the mercury arising from this electric action which must be favourable to the formation of ozone. I have to mention that to attaiil. high vacua the fall-tube must be clean as well as the mercury. The length of the fall-tube in the instrument before US is calculated for the use of a liquid having the specific gravity of mercury.Of course as the specific gravity of the liquid employed becomes less the fall-tube must be longer. Practically however water is the only liquid that need be considered in place of mercury and I have no doubt that an instrument adapted for water would fiirnish a simple and most efficient exhausting machine. It is cot unlikely that snch an instrument might possess advantages wltich air-pumps of other constructions have not particularly in hilly countries where the large volurrie of a natural waterfall might be rendered available. i.now come to consider the way in which this instrument acts. It is obvious that it stands in a near relation to the Trompe or Catalonian bellows the old arid well-known contrivance for pro-ducing a blast.My iristrunierit is merely the reverse of the trompe with this addition that the supply of air is limited while that in the trornpe is unlimited. The theory which explains the action of the trornpe will at the same time explain the action of my instru- ment. The theory of the trotnpe has repeatedly been treated by distinguished philosophers as Venturi Magnns Buff and others. It would lead me too far to enter upon a criticism of their opinions which appear to me partly erroneous partly not to the point. In my opinion the action of both instruments may in all cases be satisfactorily deduced from Kepler’ s law of the iiniformly accele- rated motion of bodies. When the clamp z is opened ouly n certain and almost uniform quantity of mercury (or any other liquid) can pass at a given time.As soon as a particle of mercury has arrived at x it is under the influence of the general law of gravitation. It must sink and move with uniformly accelerated VOL. xvirr. C SPRENQEL’S RESEARCHES ON THE VACUUM. velocity. The same may be said of the second or third particle of mercury; but while the second one is starting the first one has accomplished a portion of its way and when the third is starting the distances between one and two and two and three are not equal but unequal. A vacuum must therefore have been formed between them and hence the tendency of the air to restore the disturbed equilibrium ie. by rushing in if the instrument is open or by expanding if a receiver is attached.If the tube into which the liquid runs is larger than the column of liquid which the atmospheric pressure can support the air in the receiver will of course expand to its last degree. If the mercury is allowed to fall down in c d in drops it will act in exactly the same manner as the piston in a common air-pump. These drops are so to speak liquid pisto 11s. The chief excellence of this instrument appears to me to be its simplicity and the great perfection with which it performs its work. To ascertain the degree of exhaustion I had at first to resort to a comparison with the barometer but 1 have not been able to make a barometer in which the merciirial column stood higher than in the gauge of my instrument though the barometers were constructed with care and the readings made by means of a cathetometer.Though my instrument was not air- tight and consequently riot perfect this apparent equality of the levels in the gauge and iii the barometer is easily accounted for upon reflection by the fact that the liuman eye is not able to dis- tinguish between TB$Tc or even i.&T part of a millimetre. But being curious to see how ninch the instrument even in its present imperfect state can do I have taken particular pains to ascertain it; I have tried diffcrent WitYS but T will describe only that which appears to be the hest and most efficient. It is simply the application of D urna3’ method for the determination of vapour- densities.I took a receiver of the form R (Fig. Z),a bulb extended on both sides into a capillary tube one of which was open and attached to the instrument while a portion of the other was broken off and the aperture sealed. The part taken of and having consequei:tly the same calibre as the portion left attached to R was preserved. The receiver was now exhausted and taken off by sealing it at A. This point was broker1 under the mercury which had just run through the instrnunent. I did this to meet the objection that boiled mercury might absorb the remainder of the air in R while on the other hand mercury containing more air SPRENGEL'S RESEARCHES ON THE VACUUM. 19 might give off some of it and allow it to enter the vacuum. If now the receiver had been perfectly exhausted the mercury would have filled it completely.This however was not the case a very small air-bubble always remaining at the end of the sealed capillary tube. The capillary tube was broken cjff at f and the mercury contained in R was collected and weighed. Inh the capillary tube first broken off from tile receiver I now introduced by suction a small particle of meicury of exactly the same length as the particle of air in f. This mercury was then placed in a delicate balance and weighed. The weight of this particle of mercury bears the same proportion to the weight of mercirry in R as the weight and volume of air remaining in R after ex- haustion bears to the weight and volume of air in R before exhaustion. The highest proportion I have attained in this way is +g5- and upon the average I consider it not a difficult thing with the present means to exhaust a receiver to Ts&aco From this it is obvious that a barometer may be made by simply exhausting and sealing a tube one end of which is then broken under mercury.I have actually made some in this way. I have applied the finest reaction for the presence of gases viz. the absence of any electric discharge in a perfect vacuum.* The few tubes I have made hitherto always showed a slight discharge which however I have chiefly att.ributed to the presence of mercurial vapour though I could have ascertained it by means of spectrum analysis. I have tried to reiiiove this vapour by introducing between the instrument and the elect rical tuhe a tube exposed to a cold of -10' C.or filled with fiiiely divided gold or freshly ignited charcoal but the intensity of the whitish- green electric light appeared to be not much diminished by these means. From this I infer that the mercurial vapour has either riot been condensed or the supporter of light is due to another body. Being aware of the subtlety these experiments require and of my shortcomings in their perforoxmce I should not like to say more about them now but I hope to repeat and study them with care hereafter. At any rate I have learned this much that duriiig the exhaustion with my instrument the colours of the electric discharge change from intense red and blue to faint white and green; that I have passed the limit at which the density of the air is most favourable to the electric discharge ; that the stratifications are exhibited in an admirable * Gassiot Phil.Trans. 1858-9. c2 SPRENGEL’S RESEARCHES OF THE VACUUM. manner; and that the instrument will prove useful for the per- formance and study of these experiments which on account of their beaiity have excited so large an interest. Before concluding this paper T sl?orild like to say one word more about the theory of the action of the instrument. Is the action entirely due to the accelerated velocity of the mercury and the elasticity of the air? I answer yes. Struck hy the extraordiriary attenuation of the air and misled by Ventnri’s theory I was at first much inclined to attribute the action partly to two other agencies the attraction of gases to liquids and their abwrptioii by liquids.But the follming experiments showed me that I was mistaken. I forced water through short T-pieces at different velocities using from a slight pressure up to that of several atmospheres and I have not been able to raise water in a tulle connected with the other branch of the T-piece to a greater height than that corresponding to the length of the tube from which the water was expelled. But this does not show so much as the fact that when the calibre of the fall-tube is larger than 2+ milliinetres it is impossible to raise the mercury in the gauge so high as it starids in the barometer however long the mercury ma>* be allowed to run and whatever quantity may be used.This shows that the action is entirely mechanical that tli= air expands and is cut off portion by portion by thy falling drops of mercury and that when the air is highly attenuated these drops must entirely fill the tube and even exercise a slight pressure against the sides of the fall-tube otherwise the action will cease as in a common air-pump through the rron-action of the valves. I am under the impression that the use of better materials and the application of greater skill than I have hitherto employed will be followed by still bettcr results and will not improbably furnish instruments capable of producing vacua perfect to our senses ; and even if we should not succeed in riiaking a perfectly air-tight joint the end will still be attained if we can only succeed in carrying off the air more quickly than it can enter.At any rate the immense elasticity of air is here displayed in a stinilting manner and there is a very wide interval between the attenua- tion of 1,300,000 to the density of gases which must exist in the powder-chambers of carmons or mines at the nioment of explosion. Another striking fact is that Bxhaustioa of mB$mThas been made with cold common mercury doubtless containing a considerable quantity of air and moisture which one would expect to be set free BROUGHTON ON ANHYDRIDES AND ETHERS. and enter the vaciium as soon as the mercury so violently agitated passes along the fall-tube. But the particles of these absorbed gases which are set free on boiling must at common temperatures be so intimately connected with the mercury that their expanding or gaseous properties are lust as in the oxygen of oxide of mercury.The main fact which I have established in this paper may be shortly stated to be that ij'a liquid be allowed to run down a tube to the upper part of which a receiver is attached by means of a lateral tube and if the height at which the receiver is attached be not less than that of the column of the liquid which can be sup-ported by the atmospheric pressure a vmuum will be formed in the receiver minus the tension of the tiquid etnployed. The properties of highly rarefied gases and the ccrnditions of that remarkable space it1 which there is nothing have hitherto been scantily examined though this subject is suggestive of in-teresting questions the solution of which I hope to treat of in my further investigations that border on the so to speak negative side of naturaI philosophy.The above experiments * were performed in the laboratory of St. Bartholomew's Hospital and I am glad to have the oppor- tunity of acknowledging most gratefully the facilities which have been offered to me by Dr. Odling in the prosecution of them. The instrument may be seen at Elliott Brothers Strand London from whom it may be obtained.

ISSN:0368-1769    

DOI:10.1039/JS865180009b

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

BROUGHTON ON ANHYDRIDES AND ETHERS. IV.-On a New Reaction for the Production of Anhydrides and Ethers. By JOHN BEOUGHTON, B. Sc. Chemical Assistant Royal Institution. THE reactious which are employed for the preparation of the anhydrides of the monobasic organic acids are those originally discovered by Gerhardt where either the chloride of an electro-nemative radicle is made to act on the corresponding alkaline salt, .? giving rise to the production of an alkaline chloride and the anhydride ; or the same decomposition is indirectly superinduced * Communicated to the Chemical Society June 16th 1864. BROC'QHTON ON A NEW REACTION FOR THE by allowing the pentachloride or terchloride of phosphorus to act on the alkaline sslt. These methods therefore essentially consist rather in an almost synthetical formation of the anhydride by a process of double decomposition aualogous in it3 nature to those by which the com- pound and double ethers are produced than in a direct elimina- tion of the anhydride froin the salt of which the reactions for producing nitric and carbonic anhydrides afford familiar instaiices.In addition to the above methods is that described by Gal ( Compt. rend. lvi. 360) who by acting on caustic lime and baryta with the chlorides of acetyl and benioyl obtained the correspond- ing anhydrides. As this method obviously necessitates the employ- ment of the chloride of phosphorus its principle rests mainly on the same decomposition as that discovered by Gerh ardt. It was therefore thought that a reaction by which the anhydrides of the organic acids could be more directly eliminated from salts in the same manner as some inorganic anhydrides would possess considerable interest both in a practical and in a theoretical point of view.For this purpose several attempts were made to procure acetic and benzoic anhydrides by the action of boracic acid on the potassium-salts of these acids ;but this method as might probably have been foreseen failed to produce the desired substances. It then occurred to me to try the effect of bisulphide of carbon. This substance was shown by Freniy many years ago to be readily decomposed by heated metallic oxides into carbonic anhydride arid a metallic sulphide and also when heated with water to a high temperature to form sulphuretted hydrogen and carbonic anhydride (Schl agdenhauffen J.Pharm. [3] xxix. 491). It was therefore thought probable that by acting on the dry metallic salts of the organic acids with bisulphide of carbon the metal would be converted into sulphide and the anhydride set free. With this view the following experiments were per-formed :-Crystallised acetate of lead was dried for several hours at about l?O°C.,and reduced to as fine a state of division as possible and a small quantity was placed in a strong glass tube which was then one-third filled with dry bisulphide of carbon sealed and heated in an oil-bath to about 15GOC. After an hour's heating the contents of the tube had become quite black and after a few hours' exposure the tube was removed from the bath allowed to PBODUCTION OF ANHYDRIDES AND ETHERS.2s cool and then opened when a violent escape of gas took place attended with a strong pungent acid smell. This gas on being allowed to pass into baryta-water was found to be carbonic anhy- dride. Several strong tubes of hard glass were thencharged with 20 grammes each of dry acetate of lead and as much bisulphide of carbon added as was necessary to make on agitation with the acetate a mixture of a creamy consistency. The tubes being then rather more than one-third full were sealed and heated in the oil-bath to a temperature of 165°C. The mixture quickly assumed a black colour and after some hours' heating one of the tubes by exploding with great violence gave warning that a large amount of gas had been liberated.After this it was found ad- visable to open the tubes once a day in order to let the carbonic acid escape ;and with this precaution the digestion was continued till it was found that on opening the tubes only a slight rush of gas took place. The reaction was then juciged to have practically terminated. The liquid contents of the tubes were then poured off as far as possible and the remainder adhering to the solid sulphide of lead was separated by distillation at a moderately high temperature and the whole fluid product thus obtained was submitted to distil-lation. The first product passing over was the excess of bisnl-phide used after which the temperature of the boiling liquid gradually rose when some acetic acid with a trace of acetone made its appearance till the temperature gradually rose to 13'i°C.and remained constant till the whole had passed over. The portions of distillate collected near the latter temperature had a pungent acid odour attacking the eyes and nostrils; when mixed with water it sank and gradually dissolved with rise of temperahre. On mixing it with alcohol the odour of acetic ether was produced. To decide the matter an analysis was made of the portions which boiled at 137". 0-3010 grm. burnt with oxide of copper and oxygen gave 05170 of CO, and 0.1636 of water. Calculated. Found. c* 48 47-05 46.84 H6 6 5.88 6-03 03 48 47-07 I 102 100.00 BROUGHTON ON A NEW BEACTION FOR THE The liquid was therefore acetic anhydride and its production can be expressed by the equation- 2 r2%$!Io 1+ CS = 2PbS + C02 + 2 [c21E-I,o01 C2H30} L C2 H3O}o Experiments with acetate of silver gave a similar result with even greater readiness.The above reaction of bisulphide of carbon it will be perceived is susceptible of at least three important applications for the for-mation of organic bodies if it prove to be ill any respect a general one. 1. The production of anhydrides as above from metallic salts. 2. The formation of compound ethers by allowing the anhy- drides in the nascent state to react on an alcohol. 3. In certain cases for the isolation of anhydrides of electro-positive radicles or ethers.For the second application it was proposed to produce an ether of acetic acid which had not hitherto been successfuliy prepared and for this purpose acetate of phenyl was chosen. This sub-stance Scrugham (Chem. SOC.Qu. J. vii. 241) attempted to procure by acting on acetate of potash with an alcoholic solution of phosphate of phenyl but did not succeed in obtaining it pure. Berthelot had found during his experiments on etherification that a small percentage of acetic acid entered into combination with phenylic alcohol when heated with the latter in sealed tubes. In order to procure this ether acetate of lead was at first sealed up with an equivalent quantity of pheriylic alcohol and an excess of bisulphide of carbon ; but after some experiments it was found better to operate with only half an equivalent of phenylic alcohol as the presence of some of the latter in an uncombined state seriously affected the eventual separation of' the acetate in a state of purity.The following was therefore the metJhod adopted :-20 grammes of well-dried and finely-divided acetate of lead was sealed up in strong tubes with 3 granimes of phenylic alcohol and a considerable escess of bisulphide and heated in an oil-bath to about 170°C. The reaction soon commenced and proceeded with more regularity than in the preparation of the anhydride since the lead- salt is soluble in the alcohol so that the bisulphide is enabled to act with greater readiness. It was found necessary to open the tube daily for it was shown by some explosions that the pressure PRODUCTION OF ANHYDR1I)ES AND ETHERS.of the liberated gas was very high. When the action had ceased the liquid products were separated as above described and re-distilled. After the excess of bisulphide had distilled acetic acid in considerable quantity passed into the receiver then a small quantity of acetic anhydride after which the temperature rose rapidly to 190"C. when a liquid of a pleasant empyreumatic odour made its appearance and when the temperature had attained 310" C. the whole had passed over. The portions distilling above 190' were rectified and by re-peated fractioning the greater part was obtained of a constant boiling point of 200". This was submitted to analysis as follows by combustion with oxide of copper and oxygen :-I.0.2142 gramrnes gave .5554 GO and *1133H,O. 11. 0.1964 grammes gave -5098 CO and -1060 H,O. Calculated. r. II. c 96 70.59 707 I 70.78 * * 5-88 5.87 5.99 0 32 23.53 -136 100.00 The vapour-density of the liquid was taken as follows by Gay Lussac's method wing a bath of spermaceti :-Weight of liquid employed 0.2299 grm. Observed volume of vapour 70.128 cc. Temperature 1218"C. Height of barometer 744.5 mm. Difference of heights of internal and external mercury 32 mm. Height of column of spermaceti 230 rnm. at 45'. These data give sp. gr. of vapour 4-72 The calculated density of acetate of phenyl is 4-59. The liquid therefore was acetate of phenyl. Acetate of phenyl is a colourlesv liquid boiling at 2OO0C.,of a peculiar and fragrant odour which is very persistent; its sp.gr is 1.074 being somewhat heavier than phenylic alcohol as acetic ether is heavier than ordinary alcohol. Though quite colourtess when freshly distilled it becomes somewhat yellow by keeping. It is slightly soluble in water in which it sinks and to which it imparts its peculiar odour. It is neutral to test-paper and is not decomposed by boiling water ; even when heated with water to 180" BROUOHTON ON ANHYDRIDES AND ETHERS. it acquires but a very slight acid reaction. Boiling solutions of the fixed alkalis gradually dissolve acetate of phenyl with formation of an alkaline acetate and phenate. Its index of refraction is the same as that of German fusible glass on which account tubes of the latter become invisible when immersed in this ether.It will appear from the above experiments that this reaction of bisulphide of carbon will most probably be found of service in isolating anhydrous acids in cases where the ordinary methods are riot convenient and will also it is believed receive many applica-tions as a general mode of preparing compound ethers since it has the advantage of being applicable to small quantities. Phe-nylic alcohol which has hitherto been found so difficult of etheri-fication may probably by the above process yield its full complement of ethers in the manner of alcohols of other series. Experiments have been commenced to illustrate the third application of this reaction namely that of eliminating phenylic ether from phenate of lead.Whether the method be applicable as a means of procuring double ethers and anhydrides further experiment must show. In conclusion the following desiiltory qualitative experiments have been tried :-Chloride bromide iodide and fluoride of lead are not attacked by bisulphide of carbon. Nitrate of silver is most readily acted on by bisulphide of carbon with production in addition to sulphide of silver of a green liquid and a white solid substance ; but on attempting to open the tubes they have burst with a most violent explosion. Sulphate of lead is not affected by sulphide of carbon. Benzoate succinate and ferrocyanide of lead are readily acted on by the bisulphide. Formate of lead is entirely converted into sulyhide by bisulphide of carbon with much evolution of gas; traces of a strong acid are evolved together with a sulphur-compound of a powerful odour ; all attempts to obtain formic anhydride have been unsuccessful the latter being apparently entirely decomposed into gases.Oxalate of lead is entirely unaffected by sulphide of carbon at a high temperature. I take this opportunity of expressing my thanks to Professor Frankland for opportunity and leisure to make the above experi- ments.

ISSN:0368-1769    

DOI:10.1039/JS8651800021

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

27 V.-Laboratory Memorandu. By ROBERTWARINGTON, Junr. Assistant to Professor of Chemistry R. A. College Cirencester. I. The Action of Ferricyanide of Potassium upon Ferric Salts.-Most works on chemistry describe this reaction as producing a “dark-brown,” or reddish-brown” fluid and state that no preci- pitate is formed;* some BIitnuals however tell usthat a “greenish,” or even a “dark-green” liquid is the resu1t.t These statements are all incomplete and may possibly mislead. First as to the colour. The dark-brown liquid is produced only when the ferricyanide of potassium is in excess of the ferric salt ; the tint in this case is a dark sherry-brown. When the propor- tions are reversed and a drop or two only of the ferricyanide mixed with an excess of ferric chloride a brilliant emerald-green tint of a slightly bluish tinge is the result.If the proportion of ferri- cyanide of potassium is then gradually increased the colour is first changed to sap-green then olive-brown and at last reaches the dark sherry tint before described. The whole series of colours is well seen if a single drop of ferricyanide of potassium is allowed to run down the side of a test-tube half filled with dilute ferric chloride ;a brown ring forms at the surface where the ferricyanide is in excess from which streaks of colour slowly descend their tint changing from brown to bright green as they fall further towards the bottom. It appears then that the colour produced on mixing an alkaline ferricyanide and a ferric salt is essentially dependent on the pro- portion of each which may be present.Lastly as to the statement that the liquid remains clear. This is true only when the solution is sufficiently acid ;basic ferric salts afford an immediate pale brown precipitate with ferricyanide of potassium . These results were all obtained with a freshly prepared solution of the ferricyanide. 11. The Solubility of Magnesia in 9lkaline Salts.-That magnesia dissolves in salts of ammonium with evolution of free ammonia is a sufficiently familiar fact. That the presence of ammonium- salts hinders or entirely prevents the precipitation of hydrated magnesia by an alkali is equally well known; but it is not per-* So Rose Fresenius and Gmelin. t ThusMiller and Northcote and Church.WARINGTON S LABORATORY MEMORANDA. haps so generally understood that salts of potassium and sodium have an exactly similar effect though in a far smaller degree The action of ammonium-salts in preventing the precipitation of magnesia is usually explained as owing to the formation of double salts of magnesium and ammonium. If this theory be correct then the presence of uny soluble base forming double compounds with magnesium ought to have a similar effect and consequently we should expect that salts of potassium and sodium would in this particular behave like salts of ammonium. Magnesia dissolves to a small extent in a strong solution of a salt of potassium and also in salts of sodium the alkaline salt being in this case evidently decomposed as the liquid strongly reddens turmeric paper.The following experiments were made as to the faculty of alkaline salts to prevent the precipitation of hydrated magnesia. Two equal volumes of a solution of chloride of magnesium were taken; in one of these 200 grs. of chloride of potassium were dis- solved; both were then treated with equal volumes of a solution of caustic potash; and after standing some hours in a warm place filtered and the magnesium in the filtrate (that there- fore which the potash had failed to precipitate) estimated by phosphate of sodium in the usual way. The experiment with chloride of potassium yielded 1.54 grs. oE Mg,P,O, the other only 1.39 grs.; the potassium-salt had clearly then to a slight extent prevented the precipitation of magiiesia.An experiment with chloride of sodium yielded a similar result. Trial was also made with sulphate of magnesium the sulphates of potassium and sodium being added. The amounts of magnesium unprecipitated by the potash are shewn by the following weights of pprophos-phate obtained :-With sulphate of magnesium alone . . .. . . *15grs. and sulphate of potassium *5O ,, JJ J? >s >) and sulphate of sodium. . -56 , Another experiment in which caustic soda was the precipitant gave similar results. With sulphate of magnesium alone . . .. . . -94 grs. 9 11 and sulphate of potassium 1.15 , J J> and sulphate of sodium. 1.35 , When these experiments were repeated with an increased quantity of caustic potash or soda the effect here noted practically WARINBTON’S LhBORllTORY MEMORANDA.disappeared a trace oiily of magnesium being found in any filtrate ; this indeed took place when the amount of potash was increased by one-half or even less. The excess of potash doubtless decom- posed the double salt first formed in the same way that a large excess of ammonia precipitates hydrated magnesia even in the presence of sal-ammoniac. It appears then that salts of potassium and sodium do really hinder the precipitation of hydrate of magnesium,* though to not nearly tlie same extent as salts of ammonium ; a result which well accords with theory as the double compounds of magnesium with tlie former salts are well known to be far less stable than those with the latter.Another fact in connection with the soliibility of magnesia in alkaline salts is the decomposition of this solittion by water under certain coiiditions For instance if a strong solution of magne-sium be mixed with sal-ammoniac and free ammonia the pro. portion of the two latter being so adjusted as just to prevent pre cipitation on standing the equilibrium of the mixture thus formet! is destroyed by the addition of water and maguesia is precipitated In one experiment a mixed solution of the chlorides of magnesinni and ammoiiium was treated with twice its volume of the strongest ammonia; at the end of twelv; hours the solution was still per- fectly clear An exactly similar mixture was prepared and diluted with water to three times its bulk; at the end of twelve hours 8 considerable precipitate of magnesia had fallen.Salts of ammonium appear then to hinder the precipitation of magnesia in proportion to their conceutration. This fact serves to explain a phenomenon sometimes observed when making determinations of phosphoric acid. If the washings of the phosphate of magnesium and ammonium are allowed to mix with the main filtrate an opaque ring is often formed at the junction of the two liquids alarming the operator with the idea that his precipitate is washing through ; the washings however if collected separately are found to be perfectly clear. The cause of this appearance is probably the precipitation of the excess of magnesia on diffusion into the wash-water. * According to L o n g c h a m p (Ann. Chin Phys. [3] xii. 255.) the precipitation of carbonate of magnesium is less complete in proportion to the amount of alkaline salts present.

ISSN:0368-1769    

DOI:10.1039/JS8651800027

出版商:RSC    

年代:1865

数据来源: RSC

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30 VI.-Noteon the Bwiling Points of Isomeric Ethers of the Formula CnH,nO,. By J. ALFREDWANKLI-N. FROMKopp's paper it would seem that those ethers of the fatty acids which are isomeric with one another should have the same boiling point or that all the ethers having the formula C,H,,O, in which n has a constant value have the same boiling point This proposition and its consequences have found a place in the Handbook s.* Having had occasion to prepare valerianxte of ethyl and acetate of amyl both of which have the same total formula viz. I have observed that thcre is a coiisiderable difference in their boiling points. Valerianate of ethyl boils at 133"C. ;acetate of amyl at 140"C. The boiling point of acetate of amyl was found hy Cahours to be 125"C.but it is probable that there was arnylic alcohol present iu the specimen examined by that chemist. A mixture of acetate of amyl with a good deal of amylic alcohol and a little moisture would not be distinguishable from pure acetate of amyl by a combustion. The acetate of amyl which was employed for the determination just given was prepared so as to be free from arnylic alcohol. That it was tolerably pure was ascertained by an alkalimetrical analysis. The natural conclusion from this and a number of facts of a like kind is that Kopp's laws respecting boiling points are not much to be depended on. From the glycols we have learnt that it is not universally true tliat homologous bodies rise in boiling point as they increase in complexity and a careful examination of almost every homologous series discloses the fact that "the iucre- ment "is not uniform in all parts of the same series.Thus for instance iodide of riietliyl boils at 43OC. iodide of ethyl at 73",and iodide of amyl at 146"C. giving an increment of 30' for the first additiou of CH, and an increment of J2-O or 24.3' for each CH between ethyl and amyl. * See Kekuls's ''Lehrbuch der Organischen Cliemie," dritts Lieferung page 601 ;also Limprich t's bmk page 256 et seq. BASSETT ON THE ACTION OF CHLOROPICRIN ETC. Again zinc-methyl boils at 46"C. zinc-ethyl at 119"C. differ-ence 73"for CH,; whilst zinc-amyl boils at 22OOC. difference for CH equals 1%' or 33.7". There is also the well known example of methylic alcohol which boils at 65O C. instead of at 59"C. or 60°C. as Kopp's theory would require. Higher up in the alcoholic series we encounter Wur tz's isomeric amylic alcohols having different boiling points and then the isomeric hexylic alcohols. Although it will be ob-jected that the hydrate of amylene and the P-hexylic alcohol are not true homologues of ethylic alcohol still the unexpected boiling points of these bodies shows that mere inspection of the molecular formula of an alcohol is very little guide to the boiling point of that alcohol.

ISSN:0368-1769    

DOI:10.1039/JS8651800030

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

BASSETT ON THE ACTION OF CHLOROPICRIN ETC. QIL-Note on the Action of Chloropicrin and Chloroform on Acetate of Potash. By HENRYBASSETT. ALTHOUGH the experiments described in the following short uote have not led lothe production of any new substance I venture to think they are of some interest as a further example of the reactions of these bodies and as tending to confirm the views as to their constitution arising from the behaviour of their ethylic derivatives ;nainely that the groups C and CH contained in them have a decided tendency to form the correspouding carbonic and formic acids in preference to giving rise to any tetra- or tri-atomic alcohoI derivatives. Chloropicrin heated to 100"in a closed vessel with fused acetate of potash and alcohol is decomposed with great readiness.No gas is disengaged but a considerable quantity of chloride of potassium is fornied rind the solution becomes acid. On cooling. a crystalline salt is deposited in large quantity. The experiment was tried at first ivith four equivalents of the acetate to one af chloropicrin but it mas found that a large quantity of the latter remained unacted upon after twelve hours' heating although the reaction appeared to be completely finished. The qiiautity of acetate was therefore increased in subsequent experiments until BASSETT ON THE ACTION OF CHLOROPICRIN with nine equivalents of acetate it was found that very little ii any chloropicrin remained. The alcoholic solution was filtered hot from the chloride ot potassium and gave a large crop of needle-shaped crystals on cooling.A further quantity was obtained from the mother-liquor by distilling off the alcohol in the water-bath. In this distillate which had an acid reaction the smell of acetic ether mas very perceptihle. The salt was recrystallized from alcohol drained and dried as completely as possible by presswe and then left over sulphuric acid in vacuo for several hours. The dry salt thus obtained was not nearly so deliquescent as ordinary acetate of potash and rotated violently on the surface of water. On heating it gave off a large quantity of acetic acid and left a fused mass of the normal acetate of potash. Submitted to aiialysis it gave the following results 1. -499 grm. evaporated to dryness with hydrochloric acid and ignited gave -238grm.chloride of potassium. 2. *3065 grm. burnt with chromate of lead gave -561 grm. carbonic acid and -213 grm. mater-numbers which agree perfectly with the composition of bi-acetate of potash as will be seen by comparing the percentage amounts :-Exper. C,HjK04 c 30 21 30.38 H 4.67 4%3 K 24.95 24.68 0 40.17 40.91 i00.00 1oo*oo The reaction taking place is as follows:-CNO,CI + SC,H,KO + 3C,H60 = 3KC1 + KNO -+ K,CU, + 3C,H80 + 3C,H,KO,. Acet ether. Biacet. Potash. The presence of nitrite and carbonate of potash was distinctly shown by the usual tests in the precipitated chloride of potassium. Chloroform heated to 100" with acetate of potash and alcohol was only slightly attacked but at 125" a large quantity of chloride of potassium was formed.In three or four hours the action wa8 AND CHLOROFORM ON ACETATE OF POTASH. complete and the solution M hen cold deposited a large quantity of crystalline salt. On opening the tube a small quantity of car- bonic oxide escaped. After distilling off' the alcohol which smelt of acetic ether the remaining salt was crystallized and dried when it presented exactly the characters of that obtained from the chloropicrin experiments and the identity of the two salts was shown by a potassium estimation. 04595grm. gave $22 grm. chloride of potassium correspondiiig to 25-07p. c. of potassium. The reaction in this case is perfectly similar to the former one. CHCI + 6C,H3K0 + 2C,H60 = 3KC1+ CHKO + 2C,€I,O, + 2C,H7K0,.The formate was readily detected in the salt obtained by evapora- tion of the mother-liquor from the bi-acetate by the reduction of bichloride of mercury and by the evolution of carbonic oxide when warmed with sulphuric acid. The ease with which chloropicrin is attacked by reagents sug- gested an experiment with aniline; in fact on heating a mixture of one part chloropicrin with three of aniline to 145" and then removing the lamp a violent reaction is established accompanied by the evolution of a cousiderable quantity of nitrogen. Boiling water extracts from the product a certain quantity of a red colouring matter similar to that originally obtaiued by €10 fniann from the tetrachloride of carbon; the solution also contains the hydrochlorate of a solid base which was purified by precipita- tion and crystallisation and converted into a platinum-salt. -4605 grm. gave 991 grm. platinum corresponding to 19-76 p. c. the platinum-salt of carbo-triphenyl-triamine containing 2G.01p. c. I am at present studying the action of chloropicrin on cyanide of potassium and anticipate from it some interesting results. VOL. SVIII. D

ISSN:0368-1769    

DOI:10.1039/JS8651800031

出版商:RSC    

年代:1865

数据来源: RSC

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DEASE AND BRADY ON MICROSCOPICAL VIIP.-On ikIicroscopicu2Research in relation to Pharmacy. By HENRY F.L.S. DEANE,F.L.S. and HENRYB. BRADY [Read at the Bath Meeting of the British Pharmaceutical Conference Sept. 1864.1 WE have chosen for the particular subject of the present commu- nication the various preparations of opium. Whether regarded in respect to their importance in the practice of medicine their variability in strength and character or the peculiar conditions in which the active matter exists in the crude drug no better subject could be found for the purpose in view. Opium as is well known is an extremely composite substance being a pasty mass formed of resinous gummy extractive and albuminous matters containing a larger or srrialler percentage of certain active principles diffused through it.These principles are morphine narcotine (with its two homologuesj codeine narceine mecoiiine thellaine and papaverine either existing free or in com- bination with meconic sulphuric or other acids the sum of the crystalline constituents exclusive of inorganic salts contained in good samples of the drug being from twenty to thirty per cent. of its entire weight. Any preparation exactly to represent opium must contain the whole of' these principles as indeed the tincture may be said fairly to do. It has however been shown that some of the principles are inert and others even deleterious in their action and we have coiisequently had a class of preparations introduced wliich are understood to be of superior efficacy not from their containing any active matter wliich the tincture does not contain but because they aye free from wrtain substances which are retained by it.Narceine meconine and mecoriic acid are believed to be inert whilst narcotine possesses properties widely different from those for which opium is usually employed. Of the bulkier constituents the resiii appears to be worse than useless whereas the bitter extractive though opinions differ with rcgard to its precise pro-perties seems at any rate to increase the narcotic power of the inore active constituents. A typical preparation of ol'ium should therefore at least contain the whole of the morphine and codeine with meconic or sorric other acid to keep them in solution arid the bitter extractive.Codeine itself and tlie salts of both codeine RESEAKCH IN RELATION TO PHARMACY. and morphine are readily soluble in either water or alcohol; the remaining principles are fully dissolved by alcohol but scarcely soluble in water ; hence in the preparations alluded to water rather than alcohol is used as the solvent. The process we adopt in examining the constituents of a fluid preparation of this sort under the microscope is a very simple one. Having as a preliminary step taken the specific gravity and ascertained the percentage of carefully dried extract contained in it we evaporate a small quantity usually from four to six drachms on a sand-bath in a watch-glass to about the consistence of treacle. It is then poured upon a slip of glass and covered with a piece of thin glass and after standing a few days it is sealed in with gold-size.Crystallization sometimes commences before the preparation is removed from the watch-glass sometimes immediately after transferring to the glass slip but in many cases not for several days. The time taken is dependent on one of two influences viz. the quality of the opium and the exact degree of in-spissation. In determining the value of a preparation from the appearance of this extractive under the microscope we do not rely entirely upon the amount of crystallization; it is requisite to go one step further to obtain the full value of our labour and by investigating the form and physical characters of morphine and its compouncis of codeine narcotine meconic acid &c.place ourselves in position to see the significance of the appearance the slide exhibits and to identify any crystalline principles which may be present. Never-theless even in the absence of very accurate kriowledge any one who will make a few experiments for the sake of practice will scon be able by observing the presence or absence the abundance or scarcity of certain forms of crystals easily seen in typical speci- mens to pronounce with little hesitation on the quality or genuine-ness of samples of any of the ordinary preparations of opium. Before proceeding to speak of the opiates which have come under our examination it may seem necessary to say a few words on the forms assumed by the various opium principles and the physical characters their crystals present.This together mitt1 certain drawings we have made carefully from specimens will afford a key to our further remarks. In the first place :-iMorphiiie.-The pure alkaloid crystallizes in right-rhombic prisms n2 DEANE AND BRADY ON MICROSCOPICAL often running into needles. The single crystals have but little effect upon the polarized ray but where the solution has been concentrated (as from alcohol) and the acicular crystals are much overlaid they present a good deal of colour. (Plate I fig. 1.) It is exceedingly difficnlt to say in what condition morphine exists in opium; we are well aware that it has been set down its meconate with a smaller perccntage of sulphate but we have reason to suspect that sulphate is present to a larger extent than is generally supposed.The messing and manipulation which all kinds of opium appear to undergo before they reach this country renders the belief which is suggested by other circumstances that a portion of the meconic acid is decomposed extremely probable. It is scarcely likely that a substance which even boiling water de- composes with evolution of carbonic acid should remain unchanged through the various treatments to which the drug is subjected. Meconate of LWorplhe is set down in chemical works as being uncrystztllizable a statement to be accepted with reservation ;for by careful manipulation peculiar conical crystals may be obtained either from the solution of the commercial salt in dilute alcohol (Plate I fig.3 b.a.) or by the evaporation of mixed solutions of morphine arid meconic acid (Plate I fig. 3 b.6.). These crystals do not resemble any that are found on evaporating opium solutions ; but as we have said the subject requires more investigation than we have as yet been able to give to it. SuZphate of Morphine takes the form of small flat-ended prisms with a strong tendency to collect in radiating tufts; only the larger flat crystals polarized (Plate I fig. 3a). Codeine crystallizes in octahedra running into four-sided prisms. In the octahedral condition it is not easily mistaken for any other of the oplurn-alkaloids but the prisms strongly resemble those of narcotine. (Plate I fig. 4 a). They may be distinguished by their not presenting the fluted or striated surface which crystals of narcotine have and by their much less striking effect on the ray of polarized light.Narcotine occurs in the form of prisms with oblique one-or two-faced ends. As above stated tlie surface of the crystals is fluted or striated and on pressure they break up into tolerably regn!ar smaller crystals (Plate I fig. 2). Owing to a sort of composite structure they have very marked effect on the polarized rap more striking indeed than any other of the opium principles. Were it llot for this propcrty they would be distinguished with great diffi- RESEARCH IN RELATION TO PHARXACY. culty from many other crystalline substances which they resemble in form. There is a tendency as in other cases to cluster together in more or less radiating tufts but the individual crystals still keep their shape and do not degenerate into mere radiating plumose needles like those of narceine.Narceine.-As narceine exists in opium in about the same per-centage on the average as morphine and narcotine it is of greater consequence in these investigations than it is in a medical point of view being probably an inert substance. It is readily soluble in alcohol and slightly so in water aid therefore must exist to con- siderable extent in most of our preparations. The absolute form of the individual crystals it is impossible to determine but the masses of delicate somewhat opaque silky needles either radia- ting from a centre or taking au irregular feathery shape are very characteristic and the absence of any effect on a ray of polarized light is a negative property of importance.(Plate I fig. 6 a). Meconine occurs in six-sided prisms with dihedral summits atid has little if any polarizing power. (Plate I fig. 5 a). Tltebaine is readily soluble in alcohol slightly so in water. From solutions in weak alcohol it crystallizes in beautiful rectan- gular plates often associated in tufts more or less radiating from a centre. (Plate I fig. 4 b). It is a most beautiful polarizing object. Papaverine is present to so trifling an extent that it scarcely requires notice. The little which is dissolved by boiling water crystallizes out again on cooling in minute needles often aggregated ill rounded balls so closely packed as to be quite opaque.The large crystals obtained from the alcoholic solution possess slight polarizing properties (Plate I fig. 6 6). 17leconic Acid-Although the meconate of morphine in opium is an acid salt it seems probable that part of the mcconic acid is also there in a free state j at any rate we frequently find it in preparations. As it is soluble in both alcohol and water prepam- tions are pretty sure to contain whatever quantity does exist in the crude drug unless it has been removed by chemical means The form of the crystals is primarily a square prism but we have only seen this in minute examples and it is very difficult to trace the relationship to this type in the flat pointed lozenges some-what resembling the attenuated forms of' uric acid which gene..rally occur. Even these frequently run into still more stfange varietal shapes whose oiily resemblance to the lozenge-form exists ’DEANE AND BRADY ON MICROSGOPICA& in their broad centres and two pointed ends (Plate I fig.5 6). They all have some effect on the polarized ray. Boiling water decomposes meconic acid; carbonic acid is given off and comenic acid a substance we have not yet studied is formed. We may now proceed to the practical application of the facts enumerated and detail the results of the examination of the many prepsrations which have come under our notice. of Turkey Opium we have investigated-firstly the tincture prepai-ed by ourselves from different samples of opium as well as specimens procured from certain well-known operative chemists ; secondly the extract ; thirdly the wine; fourthly the more or less aqueous solutions sold as Liquor Opii Sed:itivus Battley’s one or two samples prepared by ourselves and specimens procured from four well-known firms ;and fifthly certain proprietary opiates viz.“Black Drop,” ‘‘ Jeremie’s Sedative,” ‘(Nepenthe,” and that sold as “ Solution of Bimeconate of Morphia.” We have drawn careful figures of the appearances presented by the whole of these which will do more than any description towards giving a correct understanding of the facts elicited; at the same time it may be necessary to draw attention to some matters of importance in connection with them. Tincture yields on evaporation crystals of almost the whole of the opium principles and we find that as the spirit volatilizes the resiii is also precipitated in an insoluble form.Our own prepam- tion from different samples of good opium is tolerably constant (Plate 11 fig 1a and b) and agrees in appearance with a speci- men procured from a manufacturing house of some standing (Plate 11 fig. 3) ; but neither are quite sorich in crystalline prin- ciples as a sample furnished to us by our friend Mr. Morson (Plate 11 fig. 2) which Beems to have been prepared from pecu-liarly fine opium. Extracl shows a much smaller proportion of narcotine crystals with abundance of morphine salts and tufts of narceine (Plate 11 fig. 4). Turkey opium is not rich in codeine and we suppose that in extract prepared from it this principle is retained diffiised through the‘ bitter matter.A specimen of conzmercial extract of opium which we have seen recently imported from the East is a very ditl’erent substance showing fewer morphine crystals but a large proportion of codeine (Flate 11 fig. 5). Wine.-The mucilaginous matter of wine very much retards if it does not entirely prevent the formation of crystals upon eva- RESEARCH IN RELATION TO PHARMACY. poration and consequently we can say but little respecting the appearance presented by the extract obtained from vinous solu- tions. Liquor Opii Sedativus.-The styiking appearance resulting from the evaporation of Battley’s Sedative (Plate II1,fig. 1)first drew our attention to the mode of investigation now described.We have examined it frequently and have always met with the same characters. The slides present an almost opaque mass of crystals of morphine-salts and codeine with a very small proportion of narcotine (and meconic acid?) and so far as we have observeci complete absence of resinous matter and narceine. Any one who has studied the microscopic characters of this preparation will readily understand how it has kept its place with the profession. We have necessarily thought much as to its probable mode of preparation and cannot see any reason to doubt the statement made by Dr. Pereira on the authority of the late Mr. Battley himself that spirit and water were the only solvents used in its preparation from Turkey opium.Dr. Christison discredits the statement on the ground of the comparative absence of meconic acid; but as we have before said boiling water is sufficient to decompose that acid and therefore the argument is not a valid one. Though we have experimented much with a view to prepar- ing a similar liquor we have not yet arrived at an i.dentica1 result. PlateIII fig. 2 a and b shows two preparations with similar per- haps nearly equal sedative properties to the original fluid; but it will be seen they both ciiffer considerably in the crystalline matters they contain. The preparation which gives results most nearly like Battley’s of any which we have had opportunity of testing is that made by Mr. Morson of London (Plate 111 fig. 3). Of three other makes which we have examined one (Plate 111 fig.5) is largely charged with resinous matter and the proportion of crystalline constituents is so minute that we are satisfied its activity must be very small; another (Plate 111 fig. 4) gives a few morphine crystals a good deal of narcotine and more nar- ceine; a third (Plate 111 fig. S) is chiefly remarkable for its lack of everything crystalline. There are certain preparations to which we must next allude which give little or no evidence as to the active matters they hold in solution by crystallizatioii on evaporation. As examples we may instance Vinum Opii amongst officinal and Braithwaite’s black drop Nepenthe and a fluid sold as “Solution of Bimeconate 4!0 DEANE AND BRADY ON MICROSCOPICAL of Morphia,” amongst proprietary formulze.That there should be exceptional cases in which the reaction with a certain peculiar set of tests is doubtful is onlp what might have been expected and it can scarcely be regarded as a weak point in their application. Scarcely any chemical test we u~e but is open to some contingency of the same sort but as long as we know the conditions of uncer-tainty it is no drawback to its employment ;it only becomes neces- sary that these conditions should be investigated atid comparison becomes easy. We have found that when opium is exhausted the liquor eva- porated to an extract and this extract redissolved in alcohol tl;e tendency to crystallize is very much lessened or entirely destroyed. The cause of this we are not yet able to explain with certainty but may state the fact as one which we have noticed in relation to every sort of opium we have worked upon.It will account for the very sparing indications of crystalline principles from all preparations made bp redissolving in alcohol a once-formed extract. The residue not taken UJ) by alcohol in the experimcnt is readily soluble in water and contains certain crystalline matters which we have not yet examined sufficiently to report upon. Again the siibacid viscid matter left on evaporating wine prevents crystallization coiisequen tly Vinum Opii gives a clear non-crys tal- line extract ; we believe this also to be the reason why one of the proprietary .preparations named yields the same result as it seems to us to be a mere solution of morphine or one of its salts in wine and not to be made direct from opium.The well known “ black drop” gives no crystals upon evaporation but in their place a peculiar deposit consisting of an amorphous almost opaque fzcu- lence. This is probably owing in great measure to viscid matter held in solution which on evaporation becomes insoluble though Some change and is precipitated carrying clown with it the active matter. We kuow too little of the solvent emFloyed to speak very positively but if the cowmonly received theory be true,-that it is made by a fermentation process in which impure malic acid is concerned,-we can readily understand how viscid orgauic m;ttter may be present in sufficient quantity to produce the result alluded to.In addition to the preparations of Turkey opium we have also llad the opportunity of experimenting on small quantities of the Patna Malwa and Persian varieties arid a11 of them prescrit pecu- liarities of interest. An aqueous extract and a tincture have been RESEARCH IN RELATION TO PHARMACY. made from each and from the Patna sort sufficient has remained to make a specimen of liquor. The most striking fact in connection with the whole of them is the existence of large quantities of codeine. In the extract of Yatna opium (Plate IV fig. 1)it is the chief crystalline constituent and though the liquor (Plate 11 fig. 6) shows abundance of the other opium principles it evidently owes its narcotic effect much more to codeine than Turkey opium does.We have the experi- ence of an opium-eater on this point; he states that the quantity required to produce the effect is larger but there is less discomfort in the after effects than with other sorts. Malwa opium (Blate IV fig. 2 and 5) shows more narcinc and narcotine but in the tinc- ture we have in additioir to a mass of minute crystals certain larger prisms which are probably codeine. Persian opium (Plate IV fig. 3 and 6) also evidently contains a large proportiori of narcotine and codeine. We stated at the commencement that this must be looked upon only as a preliminary research there rsmaiuing many pgints on which our information is far from complete. In continuing the inquiry we intend to devote ourselves chiefly to the elucidation of certain particulars.Firstly the condition or form of Combination in which morphine exists in crude opium ; secofiicily,the relation of extract of poppy to opium in respect to crystallirie principles; and thirdly the influence which the extractive matters may have in altering the crystals obtained in opium solutious and the vnria- tions of the normal forms iiiduced hy this cause. The general conclusions we have arrived at in addition to a knowledge of the appearances presented by typical and special preparations of Turkey Patna Malwa and Persian opiums are mainly these :-That tincture most nearly of any of the preparations represents the properties good and bad of the crude drug. That when crude opium is taken up with proof spirit as in tincture the resin separates on evaporation.That the preparations which have held their ground with the pgblic and the medical profession in spite of their cost differ from the tincture in comparative freedom from resin and narcotine and in containing only a diminished quantity of meconic acid. That in the preparation of extract of opium it is important to use a large quantity of distilled water to ensure the separation of narcotine and resin. DEANE AND BRADY ON MICROSCOPICAL That when extract of opium is dissolved in water filtered and evaporated again to an extract a second or tliird time the crystals frequently differ considerably from those seen in the normal or first formed extract. That when extract of opium is taken up with rectified spirit 56" O.P.and evaporated again to an extract crystallization does not take place or only to R very trifling extent. That morphine and its salts and perhaps other opium principles do not crystallize readily from their solution in wine. Finally it remains for us to express our obligation to our friends Mr. Morson of London and Messrs. T. and €1. Smith of London and Edinburgh for the courteous way in which they have assisted us with specimens when working upon those of the allialoids which exist only in minute quantities in opium ; without this assistance we could scarcely have procured them iu a state of reliable purity. RESEARCH IN RELATION TO PHARMACY. EXPLANATION OF PLATES.PLATE 1. Xmwopical Anewance of Opium Princtples. Fig. 1. Morphine. 2. Narcotine. , 8 a. Sulphate of Morphine. b. Meconate of Morphine. ba. Commercial salt crystallized from solution in weak alcohol. bb. Crystallization from mixed solutions of Morphia and Meconic Acid. Fig. 4 a. Codeine. aa.Cryetallized from Alcoholic solution. ab. Crystallized from Aqueous solution. 6. Thebaine. , 5 a. Meconine. b. Xeconic Acid. ,) 6 a. Narceine. b. Papaverine. bu Crystallized from Alcoholic solution. bb. Crystallized from Aqueous solution. PLATE 11. Fig. 1. Tinctura Opii (Turkey Opium) prepared by the Authors aa standard. , 2 3. Specimens of Tincture alluded to in the text. , 4. Extracturn Opii (Turkey). , 6 a. Commercial Extract of Opiim imported.b. The same redissolved filtered and evaporated. , 6. Liquor Opii Sedativus prepared from Patna Opium. PLATE In. Liquor Opii Sedativus (Turkey Opium). Fig. 1. Battley’s. , 2 a,b. Two specimens prepared by the Authors by elightly differed processes from different samples of opium. , 3. Mr.Morson’s alluded to in the text. , 4 5 6. Specimens sent out by three operative chemists of standing in London. PLATE IT. Fig. 1. Extracturn Opii prepared from Prrtna Opium. 2. , I Malwa Opium. $9 2 9) Peraian Opinm. ’* 8) , 4. Tinctura Opii prepared from Patna Opium. 5. Y , Malwa Opium. #S ? 6. 9 , Persian Opium.

ISSN:0368-1769    

DOI:10.1039/JS8651800034

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

SPILLER ON THE OXIDATION IX.-On the Oxidation of India Rubber. By JOHNSPTLLER, F.C.S. ABOUTfour years ago Dr. A. W. Tlofmann commnnicated to the Chemical Society an. interesting research which treated of the changes that gutta-percha is found to undergo bp free exposure to air under ihe influence of a hot climate and the author brought forward conclusive evidence to show that the deterioration in quality observed in the coating of the Indian telegraph wires was to be accounted for by the gradual oxidation of the natural gum.* From a similar point of view I have lately had an excellent oppor- tnnity of studying the nature of the changes produced in caoutchouc by the operation of like influences. The example to which I beg leave to call attention is one of a very instructive character and indicates a condition which must be observed in the India-rubber mnnufdcture whenever it is desired to ensure the permanence of an unvulcanized material.An article is known in commerce under the name of “Patent Waterproof Felt,” which is manufactured largely for the purposes of a cheap packing and is used in the exportation of silk and other valuable fabrics stationery goods etc. which are liable to be damaqed by water. This material is sold in sheets of great length and usually about a yard wide; it appears to be made by cement-ing or matting together the Fres of cotton wool through the intervention of India-ruhber paste or solution so that after the evaporation of the coal-naphtha or other solvent and passing through rollers a continuous and water-repellent fabric is pro-duced.About six years ago I prirchased some of this so-called waterproof felt and made some useful applications of it in the way of photography; some of the material had however been laid aside until a few weeks since when upon examination it proved to possess no longer the close structure and waterproof qualities of the original article. It then occurred to me to examine once more the material in the same manner that I had tested it six years ago viz. by extrachng the India-rubber with benzol and noting the character of the film left upon the evapo- * Chem. SOC.Qu. J. xiii 87. OF INDIA RUBBER. ration of the solvent. The original fabric thus treated furnished a beautifully white cotton flock and a solution which being evaporated left a highly elastic film of pure India-rubber; but these characters are no longer possessed by the fabric examined at this later period By digesting with benzol the cotton fibres are left; in a discoloured coiidition and a solution is obtained which upon evaporation yields a resiu or brownish yellow brittle substance closely resembling shellac.A considerable quantity of this altered India-rubber has been extracted by solvents and its properties may be thus characterized :-It is freely soluble in alcohol especially if warmed in chloro- form wood-spirit and in benzol as already stated. It is not appreciably soluble in oil of turpentine or bisulphide of carbon and but sparingly so in ether.In alkaline solutions both caustic and carbouated it is freely soluble and niay be again precipitated 011 neutralising with acids. Like India-rubber itself it becomes bleached upon iminersion in aqueous ammonia. The resin fuses below the temperature of boiling water and when more strongly heated in a retort gives off an amber-coloured oil of agreeable aromatic odour besides furnishing water a proof of its containing oxygen. At ordinary temperatures it is extremely brittle and highIy electric so much so that it cannot be powdered in an open mortar without considerable loss. A glass rod coated with the substance exhibits the phenomena of ‘‘resinous electricity’’ when rubbed with silk. The chief examination has been made upon the substance extracted from the fabric by warm alcohol which leaves insoluble besides the cottoil a very small proportion of unchanged India-rubber easily separated by filtration and the amount of the brittle resin extracted in this mariner from a square foot of the fabric weighed after complete evaporation of the solvent over a water-bath 74 grains.A quantitative analysis of this substarlce has been made and the numbers furnished by com- bustion with oxide of copper indicate the following percentages which I have placed in juxtaposition with the figures reported by Dr. Hofmann for one of his compounds :-India rubber. Gutta percha. J. S. A. W. H. Carbon .. . . 64.00 62.79 Hydrogen .. .. 8.4.6 9.29 Oxygen .. .. 27-54 27.92 HOW ON A DENSE BRINE For the reasons adduced by Dr. Hofmann in the case of the altered gutta-percha examined by him I abstain from constructing a formula and merely regard this substance as an oxidation pro- duct formed directly from caoutchouc by the absorption of atmo-spheric oxygen in much the same manner as resins are formed from essential oils and other hydrocarbons.

ISSN:0368-1769    

DOI:10.1039/JS8651800044

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

HOW ON A DENSE BRINE X.-On a Dense Brine from Saltsprings Nova Scotia. By Prof. How D.C.L. University of King’s College Windsor N.S. THE analysis of mineral waters is a subject full of interest. Chemists see in every instance means of comparison respecting the accumulation of ingredients in the solvent and matter for argu- ment concerniiig the chemical changes capable of producing the associatioris observed. The s:gnificance of water analyses when properly executed and reasoned on is shown by the amount of criticism which has appeared* of late years on the want of uniformity in the modes of arranging the results both BY regards the standard of quantity and the principles upon which allotment of the constituents ehould be made. Geologists consider the nature and quantity of the contents of waters in connection with the sources of the elements and find in waters at once the proofs and the agents of important changes in the composition of the earth.Every one mill remember what use was made of such el-idence in the Presidential address of Sir C. Lyell at the late meeting of the British Associatioil at Bath. The importance of the researches of Forchhammer on the constitution of sea-water has been still more recently declared in the annual address of the President of the Royal Society. Physicians and invalids need only be reminded that curative properties may be at once justly assigned to a water in consequence of its analysis having been minutely made. 3t is curious that among the analyses recorded of late years few or none are of waters of brine-springs excepting the very it See for esamples R.Ha in es M.B. in Chemical News iv 29 and Editorials in the kame Journal iii 285 315. Also Miller ii 1088 flst ed.). FROM SALTSPRINGS NOVA SCOTIA. valuable series by Hunt in the ‘‘Geology of Canada.” Several most interesting waters have been examined in which chloride of sodium is a chief constituent but its amount is so nearly approached by that of some other salt that such waters are properly called strongly saline in contradistinction to true brines in which com- mon salt is by very much the prepmderating ingredient. I hope the following account of a true brine will be acceptable. The water is remarkably dense and presents some interesting features in its composition :-Nova Scotia affords a considerable number of waters rather strongly charged with mineral matters springing up in rocks of different geological age.Of these I have described several and one,* arising at Bras d’Or in Cape Breton in rwks probably of Silurian age has so far as the relative arnoiints of chlorides and sulphatea are concerned a decided resemblance to that of Wheal Clifford analysedt by Pro. W. A. Miller and described by Sir C. Lyell at Bath. (Wheu I analysed the Bras d’Or water czsium and rubidium had not been discovered and I had only material to determine the leading ingredients.) In both these and in some similar waters described hy Hunt,$ srilphates are very small in amount ;in most of tliese Canadian waters indeed they are absent while chloride of calcium chiefly abounds with chloride of sodium.Other waters of this province have a large amount of eulphate of lime,§ and exceedingly little chlorine. The water now to be described contains an unusually large quantity of both common salt and sulphate of lime. The water rises in the carboniferous system and most. probably in the beds called here the gypsiferous limestones. Tliis system is known to furnish brine.springs in various parts of the province and salt has been made from a few of them including the subject of this paper. The particular locality of this water has its name from the number of its “salt-springs,” for as I am informed by the Rev. Mr. M‘Kay who occupies the manse at the spot and who kindly collected the water for my experiments there are several small salt-springs found liere along a low bank over the length of 150 yards along which course the salt water oozes out at many intervals depositing salt at some places.Besides tliese there are the principal spring from which the water was not * Chemical News ix 97. + Chemical News x 181. Geology of Canada p. 647. $ Chemical News x 98 and Trans. N. S. Inst. ii. HOW ON A DENSE BRINE taken for some reason connected with the state of the neighbour- irig river and also a spring rising at about 9 yards distance from tliis in a hole dug by a company who made salt from the water about twenty pears ago. From this last spring the water analysed was taken in September 1864.Mr. M'Kay tells me the water is applied externally for the cure of rheumatism and he believes it to be effective. I imagine the spring to be thermal for my attention was first drawn to it by a gentleman mentioning as ZL singular circumstance tliat the rocks forming the basin of the water in which he bathed were sensibly warm to his feet. The water as received contaiiied floating organic matter in small amount arid on standing it smelt very decidedly of sulphuretted hydrogen due of course to the reduction of asulphate. To ohtain ail idea of the amount of change occurring under these circum- stances I determined the sulphuric acid twice at an interval of a full month The first experiment gave 92.799 grains SO per gallon. , second , , 91.020 , 99 >) It appears then that the waters alter considerably from this cause which is often observed in operation.On this account the total lime magnesia and sulphuric acid given below are as found in portions of the water taken for analysis on the same day; the chlorine was determined four days after. The first alkali deter- mination proving unsuccessful I could only take that made about a month later than the experiments mentioned and I found the chloride of potassium to be very small in amount. Phosphoric acid was found in decided quite determinable quantity and I believe the precipitate formed on bJ- boiling contained a portion of this acid for in an analogous water I proved it to be present in the peroxide of iron obtained from the carbonates thrown down Boracic acid was also clearly indicated after evsporatiug about 22,000 grains of water and testing with turmeric paper the liquid which drail;ed from the nearly dry residue rendered acid by hy- drochloric acid especially by dipping and drying the paper several times in succession.Bromine was detected without difficulty in about 8,000 grains bnt iodine could not be found in the same quantity. Nitric acid could not be found in the residue of 22,COO gratins. The following are t,he results of the quantitative analysis so far as it was attempted the substances actually found bcing these :- FROM SALTSPKINGSJ NOVA SCOTIA. Grains Grains. Grains. in a gallon. 14,000 water gave by boiling *755CaO.CO = CaO.CO 3.775 J> >, J> *775ZMgO.PO,= MgO.CO 2*93;L JJ >J >> 0025Fe,O = FeO.CO 0 181 J> 2>500 )J *O20 SiO = SiO 0-560 JJ >J ;J 9.475 BaO.SO = SO 91.020 >, JJ ) 5.870 Ca0.C02 = CaO* 89.920 J Y> 1) 1.2802MgO.PO,= MgOt 12.910 300 ¶J 44.400 AgCl = C1 2561*a06 ,J 800 >> 47.240NaCl = NaCl 4133.500 JJ By calculating on the pim of Fresenius we obtain as existing in the water these constituents :-Per cent.Grains per galIon. 0. Carbonate of Lime .. .. -00539 3.775 Carbonate of Magnesia .. .. *00418 2.932 Carbonate of Iron .. .. .. *00025 -181 Silica .. .* .. .. .. -00080 -560 Sulphate of Lime .. .. .. -22104 154.730 Chloride of Calcium.. .* .. -07415 51.910 Chloride of Magnesium .. .. -03904 27-330 Chloride of Sodium (+ a little KCl) 5.90500 4133.500 Phosphoric Acid Boracic Acid Undetermined.Bromine i Organic Matter --6.24985 4374.918 Specific gravity at 53" Fah. . 1046.69. The total weight of solids contained is very large. The follow- ing list shows the contents of some waters selected from the very limited number of those holding more than 1,000 grains in the gallon :-* After deducting CaO = CaO.CO thrown down by boiling. + After deducting MgO = MgO.COn thrown down by boiling. VOL. XVIII. E HOW ON A DENSE BRINE Gains in a gallon. ‘I’he most strongly saline water of Cheltenham contains .. .. .. .. .. 1033*600* The strongest brine of Canada contains .. 1469-909t Sea-water (mean quantity) contains .... 2401280Q The second strongest saline water of Canada contains .. .. .. .. .. 3242.260f‘ The water of saltsprings Nova Scotia contains 4374,918 The strongest saline water of Canada contains. . 4762,960t The water of the Dead Sea (largest amount found) cont aim .. .. .. .. I8550*000~ If we compare the Saltsprings-brine and some other waters rich in chlorides with sea water as regards the relation of chlorine to sulphuric acid we observe great dissimilarity ;thus :-c1. so,. In the strongest Cheltenham water the relation is as 100 32-10 In Sea-water (interior of Baltic) ) , 100 14.9711 , (open ocean mean) , , I00 1‘1*89[1 7, In Saltsprings water , 100 3.55 In VC%eal Clifford 9 , 100 1-83 In Dead Sea 9 , 100 0.35 On the other hand out of 21 Canadian waters abounding in chlo-rides sulphuric acid is found in five only and in these in quite small proportion ; and the same is the case in the Bras d’Or water before mentioned as resembling these and the water of Wheal Clifford.Although the relative amount of sulphuric acid is low in the Saltsprings water as compared with that in sea-water the quantity of sulyhate of lime it forms is larger than is found in most waters. In looking over numerous analyses I have met with few waters which resemble closely or exceed the Saltsprings and some other Nova Scotia waters in this respect. The following * Scudamore quoted in Abel and Rowney on Cheltenham WatersJ Chern. SOC.Qu. J. 1848 vol. i. p. 193. -f Hunt Geology of Canada pp.547 548. 5 Forchhammer Proc. Roy. SOC in Chemical News x 293. Booth and Muckle Jahreabericht 1849 p. 613. II Fo r c h h a m m e r Eoc. cit. the other calcillations are mine from published analyses before referred to except in the case of the Dead Sea ; the analgsis of thia taken is by Mar c h a n d Jahresbericht 1840 p. 613. FROM SALTSPRTNGS NOVA SCOTIA. 51 list shows in round numbers the amount of sulphate of lime contained in some of the waters be€ore adverted to and in some others :-Grains in aga:lon. Bras d’Or water Cape Breton contains Sulphate of Lime 1 Wheal Clifford water Cornwall >9 J? 12 Dead Sea water ,3 9 61 I?ath water YY >> 96 Sea water (British Channel) >9 ,? 98 Che1 tenham water (strongest) St.Catharine’s water Canada > 9) , > 116 153 Spa Spring water Nova Scotia >I ,I 106 Wilrnot water 9 >J > 12 4 Saltsprings water 9 >¶ > 158 Wilmot water ¶Y I> ,> I61 Ivandn water The Banat ,9 9) 195 I As according to Fresenius 70,000 grains of pure water can dissolve only 163 grains of sulphabe of lime it appears that two of the Nova Scotia waters are very nearly saturated while that of Ivanda in the Banat is considerably supersaturated. Hence we have in the latter case an illustration of the way in which the solubility oi salts is modified by the presence of others. l’lie analysis of Iranda water is contained in an account of some mineral waters published at the London Eshibition of 1862; it is by Ragsky. It will perhaps be agreeable to some to see what other salts are present in the water to account for the pre- sence of so much sulphate of lime ;the leading constituents are in round numbers :-Grains in agallon.Sulphate of Lime .. .. .. 195 Sulphate of Soda .. .. .. 881 Chloride of Magnesium.. .. .. 109 Nitrate of Magnesia . . .. .. 21 -Amount of ingredients being . . 1238 ahd sulphate of sods is one of the salts mentioned by Fr eseniu s as increasing the solubility of sulphate of lime. I may meiition that in the Spa Spririg and Wilmot waters in the list above EfL HOW ON A DEXSE BRINE given the total contents per gallon are respectively in round tiurnhers 138 and 141 grains so that the sulphate of lime is by much the leading ingredient.While upon the subject of the solubility of salts I venture to touch upon two other cases in hopes of exciting useful discussion in an assemblage of chemists. One of‘ these is the solubility of carbonate of lime in water. According to Fresenius (Quantitative Analysis 3rd ed. p. 496) “the simple carbonates of lime and magnesia are not altogether insoluble in water and to be as nearly accurate as possible proper correction must accordingly be made for this in the calculation.” On consulting p. 634 at experiment 25 we find that 10,601 parts cold water dissolve 1 part of carbonate of lime; hence a gallon= 70,000 grains of water must dissolve 6.58 grains. Is this amount allowed in all .water znalyses where the salt is met with? We have only to calculate the results given to find that it is not though it is found necessary :,ometimes when there are not sufficient acids for the bases to calculate the snperfluous bases as carbonates as is stated to be the in Abel and Rowney’s analysis of Cheltenham waters (Chem.SOC.Qu. J. I 193 1848) where in one case 22.08grains of carbonate of lime are given while only 12.36 were actually found per gallon. I observe that at the meeting of the Chemical Society held February 5th 1863 this question of the solubility of carbonate of lime was discussed and it was then stated by Dr. Paul (Chemical News vii. p. 80) “that experiments of Fresenius and Dr. E. Nicholson prove that aboiit two grains per gallon is the utmost limit of the solubility of czr-bonate of lime in water.” The President Dr.Hofmann said “in his opinion the amount of carbonic acid required to dissolve carbonate of lime was considerably less than that dciiianded to form bicarbontte of lime ; the proportion however did not appear to be always definite.” Nothing more transpired ns to the actual amount of the salt dissolved by water. The secorrd case is the solubility of carbonate of magnesia in water. To what extent is the salt soluble in pure water? As to its solubility in mineral water Dr. Sterry Hunt says (Geology of Canada p. 557) “It is well known however that an excess of carbonic acid is not necessary to retain carbonate of magnesia iu solution. Carbonate of magnesia is soluble to a considerable extent in an excess of carlionate of soda or of chloride r,f mag-nesium ; and a large quantity of magnesia may be held in solution FROM SALTSPRINBS NOVA SCOTCA.in the form of sesqiii-carbonate.” Under these circumstances what becomes of the ‘‘proper correction’’ of Fresenius “for the solubility of carbonates of lime and magnesia in wuter,” and what reference can be made to the amount of those salts dissolved even when water containing them has been boiled to the expulsion of all carbonic acid if it depends on the nature and quantity of other saltps also present. It was mentioned in a previous page that the Saltsprings water rises in the gypsiferous rocks of lower carboniferous age; it is interesting to find evidence of salt existing in these rocks as this circumstance as well as the occurrelice of gypsum makes them resemble the new red of England.As before stated numerous saltstirings are known to arise in the carboniferous system iii different parts of this province and I may add that at one plsce Antigonish 50 miles from Saltsprings is the c‘ Salt pond,” and at another Whycogomagh in Cape Breton 100 miles from Sdtsprings is the “Salt mountain,” supposed to have been so called from the presence of brine-springs. No beds of salt have been met with but I have small quantities of crystallised rock- salt from a gypsum quarry at Windsor in which several years ago,” 1 proved the existence of sulphate of soda and natro-boro-calcite and subsequeritlyt of sulphate of soda holding im- bedded a new borate which I called cryptomorphite.In this connection the detection of boracic acid in the Saltsprings water arising some 60 miles from Windsor has peculiar Interest. It is possible that there is a coustaut association of those substances which have thus already been found together in greater or smaller quantities in gypsum or in waters froin gypsiferous rocks viz. common salt sulphate of soda magnesia-salts and boracic acid with the gypsum forming the enormous deposits of this rock in Nova Scotia. The significance of these bodies occurring together will be seer. by consulting Hunt’s papers 011 the formation of gypsum and magnesian rocks (Sill. Am. J. [a] xxviii. 365 et seq.) Beds of limestone rich in magnesia are soine-times found e.g. at Walton contiguous to beds of gypsiim. Much however remains to be learned respecting the relations of these rocks; in the meantime it is well to put upon recurd such facts as are gathered concerning them. * Sill. Am. J. [Z] xxiv 230. f Ibid. xxxii 9 and Edin. New Phil. J. 1861.

ISSN:0368-1769    

DOI:10.1039/JS8651800046

出版商:RSC    

年代:1865

数据来源: RSC

摘要:

54 RONALDS ON THE MOST VOLATILE CONSTITUENTS XI.-On the most Volatile Constituents of American Petroleum. By EDMUND Ph.D. RONALDS [From the Transactions of the Royal Society OP Edinburgh.] CRUDEAmerican petroleiim evolves at ordinary temperatures a quantity of gas which takes fire on contact with flame and when mixed in certain proportions with air produces an explosive mixture. It is in consequence of this property that it has been thought necessary to pass a very stringent law known as the Petroleum Bill with a view of preventing accidelits from thc incautious storing and handling of the oil. The more volatile liquid products obtained by distilling the crude oil are still more highly charged with combustible vapour which when these liquids are again distilled escapes cordensation even by the most powerful freezing mixtures.The liquid constituents of petroleum have now been carefully studied by Messrs. Pelouze and Cahours and some of them also by Mr. Schorlemmer. These eminent chemists have shown that the oil consists essentially of a mixture of the homologues of marsh gas having the general formula It was during the collection of the more volatile of this series of compounds with a view to their analysiu in which object I have now been forestalled that my attention was drawn to the large quantities of incondensable gas which escaped at each successive fractionation arid it appeared desirable to ascertain whether the gaseous ingredients of the oil belonged also to the same series or mere accompanied by other hydrocarbons.With this object in view and still waiting the arrival of some specimens of oil col- lected and secured in hermetically sealed vessels direct from the oil-wells I was euabled by the kind permission of Mr. Shand of Stirling to collect the gns which floated over the surface of the crude oil in the barrels in which it is imported into this country. 1 also obtained from the same manufacturer some of the very first proifucta of the stills employed in refining the petroleum on a ilianufact uri ng scale. The gas floating over the surface of Pennsylvanian oil was col- lccted at a temperature of -1" C. aud was observed to contain OF AMERICAN PETROLEUM. combustible ingredients. It took fire instantly on being brought into contact with flame burning with a very failit bluish light but without explosion.From Canadian petroleum which is of much thicker consistence no combustible gas was obtained at that temperature. The gas was collected over water by simply removing the ori-ginal wooden bung of the casks and inserting immediately a ccrk bung furnished with a tube for the delirery of the gas and a long shaiiked funnel tube through which liquid petroleum was poured. Thus obtained the gas was of course a mixture of air and liy-drocarbon; it was not affected by fuming oil of vitriol nor mils bromine-water discoloured by it It was hence inferred that no perceptible quantities of the olefiant series were present and the temperature of collection is suflicient guarantee fcr the absence of any known members of the benzole series.The qas was treated over mercnry with solid potash and pyro-gallate of potash successively when it yielded- 1.27 per cent. of carbonic acid and 6.58 , , oxygen. The residue analysed eudiometrically gave the following re-€111ts :-Gas collected from the surface of Pennsylvanian Petroleum at a temperature of -1" C.,jt.eed from Carbonic Acid by Potash and from Oxygen by Pyrogadlic Acid. m. pressure. I- I-1-1- GaS .. .. .. Do. + air.. * .. Do. + do. -I-oxygen .. Afterexplosion .. .. Aiter absorption of CU .. After addition of hydrogenAfter explosion .. . . . . .. .. .. . . .. 133.1 392.8 465 .6 421.3 383.4 474 3 346.5 0.3099 0-5666 0.6391 0.6940 0.5515 0 6395 0 ,5062 39.934 215 47 288.92 245 09 205.23 299 .I5 152*86 Deducting the nitrogen or 23.4 vols.= 54 per cent. of the original gas we have here a relation of hydrocarbon to condcn-sation and carbonic acid as- 16.534 43.83 39.86 or 100 265 241. 56 RONALDS ON THE MOST YOLATILE CONSTITUENTS The oxygen consumed amounts to 67.16 vols. or 4.06 times the volume of the hydrocarbon. The members of the olefiant and benzole series being absent it may fairly be inferred that the hydrocarbon resembles in constitution the liquids with which it is associated ; and if this be the case the gas must be a mixture of the hydrides of ethyl and propyl the former of which requires a relation of hydrocarbon to condensation and carbonic acid as-1 2.5 2 while the hydride of propyl requires a relation of 1 3 3.By calculation from the numbers above it can be shown that the gas analysed must have consisted of a mixture of these gases in nearly equal proportions or of- C,H6 hydride of ethyl 7-94 C,H, hydride of propyl 8.01 -the correctness of which is confirmed by the amount of oxygen consumed being about the mean of the quantities required for the combustion of these hydrides separately. Hydride of ethyl requires 3.5 times its volume of oxygen. Hydride of propyl requires 5 times its volume of oxygen. The ~RSfloating over the surface of the petroleum is tlierefore composed of-Carbonic acid .. .. l*27 Oxygen .. .. 6.58 Nitrogen .. {:::68)Hydrocarbon .. 54. 38.15 In this condition the gas is not explosive and would only be-come so on being mixed with a large volume of air.The most volatile liquid obtained by collecting the very first runnings from the stills employed in the process of refining pe-troleum has a specific gravity of 0.666. It is not seiisibly affected by nitric acid by oil of vitriol or by bromine. When distilled it begins to give off bubbles of gas in abundance at about 25" C. but after a few minutes all appearance of boiling ceases although large quantities of gas and condensable liquid continue to pass over up to 65' or 70' C. and the whole liquid is evapo- rated below 100" cent. OF AMERICAN PETROLEUM. This liquid resembles very closely the '' kerosolene" or "keroso-form" which an American physician of New Y ork has introduced as an anzesthetic agent ; and I am indebted to Dr.Simpson for the opportunity of comparing it with a specimen of the latter. The specimen lent me by Dr. Simpson was quite indifferent to the above reagents It had a specific gravity of -6336. It began to boil at 28O C. and was almost completely volatilised at 70" C. so that it must have been composed almost exclusively of a mixture of the Eydrides of amyl and hexyl while the crude volatile product from the manufactory contained in addition to these hydrides some incondensable gaseous products and a con-siderable quantity of the hydride of heptyl. The incondensable gases dissolved in this most volatile liquid were expelled by gently warming a large quantity (about two gallons) of-liquid and passing the gases before collecting them over water through a long metallic worm surrounded by a freez-ing mixture composed of ice and salt the whole apparatus having been filled previously with carbonic acid to expel air.The first two portions which were collected showed after sepa- rating carbonic acid and oxygen little difference in compositicn from that already analysed and which had been collected from the surface of the crude oil. I omit the details of the analyses of these two and submit only the results which correspond in both cases with a mixture of the hydrides of ethyl and propyl. Gas. Condensation. Carbonic Acid. 23.947I.{y;; . 2-77 Oxygen consumed .. 19*04.5 242 32.338 11.{7.y;; * 20.70 280 17.586 240 Oxygen consumed ..31-07 The gas coming over a little later from the same liquid was found to approach nearer in composition to pure hydride of propyI :1s is shown by the following analysis. This portion was treated with potash before being introduced into the eudiometer but the oxygen which it contained was not separated before combustion but was estimated in a separate experiment and found to amount to 2.44 per cent. of the gas burned. RONALDS ON THE i\lOS'r VOLATILE CONS'I'ITUENTS Corrected 1-01. Observed at 0" and 1 m. Volume. pressure. Gas .. .. .. .. 39 -723 0.2817 15 *1 10.604 After addition of oxygen.. .. 160 -0 *3939 16 -59.548 After addition of air .. .. 260 -125 0 4917 14 -5 121 -46 After explosion .... .. 236 386 0.4660 16 -5 104 .33 After absorption .. .. .. 204.386 0 451 75. 87 -276 After admission of hydrogen .. 357.161 0.603 14-204 *53 After explosion .. .. .. 231.225 0 *4613 13*6 102 +29 Deducting the nitrogen and the 2.44 per cent. of oxygen con-tained in the gas we have here the ratio of hydrocarbon to con-densation and carbonic acid as 5.984 17-13 16.954 -100 286 283 Hydride of propyl C,H = 2 vols. requires a ratio of 1 3 3. The quantity of oxygen consumed by the hydrocarbon is 4.67 times its volume while pure hydride of propyl would require 5 times its volume. The gas collected at a still later period from the same liquid was free from carbonic acid oxygen and nitrogen gases arid agreed in composition with a mixture of the hydrides of propyl and butyvl.Observed Pressure. Tern p. at 0" and 1 m. Volume. Cent. pressure. -I--Gtas .. .. .. 43 *034 0 -2821 19 *5 11.335 After addition of oxygen.. 151 -465 0*3837 19.9 54 .454 After addition of air .. 417 * 0 .6439 20 -6 249 -70 After explosion .. . . 372 644 0 .6038 16 -7 212.05 After absorption . . .. 321 * 0.566 15 .2 172.11 After addition-of hydrogen 405 * 0.649 17 -247 -45 After explosion .. .. 353.032 0 *5846 15 *2 195 52 The relation here of hydrocarbon to condensation and carbonic acid is as-11.335 37.65 39.94 100 332 352 The oxygen consumed is 5-88 times the volume of gas burned OF AMERICAN PE'I'ROLEUM. while hydride of butyl alone requires 6.5 times its volume of oxygen for combustion.The gas evolved on warming the light spirit of petroleum as it is prepared for sale after having been kept however for some months in a vessel not hermetically sealed mas found to be a mix- ture of nitrogen and oxygen with nearly pure hydride of butyl. After separating by potash the carbonic acid which had been allowed to occupy the space above the liquid the gas was analysed ; the oxygen which it contained was estimated by pyrogallate of potash in a separate experiment arid amounted to 15-37 per cent. Observed Volume. Presaure. pressure. I__--- Gas . . .. .. .. 73 *2 0 -2399 7. 17 *25 After addition of air .. .. 273 -3 0.4360 5 .2 117.11 After addition of oxygen..Alter explosion .. .. After absorption .. .. After admission of hydrogenAfter explosion ... .. .. .. .. .. 334. 288 *5 228 -5 330 317 * 0 4976 0 ,4523 0,3995 0,5022 0 -4799 5 .7 6.4 10.2 13 * 12 .2 162 82 127.5 158 .2 145 86 87 -398 Deducting the nitrogen and oxygen contained in the gas we have here a relation of hydrocarbon to condensation and carbonic acid as,-9.64 35.32 39.532,or as 100 366 409 closely corresponding to the relations in hydride of butyl which are,-] :3*5 4. The gas was therefore composed of-28.74nitrogen 15.37 oxygen 55-89hydride of butyl and it would appear from this experiment that the light volatile liquids absorb and retain oxygen in greater proportion than that element is coutairied in atmospheric air. The liquid condensed by the freezing mixture during the collec- tion of these gases and that obtained by subsequently heating the large body of liquid from which they were expelled to a higher temperature not exceeding however 30" C.or the boiling point 60 RONALDS ON THE R1os-r VOLATILE CONSTITUENTS of hydride of amyl mas redistilled. It began to boil at 0" C.; a considerable portion passing over betarem 0" and 4" was collected separately ;another fkaction between 6" and 8" was also collected apart ; the remainder nearly all distilled below 15" cent. The liquid distilling between 0" and 4" C. is nearly pure hydride of butyl which has not yet been described. It is a per-fectly clear colourless very mobile liquid having an agreeable sweet smell but eluding by its great volatility the sense of taste. It is insoluble in water but dissolves in alcohol and ether and alcohol of 98 per cent.absorbs between 11 and 12 times its volume of the vapour at a temperature of 21O.5 C. It burns with a yellow not very luminous flame. Mixed in the gaseous state with twice its volume of chlorine liquid chloride of butyl is formed and the original 3 volumes become condensed into 2 volumes of hydrochloric acid. The specific gravity of the liquid at 0" C. is 0.600. It is therefore the lightest liquid at present known. The vapour-density determined by Durn as' method the vapoiir being absorbed by alkohol gave he following results :-Temperature of air ...... 13'8 C. Temperature of sealing ........ 40" C. Barometer ............ T615 m. Capacity of globe .......... 185.6 ce.Empty globe .......... 30.577 grms. Air bubble ................ 7.8 cc. Globe and substance ,.,. 30.788 grms. Temperature of alcohol ........ 14" C. Hence vapour-density = 12-11. Hydride of butyl C4HI0,requires by calculation 2.006. The liquid analysed eudiometrically in the gaseous state gave the following numbers :-Analysis of Butyl Hydride. Temp. Corrected VO~. OybGr Pressure. pressure. Cent. at 0" and 1m. aas ........ 35-04 0.1944 M. 5°C 6 -691 After addition of oxygen.. .. 326 . 0.4810 4-8°C 154.11 After explosion ...... 294.8 0 .4507 4°C 130.95 After absorption of COZ .... 256. 9 0 *4215 9°C 104.33 Hence we have,- OF AMERICAN PETROLEUX. Gas. Condensation Carbonic Acid. 6.631 23.16 26.12 100 346 390 or Hydride of butyl requires- 100 350 400 The liquid collected between 6" and 8" C.is not very different from this last. It is however a mixture of hydride of amyl with liydride of butyl. Its sp. gr. at 0" C. was found to be *6004. The vapour-density was 2.178 and the composition in the gaseous state is shown by the following numbers :-Temp. Corrected vol. Pressure. Cent. at 0" and 1 m. pressure. -I-Gas .. .. . . .. 15.3 0.4392 19-3 9 -39 After oxygen .. .. .. 264.5 0.6912 19.3 185 *22 After explosion .. .. .. 223 * 0,6509 17.9 149 -12 After absorption .. .. .. 166'8 0.6154 19 *5 106 -78 Hence we have,-Qas. Condensation. Carbonic Acid. 9.39 36.10 42.34 100 384 450 or Hydride of butyl requires,- 100 350 400 It was not to be expected from the manner in which the gases were collected that any single portiou woiilcl correspond exactly in composition with any member of the series and some attempts which were made to separate the gases from each other by wash- ing with alcohol did not yield more conclusive results than those already obtained with the mixtures.From the foregoing experiments we may I thiuk safely con- clude that all the homologues of marsh gas excepting marsh gas itself are present in the liquid as it comes to this country and there appears to be little doubt that marsh gas and perhaps even iree hydrogen will be found among the gases which are evolved with the oil at the springs.

ISSN:0368-1769    

DOI:10.1039/JS8651800054

出版商:RSC    

年代:1865

数据来源: RSC