摘要:

ANIMAL FOOD 1N RELATION TO BREAD. XI. -Analysis of the Water of a Spring at Billingborough Lincolnshire. BY J. W. KYNASTON BTUDENT IN THE LIVERPOOL COLLEGE OF CEEMISTRY. THEvillage of Billingborough is situated about nine miles from tIlc shore of the German Ocean on the borders of what a few years agc; was known as the Lincolnshire fen lands all appearance of which however have by cffectual drainiiig entirely disap- peared for a distauceof three miles; these lands now forming a portion of onc of the most valualde of the Crown estatcs. The village derives its name from the peculiar phenomena of ebullition iu the water of the spring its origiual appellation having been " Boiling-borough." The source of the water is supposed to be the River Trent which AOWS at a distance of many miles from the spring.Tho water was exaniiiicd by Sir J oscph Ban k s arid pronounced to bc the purcst in lhiglaid with a single exception that of the cele- KYNASTON ANALYSIS OF THE brated well at Malvern. No comparison between the two waters can however be made as no complete analysis of the latter exists. The author has been unable to find a record of Sir Joseph Banks’s statement with regard to the purity of the Billingborough water and regrets that his results do not confirm the very flattering report said to have been given of this famous spring. The water is nevertheless very highly valued by the inhabitants of the neighbourhood ; and certainly its beautifully clear and sparkling appearance and the fact that in many of the villages of the district scarcely a drop of drinkable water can be procured secm to justify the universally favorable opinion entertained of it.With regard to the temperature it is said to vary and rather curiously become warmer in winter than in summer. This state rnent is not substantiated by experiment. The water has in all probability the same temperature throughout the year and is supposed to become warmer in winter because of the depressed temperature of the air and surrounding objects. On the 30th October 1858,it was 51’ Fahrenheit. Exainiization of the gases evolved.-These were collected in the ordinary manner. A few minutes sufficed to fill a pint jar. Car-bonic acid was absorbed by a solution of potash and the oxygen by phosphorus; the remaining gas was found to be pure nitrogen.The determinations gave the following results centesi- mally :- Cubic inches. Carbonic acid . . 3.428 Oxygen . 4-143 Nitrogen 92.429 Eximinutioiz of the wuter.-Qualitative examination shewcd thc prescnce of sulphuric silicic and carbonic acids chloriiic lime Iuagnesia iron potassa and soda together with tmccs of nitric aid phosphoric acids and of ammonia. The determinations were con- ductcd as follows :-To estimate the whole quantity of carbonic acid one gallon was taken and added to a mixed solution of chloride of barium arid ammonia. The precipitate was transferred to a Will and k’rese- ili us’s alkalimetrical apparatus and trcatcil with nitric acid. ‘I’Iic BILLINQBOROUQH SPRING WATEK.amount of carbonic acid eliminated was 18-80 grains and as subsequently calculated exists as follows :-In combination . . 7.9207 Free . . . 10.8793 18*8000 Sulphuric acid was determined in the portion of the precipitate undissolved by the acid in the preceding operation. It amounted to 4.2426 grains. Chlorine estimated as chloride of silver in 24 ounces gave 1.0625 grains per gallon. The total amount of fixed matters was ascertained by boiling 88 ounces separating the precipitate by filtration and afterwards evaporating to dryness below 212O. After drying the residue at about 300' and weighing it was ignited when a strong smell of burning feathers characteristic of nitrogenous organic matter was perceived.The ignition was continued until the disappearance of all car- bonaceous matters and the residue again weighed. Calculated per gallon the results are as appended :-Grains. Precipitate by boiling . . 15,3144 Residue . . 12.9859 28.3003 Loss on ignition . 2.3713 25.9290 The quantity of lime was deduced by precipitation as oxalate from one gallon and gave 11.230 grains. Lime was also estimated separately in the Precipitate by boiling and in the residue of sub-sequent evaporation and calculated pcr gallon gave- Qrains. In precipitate . . 8.2131 In residue . 2.8489 1100620 Total magnesia estimated as yyrophosphate was- Grain per gallon. In precipitate by boiling . . 0-1969 In residue . . 0.5575 0.7544 KYNASTON ANALYSIS OF THE The amount of iron was determined as sesquioxide in the precipi- tate by boiling and gave calculated per gallon 0.4267grain Fe20,.The total quantity of soda and potassa was estimated in the residue of evaporation as chlorides of the metals and calculated per gallon gave 3.283 grains of mixed chlorides. The quantity of chlorine in these salts was determined by precipitation as chloride of silver and found to be 1.8664 grains. From these data the rcspective amounts of chloride of sodium and potassium were calculated. The result was- Gtrains per gallon. Chloride of sodium . . 2.329 Chloride of potassium . . 0.954 3.283 A direct determination of the chloride of potassium was also effected by combining this salt with bichloride of platinum and the yield was 0.9748 grain.Lastly the silica estimated in the residue of evaporation gave 0.667grain per gallon. The annexed table shows the composition of the water as calcu-lated from the results enumerated above together with the mode of arraiigement of the several ingredients. The amount of carbonic acid in the free state is 10.8793grains = 23*0?cubic inches per gallon. The apparent discrepancy between the weight of the residue of evaporation and that of the total amount of the several consti- tuents as Calculated from the analysis admits of easy explanation. During the evaporation decomposition ensues between the chloride of magnesium and thc alkaline carbonate thus :-MgC1+ M0,C02 = MgO,CO + MC1. On subsequent ignition the whole of the carbonic acid combined with magnesia amounting to 0.613 grain is expelled together with a portion of that which is asso-ci:kd with lime.Tiien the iron calculated as carbonate of the putoxide would exist iu the precipitate by boiling as sesquioxide mdcing a difference of 0.1917 grain. And again during the ignition of the residue the silicic acid expels carbonic acid and tlie carbonaceous matters reduce a portion of sulphate to sulphide thus :-KO,SO + 2C = KS + 2C0,. Taking into considera- tion thesc sources of loss it will be secn that the two numbers do not vary bc~wiidtlie allowable limit. With regard to the orgauic matter it is evideiit from thc above -I Sesqui-:arbonic lulphurii 3hlorinc Lime. dagnesia oxide of In one gallon of water.C.r a ins. acid. acid. Soda. Potassa. Si1ica. iron. Carbonate of Lime -14-6660 6-4530 8.2131 Carbonate of Magnesia -0.4135 0.2166 0.1969 Carbonate of Iron -0,6187 0 2347 0.4267 Sulphate of Lime -6.9189 4.0700 2.8489 Sulphate of Potaasa -0.3759 0.1726 0.2031 Chloride of Magnesium -1.3240 0.9895 0.5575 Chloride of Potassium -0.1534 0.0730 0.0968 Carbonate of Potassa -0.4402 0'1404 0,2998 Carbonate of Soda -2.1100 0 8760 1.234 Silica --0*6670 0.6670 Nitrate of Ammonia -traces Phosphoric Acid -7) Organic Matter ->-27'6876 7.920'7 4.2426 1-0625 11.0620 0.7544 0 4267 1.234 0.5997 0*6670 HOFMANN Oh' AMMONIA that the loss of the residue of evaporation by ignition cannot be taken to rcpresent thc amoimt prcsent; nor can it be ascertained with positive accuracy.From calculation it appears to be about 0.75 grain per gallon and certainly does not exceed one grain A concise and accurate rncthod for the determination of organic matters in water is much to be desired. It remains to be noticed in connection with this water that there is within a distance of twenty-five yards of the spring mother one of a totally different character having a strong chalybeate taste and much famed for its tonic qualities ; and close to the latter is yet another containing but little iron and famous as an application to ulcerated eye-lids.

ISSN:1743-6893    

DOI:10.1039/QJ8601200057

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

HOFMANN Oh' AMMONIA XI.-On Ammonia and its Derivulives.-Conclusion of a Discourse delivered to the iWembers of the Chemical Society of London. BY PROFESSOR HOPMANN. B. AMIDES. BY this term Chemists have designated a very large class of substances derived from ammonia by substituting for the hy- drogen acid-radicals whose presence destroys the fundamental cha- racter of ammonia viz. its power of combining with acids. The amides have been often defined as neutral derivatives of ammonia similar in constitution to the amines. But it ought to be noticed at once that the division of the ammonia-derivatives into amines and anaides is essentially artificial; there is in fact a gradual transition from one group to the other and frequently we meet with substances the position of which in the system is uncertain.Allusion has already been made to the extreme weakness of the saline compounds of many amines some of which are decomposed by mere contact with water. On the other hand,recent researches have proved that in several substances long considered as well established amides the basic character of the mother-compound is far from being extinct and that under special circumstances combinations with acids may be formed in many respects analo- gous to the ammonium-salts but of comparatively little stability. A much more characteristic mark of distinction between the AND IT8 DERIYATI YES. amines and amides is furnished in the deportment of the two classes under the influence of decomposing agents.We have seen that hitherto very few processes are known in which the amines yield up in any form the radicals whose introduction into ammonia has produced them. The amides on the other hand are readily decomposed into ammonia and the hydrated oxides of their radicals. The simplest manner of distinguishing an amine from an amide consists in boiling the compound under examina-tion with potassa when the amine remains unaltered the amide evolving ammonia with formation of a potassium-salt. With very few exceptions the amides are artificial compounds. Some of the processes which give rise to their formation are of very general applicability so as to adinit of the production of an almost unlimited number and variety of these substances. a. Monamides.By this term we designate the amides derived from one molecule of ammonia. The monamides like the monamines may be classed in three subdivisions according to the number of hydrogen-equivalents in the ammonia-molecule which are replaced. We distinguish-a. Primamj monamides. p. Secordary rnonanaides. y. Tertiary monamides. N H H The primary and secondary monamides are solid crystalline bodies fusible and volatile at high temperatures without decom-position ; the tertiary monamides arc partly liquids likewise volatile without decomposition. a. Primary Monamides. From the very considerable number of substances belonging to this class we select the following terms as illustrations; almost every one of them represents a homologous series.Acetamide C,H,N02 - €I HOFMANN ON 4Bf MONTA Chloracetamide C,H,ClNO c4"c"021 H H C,Cl30 Tric hlor met amide C4 H,C1 ,NO H ]N H CHO Butyramide C,HyKO 'd 'IN H Benzamide 7N '2 14 '' H '14 (E149N04)02 Nitrobcnzamidc H H Cinnamide C18H9N02 H Anisamide H Cumaramide H Sulphophen yl- amide H The monamides stand in a very simple relation to the ammo-. nium-salts of the monobasic acids from which they differ by containing 2 equivs. of water less. In some cases they may be actually prepared from the ammonium-salts by simple dig- tillat ion. CHO c4H302) 0 = H,O + *H3 'It. CH4YI H Acetate of amoniurn. Acetamide. A better process consists in submitting to the action of heat a mixture of the potassium-salt with chloride of ammonium.[H,N]Cl+ c14HK5021 0 = H,02 -t KC1 + c14g5021 I3 Benzoate of potassium. Benzamide. The ethers of the monobasic acids (methyl- ethyl- even glyceryl- compounds) when treated with aqueous or alcoholic ammonia are likewise converted into monnrnides. H3N + 'SH7",) 0 = CH 4H5) 0 + C4H5 H Butyrate of ethyl. Alcohol. Butyramide. At the common temperat ure protracted contact is required but under pressure at temperatures between 110" and 120° the reaction is readily accomplished. In a similar manner the anhydrous monobasic acids the so-called anhydrides are converted into monarnides by treatment with ammonia. -Cinnamic anhydride. Cinnamate of ammonium Cinnamide. The most general rapid and elegant process for the preparation of the monamides consists in treating the chlorides corresponding to the acids with gaseous ammonia or with dry carbonate of ammonium.Chloride of anisyl. Animmide. 2H,N + (Cl,H,04S2)C1 = [H,N]Cl + H """""'"'I H ~~ Chloride of sulpho-Sulphophen ylamide. phenyl. The primary monamides are readily converted into the ammo- nium-compounds of the monobasic acids by the assimilation of VOL. XII. F fit> JTOFMANN ON AMMONlA 2 cquivs. o€ water. Sometimes the transformation is cffcctcd hj simple cbullition with water it is so illvariably by treatmctit with minernl acids or more readilg still by boiling with potrtssa- 8. Secondary Monamides. This class is most numerously represented.It may be conve-nicntly subdivided into 3 groups according to the manner in which the 2 eguivs. of hydrogen are replaced. 1. Substitution of 2 monatomic acid-radicals either of the same or of different kind. 2. Substitution of 1monatomic acid-radical and 1 monatomic alcohol-radical. 3. Substitution of 1diatomic acid-radical. 1. As illustrations of the first subdivision we quote-C4H302 Diacetamide C,H,NO4 = c4H302)N H Di sul phopheny1-C24H,,N0f%S4 = C12H504S2 amide 2H504s21 H Sulphopheny1 ben- c26H11N06S2 = C14H!j02 zamide c1=H504s21 H These bodies are obtained from the primary monamides by the action of monatomic chlorides when hydrochloric acid is eliminated ''12H504S2 H + (C,,H,O,S,)Cl= HC1 + C,,H,04S N, "'""""'"1 H Chloride of sulphophenyl.H Suphophenyl. Disulphophenylamide. amide. or by treatment with hydrochloric acid ammonia being separated in the form of chloride of ammonium. Acetamide. Diftcetamide. AND ITS DERIVATIVES. The action of acids and alkalies upon the secondary mona-mides climinates ammonia with reproduction of the acids whose radicals are present. 2. The following are members of the second subdivision of the secondary rnonamides ; in these substances oiie equiv. of ammonia-hydrogen is replaced by an acid-radical the other by an alcohol- radical. Methylacetamide Ethylacetamide Phenylace tamide Phenylbutyramide Phenylbenzamid e Phen ylanisamide Phenyloxaluramide The substances belonging to this group are formed by sub-mitting the primary monamines to the several processes which when applied to ammonia furnish the primary monamides.If we bear in mind the large number of primary monamines with which we are acquainted or which may be obtained by known processes it is obvious that the group of the secondary mona- mides must be almost unlimited. Comparatively few of these substances have actually been formed; the only moramine some- what inore minutely examined in this direction being phenyla-mine. The following examples illustrate the formation of these substances F2 HOFMANN ON AMMONIA Distillation of the Salts of Primary Monamines. N HCl+ c4E3021 O,= KC1+ H202+ H J H Hydrochlorate of phenylamine.Acetate of potas-sium. l'henylacetamide. Treutment with Ethers. Methylamine. Acehte of ethyl. Alcohol. Methylacehmide Action of Acid-anhydrides Phenylamine. Butyric anhydride. Butyrate of aniline. Phenyl butyrarnide. Action of the Chlorides of Monobasic Acids. C12H5 C12H5 1+ N (C16H,0,)C1 = R N HC1+ C16H704]N -I H N _ _ _ ~ -Phenylamine. Chloride of anisyl. Hydrochlorate of Phenyl-anisamide. phenylamine. Secondary rnonamides lastly have been obtained by the action of acids upon some of the tertiary monamides. Cyanate of ethyl. Acetic acid. Ethylaetamide. These substances may probably be produced also by treating the primary monamides with the bromides and iodides of the alcohol- radicals. The action of acids and alkalies upon these mixed secondary mouamides gives rise to the reproduction oE the acids and of the monamines the radicals of which are associated in the monamide.AND ITS DERIVATLVES. 3. Th? members of the third group of secondary monamidm those in which the 2 equivs. of hydrogen are replaced by one diatomic acid-radical were formerly designated by the term imides which is still occasionally used. The following table in-cludes nearly all the compounds of this kind which are at present known Carbonylamide (cyanic acid) C,HNO = gH2(C 0 )//I N Sulpho-carbonylamide (sul-C2HNS p hocyanic acid) - (c22)”) N Succinimide . . . . . C,H,NO = (c83041”1 N Citraconimide . . . . C,,H,N04= (c10g404)”) N Pyrotartrimide . . . . Cl,H,N04= (c10g604)”) N Yhtalimide .. . . . C16H,N0 = (c16z404)”/. N Camphorimide . . . . C2,H,SN0 = (C20;1404)’/] N Some Chemists am inclined to double the formula? of this sub-division of the secondary monamides and to view the iinides as secondary diamides. For instance-Succinimide 2C,H,NO = C16Hl,N,08 Phtalimide 2C16H,N04 = C,,HloN2Q (c20H1404),”] N, Camphorimide 2C2,H15N04= C40H30N208 H2 There are however at present no experimental data on which this view can be safely founded. The imides represent the acid ammonium-salts of the dibasic acids minus 4 eq. of water. Acid siicciiiatc of Succinimide. ammonium. I-IOF&IANN ON AMMONIA This equation represents in fact the most general process of formation of the imides.All the compounds mentioned in the above list with the exception of carbonylamide may be obtained by the distillation of the acid ammonium-salts. They are also obtained by the action of ammonia on the anhp- drides of the dibasic acids. Succinic anhydride. Succinate of am-Succinimide. monium. The action of heat upon the primary monaniidic acids and on the primary diamides (two classes of ammonia-derivatives of the dibasic acids which will be mentioned in the subsequent sections of this paper) likewise gives rise to secondary monamides. In illus- tration of this the formation of succinimidle in these rea,ctioris may be quoted Succinamic acid. Succinimide. --.____ ~ Snccinyl-diamide Succinimide (succinamide). Cyanic acid (carbonylamide) has been lately obtained by a per fectly similar process viz.the decomposition of a diamine under the influence of agents capable of fixing ammonia. Urca dis- tilled with anhydrous phosphoric acid yields cyanic acid Urea. Cyanic acid. Originally its is well known cyanic acid 'ems produced by the action of heat on the triamide cyanuric acid Cyanuric acid. Cyltnic acid Many of the secondary ruonamides possess the characters of weak acids being in fact capable of exchanging the unreplaced equivalent of hydrogen for metals. Mixed with an ammoniacal solution of nitrate of silver many of them yield well-defined silver- salts. Under the influence of acids and alkalies the secondary mona- mides are converted into ammonia and the acids from which they have been actually derived or may be imagined derivable.7. Tertiary Monamides. In these substances radicals are substituted for the three equi- valents of hydrogen in ammonia. The substitution may be accom-plished in a great variety of ways. 1 Substitution of 3 Acid-Radicals. Sulphophenyl-diberizamide C,,H15N0,S = C14H502 N C14H502c12H504s21 Acety1-sulp hop hen yl-benzamide C30H13N08S2 = C12H504S2 C4H302C14H502 1 Sulphopheny 1- benzo y1-cuminamide C4GH2,N08S2 = C14H502 Nc12H504s21C20HI102 No compound has hitherto been produced in which the 3 equivs. of hydrogen are replaced by 3 equivs. of the same acid-radical. The bodies enumerated in the above list have been obtained by the action of the chlorides corresponding to the monobasic acids upon the silver-compounds of secondary mona-mides.Sulphophenylbenzoyl-Sulphophenyl-benzoyl-argentamide. cuminamide. The alkalies decomposc these compounds with evolution of ammonia and reproduction of the acids of the radicals. HOFMANN ON AMNONIA 2. Substituiion of 2Acid-Radicals and 1 AlcohoERadical. This group which must include an endless number of terms is as yet very scantily represented C4H5 Ethyldiacetamide C12H11N04 = c4H3021 C4H302 Phenyldibenzamide C,oH15N0 = C12H5 c14H5*21 N c14H502 The most general mode of forming these substances consists in the action of the chlorides corresponding to the monobasic acids upon the secondary monamides. Phenylhenzamide. Phenyldibenzamide. Ethyl-diacetamide has been obtained by a process which is as yet rather exceptional but probably capable of very general applica- tion viz.the action of acetic anhydride upon cyanate of ethyl which itself may be viewed as a tertiary monamide. C4H5 '2'4 '2 = + c4H302] C4H302 Cynnate of ethyl. Acetic anhydride. (Ethylcarbonylam ide.) Ethgldiace tamide . The action of the alkalies on these compounds gives rise to the reproduction of the monamines and of the acids whose radicals are present. Tertiary monamides containing 1 equiv. of acid-radical and 2equivs. of alcohol-radicals have not yet been obtained; a variety of processes however suggest themselves for producing them. They are sure to be formed either by the action of acid-chlorides upon the secondary monamines or by the treatment of primary monamides with an excess of alcohol-iodides.3.Substitution of 1 Monatomic and 1 Diatomic Acid-Radical. The only known compound of this kind is-Succinylsuphopheuylamidc C2,H,N0 S = (~*H404)'1 ? N C,,H,O$ i AND ITS DERIVATIVES. 73 which is formed by the action of chloride of sulphophenyl upon succinimide. (csH404)N) N + (C,,H5O4S,)C1 = HC1 + (CsH404)”1 N H C12H504S2 Succinimide. Succinyl-sulphophenylamide. 4. Substitution of 1 Diatomic Acid-Radical and 1 Alcohol- Radical. This is the most copiously representcd group of tertiary mona- mides. Cyanate of ethyl (Ethyl. carbonylamide) Cyanate ofphenyl . . . C6H,N02 C14H5NO2 = = (:;3)JN Sulphocyanide of phenyl . .C14H,NS = (~~~1$~~N Phenyl-succinimide . . . C,,H,NO = (c8H404)” Phenyl-citraconimide . . . C,,HgNO = ‘~:%~04)f3 N Phenyl-phtalimide . . . C2sHgNO4 = ~~~~~04)r’) N Phenyl-camphorimide . . C,,H,,NO = (C20H1404)”) N c12E15 It has been mentioned that some of the secondary monamides may with some probability be regarded as secondary diamides. If this view be adopted the corresponding tertiary monamides have to be classed with the tertiary diamides. We shall return to these bodies in a subsequent section of this paper. The substances belonging to this subdivision have been obtained in a great variety of ways. Cyanate of ethyl and its homologues are readily formed by the action of the sulphovinates on cyanate of potassium (carbonyl-potassamide).Cyanate of Sulphovinateof Cyallatc of ethyl. potassium. potassium HOFMANN OK AMMONIA Thc corresponding phenyl-compounds are generated by sub-mitting the secondary diamides dipheiiyl-carbony 1-diarnide and diphenyl-sulphocarbonyl-diamideto the action of agents capable of fixing phenylamine such as anhydrous acids chlorides etc. Carbonyl-diphenyl-Phenylamine. Phenyl-carbonyl diamide. amide. The following are processes of even more general applicability Action of diatomic chlorides upon primary monamines. Pheny lamine. Dichloride of buccinyl. Hydroc5lorate of phe-nylamine Phenyl-succinimide Treatment of’ the hydrated diatomic acids with primary moua- mines. Phenylamine. Citraconic acid. Phenylcitrsconimido. Treatment of the auhydrides with primary monamines.Phenylamine. Phtalic anhydride. Phenylphtalimide. The majority of the tertiary monaniines belonging to this class have been produced from phenylamine (aniline) and are occasion- ally designated as aniles. Thus phenyl-succinimidc is frequently called succinanile e tc. AND ITS DERIVATIVES. By the action of alkalies these monamides are converted into primary monamines the acid-radicals forming the alkali-salts of their acids. -Cganate of ethyl Ethylamine. Carbonate of potassium. Phenyl-camphorimide. Phenylamine. Camphorate of potassium. When treated with ammonia or monamines many of these com- pounds yield diamines or diamides. Phenylamine. Sulphocyanide Diphenyl-sulp hocarbony1- of phenyl.diami d e . Others when submitted to the action of ammonia are converted into the ammonium-compounds of amidic acids. -Phenylphtalimide. Phenylphtalamate of ammonium. 5. Substitution of Triatomic Radiculs. Under this head the interesting and numerous grou? of bodies known as nitriles must be mentioned. The origin of the nitriles and their heliaviour under thc influence of reagents resemble in many respects the origin and behaviour of the monamides in general. Still they present many peculiar characters of their own and their position in the system is by no means finally established. Formonitrile formylamide C2HN = (C,H)q (Prussic acid) Acetonitrile vinylamide C,H,N = (C,H,)”’N Propionitrile allylamide C6H,N = (C,H,)”’N Benzonitrile C,,H,N = (C,,H,)”’N Cumonitrile C2,HllN = (CPOH1I)’”N The nitriles are derived from the ammonium-salts of the monobasic acids or from the monamides by the loss respectively of 4 or 2 equivalents of water.H3°21 0 = 2H20 + (C,H,)”’)N gH,Nji Acetate of Acetonitrile. ammonium. Acetamide. Acetonitrile. The nitriles are occasionally obtained by the destructive distilla- tion of either the ammonium-compound or the moiiamide ; their preparation succeeds however best when the monamide is sub-mitted to the action of anhydrous phosphoric acid or of penta-chloride of phosphorus. These reagents are thus converted re- spectively into pyrophosphoric acid and chlorophosphoric acid the latter being eliminated in the form of oxychloride of phos-phorus and hydrochloric acid.C6H502) N + PO = H2P0 + (C,H,)”’N 142 Propionamide. Propionitrile. C14H502! N + YCI = 2HC1 + YCl,O + (C,,H,)”’N H 1 Benzamidc. Benxonitrile. A Nl ITS 1)ERIVATIVES. In reprcsenting the nitriles as tertiary monamides we assume in them the existence of the triatomic radicals (C2H)”’ (C4H3)”’ (C6H5)’” (ClQH5)’” etc. These radicals are known to exist in a series of chlorides and bromides. Bromoform ....... Tribromide of vinyl ..... Tribromide of ally1 ..... And even in oxygenated combinations such as Glycerin ........ for instance. Some of these bromides are actually convertible into nitriles by the action of ammonia. Thus bromoform when exposed to the action of ammonia under pressure is known to yield prussic and hydrobromic acids H,N + (C,H)”’Br = 3HBr + (C,H)”’N which being fgrmed in the presence of an excess of ammonia are transformed into cyanide and bromide of ammonium.The nitriles have been produced however also by different processes. The ordinary mode of forming prussic acid is not favourable to the assumption of a molecule C H in this compound nor is this view supported by the deportment of prussic acid under the influence of metallic compounds. The facility with which the hydrogen in this acid is replaced by metals altogether precludes the idea of associating it with the carbon in accordance with our present conception of the manner in which these two elements are united in organic molecules. The other nitriles may also be obtained from cyanogen-compounds.Propionitrile is readily formed by distilling cyanide with sulphovinate of potassium. KC,N +‘,KH,)(SO,) = (SO,) +CGH5N Cyanide of potassium. Propionitrile. Add to this the fact that the supposed triatomic molecules HOFMANN ON AMMONIA have not yet been transferred from the nitriles into compcjunds of a more unequivocal constitution and we have sufficient reasons to assume that the nitriles are constructed upon the chloride-of- sodium-type. Formonitrile C,HN = HC,N Hydrocya2ic acid Acetonitrile C,H,N = (C H,)C2N Cyanide of methyl Propionitrile C6H,N = (C H,)C,N Cyanide of ethyl Benzonitrile C,,H,N = (C,,H,) C,N Cyanide of phenyl It deserves to be noticed that the nitriles yield up cyanogen only under the influence of the most powerful agents of decompo-sition such as potassium at high temperatures.Submitted to the action of alkalies and acids they reproduce ammonia and salts of the acids from which they are derived. b. Biamides. The diamides are derived from 2 molecules of ammonia and stand in the same relation to the monamides as the &Lamines to the monamines. They may be conveniently divided into primary secondary and tertiary diamides. a. Primary p. Secondary y. Tertiary Diamides. Diamides. Diamides. k A glance at these formulae suffices however to show that according to the number and nature of the replacing radicals many inter- mediate classes and subdivisions may be assumed. a. Primary Diarnides.In this group of diarnides 2 equivs. of hydrogen in diammonia are replaced by one diatomic acid molecule. Oxamide = (Oxalyldiamide) C,H,N,O AND ITS DERIVATIVES. Fumaramide -(Fumaryldiamide) Ct3H6N204 -Carnphoramide No --(Camphoryldiamide) 20 18 2 H2 The primary diamides correspond to the neutral ammonium- compounds of the dibasic acids from which they are derived by the elimination of 4 equivs. of water. Oxalate of ammonium. Oxamide They are in fact frequently produced by merely distilling the neutral ammonium-salts of dibasic acids. Oxalate of ammonium when submitted to dry distillation yields as the chief product of the reaction oxamide. This substance the first amide ever pro-duced was originally obtained by this process.Again the neutral ethers of the dibasic acids treated with an excess of ammonia are readily converted into primary diamides. -Oxalic ether. Alcohol. Oxamide. Succinic ether. Alcohol. Succinamide. Primary diamides have also been obtained by the action of ammonia on the diacid anhydrides. 2H,N + (C,,H,60,)”02 = H202 + H2 Camphoric anhydride Camphoramide. It is ~wohablethat the action of ammonia on diatomic chlorides IIOFMANN ON AMMONIA under appropriate circumstances will also furnish primary diarnidcs. For instance Chloride of succinyl. Succinamide. This process which has not yet been studied mould be perfectly analogous to that which gives rise to the formation of urea in the action of phosgene gas upon ammonia.Under the influence of acids and alkalies the primary diamides yield ammonia and dibasic acids. p. Secondary Diamides.. The members of this group hitherto produced generally con-tain in addition to 1diatomic acid-radical 2 monatomic alcohol- radicals. As illustrations the following may be quoted. Diphen ylcarbamide (C202)’’ (Diphenylcarbonyl-C26H12N202 = (c1gH5)2] N2 diamide) H Diphenylsuccinamide C,,H 16N20 -H2 The secondary diamides are obtained from monamines by the processes which applied to ammonia give rise to the formation of primary diamides. 1. Distillation of the compounds of primary monamines with dibasic acids. Oxalate of phenylamine. Diphenyloxamide. AND 1TS DERIVATIVES. 2. Action of primary monamines on the neutral ethers of dibasic acids-Eth ylamine.Oxalic ether. Alcohol. Diethyloxamide 3. Treatment of the anhydrides of dibasic acids with primary monamines. Naphtylamine. Disulphide of carbon. Dinaphtylsulpho-carbamide. 4. Action of the chlorides of dibasic acid-radicals upon primary rnonamines-Phenylamine. Phosgene-gas. Hydrochlorate of phenglamine. Diphenyl carbamide. When submitted to the action of acids and alkalies these diamides regenerate dibssic acids and monamines. As has been already stated that some Chemists are inclined to class with the secondary diamides some of the substances which have been enumerated among the secondary monarnides. Succinimide Citraconimide (C H404)”) N; (c8Eto4)g1N2H H(ClOH4O,)”5 N; (cloH 42) ’’1N Disuccinyldi-amide Dicitraconyl diamide Yhtalimide (C,,H,O,)”tH N; (C,GII,o,12”) N,H Diphtaly ldi-amide VOL.SII. G JIOFMANN ON AhIllIONJA This view which is not yet established cxperirnentally but receivcs some support from analogy deserves to be further elaborated. In connection with the secondary diamides a group of coni-pounds may be mentioned which holds a position intermediate between the primary and secondary diamides. Urea when exchanging 1 equiv. of hydrogen for 1 equiv. of a monatomic acid-radical entirely loses its basic character being converted into diamides in which 2 equivs. of hydrogen are replaced by diatomic and 1 equiv. of hydrogen by monatomic acid-radicals. These suhstanrcs are formed bp the action of acid chlorides upon urea.Urea. Chloride of acetyl. AcetyI-urea. Another compound belonging to the same class is-Phcnyl-oxalyl- diamide C,6118N,0 = &:&)//] N, Phenyl-oxamide H3 which is formed by the action of acids upon cyanphenylamine 1 + 2H,02 + 2HC1 = “i H H Cyanphenylamine. Hydrochlorate of phenylamine. Pheny1:oxam ide. oxamide aud diplienyloxamide being simultaneously prod wed. AND ITS l>ERIVATlVEG3. y. Tertiary Diamides. This group the members of which may be formed by a great variety of processes has as yet few representatives. In the fol- lowing table will be found nearly all the compounds of this class which have been produced. Trisuccinamide Succinyl-diuulpho-phenyl-di benzoyl- diamide Diphenylcnrbonyl-oxaly 1-diarnide" Hy drobenzamide Furfuramide Hydrosalicy lamide Hydranisamide To this group phenylaconitimide and phenylcitrimide may be added although these substances stand between the secondary and tertiary dinmides only 5 equivs.of hydrogen in diamrnonia being replaced. Phenylaconitimide C36H,4N20 = N2 H Phenylcitrimide C,6H16N,0 = (C12H& N, '"""'""7 H The processes in which tertiary diamides are formed may be illustrated by the following equations * Unpublished Rwearches. 92 HOFMANN ON AMMONIA Succinyl-argentamide. Dichloride of SIIC Trisuccinamidc cinyl. 2 I C12H504‘1N] +(C~H4O,’)‘‘C1,=2AgCl rC HOS L I4A; Sulphophenyl-bcnzoyl-argentamide Dichloridc of succinyl. Succinjl-disulphophenyl-dibenzoyl-diamide.(C202) C3&Il3N5 + 3H,02 + 3HC1 S([II,N]Cl)+(C404)” = Dicyanmelaniline. (C12H5)2 Diphenylcarbonyl-oxalyldiamide. Hydrobenznmide furfuramide hydrosalicylaniide and hydrani-samide are formed by the action of‘ ammonia on the benzoic furfuric salicylic and anisic aldehydes. Tlte process is sufficieutly illustrated by quoting the cquation wliich represents the forrna- tion of hydrobenzamide. Oil of bitter Hydrobenzamide. almonds The peculiar trslnsforinatioii of these substances which are often designated as hydramides into basic compounds has been already noticed. Phenylcitrimide (diphenylcitrgl~ii,zmide)has been obtained by the action of phenylamine upon citric acid. Phenylamine. Citric acid.Diphenyl-citryldiamide. Phenylaconitimirle is fornted in a similar manner. It hits alredy been mentioned that some Chemists are inclined to double th, forrntih of several of the primwy and secotlrbry rnonaniidcs aild to vicw them ns pitnary and sccoiidwy rliacnrides. AND ITS DERIVATIVES. If this view be adopted it must be extcnded to the corresponding f crtiary monamides which are thus converted into tertiary diamides. Diphenyldi-N succinyldi-H4°4),.)(c(‘8N; Phenplsuccinimide ) (?SH,O4)’’t amide. C12% 12 5 2 Quite recently some very iuteresting ammonia-derivatives have been produced,” which will probably find a place among the diamides although their constitution is riot yet sufficiently elabo- rated. In a former part of this paper allusion has been made to the transformation of the primary monarnincs into the corre- sponding alcohols by treatment with nitrous acid.The change consists in the substitution of 20 for HN; phenylamirre is thus converted into phenyl- alcohol nitrogen being evolc ed. The action of nitrous acid on the amides is very similar; acettt- rnide yields acetic acid water and nitrogen The reaction assumes however a very different form when the nitrous acid acts on the alcoholic or ethereal solutions of these substances. In this case no nitrogen is evolved the changc con- sisting simply in the eliminatioii fhn 6 equirs. of the oTigind cO~~~OUL~(I, of 3 equivs. of 1iyv;irogcn~)yt\e oxygen of the nitrous acid; the nitrogen of which enters into the new derivative.Thc following cquatiou represents the transformation of phenyl-2(C12H7N) + NO = 3130 + C,,H,,N P henylamine. New derivat’ive. Unpublished Resear cliesby I?Griess HOFMANN ON AMMONIA This remarkable body is obviously derived from 2 molecules of ammoilia in which 2 equivs. of hydrogen are replaced by phenyl and 3 by nitrogen which entering as an element of tria-tomic substitution-power links together 2 molecules of the original compound (N)“’1 Nitryl-dipheriyl-diamide (C,2H5)2 H J” A glance at this fogmula shows that the new body corresponds both by its formation and by its composition to the diamine pro-duced by the action of chloroform upon phenylamine (C2 H)’” Formyl-diphenyl-diamine (C12HJ2IN2 H Nitrophenylamine and probably all other primary monamines give rise to the formation of similar derivatives.The nitro- phenylamine-derivative is-(N)”‘ Nitryl-di-nitrophenyl-diamide [C,,(H,,NO,) ] N, H c. Tyiarnides. The number of amides corresponding to 3 molecules of ammonia which have hitherto been produced is so small that subdivision is as yet scarcely necessary. The only primary triamide known is -Citryltriamide CI2H,,N,O -N3, (Citramide) H3 which is formed by the action of ammonia upon citric ether Citric ether. Alcohol. Citryl-triamide. The group of secondary triamides is represented by two terms viz. :-(VO,)”‘ (Phosphanilide) Phosphoryltriphenyltriaaiidei1 c,,w l8N,P02 =Fb2f15) 3 N39 and €1 n I AND ITS DERIVATIVES.Citry ltriphenyltriamide ’ C,,R2,N308 = iE:sa,.) N,. (Phenylcitrarnide). i H3 These two bodies are forrned by the action respectively of oxychloride of phosphorus and of citric acid upon phenylamine. Phenylamine. Trichloride of Hydrochlorate of phosphoryl. phenylamine. -Phospholyl-triphenyl -triamide. .-Phenylamine. Citric acid. Citryltriphenyltri-amide. Also cyanuric acid when referred to ammonia appears as a secondary triamide. C6H,N,06 = (CZHZ, 8 )I’ ”)S As a tertiary triamide cyanuric ether may bc quoted Cyanuric ether C,,H,,N,Q6 Phosph ides. The remarkable analogy which csists between the derivatives of am inonia and those of phosphoretted arsenetted and antimo- netted hydrogen has been already pointed out in the previous section in which the basic derivatives of these compounds were enumerated.It is very probable that the progress of science will gradually realize in the phosphorus- arsenic- and antimony- series all the terms which are at present known only in the nitrogen- group. As yet only two compounds are known which correspond witli the aiiiidcs and which accordingly might be designatcd as 1 hosphidcs. They are- HOFMANN ON AMMONIA Trichloracetyl-phosphide c1 = "!2'2] P and (Chloracetyphide) 1423 H C14H502 Tribenzoyl-phosphide C4,HI,PO6 = C14H502] P C14H502 These substances are formed by the action respectively of chloride of trichloracetyl and of chloride of benzoyl upon phospho- retted hydrogen.H3P + (C,C1,02)C1 = HC1 + c42021 Chloride of w ~ trichloracetyl. Trichloracetyl-phosphide. C,4H502 3[(C,4H,0,)C1] = 3HCl + C,,H,02] P Chloride of benzovl. C,4H50 Tribenzoylphos-phide. Metalamides. Substances derived from ammonia by the substitution of metals for the hydrogen are comparatively rare although the term amide was originally used to designate exactly compounds of this des- cription the amides of potassium and sodium being the earliest representatives of the whole class. As yet only primary and tertiary metalamides are known. Primarg Metalamides. Potassarnide = KH2N = HKlN H Sodamide = NsH2N = H N H "s Zincamide = ZnH,N = g] N H rllilc two former bodies are produced by exposing potassium arid builiuiii to a current of dry ammonia when liydrogen is evolved.lip I-K = kH23 -t H Zincamide has been only lately discovered; it is formed in a very interesting process viz. the action of zinc-ethyl upon ammonia hydride of ethyl being the complementary product. H,N + ZnC,H = ZnH,N + C,H,H Zinc-ethyl. Hydride of ethyl. It may be that the substances produced by the action of ammonia upon the oxides of gold and silver the composition of which is not finally settled are similarly constituted. Secondary metalamides are not known. Tertiary Metalamideu. K Tripotsssami d e K,N = ;IN Trizincamide Zn,N Trimercur amid e Hg,N Tricuprosamide Cu,N Tripotassamide and trizincamide are formed by the action of heat upon the primary amides of the same metals ammonia being generated 3KH2N = K,N -t 2H3N Trimercuramide and tricuprosarnide are obtained by submitting the metallic oxides to the action of ammonia H,N + 3Hg0 = Hg,N -!-3HO 2H,N + GCuO = (CuJ’,N + 3H20 + N Organo- Metalamides Many of the primary and secondary amides and amines are capable of exchanging ax1 equivalent of the unreplaced ammonia- hydrogen for metals a peculiar class of mixed amides being thus produced several of which have hem already rueiiiioned ill the HOFMANN ON AMMONIA preceding paragraphs Most of these bodies are formed by pro-cesses similar to those which convert the ordinary acids into saline compounds.Secoltdary Organo-Metalamides. (Sults of Amides.) Benzoyl-mercuramide (Benzamidate of Cl,H6HgN0 = Hg mercury) C14H502 H IN Sulphopheny1-argentamide (Sulphophenylamidate Cl,H6AgN0,S2 = c’2y4s21 of silver) H Acetylzincamide c H302 ).(Acetamidate of C,H,ZnNO - Zn zinc) -%H5 Zn H ). Phenylzincamide Cl,H6ZnN -H Oxacetylargentamide (Acetamate of silver C,H4AgNO, glycocol-silver) H Oxybenzoylcupramide (Benzamate of copper) C14HGCuN04 = H The two last compounds however may more appropriately be considered as salts of amidic acids. (See further on). Tertiary Organo-Metalamides. a. 2 Nonatomic Acid-ltadicals and 1 Metal. C12H504S2) Sulphophenyl-henzopl-C26H10AgN06S2 = argentamide Ag C14H502 i” c4 H5 Diethylzincamide C,H,,ZnN -0xacetyl-benzoyl-argen-tamide Cl,W,AgN06 = (Hippurate of silver) ‘14 Ag Benzoyl-salicyl-] 5’2 argentamide (Benzoyl-salicylarate C2,H ,,AgK06 = C14H504 of silver.) hF AND ITS DERIVATIVES.The two last substances may likewise be referred to the amidic acids. b. 1 Diatomic Acid-Radical and 1Metal. Carbon yl-potassamide C2KN0 = ('20$)" ) N (Cyanate of potassium) Sulphocarbonyl-plumbamide C2PbNS2 = ('2'2)" Pb 1 Sulphocyanide of lead Succinyl-argentam ide Succinimidate of silver C,H,AgNO,= Organo-Metal-Diamides. Very few terms of this class are known. ('4O4)'?. N Oxalyl- dizincodiamide" C H2Zn2N20 = Zn2 J H2 If succinimide be viewed as a diamide a similar constitution must be attributed to the silver-compound above quoted. Disuccinpl- diargento- diamide C16H8Ag2N208 = Some Chemists are inclined to classify with this group a com-pound produced by the combination of sulphophenyl-benzoyl-iirgen t amide with ammonia.Sulphophenyl-benzoyl-argent o-diamide C'26H13AgN206S2 = Ag H3 But it is more probable that this substance is simply an argen- tammonium-subs ti tute viz. :-Sulphop henyl- b enzoyl- argentamonamide Organo-Metal-Triamides. To this group belong the salts of cyanuric acid if this acid be vicwed as a triamide * This substance appears to exist in combination with zinc-ethyl. HOFXANN ON A;\I[MONIA -_ -___ Tricarbonyl-Tricarbonyl-metal-Tricarbonyl-dimetal-Tricarbonyl-triamide. triamide. triamide. trimetal-triamide. Most of the organo-metalamides are formed by applying to the amides processes similar to those which convert the ordinary acids into saline compounds.The only reaction which deserves especial notice is the transformation of aniidcs into inetalamides by the action of zinc-ethyl In illustration the following equa- tions may be quoted = C,H,H + c12Ei] N H Zinc-ethyl. Hydride of ethyl. H Pheny lamine. Phenyl-zincamide + C,H,Zn = C4H5H + qN Zinc-ethyl. Hydride of ethyl. Zn Diethylamine Dietb y1-zincamidc . Metal-Phosphides Metal-Arsides and Metal-Xtibides. ‘The primary and secondary terms of these groups are unknown. Among the tertiary terms the following may be quoted Trimret alphosphides. T’ricobd tpho sphide co ‘rrirrickelyhosphide Ni Tricuprosophosphide {:::;’[ P (CU2)’ Tricuprophosphide 21P cu .-.AND IT8 DERIVATIVES. 93 Trinzetalarsides. Tricuprar side cu Trimercurarside* As Hg Trimetalstibides. Triargent ostibide Sb Ag Ferro-dinickelstibide (Nickel-antimony ore) Comparatively few processes are involved in the formation of these bodies. The majority are produced by the action of the trihydrides of phosphorus arpenic and antimony? upon metallic salts H,P + 3CuN0 = 3HN0 + Cu,P H,P + 3Cu,Cl = 3HC1 + (Cu,)’,P H,As + 3CuC1 = 3HC1 + Cu,As H,Sb + 3AgN0 = 3HN0 + Ag,Sb Metalphosphides have been obtained also by the reduction of phosphates in hydrogen gas Co,PO + 8H = 4H202 + C0,P. * This body exists in combination with chloride of mercury (Hg,As + 2HgC1 = HgCl + [Hg,As]Cl a double salt of chloride of mercury and chloride of tetramer- curarsonium) in the precipitate proc’-uced by arsenetted hydrogen in ti solution of corrosive sublimate..t. Phosphoretted arsenetted and antimonetted hydrogen exhibit towards the metals the deportment of tribasic acids. It is worthy of remark that phosphorus arsenic and even antimony are generally remarkable for their triatomic dispositions. Phosphoretted hydrogen associating step by atep with 4 6 and 8 equivalents of oxygen becomes hypophosphorons phosphorous and phosphoric acid Phosphoretted hydrogen H :}P Hypophosphorous acid :}Po* (2) H Phosphorous acid H PO, H”) Acid Derivatives oj Ammonia constructed upo” the Water-type. In a previous section of this paper it has been pointed out that the hydrated oxide of ammonium a body of so little permanence that in the moment of its liberation it splits into ammonia and water is capable of acquiring considerable stability if part or the whole of its hydrogen be replaced by other molecules.By the substitution of such metals as platinum palladium and iridium for one equivalent of hydrogen the hydrated oxide of ammonium is converted into powerful non-volatile potassa-like bases; and a similar transformation takes place when the four hy-drogen-equivalents of ammonium are replaced by alcohol-radicals. It deserves to be noticed that no organic ammonium-derivatives of basic properties are known in which less than 4 equivs. of hydro-gen are replaced.The hydrogen in hydrated oxide of ammonium may also be replaced by acid-radicals. The products which are thus generated Phosphoric acid :}Poq H Arsenetted hydrogen in a similar manner is transformed into arsenic acid H Arsenetted hydrogen H ]Ss H Arsenic acid H The natiire of antimonic acid is not finally settled but the composition of the sulphantimoniatea also points to a triatomic character *4ntimonetted hydrogen H Sulphantimoniat e zi 1 of sodium SbS (Schlippe’s salt) Na Nitric acid is essentially a monobasic acid nevertheless the few basic nitrates which are known contain 3 equivalents of metal. Ammonia H Basic nitrate of %)no, mercury Hg have distinctly acid properties and have been designated as ami-dogen-acids as amic or amidic acids.The members of this group whicb have hitherto been obtained almost exclusively correspond to one molecule of hydrated oxide of ammonium ;but as we have seen that in the formation of the polyamines arid polyamides two or more molecules of ammonia are capable of coalescing so we cannot doubt that the presence of polyatomic acid-radicals will link together two or more molecules of hydrated oxide of ammonium. Sub-stances admitting of such interpretation are in fact known and the progress of Chemistry therefore will inevitably lead to the distinction of monamidic diamidic and triamidic acids. The monamidic acids according to the number of hydrogen-equivalents replaced may be subdivided into primary secondary tertiary and quartary acids.Primary rnonamidic acids have never been obtained; the com-pounds belonging to the group of amidic acids acquire sufficient stability two or more equivs. of hydrogen are replaced by acid-molecules one of which must be diatomic. Secondary Monamidic Acids. Carbainic acid* C2H3N04 = Sulphocarbarnic acid C2H3NS = Sulphamic acid H3N06S2 = Oxamic acid C,H3N06 = Succinnmic acidt C,H,NO = Sebamic acid C20H19N06 = Citraconamic acid C,,H,NO = +. Known as ammonium-salt in what is generally called ailhydrous carbonate of ammonia and also in urethane. Only kniwn a9 silver-salt. 96 EIOFMANN ON AMMONIA Camphoramic acid C2,H1,NO = H Phtalamic acid Malamic acid (Aapartic acid) C8H7N08 = The amidic acids differ from the acid ammonium-salts of dibasic acid by 2 equivs.of water which they contain less. In many cases they are simply formed from these compounds by the elimi- nation of this water from the dry compounds under the influence of heat. Acid oxalate of Oxamic acid. ammonium. Aeid malate of Malamic acid. ammonium. Sometimes it is sufficient to boil the solution of the ammonium- compound. Thus cornenate of ammonium is transformed into comenamate of arnmoninm Comenate Comenamate of ammonium. of ammonium. A second method of forming amidic acids consists in submitting the anhydrides of dihasic acids to the action of aminonin. 2H,N + (C202)”02= [(C202)”1’42N1 Anhydrous Carbamate carbonic acid. of ammonium.AND ITS DERlVATIVES. 97 (C,S,)”S + 2H,N = Bisulphide of carbon. Fulphocnrbauiatc of smmonium. Anhydrous Piitahmate of aimioiiium. Phtalic acid. (C,,H140,)”0 + 2H3N = --. Anliydrous C,unpllornmate of ammonium. camphork acid. Tlie acid ethers of some ilibasic acids when treated with ~YI-inoiiia also yield aniidic acirls hIethj1-salicylic acid S,tlicyl,zmste of ammoninm. Methyl d alcohol. Oil of Gaultheria procnnibcns Amidic acids may also Be conveniently produced by the actioii of water upon the secondary stmidca containing a. diatomic acid radical wliich are often designated as iniidcs. Instead of‘ the imiile one of its nictallic derivatives may bc employed. The reaction wliicll consists in the assimilation of 2 equivs.of water is generally accomplished by boiling tlie amicie I\ ith amrnouia and occsdonrrlly with carboilate of Podiuni. (c8H404)”? iN + H20 = (CSH-k04) ”H2N1 0, & Ab” I Succinyl-argenta-Snccinamateof mide. silvcr. By a similar fixation of 2 equics. of water many primary diainides are converted into the ammonium-compounds of secau-dary arnidic acids. In this manner asparagin (malamidc) is CON-vertecl into aspartate (maliinmte) of ammonium Asparag 11. Aspu tatc of nwtnonium. VOL. XlI. H HOEMANN ON AMMONJA sebamide into sebamate of ammonium. -Sebamidc. Sebamate of ammonium. Lastly some peculiar reactions may be mentioned in which the ethers of the nmidic acids are formed. Chlorocarbonate of ethyl when treatecl with ammonia yields carbamatc of ethyl generally calliecl urethuize.Chlorocsrbonate Carhamate of ethyl. of ethyl. Oxalate of ethyl gives with a small quantity of alcoholic ammonia oxamate of ethyl (oxamethane) . Oxalic ether. Oxamate of ethy?. Alcohol. It is very probable that Chemists will ultimately recognize as true amidic acids a number of compounds the constitution of which is still under discussion. In a previous section of this paper we have enumerated a series of remarlcable bodies which hold an intermediate position between acids and bases. Glycocine and daniiie benzamic and anisamic acids have been viewed as primary inonamines as ammonia in wliich 1 eq. of hydrogen is replaced by monatomic uiolecules j but they may be equally well considered ns smiclic acids if TJ-C assume in them the existence of diatomic radicals.Glycociiic CHO (Acetamic acid C,I15N0 = 4H3 ‘1N glycolylamic acid) €1 J Alaniiie CHO (Propionainic acid C6H,K04 = ‘I$ ‘IN lactglamic acid) H AND ITS DERIVATIVES. Renzamic acid Anisamic acid The view which claims these substances as nniidic acids is sup-ported by many important facts. All these bodies contain I mole-cule of hydrogen in a remarkably mobile condition readily re- placeable by metals and readily re-assumable much more so than in undoubtedly established rnonamines and monamides. Their formation is liliewisc in fa\ our of this view ; chloracetic acid and nitrobenzoic acid vliich are respectively convertible into glycociiie and benzainic acid obviously still 1etain the origiml construction of acetic and benzoic acids.Considered as aniidic acids glycocine and benznniic acids are likevise constructed upon the water-type. Acetic acid Chloracetic acid Acetamic Gly colylamic acid Benzoic acid Nitrobenzoic acid Amidobenzoic Benzamic acid HOFMANN ON ANMONTA The transformation if I niay say so is accomplished on the lcft-hand side of the water-bracket. At the conclusion of this paper some remarliable derivatives of these bodies of very recent date will bc noticed wliich are per-fectly unintelligible niilcss IT-cview thc mother compouirds as ainidic acids. The forma.tiou of these substances has been iaentioiied in the chapter on the fornration of the organic bases.Tertinry Monamidic Acids. a. Substitution of 1monatomic and I diatomatic acid-radical. I Salicyl-benzamic C NO -[(C,,H,02)”(C,,T-I,02) HNJ acid 23 11 6. Substitutiou of 1 diatomic acid-radical and 1 monatornic alcohol-radical. Phenyl-carbamic acid (Anthranilic acid) AlnqTl-sulphoear-bamic acid Plmiyl-snlphamic acid (Sulphanilic acid) Plienyl-malamic [(C H 0 )” C 21ij)HNj acid CPOfIllXO8= H 1’2 (Malanilic acid) If glycocine be viewed as a secondary arnidic acid ax glycoly-lamic acid hippnric acid becomes a tertiary amidic acid. The tertiary aniidic acids which contaiii 2 acid molecules arc simply obtained by the action of monatomic chlorides upon secondary amidic acids. Salicylamic acid.Chloride of benzoyl. Salicgl-benzamicacid. The teytiary acids containing 1 diatomic acid-moleculc and 1 monatomic alcohol-molecule are formed by submitting mona-mines to those processes which when applied to ammonia give rise to the formation of secondary amidic acids. Action of heat on the acid salts of primary mommines wit11 diatomic acids. Acid oxalate of Ethyl-osamic acid. e thylamine. Acid sulphnte of Phenyl-sulphamic acid. phenyiamine. Acid itaconate of Phenyl-itaconamic acid. phenylamine. Action of the anhydrides of dibasic acids upon the primary inonamines. Amylamine Artlyl-snlphocarbamatc of arnyldmi r:e. Phen y lamine. Phenyl-camphoramate of phenylarnine. Action of water upon tertiary monamides containing a diatomic acid-radical and a monatomic alcohol-radical.The largest number of tertiary amidic acids has been procured by this process which is conreniently accomplished by ebullition with ammonia. Phenyl succinimidc. Phenyl-phtaLmidc. Phenyl-phtalamic acid. Some of the tertiary monamidic acids have been obtained iu reactions which are as yet isolated. Phenyl- carbamic (ant hranilic) acid is formed By the action of hydrate of potassa upon indigo. Anthranilic acid. The only terms of this class which are at present known are the following :-Yhenyl-aconitamic acid Cg4H9P;; O,= I](C,,€i,OG)’”(C H )N] l2 5H 102 The former of these compounds is produced by the action of heat upon the citrate of pheiiylamiiie coiitailriing 1 equiv.of the base. C‘itrateof phenylamine. I’heujl-citramic acid The second is obtained in a rel-narlcalolcpracess. The action of pentachloride of phosphorus upon phenyl-citramic acid gives rise to the formation of a very interest iiig chloride coxrespond- ing on the electro-negative side of the series to chloride of ammonium as chloride of tetrethylamrnoiiiuin does on the electro- positive side. Phenyl-citramic acid. -t 1 (Cl,H,O,)”(C 12%) N3c1 Chloride of phenyl-monityl-ammonium. The chloride of plnenyl-acouityl-ammonium when coming in contact with water splits into hydrochloric and phenyl-aconitamic acid. Chloride of phenyl-aconitgl-ammonium. Phenyl-aconitamic acid. HOEBIANN ON AMMONiA Dicimine-Amidic Acids.In tracing the liistoq of the basic derivatives of ammonia we were led to the nwimptiou that compouiid monatomic metals similar to amnioninin may bc formed by thc association of 1 equiv. of hydrogen irot oiily mitli 1 moleculc of ammonia but with 2,and perhaps with 3 molccdcs of :tinmonia. We arrivcd in this rnanim at co~nnpo~~uds of niona~iile-amInoiiiL~nl,diarnine-aminoniurn and triamiiic-a~moilium,and we quoted several sub-,stances which appear to he constructed upon this type one of the most conspicuons nicmbcrs of the grotip being perhaps the- Hydrated oxide of rn~4Jigl-diethY1ene-diI~hel~yl-[(C,H3) ((C4H4)1’2 1 0, (C 2H,),N,)] diamine-ammonium €I Some similarly coiistructed conipouiids appear to exist moiig the acid derivatives of‘ aminouia.Their nimbcr is cs yet ~ci*y limited. Oxalyl-nitr opheny-lenc-dismine-sin iclic acid (Nitrazophenyl-oxamic acid) Citraconyl-nitro-phenylene -diamine- amidic acid (Nitrazophenyl-citraconamic acid) Di phen yl-citry1-diamine-amidic acid (Citrobianilic acid) = c1-I((C12~W*)’T*2HJ2H”) €1 3 The two former of tlicsc compounds are produced by the action of heat upon the acid ~zophenylaniinc-saltsof oxalic and citra-conic acids with clirnination of water. ” Kp,) -) ‘4 HJCIT(((:,,[T~,,NO,J)”II,N,)] -Acid oxalatc ofasophcnrlamine. AND ITS DERIVATlVl23. Witmzophenj loxsmic acid. Citrobiaiiilic acid is formed by heating phenyl-ci trarnidc with ammonia to a teiiiperatiire of 165” C. when 2 ccpiw. of water are fixcd and 1 equiv.of‘ phenylamine separates. Triphenyl -citryl-triamid e. Djphcnyl-citryl-diamine-amidic acid. Phenylamine. These remarkable compounds haw been oiily i4ecently disco- vered;* their study is not yet completecl. The diamidic acids correspond to 2 molecules of rrater and represent among the acid derivatives of ammonia the hydrated dioxides of diitmmonium among the Bases. If we rcpresent by the terins benzoylene and anisylene two diatomic molecules C1,H402 and C16H604,which we conceive to he generated rcspectively from benzoyl C,,H50, and anisyl C16H,04,by the elimination of 1equiv. of hydrogen the diamidic acids to which we allude may be thus represented n’itryl-dibenzoy-C2,TT lN,O = [(N)”’(C1,H,02)2”EIN2] ’’1 lcne-diamic acid H2 .) O4 The formation of these acids is exceedingly interesting.They arc obtained by submitting alcoliolic solutions of benzamic and anisamic acids (secondary monamidic acids) to the action of nitrous acid when 3 equivs. of hydrogen are eliminated from 2 equivs. of these acids by the oxygen of the nitrous acid whose nitrogen entcrs into the new system linking together by it P. Gr i e ss Unpublished Researckce HOFRIANN ON AMMIONLA its triatomic substitution-power 2 moleeulcs of the origird compounds. Benzamic acid. Xitl.yl-dibenLoyleiie-dia~icacid. Anisamic acid. Nitryl-dianisylene-diamic acid. Triamidic acids have iiot yet been obtained They will probably be produced by the aclioii of nitrous acid upon the alcoholic solu- tions of tertiary monamidic acids.Hippuric acid thus treated might possibly be converted into a trihasic acid of the formula :-In the preceding paragraphs I have endeavoured to give an outline of the chemical history of the type Ammonia such as it exhibits itself at the present moment. No department of Che-mistry perhaps reflects in a more saliciit manner the rapid progress of science during the last quarter of a century. Nearly all the bodies mentioned in this paper were discovered during that period; nine-tenths in fact the very compounds which have most assisted in the elaboration of our theoretical views are the fruits of the last ten years. Though much has been achieved more is left to be done. But even now while so many known substances remain to be finally grouped and classified and while countless groups and classes remain AND 1TS DERIVATIVES.to be discovcrecl yet tlic general features of tlie system are distinctly perceptible and tlic time i4 rapidly approachiiig when losing sight of the chaotic inass of overwhelming detail the eye may rest with complacency upon the simple beauty of the law which governs the construction of the bodies belonging to the type of ammonia. In coiiclusion I append a table enibodyiiig in a synoptical form the principal groups of ainmonia-deriv,2tives enumerated in tlie ... preceding pages. TYPE AMMONIA. Positiae Series. Aeyatioe Series. Substitution of Basic Radical.. Substitntion of Acid Radicizla AMINES. A MIDES. iMonxmii es.Priiiiary nionarninea Secondary lnonsmines A H 1N 1N H JIon nit(ides. Primary monsmic~cn Secondary monaniides I1 Tertiwy rnonaminea N lertiary moiiamidce C TYPEDu~uoara. Diamines. Diamides. k2 Primary diamines H ,/ N Primary diamicles H2 Seeondary diamines N Secondary diamides Tertiary diaminea N Tcrtiary diamides Trianiines. Triawiides. Primary trinmines Tertiary triamines TYPE T~;TRBMMONIA. Tetramine8. Tetrainic?es. Tertiary tctraininco TTPEHYDRATED (Water). OXIDE OF AMNONIUM [Hq o2 iliiormmidic Acids. Primary monammonium-bases [AH”] 1 o, (Mctalamm onium-bases.) [ABH,N] II 0 Secondary nionamidic acids. 1 1 iaB‘HN1I3 0 Tertiary monamidic acids Q11artary monam monium.baw [ABcDEj 1 0 Quartaq monaniidic acids.CH(H3W o2 1 11 Dianiine-Atnmonium-Bases. Dimtine-Amidic Acir7s. Primary diamine-ammonium-bases [H(A H,N),] (~Ietal-ammonium-t)asea) H 1’2 [H(ABI\y),] 1 o Secondary diamine-smlidic acids. [H(ABCN),] 1 Tertiary cliamiiie -ami3ic H j 2 acids. Qlmrtary diamioe-ammoiiiuni-bases. [A(BODY),] I3 102 TYPE~IYERATED OP DInairomuJr. DIOXIDE IXammodum-Baues. Diamidic Acids. ............ Qu artnry cl iarnmonium-bases L’2B2’”22j’’ 1 0 Qaartary ciinmidic acids.

ISSN:1743-6893    

DOI:10.1039/QJ8601200062

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

XTK-On sowe Derivatives fron2 the Qlejnes. BY FREDERICK P1i.D. GUTHR~E THOSE hydrocarbons which consist of equal numbers of eqniva-lents of hydrogen and carbon (I1 = 1 C = 6) of which etEiFlene is the histcricd prototype have of late received a large share of the attention of chemists. During the first quarter of the present century the separation of ethylene from ethylic alcohol by suk-stances which have strong affinity for water mas accepted by many as evidence of this body heiiig the true radical of alcohol. The possibility of the synt?ieais of alcohol from the same hydrocarbon 110 GUTIIBIE OK which was early indicated and mliich has of late weeivecl completc corroboration naturally supports tlie samc view. The isolation of the so-called organic radicals the hydrides of the olefines and more especially the ~i2cliiiiwof their isolatioii has so far substantiated their chin? to beiiig J-icmecl as raclicals in the earlier restricted sense of the TTO~~; but the idea conveycrl by tlie term radical has meanwhile undergone a wide extension.In order to define the sense in which I employ this term it may lie remarked that between a compoL1jld body and its nltimate elements there exist certain possible derivatives of an inferior ‘< order,.” each of which as well as the ultimatc elemcntv tliem- selves has strictly an equal claim to be considered as a radical of the body. Thc number of such dcrii-ativcs deycncls of course upon the complexity or cmfeYi.9 pcwibus upon tlic equivalent of the original substance.Thus from ethylic alcohol we may obtain aldehyde liydride of ethyl etliyl ethylene hydride of methyl carboiiic acid water aucl others ; each of which is a proximccte radical in distinctioii to car- bon liychgen and oxygen m-hich are ulfiniaie radicals or elements. In tliis sense a radical is nothing more tliaii a proximate clement or molecule and the continual reappearancc of one aiict tlie same such molecule is to be takcn less ns proof of an innate comlsiiiing effort of its part. tlim as evidence of uniformity in the pligsical influences to whicli it is subjected. The arrange- nierit of tlic constituents of a substance and the expression thereof by a formula can only be considered absolute as long as such influences remain irivariablc.But when the latter are so changed as so affect a recomposition of the elements in a different order then the ratioiial formula iiiust recognize such rearrange- ment and vary in accordance nith thc forces which effect it. TThen therefore one body determines the splitting of a complex second body into certain molecules such molecules arc the radicals of the second body re7atiw7y to the first and to the physical condi- tions accompanying the change. Partly on account of the olefines being in tliis sense radicals of their alcohols partly on account of their belonging to the class of SO called diatomic bodies 11 hose discussion lias throrri rnuch light on organic chemistry I have thought them deserving of special study. Ethylene has the property of combining directly with tmo equivalents of chloriiie broniiiie aid iodine forming therewith the well known compounds C,H,Cl, C,H,Br2 C,H,I, for our SOXG DEBIVATlVCS FROM THE OLEFINES.111 knowledgr of which we are indebted to Deimaiin and his asso-ciates to Balard and to Faraday respectively. Liimig has moreover shown that the corresponding sulphur-compound C,H,S, may be obtained by the action of protosulphidc of potassium upon the first of these bodies. Although inany derivatives have been ohtaineci from these substances both by the substitution of the lialogeris for liydrogeu and by the eliminatioii of the Iiydracids by alldine oxides their history is still very incomplete firstly inasmuch as the analogy between tlie ethylene compounds and those of the higher olefines is very imperfect ; arid further because few successful atteiiipts have been made to determine the charac- tcr of the diatomic haloid-molecule in the sense of ascertaining if and when one or both of its atoms may be replaced by similar oues,or by molecules functioning as such.A description of some experiments performed in this direction furilishes tlie matter of the preseiit memoir. In selecting soit able olefines etliylenc aiid amylcne appeared to offer tlie greatest promise of interesting results partly because they can both be obtained in a state of great purity partly because being somewhat widely separated upon the olefine series analogous derivatives or reactions conimon to both would point to similar ones in the two intermediate terms propylene and hutpleiie ; while the nature of their dissimilarities would also to some extent indicate the nature of the derivatives from the same two bodies and their beliaviour under sirnilm conditions.My first object was to combine these two olefines with some of the combinations of the halogens vhicli are known to exist and some of which are esliibited in the following table :-c4 ClBr Br2 C1I BrI I c10 BrO 10 0 ClCy RrCy Icy OCy Cy fClS BrS JS 0s CyS S, 7c1s2 Although some of these bodies have iiot yet bcen obtained and the definite nature of the composition of otliers is still doubtful yet there can be little question as to tlie possibility of the existence of all. As howeverj the members of the first or chlorine column have been most fully studied aiid as chlorine itself shows pre- eminently the power of conibiniiig with thc olefines tlic bcliavionr of these cliloridcs towards ethylene and amylene was tlic first subject of iiw estig~t ion.I shall call the body CIS, the bisulp!iide of ciilorinc and tl!c body C1S or Cl,S the chloride of sulphur; it will be seen in the sequel that this nomenclature avoids the introduction of ax ambiguity in speaking of the derivatives of the two compounds. Action of bisu&l~ide of chlorine zqioiz anzyb?ze.-Into a flask containing 52 grnis. of bisulphirle of chlorine pure and dry ainylciic was allowed to drop slowly the flask ‘hcing l<ept cold by agitatioii in water. Immediate combination nccompslnied by tile liberatiox of heat ensued 110 permanent gas bcing evolved.Tlie amyleiic was added until no further evolution of lieat occurred on the addition of fresh quantities. Tlie flask containing the prodiwt so obtained was then heated for several houm in a n-ater-bath at 1OOOC. A distillate was tliereby obtaincd wliich coiisisted entirely of the excess of arnylene only contaminated by a slight trace of hydrochloric acid. The residue in the flask mliicli had deeperiett somewhat iu colour wcighcd 10b grms. The bisulphide of chlorine had therefore conibiiied with exactly its own weiglit of amylcne that is 52 grms. In another experiment 51gyms. of this bisulphidc combined with 52.1 grins. of aiiiyleiie giving 103.1 of product.If now onc iiiolecule of the bisulpliiclc comliined with oiic inoleculc of amylene 52 grnis. of the former would reqiiirc 53.9grins. of the latter giving 105.9 grnis. of‘product ; and 31 grms. of the foriiicr WOLM require 52.8 grms. of the latter giviiig 103.8 grin<. of pro-duct. The quantities actually found slmv that this had been iii fact tlie proportion of combination thc numbers being as nearly in accordance as synthetical experiineiits of this kind allow. Tlic substance so formed was not rendered in the lcast trirbid on digestion idh water showing that the whole of’ the bisulphitlc was in combination. Bcfore sthjccting tlic compound to analysis it was clecolorized as far as possible by being dissolvcd iii aboLlt fonr times its own weight of ether and digested with animal charcoal.After filtering espelling the ether in a mater-bath alld drying in T-~CLIO over sulphuric acid c7 product was obtaii1ec1 the SOME DERIVATIVES l'KO\I TIIF OLEFISES. mialpis* of ~vhicli confirme3 the above synthetically derived composition. I. 0.4721 grm. gave 0.4741 grm. of chloride of silver. 11. 0.4734 grm. gave 0.7530 grm. of sulphate of baryta. 111. 0.4239 grm. gaye 0.6808 grm. of carbonic acid arid 0.2849 grni. of water. Cdculated. FOUIld. I. 11. 111 99 c, 43.64 )I 43.80 I-l*o 7*27 >> >> 7.47 J9 I> s 23.27 23.93 C1 25-82 2 k78 >> >J -I 100~00 This body may therefore be called the BisuZpi'tochZoride of amylene. Its formula is C,,H,oS,CI.Bisulphochloride of' amylcne is a transparent liquid of light ycllom colour and syrupy consistence; it is miscible in all proportions with ether soluble in strong alcohol especially on warming but quite insoluble in water. Its taste which is at first insipid becoines very pungent and bitter; its snicll is faint and at first not unpleasant; it hecornes however very fetid when csposed to the air. Heated by itself it blackens leaving a carbonaceous residue and giving off compounds containing sulphur as well as hgclrcsulphuric and hydrocliloric acids Hence neithcr its boiling point nor vaponr-dcnsity could be determined. Its specific gravity is 1.149 at 12°C. Actio~zqf Bisdj17ride qf Cliloriwe oia Efhghe. Dry ethylene may be passed for Iiorurs through bisulpliide of chlorine at temperatures varying from 0" to IOOOC.witliout the occurrence of any appreciable chemical change the rcsulting liquid being coinplctely decomposed by water and the products being identical with those dne to the dccompoaition of pure bisulphide of chlorine by the saiiic liquid. Remembering however the readincss wi tli which arnylene con'.-biiies with the same body there call be little doubt but that on employing an arrangement by wliich the cthj-lene and bisulphide we brought together under increased pressure the two would * In this and subsequent analyses the chlorine was determined by heating with quick lime the sulphur with carbonate of soda and chlorate of potash the carbon and hydrogen with oxide of copper using the ordinary yrecxutions.TOT,. xr I 114 GUTHHIE ON mite directly aid give a product similar to the above described amylene conipounil . Action 0s C?tlorii!e of Su@ur zipon Anzylene. It has been called in question mhether the instable body chloride of sulphur which contains chlorine and sulphur in equal numbers of atoms (SCl) is really a definite conipound or a solution of chlo-rine in S,Cl or a mixture of S,C1 with the hypothetical analogue of sulphurous acid SCl,. The ready elimination of chlorine which it undergoes on distillation and the consequent continual diminution of the amount of chlorine in the successive distillates can how-ever scarcely be accepted as evidence of the heterogeneous nature of the substance,-innumeraBle instances occurring in which bodies whose composition is unquestionably definite undergo a similar decomposition even at low temperatures (such are the hydrate of chlorine the bisulphide of hydrogen etc.) .* The chloride of sulphur employed in my experiments was obtained by saturating the bisulphide of chlorine with dry chlorine at 10°C.and collecting the distillate obtained from this product which came over on rectification between 70' and 90°C. Thc action of this body upon amylene is one of very great energy; the two liquids when brouglit toge-ther hissing as when anhydrous phos- phoric acid is thrown upon maier Even when thc liquids are kept quite cold a slight evolution of permanent gas attends their combination. The following arrangement was found con- venient in following this reaction and esamiuing the gas evolved.Into a flask immersed in ice-water 19%grrns of chloride of sulphur were brought. Tlic flask was provided with n funnel-tube bearing a stop-cock liulb and gas-deiivery tube. The bulb of the funnel-tube was filled with dry amylene. On turning the stop- cock a very little way a portion of the amq'lene entered the flask; * Carius (Ann. Ch. Pharm. oi. 294,) has satisfactorily shewn that the ~olidbody said to be produced by the actjGn of chlorice iipon S,Cl contains oxygen introduced by moisture in the chlorine the heat thereupon evolved and thc consequent expansion of the T'RPOU~in the flask cliecliecl the ingress of tlie stniylene; ant1 tlie excess of penaanent gas being forced to bubble through the latter was thereby deprived of all traces of mechanically diffused vapour .of c1;loride of sulphuy..1111 this manlier the action lwas made intermittent aiid sc1.f-regulating. The permanent gas evolved was hornever sinall in quantity and resulted from thc action of the excess of chlorine npoa the amylene. \Ye shall in fact subsequently see that unless very great precautions are eiiiployed chlorine docs eliminate hydrogen from amyleizc. As soon as nil cxccss of aiiiyleiie had been acided the funnel- tube ~2s removed and the flask heated for some hours in a water-bath. The product so obtained was digestcd in a water-bath wit11 dilute caustic soda then washed q-ith water dissolved in ether shaken with siiinial clia-rcoal filtered warmed ia a \\rater-bath to expel the ether and dried in vrzmio over sulpliuric acid.Thc product weighctl 31 grim. The weight of conibiiierl srnyleiie was therefore 11.4 grins. (iicglecting the small quantity of hydrocliloric acid evolved). I€two niolccules of tlie cliloride of sulphnr unitc with one of amylene 19.6 grms. of chloridc of sulphnr would combine with 13-3grms. of amyleiie giving 32.9grms. of product. The analpis of the body prepared as above described showed that such direct combination had in fact been effected. I. 0.3723 grm. gave 0.1831 grin. carboiiic acid aid 0.1786 grm water. IT. 0.4280 grx. gave 0.5260 grin. sulphate of bnryvia. 111. 0.1437 gym gave 0,7113 grin. chloride of dver. Ca1v nlate(1.Ponnd. 1. 11. 111. GI 3 li.88 36.39 J )Y H, 5-81 5.33 YY YJ s 13-61 ,> 16.86 9) ('I2 40.70 >? 39.6 1 YY 100.00 This body may be called tlie Bichlorosdpi'eide of anzylene. Its specific gravity is 1.138 at 1-4'PC. Tts ealour is similar to that of the bisulphocliloride but deepc-r ; its oilour is moi-c penetrating. It is miscible I\itli ether duble in hot alcohol. Likc the bisul- phocLloride it is net yolatile by itself 11ithout decoiniposition. Heated with alcoholic soluti~nof caustic potash it gives rise to I2 volatile prodacts having the same pliysical properties and king in all probability identical m it11 those produced by the same reagent upon the 1)isulpIiocldoride of amyleiie. We shall suhse-queritly discuss the proJncts produced in both cases ; the fact however that the potash removes the whole of' the chlorine from the Isichlorosnlphi~e,may be here noticed because it proves that this body does not contain bichloride of ainylene; for the latter body when treated with the same reagent gives lip half its chlorine in cornbiriation with 1q-drogen being converted into chloride of fusyl* (Cl,H9C1 ) Action of Chloride of Sulphur upon Ethylene.Ethylene acts with so much less energy than arnylene upon chloride of sulphur that it is necessary for the chloride to present as large a surface as possi-ble to the ethylene in order that combination may be effected. An or-dinary bulb wash-tube (fig. 2) answers for this purpose. Into such it tube chloride of sizlphw* was ~,ronght and d1*y ethylene allowed to hih -Mc slowly tlwougli.The bulb-t ulie was at first immcrscd in cold water. However dry the ethylene may be aid however slowly it is delivered complete absorption neyer occurs a certain quantity of the excess of chlorine in the cliloride cleconiposiiig a portion of the ethylene (as in tlic ordinary process of formiiig bicliloride of ethylene mhcii the combination balloon becomes too hot or too strongly illumiriat ed) and giving rise to hydrochloric acid. The ethylene should be allowed to pass through at the rate of about rz bitbble in a second. As the saturation appmchcis completion (a process which with two or three ounces of thc chloridc occupies about twelve honrs) the liquid in the Iiulb-tube loses colour changing from tlic gsrnct-red of' the chloride of ~111-phur to the straw-yellow of the bisulphide of chlorine; at the same time heat ceases to be erolved.In order to complete the * Here and subsequently I call thc bodies C,H and C,,Hg aiizgi andfics.i$respec-tively reserving the names acetyl and vsleryl for the oxygenated raclicsls C,H30 and C,,H,( rc-action as far as possible and to remove any bicliloride of ctliylene formccl the bulb-tube must be heated in a water-bath to 100°C. and a more rapid current of ethylene passed through for an hour or two. It seeins however impossible without expending an unreasonable time to combine all the chloride with ethylene the gradually increasing dilution of the uncombined cliloride of sul-phur in the liquid product of tlie combination being unfavourable to the exercise of its affinity.To remove the uncombined chloride of sulphur the liquid contents of the bulb-tube mere dropped into water at 80°C repeatedly and vigorously sliaken with fresh quantities of water at the same temperature and allowed to stand for some days in contact with dilute caustic soda. The resulting product is a heayy liquid sluggish and opaque fi'orn suspended sulphur. The latter is removed by shaking the liquid with about 100 times its volume of dry ether filtering clriving off the ether by the heat of a water bath rcdissolving in a miiiirriuin of ether filter- ing evaporatiiig and finally dryiug in z'acuo over sulphuric acid. I. 0.2705 grm.gave 0-2000 grm. carbonic acid arid 0.0671 gym. water. 11. 0.1844 grm. gave 0.3540 grm. sulphate of baryta. 111. 0.2957grm. gave 0.6110 grm chloride of silver. C&lculJted. Found. T. 11. 111. (1 . 18.3.2 20.1'1 Y? >? H4 . 3.05 2-76 I? Y S . 24.43 c1 . 54.20 ,> Y> 25-74 >Y 3 51-19 100.00 These results agree suficiently with the formula C,lII,S,CI,. Tlie body so found is therefore a result of the direct cornbination of chloridc of sulphur with ethylene being the bichlorosulphide qf ethylene. In colour bichlorosulphide of ethylene is almost ideriti- cal with the bisnlphide of chlorine. Its smell is pungent mid iiot unpleasant resembliiig that of oil of mustard; its taste is astrin- gent and similar to tlmt of horse-radish.The small quantities of vapour which it diffuses attack the thin parts of the skin as between the fingers and around tlie eyes destroying the epidermis. If allowed to remain in the-liquid form on the skin it raises a blister. It is soluble in about fifty times its own volume of boiling ether slightly soluble in hot almost insoluble in cold alcohol and quite insoluble in water. Ilcstd by itself bichlorosulphide of ethylencis decomposed giving off liydrochloric and hydrosulphuric acids besides bodies containing carbon and sulphur and leaving a carbonaccous residue. Its specific gravity at 13OC is P.4d8. In looking back upon these bodies C,0H,0S2C1 Clo€IloS,Cl2 and C4H4S2C12,and admitting them to be analogues of bicl-rlorideof ethylene we seen1 at first at liberty to choose between two views as to their rational composition.The inorganic molecnle for instance of the body Cl,BloS,Ci may be regarded as consisting of chloride of sulphur and sulphur. So that preserving thc above indicated analogy its formula would bc written Cl,H1 .Is fSci or secondly as chlorine and sdplmr C,,H, ('2 where the t~o atoms of sul-phur are monomoleculw. Nor can the existence of such bodies as C,H,S be considered hostile to the latter view for sulphur is ppe-emineiitly polybasic. Rut we are iiot in the same manner at liberty to choose 1;etmeen the formulz C,,H, (s2gt aud C, {!:: to represent tlie bichlorosulphicle of amylene because the existence of C1,1-T.1,S2C1 proves that S2C1 is Iimolecdar and hence t5at the secorid of the above formulze iiiliiiely CloH1 (E is done admissible.Admitting then the formula C,,Hlo {% we must allow SCl to be mouornolecular and hence returning to the bisulphochloride of amylene its formula must be C,,H, {:" arid not Cl0Hlo {3.The rational formula of the three bodies :\re hence probably-CloHlo{:'' BisuIphocbloride of Arnylene. C,,H, Bichlorosulphide of Amylene. {gg: jsCl C,H SCl Bichlorosulphide of Ethylene. {Ecl But although the formulae C,,H, is the most rational statical formula for the bisulphochloride of amylene me shall see SOME DELCIVJ~'~'IVES E'HOY THE OLEPIN NS. 119 that towards certain substances it behaves like the chloride of a sulphur-containing radical ClOHlOSa. The behaviour of ethylene towards chloride of sulphur is furthsr of interest as affording I believg proof that the latter body is 11 definite coqourid or at all events that it does not consist of bisulphide of chlorine and dissolved chlorine.For were this its composition the free chlorine YY odd uuquestionably combine mit11 the ethylene; but as direct experiment described before has cou-J-inced me that ethylene is almost entirely without action on bisulphide of chlorine under the circumstances by which biddo-rosulyhide of ethylene is actually produced the latter body (bisulphide of chlorine) bring deprived of the excess of chlorine woulcl remain unchanged whereas in fact it is almost completely combined with the ethylene. Moreover in the synthesis of the bichlorosulphide of amylene if half the chlorine in the chloride of sulphur hail acted inde- pendently of the other half the reaction would have been as follows :-:J (S2C1 + C1) + 3 (Clo~Ilo)= 2 (Cl,H,,S,Cl) + C,,H,,C12; accordirig to which 19.6 grms.of the chloride would have required 19.5 grms. of amylene instead of 11.4 as observed a difference beyond the limits of observational error. Actiorh of ammonia upon bisulphochloride of amyiene.-Aqueous ammonia may be digested with bisulphochloride of amylene for hours without any sensible change taking place. On warming an alcoholic solution of the bisulphochloride of amylene with an alcoholic solution of ammonia an immediate and abundant precipitation occurs. The following process was followed in tracing this reaction :-About 50 grms.of the bisulphochloride in alcoholic solution were heated in a water-bath in a retort connected with an inverted condenser. Ammonia evolved from an aqueous solution and not dried was passed through the tubulus and made to bubble through the alcoholic liquid. The gas having been passed through for several hours the contents of the retort were allowed to stand for 24 hours. At the end of that time they smelt strongly of ammonia. The liquid was then filtered the insoluble portion being mashed with ether. This insoluble residue was a white crystalline powder which after drying in 'uamo over sulphuric acid was not attacked bv bydrochloric acid; it gave off hydro- cliloric acid without blackening on treatment with bulphiii'ic iici(1.0.1396 grm. gave 0.3708 grm. of chloride of silver. 0.1623 grm. gave a platinum-salt containing 0.2098 grm. of platinum. Calculatcd. Pound. 5111 . . 33.63 34.84 C1 . 66.35 65.67 It was therefore pure chloride of ammonium. The filtrate from the chloride of ammonium did not coiitaiii any sulphide of ammonium. On evaporating off the alcohol from a water-bath and adding water a heavy liquid was separated which after washing with water still contained a small quantity of chlorine. To reniove this it was 'heated for fie hours in a sealed tube in a water-bath at 100°C. with a fresh quantity of alcoholic ammonia. Thereupon a fresh crop of chloride of ani-monia was produced. Thc mother-liquid vas drained off heatcd for some liours in a basiii,in a water-bath and precipitated with water (as long as alcohol is present large quantities of the product arc retained in solution these may be completely preciliitated bv adding aqueous ammonia).The heavy liquid mhich separated out aftcr mashing and mechanical clrying was dissolved in ether digestcd with animal charcoal filtered the ether expelled by thc heat of the water-bath and the product finally dried in vaczco over sulpliuric acid. This substaiicc showed ou aiialysis the following percen tsge composition :-I 0.2134 grm. gave a platinum-salt containirig 0.0123grm. platinum. 11. 0.2129 grin. gave 0.1752 grm. water and 0*4011grm. carbonic acid. 111. 0.2763 grni. gave 0*2211 grm. water and 05284 grm.carbonic acid. IV. 0.2405 grm. gave 044790grm. sulphate of baryta. Calculated. Found. I 11. 111. J\. (N) lql 8 C, 0 . . . . . . . . 0.00 9.25 26.89 50.42 13.4-h 0.82 , , , , >? 91h , 51-38 ,> > 9-13 , 51.19 9 I> I> , , 27-15 ,) , , , 11.72 The amrnoiiia is widcntly present as an impurity 0111~7 probably either as chloride of ammonium or as bisulpliiclc of fusylamine tlie latter siipposition heing the more probabk owing to tlie escess of carbon found; in either case the amount of oxygeii nould be increased by its removal. The body formed is the Iqdrnted oxide of bisu@ltamyZene CloHloS,O.HO its formation taking place according to the equation-CloHloS2Cl + NH,O.IIO = NH,Cl + C,oH,,S,O.T~O The nlcohol einployed serws only as a solvent medium and remains chemically passive.Tlte forniation of this body under the circumstances above-ineiitioned namely the assumption of matcr in its generation is another and instructive example of hydration by means of ammo-nia a phenomenon which is generally sigiiificaiit of the formation of ail dcoliol. The hyclrated oxide of bisulphamyleiie is iiot volatile without decomposition ; mlicn lieated it emits a most fcetid odour blackcns aid leaves a carbonaceous residue. Its specific gravity at 8'C. is 1.049. It is quite transparent viscid and of an orangc-yellow colour :its smell is faint and meaty. It is insoluble in water but miscible with bisulphide of carbon ether aid absolute alcohol. The action of alcoliolic caustic potash upon bisulphocliloricle of ainylenc is similar to that of ammonia.On heating the bisulphochloride for a few minutes in a water-bath with ail excess of' alcoliolic caustic potash the whole of the chloriiie separates out as chloride of potassium the liydratcd potash giving rip both oxygen and water aid converting the bisulphochloride into the hydrate of the oxide of bisulphamplene. c,,~r,,s,ci+ KO,HO = C,,H,,S,O.HO + ~ci Five gyanimes were treated in this vay with alcoholic potash. The excess of alcohol being expelled on a water-bath tlie residue was washed with water and dried in vcm~oover sulphuric acid. 0.3225 grm. gave 0 2759 grm. water and 0.6050 grm. carboiik aciit. Calculatcd. Found. G" I 50.42 51.16 1311 ' . 9-25 9-50 s2 02 BUTHRIE ON The water wit11 mhicii the liquid lin I !ic<l!i ~~~tb:i( rl (lid lint call-tnin any sdphide of potassium.The liquid obtninetl by ca2:1 ,iic poiash is therefore idelltical with that formed by nnimo:iin. AiyueouJ c.instic potasli lilir aqucous ammonia dots riot exert any action npon Iiisulpliochloric!e of amj-hie. As liisulphoctiloridc of nmg.;eme is coiir.crted into a iiydraterl oxide by the hydrated oxide ~f an nlldine mctd YO is it convertxi into ail ailhydrous oxide by an ~.uliyclrousmetallic oxide. This iu the case eveii when water is preseut so long as tlic htkr is not iii chemical combination with the oxide cmplo~~cd ; for csamptt :-h large cxcms of oxide of lend (PbO) was digested o~era matcr- bath for several hours with an alcoholic solution of biau1phocl:loride of aq-lene tlic slcoliol being continuallJr rciien ed as it evaporated.As soon as a drop of tlic solution showxl on testing; that t'ie mhole of tlie chlorinc lid Ixmi rc-inm-cil frcah alcohol was :~ddcd the product filtered the filter mas!ied nilil-1 slcuhol and the iiitrrttc evaporated and dried in Z'CICLCO over sulptiuric acid. -2u almost colourless lieavy liquid ims obtaiued TI liich ;~t'txdrj-ing gave thc follomiiig percentage coiiipositioii I. 0.2576 grm. gavc 0*209hgrin. water and O*Ji87gr111. car-bonic acid. 11. 0.3222gnu. gave 0.6856 griii sulphatz of Ixwyt:~. 11. This agrees with the composition of oxick of bisc~Zphunzy laze C,,H,,S20 :-the oxide of lead having simply substituted oxygen for chloriiie.The oxide Qf bisu1pl:amglcnc is an almost colourless yellowish sluggish tmnsparcnt liquid of nauseous tastc and smell it is not volatile without decomposition. It is miscible with alcohol ether mid bisulphide of ca~bor inriirisciblc with wnto,r; its sp:c;fk grarity is l*OW at 13°C. It is noteworthy that in the preparation of thc hydrated oxidc of bisulphsniylerie described before if the solutioii of potash in idcohol contaiiied a veq large cpmtity of potash a product was cbtained coatailring aii atnouut of carbon iuteraediate between that of the simple. oxide and the hydrated oxide. This is tin-cloiibtcdly due to the actual formation of some oxide by the 113-drated pot ash.* The differelice in chemico-ne~;;ltivisin of the chlorine aid sulphur iii the bisulphochloride of ainylciie and tlir consequent iiitrodu -tion of oxygeii in piace of the former elerricnt evinccd in the above reactions qIiFqests at oiice thc possibility of introducing an organic group in place of the chlorine from some cornpouiid in which such group is itself chemico-negative.The ethylates of the alkalis offx us examples of such bodies and the discoverer of zinc-etlryl liaj placed a further instance of the saine class in the hands of' chemists. Nevertheless the first of tlx reactioiis indicated docs iiot appear to take place wider ordinary circumstances. If ethylat, of' soda and bisulphochloride of nniylene be warmed together the two react with considerable euergy. Iu an experiment of this kind an excess of ethylate of soda was warmed in a flask with bisulphochloride o€tlmyleiic chloriclc of sodium was formed.The resulting liquid mas shakcii with water and the product formed mas extracted by ether. After filtering craporating washing and drying the ethereal solution it mas analysed. (It did not contain chlorine and the wash-water was fibee from sulpliur.) I. 0.3424grm. gave 0.6878 grin. carbonic acid aud 0.2787 grm. water. In a second portion from anothw yurtutity ill the yrepai*atioii of which the utmost pains were taken to leave the ethylat: of potash free from hydrate of potash 11. 0.3759 grm. gave 0-7339 grm. carbonic acid and 0.2974 grm. water. These resnlts agree far bettcr with the simple oxide of bisulph-amyleiie than mitli the ethylate of oxide of bisulpkamylene sought.* This anhydrous oxydstion hitrruoniAed with the tct that hydrated potash dis-solved in amylic alcohol reaats upm iodide of ethyl forming ethylate of amyl. 'See Phit.Mqp Septembcr 1837.) 124 G L TllKIE ON Found. CI 011,os,o I. IT. C,,II,,S20.C,H,0 C. 54*54! 54-78 54-83 57.15 11 . * 9.09 9.05 8.70 1090 Hence the ethylatc of potash does not act as the hydrate of potash that is the oxide of ethyl does not combine with the oxide of i)isulyhamylene 011the formation of the latter. In other words thcre is no double ether formed. The ethylate of potash in short has the same action as oxide of potassium would undoubtedly have and as we have already seen the oxide of lead to possess.11-1 consequence of this negative result I have not submitted the bisulphochloride to the action of other allisline ethylates. We hare already discussed the action of hydrated potash upon bisulphochloride of amylene at temperatures below 100OC. If liowcver after the two have reacted at this temperature the pro-duct be submitted to distillation in presence of an escess of potash further decompositions are effected. In tracing these the following method TI-BS puwed. Caustic potash was dissolvecl in alcohol and evaporated so far that it solidified on cooling; it was then brought into a tubulated retort connected with R very well cooled condenser and heated till it became quite fluid. Bisulphocliloride of amylene was allon-ed to drop upon it tlirough a funnel-tube passing tlirough the trtbulus and provided with a stopcock.The temperature was at first moderated the first action (the formation of the liyvdrated oxide of hisulphamylene) beiiig determined at low temperatures. Increased heat was gradually applied until the lower part of the retort became red-hot oily drops still continuing to pass 01~2'. When the distillation was complete water way addecl and the light liquid which thereupon separated out was ~~~aslied with water and dried over chloride of calcium. The \7olulne of product so obtained was ahout two-thirds that of the amylelie compound employed. On rectification it began to boil between 50' and GOOC. The boiling point remained for some time stationary between 110' and llijOC after which it rose rapidly.There were consequently at least thee liquids present ; fortu-nately Ilowever their respective boiling-points were so far apart as to allow of their separation by rectificatioii. TElc more volatile portion was submitted to rectificatioii by itself thc distillate being collected in an artificially cooled con-denser. A considerable product was obtained having the fixed boiling- point 3cS0c. I. 0.1635 grm. gav4 0*;5093grin. carbonic acid nnd 02132 grm. water. 11. 0.1751 grm. gave 0.0362 grm. sulphate of bsrptn. 111. 0.1743 grm. gave only cz trace of chloride of silver. This body was therefore ainylene; the presence of sulphur is due to the body next to be described with which the amyleiie man contaminated and which could not be completely separated by rectification.The portion of the original distillate which came over between 110' and 115°C. was next submitted to rectification. Tts boiling-point after four rectifications became constant at 112OC. 0.2687 grrn. gave 0.57'46 grm. of sulphate of baryta. 0.2581 grm. gave 0.5615 grm. of carbonic acid and 0.2276 grrn. of water Calculated. Fonnd. I. 11 s GI 0 ' 31-68 59.40 29-29 J7 >9 ,513.33 H9 . 8.131. 99 9-84. c__ 9999 This substance the hisulphidc of fusyl C,,119S2 is pcrfeclly colourless and transparent miscible in all proportions mith ether soluble in alcohol insoluble in water. Its snicll is not disagreeable. Its specific gravity is 0.880 at 13°C. The analysis given would not by itself be conclusive as to the composition of the above-described body.Both 1)isulphideof amyl and amyl-mercaptan as well as bisulphide of amglene mould give analytical results according with the above within the limits of analytical error. My reasons for assigning to it the above com-positions are (1)its boiling-point bisulphide of amp1 boiling at 250°C.; (2) its indifference both alone and in alcoholic solution towayds both yrotoxide of mercury and acctate of lead with mliic'li ainyl-inercaptan conibincs with great cncqy ;and (3) its being a ~olati!~ liquid soluble in ether aid alcohol bisulpliicle of ethylene being non-volatile and insoluble in these media. &sides these two products bisull~hochloric~.~ of amylcne giws rise in presence of caustic potd at high temperatures to other volatilc products of boiling-points above 112°C.which I liave not examined. hTone of the bodies described above became solid at -18OC. A description of some derivatives from the other two sulphuy-cliloriiie compounds above described C,,H,,S,CI and C,€I,S,CI as well as of some direct derivatives froin the two olefiiies Ib reserve for a future communication. Since writing the above I hare succeeded in combining etliyleiie with bisulphide of chlorine in such a manner as leaves 110 doubt that the product is C,II,S2C1. If this be the case there can be little doubt but that such a body mill give rise to a series of coni-pounds similar to those cousidered ahore belonging to the corres- ponding amplene-olefinc.

ISSN:1743-6893    

DOI:10.1039/QJ8601200109

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

126 BY G. G. STOIXS,Sec. E. S. LUCASIAX PROFEPQOR Or NdTHbKhTICS IN TEE UBIVERSlTY OF CAMBRIDGF. THE crystallizable substame the existence of which in the bark of the horse-chestnut I noticed in a fornicr communication to thi3 Society," and to wliich I ga\-c the mnie paviin together with zsculia yhicli it closely resembles ill its properties may be thuq prepared. A decoction of the hmk havirig becii made arid allorred to grow cold there is addd a prrsalt of iron such as pernitrate nntil on testing a sample by the addition of ammonia the pre-cipitate separates at once in distinct flocks leaving a bright pale yellow highly finorcscent fluid giving a mixture which filters readily. The whole is then precipitated by ammonia and * Chem. Soc. Qu. J. vol.xi. page 17. filtered ; about one-fourth of tlic aminoniacal filtrate is precipi- tated nitli acetate of lead avoiding an excess ainnionitt being added if required ;the mixture is restored to solution by the addi- tion of acetic or dilute nitric acid added to thc remainder of the first filtrate previously acidulated ; tlic whole precipitated by am- nioriia and filtsrecl ; and the filtrate precipitatccl by ammoniacal acetate of lead and filtered. The two precipitates arc collected separately and treated with acetic acid until they are dissolved or at hst wholly broken up filtered if need be aid set aside in a cool place. The second precipitate yields mculin which makes its appearance as n light precipitate appearing under tlie micro-scope to consist wholly of minute ncedes.The first precipitate yields paviin which ordinarily crystallizes in tufts of very long sleder silky crystals. When the solution is comparatively impure it sometimes crystallizes very slowly in shorter and far thicker crystals. The crystallization of pavjiii is sometimes remarkably facilitated by dropping in a very minute portion of the substance from a previous preparation. When the crystallization mhetlier of zesculin or of paviin ceases to progress the mass of crystals is thrown on a filter chained and pressed out. The niotlier liquors being similarly treated by partial precipitation yield additional quantities of the substsnccs. The mculin thus obtained after merely pressing out the cry-stals without m~ashing is usually snow-white.The paviin which appears to be naturally sliglitly ycllow is often mixed with a brown product of decomposition oi otlier substances which Iiow-ever hing insolublc in water is of little consequence. The properties especially thc optical properties of paviin so far as I have observed appear to be absolutely idcritical with those of frssin a crystallizablc substance discovered iu tlrc bark of the ash by tlic Prince of Salin-Horsirnar,* who has favoured me with a specimen. The siibstancex wonld seem to be identical,? but analyses arc yct wanting. Accordingly it is unnecessary to describe the properties of paviin. I will limit myself to two observations relative to horse-chestnut bark in ~vhiclioptics corns in aid of chemistry.The quantity of paviin contained in horse-cliestniat bark is larger than I had at first imagiued. I find that in order to niatch a I’ogg. Ann. c. 607. 9 I find fi’axin like paliiii to Ec slighily FoluLlc in ether at least mashed cther. the tint of the fluorescent light of a decoction of liorse-clicstnut bark by a mixed solntion of' mculin and paviin tlie substance3 must be present in the proportion by weight of' about 3 to 2. Tliz relative proportion of paviin as compared with zesculin actually obtained is liable to be much less tlian this which arises I believe from tlie circunistaiice that paviin from its somewfrat stronger afinitics is less easily separated than esculin €rom certain readily decomposed substances present in the decoction.The production of' xwuletiii from aesculiii may bc elegantly followed by combining the optical and chemical properties of tlic substances. A solution liable to contain zsculetin is acidulated if not already acid and agitated with about an equal volume of ether The ether withdraws the aesculetin and when the whole is examined by daylight transmitted through a deep manganese purple glass (Phil. Trans. 1853 p. 385) the zescaletin shoti-sitself by the strong fluorescence of the ethereal solution. In this tvay it is easy to tell what acids give rise to thc formation of zw.dctin by lioiling a teaspoonful of water containing sap the hundredth of a grain of axmdin with the acid to be tried. It is easy too to demonstrate the absence of mculetin in the bark itself and it? presence in a decoction which hag stood soine time. In describing an analysis of horse-chestnut bark not yet eom-plete Rochleder mentions a warly neutral" crystallizable substslice mhich nccon2panies ~sculinin smull quantity. If this be paviin as seems probable tlie subject is at present in the liaiids of Rochleder who has also undertaken the andpsis of fralin.

ISSN:1743-6893    

DOI:10.1039/QJ8601200126

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

[BY HEKRY E. l%OSCOE alld v:ILLIATtl I)ITTU AX. THEimportant investigations of the relations exhibited in the absorption by water of the more commonly occurring gases lately made by Bunsent and his pupils have established the truth of the law originally enunciated by Heiiry and Dalton according to which the quantity of a gas dissolved in a liquid at a constant * Gmelin's Haadbuch vol. 8 (lSJrS\ p 25. -t. See Banwn'q Gwometry. Imtdon j Walton and Msl)erl?-. Pqe 128. temperature is directly proportional to the prmslire whei,her total or partial under whicl-1 the absorption t:hs place. The theoretical explanation given by Dalton of this simple rcla- tion according to which the law must be considered as a special case of the law of Boyle can scarcely be adopted at the present clay.It is on the contrary far more probable as Bunsen believes that the general lam expressing the true relation between the amount of absorbed gas and the pressure is an estrcmely complicated one which only appears to possess the simplicity expressed by Dalton’s law betmecn certain narrow limits of pressure and temperature. There are especially t\.co conditions uiicier wliich the deviations from this simple but less general law niay become perceptible ; in thc first place namely under pressures and at temperatures at which tlie gas approaches tlie point of liquefaction ;secondly in clzscs in which the so-called chemical attractions begin to exert their influence. In order to throw some little light upon the phenomena of gns-absorption occurring under one or both of these conditions we have iii the following communication to detail the rcsults of csperiments made upon the absorption of hydrochloric acid and ammonia by water under varying conditions of pressure aid tem- perature.A. EXYERI3IENTS WITH IIYDROCIILOKTC ACID. I.-Relatio?a belweeta the amount of Hyd?*ocMorricAcid Gas ab-sorbed iiz ?Yater at O’C. und the pressure under tuhieh the wbsorption occurs. In fcw of the numerous experiments given by Bunseri in proof of the truth of Dalton and Henry’s law have the alterations in the amount of the absorbed gas been effected by the variations of tIic total pressures almost all the examples showing the applic- ability of the lam being proved for partial pressures with mixtures of different gases.Experiments made by one of us,’k shomd on the other hand that chlorine gas in its behaviour to water forms an exception to the general rule inasmuch its it was found that the amount of dissolved chlorine is not olily dependent upon the prtial presswe but is also influenced by the chemical nature of the diluting gas. As a similar disturbing presence-action cf tlie diluting substances might possibly occur in the two gases t‘ncler * Roscoe Chem SOC.Qu. J. vol. iii p .14. VOL. XIT. A investigation it was advisable to determine the quantity of gas absorbed under different amounts of direct pressure. For this purpose we have mode use of a nicthocl by means of wliich wc are enabled to dctcriniiie tlie so1ul)ility of hydrochloric acid atld ammonia under direct pressures varying from a fcw iuilliineters to two nietcrs of mercury.The essential featurcs of this method consist in saturatiiig n certain quantity of water contained in a bulbapparatus of known weight and capacity with the pure gas at a given temperature and under a giveri pressure. When the liquid was satnratcd the bulb was hermetically sealed the total weight determined and tlic amount of contained gas awertaiiied by analjsis. In this way a11 the data iiecesswy for the calculation are obtained. According as the determination was required uiirler pressum equal to less than or greater than the atmosplieric pressure certain special arrangements were adoptccl. For the purpose of deteriniiiing the sdubility of hydrochloric acid gas under the orclinclry atmosylieric pressure a moderate current of gas e\-olved and purified with all due precautions wa9 passed into from 0.5 to 2 grmmes cf water contairicd in the glass bulb apparatus fig.I of known Ti-eight and capacity (from 10 to 13 cbc.) joined to the v-asliing bulbs of tlie evoln-FIG. 1. ~ tion flask by shccl ca~utchouc tubes. For obvious rcasons 0°C was the tcmpersturc chosen 3s that at which all the pressure dctmnimtions should Fc made 2nd the bulb-'vessel WRS thereforeplupged into a bath of fiiiely pomdcd and melting icc. In a seyies of preliminayy eipcrimcnte we had detcriiiiiied the time which elapsed €ram tlle com- mencement of tlic edution until the water in the bulb was saturated and liacl attained thc constant tempcmture ~ -of the bath.To cnsure the establishment of the rcquircd absorptiometric equilibrium we allowed in the actual clcterminations the passagc of the gas to coutiuue €or half an hour after this point of saturation had becn attained. The bnll) wm then completely closcd bp first pressing the sheet caoutcLouc joining ilearest the evolntion-vessel and then that on thc limb from which the gas escaped into the atmosphere with suitable screw-clamps. After having separated the bulb-vessel from tlie other parts of tkc apparatus it was cooled down in a freezing mixture to R temperature considerably below OOC and herrneticdly senled at bb before the blow-pipz HYDROCHLORIC ACID AND ABTNONIA.The barometric pressure was then observed the bulb and its contents accurately wcighed and the total hydrochloric acid deter- mined by volumctric analysis with silver the bulb being broken under water and an aliquot portion of the resulting mid liquid employed for analysis. From these data the weight of hydro-chloric acid absorbed by oiie gramme of water is easily obtained. The capacity of the bulb and the volume of liquid being known the weight of gaseous hydrochloric acid contained above the liquid can be found and then the weight of dissolved hyclro. chloric acid and the weight of the water can be calculated from the direct observations. In order more clearly to illustrate the details of the method we give all the data obtained in one experiment for the deter- mination of the solubility of hydrochloric acid at 0" C.and under R haromctric pressure of 0.7398 meters of mercury. Weight of apparatus empty = 9,5532grms. Capacity of apparatus to bb fig. 1 = 6.5 cbc. Weight of apparatus + contents at 0*76mand I5 OC = 10.9768 grnis. Ditto + contents + displaced air = 10.9848 grms. The total content of the app-aratus was diluted FIG. 2. with water to 183.1 cbc. and of this acid liquid 50 cbc. were taken for analysis. This quantity required 4.875 x 108 milligrammes of silver for* complete precipitation ; hence the total amount of hydrochloric acid is 0.6515 grm. In order to obtain the amount of dissolved hydi*ocl~lo~ic acid we must subtract from this total quantity the weight of 5.4 cbc.(the capacity of apparatus-volume of liquid) of gaseous acid = O.COS5 grm. We theu have 0-6430 grm. of hydrochloric acid absorbed in 1.4316 -O*G515=0~7801 grms. of water ; or 1 gramme of water alisorbs under tlic circnnistaiices of the experiment 0.8241 grm. of hydrochloric acid which measured at Go C. and under a pressure of 0*7P1; occupies a volumc of 405.3 cbc. When the solubility of the gw under pressures less thaii one atmosphere was required the follow-ing modification of the method was emploTed. In place of the apparstl-is fig 1 a simple bulb a fig.2 K2 132 ROSCOE AND DTTTSIAR ON THE ABSOItL’TIO’N OJ? of about 10 cbc. crtpacity blovn 011 to the end of a glass tul)? was used as the saturating vessel.Into this weiglzed bulb con- taining about 2 grms. of water pure hydrochloric acid gas was passed at a temperature of -15’ C. until the liquid was completely saturated. The delivery tube through which the gas entercd was then removed and whilst the bulb still remained in thc freezing mixture a carefully prepared tube of sheet-csout-chouc b fig 2 containing a spiral of platinum mire mas made fast to the end of the bulb-tube. This caoutchouc connected the bulb by a moveable but perfectly air-tight joint vith a vertical baro- meter-tube c divided into niiilimetcrs and previously filled with the gas the lower end dipping under mercury. The freeziilg mixture was now removed from tlie bulb and the temperature of the liquid gradually rose whilst thc dissolved gas was rapidly disengaged making its escape from the loner end of the baro- meter-tube 6 though the mercury into a layer of‘ water 20 placed to receive it.As soon as the escaping gas was seen to be complctely absorbcd by the lapr of water so that absence of any trace of air was ciisured the liquid in the bulb was carefclly warmed by means of a water-bath to some tenipersture above 0’ C. which was more nearly regulated by the amount of pressurc wder which the solubility had to be determined. After the requisite quantity of gas had thus been expelled froin the apparatus the bulb was again plunged into a bath of melting ice and tlie liquid allowed to attain the temperature of zero. No sooner however does the temperature of the liquid diminish than a portion of the gas above the water is again absorbed and a consequent rise of the column of mercury in the bcarometric- tube c occurs the amount of this rise depending upon tlie quantity of gas previously expelled.By coutinually shaking the bulb the level of the mercury in the tubc was soon brought to a constant point ;and after tlie meniscus had remained stationary for ten minutes during which time the liquid was constantly agitated the layer of water was removed; and the height of the coluinn read off on the divided scale. The bulb was then completely closed by pressing the caoutchouc tube with a scrcw-clamp re-moved from the apparatus and hermetically sealed at g. After weighing the analysis and calculations were made exactly as in the foregoing example.In this way by allowing different quantities of gas to escape the saturation may be effected under pressures within the limits of the barometric variation or under pressures equal to a few millimeters of mercury. IIYDEOCIILOEIC ACID Ah’D AMRIONIB. The determinations of the solubility of hydrochloric acid under l’rcssures greater than that of the atmosphere were made by sim-ply leading the gas through water contained in the bulb apparatus fig. 1 under the reyuircd pressure. This pressure was obtaincd by nieaqs of the arrangclnent represented in fig. 3. The gas issuing FIG. 3. from the bulb-apparatus c enters the vesd d (“nil thciicc lias to pass through a column of mercury e of the requisite depth. ‘1he exact press:ire was rnemmd by tlic rise of mercury in the dividcd tube f fixed tightly by means of a massive caoutchouc stopper into the vessel d vhich also serves as an air-chamber to cqualise the mriations of pressrarc.The difficulty of obtaining joints mliicli will stand a pressure of smeral atmosplicrcs and yet can be per-fcctly closed by scrcw-c1ampsJ ms overeonie by thc following simple arrangemefit. The saturation bdl~ TIW joined to the dtlier parts of the apparatns by means of wrell-madc sheet-caoutchouc tubes which were so attachcd tht the eiicls of thc glass tubes were left about 10mni. apmt ; outsidc this middlc portion of thc caoutchouc a piece of eoppcr or hrass foil a-bout 20 mm. broad was tightly ~vvrapped,and this copper Ti-as overlapped at each end of the caoutchouc witlr strips of lead foil ah about 20mm.broa 1 the whole arrangement with the exception o€ the caitml pmt of' the coppcr foil lseirig tlicri tightly hd round with soft copper wire. Thus connected thc appwatns var i:,:2~able within ccrtaiii limits codd be perfectly clod by thc scrmr-clamps at pleasup? and was absolutcly air-tight under pressures up to the2 atimspheres. In the actual experiments tlie gas was allcmed to pass through the bu!b apparatus escaping fi-om below tlic colunin of mercury e uiitil thc liquid had attained the temperature of the ice-bath and wif,s perfectly snt-Lu.ntecl with gas. The variation of the lcvel of the coluzlzni of mercury in the manomcter tube f vas continuauy obscrved (luring the ~vrrholec011rse of the csperimcnt the mean height being taken as gi\7ing tlic pressure of tlie gas ; tlic apparatus \\as $hell closcct 011 tlic sick of the cvolutiJa -\.csscl by n screw-darq ; tht height cf thc mercury agr,in noied ; and the sccoricl liirib of thc bull closccl in likc ~nanncr.T'liz ~esscicontaining tile saturated liqd ws now remowd from the other pnrt of the apparatns and plnnged into a freezing mixtune composed of two p;arts of cq stnllizecl c:iloride of calcium and three parts of finely pon dcred ice As sooii as tile liqd 11nd attained the temperntura oi" ihc bath (-3G0 C) the ten,+ionof its yapour bccmie less thail the brli oinetric prcscui*c :,id the bulb-apparat ns was ltcrmctically cpicsccl before the blow-pipc. After regaining the oi*dina~y atmos-phcric teniperaturc thc bulb thus filled 11 as weighed and tlls con-tents analyscd in the ixmncr alrzatly described cnrc being tczlieii again to cool the liquid in a freezing mixture bc€o:ore operliiig under ~mter.HYI~ROCNLORIC ACID AND A3IMONIA. C. 0' atwtcrbyrtl.sod~cddrochloric acid hjofzmountbctween the The results of teii experiments condwtd according to thr tlirec diffcrent methods are thrown together in the following Table. TABLEI. At the temperature 0.C. oiie gramme of water absorbs G grammcs of hydrochloric acid gas under the partial pressure ofX.I' meters of mercury. Ko.1 2 3 4 5 G 7 8 9 10 I?. 0.058 0-321 0.5G9 0.735 0.737 0'755 0.932 0.937 1.263 1.270 --_I_----G. 0.614 0.746 0 796 0.SB-i O*S21 0.82 G'S51 0.S51 0.690 O.SS7 By nicaiis of thcsz dirzct observations the values in Table 11.ivcrc obtaincd by graphic interpolation. From these as also from tltc curve HC1 (Fig. 4) we obtain a clear idea. Gf the relation mid the pressure under whie!i tlic nbsciytioii OCC~I rs. TABLE IF. 1'. 0.75 0-so 0'90 1'00 1.10 1.20 1.30 A glance at the numbers in Table 11 or at the curve HC1 (Fig. 4) reiiders evident the singular fact that tlre amourit of hydrochloric acid gas absorbed by water at alters but wry slightly with OOC. the pressure a variation of pressure from 1nieter to 0.5 meter producing a dimiiiutioii in the quantity of absorbed gas of onlr 8.7 instcad of 50 per cent. Hence it is seeu that in this case the law of Heury is not even appi*oxiinately applicable.A plausible explanation of thc slight influence exerted by pres-sure on tlrc quantity of hj;drochloric acid dissolved by water at * By partial pressure we here signify the total pressure under which the aboiption occurs minus fhe tension of aqueous vapour at 0°C. 136 ROSCOE AND J>1TTMAR ON THE ARSORPlXON OF 0°C. might be given by supposing that the absorbed gas consists of tnio portions one of which is cheinicalIy combined with tlic watcr and the other absorbed in accorclance nith the law. A larqc portion of the cwvc HC1 (fig. 11) being identical with the straight line cd would seem to bear out this supposition but the experiments made at pressures below 0.60" show that the curm deviates from the straight line and that therefore this hypo-thesis must be abandoned.We must however allow that some portion of the dissolved liydrochloric is independent of the pressure as the gas cannot be totally expelled by boiling or displaced as we shall presentIy show by an atmosphere of another gas. ST.-ReZotion betzueen the Amount of Hydrochloric Acid Gas nbsorbed in Water under. the ordinwry Atmo,ylteric Pwssurcs and the Temperature at which the Absorption occurs. All these determinations were made exactly according to tlic ethod already described for 0' C. under the atmospheric pressure. The temperatures above 0"C. were obtained liy placing the appa-ratus (fig. 1)in a water-bath which we succeeded in Beeping to within 3$"C.of the required temperatnre by means of the usual arrangements. The indications of the thcrmomcters we employed vere corrected by a complete serics of comparisons with a normal iiistrumcnt from the Kew Observatory liiiirlly lent by Dr. Joule. The following Table III coritains tlic results of the cxperimentx :- TABLE111. Oue gramme of water absorbs under the atmospheric Ims- sure B and at the temperature t"C. G gramines of liydrochloric acid gas. The reduction of these numbers to 0*760". or any other constant pressure mould ham cntailed for each temperature a similar series of pressure experiments as that rnadc as 0". Con- 137 HYDXOC HLO&TC ACiD AND AMIIOKIA. sicleriiig therefore thc slight influciice of pressurc at this tewpera- ture wc have thought it best to lea^ the experimental results uncorrectecl supposing that they mere a11 made at 0.760".The iiuinbers in thc following Table IV give the weights in gramines (G.) of hydrochloric acid absorbed under tlic barometric pressure 0.760" by 1grni. of water at the temperatures to,tlic values being obtained by graphical interpolation from the direct experimental results in Table III. toc. grms. t"C. grrns. toc. grms. ,toC. grms. _I_ OU 0.825 16" 0 742 32" 0.665 48" 0.603 2" 0.814 18" 09'31 34" 0'657 50" 0.596 4" 0804 20" 0.721 3G0 0.649 52" 0.589 6" 0.793 22" O*ilO 38' 8.641 54" 0.582 8" 0.783 24" 0.700 40" 0.633 5G" 0.5'75 10" 0-772 2G" 0*601 42" 0.626 58" 0.568 12" 14" 0,762 0.752 28" 30" 0.682 0.673 44" 46" 0 G18 0.611 60" 0.561 The curve cc (Fig.5) represents the relation lietween the tem- perature taken as abscissa anci the a-eight of gas absorbed uncler O-YGOnl talccii as ordillate. The foregoing experiments as well as many older observations show conclusively that the laws regulating the absorption of liydrochloric acid in water are totally diiereiit from tliose which the other gases obey. When aqueous solutions of other gases even the most soluble such as ammonia arc heated the dissolved gas is quickly displaced until when the water has becn boiled for a short time all thc absorbed gas has disappeared from solution. In accordancc with the law of D a1 t 011 and Henry me know too that most gases are expellecl completely from water at temperatures lower than 100" C.when a constantly renewed atmospliere of a forcigii gas is brought into contact with the solution. The greater or less solubility of the gas effects in 110 may this expulsion ammonia beiiig completely driven from solution by a current of atm osplieric air. Dalton long ago sliotr-edthat hydrochloric acid forms an excep- tion to this rule and Bineau corroborating these results provcd that aqueous hydrochloric acid whether saturated or otherwise if boiled under the ordinary tttrnospheric pressure at last attains a pint at which anhydrous acid awl maier distil CVC~ill t!:c same proportioils in which tlicy arc contaii!ed in tlie rcsidne. The composition of tlic aqueous acid thus olhined was found by Bineau to corrcspund closely with thc forill1da NC1+ lCiH0 The same cliernist further found that this acpeous acid mhcn exposed at ordinary atmospheric tcrnpcraturcs to dry al~,con-tinucs to lose water until a coiistaiit composition is again attained which is represented 13y the ntomic relation IHCl + 12 HQ.From these obsei.vatioiis of Binem it would nppcar tht hydro- chloric acid forms at least two 111-drnteswliich iiiny l;c i-cgartlcd as c’l-leniical compouiids and that all ,zqii:om Folntioiis of this gx may be supposccd to lie niistures of one or both of these lryrtrates with excess either of acid OY water. It is homevey also possible that the fact that these tn-o acids have an atomic compo- sition is purely accidental and does not therefore imply th, existence of any points of iiiaxiniuni attracticri suflicieiit to justify the assumption of definite cheinical combination.The coustsncy cf the boiling point of the aqueous acicl containing HC1 + 16 HO as observed by Bineau in no way proves the existcrice of a che-mical compouiid as this sarnc reslult might equdly wcll ensue from simple physical causcs. Ths for instance it; is possible t!~ conceive of a inisture of tivo liquids wlios2 vnpcurs posscss %it tlic same temperature difkrent tension.; such that I\ hcri cbnlliti3;i commences at n given tcrnperature and uncl;.r a eorrcspondiu;. yrcssnre the 1)ropohoii betmwn the xeiglits of the two ~apxws distilliiig OVC~is the saint as that in vliiclr t1i3 liquids I:z-~,c ILW mixcd ; imd that thcreforc tlic inixturc boils nt a constaxt tcw-peratux without unciergoing any clisuge in its comipositioii.TVe thus see that under given circumstances of teiqxrature and pressure n inlixcd liquid may net p.3 regards boiling point like a uniform clmnical conibiriation ; thc latter mmt liowcver retnin its properties witliin a certain range of varied plij-sical conditioi13 when the mixture is unable to clo so. Accdiiig t~ receisrecl ideas a chemical compound may be defined as a substance t~-hos;= CG~I-stituents are unitcd in atomic proportions able as a milole to withstand a certaiii amount of change of p1iysical conclitions without alteration. If thcn Ulircau’s ncids aye really clcfnite hydrr,tcs they must he cap;iblc of existing undcr pressures greater or leas than that of tlie atmospliere and aqueous hydrochloric acid distilled under such circumstances ought lik eiyise to attain a constant composition of HCL +1GHO.I1YDI)IOCHLOI~IC ACID AND .IiU3fIOKIA. In order to determine which of these two hypotheses is the correct one we in the first place repeated Bineau's experiments for the purpose of cxawining what were the actual deviations from the theoretical results the supposition of atomic rclsltions not being admissible in the case in question owing to thc accuracy of the analytical results iinless a very close approximation is obtained. In thc first series of experiments we boiled a liquid which contained 18.5 per cent. of anhydrous acid in a retort collecting portions of the residue from time to time and analysing them by means of silver.The boiling poiiit of the liquid soon became con- stant at 110"C. and after a considerable portion of the acid had distilled ocr the residne containcd 20.16 and after further dis- tillstim 20.21 per cent. of hydrochloric acid. A second series of experiments with an acid containing 24.8 per cent. HC1 sliowecl that when the liquid was reduced to + of its original volume the residue had a composition of 20.39 per cent. and that nhen half the liquid had been distilled the rcmainder contained 20.29 per cent. of anhydrous acid. In a tliird experiment the composi-tion both of the distillate and residue of an acid which contained 20.28per cent. cletermined in successive portions garc the fol- lowing results from which it is seen tliat the composition of tlic distillate was by no mean3 so constant as that of tlic residue.An explauation of this fzct mill be giveii in tile sequcl :-NO. 1112131415 A fourth determination was made by distilling an acid con- taining 20.14 of HC1 and therefore weaker than the 16 atom hydrate in three different portions examining the composition of the residue in each case. ~ ~ Fraction of vol. after distillation 4 ii -I 1 Per cent. of HCI before distillation 20j4 20-14 20.14 Ditto in residue after distillation 20.27 20-24 20.24 From the mean of these 10 experiments we find that the residual aqueous hydrcchloric acid boiling at 110" C. undcr tlic crdiriary atmoepheric pi cmures contains 20.25 per cent.of' anhy-drous hj drochloric acid. The calculated per centage composition of HC1+ 16 HO being 20.22 we conclude that under pressures nhich differ but slightly from O*7GOm the composition of the acid which lins a constant boiling point is that indicated by Bineau's formula. In order now to determine whetlier the aqueous acid having the cornposition HC1+16HO can be regarded as a definite chemical combination unalterable under change of physical coil- ditions we distilled this same acid under pressures varying con- siderably from that of the atmosphere determining in each case the composition of the residue. Experiments instituted for this purpose at pressures both greater and leas than the barometric one showed that distilled under other pressures than Oa76Om the 16-atom hydrate is dccom-rosed but that for evcry pressure an aqueous hydrochloric acid exists wliicli when distilled under that pressure possesses a fixed composition and boiling point.The distillation of aque-FIG.6. ous hydrochloric acid under pressures less than 0.'7Gmwas accomplished by connecting the flask containing the acid a (fig. 6) with a large bolt- head of 20 litres capacity B which could easily be mi-dered vacuous A divided barometric tube c (fig. 6) gave the pressure under which the distillatioil took place. As soon as the air had been removed from the apparzhs to the extent required the acid was heated to boiling wliilst the bolt- hcad nas Iiept cold by a stream of water. By occa-sionally opeiling a stop-cock on the tube f (fig.6) con- HYDROCHLORIC ACiC AXD AJIlIONIi\. 141 necting the apparatus with the vacuous cylinder of a large air pump the mercury in the tube c could be kept within 5 mm. of the required height during the whole course of the distillation. The coqposition of the acids boiling under pressures greater than that of the atmosphere mas obtained by distilling the liquid under a column of mercury of the required height. For every pressure at least two experiments were made one starting from a weaker and the other from a stronger acid than that fouiiil in the residue after distillation. The following Table V contains the direct experimental resnlt3. Column I gives the riumber of the experiment; column 11 t?ie pressures expressed in meters of mercury under which the distillation mas made ; column 111 the quantity of hydro-* chloric acid contained in 100 parts of the liquid before distilla- tion ; column IV the quantity contained after distillation.Th? numbers rnarkcd* arc those which correspond to definite hydrates thus 23.8per cent = HCl + 13HO. 22.3= HCl + 11110. 213= HC1+15HO. 2022 =HC1+ 161IO. 19.3= HCl+ 17IIO. 18.B =E-rci+i81-ro. T~BLEI-. I. 11. 111. IT. I. 11. 111. IT. I. XI. 111. IV. --c----_I_ --_I-__. 1 0.064 20 '2* 23 -3 12 0-3s 21.7 21 *3 23 0 -165 20 *20* 20 '231 2 0.065 23 -8 22 'I) 13 0 *3s 21 -6 21 -5 24 0 -768 20 '20* 20 911 3 0.100 21.3* 221.9 14 0 -49 21 -0 0.96 20-2" 20. 0 4 0 *loo 23 *8* 23 -0 15 0 *49 21 -3% 1-10 18' 0 19.6 5 0.100 22 *s 22 *8 16 0 *43 21.3* 1. 10 20. 2" 19. 6 6 0 *210 21 -3 22 *2 17 0 *63 20 -2" 1' 77 IS' G 1s. 5f 7 0 *210 22 a5 22 -2 18 0 -63 20 -2% 1. 77 19. 0 18. 5" + Y 0 *210 22 3 22 *I 19 0 -63 21 -3' 20-G I 30 2. 46 1s. 0 18. 2 I 9 0 *030 21 -3+ 21 *7 20 0 -63 21.3 6 20 -6 31 2. 51 18' 0 15. 1 10 0 0030 23.8 22 -0 21 0 *63 20 -7 20 *6 32 2' 51 18. 0 18-1 i 11 0 -030 21 *7 22 0 *63 20 % 20 *7 33 2-51 18. o 1s. 0 XIYDROCIILORIC ACID AXD AMiW0Xl-i~ From these direct observations the following interpolated values are obtained. The column marked P shows the pressure in metres of mercury uiider which aqueous liyclrochloric acid must be distilled to attain the constant composition given in thc next column.TABLEVI. Per Centageof HC1. Per Centageof HC1. of I-ICl. Per Centageof HCl. 23.2 20'4 19.3 2.0 18.5 22.9 20.24 191 21 18.4 22.3 21.8 20.2 19*9 I9'O 18.9 2*2 2.3I 15.3 18.2 21.4 19 7 1S.8 2.4 18.1 21.1 19-5 1S.7 2.5 18.0 20.7 19.4 16.6 1 I F Hence it is evident (1)that there exists for each pressure a corre-sponding aqueous hydrochloric acid which undergoes no change in corn position when distilled under this pressure and therefore has n constant boiling point; (2) that the composition of these aqueous xids is different; for each pressure a gradual change in pressure 1)ehig accompanied by a gradual alteration in the per-centage of 3iydrochloric acid. The relation between the composition of the acicls of constant boiling points and the pressure under vhich they are distilled is represented by the curve Fig.7,in i~hich the oi-dinatcd give the per-centage quantity of anhydrous acid and the abscisszc the corresponding pressures. Having shown that the curve Fig. 7 does not present any discontinuity we must adinit that the aqueous acid boiling without decomposition under the ordinary atmo- spheric pressure at lIO°C. cannot be regarded as a true chemical hydrate capable of existing within n certain altered range of physical conditions. It next became necessary to determine whether the other acid of fixed composition described by Bineau possesses a greater degree of stability than the am just examined For this purpcsc we shortened Bineau's process of preparation by passing a continuous current of dry air through aqueous acid coiitained in the hurette- shaped vessel represented in Fig.8. The tube c (Fig. 8) was 2ttacheci to a suction-aspirator and the dry air passed through the liquid from the tube d a thermo-meter b giving the teniprature of the experiment. An aqueous acid containiiig 20.2 p. c. of hydrocliloric acid was placed in the apparatus (Fig. S) and a current of dry air allowed to pass continuously tlirougli the liquid for some days at the ordinary atmospheric temperature (about 1CrOC.) At the expiration of this time more than % o€ tlie liquid had been volatilized atncl the resi- due contained 23.3p. c. of hydrochloric acid ; after thc air lind passcd through €or some clap longer the residuc contained 25.0 per cent.; on passiing more air through this liquid no further change of composition was effected an analysis made two days later giving 2%-9per cent.This number although not exactly agreeing with tlic theoretical result HC1+ l2HO nhicli requires 2.5-211.c. of lirdi'o-chloric acid corresponds sufficiently well to render Binem's sup-position of the existence of a 12-atoin hydrste plausible enough. In order to determine whether the hypothetical hydrate preserves its composition under change of phgsical conditions we deter-mined the amount of hydrochloric acid contaiued in aqueous acictq through which a current of dry air liad passed at different tempera- tures until no flirther alteration in composition took place. Thc follo~i~ing Table (VII) gives the direct experimental results.Colunin I shows the tempemturc of the liquid through which thc aiy passed ;11 the duration of the experiment in hours ;III the quan-tity of hydrochloric acid contained in 100 parts of tlie acid befom the experiment ;IV the per-centage of IIC1 after the experiment. TABLEV-PI. I. XI. 111. IT. I. 11. 111. IV. I. 11. 111. IV. I__-_-0" 20 0" 10 45.3 32.0 --I-- 32.0 / 0" 23.9 '1 10' G - 25 0 20'2 25.0 23.3 30" 62' -_A_-5 24.1 5 22.8 24'3 22'9 0" 15 23.9 27.2 10" 49 23'3 25.0 Ii+CO 2 22.0 22.2 00 G 27.2 26-4 100 48 25'0 24O9 85" 1 21.7 21.7 0" 16 2G-4 25'6 30" 4 23.5 24.4 91" - 21.3 21.4 0" 20 25'6 24-8 30" 4 24.4 98"24.1 /I/I -21.1 I 21.1 TIk'DROCflLOEIC ACID AXD AJI3IONIA.145 At the higher temperatures the ciwrent of air was allowed to pass through until about 3 of the liquid had been volatilizcd. Table VIII contains values interpolated from the direct expe-rim ents . TABLEVIII. Grms. of Grms. of Grms. of t" ?ercents. HCI. com-'ercents HC1. can-Pcrcents. HCI. com-of HCI. bined with to of HCI. binedwith to of H.C1. bined with 1gr. of HO 1gr. of 110. 1gr. of HO. 0 25.0 0-333 40 23.8 0.312 80 22.0 0.283 5 24.9 0.331 45 23'6 0.305 85 21.7 0 278 10 24.7 0'328 50 23.4 0.305 90 21.4 0'273 15 24% 0'326 55 23.2 0.302 95 21.1 0.267' 20 24.4 0-323 60 23-0 0-298 100 20.7 0.261 25 24.3 0.320 65 22.8 0.295 110 20'24(2) 0.2538( 2) 30 24.1 0,317 '70 22.6 0.291 35 23-9 0'315 75 22-3 0.256 -These experiments show that the aqueous acid approaching the composition HC1+ 12I-I0possesses no higher claim to be consi-dered as a true hydrate than HC1 + 16 HO a gradual alteration in the temperature at which the current of air passes producing a corresponding gr.adud alteration in tile composition of thc acid.A singular relation lias been found to cxiat between the aqueous acids prepared by passing a cwrcnt of dry air tlirough the liquid at a constant tcnipcrature until 110 further change occurs and those obtaiiied by distillation under different pressures. It lins heen found that the cornpsition of the aqueous acid prepared in these two different ways at the same temperature has an identical composition ; thus for instance an acid distilled under the pres-sure 0.38 meter boiling at R temperature of 91°C.contains 2l-3 per ccnt. of hydrochloric axid wldst any czqueous hydrochloric acid heated with a current of dry air under the common atmospheric pressure at 91°C. attains the coilstant cornpsition of 21.4 per cent. of anhydrous acid. This is clearly seen in the annexed Table in which Division I gives the pressures boiling points and composi-tion of the acids distilled under various pressures found also in Table VI; and Division I1 the composition of the acids nnalterable by passage of a current of dry air at the same tanperaturcs VOL. XII. L 146 ROSCOE AND DITTRlhTt ON THE ARSOXPTION OF TABLEIX. II. Pressurc Boiling Contains Contains point. in meters. p.c. of HCI. '* p.c.of HCI. 0.10 GI" to 62" 22.8 (iP 22.9 0.21 76" to 77' 22.1 7;1O 22 2 0.30 84" to 85" 21.7 85O 21-7 0.38 91" 21.3 91Q 21.4 0.49 97" 20.9 98 21.1 0.62 103" 20-6 - From the foregoing experiments we may safely conclude that the supposition of the existence of hydrates of hydrochloric acid containing 12 and 16 atoms of water is unfounded. It is,however remarkable that the boiling points of the acids of constant com-position all lie about 9°C. higher than the boiling points of'wate~ under the same pressures. If tlien we were to consider every aqueous acid as a mere mixturc o€ watcr and liquid liydrochloric acid the body thus produced must form a most remarlrablc exception to any relations at present lrizown respecting the tensions of inixed vapours.We are therefore iiiduceci to adnzit the existence of certain attractions between the molecules of hp-drochloric acid gas and irater which if they do not give rise to definite chemical combinations are at any rate essentially differcnt from the attractions exerted between water and the other even the most soluble gases. We may shortly explain the results of ow experiments by sup-posing that certain definite chemical compounds of water and hydrochloric acid exist but that they undergo a gradual altcration with variation of temperature so that for every temperature n definite combination exists which at this tcmperature remains unchangcd by exposure to a current of dry air and may be boiled without changing its composition if the pressure is such that the liquid boils at this same temperature.+ This explanation can how- * By this we do not mean to imply tlist the acid does not undergo decomposition upon distillation; on the contrary we believe that the vnpour of aqueous hydrochloric acid must be regarded as a mere mixture of anhydrous hydrochloric acid and steam (1).Because Binean showed that the r7apour of tlie so-called iG-atom hydrate contained its constituents uiicondensed ; (2). From our own experiments which prove that the composition of the distillatc of this same acid is variable if the condenmtion is not complete. IZYDROCHLOIZIC ACID AND AiIllSIONIA. ever only be regarded as a mode of representing our results which indeed may be accounted for by inany other suppositions such for instance as the existence of other hydrates having definite atomic compositions 0' Water at B.EXPERIMENTS WITH AMMONIA. I.-Rela!ion between t7ie amount of Ammonia Absorbed zn C. uncl the Pressure ulider which the Absorption occurs. In a paper published in Liebig's "Annalen" in 1856 Carius details the results of a series of determinations of the solubility of ammonia in water at different temperatures and under the ordinary atmospheric pressure ; he likewise gives experiments which would show that in mixtures of ammonia with other gases the quantity of the former dissolved in water is strictly in accorti-ance with Dalton's simple law. That a gas so soluble as ammonia in water should be absorbed iii direct proportion to the pressure appeared so remarkable that we deemed it advisable to control these results by determinations made at 0"C.under direct pres- sures both greater and less than that of the atmosphere. For this purpose we in the first placc determined the quantity of ammonia absorbed in water at 0"under the ordinary atmospheric pressures employing exactly the same metliod that has been described under hydrochloric acid. Experiments thus made with every precaution gave as the weight of ammonia absorbed by 1 grm. of water at 0" C. numbers diEering widely fi-oin those obtained by Carius. In order to ascertain the cause of this dis- crepancy we repeated the experiments precisely according to thc method which he had adopted; but in this way we also obtaincc? results which not only differed from those formerly found but varied among themselves.As the result of a long critical investi- gation of both methods we arrived at the conclusion that the plan adopted by Carius viz. that of saturating vith ammonia mater contained in a tube open at top to the air was liable to such con- siderable sources of error as to preclude its employment for exact measurements whereas the method we have employed is free from such objections. L2 148 ROSCOE AND DXTTJIAI ON TI~EABSORPTJONOF The chief causes of uncertainty in Carius' method mere to be found in the facts I. That the time mliicli elapses before the liqnid attains a con-stant temperaturc is much longer than was imagined.IT. That the reqnisite absorptiometric equilibrium between the amount of clissolved gas and the temperature can never be brought about; with certainty when water is saturated with ammonia in an open tube owing to the rapid and irregular diffusive interchange continually going on between flie dissolved ammonia and the atmospheric air above tlte liquid.* 111. That the nrinierical rz;(.lts arc dependent upon a doubtful series of spcific gravity detcrminxtioiis. The folloming csiiinzitions of' the solubility of amnionin in water at 0°C. under pressures var~iiig from 0.018 to 1.96 meters of mercury were mnde according to the methods already describcd. The total quantity of ammonia contained in the hulb-vessel mas determined by first supersaturating with a standard hydro-chloric acid the strength of wliich was exactly ascertaimd by analysis with pure silver ancl then adding a standard soda-solution until the point of alkalinity was reacliecl.Oniy in the cxperiincnts made under pressures greater than that of the atmosphere did me adopt a plan slightly different from the foregoing. In these cases we saturated water contained in the bulb-apparatus (fig. l) with ammonia at a temperature of * The following experiment as being one out of a number may be cited in proof of the above assertion. About 10 grms. of water was placed in an open tube of the dimensions used by Carius and through this ammonia was passed the whole being plunged in a bath of melting ice. At the commencement of the experiment a thermometer placed at the trottom of the liquid showed a temperature of + 20"C; as soon as the evolution of gas had continued for 15minntcs the ammonia began to p?ss through unabsorbed and hhe temperature sank to + Go;after the gas had pabaed through for 15' longer (the extent of time allowed by Carius) the temperatiire mas still 4"-8; 12 minutes later the temperature had sunk to -I-OO.7 and after 13 minutes more to -t-OO.5.The gas now passed somewhat more slomly through the liquid and at 10 minutes after the last observation the thermometer showed a tem-perature of -OO.2 which five minutes later diminished to -0'9 and at the moment of the stoppage of tEe current of gas the mean temperature of the liquid sank to-1".2. The temperature of the liquid at the surface exposed to the air was however milch lower the thermometer when placed at the surface showing a temperature of -3O.2 ereu when a rapid current cf gas passed through the liquid.So great indeed is the absorption of heat in this change of ammonia from solution to the gaseous state that we have easily succeeded in freezing about 20 grms. of mercury by passing a rapid ciurent of air through D few cubic-ccntimcters of sater snturatcd with ammonia at -10" c. HYDBOCHLOKIC ACID AND ANllfOXIA. under different pressures. C. 0' ments made at -3OOC under the atmospheric pressure then sealed one limb of thc apparatus whilst the other remained connected by an air-tight joint to tlie manometer d (fig. 5). The bulb was now gradually allowed to attain the temperature of Oo and when all evolution of gas had ceased and the height of the column of mercury in the tubc remained perfectly coiistant the appratus was closed in the iisual manner and the ammonia determined by analysis.The following Table X. contains the dircct results of' espcri-P signifies the partial pressure of the gas in metres of mercury; G tlie weight in grammes of ammonia absorbed under tlie circiimstances of the experiment by 1 grm. of mater. Expcrimeiits I to 7 were made under pressures lower than one atmosphere ; experiments 16 to 23 under pressures greater than an atmosphere ; the remaining experiments Nos. 8 to 15 under common :ttmospheric pressure. A graphic representation of all the results enabled us to reduce the latter experiments to 0.76" and the numbers thus obtained are also found in the table.From these numbers an idea of the trustwortliinesx of the method may be obtained. We find that the maximum deviation from the mean result is 877-l-10 and-14 whilst the mean deviation is + 6 or 0.7 per cent. of the whole TABLEX. No. P. G. No. -------<-. 1 0-018 0,074 8 2 0.097 0.274 a 9 P. 0'753 C"759 G. 0*876 0.869 No.to 0 *76m. 0.875 1 16 0.869 17 P 0.904 0.912 CX. 0.955 0.994 3 0*241 0.463 10 0.759 0'882 0.883 18 1.261 1.292 4 5 0.268 0-452 0.478 0.652 11 12 0.761 0.762 0.857 0.864 0.870 0'863 19 20 1.264 1.260 1.268 1.248 67 0-707 0.712 0-845 0.855 13 14 0.763 0.763 0.769 0.889 0.878 OW1 0.887 0.876 0'885 I 21 22 23 1'251 1.960 1.963 1.290 2.134 2.137 From the direct observations the annexed iiiterpolated valucs are obtained.In Table XI. P again signifies the partial pressure of the gas and G the weight of ammonia absorbed in I grm. of water at OOC 150 ROSCOE AND DITTMAlt ON THE ABSORY'J'ION OE' TABLEXI. G. p. G. G. G, P. -/I-I)--I-P. -0.00 0.01 0'000 0.044 0.25 0'30 -I_ 0.465 0.515 I 0.85 0.90 0.937 0.968 1 1.45 1-50 1.469 1'526 0.02 0-03 0.084 0.120 0.35 0.40 0.561 0307 0.95 1'00 1001 1037 1'55 1 GO 1,584 1.645 0.04 0.149 0.45 0-646 1-05 1.0'75 1-65 1.707 0 05 0.175 0.50 0'600 1.10 1.117 1-70 1.770 0.75 0'228 0.55 0.731 1-15 1.161 1.75 1*825 0*100 0.275 0.60 0.768 1-20 1.20s 1-80 1.906 0.125 0.150 0.315 0.351 0'65 0.70 0.804 1.23 1.255 1.310 I 1-85 1'90 1.976 2.046 0.175 0.200 0.382 0.411 0.75 O'SO 1.361 1.415 II 1-05 2.00 2.120 2.195 'I'lie graphic representation of the relation between absorbed gas and pressure is well seen by reference to the curve NH, fig.4. From this curve as well as from the foregoing numbers it is evident (1) that the quantity of ammonia absorbed by water at that(2)andproportional to the pressure; beingfromfarisC. 0' for equal increments of pressure up to about 1 metre of mercury the corresponding increments of absorbed ammonia continually diminish hut that above this point the amount of dissolved gas increases in a more rapid ratio than the pressure. A comparison between the curve and the straight line b cutting it at the point corresponding to the pressure O*7cjn1 and pssing through the origin shows clearly the great differeme which exists between the simple law of Henry and the lam regulating the absorption of under different pressures 0' ammonia in water at I.-Relation between the amount of aminonin absorbed in water under the ordinary atmospheric pressures and the temperature at which the absorptiow occurs The experiments made with ammonia at different temperatures were conducted exactly according to the method described under hydrochloric acid.The following were the results obtained. Column I contains the observed barometric pressures ; column 11 the temperatures; column 111 the weight in grms. of ammonia absorbed by one grm. of water. TABLEXII. 1 0.760 m. O"0 c. 0.875 grm. 2 0.764 d"2 0.756 3 0 749 6"Y 0.723 4 0.749 6'9 0-726 5 0-742 15"4 0.586 6 0.755 15'4 0'589 7 l 0.744 24"l 0,465 8 OT51 24'1 0'471 ~ 9 0.768 36"3 0,350 10 I 0'760 35"3 0.354 11 0.768 54'2 0'202 ~~ As the influence of pressure on the amount of absorbed gas is in the case of ammonia very considerable it was impossible to reduce these results to a constant partial pressure.We therefore give the following values interpolated undcr the supposition that all the experiments were made under pressure of 0*76m,only as an approximation to the truth. Column 1. of the annexed Table contains tlie temperatures; column I I. the corresponding weight of ammonia absorbed by one gramme of water. TABLE XIII. I. ZI. I. 11. I. 11. 7- 0°C. 0*875 16°C. 0.582 4aoc. 0.244 2" 0.833 18' 0'654 50" 0.229 4" 0.792 20" 0.526 36" 0.343 52" 0.214 6" 0.751 220 0499 38" 0.326 64' 0.200 8" 0,713 24" 0.474 4O0 0.307 86' 0.186 10" 0.679 26" 0.449 42" 0.290 12" 0.645 28" 0.426 44" 0.275 14" 0.612 30" 0.403 46" 0'259 --These numbers and the curvc b (fig.5,) show that the amount of absorbed ammonia varies much more considerebly with change of temperature than is the casc with hydrochloric acid.

ISSN:1743-6893    

DOI:10.1039/QJ8601200128

出版商:RSC    

年代:1860

数据来源: RSC

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WOOD ON BASES XVI.-On Buses produced by iiifrous Substitution. BY c s. ~‘OOD INhis remarkable memoir” on the action of reducing agents on nitro-compounds in which he first pointed out the formation of organic bases by the substitution of hydrogen for oxygen Zinin has recorded some experiments on the deportment of dinitro-naphtaline [nitronaphtalese] with sulphuretted hydrogen. He states that this action gave rise to the formation of a basic com- pound crystalliziug in delicate copper-red needles md yielding with acids white scaly salts. In a subsequent paper? Zinin returns to the action of sulphu-retted hydrogen upon dinitronaphtaline and gives a fuller account of the products obtatined in this process. He states that the base thus produced crystallizes in colourless needles of great brilliancy which contain C,,H,N or C2,H,,N,.This body possesses well- defined basic properties and is described under the name semi-naplitaZidarn. From this latter communication it would appear that the copper-red coloration originally observed was due to the presence of a foreign colouririg matter which can be separated by crystal- lizing the base alternately from water and alcohol. Subsequently the same body appears to hare been observed by Laurent,f who states that the action of sulphuretted hydrogen upon dinitronaphtdine gives rise to the formation of a carmine-red alkali. He did not however analyse this substance and the dis- covery of nitraniline 6 having established the existence of basic nitro-substitutes the compound in question has hitherto been considered to be nitronaphtylamine.At the suggestion of Dr. Hofmann I was led to examine this body and as my results do not agree with the above supposition I beg to lay them before the Chemical Society. To prepare the red base a quantity of dinitronaphthaline is intro- duced into a flask together with some weak alcoholic ammonia; the latter should be sufficient in quantity nearly to dissolve the ilinitronaphthaline. It is then heated to the boiling point and a * Bulletin Scientifique de St. Petersbourg x 18. -/-J. pr. (Ihem. xxxiii 29. Compt. rend. xxxi 638. Q Muspratt and Hofmann Nem. Chem. SOC.vol. iii. Pit0l)UCCU BY NITROUS SUBSTITUTION. stream of sulphurctted hydrogen passed through it for some hours or until the spirit has nearly distilled off.Sulphuric acid is then added until the solution has an acid reaction; it is then boiled and rapidly filtered while hot. The filtrate on cooling deposits a quantity of crystal3 of the sulphate which may be purified by a fern crystallizations from boiling water. The addition of ammonia to the solid salt immediately decomposes it changing the colour to a fine dark carmine-red. The base thus liberated is washed with cold water to free it from ammonia and finally purified by recrystallization from water or very dilute spirit. Thus prepared the substance for which I propose the provi- sional name Ninaphtylamine,is a light flocculent mass composed of beautiful little acicular crystals which are partially decomposed by exposure to a temperature of 100OC.It is extremely soluble in alcohol and ether ;insoluble in cold water ;soluble although with difficulty in boiling water. For combustion the substance was dried in wacuo over sulphuric acid. I. 0-21grm. of the base gave- 0.5375 grm. of carbonic acid and 010950 grm. of water. The percentage composition thus given is-Carbon . . 69.76 Hydrogen . . . 5.02 A sccond combustion gave similar results XI. 0.28955 grm of the base gave- 0.7405grm. of carbonic acid aiid 0.127 grm. of mater. Thc percentage cornpodion being- Carbon . . 60.72 Hydrogen . . . . 4-87' 111. A determination of the nitrogen was also made by the pro-cess of Dumas; in this case also the substancc wits dried over sulphuric acid it2 vacuo.0.4700 grm of the base gave- 67*0cubic centimeters of nitrogen gas the baroiiietric pressure being 0*7714m.and the tempcraturc of the water 12OC. These results lead to the following expression C,OH,"O2* Theory. Experinicrit. Man. m 20 eqnivs. of Carbon 120 (59 7'7 G9"iG 69.72 .. 69.74 8 , Hydrogen 8 4.65 5-02 4.5'7 .. 4.945 2 ,) Nitrogen 28 1628 .. .. 17.22 1722 2 ,$ Oxygen 16 930 .. *. .. .. 1 , Ninaphtylamine 172 100-00 This formula which I propose has been confirmed by the examination of several of the salts of the new base. SuZphate of Ninaphtylnmitte is obtained either by recrystallizing the crude salt formed in the preparation of the body or by dis-solving the base in dilute sulphuric acid.It forms hit^ scaly crystals which are decomposed by repeated crystallization from pure water. It is also partially decomposed by exposure to 1000C. The salt dried in vacuo over sulphuric acid gave the following numbers-0.20276 grm. decomposed by chloride of barium gtlre-0*10800grm. of sulphate of barium. The formula 2C,,H,N,0,.H2S208 requires the following valiies- Theory. Experiment. 2 equivs. of Ninaphtylamine 344 77.83 77.7 98 1 , Hydrated sulphuric acid --22-17 22.3 1 , Hydrosulphate 442 100*00 100.0 Hydrochlorate of Ninaphtylamine.-W hen the base is dissolved in hydrochloric acid a fine white salt is produced which crystallizes in needles. It is easily decomposed by water and by exposure to 1oooc. P1COL)IICEI) UY NLTUOUS SUBSTITUTION 0.1752 grm.of the base decomposed by nitrate of silver gave-0.1200 grm. of chloride of silver. This result agrees with the formula- C2,H,N,02.HC1. Theory. Experiment. I equiv of Ninaphtylamine 172.0 82.49 82.63 1 , Hydrochloric acid 36.5 17-51 17.40 I__ II_ -208.5 100.00 100*03 The platinum-salt of Ninaphtglarnine forms rather soluble yel- lowish biw;vn crystals which may be dried at 100°C. without decomposition. It is best prepared by adding a concentrated solution of bichloride of platinum to an alcoholic or etherial solu-tioi of the base also concentrated. It has the usual constitution containing C2,H,N202.HC1.Pta, as will be shown by tlie following numbers- I. 0.405grm. of the salt gave on combustion-0*471grm.of carbonic acid and 0.099 grm. of mater. 11. 0.168 grm. of the salt gave on ignition- 0.0437 grm. of platinum. Theory. Experiment. 11. 20 cquivs. of Carbon 120 31.73 31'7 .. 9 ) Hydrogen 9 2.38 2-72 .. 2 ) Nitrogen 2s 7-40 .. .. 2 ?> Oxygen 16 4.23 .. .. 3 ,a Chlorine 166.5 28.16 .. .. 1 , Platinum 98.7 26-10 .. 26'01 1 ) Platinum-salt 578.2 100*00 If it be permitted in the absence of further experimental evidence to speculate on the molecular constitution of tlie body which forms the subject of this papcr the simplest interpretation of its formation and composition would be to view it as a substi- tution-product of naphtylamine in which hydrogen is replaced by binoxide of nitrogen thus differing from ordinary nitro-~ub- WOOD ON BASES stitutes which arc assnmcd to contain the tetroxide of nitrogen ; thus-Its formation would then be represented by the equ at'ion-C,o[Hg(N04)2] f 8HS = 6HO + 8s + C2,H8(N02)N Dini tronsph taline Ninaphtylamine Bodies in which binoxide of nitrogen figures as a material of substitution are as yet extremely rare whilst nitro-substitutes containing thc dements of hyponitric acid are of the most general occurrence.Some cliemists have considered nitrous ether as a binoxide of nitrogen derivative of alcohol;thus-0 Alcohol . ' C4H602 Xitrous cther 02 c4 {ZJ The most interesting ilhzstrtions of this kind of substitution Iiowevcr have been furnished by Mews. Perlrin & Church* in thc colouring matters produccd by the action of nascent lrytlrogen on diuitro-substitutes or of nitrous acid on certain inonamincs.Phenylamine . 0 C,2W Nitrophenyline C12(t@- Naphtplamine . C,,H9N Nitrosonaph tgline Expressed by these formulze these substances appear to be very closely allied to the basic body which I am describing. In fact * Chem. SOC.Qu. J. ix. 1. PRODUCED BY NITROUS SUBSTITUTION. 157 nitrosoiisphtyline has the same composition as ninaphtylainine ; but even a superficial comparison of the properties of the two bodics excludes any idea of their identity. It deserves to be noticed that the formula? of the colouring matters in qucstion have not as yet been finally established by the analysis of any compounds; they appear like colouring matters in genera! to be of an indif- ferent character.It is not improbable that these coloured deriva- tives may be formed by the association of several molecules and this idea receives some support from the discovery of ninaphtyvln-mine. The formation of this body promises to add considerably to the number of thc nitro-substitutes of the aromatic monnmines. To each of these probably corresponds a nitrous and a nitric substi- tution basc; but a9 yet wc are unacqiminted with a singlc one in which both derivatives are known as shown by cz glancc at the groups best known. Phenyl Group. Phenylamine [aniline] Nitrophenylamine . . C,,(HJy] ;?J H Naphtyl Group. Naphtylamine . . ““g3 N 11 Ninaphtylamine . H . Unknown . I3 C20(H6N3)l The experiments just described were performed in Dr. Hof-mann’s laboratory and I take this opportunity of thanking him for his kind advice throughout the investigation.

ISSN:1743-6893    

DOI:10.1039/QJ8601200152

出版商:RSC    

年代:1860

数据来源: RSC

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158 FIELD ON TEE ACTION OF XVII.-On the action of Hydrochloric Acid upon Xulphide of Mercury in the presence of certain other substances. BY FREDERIC FIELD. INmy late memoir upon the mineral ammiolite,” a method was described for the separation of mercury and antimony by heating the sulphides of those metals in hydrochloric acid. The experi- ments were tried upon the temulphide of antimony and answered extremely well as only moderately strong hydrochloric acid was employed and the liquid subjected to a heat below ebullition. Whsn pentasulphide of antimony is present sulphur is eliminated and a solution of terchloride is formed SbS + 3HC1 = SbCl + 3HS -I-2s. The mercurial sulphide is consequently mixed with free sulphur which renders an estimation of that element imperative in order to arrike at the amount of mercury.The difference of opinion which arose between Domeyko and myself regarding the state in which the antimony existed in ammiolite led to a somewhat lengthened discussion upon the nature of that mineral he affirming that it was as antimonic acid while my own conviction was in favour of teroxide. As the inves- tigation of ammiolitc had occupied both of us for many months the mineral assumed for us at least an interest which it probably would scarcely have claimed for those not engaged in its research; but one or two facts have been elicited during the analysis which are somewhat interesting and important and have not been as far as 1 am aware recognized in chemical science.On boiling ammiolite with hydrochloric acid nearly all the antimony and much of the mercury is dissolved ;and upon the addition of iodide of potassium in excess to the solution the precipitated iodide of mercury is redissolved arid the liquid remains ueariy colourless. From this it mas iuferred that the antimony existed entirely as teroxide inasmuch as the higher oxides of that metal when in $elution in hydrochloric acid eliminate free iodine upon the addi- tion of iodide of potassium. Bunsen in a recent paper recom-mends this test for the degree of oxidation of antimony when in solution. M. Dom eyko mentioned to me that on boiling aul- IIYDROCEILORIC ACID UPON NERCURY. phide of mercury with antirnonic acid in strong hydrochloric acid the whole of the sulphide was dissolved and a yellowish white powder remained which he believed consisted principally of sub-chloride of mercury (calomel).As hydrochloric add has very little action upon sulphide of mercury unless highly concentrated and at a boiling temperature it occurred to me that it mould be interesting to examine how far this acid influenced thc solubility of the sulphide not only when in conjunction with antimony but also with other bodies that might probably be associated with it in the mineral world. Antimonk Acid.-When antimonic acid and sulphide of mer-cury are boiled together in hydrochloric acid rapid decomposition takes place after a few minutes. Vermilion for instance speedily loses its colmr ; a clear solution is formed with a small deposit of sulphur and the antimonic acid is reduced.The reduction of the sliitimonic acid is more apparent when a large excess of sulphide of mercury is present. The riaction is probably more complicated as there is a slight evolution of sulphurettcd hydrogen during the ebullition. A solution of terchloridc of antimony in strong hydrochloric acid does not act upon sulphide of mercury. Arsenic Acidwhen arsenic acid is boiled vith sulphide of mercury in hydrochloric acid the decomposition is very rapid The residue is yellom consisting entirely of sulphur which after continued boiling separates in clcar ycllow globnles. It is rather more difficult to understand the reaction in this case as the arsenic acid does not seem in any great measure to bc reduced.On filtering the liquid from the sulphur and evaporating rather large crystals are formed of chloride of mercury and on evapo-ration to dryness the residue instantly redissolves in water. On addition of ammonia to the solution a white precipitate is pro-duced and from the filtrate sulphste of magnesia gives immedi- ately a crystalline precipitate of zimmonia-magnesim arseniate. Indeed although the sulphide of mercury was sometimes used in considerable excess little if any arsenious acid could be detected. Sesquichloride of Iron with excess of hydrochloric acid when boiled with sulphide of mercury is reduced after ebullition for a few hours much sulphur being deposited. Protochloride of Copper is very quichly decomposed ; sulphur is eliminated and the liquid assumes a d2yk brown colour indica- 3 60 KORJIAX TATC ON tivc of the solution of subchloride of copper in hydroddoric acid.After evaporation water precipitates a crystalline J\ liite powder which consists entirely of subchloride of copper. Peroxide of Naizyanese. -When peroxide of nitulgancsc is boiled with hydrochloric acid and sulphiile of mercury the latter is instantly decomposed with separation of sulphur. When the sulphide is in excess 110 chloriirc is evolved.* MnO + 2IIC1 + HgS = MnC1 -i-IIgCl + S + 3H0 Seespichloride of Chromium in strong hydrochoric acid exert9 no action upon sulphide of mel*cui*y even after long boiling. Sesquichloride 0s Uranium 11nder simi1ar ci rcu instances pro-cluces no effect. The above reactions tend to prove that where certain su1)-stances are associated with antimonial compounds the degree of the oxidation cannot be determined after its solutioii in hydro-chloric acid. Although I still am of opinion from various reasons that the metal exists as teroxide in the rninerai the non.disen-gagement of free iodine on addition of iodidc of potawiiim cannot be considered as by any means conclusive.

ISSN:1743-6893    

DOI:10.1039/QJ8601200158

出版商:RSC    

年代:1860

数据来源: RSC

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3 60 KORJIAX TATC ON XVII1.-On the actiofa of Bomcic Acid zpon the Sdfs of the more Volatile Acids nt high Izwperuizwes BY A. NOEMAN TATE STUDENT IN TEE LIVERPOOL COLLEGE OF CHEMISTRY. ITis stated in most of the Chcmical moAs of note tlint boracic acid expels the more volatile acids from their salts at high tempe-ratures. * Von Kobe11 has shown that when mctallic iron is heated with binoxide of manganese and hydrocliloric acid no chlorine is evolved and the dimcultly soluble binoxide is entirely decomposed. I have found thdtt tlie same reaction takes place with metallic' copper. When the finely&-\. idcd mctsl is tre2ted mi th hydrochloric acid and binoxide of manganese added the metal is immediately dissolved no evolution of chlorine takes place and a very rapid solution is eii'ccted a small residue of silica (from the native manganese ore) alonc remaining.Should there- fore either iron or copper be introduced into oxide of manganese it would be impos-sible to estimate the aniount of 3€n02by the quniitity of chlorine evolved. THE ACTION OF BORACIC ACID &C. In the English trauslation of Gmelin’s Cliemistry the follon iiig passige occurs At a red heat boracic acid eqcls all acids wllicll me i-iiorc volatile than itself.” Brande says ‘(The affinity of boracic acid for bases in the liumid way is fecble little exceeding that of carbonic acid; but at a red lieat it displaces all the more volatile acids.” Professor Graham observes “At a red heat this acid (boracic acid) decoinposes men the sulphatcs from its comparative fixity.” Sir Robert Yane in hisElcments of Chemistry states “If a misture of sulphatc of soda and boracic acid bc heated to redness in a crucible the sulphuric acid mill be driven off in consequence of its volatility mhi2st tlre fixed boracic acid will remain coni-billed with the whole qualztity of tile base.” I give in the following pages the results of some experiments of my own on this subject which however contradict in a certain degree the foregoing statements especially the last.The boracic acid used in all the following experiments cvas per-fectly anhydrous and carefully prepared by myself for the purpose. Action upon the XuZpliates.-The sulphates of potassa and soda mere clioseri for most of these experiments on acconnt of their stability.Experiment 1.-I mixed 0.435 grm.of sulphate of potassa =0.20 grm. of sdphuric acid (SO,) and 0.173 grm. of anhydrous boracic acid which is in the proportion of one equivalent of each; placed the mixture in a platinum crucible protected in the usual way and heated for some time in a climcoal fire. The crucibles were then removed and subjected to the heat of a blacksmith’s fur-nace for about tn-enty minutes. The €used mass mas then taken from the crucible dissolved in water the solution aciclulated with nitric acid and chloride of barium added to precipitate the sulpliuric acid remaining. There was obtained 0.410 grm of sulphate of baryta = 0.140 of sulphuric acid showing a loss of not more than 0-060 grrn.of that substance. Exp. 2.-A mixture of 0.355 grrn. of sulphate of soda = 0.200 grm. of sulphuric acid and 0.35 grm. of boracic acid or in the proportion of one equivalent of the former to two of the latter was treated in the same manner as mixture 1. BaO.SO obtained 0.440 grm. = 0.150 grm. of SO = 0.05 grm. loss cf SO,. The following mixtures were heated in a charcoal fire and voc. XTI. M 162 NOEMAX TA'I'C OX kept in a state of fusion at a very strong redheat until they ceased to lose weight the time vwyiug from an honr and a-half to two hours and a-quarter. The fuscd niass mas afterwards dissolved in water and the sulphuric acid remaining was determined as sul- phate of baryta in the usual manner. Esp. 3.-0.870 grm.of sulphate of potassa =0*400grm. of sulphuric acid and 0.350 grm. of boracic acid or one equivalent of each. Sulphate of baryta obtained 0.959 grin. =0.328 grm. of sul-phuric acid =0.072 grm loss of sulphuric acid. Exp. 4.-0*71 grm. of sulphate of soda =0.40grm. of sulphuric acid and 0.35 grm. of boracic acid or 1equiv. of each. Sulphate of barytn obtained 0.967 grm. = 0.33 grm. of sulphuric acid =0.07 grm. loss of sulphuric acid. Exp. 5.-0*71 grm. of snlphate of socla =0.40 grm. of sulpl~uric acid and 0.70 grm. of boracic acid or 1 equiv. of the former to 2 equiv. of the latter. BaO.SO obtained 0909 grni. =0.31 of SO =0.09 grrn. loss of SO,. Exp. 6.0.71 grm. of sulphate of soda or 1 equiv. and 1.440 grms. of boracic acid or 4 equiv.BaO SO obtained 0.688grm. =0.236 gym. of SO =0.164 grm. loss of SO,. Esp. 7.-0*71 grin. of sulphate of soda and 3.50 grms. of borncic acid or 1 equiv. of the former to 10 equiv. of the latter. BnO*SO obtained 0.379 grm. =0.13 grm. of SO =0.27 loss of SO,. Thinking that perhaps if the two substances were still more intimately mixed all the sulphuric acid might be expelled 1 dissolved them in water Exp. 8.-0*71 grm. of sulphate of soda (1 cquiv.) and 0.10 grm. of boracic acid (rather more than 1 eqniv. to allow for any loss cluring evaporation) were dissolved and evaporated to dryness and the residue was fused ltecping it a strong red heat until it ceased to lose weight Snbszquent estimation of sulphuric acid yielded 0.9'72 grm. of BaQ,SO =0.333 grm.of SO =0.67 grm. loss of SO,. Exp. 9.-A mistwe of 1-42grms. of sulphate of soda and 0.35 grm. of boracic acid or 2 equiv. of the sulphate and 1cquiv. of the acid iv'aa treated as mistnres 3 to 7. BaO,SO obtained 2.13 grms = 0.730 grm. of SO =0.07 grm. loss of SO,. Exp. 1O.-I next cuperimented upon a mixture of sulphate of soda arid perfectly anhydrons biborate of soda 0.71 grm. (1 equiv.) of the former and 2.02 (2 equiv.) of the latter After THE ACTION OF BORACIC ACID &C. being heated and kept in a state of fusion for half an hour it was found not to have lost weight. The two substances were thoroughly mixed after fusion and not separated as in the other mixtures. The addition of 0.35 grm. of boracic acid and subse- quent fusion produced however a separation of the substances into two layers and a very slight loss of SO,.Exp. 11.-I next fused a mixture of anhydrous sulphate of magnesia and boracic acid having the latter in large excess. All the sulpliuric acid was not expelled there being sufficient left to produce a copious precipitate of sulphate of baryta upon addition of chloride of barium to the acidified solution. I did not try this experiment quantitatively Exp. 12.-Was made with a mixture of sulphate of baryta and boracic acid in equivalent proportions viz, 1.166 grms. of the former and 0.35grm. of the latter. There remained after hating 0.814 grm. of BaO.SO = 0.2’79 grm. of SO = 0.121 grm. loss of so,. In all the foregoing experiments with the exception of the last and the mixture of sulphate and biboratc of soda the two sub-stances however intimately mixed previously even when dissolved and afterwards evaporated to dryness as in No.9 separated during fusion into two layers owing to tlieir being of different densities when in that state. I endeavoured to produce combination by stirring but Tyas unable ta do so. Upon coaling the sulphate appeared as a white crystalline mass at the bottom of the crucible whilst the boracic acid appeared as a colourless transparent glass above the sulphate. This clear glass however when carefully separated from the white mass of sulphate dissolved in water and the solution acidified with nitric acid yielded upon addition o€ chloride of barium a rather copious precipitate of sulphate of baryta showing that some at any rate of the sulpliate had been thoroughly mixed with the boracic acid without losing its acid.From a review of the above experiments it mill be seen that boracic acid does expel some of the acid from sulpliates at high temperatures but not at all in equivalent proportions as would be inferred from the statements before given; nor is the amount driven off in any relative proportion. Neither does it appear to make any difference what quantity of sulphate is present. The following table shows the quantity of sulphuric acid driven off by the boracic acidin the various experiments in proportion to the weight of the latter used :-Bt 2 . 17.14 per cent. b 11.28 , 20.57 , 20.00 9) 12.83 , .11.71 , FW i-il ,) . 19*1l! ,) . 20*00 , 34.57 , The fact that the two substaces separate when in n state of fixsion would rather lend us to think that the obstacles to the expulsion of the whole quantity of sulphuric acid are partly mechanical ;for it would naturally be expected that if boiwic acid cxpels some sulphuric acid it mould expcl it equivalent for eqni-dent; and it also appears straige that it sliould eliminate a larger quantity from sulphate of bzlryta than fr'oin sdphate of soil?. But then again tlie circnmstancc of the clear ghss containing sulphuric acid which must have been tlioroughly inised with the lioracic acid and therefore have offcrcd no izlzchanicd oh hcle tc its expulsion would favour the ticlief that sulphuric acid l~q c'r".I at a strong red heat a more porn-erftll affinity far the base t!!:an boracic acid has.This belief is also strecgthcncct by th rcsuit3 of experiment 11 ; for certainly if a base like izlc?gLicsifi gives off a portion of its acid when heated alone it may be cxcpccted tliit when anothcr acid likc boracic wid is present as me may term it a predisposing cause a111 the sulphuric acid woulcl be expelled. When hornever the sulphates of zinc and niclrel and one 01' two similar sinlphates are fused with boracic acid all the snlphuric acid is expelled and c1 borate of ziiic &c. remains This cmnot however be taken as a proof that the acid is driven off by t11c boracic acid for these sulphates are cleconipcsed when heated alone all or very ncarly all the acid being evolved.Action upon Cldorides.-In order to try the action of boracic acid upon chlorides at high temperatures I fused together chloride of sodium and chloride of potassium with that acid. In both cases the same separation took place as in tlie case of the sulphates and R portion of the chloride volatilized unaltered. The two sub-stances mere also clissolved in water the solution evaporated to dryness axid the residue fused. Here also a separtion took place and the chloride volatilized unaltcrzd as in the other expcri-rnents. I afternards fuscd togetliel* misturcs of 'ixwacic acid and chlo- ride of barium and chloride of calcium. These substances also separated wlien fuscd. These mixturcs verc hnated for several hours without drivirig off the chlorine hxt there was a gradual loss of that element.After cxposure to n strong red heat for nearly six hours G.100 grin. xis lost from LZ mi.rture containing 1.06 grms. of chlorids of bnriuni ad from a mi;ture containing 0.755 grm of chloride of calcium 0*08grni. Action upon Iodides nizd Bromides.-TVhcn a mixture of boracic acid awl iodide of potassium was heated to redness a similar result ensued as when chloride of potassium was used viz. a sepa-ration of the two substaiicea and partial volatilization of the iodide. Slight traczs of iodine vapours were however perceptible. With bromide of potassium no raponrs of bromine or my &-composition whatever were disccriiible. Action zpon Nitrates and Carbonates.-Both nitric and carbonic xids are completely expelled from their salts by boracic acid at a red hcat as is geuerally understood.From these experiments it appears then that the statcments given at the commencement of this paper are incorrect; for cer- tainly we are led to infer that boracic acid expels the whole of the more volatile acids from their salts at a red lieat which is dccidedlg riot the case. In conclusion I wodd reniark that these experiments many of them suggested by Dr. Muspratt whose advice during the investigation greatly assistcd me have bcen repeated scveral times in order to test their accuracy. I intend shortly to investigatc the action of silicic aud phos-phoric acids upon the salts of other acids at high temperatures.

ISSN:1743-6893    

DOI:10.1039/QJ8601200160

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

166 ANNIVERSARY R!IEETlNG OF THE CHEMICAL SOCIETY. March 30 1859. Dr. MILLER,Vice-President in the Chair. The following Report was read by the Secretary ltEYORT OF THE PRESIDENT AND COUNCIL. THECouncil have much pleasure ill congratulating the Fellows upon the prosperous condition of the Society. During the past year the meetings have talreii place regularly at Burlingtoil HOIIISC, on the first and third Thursdays in the month; and judging from the large attendances the Council after two years experience have every reason to bc satisfied with the change of locality and day of meeting whereby the Fellows of the Chemical Society are brought iiito association mitli those of the Royal and Linnaean Societies. During the past ycar tbe Chemical Society litis increased tlic number of its Fellows from 277 to 302 as shewn in the followiiig statement Number of Fellows at last Anniversary March 30 1858 .. 277 Fellows since admitted . 34 Fellows deceased . . .3 Fellows removed in defavlt of subscription . 6 Increase 25- Present nuniber of Pellows 302 Foreign Members . . 24 Associates . 9 L - REPORT OF THE I’RESII)I<ST AKD COUNCIL 1G7 At the last Anniversary tlie number of Associates mas thirtceIl. Of these three have since been elected Fellows and five havc ceased to be Associates in conseqnence of tlie time for which they were elected having expired. Four fresh elections have beer1 made so that the present number of ilssociates is niire. The names of the deceased Fellows are I1u gli L ee P c?.t t in s on F.R.S . Ncwcastle-on-Tyne j Th oru ton J ohi1 11er apat h Bristol; William Gregory M.D. F.R.S.E. Edinburgh. Mr. Pattinson was one of the original Members of the Chemical Society. The following Papers twenty-fdur in number have been read at the Meetings of the Chemical Society between March 30 185$ and March 30 1859. 1. “On a New Method of preparing Propionic Acid :” by Mr. J. A. Waiiklyn. 2. ‘‘On some Compounds of Iodide ad Bromide of Mercury with the Alkaloids :” by Mr. T. B. Groves 3. On the Quantitative Estimation of Sulphides Sulphites Hyposulphites and Sulpliates in the presence of one another :’’ by DIP. J. W. Kynaston. 4. On Nitrate of Amy1 and its Derivatives .” by Dr.I?. Guthric. ‘C ti. ‘‘On a New Method of preparing Peroxide of Chlorine :” by Messrs I?. Crace Calvert and E.Davics. 6. ‘(On the Deposits found in the Chimncys of Gold and Silver Reverberatory Furnaces :” by Mr J. Kapier. 7. ccOii the Formation of Chrysammic Acid by the Action of Nitric Acid on Aporetin:” by Dr. Warren De la &ue and Dr. Hugo &fuller. 8. “On the General Action of Oxidizing Agents on Sulphocyanides and on a special reaction attending the use of Nitric Acid :” by 3Ir.E. A. Hadow. 9. Mineralogical Contributions containing Notices of Meteoric Iron from Zacatecas in Mexico ; Pseudomorphous Cinnabar from Spain; Libethenite from Southern Africa ; Columbite from Greenland :” by Dr. 13ug o 31uI1 er.10. “On the Prodnction of some ncw Ureas :” by Dr. H ofm ilii n. I 1 ‘(On the Analysis of the Water of a Spring at Billingborough in Lincolnshire:” by Mr. Kynilston. 12. ‘‘On Bibroniacctic Lici.l :” by Rlessrs. Perkin and Diippa. 13. cc Oil the halysir of the Water of Holywell North Wales :” liy Mr. James Bsrratt. 1-1. “On the Itelations of thc Atomic Weights of the Elements :” by Mr. J. Mercer. 15. “On thc Detection of Alum in Bread:” by Mr. John H or sky. 16. u On some Minerals containing Arsenic and Sulphur from Chili :” by Mr. F. Field 17. C‘Onthe Prescnce of Ammonia in Ice and on the Action of Ice-water upon Lead :” by Dr. 31ed 1o ck. 18. On Titanic Acid :” by Mr. E.Riley.19. cc On the Conversion of Lactic Acid into Propionic Acid :’’ by Dr. C. Ulrich. 20. “On some Native Combinations of Ode of Mercury and Oxide of Antimony :” by Mr. F. Field. 21. “On the Constitution of Lactic Acid:” by Professor Kolhc. 22. ‘‘On a New Method for the Qmntitative Estimation of Nitric Acid :” Ly Dr. Pugh. 23 ‘(OH Sorbic Acid :” by DP.IIof m mi n. 24 On some Derivatives from the Olefines :?’ by Dr. Guthrie. Discourses ha1e beeii delivercd ‘(On Atoms and Equivalents :” by Dr. Odling. cc On the Air of Towns :” by Dr. R. Angus Smith. (‘On Ammonia :” by Dr. Hofmann. (f On the Composition of the Animal Portion of our Food and on its Ttclation to Bread:” by Dr. Gilbert. ‘l 0:i the Colouring Matters of Madder :” by Dr.E. S ch uuck. It will hz eiideirt froni the abo7.e list thd iiot only 178s chemistry been stcadily progressiug during the past year but tliat contributions of very considerable interest have becii madc to this Society. The papers of Messrs. Perkin & Duppa and of Dr. Ulrich liavc gone far to establish the position of the glycolic and lactic acids in their relations to the fatty acids of the primary series ;while the cnrious results of Mr. TV anld y 11 mliicli resdted in the formation of propionic acid €ram the atstion of carboiiic anhydride upon sodium-ethyl point out a Dew mode of transfer-ring compounds from one homologous group to that iinmc-diately bclom it. Dr. M ofintcnn’s researches on the amnouias and urcas have undergone great elaboration while his investiga- tion of the distillate from the juice of the moantain-ash berry has resulted in the discovcry of a new fatty acid of great interest both in its composition and properties.It is unfortunate that the examination of natural organic pro-dncts has of late been somewhat neglected for by such investiga- tions only can chemists hope to fill up the many gaps that now exist in the series of organic groups the completion of which is esscntial to the comprehension of the collateral relations of organic bodies. The departments of mineral and analytical chemistry havc lilrewise received valuable contributions amoilg which may lie meutioned in particular Dr. Pu gh’s iiigenious process for thc estimation of nitric acid.The Council have also to congratulate the Society upm that great iudication of proapcrity a good balance-sheet. During the past year death has remcved froin among us a man wliosc active labours in scicnce both in its abstract and applied fields have gained for him a wick- spread and well-earned reputation; we allude to Hugh Lee Pattiuson who cspired at his residencc at Scot’s House Newcastle-L~pon-T~ne cn thc 1lth Nov. 1858. Our lamented Fellow was born at Alstoii ithere his parents belonging to the smaller laiidholders of‘that locality had for gene-rations resided and in which placc lie received such an eclucation as its scliool a3ordeil. His however was noi one of t?iose minds wliich are dependcut for their development on the assistance of others.Gifted with grcat powers of obscwation and enclowccl with habits of accurate thought Mr. Pat tinson at an early period in life gave proof of an intellect of no common order. A subordinate appointment at a soapery in Newcastle gavc him an opportunity of pursuing his studies in chemistry to which his attention had been directed by accidentally hearing a lecturc on that science. These studies were pursued with such arclour aiict perseverance that a few years aFher\varcls n~hcii the Cornmissiori ers of Greenwich IIospital required an assay master for their mines ill Alston Moor hL*. Pnttiiisoii TV~Sfouacl by the authoritics to have sufficieiitly qualified hirnsel€ by self-ins truction to nndertalie the very responsible duties of the situatiw.This new field af6orded him ample scope for pursuing his favourite investigations ; and among the varied subjects wliich engaged his attention the process as then carried on for sepa-rating silver from lead occupied a prominent position. Previous to thc discorcry which connects liis xitime iii so distinguished a way with metallurgical science silver was obtained from its associated lead by the conversion of the last-named inetal into litliarge lcxving the pure silver behind which lithnrgc had to bc reconvertcd into lead at considerable expense in each process and with considerable loss of metal. After agreat number of urisiiccessful attempts to effect tlic separation of these substarms by a less circuitous method 14r.P attin son discovereci that a mixture containing only a very few ounces of silver to the too of lead appeared to rcsolve itself into two portions one remaining fluid afcer the other had assumed a solid and granular condition. It occurrecl to him that possibly tliere rnigJit bc a cliffereiicc in the quantity of silver con- tained in these two portions. nepeatecl espcrimcnts established tlic corrcctncss of this supposition and its value 3s applied to sepa-rating the two mctals was at oilcc pcrfecily apparent The process after beiiig matrired was patcntcd 211~1wry scon became csten-sively used as the Pattinso?i yroccss of dcsilwrizinx lead. It3 economy of application was siich that certain lciiids of this metal which previously would not bear tlic cxpcnsc.of having the silver extracted could iiow be profitably handed over lo the refiner and this to such an extent that it has bccii estimated that 54,000 Ounces of silver are now annually added to our productions of this precious metal which previous to Rfr. Patt in son’s discovery woulcl have remained uselessly as an impurity of lead. At a later pcriod JMr Pattinson added to tlic actrantages lic had conferred on applied chemistry by his discovery of a simple means of extracting magnesia from thc limestone rock containing that earth by means of carbonic acid; and afterwards returning to his original field of investigating the properties of lead he discovered a rapid method of producing> direct from lead ore a beautifd pigrricnt now extcii- sively used arid known as Pattinson’s oxychloriclc of lend.The manufacture of these two substances forms the chief produce of a very extensive manufactory> etablislicil by him ad his partners at Washington in the county of Durham. IIis position as one of the proprietors of these works together 11itli bcing largely intc- restcd in those of a still more extensivc clwacter at Felling for the manufslcture of soda alum bicarbonate of soda and other sub-stances gained for MY.Pattinson a very prominent place among the chemical manufacturers of this kingdoin. The scientific pursuits honcver of our deceascd membcr wrc neither exclusively directed to the acquisition of wealth nor to thc founding cf lucrative concerns. A considerable amount of atten-tion was bestr;;ved on the study of electricity and the allicd science of magnetism; and it mas by his acute observztion thLt the develop- ment of frictional electricity was first detected in high pressure steam when escaping from a small aperture.Subsequently he devoted much time to the study of astronomy and at great expensc ercctcd at Scot’s House a very powerful telescope equa- torially mounted an instrument which wm cmployeil by Professor Smythe in his observations on the Peak of Tcneriffe. The Itoyal the Astronomical and other learned Societies recog- nized the scientific attainments of Mr. Pattinson by clecting him a Fellow of thcir respective Institutions. Thornton John Hcrapath yoiingest son of‘William Hera-path Esq. F.C.S. kc. Analytical Chemist and senior Magistrate of Bristol TI~~S bom in that city in the year 1830.His chemical education was received in his father’s laboratory and his labours commenced at ;Imry early age At thirteen lie began analysis; his first published paper was printed when hc vas sixteen and his first course o€ public lectures was given when he was eighteen. He worked incessantly not only in Chemistry but also in Microscopy Botany Entomology Natural History and Philosophy. At the age of twenty-six he accepted the appointnient of chief chemist to the Mexican and South American Smelting Company for threc ycars during which time he resided at Herradura near Coquimbo in Chili and in the intervals of his duties pursued his researches into the natural productions maniicrs habits &c.of the inhabitants sending home drawings specimens or descriptions of everything he thought worthy of note. At the end of his engagement he proposed visiting Iris native land; but on his voyage home he was imfwtunatcly drx-;;.ncd on Deccmbcr Oth 1858 at the agc of twenty-eiglit. His pcrson as tall and very thin ; his cliaractcr trntliful honcst aid colzscientions. Mind-hearted and gcnerous hc "3s a univcrml favourit2 wlizreve;. lie wcnt. As a proof of his adour i:i scicnce IIC imile a long series oi c:ipzriments upon tlic physiclogical eiTects of scvcral poiscris (plrcspiiwctted oil nus-~ vomica hc.) ~qionhis OI system cortinu:rig them as far as they could be eiictured. He ra.3 an indef'ttigablc coiltyibutor to cbc-itiical scicnce liming ~JLhhh!d110 fcn.zr tliari sixty-one papers sc~e~al of wliicli appeared in the Journal of tliis Socicty.At tlic piiotl of his death he was engaged in thc prodxiion of a scrics cf tnbles of specific gavity hardncsx boiling and melting points SoluLiiity kc. or" organic and mineral substances together with a list of all lrriown organic substames; thc manuscript of which he h.s left in a state ready for p-dlic~tion. The late Professor Gregory of Edinburgh mhose death occurred on the 24th of April 1858 wzs the fourth son of Dr. James Gregory who for a period of thirty-onc yeass discliarged the duties o€ Professor of the Practice of P1ijsic in the University cf Edi~h~irgh.William Gregory was born in Dcccmber 1803 and was therefore fifty-four at the time of.his cleath. He was a graduatc in medicine of the Edinburgh school but had no heredi-trxp fondncss for tlic practics of the pro€ession iii which so many of his ancestors had distinguished tlicmselves. On the contrary at the period of his graduation his niiiid mas made up to follow chciuistry. His brotlicr J aincs Cranrford who lind previously talccn the Edinburgh medical degree-and who continned in prsctice till 1832 mhcn he JIM cut off by typlius-mcl Duiicaii IVLO at the time of his death was a Fellow of Triiiitp College Cambridge were both distiuguishcd for their taleiits and acquire-mcnts. Of Williaixi it may be ayerrecl that such was his gcnius tlislt he mould probably 1iave bcconie distinguished in aiiy depart-incnt of scieiice he might have choscn to pursue.('IIis low of' science," says llis distiiiguislicd relatire Dr. Alison "nianifestccl itself at pn early pcriod. He lid bc~ilpresent zt ail introductory lecture by Dr. Hope which was illustraicd by striking espe1-i-nicnts. Several of tlicsc expcriiuciits hz contrived to repeat by means of a rude apparatus mhich he constructed for the pnrpose. From that time he had dmap before him the object of ambition which he ultimately attaiued." Soon Pfter his graduation Pr G~cgo~y \:.cut tothe Contilielit REPORT OF TIlE PRCSIDENT ASD COI‘SCXL. 173 and thcre in tlie laboratories of foreign chemists pezfecterl his acquaintance mith the practical details of his f‘wourite science after which 11s returned to Edinburgh arid commenced public iife as an Extra-acahnical Lecturer on Chemistry.Whilst so occupiccl -as he was wont to relate-his chcmical career was well nigh sudclenly terminated by tlie accidental explosion of a large qiiiliitity of cldoyide of nitrogen in a basin. The late professor was remark-able foor his coolness and sclf-possession uiicler cii’cumstances drhidi moulcl liave been to say the least of it trying to many. 811 GX occasion duriiig his lectare a tube of peroxide of chlorinc bnrst in his liaiid and 8 fragment of glass elitering his eye cawed th aqueous humonr to escc2:3e-ne~-cPtlicl~~c~~ he proczccled with his lecture and fiiiislieil it. When Profewer Graham succeeded Dr. Edwnrd Turner in Uiiiversity College Loiidoi Di*.Gregory was apyoitited to succeed the present Master of the ?J.int in the Audcrsoninn Uni-ycrsity Glasgorr. Soon after his rmoval to that place a tempting opening in Dublin induced him to go to Ireland and comniciicc lecturing in on one of her rnctiopolitan medical schools. In 1839 he vas appointed Profcssor of 3ledicinc and Clreniistry in ICiug’s Collcge Abcrdecu and tlius became the occupant of (z chair which mcm than one of his distinguished nucestors hni ~.Irccdy filled.” In 1844 hc was clccted by the patrons to s?xccccd Dr. €1op e in the X~lix~burgli University in w1iicli collcge lie continueJ Professor of Chemistry up to the time of his death. In his system of chemical teac1iii:g Dr. Gregory assumed ths impossihility of doing justice to the sulijects-IIcat Light Elc-tricity and Magnetism-and though froin liis education tatcs arid philoso$iical capaciiy fully qualified to teach and illustrate cazh of these he considered tlie study of the irni)ouderal~les in a COLIP..~ of chemistry-propw m encronchmcnt on the time already too shorb in a university scssion.fm discusshg the chciniatry of th~ ponclerable elements. So fully hcmcvcr mcs lie dive to tlrc importance to the elieinica.1 stitdcnt of a mox than general know-ledge of these qpits thtit lie lmd devised and would liar1 his health permitted have given a separate and complete COUI’.;~of lectures upon each. “Wc had formed phiis,” says his biographer already quoted which Iiact liis licalth permitted would !:a\ c resulted in a cowse of chemical iiistrnction not surpassed in est;.iit and iinporisiice in any siiigle school in Europ.” In his manner of teaching Dr.Gregory mas simple precise 174 ANXIVERSARY BIEI!,i‘Ih’G 0%’T€XE CIXENICAL SOCIETY. and accurate. By means of a memory singularly retentive he could at any moment cover tlie boards of liis lecture-room with the most complicated organic formnlae. Having early in life attached liimself as a working chemist to the organic department of the science it was not surprising that as LZ lecturer he shodd principally delight in the delivery of the organic portizn of his course. His organic lectures were his favourites aid so efficiently was he prepared by past experimental experience and by daily reading for the enunciation of cven the latest discoveries that when lecturing on Organic Chemistry he did not employ even the scanty notes which it was his hnbit to make USC of when lecturing on inorganic subjects.As a teacher he was simple and errrnest exhibiting at all times that calm dignity and gentlemanly bearing which gave weight to liis prelections and impressed his students with coiifidence and respect. “As a scientific man,” Dr. Balfour has rightly remarked iii a bio- graphical sketch of his former colleague read to the Botanical Socie+y of Edinburgh ‘‘ Dr. TVilliam Gregory xorkecl more for utility as a teacher than for fame as a discovercr.” Amongst his published paFers may be noticed Investigation of Fat from a Putrid Aniilnal Subject ; Preparation of Hippuric Acid ; Preparation of Creatine ; On the Presence of Nickel and Cobalt in Commercial Oxiclc of Manganese ; Purification of Chloroform ;Application of Ace..tate of Lead in Sugar-refinery ; On the Ammoniacal Compounds of Cobalt ; On a Peculiar Benzoate of Potash ; On Pyroxanthine ; On the Decomposition Products of Uric Acid; On the Sponta- neous Decomposition of Allosan ;On a New Magnesian Phosphate. Besides these and many more investigations of tlie same kind Dr. Gregory contributcd to practical science improved processes for the preparation of hydrochloric acid muriate of morphia and oxide of silver. The complete knowledge which he possessed of all that had been done in chemistry up to the contents of the very last Journal ; his familiar acqunintancc with the modern languages ; and his talent for collecting and condensing what was really of scientific importance made him invaluable as a writer.He more-over wrote with ease and coulcl even under the pressure of other business write off pagcs of manuscript composition for which fern corrections were afterwards required. His class text-book was his r‘ Outlines ”-a work which has gone through several editions and mhich whilst it contains an extraordinary aniouxit of informa- REPORT OF THE PRESIDENT AND COUKCIL 1’75 tion in a compratively- small space is rernarkdde for the sirn- plicity of its arrangement and the clearness with wlkich its state-ments are expressed. From an ctlrly pcriod of life he attaclied himself to Liebig; their scientific relations were soon strengthened by personal friendship aiid their affectionatc intercoursc con-tiniiecl unabated till the last.Dr. Gregory assisted Liebig in several of his courses of experiments and some of his most important publications he at the request of his friend translated and cdited in this country. ‘‘It mas,” says Dr. Alison Ctunfortunatc for Dr. Gregory that though a man of large make and capable during youth of much exertion botli bodily ad mental he hnd neither opportunity nor disposition to take so much muscular exercise as would probably have suited his physical constitution. 111 consequence also of an attack of fcvcr in 1826 he became liable during the remainder of his life to smerc pain aid swelling in one of his legs on any niiusnd exertion.” Owing to the state of his health latterly he found it absolutely ncccssary to confine himself to siicli scientific investigations as required neither stzznding nor walking froni place to place.This sprcics of research the microscope afforded him the means of pursuing and in it lie engaged with all ilie enthusiasm of his ardent nature. Aided by his accomplished friend Dr Greville Professor Gr cgory enriched the Transactions of the Royal Society of Edinburgh with a bmutifully illustrated and laborious memoir oil thc Diatomncez. He vras in constant correspondence with microscopists iii evcry part of the world. As a friend Dr Gregory was sincerity itself. His unselfish nature was opposed to the nequisitioii of any personal advantage which mould inconveniencc anothcr and many a circumstance attributed by others to indolence on his part was really caused by tlie gciierosity of his nature.Few applied to him for relief and went empty away. Of course his generosity mas in certain cases abused. After a painful illness of considerable duration he died of it somemhat complicated disorder leaving behind him to practical scieiicc his discovzries ; to its literature his writings ; and to his frieuds-and thy are many -the mmorj of a man whose profes- sionrkl accomplishments mwe rendered more valuable by the modest graces of his private character. DRS. THE TREASURER IN ACCOUKT WITH TlIF CHEMICAL SOCIETY OF LONDON. CRS. 1858. g Y. ti. April 1. To Cash in hand .............................Ly General Printing ...................... 15 19 1 June 22. ,,Rent from Ethnological Society to March Editor of Jonid's Sdary ..........&50 185i.. .............................. 3 , Honorariuiu ....-10 2uly 21. ,)Half-yearly Dividend on $1 50 Three per cent. 60 0 0 Consols ............................. ,9 Printing Journal ...................... IGG 1 0 1839. , Librarian's Salary ..................... 15 0 G Jan. 22. ..Removal Fund ........................ .. 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ISSN:1743-6893    

DOI:10.1039/QJ8601200166

出版商:RSC    

年代:1860

数据来源: RSC

摘要:

177 X1X.-On the Action of Boracic Acid upon the Carbonates of the Alkalies and Alknline Earths. BYCUARLES L.BLOXAM. BEINGengaged in the search after a direct method of valuing commercial samples of crystallized boracic acid I made several experiments in order to ascertain whether the amount of that acid could be inferred from the weight of carbonic acid which the sample was capable of expelling from carbonate of soda. Finding that boracic acid always expelled at a high tem- perature more than a single equivalent of carbonic acid and that the numbers obtained were not concordant I abandoned this method of estimating the boracic acid. My attention was recalled to this subject by the “Researches on Silica” of Colonel Philip Yorke,” in which the author has shown that silicic acid is capable of expelling a greater weight of carbonic acid from carbonate of soda than from carbonate of potassa and still more from carbonate of lithia.Colonel Yorke also stated that boracic acid (in the form of borax) afforded results arralogous to those given by silicic acid but that the num- bers obtained did not accord well together. I then resumed the examination of the action of boracic acid upon the carbonates of the alkalies and alkaline earths; and since a paper read very recently at one of the Society’s meetings has awakened an interest in the subject I beg to lay my results before the Society in the hope OC receiving some suggestion which may help to explain them and may afford me some guidance in con-tinuing the inquiry.Action of Boracic Acid upon the Alkaline Carbonates at 212’ F. In these experimen,ts crystallized boracic acid was employed which had been precipitated from solution of borax by hydro- chloric acid purified by several crystallizations and dried in vacuo over sulphuric acid. The carbonate of potassa was employed in the fused state and the carbonate of soda sometimes in powder sometimes in fused fragments. * Phil. Tranw 185i p. 533. VOL. XII. B ULOXA31 ON 'I'IfK AC'PIOX OF The boracic acid and the alkaline carbonate were dissolved iii a few drachms of water in a platinum dish the solution evaporated to dryness in the water-bath and the residue dried in the water- oven till its weight ceased to vary appreciably.It was then dis- solved in water arid the residual carbonic acid determined by the method of Fresenius and Will. The results are contained in the followiiig tables in whicli tlie equivalent of anhydrous boracic acid (BOJ is taken as = 34.9 the equivalent of carbonic acid as = 22 of potassa = 47 of soda = 32 of lithia = 14.5. Action of Boracic Acid 018 Curbonate of Potussa at 212". One equivalent (349) of boracic acid taken in each case. No. Carbonate of potassain equivalents Carbonic acid expelledin equivalents. I . . 0.33 . . 0.33 2 . . 0.56 . 0.39 3 . . Oa84 . . 0.39 4 5 . . . . 1*!)3 1.ox . . . . 0.31 0.29 6 . . 2.90 . . 0.14 It hence appears that when three equivalents of boracic acid were employed to decompose one equivalent of carbonate of potassa the whole of the carbonic acid was expelled at 212"F.; that when the carbonate was increased a somewhat larger pro-portion of carbonic acid was expelled until the carbonate arnoiinted to nearly oiie equivalent When nearly two equivalents of car-bonate of potassa were employed rather less carbonic acid was expelled than when only one-third of an equivalent had been taken and when nearly three equivalents of carbonate of potassa were employed for one equivalent of boiwic acid not half as much carbonic acid was expelled.The smaller quantity of carbonic acid expelled in experiments 4 5 and 6 might of course be accounted for by the retention of carbonic acid in combination with the excess of carbonate of potassa but on cndeavouriiig to makc a corrcction for this I fouud that the qwwtizies of carbonic acid arid vater retained by a given weight of carbonate of potilssa at 212' F.were far from constant.* It mas not possible therefore to assign a formula to any of the residues saw that of experiment 1 which would be repre- sented as K0.3B0 with 4.3 eqs. of water.? Action of Boracic Acid on Carbonate of Soda at 212'. One equivalent (3$9) of boracic acid taken in each case. NO. Carbonate of soda in equivalents. Carbonic acid ex- pelled in equivalente. 7 . . 0.33 . . 0.33 8 . . 0.51 . . 042 9 . . 1.17 . . 0.43 10 . . 1-24! . . 0.52 11 . 1.44 . . 0.55 12 - . 3-53 . . 066 These results are directly opposite to those obtained with car- bonate of potassa for the quantity of carbonic acid expelled increases progressively though not nearly in the same ratio with the quantity of carbonate of soda employed.Here also however we find that the whole of the carbonic acid is expelled when three equivalents of boracic acid are allowed to act upon one equivalent of carbonate of soda. * Three experiments were made in which weighed quantities of fused carbonate of potasw were dissolred in water the solution thoroughly saturated with carbonic acid evaporated to dryness on the water-bath and dried in the water-oven till the weight was nearly constant ; the mass was then dissolved in water and the carbonic acid determined by Fresenius and Will's process. The composition of the residue was-J. IT. 111. Potassa .. 1 eq. . 1 eq. . 1 eq. Carbonic acid . 1.35 eq. . 1-18cq. . 1.18 en Water . . 1-01 eq. . 1'10 eq. . 1-24 eq. On dissolv'ng 22.16 grns. of fused carbonate of soda in water and treating it in exactly the same way 21.10 grns. of the carbonate were obtained showing that in this case no carbonic acid and water hail been retained. + A crystallized terborste of potsssa was obtained by Laurent c0ntainir.g 3 eqq ofwater. N3 BLOXAM ON THE ,wrmN OF Having proved by direct experiment that carbonate of soda was not capable of retaining any excess of carbonic acid at 21ftoF. I was enabled to calculate the compositioii of the borates of soda formed in these experiments and found that except in euperi- ment 11 a definite formula might be assigned to them; thus:- No.7 gave 2 (Na0.3B0,) + 7H0. 8 , 3 Na0.7B03 + 9HO. 9 , 3 ATa0.7B0 + 6H0. 10 , NaO.2B0 + 4*3HO. 12 , 2 Na0.3B03 + 66HO. Action of Boracic Acid upon the Alkaline Carbonate4$at a dtdl red heat. In these experiments the materials were heated in platinum crucibles over the flame of an ordinary argand gas-burner fur-nished with a copper chimney about six inches high and supplied with as much gas as it could burn without smoking. The boracic acid was employed sometimes in the crystallized state sometimes after having been dried in the water-oven.* The alkaline carbonates were powdered and mixed with the boracic acid in the crucible. The mixtures were weighed at con- siderable intervals until their weight had ceased to vary more than a few hundredths of a grain.The carbonic acid expelled was ascertained by deducting the calculated amount of water from the total loss of weight. No concordant numbers were obtained by decomposing car- bonate of potassa with boracic acid at a dull red heat; but it was proved that less than one equivalent of carbonic acid was expelled by an equivalent of boracic acid even when a large excess of car-bonate of potassa was employed. * Finding that the formula of boracic acid dried at 212' was given by Gmelin upon the authority of Berzelius as 3H0.2B0 I dricd 30.95 grns. of the pure crystallized mid in the water-oven ti11 its weight was constant (which required about twelve hours) when it had lost 9.17 gms. or 29.62 per cent. The formula H0.B03 would require a loss of 29.08 per cent.which is sufficiently near to the experimental result the djfferencc being due to the slight volatilization of the acid. The above formula of Berzelius would require a loss of only 21.8 per cent. It will be seen that several of the experiments detailed in this paper confirm the formula HO.RO for boracic acid dried at 212". Action of Boracic Acid upon Carbonate of Soda at a dull red heat. One equivalent (349) of boracic acid taken in each case. No. Carbonate of soda Carbonic acid ex-in equivalents. pelled in equivalenta. 13 . . 1.24 . . 1.02 (3H0.B03) 14 . . 1-24 -. 1.03 (HO.BO,) 15 * * 1-24 . . 1-07 (3H0.B03) 16 . . 1.24 . . 1.02 )) 17 . . 1.50 . . 1.00 , 18 .. 2-20 . . 1.01 (HO.BO,) 19 . . 2.90 . . 1.00 (3HO.BOJ 20 . . 3.10 . . 1-05 ) 21 . . 3-10 . . 1.02 , 22 * . 3.10 . . 0.99 , 23 . . 3.10 . . 1.01 , 24 . . 3.10 . . 1.00 ) Mean of 12 experiments 1.018 In these cases the mixture had never fairly fused but had merely fri tted together. At a dull red heat then hydrated boracic acid expels one equivalent of carbonic acid from carbonate of soda and it cannot fail to be remarked that this result is uniformly obtained notwitb- standing the great variation in the proportion of carbonate of soda employed. It appeared probable that the amount of boracic acid con-tained in a commercial sample might be inferred from the quantity of carbonic acid expelled from carbonate of soda at a dull red heat; but it was found that the borscic acid then dis- placed more than a single equivalent of carbonic acid the escape of the latter being facilitated by the presence of ammoniacal salts in the crude boracic acid.Action of Boracic Acid upon Carbonate of Lithia at n dull red heat. One equivalent (34~9)of boracic acid taken in each case. NO. Carbonate of litliia in equivalents. Carbonic acid ex-pelled in equivalents. 25 . . 3.47 . . 2.53 26 . . 3.07 . . 2.42 The boracic acid and the carbonate of lithia were both em-ployed in the fused state. Anhydrous boracic acid is able to expel 24 eqs. of carbonic acid from carbonate of lith ct (z dvll red heat. Action of Boracic Acid upon the Alkaline Carbonates cf fs Wpit red heat.The materials were fused in platinum crucibles over a Solly's gas-furnace for ten or fifteen minntcs then weighed and again ignited for five or ten minutes until the weight did not vary in any considerable degree. A few preliminary experiments were made to ascertain the effect of this temperature upon the separate re-agents; and since this has of necessity a very important bearing upon the results it may be desirable to refer to the experiments upon boracic acid since some doubt might be entertained of its resistance to so high iltemperature. 30.95 grns. (+ eq.) of crystallized boracic acid were heated to dull redness over an argand gas flame when they lost 14.13 grns. of which only 13.5 grns. would be water the remaining 0.63repre-senting the volatilized boracic acid (3.61 per cent.of the dry acid employed). 16-82grns..of vitrefied boracic acid thus obtained were heated for ten minutes in EL loosely covered platinum crucible over the gas furnace when they had lost 0.21 grn. (1-24per cent.) When again heated for ten minutes in the open crucible bubbles were seen to form within the mass and a further loss of 0.29grn. mas perceived. 5.99 grns. of well vitrefied boracic acid taken from the stock employed for the following experiments were very strougly ignited over the gas-furnace in a covered crucible for five minutes when the loss amounted to 0.14 gm.,or 2.33pcr cent. When again BORACIC .icm ON THE CARBONATES &c. 183 heated for five minutes it suffered no further diminution; ignited a third time for seven minutes it had not lost though a fourth ignition for five minutes caused a loss of 0.02 grn.On igniting for five minutes in the open crucible the loss was 0.02 grn. and in the next five minutes 0.04 grn. These numbers lead to the inference that even supposing the boracic acid to be volatilized to the same extent in the presence of an excess of an alkaline carbonate the results will be but slightly vitiated ; for taking the whole loss in twenty minutes’ ignition in the first experiment it would represent only +-of an equivalent of carbonic acid for each equivalent of boracic acid. I also convinced myself that neither carbonate of potassa Dor carbonate of soda suffered any material diminution of weight at this temperature.The behaviour of carbonate of lithia mas very different. The carbonate of lithia employed was carefully tested for all impurities except potassa and soda the absence of any material qurtn tities of these being inferred from the circumstance that 5 grns. of the carbonate when decomposed by sulphuric acid gave 7.34 grns. of sulphate of lithia representing 4.91 grns. of the carbonate. The carbonate of lithia was dried in an air-bath at about 300’ F. until its weight was constant. 12-74grns. of the carbonate were strongly ignited over the gas furnace in a covered platinum crucible until the weight did not vary more than 0.09 grn. The loss amounted to 8.38 per cent. 12.66 gms of the carbonate lost 1-05 or 8.29 per cent.13.54 gms. lost 1.14or 8.41 per cent. 5-53 grns. of carbonate of lithia ignited till its weight did not vary more than 0.01 grn. after five minutes’ ignition had lost 0.83 or 15.0 per cent. The ignited mass treated with sulphuric acid gave 7.94 grns. of sulphate which would correspond to 5-317 grns. of carbonate of lithia or 0213 grn. less than was originally taken and 0.617 gm. more than if the mass after ignition were pure carbonate of lithia. The ignited mass must therefore have contained uncombined lithia the carbonic acid having been partially expelled. The loss of lithia would be accounted for by its volatilization during the repeated ignition. 13.14 gms. of carbonate of lithia lost 1-53or 11.6 per cent.13.2 gms. lost when ignited till it absolutely ceased to diminish after five minutes ignition had lost 1.34 or 10.15 per cent. 158 gms. of carbonate of lithia ignited till the variation did not exceed 0.01 had lost 10.70 per cent. It was dissolved in water and decomposed by an excess of chloride of barium; the liquid filtered from the carbonate of baryta was strongly alkaline both to litmus and turmeric indicating the presence -of lithia in an uncombined state. On treating the original carbonate of lithia in the same way the filtrate was very feebly alkaline to litmus and not at all to turmeric. From these experiments it is evident that the carbonate of lithia is partially decomposed by a bright red heat but that only a fraction of the carbonic acid can be thus expelled a limit being reached in every experiment at which the retaining power of the lithia was in equilibrium for that temperature with the tendency of the heat to expel the carbonic acid.The maximum amount of loss it will be observed was 15 per cent. which occurred in ignition for twenty-five minutes. This is only onenfourth of the total amount of carbonic acid (60.02 per cent.) which the carbonate of lithia contains To diminish as far as possible the errors arising from this decomposition of' carbonate of lithia the carbonate used in the following experiments was always ignited at the temperature of the experiment until its weight cesscd to vary materially in periods of five minutes before adding the boracic acid.Action of Boracic Acid upon Carbonate of Potassa at a bright red heat. One equivalent (34.9)of boracic acid taken in each case. No. Carbonate of potamin equivalents. Carbonic acid ex- pelled in equivalents. 27 . . 1-23 . 0 1.08 28 . . . 1.27 . . 1.08 29 . . 2.60 . . 1.11 30 . . . 1.63 . . 1-12 31 . . . 1.73 . . 1-15 32 . . 1.73 . . 1.22 33 . 1-75 . . 1.14 34 . . 1.77 . . 1.18 35 . . 1.83 . . 1.14 36 . . 2.441 . . 1.24 37 . . 2.75 . . 1-20 38 . . . 2*77 . . 1-24 39 . . 2.81 . . 1.23 40 . . 3-18 . . 1.21 41 . . 3.53 . . 1.23 42 . . 3.69 . . 1.26 Mean of 16 experiments 1.17 The boracic acid and the carbonate of potassa were both employed in the fused state. An examination of this table shows that at a bright red heat boracic acid expels somewhat more than one equivalent of car-bonic acid from the carbonate of potassa and that the amount of carbonic acid expelled usually increases with the proportion of alkaline carbonate taken though to a comparatively slight extent the minimum being 1.08 eqs.of carbonic acid when 1.25 eqs. of carbonate of potassa were employed and the maximum 1.26 eqs. of carbonic acid for 3.64 eqs. of carbonate of potaasa. It was not ditficult to obtain a nearly constant weight in these cases one or two weighings being generally found to suffice if the mass was heated at first for about fifteen minutes and after weighing for periods of five minutes. The fused masses when cool appeared to be composed of delicate prismatic crystals of a fine blue colour for which I was unable to assign a cause.BLOXAM ON TI1E .\CTlON OF Action of Boracic Acid upof2 Carbonate qf Sodit at a bright red heat. One equivalent (34.9)of boracic acid taken in each case. No. Carbonate of soda in equivalents. Carbonic acid expelled in equivalents. 43 . 1-50 . 1.48 (3H0.n03)* 44 . 2.01 . 1-88(HO.BO,) 45 . 2.02 1.81 , 46 . 2.20 . 1.95 47 . 2-28 . 1.88 (Bb3) 48 . 2.90 . 1-89 (3H0.B03) 49 . 3.10 . 1.73 9 50 . 3-20 . 2.04 , 51 52 53 . . . 3.10 3.39 4.40 * . . 1.93 1.85 2.22 (HO.BO,)(G,) 54 . 5.41 . 2-34 (BO,) 55 . 5-44 . 2-52 , 56 . 5.58 . 2.31 , The experiments numbered 44 46 49 50 51 52 and 53 were made in a muflle the rest over the gas-furnace. * The borate here formed would have the composition 3 Na0.2B0 ; and accord- ing to amelin this aalt was obtained by Arfvedson in the fusion of borax with carbonate of soda when each atom of borax expelled two atoms of carbonic acid.Three experiments which I made by fusing borax with exceas of carbonate of soda in a hot muffle agreed very nearly with the slipposition that three atoms of car-bonic acid were expelled by each atom of borax thus producing a borate of the formula 2Na0.B03. It will be seen that this accords with the general result of the experiments made with free boracic acid viz. that each atom of the acid may expel two atoms of carbonic acid thus combining with two atoms of soda. In some analyses of samples of commercial boracic acid by this nietliod in which forty four parts of carbonic acid expelled from the carbonate of soda were taken to represent 34-9 parts of BO, the percentage of boracic acid agreed very c*’osely with that obtained by determining all the other constituents of the samples separatc‘y but the circum- stance that a large proportion of carbonic acid may be expelled by samples con- taining a small pelcentage of boracic acid in coascquence of the increase in the proportion borne by the carbonate of soda to the acid renders this method too uncer- tain except in casca were the percentage of horacic acid ia already approximately known.BORACIC ACID ON THE CARBONATES &C. 187 In the experiments numbered 46,49 and 52 the residual car-bonic acid was determined and found to confirm the result inferred from the loss of weight proving that no appreciable volatilisa?,ion of horacic acid had taken place.Thc fused masses weregreyish white never blue as in the cases where carbonate of potsssa liad been employed. Tlie difficulty of obtaining a constant weight in these experi- ments was very remarkable as many as eight or ten weighings being often found necessary. It will be noticed that the increase of the amount of carbonic acid expelled according to the proportion of carbonate of soda employed is very much more marked than in the case of carbonate of potassa the rnininum being 1.48 eqs. of carbonic acid expelled from 1.50 eqs. of carbonate of soda and the maximum 2.52 eqs. of carbonic acid from 5*44eqs. of carbonate of soda.The amount of carbonic acid expelled by boracic acid from carbonate of soda at a bright red heat may therefore be said to ratige between 13 and 2 eqs. though in the majorityof the above experiments it approached more nearly to 2 eqs than to either of these limits. The masses obtained in these fusions were always very deli- quescent and far more caustic to the taste and toiich than car- bonate of soda. Action of Boracic Acid upon Carbonate of Lithia at a bright red heat. One equivalent (39.9)of boracic acid taken in each casc. E0. Carbonate of Lithia Carbonic acid expelled in eqiiiralent8. in cquivalents. 57 2.98 . . 2-47 58 3.07 . . 2.66 59 3.47 . 2-70 60 3.50 . . 2.53 61 5-10 . . 2-45 Mean of 5 experiments .. 2.66 The results with carbonate of lithia are seen to be nearly as constant as thosc with carbonatc of potassa rtrid it was evcn 188 BLOXAM ON THE Ac'rioN ov easier to obtain a constant weight in the case of carbonate of lithia. It appears then that at a bright 'red heat boracic acid is able to expel 24 eqs. of carbonic acid from carbonate of lithia a result which agrees with that obtained at a dull red heat. Action of Boracic Acid upon the Carbonates of Buryta and Strontia. Pure precipitated carbonate of baryta is not materially affected by the heat of the gas-furnace as the following experiments prove :-14% grns. of carbonate of baryta ignited in a covered crucible for ten minues had lost only 0.04 gr. 14.42 gms. ignited very strongly for fifteen minutes had lost only 0.11 grn.Carbonate of' strontia is as would be expected decomposed to a greater extent . 15*88 grns. heated for five minutes over the gasfurnace had lost 0.25 p.; on heating again for five minutes it lost 0.02grm. Total loss 1.7 per cent. 11.84 grns. lost in four successive periods of five minutes 0.15 0.10 0.18 and 0.17 gm. Total loss 5.07 per cent 12'43 grns. lost in three successive periods of five minutes 0.29 0.16 and 0.05 gm. Total loss 4-34per cent. It will be seen however that the decomposition of carbonate of strontia by heat will not materially affect the general result of the experiments for taking even the greatest amount of loss in the above experiments it would represent only 3.74 of carbonic acid (about + eq.) lost by one equivalent (73*8) of carbonate of strontia.ACTION OF BORACIC ACID &C. Action of Boracic Acid upon Carbonate of Baryta at a dull red heat. One equivalent (349) of boracic acid taken in each case. Carbonate of baryta Carbonic acid expelled NO. in equivalents (1 eq.=98'6). in equivalents. 62 0 2.82 . 196 63 . 3.00 . . 2.15 64 3.65 . . 1.92 Mean of 3 experiments . . 2.01 In No. 63 the hydrated boracic acid dried at 212" was em- ployed; in the other cases crystallised acid was taken. At a dull red heat boracic acid expels 2 eqs. of carbonic acid from the carbonate of baryta At a bright red heat. NO. Carbonate of baryta Carbonic acid expelled in equivalents. in equivalents.65 . . 2-82 . 2.56 (3H0.Bo3) 66 . . 3.87 2.42 (BO,) 67 . . 2-94 . 2.56 (BO,) 68 . . 3-00 . 2.60 (HO.BO,) 69 . . 3.01 . 2.45 (BO,) 70 . . 3.04 . 2.44 (BO,) 71 . . 3.22 . 2.47 (BO,) 72 . 3.50 . . 2-56 (3H0.B03) 73 . . 3.65 . 2-70(3H0.B03) Mean of 9 experiments . 2.53 The fused masses obtained here had many of the properties of caustic baryta becoming heated when moistened with water which partially dissolved them yielding powerfully alkaline solu-tions which deposited carbonate of baryta when exposed to the air. In the experiments with carbonate of baryta it was remarkably easy to obtain a constant weight but I found that no advantage could be taken of this in the valuation of commercial boracic acid since the ammonia and other volatile matters favour the escape of a larger quantity of carbonic acid.VOL XII. 0 RLOXAM ON THE It appears therefore that boracic acid expels 29 eqs. of carbonic acid both from carbonate of baryta and from carbonate of lithia at a bright red heat. Action of Boracic Acid upon Carbonate of Xtrontia at a dull red heat. One equivalent (349)of boracic acid taken in each case. Carbonate of strontia Carbonic acid expelled NO. in equivalents (1 eq. =73'8.) in equivalents. 74 . . 3.67 . min. 2.37 (SHO.BO,) 75 . . 3.76 . . 2-52 (HO.BO,) 76 . . 4.78 . . 2-61 2> 77 . . 6-65 . . 2-40(3H0.B03) 78 . . 9.00 . . 2.62 9 Mean of 5 experiments max. 2.50 At a dull red heat then hydrated boracic acid expels 24 eqs.of carbonic acid from the carbonate of strontia. In consequence apparently of the difficulty of fiising the borate of strontia it was found that no uniform results could be obtained by igniting fragments of glassy boracic acid with precipitated car- bonate of strontia; it was necessary to employ the boracic acid in the hydrated state and to mix thoroughly with a glass roil> after-wards drying at a gentle heat before igniting over the gas- furnace. At a bright red heat. No. Carbonate of strontia Carbonic acid expelled in equivalents. in equivalents. 79 3.67 . 2-90 80 3-76 . . 2.92 81 3.76 . . 3.03 82 4.78 . min. 2-86 83 6.65 max. 3-18 84 9.00 . . 3.14 Mean of 6 experiments .. 3*00 It was rather more difficult to obtain a constant weight in the case of carbonate of strontia than in that of carbonate of baryta. ACTION OF BORACTC ACID &C. It may be remarked that there is just half an equivalent more carbonic acid expelled from each of these last carbonates at a bright red as at SL dull red heat. From the experiments above recorded I should infer (though the results in the case of soda at a bright red heat are somewhat doubtful) that the quantities of carbonic acid expelled by boracic acid at a dull red heat from the caybonates of soda lithia baryta and strontia respectively are approximately in the ratio of the numbers 1 2$ 2 and 2+ and that the quantities of carbonic acid expelled at a bright red heat from the carbonates of potassa soda lithia baryta and strontia respectively are approximately as the numbers 1 2 24 and 3.What explanation can be given of these results ? It can hardly be supposed that there are four different equivalent weights to be assigned to boracic acid as representing the quantities required to displace a given amount of carbonic acid from its combinations with these direrent bases. It appears far more reasonable and far more in harmony with our knowledge of the chemical relations existing between these bases and more particularly of their relations to carbonic acid to attribute the progressive increase in the quantity of carbonic acid evolved to a corresponding decrease in the chemical attraction for that acid evinced by the several bases in question.In each case the decomposition may be supposed to proceed until the tendency of the borate which has been found to take up an additional quantity of base is in a state of equilibiiuni with the chemical attraction existing between that base and the car- bonic acid. Thus in the case of carbonate of potassa the monoborate of potassa (KO.BO,) which is formed at a bright red heat has only just so much attraction for an additional quantity of potassa as is counteracted by the opposing attraction of the potassa for the car- bonic acid whilst in the case of carbonate of strontia the attrac- tion between that base and the carbonic acid is only sufficient to counteract the tendency of the compound 3Sr0.B03to take up an additional quantity of strontia.If this were the true explanation it might be expected that boracic acid which had already been fused with an excess of carl3onate of potassa would still be able to expel carbonic acid from carbonate of soda or of lithia; for allowing the KOaBO a certain attraction for an additional amount of base it will be 02 BLOXAM ON TBE capable of satisfying that attraction if the base presented to it have a weaker attraction for carbonic acid than the potassa has. (85). 15.3 grns. of glassy boracic acid were fused over the gas-blowpipe with 37.7 grns. (1.246 eq. for each eq. of BO,) of fused carbonate of potassa for fifteen minutes weighed and again ignited for five minutes when a further loss of only 0.02 gm.had occurred. The carbonic acid expelled amounted to 10.39 grns or 1-07eq. for each eq. of BO,. 14.05 gms. of pure fused carbonate of soda (0.60eq. for 1 eq. BO,) were then added and the crucible again heated for ten minutes over the gas-blowpipe weighed (loss= 1.98 grns.) again heated for five minutes causing a further loss of 0-28gm. then a gain for five minutes when it lost only 0.1 grn. The carbonic acid expelled from the carbonate of soda by the boracic acid which had been already saturated with carbonate of 2otassa amounted to 2-20gms. or 0.227 eq. for each eq. of RO present. (86). A similar experiment with 7-12 gms. glassy boracic acid (1 eq.) and 18.14 gms. fused carbonate of potassa (1.28 eq.) Fiaal variation after five minutes ignition 0.02 grn.Carbonic acid expelled from the carbonate of potassa 4-86grns. or 1.08 eq. 17.40 grns. (1.60 eq.) of carbonate of soda added. Loss in fifteen minutes’ ignition 2-07grns. Final variation after five minutes’ iguition 0.04gm. Carbonic acid expelled from the carbonate of soda by the boracic acid already saturated with carbonate of potassa amounted to 2.11 grns. or 0.47 eq. for each eq. of BO,. (87). 8.72 grns. glassy boracic acid (1 eq.) 42.52 grns. fused carbonate of potassa (2.46 eqs.) Final variation in five minutes’ ignition 0.1 grn 12-04grns. more carbonate of potassa added. Further loss after fifteen minutes’ ignition 0.32.gm. Carbonic acid expelled from the carbonate of potassa 1-30 eq 17.48 grns. (1*32eq.) of fused carbonate of soda added.Loss in six minutes’ ignition 0.64 grn. Final variation in five minutes’ ignition 0.12 grn. ACTION OF BORACIC ACID &C. Carbonic acid expelled from the carbonate of soda by the boracic acid already saturated with carbonate of potassn amounted to 1-16 grn. or 0.21 eq. for each eq. BO,. (88.)1409 ps. of glassy boracic acid (1 eq.) 4753 grns fused carbonate of potassa (1.61eq.) Final variation after five minutes’ ignition 0.03 grn. 6.97 grns. more carbonate of potassa added. Further loss after ten minutes’ ignition 0-27gm. Final variation after five minutes’ ignition 0.00. Carbonic acid expelled from the carbonate of potassn 1.14 eq. 9.43 grns. (0-42eq.) of fixed carbonate of soda added. Loss in five minutes’ ignition 0.65 grn.Final variation in five minutes’ ignition 0°08 gm. Carbonic acid expelled from the carbonate of soda by boracic acid already saturated with carbonate of potassa 1*& ens. or 0.15 eq. for each eq. BO,. (89.) 10.02 grns. of glassy boracic acid (1eq.) 63.78 grns. of fused carbonate of potassa (3.2 eqs.) Final variation after five minutes’ igniton 0.05 grn. 6.58 grns. more carbonate of potassa added. Further loss after five minutes’ ignition 0.04 gm. Carbonic acid expelled from the carbonate of potassa 1.21 eqs. 11.57 grns. (076 eq.) of fused carbonate of soda added. Loss in five minutes’ ignition 0.63 grn. Final variation in five minutes’ ignition 0.12 grn. 5-98 grns. more carbonate of soda added. Further loss in five minutes’ ignition 0.24 grn.Added 3-03grns. more carbonate of soda. Further loss in five minutes’ ignition 0.28 grn. Final variation 0*10grn. Added 4-57 gms. more carbonate of soda. Final variation in five minutes’ ignition 0.17 grn. Carbonic acid expelled from the carbonate of soda by boracic acid already saturated with carbonate of potassa 1.84 grns. or 029 eq. for each eq. of boracic acid. Added 2.75 grns. (0.26 eq.) of carbonate of lithia. BLOXAM ON THE Loss in five minutes’ ignition 0.51 grn. Final variation 0.12gm. Total loss after adding the carbonate of lithia 1.15 grn. Deduct the maximum loss ever suffered by carbonate of lithia heated alone (15 per cent.) . . 0.41 ,, -Carbonic acid expelled . . 0.74 (0.11 eq.) from the carbonate of lithia by boracic acid already saturated with carbonate of potassa and carbonate of soda.(90.) 8.09 grns. glassy boracic acid (1 eq.) 64436 grns fused carbonate of potassa (3.6 eqs.) Final variation after seven minutes’ ignition 0.12 grn. 13.05 gms. more carbonate of potassa added. Further loss after five minutes’ ignition 0.07 grn. Carbonic acid expelled from the carbonate of potassa 3 026eqs. Added 6.47 gms. (0.69 eq.) of carbonate of lithia. Loss in five minutes’ ignition 1-33grns. Find variation 0.13 grn. Total loss after adding the carbonate of lithia 2-24 gms. Deduct the maximum loss ever. suffered by carbonate of lithia alone . . 097 ,’ -Carbonic acid expelled . . 1.27(0.136 eq.) from the carbonate of lithia by boracic acid already saturated with carbonate of posassa.(91.) 9.93 grns. glassy bonric acid (1 eq.) 81.42 grns. fused carbonate of soda (5.4eqs.) Final variation afker five minutes’ ignition 0.08 grn. 12.75 grns. more carbonate of soda added. Further loss in five minutes’ ignition 0.08 gm. Carbonic acid expelled from the carbonate of soda 2-31eqs. Added 4.46 gms. carbonate of lithia (0.42eq.) Loss in five minutes’ ignition 046 grn Final variation 0.17 grn . ACTION OF BORACIC ACID &C. Total loss after adding carbonate of lithia . 1.00 grn. Deduct maximum loss of carbonate of lithia alone . . 0.67 ,, -Carbonic acid expelled . . 0.33 (-031 eq,) from the carbonate of lithia by boracic acid already saturated with carbonate of soda.We are not surprised that the amount of carbonic acid expelled is in this case so small when we remember that 25 eqs. represent the average amount of carbonic acid expelled from carbonate of lithia by boracic acid and that as much as 2-31eqs. were here expelled from the cabonate of soda alone before any carbonate of lithia was added. It still remained to be seen whether boracic acid which had been saturated with carbonate of soda was not capable of expelling carbonic acid from carbonate of potassa. (92.)1414grns. glassy boracic acid (1 eq.) 43.25 griis. fused carbonate of soda (2-01eqs.) Final variation afier five minutes’ ignition 0.05 grn. Carbonic acid expelled from the carbonate of soda 1.79 eqs. Added 31.51 grns.of fused carbonate of potassa. Instead of suffering any furtber loss the mass now actually gained 005 gm. in five minutes’ ignition; it was then heated for ten minutes when it had gained 0.07 grn. in addition and on again heating for five minutes it had still gained 0.05 grn. This result is the more satisfactory because the boracic acid had not expelled from the carbonate of soda the greatest amount of carbonic acid which it is capableof displacing and still it refused to expel any carbonic acid from the carbonate of potassa. (93.) 16-OPgrns. glassy boracic acid (1eq.) 55-51gms. fused carbonate of soda (2.4eqs.) Final variation after five minutes’ ignition 0.09gn. Carbonic acid expelled from carbonate of soda 3-86 eqs. Added 21.3 grns. fused carbonate of potassa.Further loss in fifteen minutes’ ignition 0.2 grn. ‘it is evident therefore that boracic acid which has been saturated BLOXAM ON THE with carbonate of soda has no longer any tendency to expel carbonic acid from carbonate of potassa. It appeared probable that silicic acid would be found to behave with the two alkaline carbonates in the same manner as boracic acid. (94.) 9.52 gms. (1eq.*) of precipitated silicic acid were fused over the gas-blowpipe with 46.75 ens. (2.15eqs.) of fused car- bonate of potassa till a loss of only 004 grn. was observed after five minutes’ ignition the crucible was then placed for ten minutes in a very hot muffle when it only lost 0-13 grn. The carbonic acid expelled amounted to 6.63 gms.or 0.95 equivalent for each equi- valent of silicic acid. (95.) 9-84gms. (1eq.) of silicic acid. 57.80 grns. (2.57eqs.) fused carbonate of potassa. Final variation after five minutes’ ignition 0.06. grn. Carbonic acid expelled 6.68 grns. or 0.93 eq. Added 29.17 grns. hsed carbonate of soda. Loss in five minutes’ ignition 0.79 gm. Total loss after eighteen minutes 1.21grn. (0.17eq.) of carbonic acid expelled from carbonate of soda by silicic acid already saturated with carbonate of potasaa. (96.) 10.57 grns. (1 eq.) of finely powdered rock crystal fused with 66-83grns. (2.77 eqs.) of fused carbonate of potassa. Final variation in five minutes’ ignition 0.05 gm. Carbonic acid expelled 6.96 grns. (0.9eq.) Added 18.86 grns. fused carbonate of soda.Loss in five minutes’ ignition 0.28 grn. Total carbonic acid 0.55 gm. (0.07 eq.) expelled by the silicic acid already saturated with carbonate of potassa. (97.) 9-68 ens. (1 eq.) precipitated silica and 39-60gms. (2.03eqs.) pure carbonate of soda intimately mixed. Heated to dull redness till nearly constant in weight had lost 4.87 gms. (0.69eq.) of carbonic acid. * The equivalent weight of silicic acid is here taken a 80.24 (Si02). ACTION OF BORAClC ACID &C. Heated for fifteen minutes over gas-blowpipe had lost 9.09 grns. (1.30 eq.) Heated for ten minutes in hot muffle had lost 9.79 grns. (1.39 eq.) (98.) 9.31 gms. (1eq.) precipitated silica. 34.06 gms. (2.12eqs.) carbonate of soda Heated over gas-blowpipe till nearly constant had lost 9.24 gms.(1-36eq.) of carbonic acid. (99.) 10.4 grns. (1 eq.) precipitated silica. 35.34 grna. (1.93 eq.) fused carbonate of soda. Final variation in five minutes' ignition. 0.03 gm. Carbonic acid expelled 9-92 gms. (1.31eq,) Added 47-16grns. fused carbonate of potassa and again fused. After five minutes' fusion the mass had actually gained 01 gm. (100.) 6.89 grns. (1 eq.) of rock crystal. 45.93 (2.6 eqs.) fused carbonate of soda. Final variation in five minutes' ignition 0.1 gm. Carbonic acid expelled 9.68 grns. (1.34 eq.) Added 15.28 grns. fused carbonate of potassa and again fused. Gain iu five minutes' ignition 0.17 grn, '' in other five minutes 0°08 , Final variation in five minutes 0.00 , It is evident from these results that no carbonic acid can be expelled from carbonate of potassa by silicic acid already saturated with carbonate of soda.The conclusion deducible from these few experiments upon the action of silicic acid on the alkaline carbonates at high tempera- tures agrees pretty well with that furnished by the experiments of Col. Yorke who found that 1 eq. (30.24)of silicic acid expelled 0.97 eq. of carbonic acid from carbonate of potassa and 1-42eq. from carbonate of soda. I found 0.926 expelled from carbonate of potassa and 1.35 from carbonate of soda. It was also much easier to obtain a constant weight with carbonate of potassa and the results exhibited less variation. Further experiments upon the expulsion of other acids from their salts by boracic and silicic acids appear to be required before _we can safely infer that the attraction of boracic acid SCHUNCR ON THE for bases at high temperatures ia really greater than that of silicic acid.It would appear that in all attempts to determine the equivalent of an acid by the amount of carbonic acid displaced by it at high temperatures it would be safer to employ carbonate of potassa than carbonate of soda since the latter in the case of the two acids here examined has yielded far less constant results. On comparing the action of boracic acid upon carbowate of potassa at a bright red heat with that of silicic acid I am led to the belief that if the equivalent of the former acid be taken as = 349 (BO,) then the equivalent of silicic acid must be that which corrcsponds to the formula SiO,.

ISSN:1743-6893    

DOI:10.1039/QJ8601200177

出版商:RSC    

年代:1860

数据来源: RSC