摘要:

THE JOURNAL OP THE CHEMICAL SOCIETY LONDON. aammiitae Df ~ublimtiflll. F. A. ABEL F.R,S. 1 E. FRANKLAND PH.D. F.R.S. WARREN DE LA RUE,PH.D.,F.R,S W.A. MILLER MUD. F.RS Qbifar HENRY WATTS B.A. F.R.S. NEW SERIES VOL.VI. (Entire Series VoL XXI.) JAOONDON VAN VOORST 1 PATER OSTER ROW. 1868. Lf)NDOX HARRISON AND SONS PRINTERS IN OHDTSART TO HER BUJESTY ST. MARTIN’S LANE. CONTENTS TO THE TWENTY-FIRST VOLUME. PAOX Report of Anniversary Meeting March 30th 1868 ...................... i Balance Sheet ...................................................... xxxri Proceedings at the Ordinary Meetings Session 1867-68 .................. xxxvii Donat,ions to the Library (1867-68) ....................................xlir On the part taken by Oxide of Iron and Alumina in the Absorptive Action of Soils. By Robert Warington Junr. ............................ 1 Laboratory of Owens College Manchester .......................... 19 On the Action of Perrnanganate of Potash on Urea Ammonia and Acetamide in strongly Alkaline Solutions. By J. Alfred Wanklyn and Arthur Gamgee ...................................................... 25 Synthesis of Caproic Acid. By J. Alfred Wanklyn and Robert Schenk. 31 On the Origin of Muscular Power. By E. Frankland F.R.S.. ........... 33 On the Artificial Production of Coumarin and Formation of its Homologues. By W. H. Perkin F.R.S ........................................ 53 Note on the Preparation of Urea. By John Williams. ................63 On the Pyrophosphoric Amides. By J. H. GtladBtone Ph.D. F.R.S.. ..... 64 Freezing of Water and Bismuth. By Alfred Tribe F.C.S. .............. 71 On the Isomeric forms of Valeric Acid By Alexander Pedler Esq. .... 74 On the Analysis of Potable Waters. By E. Frankland F.R.S. and H. E. Armstrong Esq. .............................................. 77 On a Simple P pparatus for determining the Gases incident to Water Analysis. By E. Frankland F.R.S. ...................................... 109 Reductiou of Carbonic Acid to Oxalic Acid. By Dr. E. Drechsel (Commu- nicQtecl by H. Kolbe) ............................................ 121 Analysis of the Water of the Holy Well a Medicinal Spring at Humphrey Head North Lancashire. By Thos. Ed Thorpe Dalton Scholar in the On some new Benzylic Derivatives of the Salicyl Series.By W. H. Perkin F.R.S. ........................................................ 122 On Gas Analysis. By W. J. Russell Ph.D. .......................... 128 On Chloranil. No. I. By John Stenhouse LL.D. F.R.S. &........... 141 Action of Nitric Acid on Picramic Acid. By John Stenhouse LL.D. F.R.S. &c. .................................................... 150 Note on Frankland and Armstrong’s Memoir on the Analysis of Potable Waters. By J. A. Wanklyn E. T. Chapman and Miles H. Smith. 152 On the Action of Oxidizing Agents on Organic Compounds in presen’ce of excess of Alkali. By J. Alfred Wanklyn Professor of Chemistry in the London Institution and E. Theophron Chapman .............. 161 Note on the Estimation of Nitric Acid in Potable Waters.By Ernest The oph r o n Chapman. ......................................... 172 Action of Zinc-ethyl on Nitrous and Nitric Ethers. By E. TheophronChapman and Miles H. Smith.. ............................... 174 On the Occurrence of Prismatic Arsenious Acid. By F. Claudet ........ 179 On the Hydride of Aceto-Salicyl. By W. H. Perk in F.R.B. ............ 181 On the Absorption of Vapours by Charcoal. Bg John Hunter M.A. F.C.S. Chemical Assistant Queen’s Collegc Belfast ........................ 186 Chemical Contributions. By Dr. H. Kolbe 1. On Carbanilic Ether. EyDr. Wilm and Dr. Wischin.-2. On Ethylic Sulphocyannte. By Mr. 1relan.-3. Direct Conversion of Ammonia Carbamate into Urea. By Alexander Basai*off.-4.On the Electrolvsis of Acetic Acid. Bv Acid.H. Kolbe.-5. On ~~~~thintrisulpl~onic Bp Dr. Theilknhl . , 192 iv CONTENTS. PAGE On the Constitution of Blyoxylic Acid. By M-.H. Perkin F.R.S. and B. F. Duppa F.R.S. ............................................ 197 On the Solubility of Xanthine (Uric Oxide) in dilute Hydrochloric Acid. By H. Bence Jones M.D F.R.S. .................................. 251 On Chemical Geology. By David Forbes F.R.S. &c. .................. 213 On the Manufacture of Glass. By Henry Chance M.A.. ............... 242 On the Tetraphosphoric Amides. By J. H. Gladstone Ph.D. F.R.S. .... 261 On the occurrence of Organic Appearances in Colloid Silica obtained by Dialysis. By W. Chandler Roberts Associate of the Royal School of Mines.......................................................... 274 Chemical Researches on New and Rare Cornish Minerals By A. H. Church M.A. Professor of Chemistry in the Royal Agricultural College Ciren- cester .......................................................... 276 On the Regenerative Gas Furnace as applied to the Manufacture of Cast Steel. By C. W. Siemens F.R.S. Mem. Inst. C.E. ................ 279 Some Experiments on the application of the Measurement of Gases to Quan- titative Analysis. By W. J. Russell Ph.D. ........................ 310 Rough Notes on the Formation of Nitre as observed in the North Western Provinces of India. By W. J. Palmer M.D. F.R.C.S. Surgeon Bengal Army and Additional Chemical Examiner to the Government of India..318 Researches on Vanadium. By Henry E. R os coe B.A. F.R.S. .......... 322 On the Solubility and Crystallisation of Plumbic Chloride in Water and in Water containing various percentages of Hydrochloric Acid specific gravity 1.162. By J. Carter Bell F.C.S. Associate of the Royal School of Mines ........................ ......................... 350 On the Reducing Action of Peroxide of Hydrogen apd Carbolic Acid. John Parnell.. ........................................... ..B! 356 Researches into the Chemical Constitution of Narcotine and of its Producta of Decomposition.-Part 11. By A. Matthiessen F.R.S.. Ltwhmr an Chemistry in St. Mary’s Hospital Medical School and G. 0. Poeter B.A. Professor of Physics in University College London............-. 367 The Calculus of Chemical Operations ; being a Method for the Investigtiom by means of Symbols of the Laws of the Distribution of Weight in Chemical Change.-Part I. On the Construction of Chemical Symbole. By. Sir B. C. Brodie Bart. F.R.S. fessor of Chemistry in tlm Universityof Oxford ........................................... 86V On Paraffin and the products of its Oxidation. By C. H. Uill and Ed. Meusel.. ...................................................... 4.4% On the Hydride of Butyro-salicyl and Butyric Coumaric Acid. By W. H. Perkin F.R.S. ................................................. S’lz On the Vapou-Tension of Formate of Ethyl and of Acetate of Methyl. W. Dittmar ..................................................By 477 On a New Form of Constant Battery. By Warren de la Rue and Hugo Muller.. ....................................................... 488 Researches on Di-methyl. By Wm. IF. Darling.. ...................... 496 On the Application of Chlorine Gas to the Toughening and Refining of Gold. By Francis Bowyer Miller F.C.S. Assayer in the Sydney Branch of the Royal Mint.. ................................................ 506 Nobe on the Specific Gmvity and Boiling Point of Chromyl Dichloride. I‘.E. Thorpe ................................................B! 514 Analysis of the Ashes of a diseased Orange Tree (Citrus Aurantium). T. E. Thorpe .............................................. ..By 515 Index.. ............................................................ 525

ISSN:0368-1769    

DOI:10.1039/JS86821FP001

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

THORPE’S ANALYSIS OF THE WATER OF THE HOLY WELL. 19 TI.-Analysis of the Water of the Holy Well,a Medicinal Spring at Humphrey Head North Lancashire. Bg THOS.ED. THORPE,Dalton Scholar in the Laboratory of Owearj College Manchester. HUMPHREY Head is a fine promontory of limestone situated on the northern shore of Morecambe Bay and the spiing issues through a fissure of the rock within a few feet from its base. The well formerly belonged to the Priors of Cartmel and its waker has long been reputed to possess medicinal virtues. Camden in the “Britt,annia,” states that so far back as in his c2 THORPE'S ANALYSIS OF THE time it was much used as an antarthritic and for cutaneous disorders. The water is perfectly clear and colourless and possesses a distinctly saline taste.It effervesces slightly on agitation indicating the presence of free carbonic acid and it exhibits a feebly alkaline reaction. On free exposure to the air it deposits a crystalline sediment consisting principally of calcium carbonate. Frequent thermometric observations made during the last two years show that its temperature is very uniform ; it rarely varies even one degree from the mean point 11.5 C. (52.7 F.) The quantity discharged through the fissure amounts to about a gallon per minute and this rate of flow is constant during the different seasons of the year. Moreover although the spring rises within ten yards of the sea at high water this amount is uninfluenced by the tide. The specific gravity of tlie water at its ordinary temperature is 1005.83 as the mean of concordant determinations made OIL samples collected on different occasions and during opposite seasons of the year.A careful qualitative analysis indicated the presence of the following bodies in estimable quantity :-BWS. Acids or Elements replacing them. Potash. Chlorine. Soda. Bromine. Lithia. Sulphuric acid. Lime. Phosphoric acid. Magnesia. Carbonic acid. Baryta. Silicic acid. Strontia. Ferrous oxide. Manganous oxide. Ammonia. In addition to the above were found traces of alumina iodine fluorine volatile and non-volatile organic matter. A special examination by means of the spectroscope was made for the recently-discovered alkaline metals in the residue obtained by the evaporation of 21 litres of the water but the search was unsuccessful.The method of quantitative analysis employed differed in no important particular from that usually adopted. It was essen- tially that detailed by Fr esenius under the head of ''Analysis WATER OF THE HOLY WELL AT HUMPHREY HEAD. of Mineral Waters,” in the last edition of his Manual. To in-sure accuracy at least two in some cases three determinations of each principal constituent were made and the amount of water taken for the several estimations was whenever prac- ticable ascertained by weight. The following synopsis shows the direct results of the de- terminations the numbers expi-ess the means of the experi- ments and give the amounts in grammes of the substances contained in 1000 grarnmes of water.1. Chlorine.. ............................... 3*31800 2. Bromine. ................................ 0*00034 3. Sulphuric acid ............................ 1.22749 4. Carbonic acid (total) ...................... 0.17259 5. Silicic acid.. .............................. 0.01753 6. Ferrous oxide ............................ 0.00193 7. Manganous oxide.. ........................ 0*00015 8. Lime and strontia together expressed as car- bonates.. ............................. 1’-057 7 7 9. Magnesia (total) .......................... 0-24602 10. Lime and strontia retained in solution’ after boiling the water expressed as carbonates.. 0.92668 11.Lime precipitated on boiling :- Total lime and strontia expressed as car-bonates.. .......................... 1.05777 Lime and strontia retained in solution after boiling expressed as carbonates*. ..... 0.92668 The remainder. ............. 0.13109 Gives in form of carbonate the amount of lime precipitated on boiling. This corresponds to lime .... 0.07341 12. Lime retained in solution after boiling :-Sum of the lime and strontia retained in solution expressed as carbonates. ..... 0.92668 Deduct the strontia (13) calculated as car- bonate ............................ 0.00333 This remainder ............ 0.92335 Corresponds to lime ........ 0.51708 * All the Btrontia was assumed to remain in solution on boiling the water. THORPE'S ANALYSIS OF THE 13.Baryta and strontia :- (a) Baryta ...".. ................ .. .. 0.00031 (b) Strontia .....,.... . . . . . ... . .. 0.00234 14. Phosphoric acid . . . .. . . ...... . ... . . .. . .,. . 0.00017 15. Lithia.. ................................ 0*00066 b. Corresponding to lithium chloride . 0-00187 16. Sodium chloride and potassium chloride and lithium chloride .. .... . . . . . ... . . .... . . 5.11537 17. Potash .. . . . ...,..."... ..... .... . . ... .... 0.06387 Corresponding to potassium chloride 0*10116 18. Soda:-Sum of the alkaline chlorides .. .. .. ... . 5.11537 Deduct potassium chloride . . 0*10116 , lithium chloride.. . . .. 0*00187 0*10303 ICI-Remainder sodium chloride ..5.00234 Corresponding to soda ...... 2.65224 19. Ammonia ... . ..,.... . . . ,... . . . . . ... . . .... 0.00016 20. Total of fixed constituents. .. . .,.... . ... . . .. 7019260 In order to facilitate reference and comparison with other mineral waters the acids and bases art! here associated after the method adopted by Fresenius founded on the assumption that the strongest acid is combined with the strongest base &c. due consideration being of coume given to the fact that the greater or less degree of the solubility of the salts considerably modifies the manifestations of the affinities. Comparison of the total amount of fixed constituents found directly with the sum of the several constituents associated in the above manner.(The manganese and iron are calculated to the degree of oxidation in which they occur in the residue dried at 180" C.) WATER OF THE HOLY WELL AT HUMPHREY HEAD. 23 Barium sulphate .............. Strontium sulphate ............ Calcium sulphate .............. Potassium sulphate ............ Sodium sulphate .............. Magnesium bromide .......... Lithium chloride .............. Sodium chloride .............. Ammonium chloride .......... Magnesium chloride .......... Calcium phosphate ............ Calcium carbonate ............ Ferric oxide .................. Mangano-manganic oxide ...... Silicic acid .................. The residue dried at 180" .. 0*00047 0*00414 1.25677 0°13031 0.34651 0.00042 0.00201 4.71189 0*00033 0.61767 0*00038 0-13071 0.002 14 0~00016 091753 -.-7.22144 7.19260 Amount of the several constituentB in one litre and in one gallon of the water :-Barium sulphate ........Strontium sulphate ...... Calcium sulphate ........ Potaasium sulphate ...... Sodium sulphate ........ Magnesium bromide. .... Magnesium iodide ...... Lithium chloride ........ Sodium chloride ........ Ammonium chloride ...... Magnesium chloride ...... Calcium phosphate ...... Calcium fluoride ........ Calcium carbonate ...... Ferroua carbonate ...... Manganous carbonate .... Silicic acid .............. Organic matter .......... Grm.per litre. 0-00047 0-00416 1.26414 0*13107 0.34353 0*00042 traces.0*00202 4.739 32 0.00033 0.62126 0*00038 traces. 0.13147 000313 0-00024 001673 traces. 7.26367 Grainsper gallon . 0-0329 0.2912 88.4898 9.1749 24.3971 0.0294 traces. 0.1414 331.7524 0.0231 43.4382 0.0266 traces. 9.8029 0-2191 0.0168 1.2341 traces. 508-5199 24 THORPE'S ANALYSIS OF' THE WATER 01. THE HOLY WELL. Cb. c. Cb. in. Gas dissolved in the water and expelled by ebullition in vacuo measured at 11**3C. and 760 rnm. barometer. . . .... . The above composition is perfectly uniform at the different seasons of the year as will be seen from a comparison of the numbers obtained &om the following determinations of the total amount of solid residue sulphuric acid and chlorine con- tained in water collected on (A) August 30th 1865 and on (B) January 1st 1867.1. Estimation of the total amount of fixed constituents. The weighed quantity of water was evaporated with a known weight of pure sodium carbonate in a platinum dish and the residue dried at 180"C. until its weight appeared constant :-Water employed. Residue obtained. Amount in 1000 grm. A. 50.1645 0.3607 7.1947 €3. 66*0903 0.4755 7.1905 2. Determination of sulphwic acid. Barium chloride producing an immediat,e precipitation in the water acidified with hydrochloric wid the estimation of the sulphuric acid was effected without previous evaporation :-Water employed. BaSOI obtained S04H2in 1000 grma.A. 135.390 0.3953 1.2281 B. 96.816 0-2824 1.2269 3. Determination of chlorine (together with traces of bromine and iodine). By Mohr's volumekric method ie. with standard ailver solution and potassium ohromate :-Water employed. Silver required. Chlorine Btc. in 1000 gms. A. 39.2872 0-3969 3-3183 B. 22.7887 0.23025 3.3181 The constant compo&ion and temperature together with the uniform rate of flow of this spring seem to indicate that it originates in a reservoir of considerable extent situated pro- bably in some extensive cavern or fissure at the junction of the slate and limestone formations. Its uniformity of composition &c. cannot be attributed to the influence uf the neighbouring ACTIO?; OF PERMANOANATE OE' POTASH ETC.tide. That such is not the case is well seen fi-om a comparison of the ratios of the amounts of sulphuric acid and cldoiine con- tained in sea-water with the amounts of these bodies deter- mined as above in the water of the Holy Well. In the former case the ratios are as 1to 8 in the latter as 1to 3. Lastly the absence of nitiic acid and the minute quantity of ammonia and organic matter preseiit in the water indicate the comparative freedom from putrescible organic remains of the strata through which the spring rises. My best thanks are due to Dr. Roscoe for the use of his laboratory in the above analysis.

ISSN:0368-1769    

DOI:10.1039/JS8682100019

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

ACTIO?; OF PERMANOANATE OE' POTASH ETC. 111.-On the Action qf Permanganate of Potash on Urea A nzmonia and Acetamide in strongly Alkaline Solutions. By J. ALFREDWANRLPNand ARTHURGAMGEE. IT haas been pointed out by Chapman and Smith," that perrnanganate of potash in presmce of excess of alkali is an oxidizing agent of a most singular kind. It attacks alcohol much in the same way that nitric acid does producing the diatomic acids glycollic and oxalic but not aldehyde nor acetic acid. It is at the same time strangely inactive towards certain substances. Boiled with oxalic acid it does not suffer any decom- position ;and as is seen in the working of thet new method for the determination of albuminoid matter in waters it may be boiled with ammonia without the occurrence of any chemical change.The following experiments on the action of this re-agent on urea ammonia and acetamide :-Urea = CONH,NH Ammonia = NH Acetamide = COCH NH will serve as a contribution to its chemical history. Urea. The urea taken for this research was prepared by the well kriown process from ferrocyanide of potassium. One of the I * Journ. of the Chemical Society [2l T p. 302,June 1867. t Ibid. v p. 449 Sept. 1867. WANKLYN AND GAMGEE ON THE samples was proved to be pure by getting it to combine with the theoretical quantity of nitrate of mercury. Another sample was analysed by Dr. Affleck who got from it the theoretical percentage of nitrogen by Dumas' method. I. 0-100grm. of urea 1-000 , permanganate of potash 10.0 , solid caustic potash 10-0 , water was sealed up in a tube and heated to 130OC.for twelve hours. After the experiment the contents of the tube were fiee from unacted upon manganate or permanganate of potash -showing that much oxidation had taken place. On opening the tube under water there was an escape of 15-7 cub. cent. of gas. In order to ascertain whether this evolution of gas was due to the permanganate givingup oxygen or whether it was an evolution of nitrogen from the urea a gas-analysis was made. (Frankland's apparahs was employed for this and the other gas-analyses given in this paper). Volume taken.. ............ 86 After adding hydrogen.. .... 139 After explosion ............ 99 The gas therefore consisted of Oxygen........ 15-50 Nitrogen ...... 84-50 100*00 Obviously therefore inasmuch as there was less oxygen than atmospheric air contains the evolution of gas in our experiment was not evolution of oxygen but of nitrogen. The space in the digestion tube unoccupied by liquid was measured and equalled 38.1 C.C. We are thus provided with data for determining whether the permanganate had evolved oxygen and also how much nitrogen came from the urea. cub. c. Volume of gas left in tube .............. 38.1 Volume of gas escaped from tube ........ 15*7 Total volume of gas after experiment .... 53.8 ACTION OF PERMANGANATE OF POTASH ETC. consisting of 8.34 C.C. of oxygen and 45-46 C.C. of nitrogen. Now the 38.1 C.C. of air originally present in the tube when it was sealed up contained 8.00 C.C.of oxygen and 30.1 C.C.of nitrogen. We have therefore- Oxygen present originally .............. 8.00 Oxygen found after experiment .......... 8.34 No oxygen or only a trace of oxygen was set free from the permanganate. Also the urea had evolved about 15 C.C. of nitrogen gae. This amount of nitrogen is not half that which the urea con- tained (0.100 grm. urea contains 37.2 C.C. of nitrogen gas at OOC. and 760 mm. pressure). A little of the nitrogen is ac- counted for as ammonia for -0032 grm. of nitrogen was found in the tube after the experiment in the form of ammonia which was distilled of and estimated by titration. There thus remains about half of the total nitrogen to be accounted for and which must hare been converted into nitric acid.The circumstance that the 1grm. of permanganate of potash had been completely reduced to the state of bi- or sesqui-oxide of manganese and that there was no evolution of oxygen gas is in itself sufficient proof that a considerable quantity of the nitrogen of the urea had been oxidized to nitric acid. In this experiment therefore a little less than half of the nitrogen of' the urea appeared as nitrogen gas about half was oxidized to nitric acid and a small portion was found as ammonia. 11. In a second experiment the proportion of permanganate was increased the object proposed being to ascertain whether greater oxidizing effect would be the result of increasing the quantity of oxidizing agent.0950 grm. urea 1-00 , permanganate of potash 10.00 , potash 10-, water were sealed up and heated to 200OC. for four hours. After this treatment there remained much manganate still unreduced. On opening the tube there was a considerable escape of gas which WANKLYN AND GAMQEE ON THE wm lost. Not so much as *OOO1 ,grm. of ammonia wae to be found in the tube. The expeiiment was repeated in order to have an opportunity of examining the gas. 0*100gm. urea 2.00 , permanganate of potash 10.00 , caustic potash 12. , water sealed up and heated to 160° C. for one hour. Abundance of manganate of potash remained after the experiment. On open-ing under water there was an escape of gas.The total volume of gas was carefully measured and found to be 47 C.C. at 11"C. and 744 mm. pressure equal to 44.20 C.C. at 0" C. and 760 mm. On analysis :-Volume taken. ............ 160 After adding hydrogen.. .... 231.5 After exploaion ............ 20'7.5 From which is deduced- Oxygen. ........ 5-00 Nitrogen ........ 95-00 100*00 Allowing for the nitrogen originally present in the tube when it was sealed up which may be done by taking the 5 per cent. of oxygen to be the measure of atmospheric air we shall arrive at the result that 33.68 C.C. at OOC. and 760 mm. is the quantity of nitrogen furnished by the urea. Thus we have :-0.100 grm. urea give 33.68 C.C. of nitrogen. Theory requires that 0.100 grm. urea contains 37.2 C.C.of nitrogen. We arrive at the startling result that by increasing the pro-portion of permauganate we put a stop to the oxidation. This fact so singular at first sight would appear to indicate that the oxidation of urea by permanganate is quick but super- ficial whilst the oxidation at the expense of manganate is slower but deeper. Obviously (as will be apparent on referring to the actual quantit'ies of permanganate and urea employed) ACTION OF PERMANBANATE OF POTASH ETC. there would still remain unattacked urea in the first experiment after the permanganate had exhausted itself and passed intornan- ganate. In the second experiment on the contrary there was enough permanganate to transform all the urea into carbonic acid w+ter and nitrogen without suffering deoxidation lower than to the stage of manganate and nitrogen once in the free state is beyond the reach of oxidizing agents.For some interesting considerations concerning the difference of action between permanganates and manganates we would refer to Chapman and Smith‘s paper which we cited ah the begin- ning of this notice. Thus far we have been dealing with very concentrated solu- tions at temperatures considerably above the boiling-point of water. Taking weaker solutions and operating at about 100°C. we meet with a similar decomposition only slower. The following experiment illustrates this we dissolved 4.75 milligrammes of urea in about 400 C.C. of pure water added a little carbonate of soda about 5 grm. of caustic potash and about 0.5 grm.of permangnnate of pot:tsh and distilled for a very long time. A slow evolution of ammonia took place. Ultimately this evolution became very slow arid then stopped. The quantity of ammonia obtained was estimated by the Nessler test and amounted to 0.575 milligramme. Theory requires 2.692 milligrammes. About 22 per cent. of the nitrogen in the urea was obtained in the form of ammonia the rest of course being either evolved as nitrogen gas or converted into nitrate. An experiment on a still smaller quantity of urea gave a very similar result. Here the remark may be made that this result is hardly compatible with Mr. Dugald Camp- bell’s statement published in the ‘‘Laboratory,” which is in effect that a weak solution of urea gives up all its nitrogen in the form of ammonia when it is partially decomposed with carbonate of soda and then attacked with potash and perman- ganate of potash.If Mr. Campbell did not get off the full quantity of nitrogen in the form of ammonia by the treatment with carbonate of soda he would not get the full quantity on employ in g permanganat e. Urea being resolved into carbonic acid and ammonia by the simple assimilation of water ACTION OF PERMANGANATE OF POTASH ETC. CONH,NH + H,O = CO + 2NH it might be supposed that an oxidizing agent applied to urea in presence of water would in effect operate on the ammonia; and on this ground it was necessary to study the oxidation of ammonia. Experiment I.-0-050 grm. of NH,CI 2.00 grm.of permanganate of potash 10.00 grm. of caustic potash 10-grm. of water was heated to 15OOC. for an hour and a half. Opened the tube ; only minute traces of gas escaped. The gaseous con- tents of the tube were analysed :-Oxygen = 23.00 Nitrogen = 77-00 100-00 showing that the minute evolution of gas was evolution of oxygen and not of nitrogen. The residue in the tube con- tained only 00033 grm. of nitrogen in the form of ammonia; therefore there had been oxidation of most of the ammonia to the state of nitric acid. In a second experiment sulphate of ammonia was substituted for the chloride of ammonium the other things being the same and the proportion the same. The temperature was a little higher than in the first experiment.Result no ammonia and no gas. A cetamide. I. 0-050 grm. acetamide 1-00 grm. permanganate of potash 10. grm. caustic potash 10. grm. water sealed up and heated to 160' C. for one hour. After the experiment there remained abundance of man-ganate but some peroxide of manganese had been deposited. No gas was given 06and only 0*0005 grm. of ammonia was found in the tube. The appearance of peroxide of manganese WANKLYN AND SCHENK’S SYNTHESIS OF CAPROIC ACID. 31 proves that reaction had taken place Nitrates or nitrites must therefore have been formed. The results arrived at in this paper are the following :-Urea and great excess of permanganate in presence of much caustic potash gives all the nitrogen in the form of nitrogen gas.Urea with less permanganate gives part of the nitrogen as gas and part as nitric acid. Ammonia whether as chloride or sdphate is totally oxidized to nitrates when heated with great excess of permanganate and alkali. Acetamide behaves like ammonia. These reactions occur at temperatures above the boiling-point of water. The foregoing result has an important bearing on the rational formula for urea and goes a long way to show that it is not the amide of carbonic acid. Ammonia and the amides yield nitrates on oxidation with alkaline permanganate. Urea if it were really carbamide should do the same but it gives nitrogen gas instead. Moreover urea as is well known is not resolved into ammonia and carbonic acid with anything like suflicient ease to admit of its being carbamide. We are f NH therefore led to write C NH for urea. It is marsh-gas OH L wherein imidogen amidogen and peroxide of hydrogen replace hydrogen. This formula is not new. Very simple and natural changes in this formula express the passage from urea to cyanate of ammonia and to carbarnide. The following formulae express the relation between guani- dine and urea :-Ouanidine Urea.

ISSN:0368-1769    

DOI:10.1039/JS8682100025

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

WANKLl?N AND SCHENE’S SYNTHESIS OF CAPROIC ACID. 31 IV.-Synthesis of Caproic Acid. By J. ALFREDWANKLYN and ROBXRTSCHENK. CARBONIC acid attacks sodium-ethyl and sodium-methyl forming propionate and acetate of soda respectively. It seemed to 32 WANKLYN AND SCHENK'S SYNTHESIS OF CAPROIC ACID. us to be desirable to obtain a parallel reaction higher up in the series. We have selected the amylic group for this purpose. Mercury-amyl was prepared by the process of Frankland and Dupp a from iodide of aniyl and dilute sodium-amalgam a little awtic ether being added in order to effect the reaction. An analysis of the mercury-amyl gave the following result proving the purity of the substance :-0.3584 pn. taken gave 0.2082 grm. of metallic mercury.Found.. .... Hg per cent. = 58-09 Theory .... Hg per cent. = 58-50 From tliis mercury-amyl we prepared zinc-amyl by digesting it with zinc as recommended by Frankland and Duppa. The zinc-amyl was then sealed up with metallic sodium and heated in the water-bath. Under these circumstances there was formation of sodium-amyl and precipitation of zinc. On leading in carbonic acid gas there was evolution of heat just as in the case of the ethyl or methyl compounds. When the reaction was over water was aclcled and the resulting dution of soda-salt evaporated to dryness in the water-bath. The residue distilled with dilute sulphuric acid gave off an oily liquid having the smell of caproic acid. This oily distillate was dissolved in baryta-water and formed a baryta-salt. About 3 grm. of baryta-salt was made. A barium determination was made 011 the dry salt. 0.2656 grm. gave 0.1697 grm. of sulphate of baryta. Ba per cent. = 37.56. Theory reqnires Ba per cent. = 37-33. A silver-salt was also inade and analysed. 0.0614 grm. gave 0.0298 grm. of silver. Found.. .... Ag per cent. = 48.53 Theory .... Bg per cent. = 48.43 The action of carbonic acid on sodium-amyl is expressed by the following equation :-London Institution 1867.

ISSN:0368-1769    

DOI:10.1039/JS8682100031

出版商:RSC    

年代:1868

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V.-On the Origi78 of iiusculur Power. By E. FRANKLAND, F.R.S. [From the Philosophical Magazine for September 1866.J UNDERthis title there appeared in a recent number of the Philosophical Magazine an able article by Professom Fic k and Wislic enus," in which these gentlemen describe the results of experiments made upon themselves before during and after an ascent of the Faulhorn in Switzerland. In these experiments the amount of measured work performed in the ascent of the mountain was shown to exceed by more than three-fourths the amount which it would be theoretically pos-sible to realize from the maximum amount of muscle-oxidation indicated by the total quantity of nitrogen in the urine. The data afforded by these experiments appear to me to render utterly untenable the theory that muscular power is derived from muscle-oxidation.Nevertheless in the appli- cation of these data to the problem under consideration one important link was found to be wanting viz. the amount of actual energy generated by the oxidation of a given weight of muscle in the human body. Fick and Wislicenus refer to this missing link in the following words :-'' The question now arises what quantity of heat is generated when muscle is burnt to the products in which its constituent elements leave the human body through the lungs and kidneys? At present unfortunately there are not the experimental data required to give an accurate answer to this important question; for neither the heat of combustion of muscle nor of the nitrogenous residue of muscle (urea) is known." Owing to the want of these data the numerical resulta of the experiment of Fick and Wislicenus arerendered less toll-clusive against the hypothesis of muscle-oxidation than they otherwise would have been ; whilst similar determinations which have been made by Edward Smith Haughton Play- fair and others are even liable to a total misinterpretatioil from the same cause.I have endeavoured to supply this want by the calorimetrical determiriation of the actual energy evolved by the combustion * Phil Mag. vol. xxxi p. 485. VOL. XXI. D FRANKLAND ON THE of muscle and of urea in oxygen; but inasmuch as uric and hippuric acids frequently appear in the urine as products of a less perfect muscle-oxidation I have also determined the calorific value of these substances and have added purified albumin and beef fat to the list.Creatine would also have been included; but although I was furnished with an ample supply of this substance through the kindness of Mr. Dittmar all attempts to burn it in the calorimeter were fruitless. In nume-rous trials under varied conditions it always exploded violently on ignition. The determination of the actual energy developed by the combustion of the above-named substances is surrounded by formidable difficulties which have probably prevented its pre-vious execution. It is impossible to effect the complete com- bustion of these bodies in oxygen gas under conditions which permit of the accurate measurement of the heat evolved; but preliminary experiments showed that complete oxidation could be secured by deflagration with potassic chlorate ; and although this method is doubtless inferior in accuracy to the calori- metrical methods usually employed it is hoped that with the corrections described below the results obtained merit sufficient confidence to render them useful in subsequent discussions of' this and allied subjects.The determinations were made in a calorimeter devised some years ago by Lewis Thompson and which I have repeatedly used with satisfaction in other estimations of a like kind. This instrument consists of a copper tube which is made to contain a mixture of potassic chlorate with the combustible substance and can be enclosed in a kind of dhing-bell also of copper and so lowered to the bottom of a suitable vessel containing a known quantity (two litres) of' water.The experiments were conducted in the following manner :-19-5 grams* of potassic chlorate to which about one-eighth of manganic oxide was added were intimately mixed with a known weight (generally about two grms.) of the substance whose thermal value was to be determined; and the mixture being then placed in the copper tube above mentioned a small piece of cotton thread previously steeped in a solution of potassic chlorate and dried was inserted in the mixture. The temperature of the water in the calorimeter was now carefully * I follow the example of the Registrar-General in abbreviating the French word grarnme to gram.ORIQIN OF MUSCULAR POWER. ascertained by a delicate thermometer and the end of the cotton thread being ignited the tube with its contents was placed in the copper bell and lowered to the bottom of the water. As Boon as the combustion reached the mixture a stream of gases issued fiom numerous small openings at the lower edge of the bell ajnd rose to the surface of'the water-a height of about 10 inches. At the termination of the deflagra- tion the water was allowed fkee access to the interior of the bell by opening a stopcock connected with the bell by a small tube rising above the surface of the water in the calorimeter. The gases in the interior of the bell were thus displaced by the incumbent column of water ; and by moving the bell up and down repeatedly a perfect equilibrium of temperature through- out the entire mass of water was quickly established.The temperature of the water was again carefully observed; and the difference between this and the previous observation gives the calorific power or the potential energy of the substance consumed expressed as heat. The value thus obtained however is obviously subject to the following corrections :-1. The amount of heat absorbed by the calorimeter and appa- ratus employed to he added. 2. The amount of heat carried away by the escaping gases after issuing from the water to be added. 3. The amount of heat due to the decomposition of the potas- sic chlorate employed to be deducted. 4. The amount of heat equivalent to the workperfomed by the gases generated in overcoming the pressure of the atmo- sphere to be added.Although the errors due to these causes to gome extent neu-tralize each other there is still an outstanding balance of suffi-cient importance to require that the necessary corrections should be carefully attended to. The amount of error fiom the first cause was once for all experimentally determined and was added to the increase of temperature observed in each experiment. The amount of heat carried away by the escaping gases after issuing from the water may be divided into two items viz. :-a. The amount of heat rendered latent by the water which is carried off by the gases in the form of vspour. P. The amount of heat carried off by these gases by reason of FRAXKLAND ON THE their temperature being above that of the water from which they issue.It was ascertained that a stream of dry air passed through the water of the calorimeter at about the same rate and for the same period of time as the gaseous products of combustion depressed the temperature of the water by only 0°*02C. By placing a delicate thermometer in the escaping gases and another in the water no appreciable difference of temperature could be observed. Both these corrections may therefore be safely neglected. The two remaining corrections can be best considered together since a single careful determination eliminates both. When a combustible substance is burnt in gaseous oxygen the con-ditions are essentially different from those which obtain when the same substance is consumed at the expense of the com- bined or solid oxygen of potassic chlorate.In the first cage the products of combustion when cooled to the temperature of the water in the calorimeter occupy less space than the sub- stances concerned in the combustion and therefore no part of the energy developed is expended in external work-that is in overcoming the pressure of the atmosphere. In the second case both the combustible and the supporter of combustion are in the solid condition whilst a considerable proportion of the pro- ducts of combustion are gases. The generation of the latter cannot take place without the performance of external work ;for every cubic inch produced must obviously in overcoming atmo- spheric pressure perform an amount of work equivalent in round numbers to the lifting of a weight of 151bs.to the height of 1 inch. In performing this work the gases are cooled and conaequently less heat is communicated to the water of the calorimeter. Neverthelesa the loss of heat due to this cause is but small. Under the actual conditions of the experiments detailed below its amount would only have increased the tem- perature of the water in the calorimeter by 0'97 C. Even this slight error is entirely eliminated by the final correction which we have now to consider. It is well known that the decompositiou of potassic chlorate into potassic chloride and fi-ee oxygen is attended with the evo- lution of heat; if a few grains of manganic oxide or better of feiric oxide be dropped into an ounce or two of fused potasgic chlorate which is slowly disengaging oxygen the evolution of ORIGIN OF MUSCULAR POWER.37 gas immediately proceeds with great violence and the mixture becomes visibly red-bot although the external application of heat be discontinued from the moment when the metallic oxide is added. The latter remains unaltered at the close of the operation. It is thus obvious that potassic chlorate on being decomposed furnishes considerably more heat than that which i8 necessary to gasify the oxygen which it evolves. It was therefore necessary to determine the amount of heat thus evolved by the quantity of potassic chlorate (9.75 grms.) mixed with one gram of the substarice burnt in each of the following deteI- minationbr.This was effected by the use of two copper tubes the one placedwithin the other. The interior tube was charged with a known weight of' the same mixture of potassic chlorate and manganic oxide as that used for the subsequent experi- ments whilst the annular space between the two tubes was filled with a combustible mixture of chlorate and spermaceti the calorific value of which had been previously ascertained. The latter mixture was ignited in the calorimeter as before ;and thb heat generated during its combustion effected the completc decomposition of the chlorate in the interior cylinder as was proved by a subsequent examination of the liquid in the ca,lori- meter which contained no traces of undecomposed chlorate.The following are the results of five experiments thus made expressed in units of heat the unit being equal to 1 gram of water raised through 1"C. of temperature First experiment .......... 340 Second experiment. ......... 300 Third experiment .......... 375 Fourth experiment. ......... 438 Fifth experiment .......... 438 -1891 Mean ................ 378 This result was confirmed by the following experiments :-(1) Starch was burnt first in a current of oxygen gas and secondly by admixture with potassic chlorate and manganic oxide. Heat-units furnished by 1 gym. of starch burnt with) 4290 9-75 grms. of potassic chlorate ................ Heat-units finmished by the same weight of starch } 3964 burnt in a stream of oxygen gas ............._c_ Difference .......................... 326 FRANKLAND ON THE (2) Phenplic alcohol was burnt with potassic chlorate and the reault compared with the calorific value of this substance as determined by Favre and Silbermann. Heat-units furnished hy 1 grru. of phenylic alcohol) 8183 burnt with 9975 grms. potassic chlorate.. ........ Heat-units furnished by- 1 grm. of phenylic alcohol when burnt with gaseous oxygen (Favre and Sil- 17842 be r m a nn) .................................. -Difference .......................... 341 These three determinations of the heat evolved by the de- composition of 9-75 grms. of potassic chlorate furnishing the numbers 378 326 and 341 agree as closely as could be ex- pected when it is considered that all experimental errors are necessarily thrown upon the calorific value of the potassic chlorate.The mean of the above five experimental numbers was in all cases deducted fi-om the actual numbers read off in the follow- ing determinations. It was ascertained by numerous trials that all the potassic chlorate was decomposed in the deflagrations and that but mere traces of carbonic oxide were produced. J o ul e's mechanical equivalent of heat was employed viz. 1 kilog. of water raised 1"C. = 423 metrekilogs. The followhg results were obtained :-Actual Energy developed by 1 grm. of each substance when burnt in Oxygen. Heat-units. Metre-1 Name of substance (dried at 100"(2.).1st 2nd 3rd Exp. Exp. Exp. Beef muscle purifiedby repeated washingwith ether ........ 5174 6062 6195 5088 5103 2161 Purified albumin .... 6009 4987 .. .. 4998 2117 Beef fat ............ 9069 .. *. 9069 3841 Hippuric acid.. ...... Uric acid.. .......... 5330 2645 5k& 2585 .. *. 5383 2615 2280 1108 Urea .............. 2131 2302 2207 2i97 2206 934 It is evident that the above determination of the actual ORIGIN OF MUSCULAR POWER. energy developed by the combmtion of muscle in oxygen re- presents more than the amount of actual energy produced by its oxidation within the body because when muscle burns in oxygen its carbon is converted into carbonic anh-ydride and its hydrogen into water? the nitrogen being to a great extent evolved in the elementary state ; whereas when muscle is most completely consumed in the body the products are carbonic anhydride water and urea the whole of the nitrogen passeg out of the body as urea a substance which still retains a con- siderable amount of potential energy.Dry muscle and pure albumin yield under these circumstances almost exactly one- third of their weight of urea ; and this fact together with the above determination of the actual energy developed in the combustion of urea enables us to deduce with certainty the amount of actual energy developed by muscle and albumin respectively when consumed in the human body. It is as follows :-Actual Energy developed by 1 grm. of each substance when con-sumed in t7te body.Name of substance (dried at Heat-units 1 Metreki'oge' of force 1 100"0.). (Mean)* (Mean). Beef muscle purified by ether . . 1848 Purified albumin . . . . . . . . . ,. 1 "4: 1 1803 Interpolating the data thus obtained into the results of Fick and Wislicenus's experiments let us now compare the amount of measured and calculated work performed by each of the ex-perimenters during the ascent of the Faulhorn with the actual energy capable of being developed by the maximum amount of muscle that could have been consumed in their bodies this amount being represented by the total quantity of nitrogen excreted in each case during the ascent and for six hours after- wards. FRANKLAND ON TTJE Pep------Actual energy capable of being pro- ] I duced by the consumption of 68,690 68,376 37.17 and 37-00 grms.of dry metrekilogs. metrekilogs. muscle in the body . . . . . . . . . Measured work performed in the 129,096 148,656 ascent (external work) . . . . . . . . } metrekilogs. metrekilogs. Calculated circulatory and respira- 35,631 tory work performed duringthe ascent (internal work) . . . . . . . . metr&ilogs. metrekilogs. 159,637 184,287 Total ascertainable work performed. . metrekilogs. metrekilogs. I { 1 The actual energy capable of being produced by the com-sumption of 37.17 and 37.00 grms. of dry muscle in the body was estimated by Fick and Wislicenus at 106,250 and 105,825 metrekilogs. The experimental determination of the actual energy deve- loped by the muscle-oxidation renders it now abundantly evident that the muscular power expended by these gentlemen in the ascent of the Faulhorn could not be exclusively derived from the oxidation either of their muscles or of other nitro- genous constituents of their bodies since the maximum of power capable of being derived from this source even under very fdvourable assumptions is in both cases less than one-half of the work actually performed; but the deficiency becomes much greater if as Fick and Wislicenus have done we take into coiisideration the fact that the actual energy developed by oxidation or combustion cannot be wholly transformed inbo mechanical work.In the best-constructed steam engine for instance only one-tenth of the actual energy developed by the biirning fuel can be obtnined in the form of mechanical power; and in the case of man Helmholtz estimates that not more than one-fifth of the actual energy developed in the body can be made to appear as external work.The experiments of Heidenhain however show that under favourable circum- stances a muscle may be made to yield in the shape of mechanical work as much as one-half of the a~timlenergy developed within it the remainder assuming the form of heat. ORIGIN OF MUSCULAR POWER. Taking then this highest estimate of the proportion of mechanical work capable of being got out of actual energy it becomes necessary to multiply by 2 the above numbers repre- senting the ascertainable work performed in order to express the actual energy involved in the production of that work.We then get the following comparison of the actual energy capable of being developed by the amount of muscle consumed with the actual energy necessary for the performance of the work executed in the ascent of the Faulhorn. Fick. Wislicenus. me trekilogs. metrekilogs. Actual energy capable of being pro. 68,376 68j690 duced by muscle-metnmorphosis } Actual euergy expended in work} 319,274 performed . . . . . . . . . . . . . . . . . 368,574 Thus taking the average of the two experiments it is evident that scarcely one-fifth of the actual energy required for the work performed could be obtaJned from the amount of muscle consumed. Interpreted in the same way previous experiments of a like kind prove the same thing though not quite so conclusively.To illustrate this I will here give a summary of three sets of ex-periments,-the first made by Dr. E. Smith upon prisoners en- gaged in treadmill labour ; t8he second by the Rev. I>. Haugh-to 11 upon military prisoners engaged in shot drill ; and the third adduced by P1a y fa i r and made upon pedestrians pile-drivers men turning a winch and other labourers. =I;*eadJwheel Bxperiments. A treadwheel is a revolving drum with steps placed at dis- tances of 8 inches and the prisoners are required to turn the wheel downwards by stepping upwards. Four prisoners designated below as A B C and D were employed in these experiments ; and each worked upon the wheel in alternate quarters of an hour resting in a sitting posture during the in- tervening quarters.The period of actual daily labour was 3+ hours. The total ascent per hour 2,160 feet or per day 1.432 mile. The following are the results :- FRANKLAND ON THE Treadwheel Work. (E. Smith.) Weight of oczgd Ascent in work per-metres. formed in 1 zt:&T corresponding in ascent* metrekilogs. 1 to nitrogen. grms. grms. A 47.6 23,045 10 1,096,942 171.3 1101 *2 B 49 23,045 10 1,129,206 174 -6 1121'7 C 65 20,741 9 1,140,755 168 *O 1080 *1 D 56 20,741 0 1,161,496 159 -3 1024 *3 I In these experiments the measured work was performed in the short space of three and a-half hours whilst the nitrogen estimated was that voided in the shape of urea in 24 hours. It will therefore be necessary to add to the measured work that calculated for respiration and circulation for the whole period of' 24 hours.This amount of internal work was computed from the estimates of Helmholtz and Fick as follows :-Internal Work. (Hel rnh o 1t z and Fic k.) I Work Actual energy I performed. required. -I__---j metrekilogs.+ me trekilogs. Circulation of the blood during 24 138,240 hours at 75 pulsations per minute} 69,120 Respiration for 24 hours at 12 pul-10,886 sations per minute ........... 21,772 I Statical activity of muscles Not determfped Not determined. Peristaltic motion ........ I , -7 ? ! 80,006 160,012 Taking this estimate for internal work the average results of the treadwheel experiments may be thua expressed :-Treadwheel 'c.tlbrk.Average external work per nian per } 119,605 metrekilogs. day ............................ Average nitrogen evolved per man} per day ........................ 17.7 grms. *t Since making use of this number I find that Dondera estimates the work of the heart alone for twentyfour hours at 86,000 metrekilograms 8 figure which is higher than thadt used above for the combined work of circulation and reapirstion. ORIGIN OF MUSCULAR POWER. IZreadwheeZ W orL-(Continued. j Weight of dry muscle corresponding } 114grms. to average nitrogen evolved per day Actual energy producible by the con- sumption of 114 grms. dry muscle 210,672 metrekilogs. inthebody .................... Average actual energy developed in the body of each ninn v1z.:-External work.. ...... 119,605 x 2 = 239,210 metrekilogs. Circulation .......... 69,120 x 2 = 138,240 9 Respiration .......... 10,886 x 2 = 21,772 97 399,222 79 In these experiments the conditions were obviously very un- favourable for the comparison of the amount of actual energy producible from muscle-metamorphosis with the quantity of actual energy expended in the performance of estimable work since during that portion of the 24 hours not occupied in the actual experiment a large amount of unestimable internal work such as the statical activity of the muscles peristaltic motion &c. was being performed. Nevertheless these experiments show that the average actual energy developed in producing work in the body of each man was nearly twice as great as that which could possibly be produced by the whole of the nitro- genous matter oxidized in the body during 24 hours.It must also be remarked that the prisoners were fed upon a nitro- genous diet containing six ounces of cooked meat without bone -a diet which as is well known would favour the production of urea. Shot-drill Experiments. The men employed for these experiments were fed exclusively upon a vegetable diet and they consequently secreted a con- siderablx smaller amount of nitrogen than the flesh-eaters engaged in the treadwheel work ; the other conditions were FRANKLAND ON THE however equally unfavourable for showing the excess of work performed ' over the amount derivable from muscle-metamor-phosis.In shot drill each man lifts a 32-lb. Rhot fi-om a tressel to his breast a height of 3 feet ;he then carries it a distance of 9 feet and lays it down on a similar support returning unloaded. Six of these double journeys occupy one minute. The men were daily engaged wit,h Shot drill.. ................ 3 hours. Ordinary drill. ............. 14 7 Oakum-picking ............ 3+ , The ,total average daily external work was estimated by Haughton at 96,316 metrekilogs. per man. The followjng is a condensed summary of the results of these experiments :-Military Vegetarian Prisoners at Shot Drill. (H au gh t on.) Average external work per man per} 96,316 metrekilogs. day ............................ Average nitrogen evolved per man) 12.1 grms.per day ........................ Weight of dry muscle corresponding) 71,9 9, to average nitrogen evolved per day Actual energy producible by the con- sumption of 77.9 grms. of dry muscle 143,950 metrekilogs. in the body .................... Average actual energy developed daily in the body of each man viz. :-External work 96,316 x 2 ........ = 192,632 metrekilogs. Internal work.. .................. = 160,012 91 352,644 7 Owing chiefly to the vegetable diet of these prisoners thiR result is more conclusive than that obtained upon the tread- wheel the amount of work actually performed being conside- rably more than twice as great as that which could possibly be obtained through the muscle-metamorphosis occurring in t,he bodies of the prisoners.ORIGIN OF MUSCULAR POWER. Playfair’s Determinations. In these determinations the number 109,496 metrekilograms was obtained as the average amount of daily work performed by pedestrians pile-drkers porters paviors &c.; but as the amount of muscle consumption is calculated from the nitrogen taken in the food the conditions are as unfavourable as possible with regard to the point I am seeking to establish; for it is here assumed not only that all the nitrogen taken in the food enters the blood but also that it is converted into muscle and is after- wards oxidized to carbonic anhydride wat.er and urea. The following are the results expressed as in the previous cases :-Hurd-worked Lnbourer (Play fair).1 I Work Actual energy performed. required. mtrekilogs. metrekilogs. Daily labour (external work) . . 109,496 21 8,992 80,006 160,012 Internal wark.. .. .. .. .. .. . . . ---189,502 379,004 Actual energy capable of being produeed from 5.5 02. (155.92 grms.) of metrekile. flesh-formers contained in the daily food of the labourer.. . . . . . 288,140 Thus even under the extremely unfavourable conditions of these determinations the actual work performed exceeded that which could possibly be produced through the oxidation of the nitrogenous constituents of the daily food by more than 30 per cent. We have seen therefore in the above four sets of experi-ments interpreted by the data afforded by the combustion of muscle and urea in oxygen that the transformation of tissue alone cannot account for more than a small fraction of the mus- cular power developed by animals ; in fact this transformation goes on at a rate almost entirely independent of the amount of muscular power developed.If the mechanical work of an animal be doubled or trebled there is no corresponding increase of nitrogen in the secretions; whilst it was proved on the other hand by Lawes and Gilbert as early as the year 1854 VOL. XXI. E FRANKLAND ON THE that animals under the same conditions as regarded exercise had the amount of nitrogen in their secretions increased two- fold by merely doubling the amount of nitrogen in their food. Whence then comes the muscular power of animals ? What are the substances which by their oxidation in the body furnish the actual energy whereof a part is converted into muscular work? In the light of the experimental results detailed above can it be doubted that a large proportion of the muscular power developed in the bodies of animals has its origin in the oxidation of non-nitrogenous substances ? For whilst the secretion of nitrogen remains nearly stationary under widely different degrees of muscular exertion the production of carbonic anhydride in- creases most markedly with every augmentation of muscular work as is shown by the following tabulated results of E.Smith's highly important espepiments upon himself re-garding the amount of carbonic anhydride evolved under dif- ferent circumstances." Excretion of carbonic anliydride during rest and mnscalar exertion :-Carbonic anhydride per hour.During sleep ...................... 19.0 grams. Lying down and sleep approaching .. 23.0 , In a sitting posture ................ 29.0 , Walking at the rate of 2 miles perhour 70.5 , Walking at the rate of 8 miles per hour 100.6 , On the treadTvhee1 ascending at the rate of 28.65 feet per minute ...... 189.6 , Jt is admitted on all hands that food and food alone is the ultimate source from which muscular power is derived; but the above determinations and considerations prove conclusively first that the non-nitrogenous constituents of the food such as starch fat &c. are the chief sources of the actual energy which becomes partially transformed into muscular work; and secondly that the food does not require to become organized tissue before its metamorphosis can be rendered available for muscular power its digestion and assimilation into the circulating fluid (the blood) being all that is necessary for this purpose.It is how- ever by no means the non-nitrogenous portions of food alone JI Phil. Trans. for 1859,p. 709. ORIGIN OF MUSCULAR POWER. that are capable of being so employed-the nitrogenous also inasmuch as they are combustible and consequently capable of furnishing actual energy might be expected to be available for the same purpose; and such an expectation is confirmed by the experiments of Savory upon rats,* which show that these animals can live for weeks in good health upon food consisting almost exclusively of muscular fibre.Even supposing these rats to have performed no external work nearly the whole of their internal muscular work must have had its source in the actual energy developed by the oxidation of their strictly nitro- genous food. It can scarcely be doubted however that the chief use of the nitrogenous constituents of food is for the renewal of mus- cular tissue-the latter like every other part of the body requiring a continuous change of substance ; whilst the chief function of the non-nitrogenous is to furnish by their oxidation the actual energy which is in part transmuted into muscular force. The combustible fQod and oxygen coexist in the blood which courses through the muscle; but when the muscle is at rest there is no chemical action between them.A command is sent from the brain to the muscle the nervous agent determines oxidation. The potential energy becomes actual energy one portion assuming the form of motion another appearing as heat. Here is the source of animal heat here the origin of muscular power! Like the piston and cylinder of a steam-engine the muscle itself is only a machine for the transformation of heat into motion; both are subject to wear and tear and require renewal ; but neither contributes in any important degree by its own oxidation to the actual production of the mechanical power which it exerts. From this point of view it is interesting to examine the various articles of food in common use as to their capabilities for the production of muscular power.I have therefore made careful estimations of the calorific value of different materials used as food with the same apparatus and in the same manner as described above for the determination of the actual energy in muscle urea &c. The results are embodied in the following series of tables; but it must be borne in mind that it is only on the condition of the food being digested and passed into the * The 1 ancet 1863,pages 381 and 412. E2 FRANKLAND ON THE blood. that the results given in these tables are realized . If. for instance. sawdust or paraffin oil had been experimented upon. numbers would have been obtained for these substances. the one about equal to that assigned to starch.and the other surpasaing that of any article in the tables ; but these numbers would obviously have been utterly fallacious. inasmuch as neither sawdust nor paraffin oil is. to any appreciable extent. digested in the alimentary canal. Whilst the force-values experimentally obtained for the different articles in these tables must. therefore. be understood as the maxima assignable to the substances to which they belong. yet it must not be forgotten that a large majority of these substances appear to be com-pletely digestible under normal circumstances . TABLEI.-Results of Experiments witlt Food dried at 100" C. in heat -units . Heat-Heat-Heat-Heat-Name of Food. units. units. units. units. 1st Exp. 2nd Exp 3rd Exp (Mean.) Cheshire cheese....................... 6080 6149 .. 6114 Potatoes ............................. 3752 .. .. 3752 Apples................................ 3776 3562 .. 3663 Mackerel.............................. 5994 6134 6064 Oatmeal (not dried) .................... 4143 4018 3857 4004 Lean beef ............................ 5271 5260 5410 5313 White of egg .......................... 4823 4940 492'7 4896 Carrots .............................. 3776 3759 .. 3767 Pea-meal (not dried) .................... 3866 4006 .. 3936 Flour (not dried) ...................... 3941 3931 .. 3936 Arrowroot (not dried) .................. 3923 3902 .. 3912 Butter ................................ 7237 7291 .. 7264 Ham boiled and lean ..................4188 4498 4343 Lean veal ............................ 4459 4595 4i88 4514 Hard-boiled egg ........................ 6455 61 87 .. 6321 Yelk of egg .......................... 6460 .. .. 6460 Isinglass .............................. 4520 4520 .. 4520 Cabbage .............................. 3809 3744 .. 3776 Whiting .............................. 4520 4520 .. 4520 Ground rice (not dried) .................. 3802 3824 .. 3813 Cod-liver oil .......................... 9134 9080 .. 9107 Cocoa nibs (not dried) .................. 6809 ' 6937 .. 6873 Residue of milk ........................ 5066 5120 .. 5093 Bread crumb .......................... 3984 3984 .. 3984 a. Bread crust (not dried). ................. 4459 .. 4459 Lump sugar (not dried) ..................3403 3294 .. 3348 Commercial grape-sugar (not dried) ...... 3277 8277 .. 3277 Residue from botlled ale ................ 3776 3744 .. 3'7'60 Residue from bottled stout .............. 6348 6455 .. 6401 ORlGIN OF MUSCULAR POWER. TABLE11.-Actual Energy developed by 1 gram of various Articles of Food when burnt in Oxygen. \ 1 I I Heat-units. Metrekilograms of force. Percent. Name of Food. of water. Natural Natural Dry* condition. Dry’ condition. -I_ ----.--Cheese (Cheshire) .......... 6114 4647 2689 1969 24 -0 Potatoes .................. 3752 1018 1589 429 73 -0 Apples. ................... 3669 660 1554 280 82 ‘0 Oatmeal .................. .. 4004 .. 1696 Flour ...................... 3936 .. 1669 Pea-meal................. .. 3936 .. 1667 Ground rice .............. .. 3813 .. 1615 Arrowroot ................ 3912 1657 1 Bread crumb .............. 3984 2231 1687 945 44.0 Bread crust.. .............. .. 4459 1888 Beef (lean) ................ 5313 1567 2250 664 70 -5 Veal.. .................... 4514 1314 1912 556 70 -9 Ham (boiled) .............. 4343 1980 1839 839 54 -4 Mackerel. ................ 6064 1789 2568 758 70 -5 Whiting .................. 4520 904 1914 383 80 -0 284 86 *3 White of egg .............. 4896 671 2074 Hard-boiled egg.. .......... 6321 2383 2677 1009 62 -3 Yelk of egg .............. 6460 3423 2737 1449 47 *o Isinglass .................. 4520 1914 Milk ....................5093 b‘s2 2157 280 87 -0 Carrots .................. 3767 527 1595 223 86 -0 Cabbage .................. 3776 434 1599 284 88 *5 Cocoa nibs ............... .. 6873 .. 2911 Beef fat .................. 9069 3841 Butter .................... .. 7ii4 .. 3077 Cod-liver oil .............. *. 9107 .. 3857 Lump sugar .............. .. 3348 .. 1418 Commercial grape-sugar .... 3277 .. 1388 Bass’s ale (alcohol reckoned). . 3i60 775 1599 328 88 -4 Guineas’s stout , .. 6401 10?6 2688 455 a8 -4 TABLE 111.-Actual Energy developed by 1 gram of various Articles of Food when oxidized in the Body. Metrekilograms of force. Name of Food. Nat,uraI Dry. condition. 1 ChePhire cheese ............ 2429 1846 Potatoes .................. Apples.................... Oatmeal .................. 1665 FRANKLAND ON THE TABLE1II.c ontinued. Metrekilograms of force. Name of Food. Natural Dry. condition. ......... Flour .........,.......... Pea-meal......,.. ........ Ground rice ,............. Arrow-root ....... ........ Bread crumb .............. Lean of beef ,............. Lean of veal ............ Lean of ham (boiled) .....,.. Mackerel.................. Whiting ....,...,......... White of egg .............. Hard-boiled egg ............ Yelk of egg ...,.......... Gelatin .................. Milk...................... Carrota ................. Cabbage .................. Cocoa-nibs ............... Butter ....................Beef fat ,............,.... Cod-liver oil .,............ Lu’mp sugar ....... ...... Commercial grape-sugar .... Bass’s ale (bottled) .......... Guineas‘s stout , .......... .. 1627 .. 1598 .. 1591 .. 1657 1626 910 2047 604 1704 496‘ 1559 711 2315 683 1675 335 1781 244 2562 966 284 1 1400 1550 2046 266 18’74 220 1543 178 .. 2902 .. 30’77 3841 3857 .. 1418 .. 1388 1559 328 2888 455 ~-TABLE 1V.-Weight and Cost of various Articles of Food required to be oxidized in the body in order to paise 140 Ibs.to the JteigJLt of 10,000 feet. External Work = one-fifth of Actual Energy. Name of Food. Weight in lbs. Price required. per lb . cost. ~ Cheshire chee8e ............Potatoes .................. Apples .................... Oatmeal .................. Flour ................... Pea-meal .................. Ground rice .............. Arrowroot ................ Bread .................... 1.156 5 -068 7-815 1.281 1-311 1 *335 1-341 1.23’7 2 -345 .. s. d. 0113 054 0 ll$ 03+ 039 048 054 134 0 4% ORIGIN OF MUSCULAR POWER . TABLEIV-continued . Name of Food. ' 1 ~~ I Lean beef ................ Lean veal ................ Lean ham (boiled) .......... Mackerel ................... Whiting .................. White of egg .............. Hard-boiled egg............ ~ Isinglws ..................~ Milk ...................... Carrots ................... Cabbage ................... Cocoa nibs ................ Butter .................... j Beef fat ..................i Cod-liver oil ............... Lump sugar ..............\ Commercial grape-sugar .. .I Basu's pale ale (bottled) " Cfuiness's stout . ,. .. I ....I lbs required . ~~ 3 *532 4.300 3.001 3.124 6 *369 8 *i45 2 209 1 -3i7 8-021 9-685 12.020 0 -735 0.693 0 *555 0.553 1 -505 1-537 9 bottles. 6 >> Price per lb . cost. .-. a. d. 8. d. 10 3 6i 10 4 3h 16 46 08 21 14 94 06 4 4a 0 64 1 28 16 0 22 0,L 5d.per qrt . 1 33 0 14 1 2h 01 1 0% 1 6 1 1% 1' 6 1 og 0 10 0 5; 36 1 11a 06 13 0 3h 0 5f 0 10 76 0 10 5 7h Food required to sustain TABLEV.-)lespiration and Circulation in the Body oj' an average iMan Weight of various Articles of during twenty-four hours .Name of Food. Cheshire cheese ............ Potatoea .................. Apples.................... Oatmeal .................. Flour .................... Pea-myal .................. Ground rice .............. Arrowroot ................ Bread .................... Lean beef ................ Lean veal ................ Lean ham (boiled) .......... Mackerel .................. Weight in oza. 3.0 13 .4 20 *i 3 '4 3.5 3.5 3 .6 3 *4 6-4 9 *3 11 -4 7.9 8 -3 Name of Food.Weight in ozs. Whiting ................ 16-8 White of egg ............ 23.1 Hard-boiled egg .......... 5'8 Gelatin .................. 3.6 Milk .................... 21-2 Carrots .................. 25-6 Cabbage ................ 31-8 Cocoa nibs................ 1*9 Butter .................. 1-8 Cod-liver oil .............. 1.5 Lump sugar .............. 3.6 Cammercial grape-sugar .... 40 These results are fully borne out by experience in many in-stances. The food of the agricultural labourers inLancashire contains a large proporiion of fat . Besides the very fat bacon which constitutes their animal food proper. they consume large FRANKLAND ON THE ORIGIN OF MUSCULAR POWER.quantities of so-called apple dumplings the chief portion of which consists of paste in which dripping and suet are large ingredients ; in fact these dumplings frequently cdntain no fixit at all. Egg and bacon pies and potatoe pies are alsovery common pikces de rdsistance during harvest time and whenever very hard work is required from the men. I well remember being profoundly impressed with the dinners of the navigators employed in the construction of the Lancaster and Preston Railway ; they consisted of thick slices of bread surmounted with massive blocks of bacon in which mere streaks of lean were visible. These labourers doubtless find that from fat bacon they obtain at the minimum cost the actual energy required for their arduous work.The above tables affirm the same thing. They show that -55 lb. fat will perform the work of 1.15lb. cheese 5 lbs. potatoes 1.3 lb. of flour or pea-meal or of 33 lbs. of lean beef. Donders in his admirable pamphlet ‘‘ On the Constituents of Food and their relation to Muscular Work and Animal Heat,” mentions the observations of Dr. M. C. Verloren on the food of insects. The latter remarks “many insects use during a period in which very little muscular work is performed food containing chiefly albuminous matter; on the contrary at a time when the muscular work is very con- aiderable they live exclusively or almost exclusively on food free from nitrogen.” He also mentions bees and butterflies as instances of insects performing enormous muscular work and subsisting upon a diet containing but the merelst traces of nitrogen.The following conclusions may therefore be drawn from the foregoing experiments and considerations :-1. A muscle is a machine for the conversion of potential energy into mecliaiiical force. 2. The mechanical force of the muscles is derived chiefly from the oxidation of matters contained in the blood and only in a very subordinate degree from the oxidation of the muscles themselves. 3. In man the chief materials used for the production of muscular power are non-nitrogenous ; but nitrogenous matters can also be emplcyed for the same purpose and hence the greatly increased evolution of nitrogen under the influence of a flesh diet even with no increase of muscular exertion.4. Like every other part of the body the muscles are co~l- stantly being renewed ; but this renewal is scarcely perceptibly PERKIN ON THE ARTIFICIAL PRODUCTION OF COUMARIN. 53 more rapid during great muscular activity than during compa- rative quiescence. 5. After the supply of sufficient albuminoid matters in the food of man to provide for the necessary renewal of the tissues the best materials for the production both of internal and ex-ternal work are non-nitrogenous matters such as oil fat sugar starch gum &c. 6. The non-nitrogenous matters of food which find tbeir way into the blood yield up all their potential energy as actual energy; the nitrogenous matters on the other hand leave the body with a portion (at least one-seventh) of their potential energy unexpended.7. The transformation of potential energy into muscular power is necessarily accompanied by the production of' heat within the body even when the muscular power is exerted externally. This is doubtless the chief and probably the only source of animal heat.

ISSN:0368-1769    

DOI:10.1039/JS8682100033

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

PERKIN ON THE ARTIFICIAL PRODUCTION OF COUMARIN. 53 VI.-On the Artaftcial Production of Cournaih and Formation oj* its Homologues. By W. H. PERKIN,F.R.S. IT is well known that coumarin when fused with hydrate of potassium yields salicylic and acetic acids. This fact has naturally led chemists to assume that there must exist a close relationship between this body and the salicylic series. No one however appears to have studied this subject and in fact when we consider the f'orrnula of coumarin and compare it with that of any member of that series we see that there is but little room for speculation; for example if we compare the formula of coumarin with that of the liydride of salicyl it will be seen that there exists only a difference of two equivalents of carbon but it must be remembered that salicylic acid does not result from the action of hydrate of potassium upon cournarin but is in fact a product of the decomposition of coumaric acid there- fore speaking correctly it is coumaric acid and not coumiirin which is related to the salicylic series.PERKIN ON THE ARTIFICIAL PRODUCTION Under the name of aceto-salicylol is described a body iso- meric with coumaric acid and this substance being an acetyl derivative of the hydride of salicyl should yield if fused with hydrate of potassium exactly the same products of decompo- sition as coumaric acid would if treated in a similar manrier. In a paper I lately had the honour of reading before this Society I mentioned that I was unable to obtain aceto-salicylol or more correctly the hydride of aceto-salicyl by the met.hod of Cahours and also that my endeavours to prepare it by the action of acetic anhydride upon the hydride of salicyl were unsuccessful.It then appeared to me probable that if the hydride of salicyl were replaced by its sodium derivative I might expect a better result thus,-Hydride of sodium-Hydride of aoeto-Salicyl. salicyl. On performing this experiment the following results were obtained. The hydride of sodium-salicyl when submitted to. the action of acetic anhydride rapidly loses its yellow colour and then dissolves; this change is attended with a very considerable ele- vation of temperature the mixture becoming quite hot. After this reaction has moderated the product when boiled for a few minutes and then poured into water sinks as an oil acetate of sodium dissolving.On distilling this oil any acetic anhydride that may have escaped decomposition comes over at first then hydride of salicyl ; the temperature then rises rather quickly and when it has reached 290° all the remaining product on being distilled into a separate receiver solidifies to a crystalline mass on cooling. This product when purified by pressure between bibulours paper aiid recrystallised two or three times from alcohol gave the following number on analysis :-I. -2396 of substance gave -6508 of CO and -0942 of H,O. 11. *2387of substance gave -6467 of CO and -0920 of H,O. OF COUMARIN AND FORMATION OF ITS HOMOLOGUES.55 These numbers give percentages agreeing with the formula -as the following comparisons will show :-Theory. Experiment. F A \ Y I. i . C ...... 108 73.97 74.07 73-81 H ...... 6 0 ...... 32- 4.11 21.92 4.36 - 4.28 - 146 10@00 It will be seen that this formula is not that of the hydiide of aceto-salicyl being deficient by an equivalent of water. It is however the formula of couma.rin. To prove that this substance is in reality pure coumarin and identical with the natural product the following comparisons of its properties with those of a specimen prepared from the Tonka bean were made. I. When crystallised from water side by side these two products could not be distinguished the one from the other the appearance of the crystals and their grouping being identica.1.11. Crystallised from alcohol side by side they appeared per- fectly alike. 111. Their melting points were also the same. IV. Their boiling points were also the same. V. When heated with strong aqueous hydrate of potassium each yielded coumaric acid and moreover the acid prepared from both specimens possessed the same melting point. VI. Fused wit,h hydrate of potassium they yielded salicylic acid. VII. They also possessed exactly the same odour. It will be remembered that some time since I made a verbal communication to the Society upon the artificial formation of this body,* but dated that I had not had an opportunity of ascertaining whether it was identical or only isomeric with the natural product ;from the foregoing comparisons however I think I may safely conclude that this artificial coumarin is the same as that obtained from the Tonka bean.It will not perhaps be out of place to make a few obser- @ Laboratory vol. i p. 136. PERKIN ON TEEE ARTIFICIAL PRODUOTION vations respecting the properties of coumaiin which I have found to differ somewhat from those described in chemical works. The melting point of this substance is nearly 20" higher than that recorded being between 67' and 67"-5C. Its boiling point is also much higher my experiments giving 290O.5 to 291OC. as the temperature whereas it is generally stated as 27OOC. It is also mentioned that cournarin is easily soluble in a solution of hydrate of potassium; this remark is perfectly true when applied to boiling but not to cold solutions of that alkali ; the slender crystals obtained by crystallising this sub- stance from water dissolving only with extreme slowness in a strong cold aqueous solution of hydrate of pota.ssium.The melting point of coumaric acid I have found to be between 207' and 208" C. 190' C. being the temperature usually given. The production of coumarin by means of acetic anhydride and the hydride of sodium-salicyl made it appear probable that if other anhydrides were substituted for the acetic a whole series of bodies homologous with coumarin might be pro-duced. This anticipation has been verified by experiment. Butyric Coumarin. Butyric anhydride acts but slowly upon the hydride of sodium- salicyl unless heat be applied the sodium compound then loses its colour and gradually dissolves; after boiling for a few minutes the product if poured into water separates as an oil the butyrate of sodium which has been formed dissolving.On rectifylng this oil butyiic anhydride and a little hydride of salicyl at first come over the temperature then rapidly increases and all the product distilling above 290" C. crystallises on cool-ing. This is rendered perfectly pure by pressure between bibulous paper and two or three crystallisations from a.lc0- hol. In one experiment I obtained three grammes of this substance &om twelve grammes of the hydride of sodium- aalicyl. When submitted to analysis it gave the following numbers :-I.-1976 of substance gave *5474 of CO and 01049of H,O. OF COUMARIN AND FORMATION OF ITS HOMOLOGUES. 57 11. -2125 of substance gave ,5902 of CO,and -1115of q0. These numbers give percentages agreeing with those required by the formula- C11H1002 as the following comparisons will show :-Theory. Experiment. I. 11. Cll.. .... 132 '75.86 75-55 75.74 Hlo .... 10 5-75 5.89 5.82 0 ...... 32 18.39 - - 174 100*00 The formula of this substance is C,H higher than that of coumarin the difference being the same as that existing be- tween acetic and butyric acids; this body is in fact a butyric counntarin homologous with the natural product. Butyric coumarin melts at from 70" to 71" C. and on cooling solidifies to a beautifid crystalline mass; at 296' to 297' C.it distils with slight decomposition. It is but little soluble in boiling water the solution becoming milky as it cools and after a time depositing a small quantity of crystals in the form of minute needles. In boiling alcohol it dissolves fieely and on standing separates fiom this solvent in large semi-opaque prisms. It is easily soluble in ether. This body possesses the odour of ordinary coumarin and also of fiesh honey. Butyric coumarin is nearly insoluble in cold aqueous hydrate of potassium and even when gently heated with a saturated solution of that alkali it only melts and floats as an oil upon its surface; if more strongly heated however it dissolves per- fectly forming a pale yellow solution; thk on being further concentrated becomes opaque and on standing a few moments an oily fluid rises to the surface which upon cooling changes to a tenacious mass; it can then easily be separated from the excess of hydrate of potassium which remains fluid.This sub- stance is a compound of butyric coumarin and hydrate of potas- sium ; it is deliquescent and very soluble in water; acids PERKIN ON THE ARTIFICIAL PRODUCTION easily decompose it with separation of butyric coumarh. When heated this compound dries up to a yellow amorphous mass and then undergoes decomposition being converted into the potassium salt of a new acid apparently homologous with coumaric acid; in fact the coumaric acid of butyric coumaiin.This acid is crystalline and easily soluble in carbonate of sodium and ammonia. For want of sufficient substance I have not been able to analyse this acid. The addition of bromine to this coizrnarh causes it to liquefy and on distilling the product a tough resinous mass is obtained giving when digested with alcoholic hydrate of potassium an acid which may be separated from the alkaline solution by means of hydrochloric acid. Ordinary coumarin when treated with bromine yields a similar product. Butyric coumarin when heated with fused hydrate of potas-sium decomposes yielding salicylic acid together with hydrate of phenyl and apparently butyric acid; but the odour of this latter compound is much masked by the presence of the hydrate of phenyl.Ckleric Cournarin. The hydride of sodium-salicyl appears to be scarcely affected by valeric anhydride in the cold but upon the application of heat thege two substances gradually react upon each other forming a clear liquid. In performing this experiment I prefer to add the sodium compound to the boiling anhydride and then to digest the mixture for a few minutes. The oily pro-duct of this reaction after being agitated with water to remove valerate of sodium is collected and distilled the portion boiling above 290"C. being kept separate. This distillate unlike those obtained in the preceding experiments does not crystallise even after standing for days and it was only by repeated trials that I succeeded in obtaining a method for its purifica- tion.This process is based upon the'propcrty of coumarins to dis solve in boiling solutions of hydrate of potassium and was carried out in the following manner :-The above oily distillate after being well agitated with a strong boiling solution of hydrate of potassium was diluted with OF COUMARIN AND FORMATION OF ITS HOMOLOGUES. 59 water and then mixed with ether to separate all oily products the clear aqueous solution when acidified with hydrochloric acid liberated the new coumarin which was taken up with ether and the ethereal solution agitated with carbonate of sodium to remove any acids that might be present. On evaporating this solution the new prodiict was obtained as an oil solidify- ing to a crystalline mass upon cooling. It wa.s then separated from oily impurities by pressure between bibulous paper ; two or three crystallisations from alcohol then rendered it perfectly pure.From twelve grammes of the hydride of sodium-salicyl and about 14 grammes of valeric anhydride I have obtained by the above method two grarnmes of this new coumarin. Two combustions of separate preparations of this body gave the following numbers :-I. ,1990 of substance gave -5600 of C02and *1153of H,O. 11. *2725of substance gave 07630of CO and -1610 of H,O. These numbers give percentages agreeing with the formula- as the following comparisons will show Theory. Experiment. I. 11 C12 144 76.59 7 6.74 76-36 6-43 6.36 HI2 12 6.38 32 17 *03 A -02 -a. -L. 188 100.00 This substance is therefore aaleric cournarin.Valeric coumarin melts at 54O C. and on cooling solidifies to a splendid crystalline mass; at 301"C. it boils a.nd distils with slight decomposition. It possesses a coumaric odour but not to the same extent as the butyiic coumarin. In boiling water it dissolves to a small extent but i8 apparently iiisoluble in cold water. It is very soluble in alcohol fiom which it crystal- lises in splendid transparent prisms nearly three-quarters of an PERKIN ON THE ARTIFICIAL PRODUCTION inch in length; they appear to be oblique six-sided prisms. This body is also very soluble in ether. This coumarin appears to be insoluble in cold solutions of the alkalies. If added to a concentrated solution of hydrate of potassium diluted with about a fourth of its volume of water and gently heated it melts and floats as an oil but when heated fwther perfectly dissolves.This solution on being concen-trated becomes milky and after standing a few moments an oily layer forms onits surface becoming a tenacious mass upon cooling; this is a compound of valeric coumarin and hydrate of potassium. This product is very deliquescent and easily soluble in water. Hydrochloric acid decomposes it liberating the valeric coumarin. If heated strongly it decomposeR yield- ing an acid most probably valeric coumaric. With fused hydrate of potassium this coumarin yields salicylic acid hydrate of phenyl and apparently a small quantity of valeric acid. When distilled with pentachloride of phosphorous it yields a viscid oil which if gently heated emits a turpentinic odour and when burnt communicates a green colour to the edges of the flame showing it to be a chloiinated body.From the preceding results we see that coumarig is but a member of a whole series of homologous bodies producible from the hydride of sodium-salicyl by means of anhydrides. The question therefore which presents itself for consideration is what is the nature of the reaction by which these bodies are formed and their consequent constitution 8 In this inquiry it will be well to consider the formation of ordinary coumarin as the history of this substance is more complete than that of its homologues. In the reaction by which this body is formed there wuuld appear to be two distinct stages the first being the formation of the hydride of aceto-salicyl thus :-CO,H CO,H (".".}())+i:}' =(c6f:}O) '~~}" Na Hydride of sodium salicyl.Hydride of aceto-salicyl. the second consisting in the formation of cournarin from this hydride of aceto-sulicyl by the separa,tion of an equivalent of water. OF COUMARIN AND FORMATION OF ITS HOMOLOQUES. 61 Respecting the first change I have found that by treating the hydride of sodium salicyl in a very careful manner the hydride of aceto-salicyl is actually formed.* The second part of this reaction is not so easy of explana-tion viz. from what part of the hydride of aceto-salicyl is the equivalent of water removed. Seeing that this change must be effect'ed either by the dehy- drat'ing power of boiling acetic anhydride or by a temperature not exceeding 300° C.it would not appear very probable that the acetylic radical was interfered with especially as acetic acid is produced when coumarin or coumaric acid is decomposed with hydrate of potassium. It is also evident that the hydride of aceto-salicyl loses its character as an acetate on changing into coumarin ; otherwise when dissolved in a strong solution of hydrate of potassium coumaxin should entirely split up instead of forming coumaric acid. Further it is evident that it has lost its typical aldehydic hydrogen otherwise coumarin would be an aldehyde. Assum-ing these considerations to be correct the change which the hpdricle of aceto-salicyl undergoes on losing an equivalent of water and thereby being converted into coumariii may be represented thus :-Hydride ofaceto-salicyl.Coumarin. According to this formula coumarin is a mixed acid radical consisting of a molecule of acetyl jointed to a molecule of a radical C,H30. This would belong to the same series as cinnamyl and I propose to name it DZptyZ. It will be well to see in what way the reactions of coumarin may be explained by this formula. I will first take the forma-tion of coumaric acid. * This substance possesses all the properties pointed out by theory namely those of an aldehyde and an acetate. It freely combines with bisulphites and with alcoholic hydrate of potassium easily decomposes yielding acetate of potassium and the hydride of potassium-salicyl.I hope shortly to give a full account of this body. VOL. XXI. B' PERKIN ON THE PRODUCTION OF COUMARIN ETC. This acid is formed by the assimilation of an equivalent of water by coumarin through the intervention of hydrat'e of potassium in the same way that alcohol is formed from ethylene by the intervention of sulphuric acid. Coumarin. Coumaric acid. Ethylene. Alcohol. Thus expressed coumaric acid wouId be a phenol and not a true acid and if' we regard the radical salicyl as a phenol as * well as an acid radical,- Salicyl.. coumaric acid likewise becomes a mixed acid radical acetyl- salicyl. The second reaction it will be well to consider is the trans- formation of coumaric acid into acetic and salicylic acids.It will be seen that this change is easy of comprehension the two radicals simply becoming hydrated. CH Coumaric acid Acetic acid. Salicylic acid. (Acetyl-salicyl) To express the formation of the homologues uf coumarin it is evidently only necessary to replace acetyl by other acid radicals. Coumarin and its homologues probably have several isomers corresponding in iiiirnber to tlzc ads isomeric with salicylic and WILLIAMS ON THE PREPARATION OF UREA. 63 if coumarins are simply acid radicals the possible number of such substances capable of existence is enormous. The following is a table of the bodies described in this paper written out according to the foregoing theoretical views. Also of coumaric acid and its probable homologues not yet analyzed-Ace& coumarin } CgH60 :$$$} (Coumarin) Acetyl-diptyl.Propionic coizmarin wanting. Butyric coumalin .. C lHl,O Butyl-diptyl. %2:} Valeric coumarin .. Cl,H,,O gig$} Yalyl-diptyl. Acetic coumaric acid ) C,H30 J Acetyl-(Coumaiic acid) ~9~803 C,H,(HO)O I salicyl. Propionic coumaric acid wanting. Butyric cciurnaric acid C ,W,,O Butyl-hop} salicyl. I am at present studying some new derivatives of coumariii and its homologues with a view of obtaining a clearer insight into their nature

ISSN:0368-1769    

DOI:10.1039/JS8682100053

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

WILLIAMS ON THE PREPARATION OF UREA. VI1.-Note on the Preparation 'of Urea. By JOHN WILLIAMS. HAVINGhad occasion to prepare rather large quantities of urea I found that the result constantly fell considerably short of what I considered a satisfactory one. This led me to consider if the ordinary mode of preparation could not be improved. upon. The result of my experiments is that cyanate of lead is F2 64 GLADSTONE ON THE PYROPHOSPHORIC AMIDES. better adapted for the purpose than the mixture of salts gene- rally present in solution when the usual process is adopted. I proceed in the following manner :-I prepare the cyanate of lead by fusing cyanide of potassium of the best commercial quality (containing about 90 per cent. of real cyanide) at a very low red heat in a shallow iron vessel; red lead is added in the usual manner by small quan- tities at a time with constant stirring so as to prevent the temperature rising too much during the operation.I prefer cyanide of potassium to ferrocyanide for many reasons but mainly because the temperature can be kept down to the lowest point. The cooled and finely powdered product is exhausted with successive portions of cokd water the liquid filtered and nitrate of barium added. Carbonate of barium is thus precipitated. The mother-liquid treated with nitrate of lead yields pure cyanate of lead; this em be washed thoroughly and dried at a gentle heat and preserved for use. Unlike cyanate of potas-sium it is a peimanent salt and could be produced as a com-mercial product at a moderate price if required. To prepare urea it is simply necessary to digest with snffi-cient water at a gentle heat equivalent quantities of cyanate of lead and sulpliate of ammonium filter and evaporate. I have found the result most satisfactory. The compound ureas may in like manner be produced by substituting the sulphates of the compound ammonias for the ordinary snlpliate of ammonium ; the experiment has been tried and found successful.

ISSN:0368-1769    

DOI:10.1039/JS8682100063

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

GLADSTONE ON THE PYROPHOSPHORIC AMIDES. VIII.-On the P~rophosphom'cAmicles. By J. H. GLADSTONE, Ph.D. F.R.S. INfermer communications" I have described three acid bodies wl-liclz ma3 be viewed as pyrophosphoric acid in which one two * Quart. Journal Chem. SOC. 1-01. 111 pp. 135 and 353. Do. do. , xmr p 225. Do. do. , XIX,pp. 1 and 290. GLADSTONE ON THE PYROPHOSPHORIC AMIDES. or three semi-molecules of ainidogen have displaced an equal number of molecules of hydroxyl. Their composition and their rela,tion to the original acid may be thus exhibited :-Pyrophosphoric acid .. .. P,H,O Pyrophosphamic acid .. * * P,(NH,)H,O6 Pyroplioaphodiamic acid .. . . P2(NH,),H205 Pyroyhosphotriamic acid .. P,(NH,),HO The basic hydrogen of these acids decreases as the amidogen increases but irk the case of the last one half the hydrogen combined with the nitrogen msy alsa be replaced by certain metals.Since these papers were written I liave come across some additional f'dcts and liave fwinecl a inore precise conception of the rational formule of these bodies. I propose to narrate these facts first and then to develop the inore complete theory. Pyrop7~osplitcmic AcitZ.-Tliis acid had hitherto been formed only by the breaking down of the higher amide under the influence of a metallic salt and heat. There is also another series of bodies-the tetraphospliamides-wllich yield it by decomposition; and in some cases I have found that a solution containing free pyrodinmic acid gnve indications of its presence after standing for some weeks at the ordinary temperature.The following experiments led me at' first to believe that it might be produced syntlietically hit tliere is no coiiclusiva proof that the compounds are not a peculiiir series of double ammonium salts. I. 0rdiii:xi-y pyrophosphoric acid was saturated with ammonia and to this solution hydri3,te of b;triurn was added iiot in excess. A precipitate was obtained which wlieii well washed aid dried gave the inclicatioiis of a pyrophosphamate ; that is when heated per se it tinned black and gave off ammonia and a peculiar sublimate. When excess of hydrate of barium was dried notliing but the pyrophosphntc wm obtained. 11. Similar experiinents w~\reretried with acetate of lead arid f'erric chloride instead of hydrate of barium and with like results.111. The insoluble modification of ferric pyrophosphate was prepared in the presencc of it quantity of chloride of ammonium. The well-xvvasliccl precipitate gave the ordinary indications of GLADSTONE ON THE PYROPHOSPHORIC AMIDES. the pyrophosphamate. In one experiment 0.427 grm. of the salt thus produced was decomposed by boiling with hydrochloric acid and gave 0.200 grm. of ammonio-chloride of platinum which is equal to 2-93 per cent. of nitrogen. Had the -whole precipitate been the pyrophosphamate the ni trogeii would have been 5.65 per cent. or nearly double that found. IV. 0.355 grm. of ferric pyrophospliate was dissolved in ammonia and reprecipitated by dilute sulphuric acid.The salt thus obtained was well washed and decomposed by hydrochloric acid when it gave 0.234 grm. of ammonio-platinum salt equi- valent to 4.13 per cent. of nitrogen. V. This experiiiient was repeated with copper instead of iron salt and with a similar result. VI. The converse of these last experiments was tried. 0.333 grm. of ferric pyrophosphate (soluble modification) was dis- solved in dilute sulphuric acid and reprecipitated by ammonia of course not in excess. The well-washed precipitate gave 0.170 grm. of ammonio-platinum salt equivalent to 3-14 per cent. of nitrogen. That the azotized ferric compound contained in these pre- cipitates is not the ordinary pyrophosphamate is shown by the followirig properties :-It is soluble in excess of either pyro- phosphate of sodium or ferric chloride; it is decomposed by cold dilute sulphuric acid; and moreover it is somewhat soluble in pure water.But while these properties distinguish it from the insoluble ferric pyrophosphamate previously known t>hey are rather suggestive of the idea that it inay be a soluble modification analogous to the soluble ferric pyrophosphate. An attempt was made to convert it into the ordinary salt by boiling its solution in very dilute sulphuric acid but without success. Ferric pyrophosphamate formed in the cold by the double decomposition of pyrophosphamate of potassium aid ferric chloride was found to be identical in properties with the ordinary salt. The action of heat upon this ferric compound is similar to its action on the pyrophosphamate but even the production of water and of the white sublimate must be taken as evidence with considerable reserve ; at any rate these substances are formed when the compound of pyrophosphoric acid and am-monia is heated per se.For analysis it would of course be necesfiary t-o prepare this GLADSTONE ON THE PYROPHOSPHORIC AMIDES. compound free from pyrophosphate or any other salt. The fact that it is somewhat soluble in water but not in a solution of cliloride of ammonium was taken advantage of for this purpose. An aqueous solution was in fact precipitated by the addition of the concentrated chloride and the white flocculent compound was quickly xvdied wit,h as little water as possible.Of what remained on the filter 0-390grm. decomposed by hydro-chloric acid gave 0.334 grin. of ainmoiiio-chloride of platinum which is equivalent to 3-35 per cent. of nitrogen. This agrees nearly with tlie amount contained in ferric pyrophosphamate viz. 5.65 per cent. but no ultimate analysis can decide between the formula P,(NH,)Fe,O,,H,O and a possible double ammo- nium salt of the composition P,(NH,)Fe,O,. Pyrop7~o~pllodiarnic Acid-I formerly published a character- istic test of this acid founded on tlie fact that when a solution containing it is rendered strongly acid and is heated with a few drops of a ferric salt the flocculent white pyrophosphamate makes its appearance. Precaution8 were given so as to avoid mis- taking for pyropliosphodiamic acid two others which I have since called tetraphosphoric compounds.With my further knowledge of .these amides I still think that tlie process may be looked upon as furnishing a characteristic test but a chemist inex- perienced in these compounds might easily be misled by the formation of the insoluble ferric pyrophosphate whicli so closely resembles the pyrophosphamate. Hence it will be generally desirable if not necegsary to dry a portion of’ the precipitate and examine which conipouiid it is by heating it per se in a test tube when the pyrophosplinte simply fuses and the pyrophospliarnate does iiot fuse but turns black at first and gives off ammonix and a little white volatile salt. This sublimate is very soluble in water riot so in alcohol its aqueous solution contains amnioiiia and some acid that gives a brown-black precipitate with nitrate of silver like phos- phorous acid.It may also be borne in mind that the pyrophos-pliamate will separate from a solution so acid as to prevent the formation of the insoluble pyrophosphate. A large excess of acid will also nearly if not antireiy prevent the formation of the compound resulting from pyrophosphorio acid and am-monia in juxta-positim. So there is little fear of error from this source. Still as the !!roof that this acid may be prepared by the GLADSTONE ON THE PYROPHOSPHORIC AMIDES. eleven methods noted in my paper rests mainly on the evidence of this test I thought it well to repent the principal expe- riments examining whether it was the pyrophogphamate that was really produced.I have found it to be so in all cases and I have no reason to doubt that in each instance it had been formed by the decomposition of pyrophosphodiamic acid. Pyr.o~Jio,~pJ~otra~~~ic Acid.-The method formerly given for preparing this body was not a productive one and the acid was apt to be contaminated with another compound unless great attention was paid to t'he temperature. The following is a far more productive and a Fetter process :-Saturate oxy-chloride of phosphorus with dry ammonia gas without regard to the rise of temperature; heat the resulting mass at about 220°C.; add water to it ; and boil for aboilt a minute. This will convert the whole of the insoluble portion into pyrophos-photriamic acid with very little loss from the production of other phosphoric compounds.This acid has also been met with among the products of de- composition of one of the tetraphosphoric amides t,hat remain to be described at some future time. Its formation along with other compounds when pentachloride of phosphorus is tlirowii into the strongest aqueous ammonia has been already noted. YheoreticaI Constitution. In my last communicatioii to this Societ,y,* I suggested as the rational formula of pyrophosphoric acid -P,(HO),O -or at greater length (Ho)20) 0;-and I expressed iny con-P(HO),O victiori that when this acid is pi-oduced by the mutual action of water and oxychloride of phosphorus the two atoms of hydro- gen in the molecnle of water art attacked simultaneously by two moleciilcs of the chloride and tlie water type is preserved in the new phosphorus compound.A similar explanation will hold good in the formation of these amides from oxychloride of phosphorus ammonia and water. When the oxychloride is exposed to a current of the alkaline gas at a low temperature it absorbs two equivalents giving doubtless the first amide thus :-PC1,O + 2NH = NH,C1 + P(NH,)Cl,O. * Journ. Chem. SOC.,vol. XX p. 435. GLADSTOYE OX THE PYROPHOSPHORIC AMIDES. 6'3 When the oxychloride is dropped into the strongest aqueous solution of ammonia it seems probable that the first action is the same. In both cases the production of the second pi-ro- phosphoric amide by the. action of water (or alkaline hydrate) may be well explained on the assumption that the two atoms of hydrogen (or ammonium) are attacked simultaneously by the chloride.The reaction must be expressed on paper in two successive stages though they probably take place together in reality :-or P2(NH2),H,0, pyrophosphodiamic acid. These forrnuh are precisely analogons to those by which the formation of pyrophosphoric acid was soirglit to be explained. But the above is not the oiily rtmiclated oxychloride from which the pyro-diamic acid may be produced. Oxychloricle of phosphorus combines with 4 equivalents of ammoilia gas giving rise doubtless to a second amide thus :-PC1,0+4NH3 = 2iYH,C1 + P(NH,),ClO When this is treated with water it is oiily necessary to suppose that the action is precisely similar to that given above the two rJtages being probably simultaneous and the resctioii being favoured in this instaaxe by the affinity of the resulting acid and alkali for one another.2P(NH2),C10 + 0 = 2HC1 + P(NH2)20}0 P(NH,),O It will be perceived tlmt hliis pyro-diamic acid is the synl- GLADSTONE ON THE PYROPHOSPHORIC AMIDES. metTical one and that the unsymmetrical pyro-amic and pyro- triamic acids are not to be produced by this kind of reaction. This acid is also formed hrectly by the mutual action of ammonia and phosphoric anhydride. Nothing can be simpler. But P,O is probably also constructed on the water-ty,pe and in that case we shall have- or P2(NH2)2H205, pyroplzosphodiamic acid.The unsymmetrical pyro-amic acid is produced by breaking down t8he symmetiical pyrophosphodiamic acid. P(NH,) (MO)0 P(MO)(MO)O 1o or P,(NH,)M,O, a pyroplzosplmmate. The unsymmetrical pyro-triamic acid is produced from an amidated oxychloride of unknown composition or by the break- ing down of tetraphosphoric compounds. As these have not yet been described I will content myself with writing down the formula of this acid in a manner analogous to its con- geners :-Pyrophosphotriamic acid ;[g;;[;;jg)}0. It is easy to understand how a substance of this cornposition when boiled for a long time with -water or heated with sul-phuric acid parts with one of its nitrogen constituents and becomes the symmetrical pyrophosphodiamic acid.

ISSN:0368-1769    

DOI:10.1039/JS8682100064

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

TRIBE ON FREEZING OF WATER AND BISXUTH. IX-Freezing of Water and Bismuth. By ALFRED TRIBE,F.C.S. PROFESSOR in his work entitled ‘‘ Heat considered TPNDALL as a mode of Xlotion,” after speaking of the anomalous expan- sion of water prior to solidification and the importance of this property in the economy of nature controverts the generally received opinion that no other bodies possess the same pro- perties in this respect and cites bismuth as a case in point. He says at page 84 ‘‘ The fact however is that the case is not an isolated one. You see this iron bottle rent from neck to bottom; I break it with this hammer and you see a core of metal within. This is the metal bismuth which when it was in a molten condition was poured into this bottle the bottle being closed by a screw exactly as ill the case of the water.The metal cooled solidified expwi(Ie,l :tiid the force of its expailsion was sufficient to burst tlic bottle. There are no fish here to be saved still the molten bismuth acts exactly as tlic water acts .7 The experiment as above detailed shows conclusively that molten bismuth expands either on cooling or freezing; but it affords very little or no proof of that ~vliich has been inferred from it. The real question obviously is not whetlier the fluid metal in returning to the solid condition rends an “iron bottle from neck to bottom,” but whether the freezing of water arid bismuth are analogous. The results and details of the experiments which have been made with a view to answer this qnestion form tlie subject of the present communication.To ascertain the general mode of solidification paraffin nitrate chlorate and hydrate of potassium and nitrate of sodium were experimented with. The first experiments were made by simply melting bismuth paraffin &c. in good sized test-tubes. The solidification of the transparent molten substauces on cooling could easily be observed to start from the bottom. The solidification of bis-muth likewise was found to commence at the bottom which TRIBE ON FREEZING OF WATER AND BISMUTH. was ascertained by pouring off the fluid metal after it had somewhat cooled. Water was observed by placing tubes about three-quarters full of the liquid in a freezing mixture-taking care to have the mixture some little distance above the surface of the wat,er.In every experiment solidification began at the surface; but in one especially ice was seen gradually to descend while in the freezing mixture to the bottom. Two or three times during the descent the tube was removed from the freezing mixture which instantly stopped the formation of ice. Thinking the tubes employed favoured the solidification of bismuth &c. at the bottom (there being comparatively a larger surface exposed to the cooling action of the air) the experi- ments were repeated in U-shaped tubes but with the same results. The experiments were likewise made in crucibles again with the same practical results. A slight modification of this form of experiment submitted the metal to it severe and what was considered conclusive test.A crucible three-quarters filled with molten bismuth was placed over a Emall Bunsen’s gas jet and in this way allowed to cool extremely slowly-at the same time cold air was blown upon its surface. It will be seen that this experiment decidedly fiavoured solidification on the surhce ; but the fkeezing of the metal commenced in every caRe at the bottom-the process being repeated several times. At this stage of the inquiry the question presented itself Have the air-currents produced by the heated tubes &c. any-thing practically t,o do with solidification at the bottom. To ascertaiii this tubes filled with melted bismuth and paraffin were placed horizontally in the centre of a cylinder which was then immediately closed.The solidification of the paraffin-it being transparent-could be distinctly seen to start from the bottom. The bismuth was ascertained AS before by pouring off the surface metal. From the foregoing experiments it appears that as a rule substances solidify upwards-water being the exception. Whe-ther water be the only exception it is certain that bismuth follows the rule. With regard to those bodics which commence solidifying at the bottom we are entitled to re;tsoii a8 follows :-As soon as a liquid begins to cool its temperature ceases TRIBE ON FREEZXNG OF WATER AND BISMUTH. to be uniform some particles being more exposed to cooling influences than others. The necessary consequence of this must be a difference in the specific gravity of the different particles which will arrange themselves accordingly.It may be assumed therefore that after a short time the denser particles will be found at the bottom and as solidification begins there the conclusion may be drawn that the point of greatest density coincides with that of solidification and it stands to reason that the particles which solidify first are the coldest. It may be concluded from this that molten bismuth on cooling does not expand before freezing as is the case with water but that it continues to contract down to the solidifying point. The rapid expansion which is well known to all chemists is due to the act of crystallisation. The reason why the metal does not rise to the surface as soon as it becomes solid although specifically lighter is siniply because it adheres to the bottom and sides of the vessel.The two following experiments confirm in a great measure the above deductions Melted paraffin and water at 100" C. were placed in tubes about six inches long closed at both ends with corks and then completely imniersed vertically in cold water for a few minutes. It was found by a thermometer that the top of each liquid was about 3' C. higher than the bottom. Hence the analogy of bismuth with water is not perfect but fails just in that point which causes our rivers and lakes to freeze from the surface and thus protect animal life. The above experiments were principally through the kind- ness of Dr. Gladstone made in his laboratory and I am much indebted to him for many valuable suggestions.

ISSN:0368-1769    

DOI:10.1039/JS8682100071

出版商:RSC    

年代:1868

数据来源: RSC

摘要:

74 PEDLER ON THE ISOMERIC FORMS OF VALEKIC ACID. X.-On the horneric forms of Lhleric Acid. By ALEXAWDER Esq. PEDLER INthe concluding pages of Frankland and Duppa's memoir on Synthetical researches on Ethers," the authors state that ordinary valeric acid rotates a ray of polarized light to the right ; whilst W urt 2; had previously asserted that ordinary valeric acid is without any action upon a polarized ray. To reconcile these discrepant observations F ran kl an d and Duppa suggested that active amylic alcohol yields an active valeric acid when oxidized and inactive amylic alcohol an inactive acid and that the sample of arnylic alcohol from which Wurtz's valeric acid had been prepared was the inactive variety. To test the validity of this suggestion the two amylic alcohols were first separated by Past eur's process and then individually oxidized with a mixture of dipotassic dichromate and sulphnric acid in the usual manner.Equal weights of concentrated sulphuric acid and amylic alcohol were mixed together the amylic alcohol being added very gradually ; the mixture was then allowed to stand for 24 hours and neutralized with baric carbonate so as to form baric sulphamylate. The baric sulphamylate obtained from the active amylic alcohol is as stated by Pasteur about .two and a half times as soluble as that obtained from the inactive amylic alcohol ; the mixed sulphamylates were consequently separated by fractional crys- tallisntion which was continued until the two salts were obtained in a state of purity.Care must be taken to keep the solut<ioiis alkaline by baric hydrate or the sulphamylates will decompose when heated. This process is long and tedious as numerous crystallisations have to be made before the perfect separation of the sulph- amylates is effected. The two amylic alcohols were obtained by decomposing the baric sulphamylates with sodic carbonate and again decom- posing the sodic sulphamylates by ebullition with excess of f Chem. SOC.Journ. vol. xx p. 102. PEDLER ON THE ISOMERIC FORMS OF VALERIG ACID. 75 sulphuric acid. The amylic alcohols thus obtained were purified by drying and rectification ; they then exhibited the following characters :-The amylic alcohol obtained from the less soluble sulph- amylate was found to boil at 129"C.and to have a penet'rating and oppressive odour which produces coughing and a burning taste. In the polai-iscope when tested with a yellow sodium flame it was found to be perfectly incapable of rotating the ray of polarized light. The alcohol obtained from the soluble sulphamylate had a boiling point of 128" C. and an odour resembling that of the inactive alcohol but more fruity; it was however equally irritating and had a burning taste. It was found to rotate a yellow ray of polarized light 17' to the left in a tube 50 cen-timetres long. For the conversion of these alcohols into valeric acid a hot oxidizing mixture was used made by dissolving two parts of dipotassic dicliromate in moderately hot water and then adding three parts of concentrated sulphuric acid.The alcohol was added through a funnel tube slowly the vessel containing the mixture being also connected with a condenser. The inactive alcohol when oxidized was converted into valeric acid and amylic valerate which latter was decomposed by sodic hydrate and the resulting amylic alcohol again oxidized. There was no effervescence when the alcohol was added to the hot oxidizing mixture. The act'ive amylic alcohol when added to the nearly boiling oxidizing mixture was found to effervesce strongly from the evolution of carbonic anhydride. On allowing the oxidizing mixture to cool and then adding more of the alcohol scarcely any effervescence was observed. It was allowed to stand for some hours and then distilled and the distillate was found to contain valeric acid and amylic valerate which latter was again decomposed and oxidized as before.The two valeric acids were freed from the accompanying water which had distilled over with them by neutralizing with pure sodic carbonate evaporating to dryness and decomposing with sulphuric acid. When dried and distilled they had the following characters The valeric acid obtained fiom the inactive variety of amylic alcohol boiled at 1'75" C. and had the characteristic persistent 76 PEDLER ON THE ISOiMERIC FORMS OF VALERIC ACID. * odour and taste of ordinary valeric acid. It was found when tested in the polariscope not to possess the slightest action on the polarized ray.It is highly probable that this acid is identical with the isopropacetic acid prm @( CMe,H)H IL COHO Or {COHO. L obtained by Frankland and Dnppa and described in their memoir before mentioned. The boiling points of inactive valeric acid and of isopropacetic acid are identical. The valeric acid from the rotating amylic alcohol boiled at about 170' C. and had t,he same disagreeable odour and taste as the inactive acid. When tested with the ray of polarized light it gave a right-handed rotation of 43 degree8 in a tube 50 centimetres long. The above observations with the polariscope were most kindly takeii by Dr. Frankland to whom my most cordial thanks are due. In order to ascertain the products of the graduated oxidation of the two amylic alcohols some experiments were made by digesting them in sealed tubes at 100" C.with ordinary chromic acid oxidizing mixture. When the rotating alcohol was thus treated it evolved abun-dance of carbonic anhydride and produced a large amount of acetic acid ; while the inactive alcohol which when similarly digested gave a mere trace of carbonic anhydride seemed to produce scarcely anything but valeric acid. The above experiments therefore indicate either that the non-rotating valeric acid of W u r t z had been made as suggested by Frankland and Duppa from a non-rotating sample of arnylic alcohol; or that the acid made fiom the mixed alcohols had been allowed to remain in contact with the hot oxidizing mixture sufficiently long to destroy the whole of the less stable rotating acid. In a future paper I hope to be able to give a more detailed description of the oxidation products of the two alcohols together with a comparison of the properties of the salts obtained .from the two acids.

ISSN:0368-1769    

DOI:10.1039/JS8682100074

出版商:RSC    

年代:1868

数据来源: RSC