摘要:

THE QUARTERLY J 0 U R N i4 L OF THE CHEMICAL SOCIETY OF LONDON. B. C. BRODIE F.R.S. A. W. HOFMANN PH.D. F.R.S. THOMAS GR.AHAM F.R.S. A. W. WILLIAMSON F.R.S. LON DON HIPPOLYTE BAILLIERE 219 REGENT STREET AND 290,UROADW-AY NEW TOL~K,us. PARIS J. B. BAILLIERE XiUE I1AUTEFEUILJ.E. MADRID BATLLY BATLLIERF CALLE DEJ. PRIWCIPP. 1855 LONDON WILSONand OQILVY. Skinner Street. CONTENTS OF THE SEVENTH VOLUME . PAGE On tho Con3titut;on of Acids nnd Balts. By William Odling. M.B. F.C.S. 1 On the Platino-tersulpl!ccyanides and tho Plstino.bisulphocyanides two new series of salts. and their decompositions . B y George Bowdler B11c k t on .F.L.S.........................................................................22 Analjsis of the Ash of Lemon.Juice . By Henry M.Witt ........................ 44. Note on Platinum accompanying Silver in solution in Nitric Acid. BJH.How 48 Note on the Valuation 01 Protochloride of Tin . By Dr.Penny .................. 50 On the so-called Iodide and Chloride of Nitrogen . By J.H. Gladstone Ph.U. F.R.S. .......................................................................... 51 On soine New Compounds of Salicyl. By Charles Gerhardt ..................... 60 On the existence of Trimethylamine in the Brine of Salted Herrings . ByGersham Henry Winkles ......................................................... 63 On th Action of Iodide of Ethjl on Toluidine. By Reginald T. Morley and John S.Abel .....................................................................68 On Red Prussiate of Potash. By William Wallace .............................. 77 Proceedings at the Meetings of the Clhemical Society ................................ 81 Notices of Papers contained in other Journals :-On a New Saline Compound of Cobalt. By E. St.E v re ........................ 86 On the Ltecoinposition of the Cyanic Etlicrs. By A .W u r t z .................... 91 On Selenide of LstIiyl or Selentthyl . By C. A.J oy .............................. y3 On tlie formation of Amarine Furfurine. aiid a new Base Anisine . ByC. 13ertagnini.......................................................... 95 On the VolatiIe Bases produced by Destructive Distillation of t.lie Bituminous Shale of Dorsetshire. By C.Gi-eville Williams .............................. 07 On Caprglnmine. By William S.Squire ............................................. 108 Critical Observations on Williamson’s Theory of Water Ethers and Acids. By I3.Kolbo ........................................................................... 111 On Dr.Kolbe’s Additive Forinule . By Alexander VVilliamson P1i.I). ... 122 Proceedings at the Meetings of tlie Chemical Society ................................ 140 Stat emen t of Accounts........................................................................ 160 Notices of Papers contained in ot. her Journals :-Chemical Analysis of the Mineral Waters of Harrogate. By A W .H o f m a n n.. 161 Note on the Decomposition of Sulphuric Acid by Peiitachloride of Phosphorus.By Alexander Williamson. Ph.D.,F.C.S. ............................ 180 On the Action of Chloride of Cyanogen on the Ammonia.bases . By A.Cah ours On the Formation of Nitride of Uensoyl from Hippuric Acid . By Dr.L i m . pricht and Von Uslar ................................................ 191 On the Alcohol corresponding to Benzoic Acid . By S.C a n n i z z a r o.......... 1y~ On an Alcohol in the Wax of the Copernicia cerifera. By Ibf .8.Mask e 1 y n e .. 192 On the Composition of a Specimen of Atmamite from the provino? of Copiapo.Chili. By Frederick Field ......................................................... 193 On the Corrosive Action of Sugar on .Iron and other Metals . By J. H. Gladstone Pl~z). F.R.S .............................................................195 Preliminary Notice on the Action of Ammonia on the Oils and Fats . ByThomas H. Rowney. Ph.D. F.C.S. ............................................. 200 On the Substitution-Compvunds obtained by the Action of Nitric Acid on Cotton. By Edward Ash Hadow .......... ............................. 301 On a New Metliod of Est. imating Sulphur . By William J.Russell F.C.S. . 212 On some New Compoundsof Phosphorous Add . By Robert Railton. 8.C.S. 216 On Nitroglycerine and the Products of its Decomposition by Potash. ByRobor t Railton F.C.S. ............................................................ 222 On some New Derivatives of Chloroform . By George Kay ........................ 224 On the Constitution ofCommercia1 Creosote from Coa1.tar .By Jas . Fairlie 232 On some New Compounds of Phenyl. By Henry Scrugham .................. 237 M a gn u s ’s Gas Apparatus for Organic Analysis .............................. 250 On the occurrence of Ozone and Peroxide of Hydrogen in the Electrolysis of Sulphuric Acid . By Heinrich Meidinger ............................ 251 New Researches on the Metals .acco~npatiyiilg Jlatinnm in the Ore. By E . Fremy................................................................ 256 Arsenides of Etbyl or Arsenethyls. By H a n s La n d o 1t .................... 268 Plumbides of Ethyl. or Plumbethyls. By K a r 1 L ii wig ...................... 268 Researches in Organic Chemistry . By A d o 1p h Y t re c k e r .................... 271 On the Compounds of Glycerine with Acids .By M .H e r t h e 1o t .............. a82 On Caprylic Alcohol and its Derivatives . By J.B ou i s ........................ 286 On the Produce obtained from Barley down in Rocks of various ages . ByCharles Daubeny. M.D. F.R.S. F.C.S ........................................... 289 Notice of further Experiments as to the Reduction of Metallic Oxides by the Peroxide of Barium. By B.C.Brodie F.R.S.................................. 304 Analysis of a Surface-soil from the Desert of Atacaxia . By Frederick Field 308 On some of t. he Thermo-electric Properties of the Metals Zinc and Silver . By Richard Adie ....................................................................300 On the Preparation of Methylic Alcohol . By William Gould ..................311 Proceedings at the Meetinga of the Chemical Society ................................. 313 Titles of Chcmical Papers in British and Foreign Journals ........................ 316 Index .............................................................................................378 Anniwreary Mcei ing ........................................................................14.4 President’s Address ........................................................................... 144. and Cloez................................................................ 15.1- On a New Series of Sulphuretted Acid6 . By Dr.A u gu 6 t K e k u 1C ............ iris iv CONTENTS . PA QE Chemical Notes . By James Spencer ................................................... 2M Notices of Papers contained in other Journale :-

ISSN:1743-6893    

DOI:10.1039/QJ85507FP001

出版商:RSC    

年代:1855

数据来源: RSC

摘要:

MR. 0;. B. BUCKTON ON 11.-On the Ptatino-tersulphocyanides and the Platino-bisulpho-cyanides two new series of salts and their decompositions. BY GEORGE BOWDLER F.L.S. BUCKTON Although the salts of platinum have been pretty closely studied by chemists and are perhaps found to be more numerous than those of any other metal there is some room for surprise that scarcely any attention has been paid to their action upon sulphocyanogen com- pounds. The only notice I have been able to find of a sulphocyanide of platinum is that made by Grotthus and quoted by Brande stating it to occur as a bulky flocculent precipitate of a yellow colour soluble in acids and in solutions of chloride of potassium and sodium but thrown down again from these solutions by alcohol.Hitherto I have not met with a substance answering these properties unless it should prove to be identical with that last described in this paper. The addition of bichloride of platinum to a cold solution of sulpho-cyanide of potassium alone gives rise to the ordinary double salt chloroplatinate of potassium with disengagement of hydrosulpho-cyanic acid. If on the other hand a strong solution of sulphocyanide of potassium be previously heated to 70' or 80' C. there is no precipitation but the liquid changes to a deep port-wine-red colour accompanied with a rise in temperature. On standing this solution deposits a multitude of brilliant red or gold-coloured plates which are very soluble in hot water. By this process much waste of sulpho-cyanide of potassium is unavoidable from the presence of free hydro- chloric acid which also decomposes the new compound into a brown flocculent precipitate if the temperature rises above a certain point.A more profitable operation consists in dissolving in a moderate quantity of water five parts of pure sulphocyanide of potassium weighed in an anhydrous state which is best obtained by fusion. Four parts of dry chloroplatinate of potassium are then added by degrees to the solution combination with which may be promoted by THE PLATINO-SULYHOCYANIDES. a heat regulated below the boiling point. A deficiency of the sulpho- cyanide must be carefully avoided as in such a case the above-mentioned brown product is an invariable result rendering the purification of the crystals exceedingly difficult.After filtering the hot liquid it is set apart to cool when the new salt is deposited in beautiful and regular hexagons often of a large size. To remove traces of chloride of potassium one product of the reaction the crystals may be redissolved in boiling alcohol and passed through a filter surrounded with hot water a necessary precaution to prevent obstruction from a too rapid crystallization. The solid salt dissolves in 12parts of water at 60' C. but is far more soluble in boiling water and still more so in hot alcohol. The crystals which are of a deep carmine red belong to the rhombohedra1 or three and one-membered system. From the alcoholic solution they often take the form of double six-sided pyramids united base to base with apices truncated ; but the aqueous solution usually furnishes hexagonal plates.With access of air this substance ignites at a very gentle heat with a blue sulphurous flame and peculiar odour. A red heat resolves it into sulphocyanide of potassium gaseous products and reduced platinum In common with all the soluble salts to be described it has an exceedingly nauseous taste and the colour is so intense that one drop of a saturated solution will give a distinct yellow tinge to a gallon of water. A pure solution does not strike a blood-red colour with sesqui- chloride of iron; but such a mixture becomes nearly black and opaque on heating from the forniation of a substance in heavy lustrous grains. Caustic potassa converts the red salt into a red gelatinous mass without evolution of ammonia which however is freely dis- engaged on ignition with soda-lime.Acted on by hydrosulphuric acid the salt is resolved into hydrosulphocyanic acid sulphocyanide of potassium and bisulphide of platinum. It is also decomposed by concentrated sulphnric and hydrochloric acids. The action of nitric acid will be afterwards referred to. The dry salt is quite permanent at ordinary temperatures ;but from its inability to bear a high degree of heat without decomposition most of the compounds to be described were dried in vacuo over sulphuric acid previous to analysis. The potassium was separated by precipitating the new acid with nitrate of silver. After removing the excess by hydrochloric acid the alkali was weighed in the form of chloroplatinate of potas-sium.BIR. G. B. BUCKTON ON The platinum was determined by .igniting the bisulphide preci-pitated by sulphide of ammonium. The carbon was estimated by burning the substance in a stream of air and oxygen observing the usual precautions for absorbing traces of nitrous and sulphurous acids. And here I may be allowed to bear a grateful testimony to the readiness and convenience in determinations of this kind afforded by the gas-furnace for organic analysis lately constructed and described by Dr. Hofmann. From the abrupt decomposition and presence of both sulphur and nitrogen in the substances to be noticed their determinations may be said to present more than usual difficulty.Attention however to slow burning is all that is necessary in these cases to procure accurate results. By the simple addition of another tube and piston nitrogen determinations may be also coil- ducted Rith great neatness and accuracy. The sulphur was determined by oxydizing the substance with chlorate of potassa and hydrochloric acid assisted by gentle heat. Sufficient boiling water was then added to hold in solution any chloroplatinat,e that might be formed and the precipitate from chloride of barium was filtered off whilst hot. This method was found to obviate the tedious washings which are necessary when fuming nitric acid or a nitrate is employed Its substitution is strongly recommended in the analysis of volatile sulphuretted com- pounds.I. 0.7554 gnn. of substance gave 0.6030 pn. of chloroplatinate of potassium. I. 0.7050 , , , 0.2230 , platinum. 11. I0.9132 , , , 0.2876 , platinum. 111. 0.5980 , , , 0.1900 , platinum. I. 1.0900 , , , 0.4582 , carbonic acid. 11. { 1.0160 , , , 0.4390 , carbonic acid. J. ‘0.7264 , , , 1.5705 , chloropiatinate of ammonium. 11. 1.0044 , , , 2.1888 , chloroplatinate of ammonium. 111. t 0.6628 , , , 1.4492 , chloroplatinate of ammonium. 1. 0.5628 , , , 1.2600 , sulphate of baryta. 11. 0.4030 , , , 0.9096 , sulphate of barj-ta. The corresponding percentages to these nurnbers are 1. 11. 1x1. 7 I Potassium 12.73 Platinum 31 -64 31*49 31.77 Carbon 11.64 11-78 -Nitrogen 13.54 13.56 13-66 Sulph UP 30.70 30.96 -The carbon nitrogen and sulphur are therefore in the proportion THE ,~LBTTNO-SULPHOCYANIDES.to constitute three equivalents of sulphocyanogen. Their union with one equivalent of platinum forms the new radical which takes up another equivalent of potassium in constructing the above salt. The name proposed for the new substance is ptatino-tersukhu-cyanide of potas&m and the formula KPtC6N3S6 or KPt 3 CyS,. The theoretical and experimental numbers are subjoined : -Theory. Experimental mean. P equiv. of potassium 39 12.52 12-73 1 , platinum 99 31.73 31.63 6 , carbon 36 1‘1.53 11.72 3 6 , , nitrogen sulphur 42 96 - 13.46 30.76 13.58 30.83 312 I oo*oo There has been therefore in the reaction a simple substitution of 3 equivs.of sulphocyanogen for 3 equivs. of chlorine in the ehloro- platinate of potassium employed Expressed in equation ; K PtCl + 3 KCyS,= KPt 3 CyS + 3 KCI. An interesting method of controlling this formula presented itself in estimating the quantity of sulphocyanogen in the compound thus comprising in one analysis the whole of the carbon nitrogen and sulphur present. A solution of the salt was precipitated by sulphide of amtnonium and heated on the water-bath until all trace of free ammonia was lost. After adding acetic acid the bisulphide of plati-num was filtered off and the clear liquid treated with nitrate of silver. The formation of acetate of silver was prevented by addition of a few drops of nitric acid. 0.7150 grms. of substance gave 1.1275 grms.of sulphocyanide of silver equiv. to 0.3999 grms. of sulphocyanogen. Calculated for 100 parts. Required. Found. 3 equivs of sulphocyanogen 55.76 55 90 We may therefore safely infer the correctness of the following equation MR. G. B. BUCKTON ON Subplatino-tersulphocyanideof mercury appears immediately as a copious curdy precipitate on adding nitrate of suboxide of mercury to a solution of the new potassium salt. It is of a deep orange colour which changes to a pale primrose-yellow on raising the liquid to ebullition. After washing it was gathered on a filter pressed with paper and dried in uacuo over sulphuric acid. Freed from water it will bear a considerable temperature without change. Heated in the air-bath to between 140' and 150' C.it suddenly swells up into a singular metallic and arborescent looking substance showing some resemblance to coarse tea.* At the same time there is a rush of gas which spontaneously kindles. No further change is observed up to 250' but below redness mer-curial fumes and cyanogen gas are liberated; and finally if exposed in an open crucible the mass fires like tinder leaving a residue of platinum. I. 0.5150 grm. of substance gave 0.1076 grm. of platinum. ,f rr. POOIO , , 0.2120 , platinum. 111. 0.9734 , ?? , 0.2052 , platinum. $9 IV. 0.9024 , , 0.2531 , carbonic acid. which expressed in 100 parts give I. 11. 111. IV. Platinum 20-87 21.19 2 1 *08 -Carbon --7.68 agreeing with the formula -Theory. Experimental mean.2 equivs. of mercury 1 , platinum 6 , carbon 200 99 36 42-28 20.95 7.61 -121.04 7.68 3 6 , , nitrogen sulphur 42 96- 8.87 20.29 - 473 100*00 In common with all the examined salts of this series subplatino- tersulphocyanide of mercury yields by dry distillation in a retort the * I have not been able sufficiently to examine this compound or arrive at any certain formula. I will only mention that 0.7092 grm. gave by ignition 0-1662 grm. of plati-num which is equivalent to 23-49 per cent. THE PLATTNO-SULPHOCYANIDES. beak of which is placed under water much bisulphide of carbon. This circumstance together with the fact verified by experiment that nitrogen also is a product explains the brisk evolution of gas and ready inflammation of the substance noticed above.The nitrogen gas was identified by conducting the reaction in a sealed tube and sub- sequently collecting the gas over water. Platino-tet.sulphocyanide of Iron.-When a slightly acid solution of sulphate of iron is added to a concentrated solution of platino-ter- sulphocyanide of potassium a black crystalline substance falls which is insoluble in water and also in alcohol. Under the microscope these grains appear as shining six-sided figures with rounded edges. They are not affected by dilute sulphu- ric hydrochloric or nitric acid but concentrated nitric acid dissolves them with formation of sulphuric acid. A cold solution of potassa converts them into sesquioxide of iron and a yellow liquid containing platinum and sulphocyanogen.To estimate the platinum in this salt a weighed portion was dis- solved in aqua regia and after dilution with water hydrosulphuric acid was passed in excess and the precipitate ignited. The filtrate treated with ammonia gave the iron as sesquioxide. The other analyses were made in the usual manner portions from different pre- parations being employed. I. 0.9966 ps. of substance gave 0.1334 grms. of sesquioxide of iron. I. , 0.3317 platiiium. 9) 1 ? 0.1426 sesquioxide of iron. 31. 6 1-(288 1s 11.1 , 0.3412 platinum. , 0.1448 sesquioxide of iron. 1 , 0.4321 carbonic acid. ?f ,? ? 0.4475 carbonic acid. T. 1.0044 , ? ,) 2.1888 chloroplatinate of ammonium. 11. [ 05956 , ?? ,? 1.3360 chloroplatinate of ammonium.11 I. 1*03172 , , 1.6775 sulphate of baryta. The percentage composition is I. XI. 111. Iron 9.35 9.51 8.99 Platinum 33.29 33.16 Carbon 11.85 11*60 Nitrogen 13.50 13.96 Sulphur 32.08 The formula is FePt 3CyS,. MR. G. B. BUCKTON ON The theoretical and experimental numbers are Theory. Experimetal Mean. 1 equiv. o f iron 28 9.30 9-28 1 , platinum 99 32.90 33 23 6 , carbon 36 1 1*96 11.73 3 , nitrogen 42 13.95 13.73 6 , sulphur 96 31.89 32.08 301 f 00.00 A substance exactly similar in appearance and general character is produced by substituting the salts of the sesquioxide of iron. It falls however only 011 boiling the mixed solutions. A qualitative examination is all that I have been able to bestow upon this com-pound.Platino-tersul~hocyanideof Silver is prepared by decomposing a solution of the potassium salt by nitrate of silver. It is a heavy curdy substance of a deep orange colour which shrinks and aggluti- nates into a tenacious mass when boiled in water but again hardens on cooling. Agentle heat causes the dry salt to swell much igniting with a blue flame if air be present. It is fusible by the blow-pipe into a metallic bead of platinum and silver by which behaviour it may be readily distinguished from the mercury salt. When recently precipitated it is soluble in cold ammonia but decomposition ensues at a higher temperature. Nitric acid also acts energetically upon it with disengagement of binoxide of nitrogen ; a yellow substance is thrown down; and sulphuric acid is formed during the re-action.The behaviour of hot caustic potassa towards the silver salt pre- sented a convenient method of estimating the proportional quan-tities of the platinum and silver contained. By this treatment 1 equiv. of platino-tersulphocyanide of silver is resolved into 3 equivs. of sulphocyanide of potassium with precipitation of binoxide of platinurn and oxide of silver in the form of a black heavy powder. Ag Yt3(CyS,) +3KO=3 (K,CyS,)+PtO,+AgO. 0.6513 grm. of substance gave by igniting the oxides 0.3538 , platinum and silver. 0.9038 , substance gave by ignition in oxygen and air 0.3061 , of carbonic acid. THE PLATINO-SULPHOCTANIDES. This accords with the above formula for the silver-salt thus : -Theory.Found. 1 equiv. of silver 1 , platinum 991 54.33 5432 6 , carbon 36 9.44 9.10 3 , nitrogen 42 11912 -6 , sulphur 96 25.11 -381 100*00 Here it may be mentioned that the platino-tersulphocyanides in many respects bear a strong resemblance to the sulphocyanides. ,4s an example it may be noticed that both their silver salts form double crystallizable compounds with sulphocyanide of potassium. The parallellism of these two substances is further carried out in their immediate decomposition by dilution with water. In the case of the double sulphocyanide of silver and potassium a simple separation of the two salts takes place every trace of silver being thrown down as sulphocyanide. In the double platinum compounds the reaction consists in a transfer of the potassium to the platinum acid and precipitation of the silver as sulphocyanide.This last substance (the product of the latter experiment) was identified by analysis as well as by a careful examination of its properties.* The clear red liquid filtered from the precipitate consisted of a solution of platino-tcrsulphocyanide of potassium. Expressed by an equation it stands thus Ag Pt 3 (CyS,) + KCyS2=AgCyS,+ KPt 3 (CyS,). Platino-tersulphocyanide of silver is insoluble in an excess of platino-tersulphocyanide of potassium. Plutino-tersu~hocyanideof Lead.-This is a remarkably beautiful substance thrown down in the form of innumerable golden plates on uniting the concentrated solutions of acetate of lead and platino-ter- sulphocyanide of potassium.The crystals which are minute but I. 0.8594 grm. of precipitate burnt in oxygen and air gave 0,2164 , carbonic acid or 6.87 per cent of carbon. 11. 0.8548 , precipitate burnt in oxygen Cyrc,. gave 0.2196 , carbonic acid or 6.99 per cent of carbon. Sulphocyanide of silver requires Calculated. Experimental mean. Carbon 7.23 6-94 MR. G,B. BUCKTON ON very regular hexagons are soluble in alcohol but less so in cold water with which they should be well washed on the filter for purifi- cation as recrystallization from a hot solution does not offer a good method from the speedy deposition of sulphate of lead and disengage- ment of hydrosulphocyanic acid an explanation of this decompo- sition will be offered when we treat of the salts of the next series.The general properties of platino-tersulphocyanide of lead are such as might have been anticipated from the examination of the iron and silver compounds and leave no doubt of its composition. Attempts were made to obtain analytical numbers but from the difficulty of procuring the substance chemically pure they are not sufficiently accurate for insertion. A subsalt of a brilliant red colour insoluble in water and in alcohol is precipitated on substituting the subacetate of lead for the neutral acetate. Its ready solubility in dilute nitric or acetic acid presented the most ready method of estimating the lead in combi- nation by precipitation as sulphate. 05000 grm.of substance gave 0.3100 grm. of snlphate of lead equivalent to 42.36 parts of lead in 100. If reliance may be placed upon this single analysis it satisfactorily points to the basic sulphocyanideof lead as its analogue. The formula for the new compound thus would be Pb Pt 3(CyS,) +PbO which requires for Theory. Experiment. 2equivalents of lead 43.36 43-46 A substance similar in properties but much paler in colour may be procured by the addition of ammonia (not in excess) to the solution of platino-tersulphocyanideof lead. Hydroplatino-tersu~hocyanicacid is most conveniently procured by precipitating a warm concentrated solution of platino-tersulpho-cyanide of' lead by sulphuric acid. The filtrate which is of a fine red colour contains tbe new acid which is capable of forming all the salts above described and deports itself in the usual manner of a true acid.From its deep hue it can be scarcely proved to redden litmus paper but it presents a decided sour and then very rough taste to the tongue. It freely displaces carbonic acid from the alkalies and dissolves metallic zinc with liberation of hydrogen and pro-duction of a bright yellow insoluble compound hitherto unexamined. When concentrated on the water-bath decomposition speedily com- THE PLATINO-SULPHOCYANIDES. mences; and on approaching dryness a brown amorphous mass very rich in platinum remains in the dish. By gentle distillation an acid liquid passes over in considerable quantity accompanied with the odour of hydrocyanic acid.The distillate furnished with nitrate of silver a copious white precipitate which on examination proved to be a mixture of cyanide and sulphocyanide of silver. The aqueous and alcoholic solutions of this acid undergo exactly similar reac-tions at ordinary temperatures and for this reason I have hitherto failed in procuring the acid in the solid state. By rapid evaporation in the air-pump over sulphuric acid a confused semi-crystalline mass was obtained; but this gave very little hope of furnishing numbers likely to prove the exact constitution of the acid in its solid condition. P~atino-tersu~hocyanide of Barium is a deep red substance crys-tallizing in long flattened prisms or in broadlaminze often of con-siderable size. Obtained by dissolving three parts of dry platino-tersulphocyanide of potassium in the solution of one part of chloride of barium in water or as an excess of the latter is desirable it may be in the proportion of nine to four.After evaporation at a gentle heat the mass may be extracted with hot alcohol which dissolves nothing but the new salt. It does not appear to be so stable as the pot assinm-compound. Platino-tersu~hocyanideof Ammonium.-The preparation of this salt by direct union of the acid and base is difficult; that by double decomposition however is very convenient. One part of dry sul- phate of ammonia may be boiled for a few minutes in a moderately strong solution of 3.5 parts of platino-tersulphocyanide of potassium. The new salt on cooling may be separated from the sulphate of potassa and sulphate of ammonia the last of which is purposely in excess by alcohol..Another solution in hot water is requisite to obtain it pure from which the new substance is produced in beautiful crimson hexagonal plates in figure much resembling thepotassium-salt. It is quite stable at ordinary temperatures but the odour of sulpho-cyanic acid is readily perceived on boiling the aqueous solution. It gives a!l the reactions of the potassium-salt. 0.5121 grm. of substance dried in vacuo,gave 0.1150 grm. of platinum. 0.8615 , ,) burnt in oxygen and air 0.3838 , carbonic acid. I , , burnt in oxygen 0.1212 , water. clearly indicating the f ormula NH Pt 3CyS,. MR. G. 3. RUCRTON ON The theoretical and experimental numbers are Theory.Experiment. n-1 equiv. of platinum 99 34-02 34.1 7 6 , carbon 36 12.37 12-14 4 , hydrogen 4 1038 1-56 4 , nitrogen 56 19.24 -6 , sulphur 96 32.99 -291 1oo*oo Platino-tel.su~hocyanideof Sodium is best procured by precipi- tating the lead-salt with sulphate of soda. It readily crystallizes in broad garnet-coloured tables which are soluble in alcohol and in water. Platino-tersulphocyanide of Copper is precipitated by mixing solutions of sulphate of copper and platino-tersulphocyanide of po-tassium. It first appears of a brickdust-red colour which speedily changes at the boiling-heat of the liquid to a black insoluble powder. It gives a fine green solution with ammonia but thesaddition of hydrochloric acid reproduces the copper-salt of a dark brown tint.General remarks upon the foregoing compounds are perhaps better deferred until something has been said with reference to the members of another series which have arisen from the search after analogous compounds to be obtained from protochloride of platinum. I proceed therefore to the consideration of Platino- bisulphocyanide of Potassium.-Sulphocyanide of potas-sium dissolves protochloride of platinum with the production of great heat. A red liquid is formed which by gentle evaporation yields crude crystals of a substance showing in a less marked degree the cha- racteristics of the former group. As in the last case the best method for procuring it consists in acting upon the double-salt of proto- chloride of platinum and chloride of potassium (chloroplatinite of potassium*) with sulphocyanide of potassium.They may be taken in equal parts provided the latter contains no carbonate of potassa or other impurity. It is only necessary that it should be in excess. As the new salt is exceedingly soluble and crystals are not well obtained by evaporation the sulphocganide should be used as a concentrated solution and not too much of the platinum-salt added at a time so as to keep the temperature within moderate limits. A * This is ?rest obtained by neutralizing the hydrochloric solution of protochloride of platinum witti carbonate of potassa. THE PLITINO-SULPHOCYANTDES. mass of small needles is deposited on cooling which should be purified from chloride of potassium by strong alcohol from which again the salt is best recovered by spontaneous evaporation.After pressing between paper to remove excess of sulphocyanide of PO-tassiurn the salt may be once more obtained by gentle evaporation from an aqueous solution. The crystals appear in stellar groups and under the microscope show tapering six-sided prisms of a fine red colour although not so intense as is observable in the potassium-salt of the prior series. At 60' F. they readily dissolve in 24 parts of water but their solubility increases at a higher temperature and in warn1 alcohol they are soluble to any extent. They are not deliquescent neither are they when perfectly dry apparently affected by a tempe-rature of 100' C.; nevertheless for analysis it was preferred to dry them over sulphuric acid in the usual manner.Nothing worthy of remark is to be observed with reference to the method of obtaining the numerical 'details here appended. 0.0132grm of substance gave by igniting the precipitate from sul-phide of ammonium 0.3920 , platinum. The filtrate evaporated with sulphuric acid gave 0.3455 , sulphate of potash. 1-0055 , substance ignited in air and oxygen gave 0.3446 , carbonic acid. 0.7060 , substance i nited with soda-lime gave : J.g 1*2000 , chloroplatinate of ammonium. 0-5140 , substance digested with chlorate of potash and hydro- chloric acid gave 09540 , sulphate of baryta. The numbers for 100 parts give results which agree most iiearly with the formula KYtC,N2S or KPt 2 (CyS,).Theory. Experiment. \ I equiv. of potassium 39-15.38 15.27 1 , platinum 99 38.98 38.78 4 , carbon 24 9.44 9.34 2 , nitrogen 28 1 1.02 10.66 4 , sulphur 64 25.18 25.44 254 100*00 VOL. VII.-NO. xxv. n Mlt. G. B. UUCKTON ON The constitution of this salt is therefore quite in accordance with what might be expected from the modification in its construction and since 2 equivs. of sulphocyanogen are found to replace 2 equivs. of chlorine the circumstance may be employed as a distinction in its name. For the compound last-described I propose the designation p2atino-bisul3Jhocywnideof potassium and for its corresponding acid hyd;l.oplatino-bisu~ho~~unic mid which although not euphonious has the advantage of expressing the arrangement of its ele-ments.The solution of the pure salt is orange-red a port wine colour denotes impurity. It copiously precipitates silver and copper-salts the former of a pale yellow the latter of a purple-black. No visible change is produced an the nitrate of the suboxide of mercury except in giving a red tinge to the liquid; and no charac- teristic precipitates are formed with nitrate of lead or protosnlphate of iron which behaviour marks it off from the platino-tersulpho- cyanide of potassium and furnishes some good distinguishing tests. It forms a yellow heavy compound with subacetate of lead which is readily soluble in acetic and other acids. PZatino-bisuEiu~ocyaiiide of Silver was examined as a control to the formula of the potassium-salt.It is a curdy subslance not unlike sulphocyanide of silver partially soluble in ammonia with decom- position. It is soluble in sulphocyanide of potassium which solution appears to undergo the same change on dilution with water as is observable in the corresponding silver-salt of the previous series. I. 0.7114 grm. of substance dried in vamo and fused with carbo-nate of soda gave 0.4552 reduced platinum and siIver. 11. 0.9518 substance ignited in air and oxygen gas gave 0*2324 carbonic acid. 111. 1.0137 substance !gnited in air and oxygen gas gave 0.2595 carbonic acid. IV. 0.6106 substance ignited with soda-lime gave 0.8316 chloroplatinate of ammonium. 'v. 0.4454 substance gave by ignition with chlorate of potash 0.6084 sulphate of baryta.VI. 0*4?494 substance gave by ignition with chlorate of potash 0.6360 sulphate of baryta. Tli E PLAT1 NO-SULYHOCYAN IDES. Expressed in percentage composition I. 11. 111. iV. V. V1. Silver ] 63.98 --Platinum Carbon -6.89 6.98 --Nitrogen --8.53 -Sdphur --19.38 19.41 These indicate the formula Ag Pt 2(CyS,) as may be seen by comparing the results found with the theoretical requirements. Theory. Experimental -mean. 1 equiv. of silver 108 64,08 63.98 1 , platinum 99 J 4 , carbon 24 7.45 6.94 2 , nitrogen 28 8.66 8.53 4 , sulphur -64 29-81 7940 323 100*00 It is scarcely necessary to mention that the salts of both acids fom powerful detonating mixtures with chlorate of potassa.Thc platim- tersulphocyanide of silver in particular inflames with the sliglitcsL friction in a mortar accompanied with a bright flame and loud report. Care is therefore necessary in preparing a mixture for analysis by a large dilution with carbonate of soda. Hydroylatino-bisulphocyanic ac.id.-This is best procured by a cautious decomposition of the baryta salt with dilute sulphuric acid. The aqueous solution is speedily decomposed by evaporation even in vacuo during which process there is an oxidation of the sulphur at the expense of the water. A red or yellow insoluble deposit rich in platinum and hydrosulphocyanic acid are the principal bodies formed the former of which will be noticed in treating of the action of' oxidizing agents.This tendency to absorb oxygen has been slightly touched upon whilst remarking the almost spontaneous decomposition of platino-tersulphocyanide of lead into sulphate of lead and other products. Sonic knowledge has been also gained whilst searching for an c*spltlnatioiiof the frequcnt cscaye of carbonic acid attendiitg the solution of chloroplatinate of potassium in sulphocyanide of7 potassium. This effervescence has been traced to the carbonate of ptassa rnore or less present in the last salt even when crystallized from alcohol. It was also found that solutions of platino-tersulphocyanide of potassium assisted by gentIe heat react in a similar manner upon the carbonate with a partial decolorization of the liquid.A red salt crystallizes out which in 110 way differs from pIatino-bisulpbocyanide of potassium whilst the presence of both sulphate and sulphocyanide of potassium is recognized in the filtrate. The first; action seems to corisist in the partial abstraction of sulphocyanogen from the platino- toiwdphoeyanide reducing it to that of the ~ec~nd series. Part of this sulphocyanogen combines with part of the potassium. The sulphur in another equivalei-st is acted upon by the liberated oxygen forming sulphate of potassa whilst the cyanogen is left to combine with the remaining potassium. The carbonic acid escapes as such. This rather complex action may be expressed in an equation which satisfies all the requirements 6(K Pt 3CyS,)+8 (KC0,)=6(K,Pt2CyS2)+Z(KS0,) -I-5 (KCy S,) + KCy + 8CO,.A slight modification also represents the change observed in the Xibad-salt by ebullition with water. The sulphuric aeid formed by secondary action isolates the platinum acid 6 (Pb Yt 3Cy S,) + 8 H0=6 (Yb,Pt 2Cy S,) +Z (HSO,) +-5 (EICyS,) i-HCy. Long-continued boiling of the aqiieous solution of platino-tersul-phocyanide of potassium furnishes also the same result. Actiorb qf Ammonia upon the platino-sztlphocyunides,-The be-haviour of this alkali towards these compounds is interesting and differs niaterially from that shewn by bases in general or the fixed alkalies. If carbonate of ammonia be added to a cold saturated solution of ptatino-tersulphocyanide of potassium the liqaid after the lapse of a few minutes fades in colour to a pale yellow; an effer- vescence sets in; and after two or three hours a considerable quantity of yellow needles radiate in all directions.The same effect is more expeditiously obtained by using caustic ammonia; but in this case it should not be in R state of coricentration as an insoluble yellow siibstance generally contaminates the product and mnch reduces its quantity. These crystals thrown on a filter may be well washed in cold water in which they arc hut 'tittle soluble and dried without TH E PLAT1NCbP ULP H OCYA IY 11) E S . 37 heat. If required of great purity they may be again dissolved in warm alcohol which takes up more of the substance than water. The crystals obtained by this second operation however are never so large but are of a finer colour.The microscope shews them to be long rhombic prisms. Heated in a dry test-tube they are resolved into free ammonia hydrocyanic acid and with access of air sulphurous acid and metallic platinum. No trace of bisulphide of carbon could be recognized under this treatment which is a departzlre from the behaviour of the piatino-sulphocyanides in general and indicates a separation from the group. 0.4885 grm.of salt dried ile vucuo gave on ignition 02772 , platinum. 0.8092 , salt ignited with oxygen and air gave 0.1986 , carbonic acid and 01320 , water. 0,5137 , salt from another sample gave with soda-lime 1.3033 ) chloro-platinate of ammoniuni. 0.4578 , salt ignited with chlorate of potassa 0.6192 , sulphate of baryta.The formula deduced from the percentage composition is PtC H N2 52 which requires Theory. Experirnent. 1 equiv. of platinum 99 56.89 56.74 2 , carbon 12 6.89 6.69 3 hydrogen 3 1.74 1.81 2 , nitrogen 28 16.09 15.89 2 ) sulphur 32 18.39 18.55 -174 100~00 This sabstance shows therefore a departure from the general series and indicates a splitting up into compounds of a different type. An examination of the filtrate after careful addition of hydrochloric acid plainly proved that the decomposition so often noticed here again takes place. It was found to contain sulphate of potassa sulphocyanide of potassium and ammonium and cyanide of amnio-nium. The change in the molecular arrangement is expressed thus 6 (K,Pt 3 Cy S2)+ 8 NH 0= 6 (Pt C €I 2 (KSO,) N S,) i--+ 4 (KCyS2)+ 2 (NH Cy S,) i-5 (HCy S,) + HCy.The same substance is more readily formed also by substitutiug platino-bisnlphocyaiiide of potassium for platino-tersnlphocyanide. As the filtrate in this case does not contain a sulphate the action is vcry siinple Kl’t 2 Cy S +NH 0=PtC 13 N S +KCyS +IIO. A preparation was made after the latter method and ignited when it was foiind that 0*4100grm. of salt gave 0.1986 grm. of platinum. Theory requires 56.89. Experiment gave 56.68 per cent. As the probability was against the above formula truly expressing the constitution of the substance some light was anticipated by a regrouping of its elementary particles. Aii intelligible forni pre-sented itself on considering the hydrogen and part of the nitrogen as ainnionia which its behaviour at a high teniperature appeared to justify and uniting the carbon sulphur and thc rest of the nitrogen as sulphoeyanogen.Taking sulphocyanide of ammonium as the type and substituting an equivalent of platinum for onc equivalent of hydrogen we then have the su&hocynnide of ylatosnmmoniuwz (Reiset’s first platinum base). Cy S by substitution N Cy S N{ ~~ A ready proof of this supposition presented itself in the direct comparison of the tvo salts. The preparation of the latter by double decomposition is not difficult. One part of fused sulphocyanide of potassium may be dissolved in water and 1.6 parts of chloride of platosammonium added.After raising the mixture nearly to the boiling point an equal bulk of hot alcohol is shaken with the liquid to illcrease the solubility of the new substance and the whole is passed whilst hot through a filter papcr. On cooling straw-coloured needles are deposited which exhibit all the properties of the formcr compound the identity with which was still further shown by a quailtit ative analysis. 0.6120grm. by ignition gave 0.3470grrn. of platinum representing the formula PtH,NCyS,. The coinposition for 100 parts reqiiires by theory 56-80 of plat i-nuill; the quantity found was 56-69. T%€EPLATINO-SGLPHOCYANIDES. 31) Sulphocyanide of platosammonium is indifferent to the action of dilute sulphuric or hydrochloric acid. The aqueous solution docs not affect salts of copper lead or mercury but precipitates nitrate of sulphate of silver as a bulky and pale yellow compound which is rich in platinum.This precipitate requires more study than has as yet been bestowed upon it The aqueous solution by long boiling liberates ammonia and deposits the yellow insoluble substance above alluded to the composition of which is yet uncertain." Caustic potassa appears to effect the same change. A temperature between 100' and 110' C. causes the salt to fuse into a clear garnet-coloured syrup which hardens on cooling and does not appear to bc further affected by a rise to 180' C. Before dismissing this portion of the subject there appears to be yet another point of view from which the salt might be regarded.Although no doubt was entertained of the correctness of the last formula some interest seemed to be attached to the circumstance of itx polymerism with another body not hitherto prepared. I have recently had occasion to show that cyanogen gas acting on oxide of diplatosammonium produces the platinocyariide of that base the for-mula of which is double that assigned by Reiset to the decomposi- tion. The true cyanide of platosammoniurn further may be obtained from the corresponding chloride by acting with cyanide of potassium. 3ust in the same manner we might expect a parallelism between platino-bisulphocyanide of diplatosammoniuin and sulphocyanide of platosammonium. This may be more readily intelligible thus 2(Ptt€,N Cy) = PtH,N, PtCyz and 2PtH,N CyS,=PtW,N, Pt2CySz --/' -/--, i-0-J Cyanide of plato-Platinocyanide of Sulphocyanide of Platino-bisulphoq anide sammonium.diplatosammonium. platosammonium. of diplatosammonium. Plutino-bisul~hocyaPzideof ~i~lu~~~a~rno~iurn falls as a vohrninous flesh-coloured precipitate on decomposing the chloride of the base by a soluble platino-bisulphocyanide. It is quite insoluble in water and also in alcohol. Dilute hydrochloric acid dissolves it rather freely. When heated on platinum foil it liberates ammoniacal gas fuses into a black bubbling mass and then burns tinder-like to a bright platinum sponge. 0.8576 grm. of substance ignited gave 0.4896 gi m. of platinum. 97 7) , ignited in oxygen ,* 0'2090 , carbonic acid. , ignited in oxygen , 0.1460 , water.0&56 : , igriited with chlorate of , 0.1512 , platinuvn potassa and carbonate of soda . . , I 0.3617 , sulyhate of bnryta. * A well-washed sample gave on ignition as much as 92.27 per cent of platinux~. It contains sulphur and the elements of ammonia. ME. Q. B. BUCKTON OX leading to the formula PtH,N, Pt 2(CyS,). The theoretical and experimental numbers are appended. Theory. Mean found. fz equivs. of platinum 198 56.90 56.94 4 , carbon 24 6-90 6.65 6 4 , , hydrogennitrogen 6 56 1.72 16.09 1*89 - 4 , sulphur 64 18.39 18.62 c__ 343 100~00 On the action ofChlorine Gas and Nitric Acid upon the Plalino-sulphocyanides.-An examination in this direction seemed to be de- sirable from the belief that the above decomposition did not show the full extent of oxidation to which the salts of either series might be carried.When commenting upon the acids it was mentioned that their aqueous solutions were resolved by heat into a red or brown amorphous substance hydrosulphocyanic and sulphuric acids. The same brown compound is formed by pouring warm concentrated nitric acid on the powdered potassium salts Experiment also proved that if a warm and rather concentrated solution of platino-tersulpho-cyanide of poiassium be subjected to a stream of chlorine the ternpera- ture rises considerably during the absorption of the gas. By decom- position of water the chlorine passes into hydrochloric acid and the liberated oxygen converts the greater part of the sulphur into sul- phuric acid.The first of these acids may be removed by evaporation on the water-bath and the latter after careful neutralization with carbonate of soda by a thorough washing with hot water which at the same time carries off the whole of the potassa as bisulphate. During evaporation the odour of hydrocyanic acid is very percep- tible. The new substance on the filter appears of all shades of colour from a bright red to a dirty brown. It may be dried at a gentle heat and then has the form of a light non-crystalline powder strongly s:)iling the hands insoluble in water and in alcohol but before drying slightly soluble iii hydrochloric acid. It is unaffected by a solution of potassa but ammonia changes its colour to a yellow hue. When ignited in a close crucible vapours of bisulphide of carbon @aidcyanogen gas are disengaged and the solid residue consists of bisulphide of platinum.The action of concentrated nitric acid is quite similar. Hydrocyanic acid and nitrous fumes are given off and in geiieral the insoluble residue is produced of a brighter colour. THE PLATtNO-PUI.PXIOCYI\NI UES. The following iiurnbers were obtained on its analysis 0 3700 grm. of substance ignited gave 0.2304 grm of platinum. OW64 , burnt in oxygen , 0.2800 , carbonic acid. , , burnt in oxygen , 0.0320 , water. 0-7334 , burnt with soda-lime , 1.1600 , chloroplatinateof ammonium. 0.5146 , burnt with chlor. of potassa ,? 0.7048 sulphate of baryta. 1.0704 , a different sample , 0,6639 , platinum., , burnt with osygcn , 0.3426 ? carbonic acid. , , burnt with oxygen , 0.0448 , water. f regret that I have been unable to prepare this substance in such a state of purity as to place its true composition beyond all doubt. I had anticipated from its mode of forniation a substance which bears towards the platino-sulphocyanides the same relation which the so-called solid sulphocyanogen bears towards the sulphocyanides. If however we calculate the water as such it will give ail excess in the experiments of more than 3 parts in the 100 taken; and the discrepancies between the other constituents will be found as great. I am therefore inclined to suppose that the hydrogen is partly accidental and that as the formula adopted has the recommendation of great simplicity and satisfies all the conditions observed in the reaction it will ultimately prove to be correct.I have thought it better in addition to the theoretical and experimental numbers to give the ratio in parts of a unit between the component parts which places their relation in a clearer point of view. The formula of protosulphocyanide of platinum is -Ptcy s,. Theory. Found. Mean. Ratio. 1 equiv. of platinum 99 63-05 62=02 62.14 1.0 1 , carbon 12 7-64 8.53 8-72 8.62 2 3 1 , nitrogen 14 8-93 9.92 -9-92 1.1 2 , sulphur -32 20.38 18.77 -18-77 1.9 157 100*00 Hydrogen . . 0.39 0.15 0.42 0.6 99.87 There remains only to show by equation this decomposition by chlorine gas. The reaction is strictly in character with those befom noticed.K Pt 3 CyS,+ llC1+16 HO=PtCyS + 12 S0,+2 HSO, H/ + 1lIICl -t2 HCy. MR. G. H. BUCKTON ON 41.2 The platino-sulphocyanides possess characters so distinct from other salts that there is no likelihood of confounding thcni with other known compounds. They are all highly coloured and take all gra- dations from pale and bright yellow to deep red. This colour appears attendant in a great measure upon the quantity of sulphur combined with the platinum since the intensity is more remarkable in the first than iii the latter series and is nearly lost in the sulphocyanide of platosammoniuni . Their ready inflammability and peculiar odour when gently heated may also be considered as characteristic. The separation of the two series is well marked by their different action on reagents which for better illustration has been arranged in the followiiig table repre- senting the precipitation or non-precipitation of a soluble salt of each series.Reagents. Platino-t ersulphoc y anides. Plat ino-hisulyhocy anides. Subsalts of mercury . . Orange precipitate . . . No precipitate liquidchanges colonc on heating. Salts of silver . . . . . Red or orange precipitate Pale yellow precipitate. Protosalts of iron . . . . Black shining grains . . No change. Salts of copper . . . . Brick-red precipitate . . Purplish-black precipitate. Sultsalts of copper . . . Rich brown precipitate . Purplish-black precipitate. Salts of cobalt . . . . . Orange-red precipitate . No change. Salts of lead .. . . . Soluble golden lamina? . No change. Basic salts of lead . . Fine red Precipitate . . Pale yellow precipitate. Persalts of gold . . . Salmon-coloured precipi- tate . . . . . . Salmon precipitate. Ferrocyanide of potassium . Prussian blue formed on A nearly white precipitate boiling on boiling. Chromic acid . . . . No precipitate . . . . A copious reddish precipi- tate with evolution of hydrocyanic acid. Saltsof platosamine . . . Copious orange precipi-tate . . . . . Fine yellow precipitate. Salts of diplatosamine . . Fine vermilion-red preci- pitate. . . . . . Flesh-c'oloured precipitate. The ready conversion of the sulphur in these compounds into sulphuric acid in presence of water is shown in an interesting manner by their action upon metallic zinc.Aqueous solutions of the potassa salt are resolved into platinuin black hydrosulphocyanic acid sulphate of potassa and free sulphuric acid which acting upon the zinc liberates a considerable quantity of hydrogen gas. A few general remarks upon the constitution of the platino-sulpho- cyanides may not be considered here misplaced. Viewing then) ac- curding to Berzelius's explanation of the ferrocyanides they must THE PLATINO-SULPHOCYANIDES. be taken as double compounds of protosutphocyanide and bisulpho- cyanides of platinum with a metallic sulphocyanide or hydrosulpho-cyanic acid; Platino-cyanides. Platino-bisulphocyanides. Platino-tersulphocyanides. ---.c-__-I ' -.-./ M CyCPt Cy M Cy S,+Pt Cy S M Cy S,+Pt 2 Cy S whilst on the more generally received idea they contain two separate radicals of acid character forming salts upon the hydrochloric acid type.The similarity of action between sulphur oxygen chlorine cyanogen &c. in combination has been frequently remarked. In-stances of substitution of sulphur for chlorine may be seen in the reactions of sulphide of potassium upon hydrochloric ether and Dutch liquid. Throughout this Paper I have assumed the existence of chloro-platinous and chloroplatinic acids from the close similarity they bear towards the platino-sulphocyanides; and I think an argu-ment in favour of their existence may be found in the construction of the latter from the former by simple substitution of sulphocyanogen for chlorine. In the same nianiier we construct the platino-cyanides bp exchanging chlorine for cyanogen although at present we want the higher number in the series.This will doubtless turn up upon a careful search. We have thus Platitto-chlorides or Platino-Platino-sulpho-chloro-platinides. cyanides. cyanides. -' LyrJ -M Pt C1 missing M Pt 3 Cy S M Pt Cl M Pt Cy M Pt 2Cy S Some interest attaches to the new acids from the large number of sulphur-atoms they contain. Platino-tersulphocyanide of potassium presents I believe the first instance of the union of sulphur with the triple cyanogen group represented by the cyanurates in which all the oxygen is replaced by sulphur. The analogy is not however strict between them since it will be seen that in the new compounds only 2 equivs.of hydrogen are replaced by metals. The same objection does not apply with reference to the fulminates. In conclusion notice should be taken of a crystalline compound described by Claus which is prepared by acting upon bisulpho-cyanide of mercury with sulphocyanide of potassium. From the for- mula given which is K Cy S + 2€IgCy S, it is clearly a double coni-pound and therefore has but little rcsemblance or conuection with the substances above described.

ISSN:1743-6893    

DOI:10.1039/QJ8550700022

出版商:RSC    

年代:1855

数据来源: RSC

摘要:

MR. H. hf. WI'PT OX 111.-Analysis of the Ash of Lemon-Juice. BY HENRYM. WITT Assistant in the Royal College of Chemistry (the Laboratories of the Metropolitan School of Science.) The following analysis having for its object the determination of the mineral constituents in the juice of lemons was made during the early part of last surnmer in the laboratory of the Royal College of Chemistry under the superintendence of Dr. Hofmann and at the request of Dr. Bence Jones. Preparation of the Ash.-The lemons (200 in number} were peeled with a bright steel knife care being taken in so doing to avoid as much as possible cutting into the juicy endocarp and thus bringing the acid in contact with the steel knife; the juice was then expressed by a hand-squeezer of wood (without any metallic hinges) and filtered through flannel into a porcelain dish in which it was evaporated to the condition of a black carbonaceous mass then transferred a portion at a time into a platinum dish and ignited until perfectly white.A qualitative exurnination was first made which indicated the presence of potassa soda lime magnesia and sesquioxide of iron; of silicic phosphoric sulphuric hydrochloric and carbonic acids. A separate and very careful examination was made for alumina but it was not detected; manganese was also separately tested for but not found. As regards the plan followed in performing the quantitative analysis it differed in no respect from that generally adopted. Without entering into details it may be stated that the part insoluble in hydrochloric acid consisted of silica and carbonaceous matter.In one portion of the hydrochloric solution the phosphate of iron the lime magnesia and phosphoric acid were determined ; whilst separate portions of the solution were employed for the alkalies and for sulphuric acid ; a nitric acid solution being used for the determination of hydrochloric acid ; and lastly a distinct portion of the ash was reserved for estimating the carbonic acid. The phosphoric acid was determined as ammonio-magnesian-phosphate in the dilute solution to which acetate of potassa had been added after separation of the lime by oxalic acid. The following are details of the results obtained. 1. Determination of silica. Weight of ash employed.Silica obtained. Percentage. I. 593835 grns. 11. 23.6165 , 0.355 grn. 0.128 , 0.5986 0.542 THE ANALYSIS OF TRE ASH OF LEMON-JUICE. 45 2. Determination of carbon. Weight of ash employed. Carbon obtained. Percentage. I. 59.3835 grns. 0,0615 grn. 0.1035 3. Determination of phosphate of iron. Weight of ash employed. Phosphate of iron obtained. Percent age. I. 24.5077 grns. 0.230 gm. 0.9385 11. 18.276 , 0.219 , 1-198 4. Determination of lime. Weight of ash employed. Carbonate of linie obtained. Percentage of litne. I. 24.5077 gms. 3.354 grns. 7-6631 11 18.276 , 1.353 , 7.4059 5. Determination of magnesia. Pyrophosphate of Percentage of Weight of ash employed. magnesia obtained. magnesia. I. 18.276 gms. 1.644 grnu.3 2124 11. 23.6165 , 2.12385 , 3.385 6. Determination of'phosphoric acid. a. In combination with lime Pyrophosphate of Percentage of Weight of ash employed. magnesia obtained. phosphoric acid. I. 18.276 grns. 0.402 grns. 1*el46 11. 16242 , 0520 , 2.0582 p. In combination with magnesia Pyrophosphate of Percentage of Weight of ash employed. magnesia. phoPphoric acid. I. 18.276 gms. 1.644 gms 5.7825 11. 23.616 , 2.2385 , 5.7106 7. Determination of the alkalies. r. 11. Weight of ash employed . . 10.86 gms. 11.948 gms Weight of mixed chlorides obtained. 7.970 , 9.04 , Corresponding to per cent of mixed 45.9355 45.9446 alkalies (KO and NaO) . -1 Weight of potassium platinum-salt } 25.077 , 26.700 ,, (KCI PtCI,) obtained hence Percentage of potassa .. 44.251 , 443.545 Y> soda . 1.6845 , 12.3996 8. Determination of sulphuric acid. Sulphate of Percentage of Weight oi azh employed. 1)aryta obtained. siilphuric acid. 1. 8.7795 6""s. 3.159 gr17s. 12.354 TI. 6.018 , 2.069 ,) 11.8ofL MR. U. M. WITT ON 9. Determination of carbonic acid. Weight of ash employed. Carbonic acid evolved. Percentage. I. 15.517 gms. 3-02grns 19-46:! 10. Determination of chlorine. Weight of ash employed. Chloride of silver obtained. Percentage. I. 8.7795 grns. 0.429 grns. 1.2079 grns. 11. 6,018 , 0.295 , 1.2090 , The following table is a synopsis of the preceding results I. 11. mean. Alkalies (KO and NaO) 45.9355 45.9446 45*9400 Potassa . 44251 43.545 43.8984 1 *6845 2.3996 2.1416 Soda .7.6631 7.4059 7.5345 Lime Magnesia . 3.2124 3.385 32987 Sulphuric acid . 12.3540 -12.3540 Chlorine . 1*200 1.2079 1*2084 Carbonic acid . 19.462 -19.4620 Phosphoric acid . 7.1971 7-7691 7.4829 Phosphate of iron . 0.9385 1.198 1.0682 05986 0.542 0*5700 Silica . Carbon . 0.1035 0,1035 *lumina f absent. Manganese 99.1222 The preceding numbers after deducting the charcoal give the following as the percentage composition of the ash Potassa . . 44-34? Soda . . 2.16 . 7*6l Lime 3lagnesia . . 3.34 Sulphuric acid . . 12-47 Carbonic acid . . 1966 Chlorine . . 1.23 Phosphoric acid . . 7.56 Phosphate of iron . . 1'06 Silica . . 057 100.00 THE ANALYSIS OF THE ASH OF LEMON-JUICE.These constituents may be assumed to be thus arranged Carbonate of potassa . . . 57.725 Carbonate of soda . Sulphate of yotassa . Chloride of sodium . Sulphate of lime . (Tribasic) Phosphate of lime . Phosphate of magnesia . Phosphate of iron . Silica . 2.265 9.293 2.026 13935 3.687 9.086 1*06O 0.570 99,647 In order to ascertain the proportion of ash in the juice a known weight was carefully incinerated in a platinum dish with the following results Weight of juice employed. Ash obtained. Percentage. I. 587.96 grns. 3-11 grns. 0.52 11. 1020.695 , 2-055 , 0.20-Mean 0.36 Hence by calculation the following was obtained as the proportion of the several inorganic constituents of the juice Inorganic constituents of an ounce Troy (480 grns.) Inorganic constituents of 1000 grains of the juice.of the juice. 0.767 grns. 0.038 , 0.131 , 0,058 , 9.215 , 0.022 , 0.339 , 0.130 , 0.018 , 0.010 , 1.728 Potassa Soda Lime . Magnesia . Sulphuric acid Chlxine . Carbonic acid 1*597grns. 0-077 0.274 0.120 0.448 0.045 0.707 , , , , , 1 . . . . . . . Phosphoric acid . Phosphateof iron Silica . . 0.273 , 0.038 , 0.021 ,) Total 3.600 On reviewing thc above-nientioned results it was felt that the objection might by raiscd that either thc whole or at. least a portion MR. HEKRY HOW ON of the iron found might have been derived from the knife employed in cutting the lemons (notwithstanding the precautions taken to avoid contamination from this source) ;consequently to remove all doubt on this rather important point a fresh portion of juice was in-cinerated the lemons whence it was obtained having been cut with a silver knife and every possible care taken to avoid the extraneous introduction of iron.In the ash thus obtained the determination of the ferruginous phosphate was repeated with the following result Weight of ash Phosphate of iron employed. obtained. Percentage. 8.225 grns. 0.12gm. 1.458 which on comparison with the preceding lead to the conclusion that none of the iron had been derived from the knife since this last deterniination indicates a still larger proportion of the phosphate than either of the former determinations.

ISSN:1743-6893    

DOI:10.1039/QJ8550700044

出版商:RSC    

年代:1855

数据来源: RSC

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MR. HEKRY HOW ON IV.-Note on Platinum accovxpanying Silver in s0lutio.n in Nitric Acid. BY HENRYHow (ASSZSTANT TO PROFESSOR ANDERSON.) Having occasion recently to reduce some silver for use in the laboratory of Professor Anderson in Glasgow from the collection of precipitates and filters preserved for the purpose I observed a phenomenon which so far as I am aware has not been noticed and which I make known to the Society in the hope of some of its members being able to afford further information on the subject. It is a well-known fact that platinum in alloy with silver does dissolve in nitric acid but I have not been able to meet with an account in any analytical work of what I observed as to its behaviour when so dissolved. Among the precipitates and filters alluded to although it was intended that none but salts of silver should be present it appears from the facts I am about to state some containing platinum mixed with silver the results of certain investigatioris of Professor An der- son had been introduced.I set about obtaining the silver in the usual way by drying up and burning the mass of residnes and paper in an iron dish and subsequently fusing the charred mass with PLATINUJI ACCOYPANYING SILVER IN SOLUTION. carbonate of soda and some borax to dissolve any iron which might have scaled off from the said dish. A button of silver was obtained which I proceeded to treat with nitric acid. I was surprised to find a blackish-brown powder remain undissolved while the whole of the silver and it alone as I thought went up in the acid.On examining the powder I found it to contain silver but in what state of corn-bination I could not determine; at the time € imagined it to be a boride but I am now inclined to think it must have contained plati- num. I regret from what I observed afterwards I did not submit it to a more rigorous analysis. The acid solut,ion of the supposed pure silver was evaporated to complete dryness and gently heated to expel the excess of nitric acid ; the residue was them. dissolved in a comparatively small quail- tity of water as a strong solution was desired; a little yellowish-broBrn powder remaining undissolved the fluid was filtered. Qn diluting a small portion of this liquid with distilled water I was surprised at seeing a white precipitate falf and was disposed to imagine that by some inadvertence some salts of bismuth or antimony bad heen thrown among the silver residues; however neither of these nietals could be detected.The whole fluid was then diluted and allowed stand a day; a precipitate formed from which the solution was poured off and again allowed to stand. It had rather a turbid appearance and I observed a sediment gradually form in the shape of paie yellow amorphous flocks which went on increasing; after about a week this was collected on a filter washed with water and examined. The sediment was found to dissolve completely in ammonia and for the most part in acetic and in nitric acid. In these acid solutions hydrochloric acid gave a large precipitate which proved to be chloride of silver ; and in the fluid aeparated from this platinum was found to be present in abundance Although 1 did not certainly detect nitric acid I am disposed to imagine from the natuix of the process by which it was obtained that this sediment must have been some basic double-salt of silver and platinum with nitric acid the liquid from which it deposited having an acid reaction.f may mention that it being found that platinum was present I precipitated the whole of the silver in the remaining fluid by hydrochloric acid and reduced it after washing by iron and SO succeeded in obtaining a pure salt of silver. I have ventured to offer this note to the Society as containing a fact I believe new and worthy of consideration in cases of analysis where silver and platinum may OCCUF together in an alloy; as without any intimation of the existence of such a compound as VOL. VII.-hTO. XXV. E UH. PENNY ON that which spontaneously deposits from an aqueous solution of nitrate of silver containing platinum the analyst may be as much surprised as I was to observe its formation and unable to account for it at once. I also think the brown powder which I have described as remaining after the solution of the alloy by digestion in ordinary nitric acid is worthy of attention and further notice.

ISSN:1743-6893    

DOI:10.1039/QJ8550700048

出版商:RSC    

年代:1855

数据来源: RSC

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UH. PENNY ON V.-Note on the Valuation of Protorhloride of Tin. BY DR. P ENN Y GIASG~VY. In a paper on the Valuation of Red Prussiate of Potash published in the ‘‘Quarterly Journal of the Chemical Society,”* Mr. Francis Leishing states an objection to the process for estimating the amount of tin in double muriate of tin by bichromate of potash. His words are cc In this instance the liquid double muriate of tin might contain a very considerable admixture of protochloride of iron without even changing its external appearance; and this in practice highly obnoxious admixture would by the sole application of the bichromate of potash test not only escape detection but the iron would actually be calculated as tin.” As this statement may lead some toreject the process without trial or perhaps induce some manufacturer of these tin-solutions to infer that protochloride of iron could be added to chloride of tin without risk of detection it may be as well to show that Mr.Leishing’s objection is really without foundation. It is quite obvious that if acetate of lead be exclusively relied upon as the agent for deterniining when a sufficient quantity of the bichro- mate of potash has been added the process will be vitiated by the presence of iron. In the description of the process however,? it is particularly men- tioned that the (( sulphocyanide test,” consisting of a mixture of pro-tosulphate of iron and sulphocyanide of potassium is much more delicate and satisfactory than acetate of lead. This test completely removes the objection arising from the presence of iron.Sesquichloride of iron cannot exist in the same solution with pro-tochloride of tin ;and accordingly no sesqui-compound of iron can be * Vol. VI 31. -f Quarterly Journal IV 239. THE VALUATION OF PROTOCHLORIDE OF TIN. formed during the addition of the bichromate until the protochloride of tin is wholly converted into bichloride and then the further addi- tion of bichromate instantly produces sesquiehloride of iron the smallest trace of which is immediately revealed by the sulphocyanide test. In point of fact instead of protochloride of iron “escaping detection,” and being calculated as tin,” as Mr. Francis Leisbing affirnis its presence would actually assist the operator in catching the precise moment when the conversion of protochloride of tin into bichloride is perfected.It might indeed be an advantage to add a small quantity of a proto-compound of iron to the tin solution in place of mixing sulphate of iron with the sulphocyanide of potassium as directed in the paper referred to. The addition of protochloride of iron to double rnuriate of tin would in practice be a truly obnoxious admixture but its presence could in no way interfere with the bichromate process for the valua- tion of tin crystals double muriate of tin &c. provided the proper test be employed. It certainly seems almost unneeessary to notice the objection as every one acqiiainted with the applications of these tin preparations must be aware that adulteration with iron would very soon manifest itself in the course of the usual operations. The justness of Mr. Leishing’s remark upon the importance of alkalimetric methods of valuation being preceded by qualitative test- ing of the substance under examination will readily be admitted and especially as the same observation may be extended to nearly all our ordinary processes of analysis.

ISSN:1743-6893    

DOI:10.1039/QJ8550700050

出版商:RSC    

年代:1855

数据来源: RSC

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THE VALUATION OF PROTOCHLORIDE OF TIN. ’Vf,-On the so-called Iodide and Chloride of Nitrogen. BY J. H. GLADSTONE, Ph.D. P.R.S. On the 17th of February 1851 I communicated to the Chemical Society a paper on the Explosive Compound usually denoiiiinated Iodide of Nitrogen in which f assigned to it the composition NHI,. The paper was printed in the following cc Quarterly Journal.” In the ‘CAn- nalen der Chem. und Pharm.” for October 1852 Bunsen published an investigation of the composition of the same substance in which he ascribes to it the formuls NH +NI, and NH +4NI, according to different modes of preparation. At first sight there would seem DR. GLADSTONE ON an irreconcilable discordance between the results of his analyses and mine ;but on closer examination this disappears for both the ttiethods by which he prepared thc explosive powder differ from that adopted by me.He forming the substance from iodine and ammonia dis-solved in absolute alcohol and never suffering it to come in contact with water finds it to be NH,+ NT,; forming it by precipitating a solution of iodine in aqua-regia by aqueous ammonia and washing it with water he finds it to be NH +4! NI,. I forming the substancc by precipitating an alcoholic solution of iodine by ammonia and washing with water found it to be NHT, which is equivalent to NH,+2 NT on Bunsen’s mode of expression and is intermediate between his two formulz. Nevertheless I thought it desirable to repeat my former analysis and to add some further observations towards the completion of the chemical history of this remarkable substance.Bunsen does not adopt my method of analysis but takes advan- tage of the reaction between hydrochloric acid and the black powder which is fully explained towards the close of my paper. As however my method by sulphurous acid gives very exact results I had recourse to it again. A portion of the explosive substance prepared and washed as before and decomposed by a fresh solution of sulphurous acid was divided into two equal parts and yielded 0.632 grm. of iodide of silver 0.620 grm. of sulphate of baryta and 0.124grm. of platinum derived from the ammonia-salt. Traces of nitrogen gas were given off during the destruction of the black powder thc amowit of which was estimated at 0.04 cub.in. Half of this would be equal to 0*0004grm. weight of nitrogen which must be added to the amount found to have been converted into ammonia. The numbers given above indicate Nitrogen . . 0.0182grm. Iodine . . 0.3404 , Sulphuric acid . . 05?131 , which divided by the atomic weights give Nitrogen . . 130 ur 1 equiv. Iodine . . 268 or 2.06 , Sulphuric acid . 533 or 4.10 , This indicating the proportion of iodine to nitrogcn as 2 1 agrees perfectly with the result of tlie analyses recorded in my previous paper. In another experiment sirnilarlp conducted there were obtained THE IODTDE AND CHLORIDE OF NITROGEK. 0441 grm. of iodide of silver and 0,281 grm. of ammonio-chloride of platinum. The same amount of nitrogen gas may be reckoned as having been evolved during the action of the sulphurous xid.These numbers indicate Nitrogen . 0*0’142 grm. Iodine . 0.2375 , which divided by the atomic weights give Nitrogen . . 101 or 1 equiv. Iodine . . 187 or 2.85 , This analysis though it indicates rather too small a quantity of iodine does not differ materially from the preceding. My former view of the composition of the explosive powder prepared by precipitating an alcoholic solution of iodine by ammonia and washing with water is therefore confirmed. The question remains whether the substance is to be considered one atom of ammoilia in which two of the equivalents of hydrogen are replaced by iodine- in fact iodimide; or whether it is to be viewed in accordancc with Bunsen’s formule as ammonia combined with two equivalents of teriodide of nitrogen? Now a body of the composition as-signed by the German chemist to his explosive powder NH,fNI, might be equally well expressed as a compolxnd of my NHI with NH I NH + NI,= N,H,I,=NHI,+ NH,I Both NI and NH I are alike hypothetical substances ;yet it appeared very possible that the action of water on the compound might throw some light upon the subject.It was found that when the black powder formed in the presence of water was washed for a great length of time the washings still continued alkaline to test-paper Black powder which had been produced by mixing solutions of iodine and ammonia in alcohol of sp. gr. 814 and had been well washed with the same alcohol gave on the addition of water a solution which was distinctly alkaline and of a slight red tint.This dour was removed by the very least addition of sulphurous acid solution. Precisely the same was observed when the explosive powder was prepared by means of absolute alcohol. A quantitative estimation was made of the washings by water of the substance precipitated in alcohol of sp. gr. 814. Water had been passed through it on a filter for thirty minutes. The slightly red salution was decolorized by a DK. GLADSTONE ON drop of sulphurous acid; it was divided into two equal parts from oiie of which 0.047 grm. of iodide of silver was obtained and from the other 0.028grm. of platinum derived from the ammonio-chloride.These numbers indicate Nitrogen . . 0.0040 grm. Iodine . 0.0253 , which divided by the atomic weights give Nitrogen . . 28 or 1 equiv. Iodine . . 20 or 0.71 , Hence there must have been free ammonia as well as iodide of ammonium a result rather favouring the view taken by Bunsen. The above-mentioned specimen of explosive iodide prepared by means of alcohol sp. gr. 814 was analysed by sulphurous acid as in the preceding instances. The amount of nitrogeri gas given off was too inconsiderable to be taken account of. The weights of the preci- pitates obtained were 0.256 grm. of ammonio-chloride of platinum 0.630 grin. of iodide of silver and 0.649 grm. of sulphate of baryta which indicate Nitrogen . . 0.0162 grm. Iodine .0.3394 , Sulphuric acid . . 0.2230 , These quantities added to those previously found dissolved in water are Nitrogeri . . 0.0202 grm. Iodine . 0.3647 , Sulphuric acid . . 0.2230 , which when divided by the atomic weights give Nitrogen . . 144 or 1 equiv. Iodine . . 286 or 1998 , Sulphuric acid . 557 or 3.86 , This result perfectly coincides with the previous analyses. The conipositivn of this specimen of explosive powder was also NHT,. The unexpected confirmation of my previous views afforded by this experiment induced me to aiialysc a sample of the black precipitate 'PHE IODIDE AND CHLORIDE OF NITROGEN. thrown down by mixing solutions of iodine and of ammonia* in absolute alcohol. The experiment was conducted with great care to prevent the hydration of the alcohol in any possible way during the course of it.The black powder obtained had precisely the same physical appearance as the specimeiis previously examined It was decom-posed and analysed in the usual manner. The amount of nitrogen gas evolved was 0.06 cub. in. half of which would weigh 0*0006grni. The weights of the precipitates obtained were 0.253 grm. of ammonio-chloride of platinum 0.539 grm. of iodide of silver and 0.498 grm. of sulphate of baryta which indicate Nitrogen . . 0,0166 grm. Iodine . 0.2903 , Sulphuric acid . . 0-1711 , Tliese numbers divided by the atomic weights gave Nitrogen . . 118 or 1 equiv. Iodine . 228 or 1.93 , Sulphuric acid . 428 or 3-63 , But these proportions approximate those of all my previous analyses.It is easily conceivable that different proportions of hydrogen should be replaced in different specimens but by what variation of circuni-stances I obtained the substance NII12 instead of that analysed by Bunsen I know not. I cm but record the result of my experiment . When the black powder is formed in the presence of water half or very nearly half the iodine employed is obtained in the solid com-pound and the solution becomes colourless or nearly so the reaction being 41+ 3NH,==NHI,+ 2 NHJ but when the iodine and ammonia are brought together in solution in strong alcohol a far smaller proportion of the black powder is obtained and the liquid remains deep-red in colour although the * Before the ammonia is dissolved in the absolute alcohol it is necessary that it be dried.The desiccation of this gas is I believe usually effected by passing it over pieces or sticks of hydrate of potash ; but I adopted another process. It was made to pass through a wash-bottle 'containing absolute alcohol iiiSo which some pieces of potassium had been thrown. Thus was secured the advantage of the gas bubbling through a liquid and that liquid a most hygroscopic solution of ethylate of potash perfectly free from water. Of course this process is only applicable for the desiccation of ammonia in cases where the vapour of alcohol does not interfere. arnrnonia be added in large excess. A considerable amount of sulphurous acid solution also is required to effect its decolorization.The addition of water causes a black precipitate which however being in a very finely-divided condition is speedily acted upon by the water and decomposed with evolution of gas-doubtless nitrogen. It is evident tberefore that although iodide of ammoiiiiim is soluble in alcohol some other compound must be here formed. The ratio between the iodine in solution and that in the precipitate was thrice determined; as also the ratio between the hydriodtic acid and the sulphuric acid formed upon decomposing the red liquid by sulphurous acid. In the first experiment alcohol of sp. gr. 814 was employed ; in the second and thira absolute alcohol was made use of. The results were Exp. 1. Exp. TI. Exp. 111. Iodide of silver from bIack powder 1.220 grm.0*898grm. 0-539grnr. J , , redsolution 3.255 , 34595 , 4.376 , ff Sulph. of baryta , 0.950. ) I*%l , 1.543 , The proportion between the two estimatioiis of iodine in these three experiments is widely different namely Exp. I. Exp. II. Exp. 111. From black powder 1 1 I From red solution 2-67' 4*00 8-12 The ratio between the iodine and the sulphuric acid formed from the red solution agrees more closely namely ~xp.r. EX^. Ir. Exp. 111. Iodine 1 eqixiv. 1 equiv. 1 equiv. Sulphurie acid 0-59 , 0.60 > 0.71 , The smaller proportion of su@huric acid would appear to indicate that the iodine exists in the red solution to a considerable extent in the form of iodide of ammoniuni ; but it miist be mixed or combined with a larger amount of the element in some other condition.In the third experiment the ammonia in the red solution was also determined. The liquid was warmed to expel the excess of the volatile alkali in fact till there was a distinct odour of iodine. It was then divided into two equal parts and proceeded with as before. The amount of ammonio-chloride of platinum obtained was 0.723 grni.; that of iodide of'silver as before stated was 4.376 grms. These numbers indicate Nitrogen -. . 0.0459grm. a Iodine 2.3572 , THE IODIDE AND CHLORIDE OF NITROGEN. which divided by the atomic weights give Nitrogen . . 828 or 1 equiv. Iodine . . 1856 or 5.66 , There is here a remarkably small amount of ammonia indicated; probably the compound first formed in the red solution is decomposed by a slight heat the iodide remaining in the liquid and the ammonia volatilizing.CHLORIDE OP NITKOGEN. It appeared highly probable that the same methods which had proved applicable to the analysis of the so-called iodide might be effective also when tried with the chloride of nitrogen. The syste- niatic analysis of this oily liquid indeed has never been attempted excepting by Bineau. In the same memoir in which that chemist attributed the correct composition to the iodide he assigned to the chloride the composition N CIS.* Since however his determinations are far from being exact doubt might still be entertained as to the actual proportion of the nitrogen and chlorine and whether the explosive liquid might not like the iodide retain some portion of hydrogen.At any rate it would be interesting to try whether the view of Bineau would be confirmed by further experiments and how far the formula of this substance might throw light upon the rational composition of the iodide. The so-called chloride of nitrogen was prepared in the usual way by the mutual action of chlorine and chloride of ammonium. For each separate analysis a globule was collected of just sufficient size; and it was washed by a stream of water until the washings gave no appreciable precipitate with a silver salt. Methods similar to those employed for the decomposition of the iodide were made use of in this case also. A stream of hydrosulphuric acid was passed for a long time through water at the bottom of which was a globule of the explosive liquid.Decomposition took place slowly sulphur being liberated and ammonia and hydrochloric acid formed but at the same time the usual action of water on the compound was proceeding and thus a little nitrogen gas was produced. This was scarcely more than a trace but uot having been collected it must have vitiated the experiments to some extent. The solution obtained after this reaction was warmed to expel the excess of hyclrosulphuric acid and filtered from the deposited sulphur. In the first experiment * Ann. Chiui. I’hye. [3] XV 71. DR. GLADSTONE ON recorded below the ammonia and hydrochloric acid were determined from the same portion acetate of silver having been employed to pre- cipitate the latter excess of silver being subsequently removed by the addition of hydrochloric acid and the ammonia converted into platinum salt.In the second and third experiments the solution was divided into two equal parts from one of which the hydrochloric acid and from the other of which the ammonia were estimated in the usual manner. The following are the results Exp. I. Exp. 11. Exp. 111. Ammonio-chloride of platinum 0.149 grm. 0.082grm. 0.254gri. Chloride of silver 0.226 , 0-138 , 0.510 , which are equivalent to Exp. I. Exp. 11. Exp. 111. Nitrogen 0.0092 grm 0.0052 grm. 0.0161 grm. Chlorine 0.0544 , 0.0340 , 0.1257 , These numbers are in the ratio of Exp I. Exp. 11. Exp. 111. Nitrogen 1 equiv. 1 equiv. 1 equiv.Chlorine 2.31 , 2-58 , 3-08 , The last of these estimations accords with Bineau’s formula but the average of them certainly does not especially when it is borne in mind that from the loss of nitrogen in the gaseous form the chlorine will be overestimated ; and thus the smallest proportion of chlorine is probably the truest. The action of hydrosulphuric acid being evidently not calculated to give an exact means of analysis sulphurous acid was had recourse to It was found that a solution of that substance in water acted slowly upon the explosive compound giving rise to ammonia and hydro- chloric acid with formation of sulphuric acid ; a little nitrogen gas was evolved at the same time but not a trace of nitric acid was formed as is usually the case when the chloride is left in contact with water.For the purpose of analysis a globule of the liquid was placed in a small basin containing R freshly prepared aqueous solution of sulphurous acid and over it was placed a glass tube also filled with the solution in such a manner that the bubbles of gas all rose into it. After a few hours the globule had disappeared a certain amount of nitrogen gas was found and its volume measured. The solution was warmed to expel the remaining sulphurous acid and divided THE IODIDE AND CHLORIDE OF NITROGEN. into two equal parts from one of which the hydrochloric acid and from the other the ammonia were estimated in the usual way. The experiment was performed twice and the following were the results Exp.I. Exp. 11. Nitrogen gas (divided by 2) 0.04 cub. in. 0.14cub. in. Ammonio-chloride of platinum 0.207 grm. 0*122grm. Chloride of silver 0.365 , 0.281 , Sulphate of baryta 0.634 , 0428 , which are equivalent to Exp. I. Exp. 11. Nitrogen 0.0139 grm. 0.0105 grm. Chlorine 0*0900 ) 0.0692 , Sulphuric acid 0.217 , 0.147 , These numbers are in the ratio of Exp. I. Exp. 11. Nitro8en 1 equiv. 1 equiv. Chlorine 2.56 , 2.60 , Sulphuric acid 5-47 , 4.89 , The results of these two experiments almost coincide,* in the proportion of chlorine and nitrogen and they agree with the average of the experiments by means of hydrosulphuric acid. The proportion between the nitrogen and chlorine is evidently as 1 2.5 ;and as there are 5 equivalents of sulphuric acid formed it shows that 25 equi-valents of hydrogen have also been supplied for the production of ammonia.The composition of the explosive chloride therefore is not so simple as that of the so-called iodide it may be expressed either as a double equivalent of ammonia in which 5 atoms of hydrogen are replaced by iodine viz, N,HCl ; or as NHCl,+ NCl,. * There appears a considerable discrepancy between the two estimations of sulphuric acid ; but it should be rememhered that in such experiments as these where a solution of sulphurous acid has been exposed for hours to the air an excess of sulphuric acid may be expested; while on the contrary the evolution of nitrogen in the gaseous con-dition will cause less sulphuric acid to be formed. Hence no doubt the deficiency in the second experiment contrasting so with the excess in the first where much less gas was produced.

ISSN:1743-6893    

DOI:10.1039/QJ8550700051

出版商:RSC    

年代:1855

数据来源: RSC

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'7 metliyl.ofsalicylateoCb%302 MR. GERHARDT 011' VII.-On some New Compounds of Salicyl. BY CHARLESGERHARDT. Chemists are aware that the salicylic ethers discovered by M. Cahours exhibit an anomaly never before observed in com- pounds of that nature. These ethers in fact though they corre-spond to neutral salicylates are capable of uniting with bases and forming metallic salts of perfectly definite character. Thus the salicylate of methyl (oil of Gaultheria pmcumbens) is analogous in composition to salicylate of silver H5 '2 1 o sdicylate of silver ; Ag nevertheless the salicylate of methyl combines with potash soda baryta &c.; so likewise does the salicylate of ethyl. In fact these two ethers exhibit the characters of true acids. The following is another anomaly exhibited by these bodies.When an ordinary ether is treated with chlorine or bromine the first effect of these agents is always to effect substitutions in the ethylic or methylic elements in such a manner as to form chlo-ruretted or brornuretted products which are transformed by alkalies not into alcohol or wood-spirit but as shown by Malaguti into acetic or formic acid. The salicylic ethers however exhibit totally different reactions; for chlorine aud bromine when they act upon these bodies first attack the salicylic elements and thus give rise to the formation of the ethers of chlorosalicylic and bromosalicylic acids &c. This difference of character being evidently due to difference of molecnlar constitution I have been led in applying my latest theoretical views to the salicylic ethers to regard them not as a molecule of water in which the 2 atoms of hydrogen are replaced the one by sdicyl and the other by methyl or ethyl but as a molecule of water in which only 1 atom of hydrogen is replaced by methylo-salicyl or ethylo-salicyl that is to say by salicyl already containing methyl or ethyl in place of hydrogen hydrate of C,H,(%H,)O hydrate of H C,H4(CH3)0 1 O methylo-salicyl.f O ethylo-salicyl. According to this view salicylate of methyl becomes the hydrate of methylo-salicyl or the oxide of hydrogen and metliylo-salicyl ; and salicylate of ethyl becomes the hydrate of ethylo-salicyl or the oxide of hydrogen and ethylo-salicyl. SOME NEW COMPOUNDS OF SALICYL.Hence it naturally follows that the compound of salicylate of methyl with potash for example is the oxide of potassium and metliylo-salicyl c,H* (C K H3) 0"0. Now as it is shown by my experiments on the anhydrous acids that the basic hydrogen in acids or the metal in salts may be replaced by oxygenated groups such as benzoyl cumyl ethyl &c. we ought if my view of the constitution of the salicylic ethers be correct to be able to effect corresponding substitutions in these bodies. This anticipation has been fblly confirmed by experiment. Nothing in fact is easier than to elherfy the salicylic ethers just as we etherify alcohol or wood-spirit. If for example alcohol or wood-spirit be brought in contact with chloride of benzoyl or succinyl hydrochloric acid is evolved and benzoate of ethyl succi- nate of methyl &c.is formed. Now when the salicylic ethers are treated with these same chlorides a precisely similar reaction takes place the product being benzoate of ethplo. salicyl or succinate of methylo-salicyl &c. In a word we may with a salicylic ether and the chloride of any acid radical produce as many compounds as with the same chloride and an alcohol. All the compounds which I have thus succeeded in preparing crystallize perfectly. Benzoate of methyto-salicy2 is obtained by causing gaul theria oil and chloride of benzoyl to act on one another with the aid of heat ; it crystallizes in beautiful rhomboidal prisms containing c7 I34 (C H3) 02 1 0 benzoate of methylo-salicyl or C7HP oxide of benzoyl and methylo-salicyl.Benzoate of ethylo-salicyl is prepared by a similar process from salicylic ether 97 H*(C HA 0,f 0 benzoate of ethylo-salicyl or c7 H 0 oxide of benzoyl and ethylo-salicyl. Caminate of methylo-salicyl crystallizes fiom boiling alcohol in very brilliant rhombic pallets C7 €3 (C H3)0,f cuminate of methylo-salicyl or C, H, 0 oxide of cumyl and methylo-salicyl. Saccinate of methylo-salicjd is obtained by means of the chloride of succinyl lately discovered by M. Chiozza and myself. It is deposited from the alcoholic solution on cooling in the form of large rectangular plates composed of fibres longitudinally attached 62 MR. GERHARDT ON SOME NEW COMPOUNDS OF SALICYI,.but easily separable. It is formed from 2 molecules of water just like succinic acid which as everyhody knows is bibasic succinate of niethylo-salicyl or oxide of succinyl and methylo-salicyl. These examples might be easily multiplied. I have likewise endeavoured to obtain the chloride of methylo- salicyl by subjecting gaultheria oil to the action of perchloride of phosphorus; hut in the very energetic reaction which takes place between these two bodies the methylo-salicyl group is decomposed and as products of the action we obtain chloride of methyl and a new chloride the chloride of saZicyl. '7 51 O21 chloride of salicyl. This body must not be confounded with that to which M. Piria has given the same name and which in my opinion represents the hydride of chloro-salicyl.My chloride of salicyl is a filming liquid which is decomposed by water like the chlorides of silicium phosphorus ethyl &c. into hydrochloric and salicylic acids. It acts violently on alcohol and wood-spirit converting them iiito salicylic ethers. This chloride of salicyl likewise affords a means of pre- paring salicylate of ethyl much more rcsdily than from a mixture of alcohol salicylic acid and sulphuric acid. M. Drion who is pursuing in my laboratory the study of tlie nc-cvly discovered compounds above mentioned has also by means of this new chlo- ride of salicyl obtained the sulicplate of umyZ which several chemists have in vain attempted to produce by the methods hitherto known. This salicylate of amyl exhibits characters similar to those of the other salicylic ethers ; it may evidently be regarded as the hydrate of amylo-salicyl '7 "4 ('5H H1l) '2 f 0 hydrate of amylo-salicyl. When treated with chloride of benzoyl it yields benzoate of amy lo-salicyl. '7 ('j 13[4 'Ill) '2 f 0 benzoate of amylo-salicyl. c H50 This body crystallizes in splendid needles. The preceding results are in perfect harmony with the theoretical views aclraiicecl in my most recent publications.

ISSN:1743-6893    

DOI:10.1039/QJ8550700060

出版商:RSC    

年代:1855

数据来源: RSC

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MR. WINKLES ON TRIMETHYLAXJNE IN SALTED HERRINGS. 63 VZII.-On the existence of Trimethytamine in the brine of salted herrings. BY GERSHAMHENRYWINKLES. In the second memoir of Dr. Hofmann’s “Researches into the Molecular Constitution of Organic Bases,” published in the Philo- sophical Transactions for 1851 we find at page 392 the following note on Propylamine “M. Wertheim the discoverer of this base believes that it stands to the unknown propyl-alcohol* in the same relation which exists between methylamine ethylamine and amylamine on the one hand and methylic ethylic and amylic alcohol on the other. It deserves however to be noticed that the formula C H N for this compound as determined by experiment expresses not only propylamine but also trirnethylamine and even methyl-ethylamine In the absence of decisive reactions it remains doubtful which of these formulE represents the base obtained by the action of soda-lime on nar- cotine.I may state here that propylamine as prepared by Wertheirn’s process and the liquid containing trimethylamine-for as yet I have not obtained this substance perfectly pure-exhibit the same remark- able fishy odour. It deserves moreover to be remarked that Dr. An-der son found that propylamine occurs associated with methylamine among the basic products of the decomposition of codeine.” To remove the doubts which existed in regard to the formula of the above-mentioned base C,H,N I undertook at the request of Dr. Hofmann the following investigation. The first consideration was how and from whence to obtain the base in a state of purity and in sufficient quantity for the necessary experiments.Besides the two sources mentioned in Dr. Hofmann’s note viz. the action of soda-lime on narcotine and the decomposition of codeine Wertheim detected its presence in the decomposition of fishy matter; I therefore resolved to look for it in the ordinary salted herrings or rather in thc briiic in which they arrive here from the coasts of Scotland and other fishing stations. * The propyl-alcohol has been since discovered by M. Chancel. This brine consisting of salt portions of broken fish roe &c. is collected by the retail dealcrs in London and sold in barrels of about 4 cwts. each to the manufacturers of anchovy sauce in the preparation of which it is largely used.Propylamine being according to Wertheim of a biglily inflammable nature I found no difficulty in detecting its presence. A small portion of the brine was acidified with hydrochloric acid evaporated to dryness and the residue introduced into a test-tube together with potassa and heated. A powerful odour of ammonia mas given off and on approaching a lighted taper the evolved gases burnt freely at the mouth of the tube. The presence of the base or of some similar bases being thus established I was now able to proceed on a larger scale. The contents of one barrel about 26 gallons by measure were acidified with crude hydrochloric acid ; filtered ; and the filtrate evaporated nearly to dryness ; distilled with lime ; the distillate again acidified evaporated and distilled with potassa thus getting rid of all the nauseous fish-oils obtained in the first process.The distillate was again acidified with hydrochloric acid ant1 evaporated down as far as the hygroscopic nature of the salts por-witted then treated with absolute alcohol and filtered in order to I-emove the large quanti-cy of chloride of ammonium present. After distilling off all the alcohol sticks of potassa were intro- duced into the retort and the anhydrous bases condensed in a cooling apparatus. During this operation a large quantity of uncondensed inflammable gas passed through the two-necked receiver and was absorbed by water. The condensed liquid proved to be a mixture of several bases at least of four the boiling-point commencing at 35' C.and rising to 14Lf.oo,remaining somewhat stationary at varions intermediate points; but as the substance prepared was not sufficient for the * experiments I proceeded at once with a second cask of herring-salt and by following a process recommended by Mr. Warren Delarue avoided the trouble and the great loss of time and sdi-stance which I had before experienced. The brine together with some lime w~s put into a copper-still having an ordinary worm-tub as coridensor ; a pipe connected with a large steam-boiler and open at the end mas passed through the lid to the bottom of the still. By this arrangement steam at a high pressure was forced through the mixture of herring-salt and lime carrying with it all the volatile products set free by the alkali.TRIMETHYLAJIINE IN THE BRfYE OF SALTED HERRXSGS. The first six gallons of this distillate being an aqueous solution of *he bases was acidified with hydrochloric mid evaporated and treated with absolute alcohol in the same manner as the first portion. And here I should mention that chloride of ammoihm though slightly soluble in absolute alcohol seemed to lose that solubility in the presence of the hydrochlorates of the bases for which I was in search as I could not detect a trace of ammonia in any of the further manipulations. After evaporating the alcohol the concentrated aqueous solution of the hydrochlorates was gradually introduced by meam of a safety-tube into a retort filled with caustic lime the heat arising from the decomposition being suEcient to carry on the distillation without t&e aid of a gas-flame.The less volatile bases condensed as usual were collected in a two-necked receiver ;the more volatile passed from thence through several U-tubes immersed in a strong freezing mixture a form of apparatus by means of which a few days previously Dr. Hofmann had succeeded in preparing trimethylamine. Long before any trace of liquid could be observed in the globe- receiver the IT-tubes were filled with a clear colourless trans- parent fluid which had to be removed several times before the distillation was complete In this way I obtained more than a quarter of a pint of anfiy-drous base which had to be kept under ice in order to preserve it.Only a small quantity of the less volatile bases was obtained even at a high temperature; in appearance they were the same as obtained from the first operation. But as yet I have not been able to study them the more volatile ones claiming my immediate attention. The boiling point of this interesting body lies between 4O and 5' C. corresponding exactly to that of trimethylamine as obtained from the decomposition of the oxide of tetramethylammonium by heat in appearance and odour no difference can be perceived. Water or alcohol absorbs this base as rapidly as it does ammonia and mixed with about one-half its volume of water I have been able to keep it; mixed with its own bulk of water it still retains its inflammability burning like ether.It is powerfully alkaline neutralised with hydrochloric acid it forms a veiy deliquescent salt which with bichloride of platilium forms a magnificent double salt crystallizing in orange-coloured QC tahedrons. VOL. VI1.-NO. XXV F On analysis the following results were obtained *3125 grm. of platinum-salt gave -1165 grm. of platinum. >J 9, 9530 >9 , *1315 ?? ‘3680 7 , -1805 , carbonic acid. ,J 19 >f tf , *1250 9 water. Percentage. ./ -\--Platinum . 37.28 37.25 Carbon . . 13.377 Hydrogen . 3.776 The following theoretical values correspond to the formula C H hT,HC1 Pt C1 Theory. Xxperiment. OF--6 equivs. carbon . . 36-00 13.575 13,377 10 , hydrogen . .10.00 3.771 3.776 1 , nitrogen . * 1&00 5.279 3 , chlorine . . 106.50 40.161 1 , platinum . . 98.68- 37.214- 37-265 265.18 100*000 Having thus obtained the substance corresponding in com-position &c, to IVert h e irn’s propylamine T proceeded to determine the constitution. On examining the above-given formulze it will readily be seen that,in order to produce a base corresponding in its reactions to the oxide of Dr. Hofrnann’s fourth class compound ammonias we should hwe to substitute respectively one two or three equivalents of an alcohol-radical; by this method of proceed-ing the correct formula must at once be ascertained. On adding iodide of methyl to a few drops of anhydrous base combination took place instantaneously giving rise to explosions and intense heat the white solid thus formed in the test-tube being ejected with violence.By diluting the base with water or better with alcohol previous to adding iodide of methyl the action takes place in a more quiet manner. After heating the resulting iodide in order to remove the exces8 TRIMETHYLAMINE IN THE BRINE OF SALTED HERRING:'. of iodide of methyl present it was dissolved in boiling water frotn which it separated again on cooling in beautifid white rectangular prismatic crystals. Analysis of this salt dried at 100' C, gave the following results ,7512grm. of iodide of the base gave *5813 of iodide of silver. ,4138 , I> , ,3626 , carbonic acid. 9> ?> >J , ,2237 , water. Percentage. Iodine .. 63,425 Carbon . . 23.89 Hydrogen . 6-00 The following theoretical values correspond to the formula Theory. Experiment t3 equivs. of carbon 48.00 23.869 23.89 12 , hydrogen 12.00 5.967 6.00 1 , nitrogen 14.00 6.962 1 iodine 227*10 63*202 63.425 201.10 100~000 On adding to an aqueous solution of the iodide some potash the iodide separated unaltered being less soluble in a solution contain- ing that alkali than in pure water. Oxide of silver added to the solution of the above salt removed the iodine as iodide of silver without the evolution of any volatile substance even on ebullition the solution becoming strongly alka- line. These two reactions prove that the base found in decomposed fishy matter is trimethylamine and not propylamine as supposed by Wertheim.An analysis of the platinum-salt formed by the addition of hydrochloric acid and bichloride of platinum to the oxide liberated by oxide of silver as above gave the following results 68 MESSRS. MORLLEY AND ABEL ON I. -1838 grm. of platinum-salt gave *06Mgrm. of platinum 11. *3266 >? ,? -1148 93 ?? 03675 , *2420 , carbonic acid YJ >¶ J> , -1495 JJ water. Percentage. -Platinum . 35.04 35.35 Carbon . 17-96 Hydrogen . 4.57 The following values correspond to the formula c H3' I N C1 Pt C1, c H3 c H3 Theory. Experiment ,.--\^-c--- 8 equivs. of carbon 45*00 17.193 17.96 12 , hydrogen 12.00 4.298 4.57 1 , nitrogen 141.00 5.015 3 , chlorine 106.50 38.144 1 platinum 98-68- 35,350- 35.10 279.18 100.000 C HIzN C1 Pt C1, '2 =

ISSN:1743-6893    

DOI:10.1039/QJ8550700063

出版商:RSC    

年代:1855

数据来源: RSC

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3fESSRS. MORLLEY AND ABEL ON IX.-Ort the Aclion of Iodide of Ethyl on Tohidine. BY~~EGINALD AND JOHNS. ABEL, I MORLEY ASSISTANTS IN THE ROYAL COLLEGE OF CHEMIBTRY. Chemists are acquainted with the results obtained by Dr. Hof-mann in his researches on the organic bases which led him to establish the existence of four groups of bases derived from ammo- nia by the replacement of its several hydrogen equivalents by organic radicals. He pointed out at the same time a simple method of ascertaining in what group an organic base has to be classified. This method as is well known consists in treating the substance under examination with the iodide of an alcohol radical. The experiments to which we are about to refer undertaken at THE ACTION OF IODIDE OF ETHYL ON TOLUIDIHE.his invitation and carried out wider his kind superintendence refer to the examination in this direction of an orgauic base which has repeatedly claimed the attention of the facul ty-viz. Toluidiae. The origin of this body derived step by step from toluylic acid toluol and nitrotoluol places the substance on the same line with the aniline the formation of which from benzoic acid benzol and nitrobenzol is well known. The perfect homology of toluidine and aniline is moreover nnequivocally proved by their physical proper- ties. The constitution of aniline has been established it may be said beyond any doubt it has been proved that in its salts the substance may be received as ammonium in which 1 equiv. of hydrogen is replaced by 1equiv.of the hydrocarbon C1 H, to which the name of Phenyl has been given or in the free state as ammonia 1 equiv. of hydrogen of which is replaced by the same radical. Salts. Free Rases. H Aniline c1 Aniline N 1 I"f 1 salt c,!2H5 Cl H5 If toluidine is a perfect homologue of aniline its constitutioii must be perfectly similar ; so that if the latter has in fact this con- stitution toluidine must be represented by the formula H" p, Cl* H when it becomes arnmonia in which 1 equiv. of hydrogen is re-placed by toluyl C, H ; and it is this constitution which has been assumed by Dr. Hofmann in his papers on the bases. It re-mained to verify this assumption experimentally. This verification forms the subject of the present communication.We rapidly pass over the preparation of toluol from coal naphtha although we had to perform an immense number of distillations until the hydro- carbon at last boiled stationary at 111' C. (231°08F.) The con- version of toluol into nitrotoluol is attended with difficulties heat must be carefully avoided otherwise a considerable quantity of dinitrotoluol is produced which forms far more readily than dini- trobenzol. The reduction of nitrotoluol by means of sulphuretted hydrogen lastly is an operation tedious in the extreme; it can be accomplished only by a series of supersaturations and distillations. The purification of the toluidine mils effected in the form of oxalate. On account of the facility with which it was obtained we selected from among the alcohol-iodides iodide of ethyl as the substance to the action of which the toluidine was to be submitted.We now proceed to describe the results obtained in this reaction. ETHYLOTOLUIDLNE. A portion of the toluidine was sealed up in a tube with excess of iodide of ethyl and exposed to the temperature of the water-bath for two or three days. The toluidine mixed with the iodide and the whole became one crystalline mass; towards the latter part however an oily layer separated on the upper surface of the liquid. The tube was now opened and the excess of iodide of ethyl ctis- tilled off in a water-bath when iodide of ethylotoluidine remained as a heavy oil possessing a peculiar alliaceous smell; this oil was decomposed by distillation with a strong solution of potassa at a high temperature when a colourless oil distilled over lighter than water and possessing a peculiar odour.This oil the new base was separated from the water with which it had distilled over and dried over stick potash. When thus rectified its boiling point was found to be 21;' C. (422O.6F.) tlie spec. grav. being 0.9391 at 15O.5 C. (60' F,) From the comparison of the boiling points of aniline (about 180' C.} and toluidine (200° C.) we might have expected that by the introduction of 4 equivs. of carbon and hydrogen into the latter base its boiling point would have been raised about 40°C. It appears however that this rule does not hold good in all cases of this kind Dr. Hofmann having observed a similar comportment with ethylaniline.Platinum-salt of EthylotoZuidine.-This was at first prepared by adding excess of hydrochloric acid to the liquid from which the base had been separated and which possessed a strong alkaline reaction. The hydrochlorate thus formed was evapo-rated on a water-bath until when mixed with bichloride of platinum thc double sclt crystallized on cooling. In this manner a considerable quantity of a fine crystalline salt was obtained soluble iri water and when washed with alcohol of ca pale yellow colour. For analysis a portion of the crystals was TEE AC'I'ION OF IODlDE OF ETHYL OK TOLUIDINE dried in the water bath until the weight was constant and burnt as usual The quantity of platinum obtained was slightly too large for ethylotoluidine; a circumstance x-hich we explained by the possible presence of a trace of toluidine in the liquid from uliich the salt was prepared.An attempt to recrystallize the salt only resulted in the total loss of our substance by dcconiposition; a fresh portion of hydro-chlorate was prepared from some of the base evaporated 2nd mixed with bichloride of platinum ; a precipitate was formed which dissolved in excess of the bichloride from which solution the salt could not again be obtained. It was necessary therefore to add the platinum solution very cautiously and when the precipitate was formed alcohol mas added which dissolved the salt but again deposited it on agitation after a short time. In this manner with much trouble suscient platinum-salt was prepared for another determination.The double salt being very soluble in alcohol it was washed with ether; it was found to decompose at 100' C. AS the colour became darker and no constant weight couhl. be arrived at it was dried for analysis in vacuo over sulpliuric acid. 0*1580grm. of platinum-salt gave 0.0460 , platinum = 29.11 per cent. According to the formula C, H, N H C1 Pt Cl, or H the percentage of platinum should be 28.93 per ceiit. The difference is 0.08. Our next step was to confirm the composition of the base by a determination of the carbon and hydrogen. The platinum-salt being so difficult to obtain we burnt the base itself which as it darkens on keeping like aniline toluidine &c. was redistilled for this purpose.0.1425 grm. of substance gave 0.4175 , carbonic acid 0.1255 , water leading to the following percentages Carboii . * 79.90 IIydrogcn . . !)*78 The formula requires the following values Theory. Experiment /-1S equivs. of mrbon . 108= 80.00 79.90 13 , hydrogeu . 13= 9.63 9.78 1 , nitrogen . 14= 10.37 135 100.00 These numbers sufficiently establish the composition of ethyl-toluidine. Ethyfotoluidine forms crystalline compounds with oxalic and mlphuric acids. DIETHYLOTOLUIDJNE A portion of the ethyl-base was next sealed up with an exeess of iodide of ethyl and exposed for two or three days to the tempera- ture of boiling water in order to produce diethylotoluidine. After tha5 time on allowing the tube to cool and gently agitating it beautiful crystals of the iodide of the new base at once formed throughout the whole length of the liquid which dissolved again on placing the tube in the water bath.The excess of iodide of ethyl was again separated as before when the iodide of diethylo- toluidine remained in the flask &om which it crystallized in fine six-sided prisms so soluble in water that they could scarcely be crystallized from it. The salt separated from the aqueous solution in oily drops which assumed the crystalline form on being touched with a glass rod. It appeared to be decomposed by alcohol as also by continued exposure to the atmosphere. For analysis some of the recrystallized salt was dried in vacuo over sulphuric acid (the crystals having been found to decompose in the water bath) dissolved in water and the iodine determined by precipitation with nitrate of silver in the usual manner 0.3130 grm.of iodide gave 0.2520 , iodide of silver orrespo nding to percentage of iodine 1113.445.The formula c,4 I-1, C H i X HI= C, EI18N I c4 H THE ACTION OF IODIDE2 OF ETHYL ON TOLUIDINE requires 43.66 per cent. of iodine; thus proving the crystals to have the above composition. The remainder of the salt was distilled with potash and the base thus obtained on the surface of water from which it was separated. Diethylotoluidineis colourless and possesses a smell like the former compound. After rectification from potash it was found to boil at 229O C.(44AO.2 F.) thus showing another deviation &om the rule. Its spec. grav. at 19O-5C. (GOo F.) was 0.9242. The preparation of the platinum-salt of this base presented insur- mountable diEculties it could not be obtained otherwise than as a resinous mass to crystallize which all attempts were abortive. A combustion of the base was however made 0.1495 grm. of substance gave 0,4435 , carbonic acid 0.1410 , water leading to the following percentages Carbon . . 80.90 Hydrogen . . 10.47 The formula requires the following values Theory. Experiment. /--22 equivs. of carbon . . 132 80.98 80.90 17 , hydrogen . 17 10.43 10.47 1 , nitrogen . 14 8.59 -__. -. 163 100*00 The results obtained correspond therefore sufficiently with the above formulz.OXIDE OF TRIETHYLOTOLUYLAMMONIUM. It now remained for us to convert the volatile into a fixed base similar to those which Dr. Hofmann has distinguished by the laboratory term ammonium-bases. The formation of such a substance by the introduction of another equivalent of C4 H5 into diethylotoluidine would establish beyond any doubt the perfect homology of aniline and toluidine. MESSRS. MORLEY AND ABFL ON This new base might be called oxide of triethylotoluicline or oxide of triethylotoluylammonium. For this purpose we again sealed up the last base with iodide of ethyl and exposed the tube to a temperature of 100’ C. (212OF.) for some days till fine prismatic crystals of an iodide had formed in the solution.After distilling off the excess of iodide of ethyl as befwe the iodide of the new base remained as a heavy oil :this was decom- posed by heating with freshly precipitated oxide of silver when the liberated oxide of trietliylotoluylammonium at once entered into solution leaving iodide of silver. The solution after filtration was found to possess an extremely bitter taste and to be very alkaline to test-paper. With salts of the metallic oxides a solution of this base behaved in most cases similarly to potash and to Dr. Hof-mann’s oxide of tetrethylammonium thus with salts of baryta strontia lime and magnesia a white precipitate insoluble in excess was formed. The following is a list of the reactions of this substance Barium-saZls.-White precipitate of the hydrate of the earth insoluble in an excess of the base.Strontium-snZts.-Thite precipitate of the hydrate of the earth insoluble in an excess of the base. Calcium-salts.-White precipitate of hydrate of the earth inso- luble in excess of the base. 2Maynesiu.m-saZts.-VVhite precipitate of hydrate of the earth insoluble in an excess of the base. Aluminum-saZts.-VVhite gelatinous precipitate soluble in large excess of the base. Chromium-salts. -Green hydrated sesquioxide insoluble in excess. NickeZ-saZts.-Green protoxide insoluble in excess. Cobalt-salts.-Pink hydrate of protoxide insoluble in excess. Manganese-salts. -Whitish hydrated protoxide insoluble in excess. Salts of Protoxide of Iron.-Green hydrated protoxide insoluble in excess.Sults of Sesquioxide of Iron.-Brown hydrated sesyuioxide insoluble in excess. Zinc-saZts.-H;ydrate of the protoxide soluble in excess. Lead-salts.-White hydrate of protoxide soluble in excess. Silver-salts.-Brown protoxide insoluble in excess. Salts of Suboxide of Mercury ,-Black suboxide insoluble in excess. THE ACTION OF IODIDE OF ETHYL ON TOLUTDlNE. Sults of Protoxide of Mercwy.-White precipitate insoluble in excess. Copper-salts.-Blue hydrated protoxide insoluble in excess becoming black by ebullition. Cachnium-salts.-White hydrated protoxide insoluble in excess. Bis?nuth-saZts.-White hydrated teroxide insoluble in excess. Antimony-salts Teroxide.-\White hydrated teroxide soluble in excess. Salts of Protoxide of Tin.-White hydrated protoxide soluble in excess.Salt oj Binoxide of Tin.-White hydrated binoxide soluble in excess. Gold-salts.-Yellow precipitate of the double salt. Ptatinum-salts.-Yellow precipitate of the double salt. Platinum-Salt.-When the chloride of this base was mixed with bichloride of platinum a copious precipitate of a fine crystalline platinum-salt was produced which was nearly insoluble in cold water but was dissolved readily in hot water from which solution it crystallized in beautifid needles. The salt was thrown upon a filter washed and dried at loooc. Both the original and crystallized salts were analyzed. I. 0.1640 grm. of platinum-salt gave on ignition 0.0410 , platinum. IT. 0-6100grm. of platinum-salt gave on ignition 0.1515 , platinum.Theoretical Experimental percentage. percentage. Platinum . . 24.85 24.91 Recrystallized salt. 0.5212grm. of platinum-salt gave on ignition 0.1292 , platinum. Theory. Experiment. Platinum . 24-85 24.5 It appears therefore that this platinum-salt like some observed by D r. H ofni ann loses platinum by recrystallization. For combustion some of the original salt cuts employed. 76 NESSRS. MORLEY AND ABEL ON THE ACTION OF IODIIX OF KMYL. 0.5300 grm. of platinum-salt gave 0.7600 , carbonic acid 0.2690 , water and 0.1310 , platinum. The numbers required by the formula are shown in the following table together with the numbers obtained by experiment from which it will be seen that little doubt can remain as to the formula of the salt analyzed.-Theory. Experiment. 26 equivs of carbon 156 39.27 39.11 22 1 1 , , , hydrogen nitrogen platinum 22 14 98.7 5.54 3.52 2485 5.64 24*71 3 , chlorine 106-5 26.82 -_I___ 397.2 10000 These experiments establish the existence of the following bases which we place in juxtaposition with those of the homologue phenyl. Phenylamine Aniline H H Eth ylaniline C H5/N Ethylotoluidine C H5\N Cn H5 c14 H c* H5 c4 H Diet hylauiline C H5\ N Diethylotoluidine C H:] N cn H5/ c,4 H Triethylaniline N Triethytoluidine In conclusion we may observe that the combustion of this pla- MR,. WATiTJACE ON R,ED PRUSSTAT’E OF POTASH. tinum-salt as well as all the combustions made in the coinse of this investigation were performed in Dr.Hofrnann’s new gas furnace for organic analysis. It deserves to be mentioned that to ensure complete combustion the liquids were weighed in small open tubes filled with oxide of copper and a little powdered chlorate of potassa the oxygen of which expelled with the last stage of the process ensured the complete combustion of any small particles of carbon that might otherwise have remained unconsumed.

ISSN:1743-6893    

DOI:10.1039/QJ8550700068

出版商:RSC    

年代:1855

数据来源: RSC

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MR.. WATiTdACE ON R,ED PRUSSTAT’E OF POTASH. X.-On Red Przcssiate of Potash BY WILLIAMWALLACE. During the present winter I have been engaged with a series of experiments on the yellow and red prussiates of potash. In the pre- sent notice I propose to communicate the results obtained on the following points let the oxydizing power of ferricyanide of potas-sium in presence of potash; Znd the analysis or valuation of com-rnercial red prussiate of potash ;and 3rd the solubility of ferricyanide of potassium in water at different temperatures. Oxydixing Power.-The oxydizing power of ferricyanide of potas-sium especially in presence of an alkali has been investigated by several chemists particularly by Schonbein* and by Bouda1t.t The results of my experiments confirm in general those described by Schonbein and others but in a few cases differences were observed.Several reactions of considerable interest have likewise been added. The action in all cases consists in the conversion of ferricyanide of potassium into ferrocyanide by the absorption of one equivalent of potassium. In the experiments here referred to a certain amount of free alkali was invariably present and the mixtures were generally heated and when necessary boiled. The ferrocyanide of potassium produced was obtained in crystals by evaporation or by the addition-of alcohol. Of lion-metallic elementary bodies iodine was converted into iodic acid sulphur into sulphixric acid and phosphorus into phosphoric acid the latter very slowly. Hydrogen gas was not oxydized.Of the metals iron zinc bismuth lead tin arsenic and antimony * J. pr. Chem. XX 128. t Ibid. XXX,23 were rapidly oxydized but copper and mercury were not sensibly affected. In all cases in which the resulting oxides were soluble in potash the ferricyanide was rapidly and completely converted into krrocvanide the liquid becoming nearly colourless Of non-metallic Compounds hinoxide of nitrogen was converted into nitric acid sulphurous and hyposulphurous acids into sulphuric acid (the latter with difficulty) and oxalic acid into carbonic acid. Of metallic oxides the protoxides of iron manganese cobalt nickel lead and tin were raised to the state of' peroxides the suboxides of copper and mercury to protoxides sesy uioxide of chromium to chromic acid oxide of antimony to antimonic acid aud arsenions acid to arsenic acid.The protoxides of zinc and bismuth were not altered The experiments were performed by mixing ferricyanide of potassium with a salt of the oxide warming the mixture and then adding potash in excess. Of other inorganic compounds sulphide and iodide of potassiuni gave up their metal to the ferricyanide with separation of sulphur and iodine the sulphide and iodide being present in excess. The sulphur and iodine were dissolved by the potash but were precipitated 01 neutralizing the liquid with an acid. A similar action occurred with the sulphides of the heavy metals especially with those which are soruble in potash Cyanide of potassium was converted into cyanate of potash.Most organic compounds which are not of a very stable nature are more or less readily oxidized by ferricyanide of potassium in presence of free alkali. A solution of ferricyanide with potash boiled with sugar in excess was rapidly and completely converted into ferrocy- anide the sngar being oxidized to carbonic acid and water. A similar action was observed to occur with gum starch dextrin and paper but much less readily than with sugar. VT'hen alcohol was treated in the same manner the greater part of the salt was rapidly converted into ferrocyanidc j but a portion was decomposed with pro- bable formation of cyanate of potash sesquioxirle of iron having been precipitated. The alcohol seemed to be converted into carbonic acid and water.In the arts ferricyanide of potassium has been employed for dis- charging ur bleaching indigo and the colouring principles of cochineal and lac-dye. It also destroys litmus turmeric arid many other colours but does not bleach them completely. RED PRUSSIBTE Or’POTASH Valuation of Commercial Red Prussiate of Potash.-This salt is met with in commerce in two states viz. in crystals and in powder. The latter variety is sometimes prepared by grinding the crystals but more frequently by exposing finely-pulverized ferrocyanide of potassium to the action of chlorine gas. The product is a mixture of ferricyanide and chloride of potassium In its preparation a portion at least of the water of crystallization of the ferrocyanide must be retained for the dry salt is very little affected by dry chlorine gas; consequently the product uizless purposely dried must always be contaminated with a certain proportion of water.The chloride of potassium and water were found to amount to about 22 per cent of the powder when freshly prepared. Besides these there may exist accidental impurities arising from the employment of impuiu ferrocyanide a deficiency of chlorine and other circumstances ; and it might also be largely adulterated with common salt without ma-terially influencing its appearance. A simple and ready method of estimating its value is therefore of some importance. Mr. Lieshinp has recently published a very elegant process for the estimation of the amount of pure ferricyanide in the commercial product.He converts the salt into ferrocyanide by the action of sul- pharseniate of sodium; but as this reagent is difficult to prepare the application of Mr. Lieshing’s method must necessarily be limited. Many substances capable of being easily oxidized mere tried with the same object but protochloride of tin in presence of hydrochloric acid was found to be most suitable. The process about to be de-scribed is confidently recommended as being exceedingly simple and as yielding very accurate results. It is based upon the well-known reducing power of proto-compounds of tin ;and the tendency which ferricyanide of potassium has to combine with an additional equivalent of alkali-metal or of hydrogcn forming ferrocyanide of potassium and hydroferrocyanic acid.The decomposition may be thus represented 2(K,Fe,Cy,) +2 HCl+ 2SnC1=3 (K,FeCy,) +H,FeCy +2SnCl,. A large excess of hydrochloric acid is added in order to prevent the formation of ferrocyanide of tin. The action is immediate and takes place at ordinary temperatures. 100 grains of the sample of red prusviate under examination are dissolved in an ounce and a half of water and three quarters of an ounce of strong hydrochloric acid are added. An alkalimeter is filled with a solution of chloride of tin having a specific gravity of about * Chem. SOC. Qii. J. April 1853. NR. TVATALACEON ltED PRUdSIAl’E OF POTASH. 1.046 and containing in 100 measures about 35 7 grains of tin. The tin solution is added to that of the red prussiate until the latter loses the green colour that it acquires and becomes of a bright and distinct violet or blue tint without the slightest shade of green.The exact point at which this effect occurs is easily ascertained by placing a drop of the liquid on a slab after each addition of the tin liquor. The blue colour of the solution is owing to a slight decoru- position of the liydroferrocyanic acid produced during the action. A similar experiment is performed with 100 grains of pure and dry fer- ricyanide of potassium and the amount of pure salt in the sample is then obtained by a simple calculation. it was found very convenient to employ a standard solution of chloride of tin of which each division is equal to 1 or 2 grains of pure ferricyanide.This solution may be preserved without material alteration for a considerable period if kept in a properly closed vessel. The accuracy of the process depends upon the extensive colouring power of ferricyanide of potassium. Its solution in 7,000 parts of water is distinctly yellow when spotted upon a slab and communi- cates a great tint to blues. In the process just described a distinct green colouration is observed if 0.2 of a grain of the salt remain un changed in the solution. Sotubility of Ferricyanide of Potassium-Gm elin states that this salt requires for solution 3.8 parts of cold water and a smaller pro- portion of hot water; while Girardin affirms that is soluble in 2 parts of cold and in less than 1 part of hot water. Its solubility at various temperatures has been carefully detcrmined. The results obtained are stated in the following table which likewise exhibits the specific gravity of the solutions at the temperatures mentioned com-pared with water at 60’ F. Temperature. Sp. gr. Soluble in parts water. 100 parts of water dissolve 4!0° 1.151 3.03 33.0 50 1.164 2.73 36.6 60 1.178 2.54 40% 100 1.225 1.70 58.8 212 1*250 1.29 77.5 220 1-265 1*21 82.6 220’ is the boiling-point of the saturated solution. The specific gravity of the salt itself is 1,845.

ISSN:1743-6893    

DOI:10.1039/QJ8550700077

出版商:RSC    

年代:1855

数据来源: RSC