摘要:

ACTION OF BROMINE ON POTASSIUM FERRICYAKIDE. 7 6.i LX1.-The Action of Bromirze om Potassium Ferricyanide. By EDGAR J. REYNOLDS Student in the Laboratory of the Normal School of Science South Kensington. Im studying the action of the halogens on potassium ferricyanide with the view of obtaining the so-called superferricyanide of potas-sium I noticed that a black substance was produced in the later stages of the action. The formation of this was so general that the reaction seemed to merit further study; it was only observed, however when the bromine was in excess; when the ferricyanide was in excess a blue substance was formed very much resembling prussian blue but apparently it was not homogeneous and probably contained besides prussian blue Turnbull’s blue and the black substance already mentioned.It has been known for some time that when chlorine in excess is passed into a solution of potassium ferrocynnide or ferricyanide and the liquid is heated to boiling a cyanide of iron generally known by the name of Pelouze’s green is formed and that if the action is con 768 REYNOLDS THE ACTION OF BROMINE tinued this is converted into a blue compound (generally vaguely described as prussian blue). It is also stated that bromine acts in the same manner as chlorine. With regard t o the latter stage of the reaction namely the formation of prussian blue this is correct as it is also with regard to the first piqoduct of the transformation the so-called superferricyanide of potassium. But with regard to the intermediate stage preceding the formation of the blue compound, the statement is wholly inaccurate as instead of Pelouze's green we obtain a black brittle semicrystalline substance.I n my attempts t o obtain the superferricyanide I used iodine and bromine these being heated with potassium ferricyanide in sealed tubes at temperatures of 100" and 120" for several hours. With iodine the products were iodide of cyanogen potassium iodide, potassium superferricyanide and prussian (?) blue ; with bromine, bromides of cyanogen potassium bromide and a much larger quan-tity of the blue substance were formed but no trace of potassium superferricyanide could be discovered the action of the bromine being much more energetic than that of iodine. Blue compounds formed in reactions similar to this are generally vaguely described as prussian blue (as for example that formed by the continued action of chlorine On Pelouze's green).As no analyses of such compounds have been made I prepared a larger quantity by heating the mixture over steam in a flask connected with a reflux condenser as it was fonnd that the reaction went just as well as in sealed tubes. According to the proportion of bromine used and the time that the action was allowed to continue different results were obtained as follows :-I. When the potassium ferricyanide was in excess a blue com-pound was obtained not unlike Turnbull's blue in properties. 11. When bromine was in excess and the action was continued for a long time the blue substance obtained resembled prussian blue rather t.han Turnbull's blue.111. When bromine was in excess and the action was allowed t o proceed moderately and not continued too long a black substance was formed as already mentioned which proved to be a cyanide of iron. Analyses were made of these three products. The product obtained in reaction I was thrown on t o a filter then treated with dilute hydrochloric acid to free it from any hydrate or oxide of iron which it might contain and again thoroughly washed dried at loo" and analysed. The numbers obtained were as follows :-0.3137 gram gave 0.2318 gram CO, 0-2837 , 0.1560 , Fe20 = 38.49 , Fe. = 20.15 per cent. C. This gave the ratio of Fe to C as 1.91 1 a proportion somewha ON POTASSIUM FERRICYANIDE. 769 greater than it would have been had the substance been washed with cold water and dried at the ordinary temperature as during the drying at 100" there was a slight evolution of hydrocyanic acid.This would not however make any great difference and it was evident that the proportion of iron to carbon in this substance (which seemed homogeneous) was intermediate between that in prussian blue and Turnbull's blue respectively although nearer the latter. The product from I1 was treated in the same manner except that i t was dried at the ordinary temperature. Analysis gave the follow-ing results :-0.3225 gram gave 0.2401 gram C02 = 20.30 per cent. C. 0.2506 , 0.1853 , CO = 20.16 ,, 0.6028 , 0.3155 , Fe,O = 36.63 , Fe. This gives the ratio of Fe to C as 1.81 1 exactly that required for prussian blue Fe,CylB. It was in appearance very like pure prussian blue although slightly darker but probably contained also a little unchanged black cyanide of iron and a small quantity of iron oxide (due to washing with hot water).Before giving analyses of the product from 111 it will be advisable to give a more precise account of its production. It was not obtained in sealed tubes except when iodine was used the more energetic action of bromine speedily decomposing it. But when the potassium ferricyanide was heated with bromine in a flask connected with a reflux condenser the action could be moderated and a fair yield of this black cyanide obtained. A good proportion t'o use is 40 grams of bromine to 20 grams of potassium ferricyanide (a satu-rated solution may be taken) and to maintain the mixture at gentle ebullition for five or six hours.The flask containing the bromine and ferricyanide solution is connected with a reflux condenser the tube of which is of such a size that it fits accurately into the neck of the flask because as the action of the bromine has to be continued for a considerable time nothing in the form of a cork can be made use of. The junction of the tube of the condenser and the neck of the flask may be surrounded with caoutchouc tubing taking care that they fit sufficiently closely to prevent any of the caoutchouc which may be acted upon by the vapour of the bromine from falling info the flask (a better plan is to seal the inner tube of the condenser on to the neck of the flask). The substance so formed was treated with dilute hydrochloric acid, thoroughly washed and dried over sulphuric acid in a vacuum.It is advisable to wash with cold water as although the compound is com-paratively stable hot water seems to separate out a little oxide of iron and t o cause a transformation (though very slowly) into VOL. LIlI. 3 770 REYNOLDS THE ACTION OF BROMINE prussian blue. The separation of oxide of iron would appear from the fact that in testing the filtrate to see whether the washing was sufficiently complete no trace of i r m could be found in it yet after evaporating some of it to dryness over steam there was a separation of iron oxide. This could only arise from the water dissolving a small portion of the black substance which was thus decomposed on evaporation; hence the washing with hot water would probably decompose the substance although only to a very slight extent so slight that hydrocyanic acid is not always detected.For a similar reason that is a slight evolution of cyanogen it should not be dried at an elevated temperature but over sulphuric acid in a vacuum. The analyses were made as follows :-The carbon was estimated in the usual manner and the fixed residue after combustion was dis-solved in concentrated hydrochloric acid (with a little nitric acid), and then precipitated by ammonia. I n such a compound as this black cyanide it is highly important that the fixed residue should not be regarded as ferric oxide (as has often been erroneously done), because as I have pointed out in a previous paper the error may be considerable and in this particular case might very nearly amount to the difference between prussian blue and this black cyanide.In these analyses no estimation has been given of the nitrogen as it was evident from the method of formation of this substance and its decomposition by potash that it was a cyanide ; but as the analyses of M. J. A. Muller (Conzpt. rend. 104 934) had shown that the group CO occurred in some double cyanides I afterwards made several nitrogen determinations which showed that the nitrogen was combined very nearly in the form of cyanogen. It was however, remarkable that the proportion of nitrogen was always rather too low but the deficiency was too small to allow of its expression by means of formulae. The results of the analyses were as follows:-[O-3569 gram gave 0.2458 gram COz p-8278 , 0.3965 , Fe203 = 33.51 ,, 11.{ 0.8463 , 0.4323 , Fe203 = 35.76 ,, = 18.78 per cent. C. I. < 0.7352 , 0.3518 , Fe203 = 33.50 )) Fe. I 0.3783 , 0.2608 , COZ = 18.80 ,, This gives the ratio of Fe to C aa 1.78 1. 0.4455 gram gave 0.3379 gram COz = 20.69 per cent. C. This gives the ratio of Fe to C as 1.73 1. 0.3973 gram gave 0.3083 gi-ani COz 0.8217 , 0.4353 ,) FezOs = 37.08 , Fe. 1.0627 , 0.5638 ) Fe203 = 37-14! ,, This gives the ratio of Fe t o C as 1.75 1. = 31-16 per cent. C. I ?I ON POTASSIUM FERRICYAXIDE. 771 (0.3415 gram gave 0.2509 gram C02 I 0.6902 , 0.3485 , Fe203 = 35.34 , Pe. IV* 5 It was to I all appearance the purest specimen-appearing as a per-[ fectly black powder even when in the finest state of division, = 20.04 per cent.C. 0.3487 , 0.2570 , CO = 20.10 ,, This gives the ratio of Fe to C as 1.76 1. 0.4392 gram gave 0.3351 gram CO, 0.8804 , 0.4500 , Fe20 = 35-78 , Fe. This gives the ratio of Fe to C as 1-71 1. = 20.88 per cent. C. The mean of the above analyses gives the ratio of Fe to C a8 1-75 1 which is exactly the proportion required for the formula Fe3Cys. This formula does not include water as none of the speci-mens analysed were in comparable states. A specimen apparently dried as completely as possible over sulphuric acid gave numbers very nearly corresponding with the formula Fe3Cy,,4H,0 thus :-0.4218 gram gave 0.3338 gram CO = 21.58 per cent. C, 0.4545 gram gave 0.3592 , GOz = 21.55 , C, and0.0738 l HzO = 17.49 ,l H,O.and 0.0736 , H20 = 16.19 , H,O. The formula requires 21.43 per cent. C and 16.07 per cent. H,O. Properties and Reactions of the Compound. Its properties and behaviour with reagents generally resemble those of prussinn blue but it is more stable It is a semicrystalline powder, hard and brittle of a jet-black lustre and conchoidal fracture. The change in colour with cyanides of iron with the increase in cyanogen is isather curious thus we have-Ferrous cyanide (not isolated) FeCy, white. Turnbull’s blue Fe5CyI2 a fine blue but not dark. Prussian blue Fe7Cy18 a dark blue. Black cyanide of iron Fe,Cy, black. It is hygroscopic but not so much so as prussian blue. It is decomposed by potash into ferric hydrate and potassium ferro-cyanide and ferricyanide.We should expect that the reaction would be according to the equation-6Fe3Cye + 30KHO = 5Fe2(OH) + S-K8Fe2Cy, + K6Fe2CyI2, but the proportion of ferric hydrate separated is rather greater than this equation shows. Thus from a sample of the product from (11) when simply decomposed by potash without heating 19.76 per cent. Fe 3 ~ 7 72 REYNOLDS THE ACTION OF BROMINE separated ; when boiled with potash 20.70 per cent. Fe separated out of a total of 33.51 per cent. Fe. This greater proportion might arise from some having been already separated and partly from the fei-ri-cyanide formed being further decomposed which according t o Skraup takes place in accordance with the equation-3Fe2CylaK8 + 10KOH = 2FeaCy12K8 + Fe2(0H) + 1OCyK + 2CyOK + 2HzO. The decomposition by potash was precisely similar to that observed by Williamson on the green compound obtained by him by the con-tinued action of oxidising agents on the ferricyanide of iron and potassium namely first a separation of ferric hydrate and a brown liquid (containing potassium ferrocyanide and ferricyanide) which on boiling further deposited ferric hydrate.Hence the discrepancy in the two results given above (1 per cent.). After long-continued digestion concentrated hydrochloric acid dissolves it completely yielding a mixture of ferrous and ferric chlorides. Even the strongest nitric acid has very little effect but when digested with it for a long time it gradually decomposes it by oxidation. On the addition of cold concentrated sulphuric acid it is converted into a white pasty mass which would appear t o be the same product as that formed when prussian blue is treated in a similar way for when water is added to this a blue substance is formed.When boiled with excess of strong snlphuric acid it dis-solves entirely but a blue substauce is precipitated on adding water. Chlorine and bromine gradually decompose it yielding prnssian blue. By the prolonged action of tho air its colour changes to a dull blue, the substance being apparently transformed into prussian blue. It' map at first seem anomalous that both this black cyanide and Turn-bull's blue should be transformed on exposure to the air into prussian blue which is intermediate in composition between the two. But whereas in the latter case it is a process of oxidation in the former it appears to be due to the presence of moisture as if kept in a dry place it remains unchanged for st very long time.The reaction is probably as follows :-3Fe3Cye + 6H20 = Fe2(0H) + Fe,Cy, (prussian blue) + GHCy, whereas in the case of Turnbull's blue it is-6Fe5Cyl2 + 3 0 = 4Fe7Cy, + Fe203. When heated it gives off cyanogen and in presence of moistur ON POTASSIUM FERRICYANIDE. 773 hydrocyanic acid and ammonia forming ammonium cyanide. When heated more strongly in air it burns and leaves oxide of iron. Is this compound to be regarded as ferrosoferric ferricyanide, Fe1’3Fe’’’2(Fe2Cy12)2 or as a cyanide of iron similar to the magnetic oxide viz. Pe2CI,,FeCl2? The method of its formation does not afford us much assistance in answering this question as it consists essentially in the abstraction of potassium by the bromine.The whole molecule of the potassium ferricyanide is split up ferric bromide is formed which acting on the undecomposed ferricyanide might give ferric cyanide FeCy3. But the Fe atom would seem under ordinary conditions incapable of holding three cyanogen-atoms, and hence is immediately decomposed into a stable cyanide (ap-parently the most stable of the cyanides of iron) namely Fe3Cy8. Wyrouboff does indeed claim to have obtained the compound FeCyy, but has not published his analyses; and he gives the following equation to explain the reaction -2CysFeK4 + 8NH4C1 + Aq = 6CyNH4 + Cy6Fe2,3H,0 + 8KC1 + 2NHa (Ann. Chem. Phys. 47 16 284) in which NH4 stands by itself which is absurd.Endeavours to obtain this ferric cyanide FeCy, were not successful. Attempts to determine whether the view taken above of the method of formation of the black cyanide was correct (namely, the action of bromine on ferricyanide) did not meet with success. The plan adopted was by acting with bromine 011 the substance pro-duced by the action of ferric chloride in excess on potassium ferri-cyanide. Prussian blue was formed after some time but at no stage could the formation of the black cyanide be observed. The nature of the decomposition of the black cyanide by potash strongly favours the view that it is a ferrosoferric ferricyanide. This same view is also supported by the results of some analyses I made of the compound before I was aware that potassium was not one of its constituents. Thus one analysis showed 6.59 per cent. I(, 34.16 per cent. Fe and 22.83 per cent. C. Here by adding to the iron found the amount of ferrous iron equivalent to the potassium, we get the ratio of Fe C as already found that is 1.75 1 ; and it would thus seem to indicate that the displacement of potassium by ferrous iron (Fe“) takes place in the later stages of the reaction, which is precisely what we should expect

ISSN:0368-1645    

DOI:10.1039/CT8885300767

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

7 74 LXII.-Home Amines and Amides derived from the Nitranilines. By RAPHAEL MELDOLA F.R.S. and E. H. R. SALMON. IN the course of a series of investigations on diazoamido-compounds, by one of the authors and Mr. F. W. St'reatfeild the results of which have been made known to the Chemical Society in former papers the occasion has arisen for preparing a number of new or imperfectly known alkyl-derivatives of the nitranilines and it appeared of suffi-cient interest t o collect together all our results and to place them on record as a contribiition towards the knowledge of substituted ammonias. The question as t o whether there can exist more than one modification of a secondary or tertiary amine or amide has been approached by previous investigators and since the problem was first attacked by Hofmann in 1850 (Artnaleia 74 168) evidence of such isomerism has been obtained by Lossen in his well-known investiga-tions on the derivatives of hydroxylamine (Annalen 175 275 ; ibid., 327 ; 181,388 ; 182,220 ; 186,45 ; Ber.1877 2223). With respect t o the amides derived from aniline the only known case of isomerism is that of dibenzoylanilide which has been obtained in two modifications, one (m. p. 136") obtained by the action of benzoyl chloride on benz-anilide (Gerhardt and Chiozza Compt. r e d 37 go) and the other (m. p. 150") by heating phenylthiocarbimide with benzoic acid (Losanitch Ber. 1873 176). These results were confirmed by Higgin in a paper published by the Society in 1882 (Trans. 1888,132). A study of the amines and amides derived from aromatic monamines by the substitution of various radicles for the amidic hydrogen is, therefore of interest in connection with the general question of chemical isomerism and although we have at present no new evidence on this subject t o bring forward the results recorded in the present paper will furnish materials upon which it is hoped to base a, further series of experiments having for their object the discovery of new cases of isomerism of the kind indicated.The alkyl-nitranilines can be readily prepared in a state of purity by decomposing the alkyl-derivatives of the corresponding diazoamido-compounds by means of hydrochloric acid (Meldola and Streatfeild, Trans. 1887 108). It is only necessary to alkylate the dinitrodiazo-amido-compound by cohobation with alcoholic potash and the iodide or bromide of the alkyl radicle in the usual way and then to heat the alkyldiazoamido-derivative with strong hydrochloric acid till decomposition is complete : AMINEX AND AMIDES DERIVED FROX THE NITRANILINES.775 The acid solution is steam distilled to get rid of the nitrochlor-benzene and after filtration to remove tarry impurities the alkyl-nitraniline is thrown out by alkali. This method offers many advan-tages over the ordinary process of direct alkylation of the nitr-milines in the presence of caustic alkali as the alky 1-derivative has always t o undergo purification in the older method by conversion into the nitrosamine and the decomposition of the latter by cohobation with alcoholic hydrochloric acid is a very lengthened operation.1. Meth yl-paranitraniline. This compound was prepared by the decomposition of the methyl-derivative of paradinitrodiazoamidobenzene, (m. p. 219" ; Trans. 1888 666) by hydrochloric acid in the manner above described. After crystallisation from alcohol the methyl-nitraniline forms thick stumpy prisms of a yellowish- brown colour. If allowed to crystallise rapidly from dilute alcohol it separates in the form of small square tablets which nuder the microscope appear yellow by transmitted light and violet by reflected light. The pure substance melts at 152". It possesses slight basic properties being dissolved by strong hydrochloric acid but the solution becomes yellow and the free base is precipitated on diluting with water.A determination of nitrogen gave the following results :-0.0518 gram burnt in a vacuum with CuO gave 8 C.C. moist N at Calculated for 10.5" and 757 mm. bar. NO2G6H4.NH.CH3. Found. N . . . 18-42 18.37 The base is slightly soluble in hot water; readily soluble in It separates from its aqueous alcohol and the benzene hydrocarbons. solution on cooling in the form of yellow scales. Paranitroph.eny h e t h y lnitrosamine ( p ) N02*C6H4*N( C H&NO. This compound separates as an ochreous flocculent precipitate on adding sodinm nitrite to a solution of methyl-paranitraniline in hydrochloric acid. After crystallisation from dilute alcohol it was obtained in the form of straw-coloured needles and was finally purified by crystallisation from a mixture of benzene and petroleum 7 i 6 MELDOLA AND SALXON SOME AMINES AND AMIDES the pure substance forming hard and thick ochreous scales melting at 100".0.1542 gram burnt in a vacuum with CuO gave 30.4 C.C. moist W at 15.5" and 754 mm. bar. Calculated for C,H;NaO,. Found. N . 23.20 22.84 1Ket~yZacetyl-paranitranilide ( p ) NOz*CsH4*N( CH,). CzH,O. Methyl-paranitraniline was boiled for about half an hour with acetic anhydride and a little anhydrous sodium acetate. The product was washed with cold water and then dissolved in boiling water the solution on cooling depositing the acetyl-derivative in the form of rosettes of fern-like leaflets of a yellowish-white colour. The melting point is 153". When allowed to crystallise slowly from a somewhat dilute aqueous solution the substance forms long straw-coloured, slender needles.The following results were obtained on analysis :-0.1362 gram gave 0.2764 gram C02 and 0.0626 gram H20. 0.1034 gram burnt in a vacuum with CuO gave 13.2 C.C. moist N at 17.3" and 755 mm. bar. Calculated for ~9H10N203. Found. C . 55.67 55.34 H . 5.15 5-10 N . 14.43 14.67 The acetyl-derivative above described having been prepared by the acetylation of methyl-paranitraniline an attempt was made to prepare the same or an isomeric substance by the methylation of acetyl-paraniti-anilide. For this purpose the latter compound was suspended in absolute alcohol in which the theoretical quantity of sodium had been previously dissolved and the necessary quantity of methyl iodide added. The mixture was heated in a flask with reversed condenser for some time and on examining the product it was found that the sodium ekhylate had simply removed the acetyl-group the resulting compound being paranitraniline.Methy Ebenzo y 1-paranitmnilide ( p)N02*CsH4*N( CH,). C,H,O . This compound is easily prepared by heating methyl-paranitraniline for about half an hour with benzoyl chloride or with benzoic anhydride. The product after being washed with warm dilut DERIVED FROM THE NITRANILINES. 777 a,mmonia till free from benzoic acid was crystallised from dilute alcohol and thus obtained in the form of thick brown prisms melting at 111-112". 0.1480 gram burnt with CuO in a vacuum gave 13.6 C.C. N at 19" Calculated for and 770.7 mm. bar. C14H12N903. Found. N .10.94 10.71 The substance is slightly soluble in boiling water the solution depositing whitish glistening rhombohedra on cooling. This benzoyl-derivative is no doiibt identical with that obtained by Hess by the nitration of benzoyl-monomethylaniline (Ber. 1885 686). Attempts have been made to introduce two acid radicles into para-nitraniline but hitherto without success. In the first place benzoyl-paranitranilide was prepared by the action of benzoyl chloride on paranitraniline. The pure compouiid had the melting point 199" ascribed to it by Hubner (AnnuZen 208 292). After boiling for about two hours with acetic anhydride and dry sodium acetate the substance was found to be nnacetylated. In the next place acetyl-paranitranilide was heated with benzoyl chloride in order to ascertain whether acetylbenzoyl-paranitranilide could be prepared by this means but the resulting product was found to be benzoyl-paranitr-anilide the benzoyl simply displacing the acetyl-group.2. Methy 1-metanitraniline. This substance was prepared both by the decomposition of the methyl-derivative of metadinitrodiazoamido- benzene (m. p. 127-128", Trans. 1888 6679 as well as by the action of methyl iodide on meta-nitraniline in the presence of caustic soda (Nolting and Stzicker, Bey. 1886 548). The products were identical and were utilised for the preparation of the following derivatives :-Methy Zacetyl-metanit~niziae (nz)N02-C,H4*N(CH,)~C,H,0. Methyl-metanitraniline was acetylated by means of acetic anhydride in the usual way and the product crystallised from boiling water.It separates on cooling in the form of stellate tufts of thick whitish needles melting at 94-95'. 0.1132 gram burnt in a vacuum with CuO gave 13.9 C.C. N at 17" and 761.4 mm. bar. Calculated for C9H,oN,O3. Found. N . 14.43 14.1 778 MELDOLA AND SALMON SOME ANINES AND AMIDES Methylbenzoyl-iizetanitranilide (in)NOz*C,H4*N(CH3)*C,H50. Prepared by the action of benzoyl chloride on methyl-metani tr-aniline. The substance is soluble in boiling water from which it separates on cooling in beautiful iridescent scales which become silvery-white on drying. 0.1506 gram burnt in a vacuum with CuO gave 14.6 C.C. N at 15" and 763.2 mm. bar. Calculated for The melting point is 104-105". C14H12N203. Found. N . 10.94 11-39 An attempt was made to methylate acetyl-metanitranilide by the action of sodium ethylate and methyl iodide in the usual way but the acetyl-group was simply eliminated and metanitraniline left With reference t o the melting point of acetyl-metanitranilide some discrepancy exists Meyer and Stuber giving 141-143" (Annalen, 165,183) and Kleeman 141" (Ber.1886,337). Our preparation was obtained by the action of acetic anhydride on metanitraniline and after purification by crystallisation from boiling water formed white, stumpy rhomboidal prisms melting at 150-150.5". 3. Ethylnitranilines. Ethyl-paranitraniline was prepared by the decomposition of the corresponding ethylated diazoamido-compound as well as by the action of ethyl bromide on paranitraniline in the presence of caustic potash according to the method of Schweitzer (Ber.1886 149). The nitrosamine (m. p. 119.5") has been described in a former paper (Meldola and Streatfeild Trans. 1886 631). E t hy h e t y I-paranitranilide ( p ) NO,-C,Ht*N (C,H,) C a H 3 0 . Prepared by the action of acetic anhydride and dry sodium acetate After crystallisation from boiling water on ethyl-paranitraniline. the substance forms flat white needles fusing at 118-119". 01240 gram gave 0,2608 gram C02 and 0.0628 gram H,O. 0.1450 gram burnt in a vacuum with CuO gave 16.8 C.C. moist N at 20" and 754.7 mm. bar. Calculated for C10H12 N20 L Found. c . . . . . . . . . . . . . . . 57-69 57.36 H . 5-76 5.62 N . 13.46 13.15 The substance is no doubt identical with that obtained by Weller by the nitration of ethylacetanilide (Ber.1883 31) DERIVED FRO31 THE NITRANILINES. 779 Ethylbenzoyl-parar,itraniZi~e (p)N02*C6H,*N(C2H5)*C~H50. Obtained by the action of benzoyl chloride on ethyl-paranitraniline in the usual way. The substance was purified by crystallisation from dilute alcohol and was obtained in the form of bundles of flat, white needles from 8 to 2 of an inch in length. The melting point is 98". The substance is almost insoluble in hot water but readily soluble in a'lcohol. 0.2006 gram burnt in a vacuum with CuO gave 18.2 C.C. moist N Calculated for at 23" C. and 758.5 inm. bar. C15H1-LN203' Found. N . 10.57 10.20 The acetyl-derivative of ethyl-metanitraniline prepared by direct acetylation fuses at 88-89' (Nolting and S tricker Ber.1886 550). The corresponding benzoyl-derivative is a viscid oil which does not solidify on standing at ordinary temperatures. 4. Benxyliaiti-aiailiIzes. Benzyl-paranitraniline (m. p,. 142-143") obtained by the decom-position of benzylated paradinitrodiazoamidobenzene has been described with its nitrosamine in a previous paper (Trans. 1887,113). A simpler method of preparing this compound is the following :-Paranitraniline is mixed with the theoretical quantity of benzy l chloride end excess of a strong solution of caustic soda added to the contents of the flask. The mixture is kept near the boiling point for about 48 hours the loss of benzyl chloride being prevented by using a reversed condenser. When the benzylation is complete steam is blown through the contents of the flask to remove any excess of benzyl chloride and the product is collected washed with water and then boiled with dilute hydrochloric acid in order to dissolve out any unaltered nitraniline.The crude benzyl- paranitraniline can be purified by crystallisation from glacial acetic acid or from alcohol. Bertzylacetyl-paranitranil~de (p)N02*C6H4*N( C7H7)*C2H30. Prepared by the action of acetic anhydride and dry sodium acetate on the benzyl-derivative. By crystallisation from dilute alcohol the substance was obtained pure in the form of yellowish rhombohedra1 crystals fusing at 108-109". 0.1800 gram burnt in a vacuum with CuO gave 16.2 C.C. moist N Calculated for at 20" and '748.8 mm. bar. 1.5 H14 N 2 0 3 * Found. 10.13 N .. 10.3 780 AMINES AND AMIDES DERIVED FROM THE NITRANILINES. Benzy 1 b enzo y 1 -par anitranil id e ( p ) NO 2* C ,H4*N ( C7 H,) C7H6 0. Prepared by the action of benzoyl chloride on benzyl-paranitr-Crystallised from dilute alcohol it forms long flat whitish 0,1326 gram burnt in a vacuum with CuO gave 9.6 C.C. moist N aniline. needles melting at 194". at 19" (2. and 762.2 mm. bar. Calculated for CSOH16N203. Found. N . 8.43 8.34 Renzyl-metanitraniline (m. p. 107" ; Trans. 1887 114) was pre-pared by the same method as the para-derivative. Both the acetyl-and benzoyl-derivatives are viscid oils which do not solidify on standing a t ordinary temperatures. In the course of the foregoing investigation a few comparative experiments have been made with unsubstituted a,nilides :-5.Action of Benzoyl Chloride on Acetanilicle. The substances were heated together as long as hydrochloric acid was evolved. The product was then washed with water and boiled with dilute ammonia till the benzoic acid was removed. The residue after crystallisation from dilute alcohol formed small white scales melting at 161" and having all the properties of benzanilide :-0.1130 gram gave 0.3270 gram C02 and 0,0546 gram H,O. Calculated for C,H,*NH*C,H,O. Found. C . 79.19 78.92 H . 5.58 5.36 The action of benzoyl chloride is thus simply to replace acetyl by benzoyl. On the other hand benzanilide was boiled with acetic anhydride and dry sodium acetate for two or three hours at the end of which time the product was examined and found to be unaltered benzanilide, no acetylation having taken place. Benzy lacetanilide ie easily prepared by the acetylation of benzyl-aniline with acetic anhydride ; at ordinary temperatures i t is a thick, oily liquid. The same result was obtained with benzoic anhydride. Finsbu y Technical College, July 16th 1888

ISSN:0368-1645    

DOI:10.1039/CT8885300774

出版商:RSC    

年代:1888

数据来源: RSC

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781 LXIII.-Tlle Rotatory Power of Benzene-derivatives. By J. LEWKOWITSCH Ph.D. THE concluding remarks in the paper of F. Herrmann (Berichte 21, 1959) refer t o a subject on which I have been making a few experi-ments. In one of my papers (ibid. 16 1576) I mentioned that if benzene be represented by Ladenburg’s prism symbol an asymmetric carbon-atom may be contained in a tri-derivative in which there are three dissimilar radicles the position of which represented by means of the conventional simple hexagon symbol are 1 2 3 the asym-metric carbon-a#tom being that in the position 5 . Although it is vcry unlikely indeed that such substances would be possessed of rotatory power it is conceivable that they might be resolved into two substances of opposite rotatory power just as 1 succeeded in splitting mandelic acid into two optically active isomer-ides (ibid.16 2721). Through the kindness of Professor 0. Jacobsen I was enabled to examine four benzene-derivatives which seemed to be suitable for my purpose viz. :-1 2 3 /?-Metahoillosalicylic acid CsH,(CH3) (COOH) (OH) .* p-Orthohomometahydroxybenzoic acid C,H,( OH)(CH,) (COOH * Methoxytoluic acid C6H3(OCH3) (CH3) (COOH).t a-Nitro-orthotoluic acid CsH3(N02) (CH,) (COOH).f When examined by the polnriscope they did not exhibit any rotatory power. I tried to split the first three by converting them into their cinchonine salts (comp. malic acid mandelic acid). The cinchonine salts crystallised rery well indeed but the acids thrown down by ammonia from their solutions were optically inactive. The method of splitting by allowing fungi to grow in a solution containing the snbstances to be examined could only be tried with the fourth sub-stance as mere inspection of the formulze would indicate ; but even this substance has such strong antiseptic properties that Penicilliurn glaucwnz did not thrice in its solution. t ibid. 16 1964 1 2 3 1 2 3 I 2 3 J Ber. 16 1963. $ ibid. 16 1958

ISSN:0368-1645    

DOI:10.1039/CT8885300781

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年代:1888

数据来源: RSC

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LXIV.-The Solubility of Isomeric Organic Compounds and of lllixtures the Relatiom of Solubility to of Sodium and Potassium Nitrates, Fusibility. By THCIS. CARNELLEY D.Sc. and ANDREW THOMSON D.Sc. M.A., University College Dundee. NEARLY seven years ago (1881) one of us showed in an opening address given to the Owens College Chemical Society and subse-quently published in the PhilosophicaZ Magazii2e [5] 13 180 that solubility and fusibility were very closely related t o one another so that of two or more isomeric bodies that dissolves the most easily which has the lowest melting point and in which the atomic arrange-ment is the least symmetrical. Very shortly after Dr. Tilden in a paper in the Philosophical Trafisactions 1884 Part I p. 23 also this Journal 45 266 proved that there was a similar connection between the solubility and fusibility of inorganic compounds.At that time the investigation had included only a comparatively small number (58) of compounds taken at random from Watts’s Dictionary of Chemistry and involved no original experiments made with special reference to the subject. We have now extended the investigation so as to include all isomeric sets of carbon compounds whatever. Our data have been obtained partly from literature and partly as the results of our own determinations. Before giving the results of our work it will be necessary to describe the method we have employed for the estimation of the solubilities of any set of isomeric organic compounds and for the other cases referred to in the present paper.For this purpose it WRS absolutely necessary that for each set of isomerides the determinations should be carried out under identically the same conditions and t o attain this we have in all cases made the determinations for the several members of a set of isomerides simultaneously. The results, however are not only strictly comparable but are likewise a8 absolutely correct as we could make them. A set of long (110 mm.) and narrow (14 mm. outside diameter) glass phials accurately stoppered were employed to hold the solvent and various isomerides under investigation. These bottles were about two-thirds filled with the solvent and such a quantity of each of the isomerides respectively as would be more than sufljcient to form a saturated solution at a temperature 10’ above that at which the solubility was to be determined.The stoppers were then firmly inserted and the bottles Gxed in suitable clips attached to an axi THE SOLUBILITY OF ISOMERIC ORGANIC COMPOUNDS. 783 passing through the centre of a bath filled with water and so arranged that the phials were completely immersed. The axis could be kept in regular rotation any length of time by means of a small water motor whilst the bath was maintained at a constant tempera-ture by a thermo-regulator. The following sketch will represent the arrangement. ABCU is a bath made of tin-plate and styanding on a tripod. To the axis E are soldered six bras8 clips by means of which as many bottles may be fixed on the axis at the same time. FF re-presents six such phials containing the solvent and substances under investigation.Six determinations could thus be made simultaneously. GG and H is a pair of pulleys connected by a cord H being fixed on About +th the actual size. the axis of the small water-motor for driving the apparatus. L is the thermo-regulator to be used in connection with the lamp for heating the bath and K the thermometer for indicating the tem-perature. All our determinations contained in the present paper, were made at 20" C. In order therefore to obtain thoroughly saturated solutions the bath was heated to about 30° and the phials kept immersed aud in continual motion for about two hours matters being so arranged that some at least of the compounds remained still undissolved at 30° in order to avoid supersaturation.At the end of that time the lamp was turned out and the bath allowed to cool dow 784 CARSELLEY AND THONSON SOLUBILITY OF to exactly 20" C. the phials being kept in continual motion through-out. After standing for a few minutes so as t o allow the still undissolved portions to settle to the bottom of the phiais a quantity of the saturated liquid from each was withdrawn into a small tared glass bottle and weighed. This gave the weight of the solvent and substance dissolved. To determine the quantity of the latter the solution was evaporated to dryness and the residue weighed. If however the substance was volatile when evaporated this method could not be employed and in some cases very great dificulty has been experienced in making an exact deter-mination.But when the compound was coloured the quantity in solution coiild be easily estimated colorimetrically by titrating it against a standard solution of the same substance in the same solvent. In the case of acids or alkalis also the amount could be determined by means of a standard acid or alkali certain modifications however, being necessary in the presence of some of the solvents. The differ-ence between the total weight of the solution and that of the sub-stance dissolved gave the weight of the solvent which had been required to dissolve that weight of substance at ihe given temperature. By the above method results are obtained which are strictly com-parable because each set & isonerides can be worked simultaneously, whilst complete saturation is ensured and supersaturation avoided.Special tests made for the purpose showed that the phials were thoroughly tight at the stoppers even when such a volatile solvent as ether was employed. Altogether we have found the arrangement to answer admirably. This usually took about two hours. I. ( a . ) Determination of the Solubilities of 1 3 and 1 4 Nitrawiliiies (m. p. 114" and 147"). The qunnt'ity of these compounds dissolved by a given solvent could not be determined by evaporating a weighed quantity of the saturated solution to dryness on the water-bath as both of them werc slightly volatile under these circumstances. Thus 0.7015 gram of the 1.3 compound after solution in water and evaporation to dryness, weighed only 0.6280 gram or had lost nearly 15.0 per cent.in weight, while the 1*4-compound though not nearly so volatile still suffered a perceptible loss. Therefore as both met%- and para-nitraniline form coloured solutions the quantity of these compounds dissolved by a given solvent was estimated colorimetrically by titration against a standard solution of the nitraniline in the solvent under investigation. That this method gives good results was shown by the following test determinations of the nitraniline dissolved in solutions containing known quantities : ISOMERIC ORGANIC COMPOUNDS. i 8 5 Weight of nitrani- Weight found by line taken. experiment. Experiment I 0,0162 gram 0.0165 gram. . 9 11. 0.0030 , 0-0029 ,, 9 111 0-0075 , 0.0075 ,, IV 0.0099 , 0~0100 , 9 , As the colour of the solution pales somewhat when kept for more than a day especially on exposure to light it is necessary that the determinations should be made as soon as possible and that the standards should be freshly prepared.By the above method we have determined the solubility of the meta- and para-nitranilines in 13 different solvents with the results given in Table I p. 786. All the determinations refer to 20" C. Column I gives the solvent ; Column I1 the modification of nitraniline referred to ; Column 111 the number of the experiment, each of which is the result of an entirely independent determination. The determinations in a given solvent to which the same number is attached were always made simultaneously and in all respects under the same conditions. Column IV gives the weight of the solution taken saturated at 20" C ; Column V the strength of the standard employed ; Column VI the number of C.C.of this standard required to produce a colour in 50 C.C. of the solvent equal to that of tho weight of liquid in Column IV also made up to 50 C.C. ; Column VII the solubility represented in parts by weight dissolved in 100 parts by weight of the solvent ; and Column VIII the meau of the results in Column VIT. ( b . ) Determination o f the Solubility of Mixtures of Xodium and Potassium Nitrates in Water. The resnlts were obtained with the apparatus above described and in the manner already detailed except that the mixed salts were exposed to the action of the solvent for four instead of two hours. Those experiments to which the same number is attached were made simultaneously.The composition of the dissolved portion of the mixed salts was ascertained :-(a.) By finding the weight of mixed sulphates obtained from a known weight of the mixed nitrate residue left on evaporating the several saturated solutions to dryness ; (b.) By determining the melting and solidifying points of the several mixed nitrate residues. R,eference to the curves in Diagram I then gave the composition corresponding to a given melting or solidifying point. The melting and solidifying points of the original mixtures before solution and of the dissolved portion after solution and evaporation, (See Table 11 p. 789.) VOL. LIII. 3 TABLE I. I. Solrent. --Water H20 . . . . . . , -___.-Methyl alcohol CH,.OH'.. -Ethyl alcohol C,H,.OH . . Propyl alcohol C,H,.OII. , 11. hbstance :-Nitraniliii e. --meta 7 J J J 9 9 para ) J 9 9 7 1 meta pars J ) J J meta J J ) J para J J J 1 111. No. of experiment. --1 2 3 4 1 2 3 4 1 2 1 2 1 2 3 1 2 3 1 2 1 2 ----IV. Weight of solu-tion taken, saturated at 2c)" c. 4 -839 4 *716 3 -605 5 *022 4 -859 4 *S70 4 *521 4.959 2.592 2.412 2.522 2 '069 2 *393 2 -566 2.595 3 *929 2 -540 2 -388 2 '472 2 -662 2 -795 2 -840 ~ v. 1 C.C. of standard solution con-tained of nitraniline. ~ gram. 0.00081 0 *00068 0 *00098 0 * 00098 0 *00080 0.00114 0 *00062 0 *00062 0 *02208 0 *01585 0 -02789 0 -01338 --0 *0220 T A 13 L E I-con t inucd.I. Solvent. Isoarnyl alcohol CJ11~*OII Ethyl Ether (C2H,)J0 . . -Benzene CGHG . . . * . . . I w *---KJ Toluene C7Hs . . I . . . . . . . 11. Substance :-Nitraniline. --ineta para 9 , 9 -mela para ,> >> -me ta para 9 ) 9 , meta para 9 9 9 -me ta para 9 , ;> 111. No. of experiment. --1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 2 -_ _ . ~ --IV. Weight of solu-tion taken, saturated at 2OC c. 2.685 2 '378 2,414 2.288 ~ 3,399 2 *715 3 '059 2 -680 2 *426 2 *606 2 -930 2.365 2 *705 3 -726 2.413 3 *700 3 -052 3 -212 2 962 3 *417 v. 1 C.C. of standurd solution con-tained of nit raniline.gram. 0 * 02000 0 *di356 9 , 0.01587 0 -$1278 I > 0 *015'76 0 *do698 0 '01576 0 &698 > > I__-$ TABLE I-continued. 11. Substance:-Nitraniline. -meta para 39 Y Y meta para 9 , IIT. IV. v. experiment. saturated at tained of 20° c. nitraniline. gram. Weight of solu- 1 C.C. of standard No. of tiou taken solution con------1 3.119 0 *01660 2 3 -086 2 3,120 39 1 5 -487 0 -01660 2 3 * 846 1 3 -520 0- 6i 158 --------1 4 *329 O.d)1158 I. Sol \-en t. 2 1 2 1 2 Cumene C,H, ,, 4.790 9 9 ___-____- ---5 *178 0.01660 5 -992 4 '878 0&15S 3 *450 9 , -_e__--Chlorsform CHCI,. . . . . . , Carbon tetrachloride CCI,. --Carbon disulpliide CS2.1 2 1 2 4 -854 0 -01660 5.138 2.906 0 *di158 3 '416 Y9 meta para 9 ) 9 I. No. of experi-ment. 11. Composition of mixed salts sub-mitted to the action of the solvent. 1x1. Weight of solu-tion taken saturated at 20". IT. Weight of residue obtained. 1 4 2 *372 3.037 5 '036 6 *614 1 2 4 '509 4 -807 4.407 9 * 6005 8 *083 5.778 4.543 6 -019 3 -351 2 *817 -----2 *339 2 -537 1 3 4 5 ~ ~~ SO p. c. NaN03 + 20 p. c. KNO, 9 9 7 7 9 9 9 7 7 7 7 7 7 7 17 1 9 2 -523 5 *566 4 *629 3 -353 2 '574 3 *5095 1.939 1.635 2,868 3 *268 2.530 2 -001 2 *254 ~ ----1 3 4 5 70 p. c. NaNO + 30 1). c. KNO, 11 9s 91 9 91 9 9 97 9 7 9 9 1 3 4 GO p.c . NaNO,+tEO p. c. KNO, Y t 19 9 9 9 9 7 9 9 ) ~ ~~ 4 *978 5 a 573 4 '354 3.898 4.364 --1 2 ~~ 50 p. c. NaN03+ 59 p. c . KNO, 9 9 9 9 9 9 1 2 45-7 p. c. NaNO + 54.3 p.c. KXO, = molecular proportions 2) 79 9 7 5.727 4 -167 2 *669 1 -95 11. I. I No of experi. nzent. Composition of mixed salts sub-niittcd to the action of the solvent. ! I----- --1 2 1 2 103 1'. c. KNO, 7 ) TABLE 11-continzhed. 111. Weight of solu-tion take11 saturated at 20". IT. Weight of residue obtained. I-- --ISOlMERIC ORGANIC COMPOUNDS. 791 were determined in the ordinary way by heating small quantities of the substance in somewhat large capillary glass tubes attached to a thermometer immersed in a bath of strong sulphuric acid.I n the case of the pure nitrates for which an ordinary thermometer cannot well be used the specific heat method formerly described (this Journal, 29 489) by one of us was employed. The results obtained are given in Table I11 (p. 792). The relation between the composition of various mixtures of sodium and potassium nitrates and the corresponding melting or solidifying points is shown in Diagram I the thick broken curve being for the melting points and the thin broken curve for the solidifying points. By reference to these curves the composition of any mixture of the nitrates may be determined approximately if the melting o r solidifying point of the mixture be known. The form of the curves however, shows that in nearly all cases there are two different mixtures which hare the same melting and solidifying points while mixtures contain-ing from 40 to 50 per cent.of NaNO all have the same melting and solidifying points these points not being affected by alterations in composition between those limits. 11. .Eelation of t h e Solubility to the Fusiliility of Isomeric Organic Co Ynp ou nds. Raoult Pictet has shown (Compt. Yettd. 88 S55) j i r s t that the lower the melting point of a solid the longer are the oscilletions of its molecules ; and second that the melting poifits of solids correspond to equal lengths of oscillation so that t x zv = c where f is the melting point measured from the absolute zero zu the length of oscillation and c a constant. Of two isomeric bodies therefore the one with the lower melting point mill at any given temperature below the melting point have its molecules moving with oscillations of greater amplitude than the one with the higher melting point.The molecular weights being equal, the force of restitution will be less in the case of the more fusible compound and hence its molecules will be in a less stable condition, and be the more readily separated from their fellows than those of the less fusible compound. Now in order that a solid may dissolve in any liquid it is necessary that its molecules should undergo a sort of unloosening process and we should therefore conclude that of two isomeric compounds that wonld dissolve the more easily in which the attraction or the force of restitution to the mean position of oscilla-tion was the least i e .the one which is the more easily fusible. This argument shows :-Rule (1.) That for any series of isomeric organic compounds the orde TABLE 111 Per cent. NaNO in original mixture before solution. --100 90 80 70 60 50 45 *7 40 30 20 10 0 Mixed nitrates before solution. Uncorrected. Melting point. 303" 288 274 260 238 225 225 225 235 27 5 29 5 -3olidify ing point. --286 266 255 23 0 220 220 219 230 275 290 -Corrected. Melting point. 316t 298 283 268 242 231 23 1 231 242 284 306 339:: Solidifying point. --296 275 263 237 226 226 226 237 284 300 -Mixed nitrates after solution and evaporation to dryness.Uncorrcct.ed. Helting poiii t. 303 284 259 250 241 235 231 225 269 --I Jolidifying point. ---282 255 2 45 236 230 226 221 266 ---Corrected. Melting point, L 316 294 267 256 247 242 838 231 278 339 --golidifyin! point. ---292 263 251 242 237 233 227 275 ---* By t8herniometer. t Bv specific heat method or 319" bv thermometer. 8 I n taking thesc averages no greater &;gllt has been given' to the reiults from analysis solidifying points because the method of analysis employed does not admit of very great exactness, of mixed sulphates obtaincd makes a rather large error in the final result. Note.-M. p. of pure Itu'aNO = 3L43 (Braun po*qLq. Ann. 154 190) ; = 310" (Person, (Carnelley Jour.Chem. Xoc. 33 276). (Brann Zoc. cit.) ; 339" (Carnclley Zoc. cit.) ; 339" (Person Zoc. cit.). S. p. of puye KNO, (Phil. Afczg. [ S ] 18,114). Sclisffgotscli (Pogg. Ann. 102 293) gives the following as the sodium and potassium nitrates :-I00 per cent. NaNO = 313" ; 90 per cent. = 298"; 80 per cent. = 244"; EO per cent. = 229"; 45.7 per cent. (molec. proportion) = 225.6"; 40 per cent. = 280"; 10 per cent. = 311"; pure KNO = 335'3". 5 . p of pure NaRTOJ = 295" (Maurnen& Compt TABLE IV. Order of solubility. 1 2 2 4 One part dissolved by parts solvent. --___--- --1 2 1 2 1 2 3 4 39 water at 100" 155 I J ----692 water at 19' 3500 , 17 -__----- - -1 2 3 1 1 1 2 3 4 1 2 20 water at 18' 49 , 14.5' -__----.-- - - -- -----4'5 alcohol at 20° 26'7 1J 11 -a06 245 158 226 165 179 189 --, i Formula. Subst,ance. Constitution. Solvents. Authority. ---Dinaphthyl Dinaphthyl . Phenylanthraceno . Dinaphthyl 76' 154 152 187 94 192 61 82 131 51 130 180 -----a ; p p ; p a ; a -Smith Chem. SOC. Jouc. 32 562. Schellinger A&alen $02 61. Smith Chem. Soc. Jour. 32 562. Zincke Ber. 10 999. Xigatti Gazzetta 11 357. Guareachi 1 1 Annalen 222 262. 5, -____--9 9 1 ~___-___--J I , p3tilbene dichloride. a- J) . Dibromonaphthalene . 11 , Ph*C,H,Cl,*Ph . ,> . 1 all proportions in alcohol 10 of alcohol alcohol ,, ~~ ~ CloH,Br2.. alcohol 9 % 9 - -I--I- -water alcohol ether water water alcohol ether 2 1 16-5 alcohol at 56" 3 50.0 C,H60 Dimethyloxalate Isosuccinic acid . Succinic acid . (COZCHJ2 . COZH'CH (CH,) . CO,H. C02H.(CH2)2*COZH . Watts' Dict. 4 272. Wichelhaus 2eit.f. Ch. (2) 3 247. 5.5 cold water I 20'0 ) I I J, ---_.--Watts' Uict. 5 353 ; 7,1093. , 5 1091. , 3 823. , 2 349. Sorbitol . Isodulcitol . Mannitol Dulcitol 110 110d 162 182 1 1 0.6 water water ; alcohol 2, 1 , ,9 --water alcohol ether chloroform ,, 1 9 ,I 4 - I 2'1 >> 6'5 21 31.0 ), -_I-_.-_ 1500 water at 25" - -2600 water at 25" __ --~--CO,H OH COH = 1 . 2 3 . J I = 1 3 4 . $1 = 1:4:5 . I = 1 2 5 . . . . . . . . . -_.__--C8H604 .166 234 244 . 249 207 250 106 133 141 217 261 278 82 118 199 67 81 103 156 176 192 59 114 68 125 --------__ --Aldehydohydroxybenzoic acid. I ,, ,J 9 9 . ,J ,J . . 4 Tiemann Ber. 10 1562. , Ber. 12 1334. , Ber. 9 1268. , Ber. 10 1562. Matsmoto Ber. 11 122. Watts' Dict. 6 249. Schall Ber. 12 829. I h i d . ; Patern? Gazzetta 9 485. Watts' Dict. 6 715. , 6 249. Jacobsen Ber. 12 434. Schall Ber. 12 825. Gekhten B:raJ 11 1587. Schall Ber. 12 825. Swarts Be?. 15 1662. Perkin Chem. SOC. Jour. 39,426. _. -, 1 -_ -9 J J ~-2 9 I , ,J ,I --~ , J, 3 J > ---1 J, -_I__.__-,J ,J ,J water ,, CO,H OH OMe = 1 4 5 . . . . , , = 1 3 4 . -- -Ph.C(C02TI):CH .Ph.CH:CH*CO,H --~--(CO,H) :OMe = 1 2 4 , = 1:3:2 1 = 1:3:4 , = 1 4 5 . . Methoxyhydroxybenzoic acid . I I . 1 I. .~. 1 Lry.u -;id Cinnamic acid Methoxyphthalic acid Methoxyisophthalic acid . Metboxyterephthalic acid. _- ---,J ,> . CyHsOd . C,E<c!' ;. . . . . . . ----CgHsO water ,) water ether 2, I 9 , Hydrocoumaric acid Tropic acid. Hydroxyxylic acid -______-__---Dfelhoxytoluic acid . , I 1 1 I OH (CH~QCH~GO~H) = 1 2. e . . . HO*CH,*CHPh*COzH. Me,:OH:CO,H = 1 2 4 5 . . . . . . . . OMe :Me COzH = 1 :4 6 I1 = 1:2:6 2 = 1:3:6 I = 1 2 5 . . I = 1 3 4 . . = 1 2 4 -___ -----__- - -vater ,, > J -C,HI0O3 . water I I I J , ~ ~~ a-Dibromocamphor 8-Methyl-p-methoxyphenyldibromopropionate .XethJ-1-a-methoxyphonyldibromopropionate . . . ,> . -----~-alcohol ,, MeO~C6H,.C2H,Br,*C02Me = 1 2,. . I 9 = 1 2 . . , carbon disulphide; alcohol I 3 Dinitrobenzene . I I . (KO,) = 1 3 , - - 1 a )) = 1 4 90 118 172 16'9 alcohol at 24%' 26'3 , 24.8 1 - 3 __---_I_-alcohol chloroform ether benzene water ,? ,, Kiirner Gazzetta 4 305. Rinne Ber. 7 869. 2 2 Dabney Amer. Chem. J. 5 20. 9 ,> --> I , ,, I 9 ) ,, ~ ~~~~ Amidodinitrophenol . 1 ) 9 , . . ---- --Amidocaproic acid . > . water; alcohol ,) ,> OH:KH* (NO,),= l 2 4 6 + - . a s . -I = 1 4 2 6 . NH (SOz) = consec . 714 water at 22' 1 2 C6H1302N water 3 Kencki Watts' Dict.J. pr. 3 Chem. 581. [21J 15 390 27 cold water 2 43% water a t 14'5' 170 ubl. 210 120 151 140 147 238 86 116 ___--_. -___ NH2*CO*NH.CH2*Bu. . KH,*CO.NH*CHhfePr ------Watts' Diet. 6 1116. ?Yatts' Dict. 1 555. , 6 314. J J , ~ - -, 7 947. Amylcarbamide . Nitrobenzoic acid 1 . -- --_- I 3 1 28 water at 27" 79'3 , I _ _ - ~ - _ _ _ _ ,i COzH NO2 = 1 3 . , = l 2 . I ' = 1 4 . . . 400 water at 10' 2' I 400 , 22 3 1327 , 16 ~~ ORfe (NO,) = 1 2 4 . . , = 1 2 6 -_. __-alcohol Sillliowski Ber. 7 370. I , DinitranisoPl . Ethamidobenzoic acid . Phenyl-P-amidopropionic acid Phenyl-a-amidopropionic acid x-Amidohydratropic acid . Phenylmethamidoacetic acid x-DinitrodesoxybenzoYn 3- 3inchonidine .hchonine . o . e . . , . - - - - ~ - ~ _ _ ---- ~ - _ _ -J ---________-- ---,> - -alcohol ,> ,> t ,, S H E t C02H = 1 3 Ph*CH(NH2).CH2.CO$I. Ph*CHZ.CH( NHB)*COgH . . . . . . . . . . . . CH,*CPh(NB2)*C02H . NHMeGHPh.C02H Griess Ber. 5 1038. Posen Annalen 195 143. Schulze Bw. 14 1785. Tiemann Ber. 14 1976. , Ber. 14 1982. Golubeff Bull. SOC. Chim. [2] 34 345. Hesse Watts' Dict. 6 463. Ebert Ber. 9 598. 9 9 9 51 > ), 11 I alcohol I ---ether J, 1 76.4 ether a t loo 1 2118'0 , at 17 2 CloH,C1,0,S2 a-Naphthalenedisulphonyl chloride I P- I ,? 31,H,(SO,Cl) Me C1 NH = 1 4 . ?. . = 1 . 4 ?. . - 1:3:4. . $1 -L_____--9 , 1 7.5 benzene at 14' 2 1 221'o > J > J benzene and other solvents 9 , --I-- - ~~~~ 19'9 water at 17" 35.5 3 38'5 wad'r at ih0 Wroblewsky Annalen 168 147.91 ,I >, 9 I 1 ,J C7HgC1O3N, . Chlorotoluidine nitrate. . ISOMERIC ORGANIC COMPOUXDS. 793 01 sdubility is the same as the order of fusibilitly i.e. the most fusible compound is likewise the most soluble. In order to test this rule we have collected from literature all the statements which have been made as regards the solubility of isomeric compounds (a task which has involved a very large amount of labour and time) and we have found as follows :-Out of 752 cases in which the rule can be applied there are 736 in which the order of fusibility and of solubility is the same and only 16 exceptions (= 2 per cent.) in which the more fusible compound is the less soluble.This is with reierence to one solvent in each case whereas by taking all the solvents into account which bave been tried we have found that out of 1778 cases in which the rule can be applied there were 1755 which agreed with the rule and only 23 exceptions (= 1) per cent.). The following may be taken as examples (see Table IV). This table shows with what 8 great variety of compounds the rule holds good. Not only do compounds haviiig a similar constitution obey the rule but compounds likewise which have nothing in common but their isomerism. The application of the rule however does not stop here for we find that-Rule (2). In any series of isomeric acids n o t only i s the order of solubility of the acids themselves t h e same as the order of fusibility bqd the same order of solubility eztends to all the salts of the several acids, so that the salts of the more soluble a d more fusible acids are also more ensilly soluble than the correspondiny salts of the less fusible aud less soluble acids.We have been able to apply this rule in 143 cases of which 138 agree with the rule so that there are only five exceptions or about 3+ per cent. The following may be given as examples* (see Table V p. 794). The above is probably but part of a very general law viz. that the properties of the corresponding derivatives of two or more isomeric compounds arc related to one another in the same way as those of the primitive is0 mers themselves. Discussion o f Exceptions.-As we have already seen there are only 28 exceptions out of 1921 cases in which we can apply the rule as to the order of solubility of a series of isomers being the same as the order of fusibility.A list of these exceptions is given in Table VI. In this table the statements as to the solubilities are as nearly as possible verbatim with those given in the original papers. Of the above 28 exceptions 12 (viz. Nos. 1 2 3 4 5 6 7 12 13, 14 20 and 21) or nearly one-half refer to only five sets of isomerides. * In some instances the melthg points of the acids are not known in which case we have given those of the corresponding acid chlorides or amides instead CARNELLE'Y AND THOMSON SOLUBILITY 3F - I I . . . . ,. ^ . . 0 u5 u - d 0 3 0 0 0 W 4 I 0 * u -0 0 hl a'.d d I / d h l __ On5 a m dd __ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . x 6 u h? % u" ___ . . . . . . f . . . . . . . . * . . . . . . 0 U 0 5 - A - - ; ++ d c uu ~ - . . . . . . . . - - . . . . . . . . . . . . . . . . . - . . . - - -__ . . - . . . . . O . - -+ & u 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . -m m U O w "1 x-'$ Fs 00 u;l' V Y u u z"k A d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . - . . - . . .& c; ** . . . . . . m m m rid4 I1 I/ II 0 G E r:: 6 u . . . . . . * . . . . . . . . . . . . . . . 0 . . . . - . . . . . . n . . -__ ~ ~ . . . . . . . . . . I . . . . . . . . . . . . . . . . . . . . .Ccm . . . . . . . . . . . . . . . . . . . . . . . . - ~~ . . . . . . . . . . + . . . . . . . . . . . . . . . . . . - * - - I e U a FL Salt. K-toluenesulphonatc > > )) 9 ) )) Be- 9 ) ) 9 . . . . . . . . 9) )) Na-Ag-Cn or Pb-sa.lt . !) ) ) . Ba - p - naplitlialenesulpliinic ac1d 3 ) a- > > ) 1 --Constitution. (so,Iq2 = 1 3 ) = 1:4 ,) = 1:3 = 1 4 = 1:3 = 1 4 Me:SO,H= 1 3 . . . = 1 2 . ,) = 1:4 . ~ ~ ~~~ ~~ - ) ) - 1:3 . )) = 1 2 . = 1 4 . )) = 1:3 . ) = 1 z . . . = 1:4. -___-CI(,T-T;.SO;H . M. p. -of chloride 131 63 131 63 131 Qf amide 108" 136 154 108 136 154 103 136 154 of acid 1 0 5 O 63' --------high temp. --Order of solu-bility.1 2 -Formula of acid. M. 11. of amide 150° 217 150 217 150 217 150 217 158 229 158 229 158 229 ------------CgH,,O,SN Order bility of S 1 2 1 2 1 2 1 2 1 2 1 2 1 2 -.-K-naplitlialenesulplionst e . . Ba- 77 7 3 * . 9 ) , * * 1 , a -158 229 of acid 51" 87 263 2 76 -----cu- )) , * * Pb- 9 , * ' >) 7 ' f ,) ) J * ' -K-naphtlialetiedisulpl~onatc . 9 9 9 Ne- , ,7 Ca- 9 Y 9 Ba- or Pb-salt. > 2 9 9 9 ) 9 9 I 2 1 2 1 2 _I-9 . --Ba-cymenesulphonatc ) . . . . . . . . Ba-sulplinmine mesitylenate . l 91 Constitution. --_--a p p p -_-__-a ---_I__-a a p -_I---1L p n p p -_____-__-CI a p -----Me:Pra:SO,H= 1 4 2 9 = 1 4 3 Me2 (SO,*NH,) C02H = 1 3 4.5 12 = 1 3 2 5 ___--__)-TABLE VI. insoluble in alcohol ether and easily aoluble in alcohol water, water and sparingly in ether Watts' Dict. 7 570 . 2 913. insoluble in water . easily soloble. . sparingly soluble moderately soluhle. extremely soluble -___.-not very soluble in alcohol Osterland Ber. 7 1286 Markownikoff,Annalen 182,62 ,f ,1 ,, _.-- -l'erkin Ch. S O ~ Jour. 30 414 9 , 31 412 , 21 476 267 alcohol at 19' 77 14 1256 19 -- ~ slightly soluble in alcohol. easily , . . . . . . . readily , . . . . . . . -----sparingly soluble in water. Watts' Dict. 8 1157 9 9 9 I 13 --___._ Watts' Dict.6 848 . , . . . . . . . . . . . -_--Lobanoff Ber. 6 1251. 9 9 I . pretty easily soluble in hot distinctly less soluble in hot water water ------Furth Ber. 16 2182 1 9 ~~ slightly soluble in ether . . . . . . . . very 2 - -___-less soluble solvent not,. more } stated --__----Watts' Dict. 6 856 . Wallach Ber. 3 8-1.6 --.--Bechi Ber. 12 321 I [hot water much more easily soluble in ----Ber. 12 604 , ,. Aniw,len 206 167 Ba- and Ca-salts obey the rule. The sym-metry accords a i t h the m. p. but not nitL , { the solubility. Jacobsen -( _-_____ 147 , , . j bilities very close. I From C3HC1Br20 I Ca-P-chlordibromacrylate . , , -a- I 3 CBia2:CC1C02H . . . . . . . . . . . . . . . . . . . CBrCl:CBr.CO,II . . . . . .. . . . . . . . . . . -M. p. -129O 148 -liquid 112O 170 -:onstitution. -Order of solu-bility. 2 1 -3 1 2 2 2 1 2 1 3 --Remarks. Authority. 1 part dissolved by parts solvent. Name. Formula. Three exceptions since they are exceptions as regards all three solvents. The sym-metry accords with tlie m. p. but not with the solubility. Diglycollio acid crystallises with 1 mol. H,O. Would this affect the i solubility ? -- -- -HO*CH,.C'O*O'CH,'C02H + . 1 . O(CH,.CO*OH),. . Blycollic anhydride Diglycollic acid . ----CH,(CO,Me),. CHEt(CO,H) . CMe,(CO,H),. --C5Hs0 . Dimethvl malonate. Dimethylmalonic acid Ethylm"a1onic acid . P-EthoxyphenylacrIlic acid . P-Methoxyphenylcrotonic acid . Butyrocoumaric acid.---PP-Dinaphthylketone aa- 9 , PP- ,, OEt (C*H,*C02H) = 1 2 I . . . , OMe (C,H4.C0,H) = 1 4 . . . . (C,HiO) COgH = 1 2 . -_.__-__-CO(CioH;) 1) , 136 154 174 p.d. 125 135 165 -Cl1H,,O Does the batyrocoumaric acid form a coin-pound with alcohol ? ------The modification melting at 125" is said to be a physical isomeride of that melting a t 165". 8. -CZIHl~O ___-y-Dicyanonaphthalene 8- I ) ) CioH,(CN) , 204 236 2 1 2 1 -}of. Zeitsch. f. Chern. [Z] 5 571. 9. . CIBH6N2 . ~~ ~~~ Iodophenol. I ) . . . . . . . . . . . . . a . ---Iodosalicylic acid. , 0 H I = 1:3 (?) . , = 1:4(?) . CO2H:OH:I = 1:2:5 . , = 1:2:3 . ---_.-.-_.--65 89 197 198 50 63 78 104 161 U.C.181 179 193 -----The symmetry accords with the m. p. but not } with the solubility. } rule. -_.__-_._I___. &I. ps. very close. The Ba-salts obey the 10. I C6H,I01. 2 1 more difficultly soluble in Soc. Jour. 41 404. 9 easily , 9, y -Hy droxyvaleramide a-Methoxybutyramide. . a-Hgdroxyisovaleramide Ethyllactamide . CH3*CH(OB)*(CH2),*CO.SH CH,.CH(OEt).CO.XH CH3CH,.CH (OMe)GO.PI'H . CHMe,CH(OH) CO.NH insoluble in ether soluble in ether . sparingly soluble in ether. , 148 water at 25". . . . . . . . . . . . . . . . . . ---54 . 12 ~ C,H1102N & 13, Neugebauer Annalen 227 97 Duvillier Compt. rend. 88,598 Lipp Annalen 205 1 Watts' Dict. 3 452 . Claus Ber. 13 816 . . . . . . . . . . .. 1 " CO,H (NO,) = 1 3 4 . I = 1:2:4 . -__-CO,H O H (CH:NOH) = 1 2 5 . . , = 1:2:3 Dinitrobenzoic acid --Aldoxime salicylic acid . - ------The 1 .2.5-compound crgstallisea with 1 mol. HzO whereas the other is anhydrous. Was the m. p. determinedwith the former in the anhydrous state ? 2 1 -17. (The symmetry accords with the solubility but not with the m. p. The a-compound contains 2H,O and the P-compound +HzO. 1' Were the m. ps. determined in the anhydrous [ state? (CO,H),:Ilfe:NO = 1:3:5:2 9 = 1:3:5:4 a-Nitrouvitic acid. ,) 9- , 227 250 2 1 -2 1 crystallises first from water . Bottinger Be? 9 806 . second . . . . . 1 ,> . CgH70,X. ---Dinitro-a-naphthol. -B- . --___.-OH (NO,) = ~ i a @ i ; . 1 = p i ? ; p1 .18. -19. 138 197 1 The salts obey the rule. (The symmetry accords with the solubility but 1 not with the m. p. The corresponding imides agree with the rule both as to sym- 1 metry and solubility. Have not the m. pa. got transposed in the original paper ? Me (NH~CO*C,H,~CO~NH,) = 1 4. I = 1:2. 2 1 l'olusuccinamide . . . . . . . . . . . . . . . . . . - -3-Ethgldibenzhydroxamate 3- , 7, 148 160 58 63 -99 104 -263 276 d. of acid 78" 131 251 266 168 192 ----142 169 -99 104 ----_. NBz?EtO. 20 & 21. -22. -23. -24. -25. -26. -27. Cl6HI1O3N,. 2 1 -2 1 (cf. Annalen 175 326). M. ps. very close. These are physical isomerides. Ba-salts obey the rule C a - d t s do not (see No.28) ; m. ps. very close. The symmetry accords with the solubility but not wilh the m. p. , . C3HC1Br,0 I . . . CBr2:C01.C02H . CBrC1:CRr*C02H . 3-Chlordibromacrylic acid. z- , . . . . . . . . . ~-Sulphaminemesitylenic acid . . . 3 . * a . 37'1 water a t 20" Illabery Am. Ch. J. 6 157 . 18'4 , I * * . --__- ----Me COpH (SO,.KH,) = 1 3 5 6. I I = 1:3:5:2. C9HllO4SN . --From C12H120, lmmonium a-hydropiperatc. I P- I ? . , less soluble solvent not Bnri Annulen 216 172 /}The acids obey the rule. more , } stated , ~~ Sa-P-phenanthrenecarboxylate . . From ClsHl0O2 ,. . 2 1 -2 1 I . :a-dibrom~~yromucatc 9 I > From C5H2Brp03 ,. 0~CH:CBr.CBr:C~CO2H . ~~ ~~ C4H3MeK.C0,11 1 __-___-I_-From C6Hi0,N .. 2 1 Ph-P-methylcarbopyrollate ,) I . . I ,. n-y- I I di5cultly soluble solrent not 1 Ciami:ian Bey. 14 1057. easily soluble } stated I " solubility of free acids not stated. Luz:$\ ir ~ e n a ~ { ~ ~ ~ i sa<,G u ~ e ~ ~ T -- ~ ______-- ----1 The acids are also exceptions. Ba-salts obey ~ less soluble in n-ater . I M\labc1y2 Am Ch J 6 157 . !{ the rule. The m. ps. are very close (see more , , . ' > * , . . No. 22). The symmetry accords Trith the solubility but not Tith the m. p. 28. -2 1 ISOMERIC ORGANIC CONPOUNDS. 797 The above 28 exceptions may be classi6ed thus :-(1.) Five are only barely exceptions the melting points being very close viz. Nos. 11 20 21 22 and 28. The information given in respect to these is not sufficient to allow one to say whether the solu-bilities are correspondingly close except in No.22 (‘7.v.). (2.) I n No. 25 the solubilities of the compounds compared are very nearly equal whilst the melting points are not very different. (3.) In No. 27 the two Pb salts referred t o were not analysed and one or other of them might have been a basic salt and therefore not really isomeric and comparable with the other one. (4.) Seven though exceptions themselves yield salts which obey the rule (viz. Nos. 11 18 19 22 23 25 28). (5.) Three salts which are exceptions are derived from acids which obey the rule (viz. Nos. 24 25 26). (6.) Three (viz. Nos. 8 20 21) are physical and not chemical isomerides in the ordinary sense and our knowledge of the so-called physical isomerides is at present very limited.(7.) In five (viz. Nos. 1 2 3 10 and 23) the solubilities are excep-tional not only as regards the melting points but also as regards the symmetry. (The more symmetrical of two isomerides is usually less soluble than the one in which the atomic arrangement is less sjmme-trical.) (8.) I n five (viz. Nos. 4 17 12 22 28) the melting points are not only exceptional as regards the solubilities but also as regards the symmetry. (The more symmetrical of two isomerides usually has the higher melting point.) (9.) I n two (Nos. 16 and 17) one o r other of the isomerides contains water of crystallisation and it is not stated whether the melting point was determined with the anhydrous compound. If made with the hydrated compound the water would be driven off on heating, and collect iii the upper part of the melting point tube and might run down and lower the melting point of the substance if proper care were not taken.(10.) Eight (viz. NOS. 5 6 7 9 12 13 14 15) are not included in any of the above classes and SO far as one can learn from the state-ments published i n reference to these compounds there is nothing to lead one to suppose but that they are real exceptions to the rule. We may say therefore that out of the 1921 cases in which the rule can be applied there are only from 9 to 12 exceptions (= 8 per cent,.) against which so far as one can see a t present no objection can be raised. It is possible however that most i f not all of these excep-tions may on further investigation t u r n out to be due to errors either in the determination of the melting points or of the solubilities o r possibly to clerical errors 79s CARNELLEY AKD THOMSON SOLUBILITY OF The relation between fusibility and solubility may also be illustrated by a great number of cases other than those of isomeric compounds.Among these the following are noteworthy :-(a>) Allotyopic Modi$cations of the same Element.-(1.) Phosphorus. Common or yellow phosphorus melts at $Po and is readily soluble in carbon disulphide chloride of sulphur phosphorus trichloride and phosphorus pentasulphide and slightly soluble in ether turpentine, and the cssential oils ; whereas red phosphorus which does not melt below 255" is insoluble in all these solvents.(2.) SuZpphur. Common or octahedral sulphur melts at 114.5" (Brodie) and is readily soluble in carbon disulphide; whereas plastic sulphur does not melt at 120" (? Brodie) and is insoluble in carbon disulphide. ( 3 . ) Selenium. Amorphous selenium melts at a little above 100" (Berzelius) and is soluble in carbon disulphide and in benzene ; whereas crystalline selenium melts at 217" (Hittorf) and is quite insoluble in carbon disulphide or in benzene. (b.) Payafin 'Wax.-The solubility of paraffin wax in benzene is less the higher its melting point as may be seen from the following table (Wutts' Dict. 7 893) :-Quantity of pai~~ffin wax deposited at 18' by 100 C.C. of refined benzene. M. p. 35.0" 133 grams. 49.6 6 ,> 52.8 4.7 9 , 65.5 1.4 3, 80.0 0.1 >> (c.) Xiztures of Sodium and Potassium Nitrates.-Table VII (p.799) which embodies the results of the determinations already given in detail will show the relations which subsist between the fusibility and solubility of mixtures of sodium and potassium nitrates :-These results are also shown graphically in Diagrams I and 11. Diagram I gives the curves of fusibility and two curves of solubility ; in one of the latter the solubility is referred t o the percentage com-position of the mixed nitrates before solution and in the other to the composition of the mixed nitrates after solution and evaporation to dryuess. Diagram I1 gives the curves showing the actual weights oE sodium and potassium nitrates respectively dissolved Prom various mixtures of the two salts and compares these with t,he curves of total solubiliiy of the mixed salts.An inspection of the above table and accompanying diagrams (a) As regards the fusibility and total solubility of the mixed shows :-nitrates (see Diagram I) : ISOMERIC ORGANIC COMPOUXDS. TABLE VII. Per cent. of NaNO in original mixture before solution. -100 90 80 70 60 50 45 -7* 40 30 20 10 0 lfelting ?oint (cor.) )f mixture 6efol.e solut,ion. -~ 316" 298 283 268 24.2 231 231 231 242 284 306 339 Total weight )f mixed salts] dissolved by } = 100 parts of I water a t 20" J 86 -8 109 -6 136-5 136 '3 137% 106 '1 88 '0 43.5 54 *1 40 -9 33 -6 ;1-1 Veigh t of hsolred. 86 -8 96 *4 98 -0 90 '0 66 *O 53-3 45 -6 20 -8 9 -4 0 --Veight of dissolved.0 13 -2 38 *5 47 *6 40 *1 34 - 7 35 -5 33 *3 31 - 5 33 *6 --Per cent. of VaNO i n the nixture af iev 3olution and evaporation to dryness. --100 88 71.8 65 '4 62.2 60 - 6 56 * 2 35 -5 22 9 0 --Melting ?oint (cor.) of the mixed nitrates after solu-tion. -316" 294 267 256 247 242 238 231 278 339 --(1.) That the fiisibility gradually increases from pure NaN03 (m. p. 316") until the mixture contains about 50 per cent. NaNO,, and melts at 231" ; the melting point then remains constant until the sodium nitrate falls to 40 per cent. after which the fusibility gradually diminishes until pure KNOs (m.p. 339") is reached. A mixture having the molecular composition (NaNO + KNOJ contains 45.7 per cent. NaNO+ According t o Schaffgotsch (Pogg. Am,. 102, 293) the salts when mixed in molecular proportion melt at a lower temperature than when present in any other. (2.) That starting with pnrc sodium nitrate the total solubility quickly increases until the proportion of the NaN0 in the mixture be-fore solution falls to 80 per cent. after this i t remains constant until the NnNO = 60 per cent. beyond which the solubility rapidly diminishes until pure potassium nitrate is reached. A mixture containing about 45.7 per cent. NaN03 (= NaNO + KNO,) dissolves to about the same extent at 20" as pure sodium nitrate whereas all mixtures con-taining a smaller proportion of sodium nitrate are less soluble than the pure salt.The above refers to the proportion in which the salts are mixed before solution ; if however the solubilities be referred to the proportion between the two salts in the residue obtained by eva-poration of the saturated solution we find that though the general form of the curve is very siniilar to that in the first case yet the solu-bility is constant over a much smaller range of variation in the com-position of the mixed salts. Thus the maximum of solubility i 800 CARXELLEY AND THONSON SOLUBILITY OF obtained when the sodium nitrate falls to 72 per cent. and continues constant at this until the sodium nitrate falls to 65 per cent. after which it rapidly diminishes to pure potassium nitrate. It will thus be seen that the depression of the curve based on the composition of the mixture ufter solution and evaporation lies throughout its whole course within that of the ciirve based on the composition of the mixture befoye solution.This shows that before tho maximum of solubility is reached the proportion of sodium nitrate in the dissolved portion is less than in the mixture before solution whilst beyond that point it is greater. In other words starting with pure sodium nitrate, there is a smaller proportion of sodium nitrate in solution than in the original mixture until the point of maximum solubility is reached, after which the proportion of sodium nitrate in solution is greater than in the original mixture before solution. ( 3 . ) That the general form of the four curves (two of fnsibility and the other two of solubility) in Diagram I is very similar showing an intimate connection between them.The two curves of solubility, however differ from those of fusibility in one important particular, in that starting from the pure sodium nitrate end the maxima of the two solubility curres occur earlier than those of the curves of fusibility. Thus whereas the middle of the maximum of fusibility occurs when the composition of the mixture corresponds with the formula (NaN03 + KNO,) that of the two solubility curves corre-sponds approximately with the composition (3NaN03 + KNO,). That is to say the addition of potassium nitrate to the pure sodium salt affects the solubility more quickly than it does the fusibility whereas the addition of sodium nitrate to pure potassium nitrate increases the fusibility more rapidly than it does the solubility.(p.) As regards the solubilities of the sodium and potassium nitrates respectively in the presence of one another (see Diagram 11) :-(4.) That the solubility of pure potassium nitrate a t 20" (Curves B and B,) is scarcely if a t all affected by the addition thereto of the sodium salt unless the amount of the latter present in the mixture reaches about 45 per cent. before solution or 60 per cent. in the dis-solved portion. Thus a solution of pure potassium nitrate saturated a t 20° contained 33% parts by weight of the pure salt in 100 parts of water while a saturated solution obtained by treating a mixture con-sisting of 20 pcr cent. NaN03 and 80 per cent.KN03 contained 33.3 parts of potassium nitrate and one obtained by treating a mix-ture consisting of 45.7 per cent. NaNO, and 54.3 per cent. KNO, con-tained 34.7 parts of potassium nitrate. The rcsidues obtained by evaporating t,he several saturated solutions to dryness weighed 33.6, 54.1 and 88.0 grams respectively and contained 0 38.5 and 60.6 per cent. of sodium nitrate. When the mixture contains more tha hozcr~i ('hp?i/ ,So,> Sep?1%88. CAPXLLLEY & THOMSGN I DlAORAM OF THE SOLUBILITY AND FUSIBILITY OF MIXTURES OF SODIUM AND POTASSIUM NITRATES. 1W 80 20 F s P I E E ISOMERIC ORGANIC COMPOUNDS. 801 45 per cent. of sodium nitrate the weight of the potassium salt dis-solved increases until the former salt reaches about 60 per cent.after which it rapidly diminishes until the salt consists of pure sodium nitrate. The weight of potassium nitrate dissolved by a given weight of water at 20" from a mixture containing 82 per cent. of sodium nitrate is also the same as that dissolved from pure potassium nitrate by the same weight of water at the same temperature. (5.) That the solubility of pure sodium nitrate at 20" (Curves C, and C,) is at first somewhat increased by admixture with potassium nitrate ; this continues until the latter reaches about 20 per cent., after which the solubility of the sodium salt at first slowly and then rapidly diminishes until the salt consists of pure potassium nitrate. 111. InJEuence of the Nature of the Solvent. If it be true that the more fusible compound is also the more soluble it follows that:-Rule (3).For any series of isomeric compounds the order of solubility i s the same no matter what may be the nature of the solvent. We have been able to apply this rule in 666 cases and find that the whole of these without a single exception accord with the rule. A few examples in illustration of this rule are given in Table IT. It holds good not only with acids but also with their salts so far at least as the solubilities of such salts have beeu tested in solvents other than water (cf. Rule 2). It further holds in many other cases, e.g. the two allotropic modifications of phosphorus of sulphur and of selenium (see above p. 798). With the view of submitting this rule to 5~ very stringent test we have determined the solubility of meta- and para-nitraniline in 13 different solvents with the results given in Table VIII p.802.X This table shows therefore that no matter what the nature of the solvent the meta-nitraniline is always more soluble than the para-compound. The table further shows that :-Rule (4). The yatio of the solubilities of the two isomerides in any given solvent i s very nearly bonstant and i s therefo~e independent o j the nature of the solvent. This ratio varies from the extreme limits of 1.15 in the case of methyl alcohol in which the nitranilines are most soluble to 1.48 in water in a-hich they are least soluble. The ratios for the other solvents however lie very much nearer to the mean value 1.29 the greatest deviation from it in their case being confined to the second decimal place.* For details of these determications see Table I. VOL. LIII. 3 802 SOLUBILITY OF ISOMERIC ORGANIC COMPOUNDS. TABLE VIII. Solvent. Water HzO Methyl alcohol CH,O . Ethyl alcohol C,H,O Propyl alcohol CBH,O Isobutyl alcohol C,HloO . Isoamyl alcohol C,H,,O . Ethyl ether C,HloO . Benzene C6H6 Toluene C7Hs Cumene CSHIz . Chloroform CHCl . Carbon tetrachloride CC1,. . Carbon disulphide CIS2 . ~ Weight of substance dis-eolved by 100 parts by weight of solvent. Meta-. -0.11.4 11-06 7.05 5 -65 2 -64 8 *5l 7 *89 2 -45 1 - 7 1 1 *15 3-01 0 -21 0 -33 --I Para-. -~ 0'077 9 *59 5-84 4 -35 1. '91 6.29 6.10 1 -98 1.31 0.90 2 -31 0.17 0 -26 -Ratio. meta-para-1-48 highest 1-15 lowest, 1 .21 1 *30 1 *38 1-35 1 - 2 9 1 *24 1 *31 1 -28 1 -30 1 *24 1 - 2 7 1-29 - I Mean = I It will be noted that the solvents employed are numerous and very varied in character whilst a t the same time the range in solubilit,y is very great varying in the case of the para-compound from 0.077 in water to 9.59 in methyl alcohol in the latter of which therefore it is 124 times more soluble than in water.This forms a very crucial test a t least so far as regards the order of solubility. Up to the present we have only completed experiments with this single pair of compounds but we are extending the work to other series of isomerides. If this further work confirms the above results, then the solubility of any pair of isomerides A and B will be represented by the following expression which is independent of the nature of the solvent :-= constant (for any given tem- Solubility of A in any solvent Solubility of B in the same solvent persture).So that if the solubility of A in any solvent at a given temperature be known that of B a t the same temperature niay be calculated. The influence of temperature on the above ratio is at present under investigation and we are also engaged with the deter-mination of the solubility of isomerides at temperatures equidistant from their me1 ting points. The bearing of the above results on the general question of the nature of solution will be discussed lat'er in connection with other data obtained on entirely independent lines but all leading to the same point

ISSN:0368-1645    

DOI:10.1039/CT8885300782

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

LXV.-The Actio?L of Chromium Oxychloride on Orthosubstituted Toluenes. By CHARLES M. STUART M.A. Bellow of St. John's College Cam-bridge and W. J. ELLIOTT Scholar of Christ's College Cambridge. IT is well known that the action of chromium oxychloride on the homologues of benzene gives rise to the formation of solid compounds which consist of 1 molecule of the hydrocarbon combined with 2 molecules of the oxychloride and which are decomposed by water with the formation of aldehydes. V. v. Richter (Berichte 19 224) has examined the action of chromium oxychloride on orthonitrotoluene ; but although he succeeded i n showing the production of a small quantity of orthonitrobenz-aldehyde he found that for the most part orthonitrotoluene was re-formed. We have examined the interaction of ortho-haloi'd derivatives of toluene and chromium oxychloride.Ten grams of the substituted toluene dissolved in carbon bisulphide were added very gradually to a solution of 25 grams of chromium oxychloride in the same liquid which was kept cool by a stream of water. The mixture was allowed to stand three days ; the solid was then filtered off and added to water. A heavy oil separated and the solution contained in all cases a salt of chromium and chromic acid. The chromic acid was reduced by a current of sulphur dioxide. Orthoclilorotoluene and Chromium Ozychloride. The chief part of the oil which separated distilled at 205" to 210". The substance formed a crystalline compound with sodium hydrogen sulphite solution and gave with malonic acid an acid melting at 192" with effervescence namely orthochlorobenzal malonic acid.0.5011 gram take 36 C.C. N/10 AgNO solution = 25.50 p. c. C1. Theoryfor C,H4C1*COH = 25.25 ,, It is therefore orthochlorobenzaldehyde. I n this experiment we were unable to isolate any othtr compound. Orthobromotoluene and Cliromium Oxycl~loride. When the oil which separated was distilled it came over in two fractions ; the first a t 215-220" the second a t 285-235" 504 ACTION OF CHROJlIUJI OXYCHLORIDE ON TOLUEbTS. The first fraction (215-220") gave with sodium hydrogen sulphite solution a crystalline precipitate and with malonic acid an acid melting a t 198" with effervescence namely orthobromobenzalmalonic acid. 0.1843 gram required 10 C.C. N/10 AgNO3 solution = 43-40 p. c.Br. Theory f o r C6H4Br.COH = 43.24 ,, It is therefore orthobromobenzalde hyde. The second fraction (225-235') was shaken with sodium hydrogen sulphite solution and then with ether. The residue obtained by distilling off the ether from the ethereal solution was found to contain both chlorine and bromine. 0.1604 gram required 20 C.C. N/10 AgX03 solution beforc boiling with PbO, and 13.4 C.C. after boiling with PbO?. 0.2496 gram gave 0.3149 gram CO and 0.0662 gram H,O. Ttieory for, Pound. C,H4B r - CMO,. C. . 34.41 C . . 35.00 H . 2.92 H 2.07 C1. 29.65 BI= . 33.33 Br 32.91 C1. 29.58 When boiled with potash solution it is converted into the aldehyde. It is partially decomposed Its formula is therefore C6H4Br.CHCl,. on distilla tion with evolution of hydrogen chloride.Orthiodotoluene and Chronrium Oxychloride. When the oil was distilled the temperature rose slowly to 270". The distillate was shaken with sodium hydrogen sulphite solution. The larger portion remained as an oil. The aqueous solution was shaken with ether in order to extract all oil that remained. Hydrogen chloride was then added and the solution boiled; a slight smell of aldehyde could be detected and there were drops of oil on t,he condensing tube. A trace of aldehyde only is produced. Thc oil which remained after shaking with sodium hydrogen sul-phite solution was shaken with sodium thiosulphate solution in order to remove all free iodine. The residue boiled with decomposition a t 243-2 50". 0.3764 gram required 38 C.C. NjlO AgNO solution.12.7 C.C. NjlO Na,S20J solution. 0.4475 gram gave 0.1013 gram H,O and 0.4747 gram C02 THE JIOLECULAR WEIGHT OF IODINE IN ITS SOLUTIOKS. 805 Theory for Found. CcH4 1.C H Cls. C . . . . . . . . 28.9'2 C . . 29-26 H . . . . . 2.51 H 1.74 I 45.01 I 44.25 C1. 24.35 Cl . 24.42 . . . . . . . . The substance is therefore orthiodobenzal chloride. Wheri boiled wit,h potash it is converted into aldehyde. These experiments therefore prove that the action of water on the solid compounds of chromium oxychloride and ortho-substitu t ed toluenes is to produce in the first instance an ortho-substituted benzal chloride of the formula C6H,X*CC1,H; but that this in the case of tke orthochlorotoluene is entirely and in the case of the ortho-brornotoluene partially decomposed by water with the formation of an aldekyde ; while the orthiodo-compound is scarcely affected. It is extremely probable that the formation of all aromatic aldehydrs by this method is preceded by the formation of derivatives of benzal chloride. For this reason we examined the reaction between orthonitro-toluene and chromium oxychloride. Like V. v. Richter however we found that a trace of orthonitroberizaldehyde only was produced, while not a trace of a compound containing chlorine was formed but the greater part of the orthonitrotoluene was reproduced

ISSN:0368-1645    

DOI:10.1039/CT8885300803

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

THE JIOLECULAR WEIGHT OF IODINE IN ITS SOLUTIOKS. 805 LXVI.-The Molecular Weight of Iodine in its Solutions. By MORRIS LOEB Ph.D. IT is a matter of everyday observation that iodine has the property of dissolving with different colours in different liquids; in some it shows the reddish-brown hues of its solid and liquid skates ; in ohhers it acquires the violet colour so characteristic of its raponr. The inference seems very natural that this diversity of colour must depend on a different form of aggregation of the iodine-atoms within the solvent. Since the molecules of solids and liquids appear to be more complex than those of gases we might suppose that the red solutions contain more complex molecules of iodine than do the violet ones. This is in fact the usual assumption ; but apart from certain qualita-tive indications there has been no proof of its truth; quantitative evidence has not yet been forthcoming in support of the hypothesis.That I have been fortunate iu obtaining Such I owe to those new YOL. LIII. 3 806 LOEB THE I\IOLECUT,AR WEIGHT means of investqating the state of dissolved matter with which t h r happy generalisations of Raoult avid the skilful mathematical deduc-tions of van’t Hoff have furnished us. I refer to the phenomena of “ osmotic pressure,” which can be measured by the depression of frcezing point and vapour-tension which liquids experience when mingled with a foreign substance. By the advice of Professor Oitwald I undertook to attack the problem of the molecular weight of iodine in its solutions by the vapour-tension method and I now give the results of the experiments carried out under his direction at the Chemico-Physical Laboratory of Leipsic University.Two liquids a t once presented themselves as the appropriate solvents ether and carbon bisulphide ; they both have a considerable uapour-tension and they may be considered as typical of the two kinds of solrents for iodine. For whereas many iodine solutions show impure tints that in ether is of a deep reddish-brown and that in carbon bisulphide of a pure violet. It was not so easy to find a proper apparatus as Raoult’s was quite inapplicable. He operates in the Torricellian vacuum and has merely to note the comparative heights of the mercury when the solution and the pure solvent are introduced above it.In the case of iodine all contact with mercury must obviously be avoided. After various attempts the following apparatus was devised which is an adaptation of Regnault’s manometer to th OF IODINE IN ITS SOLUTIONS. 807 present purpose. It consists of two bottles of nearly equal capacity, provided with carefully ground hollow glass stoppers. To these stoppers glass tubes are adapted 60 cm. long and of about 6 mm. bore which are bent twice at right angles so t,hat there is an ascending limb and a horizontal piece of 10 cm. length each and a descending limb 40 crn. long for each half of the apparatus. The lower ends of these two tubes are connected with each other by means of a T-t,ube, to which they are joined by short pieces of very stout rubber tubing ; the third end of the T-tube serves as a communication with the exterior when needed and carries a rubber tube with pinch-cock.The communication between the two halves of the apparatus can also be interrupted by means of a pinch-cock on one of the rubber joints. Into one of the bottles the iodine solution is placed whilst the pure solvent is put into the other. These liquids are contained in glass tubes drawn out at both ends into capillaries that make an obtuse angle with the wider part. The tubes are first weighed then filled closed before the blowpipe and again weighed. They contain about 3 C.C. of liquid pass readily through the narrow necks of the bottles and can be broken by moderately shaking the bottles. Before this is done however the bottles are closed with their stoppers-smeared with deliquesced phosphoric acid to insure a perfect joint-and are placed in a water-bath of constant temperature.The T-tube is now connected with a two-necked WoulE’s bottle filled with coloured distilled water and communicating by its second neck with an air-pump. Air is exhausted until the pressure within the appa-ratus is diminished to an extent equivalent t o the amount of tension to be expected from the vapours of the liquids and the pinch-cock is then closed so as to interrupt communication with the Woulff’s bottle. The air-pump being disconnected atmospheric pressure is restored in the Woulff’s bottle and on carefully opening the pinch-cock the water is allowed to ascend half way up the long tubes ; the pinch-cock is then closed and the Woulffs bottle removed.The apparatus is thus converted into a very delicate differential manometer, affording direct readings of the difference of pressure in the two bottles in terms of water centimetres ; for convenience the t w o tubes are brought closely together (see Figure) and a scale is placed behind them. The apparatus is quite independent of changes in the atmospheric pressure ; the change in capacity caused on either side by an altera-tion in the level of the water in the tubes is moreover so slight in proportion to the volume of air in the bottles that it can rJafelg be neglected ; the effect of capillarity in the two tubes is equal and oppo-sit8e so that tliis too may be left out of acconnt. There remains only the effect of the air left in the apparatus by the air-pump.It 3 1 808 LOEB THE MOLECULAR mEIQHT is obvious that equilibrium being once established and the tempera-ture in all parts remaining the same the pressure of the air in the one half will always counterbalance that in the other. In fact, partial exhaustion was only resorted to as a means of preventing too great an outward pressure during the course of the experiment, since it was difficult to prevent leakage where there was any out,ward pressure upon the stoppers. Partial exhaustion besides obviating this difficulty proved directly advantageous by promoting a more rapid diffusion of the vapours and thereby shortening the duration of the observations. The apparatus having been made ready communication between the two halves was temporarily interrupted and the tubes containing the liquids broken by shaking the two bottles simultaneously.After 10-15 minutes communication was restored and now the level of the water in the two manometer tubes equal before was seen to differ considerably indicating a higher pressure in the bottle containing the pure solvent. Readings being made from time to time this difference of level sometimes appeared virtually constant for hours whilst in other cases it would exhibit considerable variations which I ascribe to slight inequalities of temperature and to the unequal concentration of the solution in different parts of its bottle. After standing 24 hmrs the aqueous vapour from the manometer tubes generally began to diffuse into the bottles and rendered further observations useless by moistening the ether or carbon bisulphide.The readings give the difference between the vapour-tension of the pure solvent and that of the solution ; that is the depression of tension which corresponds with the proportion of iodine to solvent in the solution. To calculate the concentration of the solution a t the moment of observation I required two data the amount of iodine and of solvent introduced into the bottle (which I obtained from the weighings of the sealed tubes and from the known strength of the solution with which they were filled) ; and secondly the amount of solvent which had assumed the gaseous state and must therefore be deducted from the original quantity i n solution. This was easily calculated by the regular gnsoinetric formula the volume of gas being 270 c.c.the temperature being known and the pressure being that of the vapour of the pure solvent less the depression formed by the direct observation. I found that I could employ the vapour-tensions of pure ether and carbon bisulphide from tables calculated from Regnault’s measurements as a few direct comparisons proved that they agreed with those given by my apparatus within the limits of experimental error. The expression for the amount of solvent remaining in the solution a t the moment of observation is there-fore OF IODINE IN ITS SOLUTIONS. 809 27O.w.( f - e) a - 7 W ( l + at) ’ where a = grams of solvent originally present; f = the tension a t the temperature t of the pure solvent expressed in millimetres of mercury ; e = the depression of tension also in terms of millimetres of mercury; w = weight in grams of 1 C.C.of the vapour under standard conditions. Now if b = the weight of iodine in the solu-tion a n d p = the ratio of solvent to iodine-I. b The concentration being thus ascertained the calculation of the molecular weight of iodine was made according to the formula-11. M and M being t’he molecular weights of iodine and solvent respec-tively. This is a working formula derived by Raoult from an expres-sion for the relation between the ratio of molecules of solvent and substance dissolved on the one hand and the ratio between the tension of the pure solvent and the depressed tension on the other where the dissolved substance itself has a comparatively insignificant tension.It is interesting to note that the latter expression was reached inde-pwdentl7 and simultaneously by Planck both papers having appeared in vol. i KO. 7 of the ZeI’tschrift fiir yhysikalische Chemie. In the following tabulated statement of my observations the first t w o columns show the weights of the ingredients of the solution originally introduced ; the third gives the temperature ; the fowtll, the depression of tension ; the fifth the true tension of the solution ; the sixth the concentration as calculated by formula I ; finally \I e have thc molecular weight as calculated by formula 11. Before giving the results obtained for iodine I think it useful to give a summary of a few test experiments made on the molecular weight of naphthalene which not only proved the trustworthiness of the method, but also showed t h a t there is no specific difference between ether and carbon bisulpliide which could invalidate the ef€ect of the great difference of the molecular weights found for iodice 810 LOEB THE MOLECULAR WEIGHT 0.1462 ---Nap h thalene in Carbon Bisu lp hide.27.5" 27 '5 27 -5 27 - 5 I e. 1 f- e. Average. - I-I-129 135 5*@52 0.2586 27.5' - 1 - 127.5 ). 132 Naphthalene in Ethyl Ether. b. 1 t. f - e . p . 1 M,. I Average. a. e. -- /-- I 2 -8359 - -21 -12 21-08 21 -14 21 -17 557 '27 557.31 557 -25 557 * 22 127 -5 6'53 127 6-53 128 Average in CS,. . M = 132 Average in C,H,,O . MI = 127.5 Theory for CloH Rill = 128. Iodine in Carbon Bisulphide.-P- a. I 6 . f - e . 373 -92 375 -05 374 -83 374 * 56 378 -48 378.48 381 -98 382 -07 381 '92 381 -82 3EU -52 381 *91 381.98 -Average. -___ } 264 } 300.5 I I I 1 ) 320 } 326.5 M,. 239 278 27 1 268 300 *5 300 ' 5 324 332 320 314 310 326 387 t. 27.3" 27.3 27'3 27 -3 27.5 27.5 27 -5 a7 *5 27'5 27 *5 27 *55 27.5 27 - 5 e. 9 '72 8 '59 8 '81 9'08 8.10 8.10 4 *GO 4 -51 4.66 4 -76 4 *80 4 *67 4.60 -8-37 8-37 8-37 8 '37 8 -46 8 *46 5 -15 5 *15 5 '15 5 -15 5 -15 5.20 5 -20 0.4026 -0 * 2504 ----0 * 2330 -Total average M = 30325 5.10 Theory for I,. Theory for 13 . M = 2.54 &I = 381 OF IODINE IN ITS SOLUTIONS.-5-27-2' 27'2 27'2 27.35 27.3 27'3 27 -3 27'3 27.3 27.4 27'4 27'45 27.5 27-5 27.5 27'5 Iodine in Ethyl Ether. 8'20 7.50 7.81 8-09 8-16 7-46 4-84 5.04 5-66 6.51 6-48 6.77 6-99 7'14 6-43 7-14 f - e . 563.69 564 -39 564 -08 567 *05 565 -90 566 *60 569 2 2 569 -02 568 *40 569 '72 569.75 570 '54 5'71 -40 571 -25 571 -96 571 *25 -P--9 -59 9 -59 9 -59 9 -60 9 'bo 7 -68 7 -68 7-68 7-68 7 -50 7'50 7 '51 7 *62 7.62 7 -62 7-62 811 M1. 498 534 512 497 492 -5 443 653 642 571 486 -5 487 468 -5 461 45 1 501 -5 451 Average. ) 504.7 I 1 j 577 *2 480 -7 I I 466 -1 Total average .. Theory for 14 . . . . . . . 511 = 507.2 & 10.5 Nl = 508. It seems very probable therefore that iodine in its red solutions has a molecular weight corresponding to Id whilst in the violet solu-tion in carbon bisulphide there is a less complex aggregation giving a value between I and I,. I may as well remark that the values for p in the ether solutions correspond approximately with the ratio of one iodine molecule in l U 0 molecules of the solutions; in the carbon bisulphide solutions this ratio varies between 1 - 100 and 1 200 Whilst greater dilution might appear more advisable from a theo-retical point of view i t offers an apparently insurmountable difficulty in practice. A glance at the formulae used in the calculation shows that the value of e enters three times in such a manner that any error attached to it would be tripled.As e decreases with the concentration it is evident that a greater dilution than that employed by me will soon bring e Do a point where the chance errors of obser-vation become proportionately very great. Hence I agree with Raoult when he says that the method of determining molecular weights by the depression of the freezing point is preferable to the method by vapour-tensions. But for the problem which immediately interested me I lacked a liquid which would solidify and also dissolve iudiue with a pure violet colour benzene for instance giving a ver 812 LOEB THE USE OF AKILTNE AS AN ABFORBEKT O F i rnyure bluish-brown. Nevertheless I endeavoured to obtain whatl c*orrobor:ctive evidence I could by experimeuting on the freezing points of iodine in acetic acid and in benzene but was forced to give up tlie attempt by the very slight solubility of iodine in these menstrua a t low temperatures ; the molecular weight of iodine as calcnlated from various series of observations seemed to increase ccntinnously with the concentration so that there was no point in t'he narrow limits between extreme dilution and saturation a t which tlie molecular weight would appear constant and could be accepted as trustworthy. A paper pub-li.shed since then by Paternd and Nasini (Ber. 21 2155) on this gubject contains a few figures for the molecular weight of iodine in acetic acid and benzene solutions but I am unable to draw auy other inference from them than from my own

ISSN:0368-1645    

DOI:10.1039/CT8885300805

出版商:RSC    

年代:1888

数据来源: RSC

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812 LOEB THE USE OF AKILTNE AS AN ABFORBEKT O F LXVII.-The Use of Aniline as an Absorbent of Cyanogeit in Gas A na lysis. By MORRIS LOEB. In a pa?er published in the Compfes Rerhdus 100 1005 some time ago Jaquemin proposed t h e use of aniline as an absorbetit for cyanogen in quantitative gas analysis without however giving details of any experiments as to the trustworthiness of the method. The proposal is B surprising one considering that hydrogen cyanide is always formed in the preparation of cyananiline; this fact is dis-tinctly stated by Hofmann (Annnlen 66 l29) who accounted for its poduction by certain secondary reactions which he studied. It is also to be noted that Jaquemin in khe same paper describes a very satisfactory method of preparing cyanogen gas in the wet way and that he probably employed t h e moist cyanogen in his experiments with aniline.As the presence of water seems to favour most of the reactions of cyanogen there did not seem to be any conclusive evidence t h a t dry cyanogen would be totally absorbed by aniline. A t all events it seemed worth while to make the experiment with cjanogen prepared in the old way and at the same time to ascertain to what extent the development of hydrocyanic acid would interfere with Jaquemin’s proposed method for gas analysis. For this purpose, cyanogen prepared from dry mercuric cyanide was brought into contact with recently distilled aniline. The gas was indeed absorbed rapidly and completely nor did a bubble of gas appeqr after 24 hours’ standing. But as soon as carbon dioxide was passed in the presenc CYANOGEN IN GAS ANALYSIS.813 of hydrocjanic acid became apparent. It was expelled from the u i l i n e by the carbon dioxide and could now be recognised both hy its odour and by the prussian blue reaction. At tbe same time a considerable quantity of carbon dioxide is absorbed by the aniline and must be held in solution as chemical union is impossible under the circumstances. As the same is said to be the case with carbon monoxide and these two gases are those which generally accompany cyanogen I fail to see how aniline can be generally useful in deter-mining the amount of cyanogen in a mixture apart from the fact that hydrogen cyanide is produced in the reaction and is itself very loosely attracted by anili tie. The experiments by which I satisfied myself of this were made last April in the laboratory of the Physical Association of Frankfort-on-Blain to the director of which Dr.B. Lepsius I am very mnch indebted. The details of a few of the most important tests are given below. I. 38.88 C.C. of cyanogen gas (under standard conditions) wwe absorbed immediately by 12.5 C.C. aniline ; after 25 hours no trace of gas had been evolved. 11. A mixture of cyanogen and dry air was introduced into a U -shaped eudiometer provided with stopcocks and filled with mercury. Aniline was first added and allowed to absorb the cyanogen and dry carbon dioxide was then passed i n ; when no further change took pl:tce the unahsorbed gas was transferred t o a test-t'ube over mercury arid brought in contact with a few drops of sodic hydrate; the alkaline solution gave an appreciable test for hj-drocjanic acid with ferrous and ferric salts.In the followirig table the measurements and the results are given :-1 t. I B. I C.C. 1 Corrected. 1 Volume of cyanogrn and a i r . ' 19 -0" 1 752 -1 ~ 60 I 55.34 ~ -Volume 22 tours after introduc-iiig aniline Polume of cyanogen absorbed After addition of carbon dioxide Volume carbon dioxide After 23.5 hour$ . Volume carbon dioxide absorbed 19.5 '752-1 7 . 7 7.09 - -- 48 -2.5 - 26.75 - 1 - 1 - I - 1 14.51 19.5 I 752.1 1 3F76 33.84 1 -- - -19.5 752.0 21.00 19.33 -111. A similar experiment performed in a somewhat different order and with the use of a straight eudiometer gave an analogous result. H = the height of the column of mercury h = the height of the column of aniline reduced to mercury 814 NILSON AND PETTERSSON NEW CHLORIDES OF INDIUM, C.C. 56.5 108.5 -43.0 -Volume of carbon dioxide. Volume of carbon dioxide and cyanogen. . Volume of cyanogen. . Vol. 22 hours after introduction of aniline . Volume of gas absorbed . Corrected. --52-03 99.91 47 -88 27-32 72-59 t. -19 *5" 19 -5 19'5 --B. '752 *1 '752 *1 '752 * 0 --47.88 C.C. cyanogen gas and 24.71 C.C. carbon dioxide have there-In this case too the residual gas had a decided fore been absorbed. odour of prussic acid

ISSN:0368-1645    

DOI:10.1039/CT8885300812

出版商:RSC    

年代:1888

数据来源: RSC

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814 NILSON AND PETTERSSON NEW CHLORIDES OF INDIUM, LXVII1.-On two N e w Chlorides of Indium and on the Tapour-densities of Indium Gallium Iron and Chromium. By L. F. NILSON and OTTO PETTERSSON. THE decisive results for the trivalency of aluminium which we obtained in our researches on alumiuium chloride (Uej'wrsiyt af K. Wetenskaps Akad. fiirliandl. 1887 No. 8 and Zeitschrift f. physikul. C'hern. 1887 4.59) rendered it most desirable that the earlier wark on the molecular weights of the chlorides of other elements of the same group should be revised. At the conclusion of our communication, therefore we invited those chemists who had previously worked in this direction to undertake this revision. In reply we received a letter from Lecoq de Boisbaudran expressing the wish that we would undertake the work on gallium and in the most obliging manner sending us a supply of pure material.Clemens Winkler wrote to the same effect in respect of indium and gallium and ac the same time placed a t our disposal a quantity of these rare elements. With these materials and those already in our possession we have undertaken the investigation. We would however observe that the amount of gallium in our possession notwitlistanding the liberality of tne above-mentioned chemists was insuflicient to enable us to investigate the gallium chlorides as coruyletely as we could have wished. V. Mepr who had already determined the vapour-density of the chlorides of iron reserved to himself the right of revisiiig the density of ferric chloride and has recently published his results (Grunewal AND THE VAPOUR-DENSITIES OF INDIUM ETC.815 and V. Meyer Ber. 1888 21 687) but as he proposed to us that we should definitely ascertain t,he molecular weight of ferrous chloride, we were prompted to undertake some experiments ou the latter. It also seemed of interest to include the chromous and chromic chlorides in our researches especially as these compounds so far as we are aware have not hitherto been examined in this respect. As will be seen from the following account several of our experi-ments were carried out in porcelain vessels at a temperature which was not accurately determined. The reason of this was that our platinum apparatus towards the conclusion of our work must have become slightly defective the leak only becoming apparent at an intense heat and under pressure; the level of the mercury in the measuring tube or of the liquid in the manometer* no longer remain-ing constant but slowly and gradually changing.As it had to be sent to Paris for repair we could not delay the completion of our experiments until it was returned; and from this time forward all the experiments were conducted in porcelain vessels the temperature being approximately estimated from our knowledge of the heat which the furnace was capable of giving. Some of the estimations were made in the vapour of boiling mercury sulphur or stannous chloride contained in tubes of hard Thiiringen glass. By means of a Muencke five-light burner it was easy to maintain the vapour of the mercury or sulphnr a t the desired height if the tube were surrounded with asbestos cardboard.Stan-nous chloride on the contrary required strongly heating in a blowpipe flame; the bottom of the tube in fact appeared to be at a low red heat alhhough Griinewald and V. Meyer (Ber. 1888 21 22 and Zeitschrijt f. physilcul. Chem. 2 184) state that i t boils constantly a t 6U6" a teniperature which the Thiiringen glass stands well. If the substance contained in the bath is not allowed to cool or solidify, several experinieDts can be made one after another without any danger of breaking the tube. A t the conclusion of the series of experiments the substance is of courde poured out of the bath while it is still liquid. I. Chlorides of Indium. Hitherto the only known chloride of indium is that whose composi-tion is represented by the formula In,Cl or InC13.When the metal * For the various details of the method of experimenting and the mode of cal-culating the results we must refer to our former paper on vapour-density determi-nations (J. pr. Chent. 1886 C23 33 l) and merely add here that the platinum apparatus we employed in the experiments in question had a capacity of 118 -19 C.C. for the cylinder which was 24.Q mm. high and 25 mm. in chameter and 7.48 c.c. for the neck which was 300 mm. high and about 5.6 mm. in diameter. That employed for the chromium chloride experiments had a cylinder of a capacity of 116.66 C.C 816 KILSOX AXD PETTERSSON KEW CHLORIDES OF INDIUM, is heated in chlorine the latter being in excess this chloride is obtained in beautiful dazzling white plates which a t a temperature approaching redness volatilise without previously undergoing fusion.Already in 1867 Clemens Winkler (J. pr. Chem. 102 96) in his preliminary investigation of the indium compounds noticed that the metal when exposed to a curi*ent of chlorine melts at first to a brown mass but he did not further investigate this substance. He however, expressed the opinion that it might possibly be a lower chloride of indium corresponding with the suboxide which he had obtained as a black pyrophoric powder on heating indium oxide at 300" in h j drogen. We have found however that indium in the stale of vapour gives three different well-characterised chlorides and =ow proceed to describe their mode of preparation properties and composition.Indium TrichZoi-ide InCl,.-Metallic indium is not; changed by exposure at the ordinary temperature to dry hydrogen chloride free from air but if heated in a current of this gas the hitherto unknown dichloride InC& (see p. SlS) is formed. If this is gently heated in a stream of chlorine it is easily converted into the trichloride having all the properties ascribed to it by Clemens Winkler. It is well known that in the literature of the subject only one vapour-density determination of this chloride occ'irs namely that made by V. and C. Moyer (Be]-. 1879 12 S l l ) in an appropriate furfiace using it tube of hard glass coated with clay and a t'emperature approaching a bright red heat ; the detisity found was 7.87 instead of 7.584 for TnC1,.According to the authors the formula of the chloride is thereby confirmed and the t'rivalency of the eiement established. They describe their investigation as follows :-" Iiidium chloride is not volatile in the vapour of diphenyl perchloride which boils far ahove 440° and sublimes but slowly in boiling phosphorus penta-sulphide (530"). At a low red heat however it sublimes easily but not very rapidly and it is only a t a bright red heat that it passes iiito the state of a normal gas. The supposition that indium chloride in the state of vapour is a mixture of C1 and an unstable In2C14 is improbable as indium does not form any derivatives corresponding with the ferrous compounds but only one series like aluminium. No free chlorine could be detected in the apparatus after the experiment, the chloride being found quite unchanged in beautiful lustrous crystals." As already pointed out however iudium forms two new chlorides, not a dichloride only but also a monochloride both of which a1.e btablo in the gaseous state and as the existence of these then unknown chlorides renders futile the remark of the learned author ASD THE VA4POVR-DESSIlIES OF IXDIUM ETC.817 Rbove quoted we felt it to be necessary to submit the indium trichloride to a renewed investigation. In order to obtain material for the vnpour-density determin a t' ion 8 quantity of indium dichloride sufficient for each experiment was first prepared by heating a weighed quantity of the metal in gaseous hydrogen chloride in a narrow drawn-out tube (see p.SlS) the hydrogen evolved being collected as usual in a Schiff's apparatus. The dichloride thus formed wag converted into the trichloride by heating it gently i n dry chloriiie free from air and then sublimed into an adjacent portion of the tube in a stream of pure carbon dioxide, so as to remove any adhering free chlorine. A platinurn tube about 20-25 mm. long was then inserted in the end of the tube which must be drawn out as shown in the figure. The little platinum tube a thus and c. forms a connection between the ends of the two tubes b By continued and careful turning of the platinum in the drawn-out openings of the glass tubes it may without difficulty be made to fit quite air-tight. If the glass tubes are carefully drawn out perfectly cylindrical and the openings but slightly conical the platinum tube remains quite firm even when the chloride is sublimed into it ; this is effected in a stream of carbon dioxide and as the platinum readily cools the chloride although so volatile condenses almost entirely in the metal tube.As soon as this is cold the chloride is turned into a little cup by means of a pair of tongs. The empty platinum tube is then weighed and also the little cup filled with chloride and inclosed in watch-glasses; in this way the weight of substance to be employed is known which in our experiments corresponded very nearly with the weighed quantity of metal taken. The calculated vapour-density' of the chloride InC1 is 7.548. Experiment 1 (see Table I p. 818) in sulphur vapour gave only a minimal vaporisation not measurable volumetrically.At the conclu-sion of the experiment howLver we observed on the sides of the glass tube several beautifully iridescent well-formed crystals of the chloride as thin six-sided plates. We can therefore confirm the statement of V. and C. Meyer that * The Meyer-Seubert atomic weights are used in all the calculations in this memoir 818 NILSON AND PETTERSSON NEW CHLORIDES OF INDIUM, gas die-placed c.c. at & and 760 -Expt. 1 2 4 5 -apour-density found. TABLE I.- Vapour-density of I n d i u m Trichloride. 6.022 7.021 6'447 7.110 Temperature determina-8.156 '7'391 6.716 6.234 Vol. of gas ex-pelled. C.C. --92 -984 98 -165 - -tion. Temp. of the mea siw-ing tube -15 -8' 14 *O 14 -8 13 *1 -Calcu-lated tempera-ture of expt.-440°1 6062 850 1048 .100-1200: Vapour-density deter-mination. Weight Of chloride in grams. -0 *0635 0 -0671 0 0560 0.0573 I VOl. of I mm. I I- -- I -Remarke. --Minimal VB-porisation. Slow vapor-isation. Rapid volati-iisation. 1 In sulphur vapour. I n stannous chloride vapour. 3 The exact tem-perature could not be determined on account of a defect in the platinum apparatus, but it was evidently higher than in Experiment 4. at 440" indium trichloride does not appreciably vaporise and that at % temperature which according to our experiments lies between 606" and 850" its vnpour-density corresponds with the value 7.548 calculated from the formula InCI,.I n boiling stannous chloride its vapour-density is somewhat higher ; as however it volatilises but slowly at this temperature it is improbable that there is any lower temperature at which an indium chloride of vapour-density 15.168, corresponding with the formula In,C16 can actually exist in the gaseous state. A t temperatures above 85@" indium trichloride a s the values we found show undergoes a progressive dissociation probably into lower chlorine compounds and free chlorine. Indium Dichloride InCl,.-If indium is heated to its fusion point in a current of dry hydrogen chloride free from air it yields indium dichloride with evolution of hydrogen ; at first indeed a reddish-brown liquid is formed containing indium monochloride (p. 820) but this as soon as the h-jdrogen chloride is in excess gradually becomes lighter and lighter and ultimately of a pure amber colour.It then consists of the pure dichloride and on cooling solidifies to a white radiated crystalline mass which if strongly heated volatilises and is deposited close to the flame in colourless needles. Any adhering hydrogen chloride may be removed by distillation in a current of dry carbon dioxide free from air. On exposure to moist air i t deliquesces AND THE VAPOUR-DENSITIES OF INDIUM ETC. 819 hnt it remains unchanged in dry air. Water decomposes the chloride with a reddish sheen (from monochloride formed as an intermediate product ?) into trichloride which remains dissolved and metallic iiidium which is deposited as a grey spongy mass ; the latter acquires metallic lust,re when conso1idat)ed to a lump by means of a glass rod.The dichloride therefore cannot exist in aqueoas solution but is decomposed with formation of the trichloride ; the reaction being-3InC1 = 2InC1 + I n . The amount of metal we obtained on treating the dichloride with water is somewhat less than that required by the equation which is doubtless to be ascribed to the formation of some oxychloride from the oxygen present. The composition of the new chloride is shown by the following syntheses and analysis. Synthesis I.-0.0573 gram of metallic indium treated as above gave the following quantities of hydrogen at 0" and 760 mm. :-Found. Cdculated. r- 7 C.C. gntm- C.C. gram. & Hydrogen. . . 11.04 0.000988 11.28 0.001010 From this weighed quantity of metallic indium 0.0904 gram of indium dichloride was sublimed into the platinum cup and used for Experi-ment 3 the calcula,ted yield being 0.0929 gram InCl supposing none of the chloride to have been lost.Xynthesis 11.-0.0966 gram of metallic indium gave-Found. Calculated. 7 I-- r-; C.C. gram. C.C. gram. Hydrogen. . . 18.60 0.001665 19-02 0.001703 Synthesis IIL -0.1203 gram of metallic indium gave 0.1940 gram of dichloride which was used in the following analysis; the calculated jield should have been 0.1964 gram. AnaZysis.-O.19%0 gram of indium dichloride was treated with boiled water. The solution yielded 0.3013 gram of silver chloride, corresponding with 0.07451 gram of chlorine; and 0.1008 gram of indium oxide corresponding with 0.0832 gram of indium.The metallic indium which separated weighed 0.0374 gram. Expressed centesi-rnally the resalts are 820 XILEON AKD PETTERSSON ISEW CHLORIDES OF INDIUX, Found. Calculated. Residual metallic indium 19.28) 62.1G 20:5Y} 61.58 Indium as oxide in soliltion 42.88 41 05 Chlovine . . . . . . . . . . . . . . . . 38.42 100.57 100*00 38.41 ~-TABLE 11. - Vapour-density of Indium Dichloride. Weigl't of chloride Expt. 1 2 3 -Vol. of gas dis- apour-dellsity Temperature determina-Temp. of the measur-ing tube. tion. Calcu-lat ed tempera-ture of expt. --Vol. of gas ex-pcllecl. C.C. -96 * 440 100 -608 -in and 760 1 mm. grams. found. Vapo iir- d en si t y deter-mi natio n.Remarks. --In platinum } cylinder. I n porcelain. The calculated vapour-density of the chloride InClz = 6.362. Indium dichloride which is incapable of existing in aqueous solution is a very stable compound a t high temperatures. At 9>8", the vapour-density foiind is somewhat higher than is required by the formula InCl, but a t higher temperatures it is quite normal. Indium MonochZoride InC1.-The circumstance that metallic indium when gently heated in gaseous hydrogen chloride the metal being in excess forms a dark-red liquid led us to believe in the existence of a lower chloride probably identical with the product noticed by Clemens Winkler on treating the metal with chlorine but which he did not examine. In order to obt,ain this in a state of purity a weighed quantity of indium was converted into the dichloride which was then distilled in a current of carbon dioxide into a neighbouring portion of the glass tube where a weighed quantity of the metal somewhat larger than the first had been already placed; the small tube was then fused off on both sides of it.On heating this tube in the naked flame reaction set in the liquid becoming blood-red and forming numerous drops like bromine which adhered to the glms. On cooling these solidified to vitreous or radiated masses aomewhat resembling haematite in appearance. The slight excess of metallic indium employed remained as a small button after the chloride had been volatiLsed in a curren AND THE VAPOUR-DESSITIES OF INDIUN ETC. 821 Weight of chloride in grams.of carbon dioxide as will be seen in the synthesis described here-after. I n thin layers the new chloride when melted is a liquid of a besutiful red in thicker layers it is almost black It soon attracts moisture from t-he air deliquesces and decomposes gradually into indium trichloride and metallic indium becoming grey in con-sequence. The monochloride is at once decomposed by water into the trichloride and metal the reaction doubtless taking place according to the following equation :-3InC1 = TnC1 + In,, the same remarks applying as in the case of the similar decom. position of indium dichloride. Synthesis.-O.llOO gram of metallic indium was heated in gaseous hydrogen chloride to convert it into the dichloride. When this had acted on 0.1160 gram of indium in an atmosphere of carbon dioxide in a sealed tube the red chloride formed was distilled off leaving a metallic button which weighed 0*0050 gram instead of 0.0060 gram.Now 0-2200 gram of indium should yield 0.2886 gram of indium mono-chloride; and in fact 0.2741 gram of this chloride was obtained The difference represents the loss occasioned by the distillation. ArzaZysis.-O*l656 gram of indium monochloride after decom-position with boiled water gave i n the solution 0.1606 gram of silver chloride corresponding with 0.0397 gram of chlorine and 0.0575 gram of indium oxide corresponding with 0.04746 gram of indium. The metallic indium which separated weighed 0.0190 gram. Expressed centesimally the results are-50’82} 76.23 23-98 23.77 100.31 100~00 Residual metallic indium.. 47.72 } ,6.33 Indium as oxide i n solution 28.62 25-41 Chlorine . . . . . . . . . . . . . . . . __.- -Of gas Vapour-$:p:$’ density and 760 mm. found‘ TABLE 111.- Vapour-density of Indium Monochloride. Experi-ment. 1 2 3 Temperatiire employed. w - 7 1300-1400” 1100-1150 1200-1 so3 Vapour-density determination. 0 -0660 9 ‘224 5 ‘534 0.0536 1 7.826 1 5.296 0.0549 7 -894 5 *377 11 In porcelain. VOL. LIII. 3 822 NILSON AND PZTTERSSON NEW CHLORIDES OF INDIUM, The calculated vapour-density of the chloride InCl = 5.140. The substance employed in Experiment 1 was not prepared in a, sealed tube in the manner above described but by the repeated dis-tillation of the dichloride over metallic indium in a current of carbon dioxide.This sample consequently in a11 probability contained some unchanged dichloride which accounts f o r the vapour-density found being somewhat too high. The vapour-density determinations given above place it oeyond doubt that the moiiochloride dichloride and trichloride of indium exist as definite compounds. The manner in which they are decom-posed by water is also of especial interest’ for with the exception of the lower chloride of gold there is scarcely an instance known in which a chloride is decomposed by water with separation of the metal and formation of a higher chloride. This behaviour of indium monochloride and dichloride shows us that indium in its solubIe compound is decidedly and exclusively a trivalent element although i t is capable of existing in combination at a high temperature as a univalent or bivalent element.Chlorides of Gal lizcm. Lecoq de Boisbaudran (Wurtz Dictionn,aire de Gkirnie Article ‘‘ Gallium ” by Lecoq de Boisbaudran) the discoverer of this element, has pointed out the existence of two different chlorides of gallium. He is inclined to regard the higher chloride as gallium hexachloride, GaR,Cls and the lower as gallium dichloride GaCI, in accordance with the views held at the time of his discovery as to the constitution of the iron chlorides and of aluminium chloride. The vapour-density determinations which he made by Dumas’ method with the higher chloride seemed also to confirm the composition assigned to it. After the introduction of the air displacement method however Friedel obtained values which indicated that this formula should be halved.13.4 at 247’7 ‘O’O ” 350 \boiling point 215-220”. Lecoq de Boisbaudran. Friedel. { 8.5 , 350 J 7% , 440 6.6 , 440 The calculated vapour-density for Ga$ls = 12.16 that for GaC& = 6-08. In order to place us in a position to decide on the true formula of this chloride Lecoq de Boisbaudran placed at our disposal the necessary material. As the vapour-density of the lower galliu AND THE VAPOUR-DENSITIES OF INDLUM ETC. 823 Experi-went. chloride is quite unknown we have also instituted a couple of experi-ments with it. Hydrogen. Found. I Calculated. Weight of metal. Gallium Trickloride GaC&.-Like aluminium bnt unlike indium, metallic gallium yields the trichloride when it is heated in gaseous hydrogen chloride.The reaction takes place at a gentle heat ; but at the ordinary temperature the metal remains quite unchanged if the gas is dry and free from air. If warmed a highly refractive liquid is formed with evolution of hydrogen and if more strongly heated this volatilises and is deposited in the tube close to the flame in long needle-shaped crystals the metal is completely converted into the chloride and leaves no residue. As soon however as the product is distilled in a current of carbon dioxide to free it from adhering hydrogen chloride a trace of a brownish-yellow slightly volatile residue is noticed in the tube ; this instantly becomes colour-less in gaseous hydrogen chloride. This appearance we believe can scarcely be ascribed to impurity in the metal employed but should more probably be regarded as due to a lower chloride corresponding with indium monochloride.Lecoy de Boisbaudran on treating gallium dichloride with much water obtained a brown subtance which i f left under water evolved gas slowly and rapidly if dissolved in hydrochloric acid. This com-pound which was not analysed he regarded as i n all probability a lower oxide of gallium. We are of opinion however that it was perhaps the monochloride of gallium which might be formed in the f'il lo wing way-2GaC1 = GaCIR + GaCI, and may be identical with the brownish-yellow substance which is formed in small quantity in the preparation of gallium dichloride (p. 824). Its true nature however must remain an open question until larger quantities have been obtained.Synthesis of Ga'lium Tric1doride.-In two experiments metallic gallium gave the following results when heated in dry hydrogen chloride free from air :-1 0 -0236 gram. 2 I 0.0220 ,, I Hydrogen at 0" and 760 mm. 11 *57 C.C. 0 *001036 gram. 11 '30 C.C. 0*001012 gram. 10.86 , 0.000973 , 10.54 , 0*000944 ,, I- I.--'-- I -82-1 NILSON AND PETTERSSON NEW CHLORIDES OF INDIUM, TABLE IV.- Vapour-densit!y of Gallium Trichloride. Vapour-density found. Vrzpour-density determination. Remarks. --- I I in 1 2 8 4 350" 0 *0543 4.40 0.0521 606 0 '0562 1000-1100 0.0567 I I Vol. of gas displaced, C.O. at 0" and 760 mm. 4 948 6 -5% 7.074 8 *457 -I 8 *846 6.118 6 *144 5 -185 In mercury vrtpour.Insulphur ,, In stannous chloride vrzpour. In furnace with platinum vessel. The vapour-density calculated on the formula GaCIB is = 6.081. If our determinations are compared with the earlier ones it is instructive to observe that gallium trichloride like beryllium chloride, aluminium chloride &c. has a vapour-density higher than the normal at the lowest temperature employed; but even at 40" it has the normal value and retains it also a t 606" in the vapour of stannous chloride ; at still higher temperatures it suffers dissociation like many other trichlorides. The difference in the values obtained by Lecoq de Boisbandran and Friedel at one and the same temperahre must be set down to the different methods employed by the two investi-gators.GaZZium DichZoride GaCl,.-According to Lecoq de Boisbaudran this compound may be obtained by heating the metal in chlorine, taking care to keep the gallium in excess. We preferred however to prepare it from weighed quantities of the metal in exactly the same way as indium monochloride. We allowed 0.0352 gram of gallium to act on the trichloride formed from 0.01 70 gram of gallium a quantity more than sufiicient to convert it into dichloride or even into monochloride. After long-continued heating and complet,ion of the reaction we opened the tube and distilled out the colourless chloride in a stream of carbon dioxide a button of gallium being left which weighd 0.0225 gram. The trichloride consequently had taken u p 0.0127 gram of gallium, or 0.0042 gram more of the metal than corresponds with the formula QaC1,.We noticed however not only that several exceedingly minute globules of gallium remained in the tube and could not be extracted but also that the tube was covered with a thin coating of the brownish-yellow substance previously mentioned when speakin AND THE VAPOUR-DENSITIES OF INDIUM ETC. 825 Weight of chloride in grams. of the trichloride ; this we are inclined to regard as a rather unstable gallium monochloride as on exposure to an atmosphere of hydrogen chloride or chlorine it instantaneously becomes white and is con-verted into colourless drops which solidify to a crystalline mass on cooling volatilise when heated and in short exhibit all the pro-perties of gallium trichloride.Gallium dichioride when melted forms a limpid refractive liquid which on cooling solidifies and becomes crystalline ; it distils when heated and is deposited on the tube near the flame in a solid state. Its vapour like that of the trichloride fumes in the air on account of its attraction for the moisture in it. E$:$r Va,pour-c.c. at oo density and 760 mm. found' TABLE V.-Vapour-density of Gallium Diddoride. Experi-ment. -1 2 Temperature employed. looo-llooo 1300-1eo0 Vapour-density determination. -I--)-0 -0402 4 -823 0.8464 1::t:o" I 3'568 Remarks. --} In porcelain. The theoretical vapour-density of the chioride GaCI2 is = 4.859. Gallium dichloride does not appear to be so stable as indium dichloride at a high temperature.Experiment 2 shows that i t is decomposed at a full white heat which is most probably to be attri-buted to the formation of a gallium monochloride and free chlorine. According to our experience dissociation of a chloride with increase of temperature only takes place when a lower chloride exists which is more stable at the higher temperature. For example in our experiments with beryllium chloride indium monochloride ferrous chloride &c. we always obtained values corresponding with those calculated however high the temperature might be; whilst all the chlorides we have examined of which lower chlorine compounds exist gave at the highest temperatures values considerably lower than the theoretical. Remarks on the Palency of the Elements of the Aluminium Group.The elements of the third group whose chlorides we have already examined give the following chlorine compound8 : 826 NILSON AXD PETTERSSON NEW CHLORIDES OF INDIUX, Gallium . . Indium . . . . . Monochloride. Not known for cer-InCl reddish-yellow, when fusedretidish-brown tainty - I -Aluminium I Wanting . . . . Dichloride. -I_-Wanting . ,. . . . GaCl, colourless fusi-ble crystalline InCl, colourless when melted amber-yellow Trichloride. --AlCl, colourless in-fusible a t the ordi-nary pressure crys-talline. GaCI, colourless fusi-ble crystalline. InCl, colourlesa in-fusible crystalline plates. It is noteworthy that aluminium when treated with hydrogen chloride displaces 3 atoms of hydrogen indium 2 atoms and thallium (according to Lepsius! Ber.1888 21 556) 1 atom. In this group also there is a decided tendency to form a larger number of chlorine compounds as the atomic weight increases. Aluminium forms but 1 chloride whilst gallium yields 2 indium 3 and thallium 4 chlorides TlCl T1,C13 T1C12 and TlCl,. The question which is so interesting theoretically as t o whether aluminium behaves towards chlorine exclusively as a triad has already been touched npoii by some French experimentalists. I n researches on the action of aluminium trichloride on metallic aluminium a t various temperatures high and low instituted by Troost and Hautefeuille (Conzpt. rend. 1885 100,1221) Hautefeuille and Perrey (ibid. 1885 100 1220) and Friedel and Roux (ibid. 1885, 100 1191) it has been shown that a grey coating is formed on the metal or a lustrous deposit on the sides of the tube.The origin of these substances however must be assigned to the presence of traces of silicon as silicon could be detected in all or a t least in most instances. Friedel and ROUX indeed state that when metallic aluminium is acted on by silicon chloride a t a red heat it yields aluminium chloride with separation of silicon. I n order to settle this question we prepared aluminium triohloride from a weighed quantity of aluminium by heating it in gaseous hydrogen chloride and then allowed i t to act on a weighed quantity of very thin aluminium foil in an atmosphere of carbon dioxide in ft sealed tube which was heated over a bare flame. By long-continued action of the chloride which under the high pressure fused to a limpid liquid the aluminium foil did indeed become superficially of a greyish colour b u t i t was otherwise unchanged.I f one end of the short tube was now heated the chloride condensed in the other colder end in beautiful well-defined six-sided tables identical in appearance with the crystals of indium trichloride. At the close of the experiment whendl the chloride had sublimed to the other en AND THE VAPOUR-DENSITIES OF INDIUM ETC. 827 of the tube the Iat-ter was opened and the residual aluminium foil with adhering traces of aluminium chloride taken out and thrown into water when after a momentary evolution of gas it completely regained its metallic lustre ; on drying and weighing i t was found to have diminished in weight by a few tenths of a milligram only.This inconsiderable loss is moreover easily explained by the action of traces of silicon chloride on the aluminium foil forming aluminium chloride and silicide of aluminium which gave the grey appearance to the foil. There is no reason to believe therefore in the existence of any chloride of aluminium lower than AlCI,; Friedel and Rfoux indeed (Zoc. cif.) are inclined to regard the amount of chlorine in the above-mentioned grey coating as evidence that a second chloride of aluminium may be found but as Hautefeuille and Perrey have shown that various oxychlorides of aluminium are formed when a mixture of chloride of aluminium and oxygen is passed over the heated metal the low chlorine found may be due to oxygen not having been completely excluded in Friedel and ROUX’S experi-ments.Moreover the vapour-density of a1 uminium trichloride as determined by us a t various tempera-tures (Zoc. nit. see also the remarks under GaZZiim Dichloride p. 825) is evidence of the non-existence of a lower chloride of this element. IV. Ferrous Chloride. V. Meyer (Ber. 1879 12 1193 and 1884 17 1335) has made vapour-density determinations of ferrous chloride under various condi-tions both in an atmosphere of nitrogen and also in hydrogen chloride. I n the last series of experiments he obtained the numbers 6-38 and 6.67 which are almost intermediate between those required by the formulae Fe2C14 and FeC12 namely 8.750 and 4.3Y5. The substance evaporates rapidly a t a yellow heat and the results of the two experiments agree very well.The values found therefore seemed to the experimenter to indicate that a t low temperatures the molecule of ferrous chloride had the formula Fe2C14 and that as the temperature rose it decomposed into FeC1 ; the temperature employed however, was not high enough to enable him to obtain values corresponding with the latter. V. Meyer considered it necessary that the question should be further investigated using platinum vessels especially as the experiments with beryllium chloride have brought to light the disturbing influence involved in the use of glass or porcelain vessels ; he has himself stated however that the glass tube in which the ferrous chloride was sublimed was not a t all acted on.As a t V. Meyer’s suggestion me have undertaken to renew th 828 NILSON AND PETTERSSON NEW CHLORIDE8 OF INDITJM, Experi-ment. investigation of this question we deemed it before all things necessary to determine whether there was really a definite limit to the vapour-density of ferroua chloride a t high temperatures. I n the two experi-ments described below made under somewhat different conditions we obtained results which not only agreed with one another but are in accordance with the values reckoned for the formula FeC12 to the second decimal place and we therefore regard the question of the constitution of Perrous chloride as resolved in so far as that the vapour of this substance at lower temperatures has a complex constitution as shown by V. Meyer's determinations and by analogy with what has been found to be the case with almost all the chlorides we have investigated chloride of beryllium and chloride of aluminium for example whilst at a white heat this decomposes, yielding a molecule of the normal composition FeCI2.In our vapour-density determinations we used vessels of Rayeux porcelain as like V. Meyer we found that the vapour of the chloride during its preparation and sublimation did not act on glass. After the experiment we found that the substance dissolved in water as ferrous chloride without leaving any residue. The substance was prepared by strongly heating soft iron wire in a platinum tube in a current of gaseous hydrogen chloride; the ferrous chloride formed was deposited i n the fore part of the platinum tlibe close to the flame as a radiated crystalline mass of the colour of siderite and was as usual enclosed in a platinum cup for the experiment.Remarks. Temperature employed. Weight of QO1' Of gas Vapour-chloride :!:f2:t density i n grams. 1 and 760 mm. found. I TABLE VI.- Vapour-density of Ferrous Chloride. I Vapour-density determination. 1300-14.00" I 0.0428 7.611 I 1400-1500 1 0.0388 1 6.922 1 $': ~}lnporcelain' The theoretical vapour-density required by the formula FeCI is 4.375. V. Chlorides of Chronzium. As is known chromium forms two compounds with chlorine to which the composition represented by the formula Cr,Cl and CrCl ASD THE VAPOUR-DENSITIES OF INDIUN ETC. 829 has hitherto been assigned as in the case of the Corresponding iron chlorides.The vapour-density of neither of these has been deter-mined and i t seemed to us a matter of no small interest to examine these along with the chlorides of indium gallium and iron. Chromiunz Trichloride CrCl,.-At the last '' Naturforscherver-sarnmlnng" in Wiesbaden we noticed the splendid exhibit of Herr H. Deibel of various chemical preparations amongst which was some resublimed chromium chloride in beautiful crystalline plates. This was obtained from him for the purpose of making the vapour-density determinations and i t gives us pleasure to testify to the purity of the specimen as established by the reduction experiment described on p. 830. The chromium chloride from exposure to the air contained a little hygroscopic moisture but this was removed by gently heating it in dry carbon dioxide free from air before weighing it out for the vapour-density determination.When the platinum cylinder was used in the determination the chromium trichloride was placed in a small platinum cup; in the experiments with the porcelain vessel a piece of a pipe stem was employed which 'was made into a convenient shape before ignition in the blowpipe flame, the one end being closed by a kaolin stopper. TABLE VIL- Vapour-densit y of Chromium Trich loride. -Expt. 1 2 3 4 5 6 7 -Temperature determination. Vol. of gas dis-placed. -95 -802 98 -888 98.824 101 *420 -- - -Tempe-sature of measur-.ng tube 9 *lo -13 -6 9.8 14 *6 --I Calculated tempera-ture. --1065' 1191 1277 1347 L100-120( 1250-135( 13 5 O-140( Vapour-density determinatior Weight ride in grams.of chlo-Vol. of gas displaced, C.C. at 0" 8 760mm 0 9864 0 -0859 0 *0882 0.0'791 0 -0578 0 *0498 0 *0638 10 -890 12 -049 12 * 581 12 -670 7 -890 '7 '440 10.770 Vapour density found. -6 *l35 5 -517 5 *421 4 -827 5 -670 5 -177 4 -580 Remarks. -I n platinum, volatilisa-tion slow. In plati-num voln-tilisation normal. I n porce-lain. I The theoretical vapour-density of the chloride CrCZ is 5.478. Chromium chloride therefore according to the determination made at 1200-1300" has a vapour-density corresponding exactly with the formula of a trichloride. As vaporisation takes place but slowly at VOL.LILI. 3 830 T\;ILSON AKD PETTERSSON NEW CHLORIDES OF I?;L)IUJI. Experi-ment. 1065" when the value found is somewhat too high there is probably no lower temperature a t which a ohloi-ide of the hitherto accepted formula Cr2Cl and vapour-density 10.956 can exist in the gaseous state. At temperatures above 1300" the chloride gave numbers somewhat too low which was to be expected from the dissociation of the tricldoridc into free chlorine and the dichloride which is stable a t high temperatures. Temperature employed. Weight of VO1' Of gas Vapour- Remarks' chlorine :!:'$ density and 760 mm. found* in grams. --- ____-_____)_I______ Chromium Dichloride CrCI,.-This compound was pepared by the reduction of the trichloride with pure and dry hydrogen a t a, temperature so low that the glass tube was not visibly red hot.Reduction Experiment.-O.2927 gram of chromium trichloride gave 0.2274 gram of dichloride a quantity which corresponds accurately with the theoretical. The dichloride employed in the following vapour-density deter-mination was prepared separately for each experiment by introducing a weighed quantity of dry chromium trichloride into a porcelain or platinum cup and reducing it in a stream of hydrogen until hydrogen chloride could no longer be detected in the gas issuing from the mercury seal of the apparatus ; the cup was then intrcduced as quickly as possible into a pair of watch-glasses and weighed. In this way a residue was obtained which always corresponded very accurately with the theoretical. The dichloride prepared in the manner described was white with a greyish shade and volatilised with greater di5culty than any of the metallic chlorides we have examined. It vaporises rather slowly even in the most intense heat of the furnace we could obtain using a Rohrbeck-Luhnie 16-fold blowpipe lamp worked with gas and air a t 2 atmospheres pressure. TABLE VIII.-~apo.zLr-densit~ of Chromium Dichloride. Vapour-density determination. 1 1300-1400° 0.0545 5 -403 7 -800 2 1 1400-1500 1 0*0561 1 5.960 I 7.278 i}hporcelain. 3 1500-1600 0'0351 6 *847 6 -224 The theoretical vapour-density of the chloride CrCl is 4.256. Thus we have found the vapour-density of chromous chloride to b ON SOME DERIVATIVES OF ANTHRAQVINONE. 831 considerably higher than that required by the formula CrCI, but as the three experiments me made show a constant decrease of density with increase of temperature there can be no doubt that chromous chloride in respect of vapour-density is strictly analogous to ferrous chloride except that it volatilises at a much higher temperature and scarcely becomes completely gaseous even at the highest heat attainable

ISSN:0368-1645    

DOI:10.1039/CT8885300814

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

ON SOME DERIVATIVES OF ANTHRAQVINONE. 831 LXIX.- On some Derivatives of Antbrapinone. By A. G. PERKIN and W. H. PERRIN Jun. Ph.D. IN a previous papel. on this subject which we had the honour of com-municating to the Society some time since (Trans. 1885 47 679), we described a series of experiments on the products of the destructive distijlation of sodium anthraquinonemonosulphonate. This salt when heated in an iron tube yielded a brownish-red dis-tillate which on examination 'was found to contain metahydroxy-anthraquinone anthraquinone and a peculiar red substance which after purification by recrystallisation gave numbers agreeing with the formula CzsH,,O6 ; it is nearly insoluble in all the usual solvents, and curiausly enough in alkalis also. On oxidahion with chromic acid it yields a white crystalline substance of the formula C,,H,O, and when distilled with zinc-dust anthracene is produced proving the substance t o be an anthracene-derivative.The remarkable character of this decomposition of sodium anthraquinonemonosulphonate has led us t o continue our experiments with a view to obtain some clue as to the constitution of the compound C2,H,,06. The extreme difficulty however of obtaining it in any quantity owing to the tediousness of it's prepara-tion and purification has prevented us from making as thorough an examination of the subject as we could have wished. We hope at some future date to be able to complete these experiments and to establish without doubt the constitution of these derivatives. Before proceeding with the examination of the red substance C,sH,406 we thought it advisable to again analyse it in order that there might be no doubt as to its formula.A quantity was therefore prepared and very carefully purified by repeated recrystallisations from glacial acetic acid. The pure substance was thus obtained as an orange satiny crystalline mass which after careful drying at 110-120" gave the following results on analysis :-3 L 892 A. G. AND W. H. PERKIN JUN. OX 0.1609 gram substance gave 0.0495 gram H,O and 0.4450 gram CO,. Theory. C 2 J ~ 1 . 1 0 6 ' Found. C . . 75-34! per cent. 75.37 per cent. H . 3.14 , 3.42 ,, 0 21-52 , 21.21 'I, I f a hot dilute solution of this substance in glacial acetic acid is slowly cooled groups of small orange-coloured cryatah separate, just visible to the naked eye ; these when collected washed and dried, present the appearance of beautiful satiny orange-coloured flakes.If hot saturated solutions are rapidly cooled the substance is deposited as an orange-coloured gelatinous mass. I n the previous paper it was stated that t.his compound C2SH1106, was converted into alizarin on fusion with potash. As it was important t o be quite sure of this the experiment mas repeated with somewhat larger quantities the decomposition being conducted in the following manner :-About 2 grams of C,,H,,O were heated with rz very con-centrated solution of caustic potash at 180" f o r about 12 hours in a closed iron tube. The contents of the tube which in appearance very much resembled an ordinary alizaih melt were extracted with boiling water the violet-coloured solution filtered from a small quantity of insoluble matter and a little slaked lime added.The alizarate of lime thus precipitated was collected well washed suspended in water, decomposed with a little dilute hydrochloric acid and the orange pre-cipitat e obtained was purified by recrystallisation from benzene. The product consisted of red needles melting at about 285" and showing all the properties of alizarin. On analysis it gave the following numbers :-0.1107 gram substance gave 0.0396 gram H,O and 0.2821 gram c 0,. Theory. C14H804. Found. C . . 70.00 per cent. 69.50 per cent. 0 26-66 , 26.53 ,, H . 3.33 , 3-97 ,, The filtrate from the alizarate of lime was of n reddish colour with a green fluorescence ; on treatment with hydrochloric acid it depo-sited a very small quantity of a nearly white precipitate which when washed on a filter changed to a dirty green.On fusion with potash and t,reatment of the fused mass with water a solution was obtained having all the properties of potassic alizarate. This substance is therefore intermediate between the red substance and alizarin ; it is probably identical with a substance C28H1107 whic SOME DERIVATIVES O F AXTHRAQUIKONE. 833 will be described later on under the heading " Action of Nitric Acid on C28H1106." When fused with potash Ci8H,iOG is probably first oxidised to C,,H,,O, which then takes up the elements of water and is converted into alizarin thus :-C:sHI,O + HZO = 2C,4H804. That such a change really takes place is all the more probable, from the fact that the substance C28H2407 when fused with potash, also gives alizarin.The residne from the fusion insoluble in water was crystallised from acetic acid and thus obtained in orange needles which were found to consist of unchanged C2sH,,0,. 0.1491 gram substance gave 0.0470 gram II,O and 0.4097 gram co,. Theory . C?,H,,% Bound. C 75.34 per cent. 75.01 per cent. H . 3.14 , 3.50 ,, 0 21.52 , 21-49 ,, Action of Sui$hwic Acid on Cz8H,,OG. Cold Nordhausen sulphuric acid dissolves the red substance forming a dirty green solntion which in contact with the air absorbs moisture, and deposits the unchanged substance as a transparent jelly. When the solution in Nordhausen acid is heated to 190" the colour gradually changes to a brownish-red and if at the end of about half an hour the mixture is poured into water it dissolves to a clear solution which on cooling sets to an opaque jelly.All attempts to free this mixture from sulphuric acid by treatment with the carbonates of lead OT barium failed owing to the salts of the sulphonic acid being in-soluble. If the mixture of the sulphonic acid and sulphuric acid is neutrslised with potash and slowly evaporated the dark solution deposits a small quantity of a crystalline salt which under the microscope is seen to consist of long needles ; these when heated to 100" fuse to a gummy mass. Fused with strong potash in an iron tube for some hours and then decomposed with hydrochloric acid a substance is obtained which dyes mordanted clot,h shades intermediate between those produced by anthrapurpurin and flavopurpurin.Action of Nitric Acid on C28H1P06. On gradually adding the red substance C,,H,,O, to cold fuming nitric acid of sp. gr. 1.5 i t dissolves without evolution of red fumes 534 A. G. RPU'D W. 13. PERKIN JUN. ON forming a bromine-coloured solution. In examining the product of this reaction the mass was allowed to stand for a short time and then diluted with water. This caused the precipitation of a yellowish-white amorphous substance which was filtered off well mashed and dried. It was then dissolved in a little hot aniline or nitrobenzene, filtered and boiling alcohol added drop by drop to the hot solution until the mixture showed a tendency to become milky.On aJlr>wing this to cool slowly minute cr-j-stals were deposited which after col-lecting mashing with alcohol and drying at l l O o gave the following iiumbers on analysis :-I. 0.1366 gram substance gave 0.0418 gram H,O and 0.3658 11. 0.1650 gram substance gave 0.0505 gram H,O and U-4420 gram CO,. gram COL. Found. Theory. f--n-- -7 C,,H,,~;. I. 11. C 72-72 p. c. 73-01 '73.05 p. c. H 3-03 , 3.40 3.40 ,, 0 24.24 , 23.59 23.55 ,, This substamnee has therefore the formula C26H1407 being produced from the red substance C,,H,,O by the simple addition of oxygen, thus :-C,H,,O + 0 = C2,H,,O,. Ci.ystallised from a mixture of aniline or nitrobenzene and alcohol, this substance C26H,407 appears iindcr the microscope as groups of short colourless needles.Prom hot acetone however in which it is only very slightly soluble it can be obtained in l a q e r crystals. It is slightly soluble in coal-tar naphtha more soluble in acetic acid. When heated it melts a t a high temperature to a yellow liquid which on cooling solidifies to a hard crystalline niass. At higher temperatures it chars only a very small quantity subliming in microscopic needles. C28Hl,01 dissolves readily in hot aniline or nitrobenzene a n d the solu-tions on cooling deposit small plates of a brownish colour. These substances which are evidently additive compounds of C,,H,,0 with aniline and nitrobenzene have not as yet been analjsecl. They are readily obtained pure by adding cautiously t o the hot solution i n aniline or nitrobenzene about twice the volume of benzene.On cool-ing the compound separates out in glistening plates. On boiling with alcohol they are quickly split u p into their constituents. Boiled with zinc-dust and potash solution C,,H,,O slowly dissolves, forming a reddish-brown solution which on shaking w i t h air instan-taneously decolorises with precipitat'ion of a white gelatinons snb-stance S031E DERIVATIVES O F BNTHRAQUIXO1U’E. 833 The following reaction is characteristic of this substance :-If a trace be boiled with a strong solution of pobash in methyl alcohol in a test-tube it will gradually dissolve with an olive-green coloratioc. On continued boiling the solution becomes darker and darker coloured as the methyl a1 coho1 evaporates the green gradually changing to a beautiful brownish-pink.On adding water a violet solution is obtained which does not decolorise on shaking with air, aud therefore possibly consists of potassic alizarate. Action of Nitric and Sublauric Acids on C,,H,,OG. If C2,HI1O6 is treated with a mixture of nitric and sulphuric acidF, ,z reaction quite different from the above takes place. In studying this, a small quantity of substance was boiled with a mixture of equal parts of nitric and sulphuric acids for a short time the product poured into water and the precipitate well washed and dried. I n order to purify it it was dissolved in hot acetic anhydride the solution poured into an equal bulk of hot alcohol and allowed to cool slowly. A beautiful yellow crystalline powder was thus obtained which on heating with potassium and then testing with ferrous and ferric chlorides was found to contain a considerable amount of nitrogen.We have not as yet analysed this nitro-derivative but its properties resemble very much those of the nitroanthraquinones except that it does not sublime when heated but is almost entirely decomposed leaving a black residue. If heated with sulphuric acid a violent reaction sets in, and on diluting the product with water a red-violet precipitate is obtained which dissolves in potash with a blue colour. When boiled with sodium sulphide a brick-red amido-compound is obtained re-sembling amidoanthraquinone with which however it does not appear to be identical. Fusion of Cz8Hla07 with Potash. In carrying out this experiment the substance was heated in a closed iron tube with concentrated potash solution for 12 hours a t 180”.The product was then boiled with water filtered a small quantity of lime added to the violet-blue filtrate again filt’ered and t h e residual violet powder washed with water and decomposed with hydrochlcric acid. The orange-coloured precipitate formed was washed with water, dried and once or twice recrystallised from benzene. Red needles were thus obtained which melted a t about 285” and showed all the properties of alizarin. The analysis gave the following numbers : 836 A. G. ASD W. H. PERKIK JUN. OS 0.1471 gram substance gave 0.0488 gram H,O and 0.3749 gram GO,. Theory. C14H8O.i. Found. C 70.00 per cent. 69.57 per cent. H . 3.33 , 3.62 ,) 0 26.66 , 26.81 ,, The filtrate from the alizarate of lime was a red solution with cz green fluorescence which on acidifying gave a white precipitate, changing to green on washing.This substance of which oiily a minute quantity was obtained appeared to be unat tacked C1YH1107. That portion of the product which was insoluble in water after re-peated recrystallisation from glacial acetic acid appeared under tho microscope as orange-red needles giving with sulphuric acid a red-dish-violet solution and in all other respects showing the properties of the red substance C,H1406. Dried a t 120" it gave the following results on analysis :-0.0859 gram substance gave 0.0269 gram H,O and 0.2365 gram c02. Theory. C28H140,. Found. C 75.34 per cent. 75.09 per cent.H . 3.14 , 3.48 ,, 0 21.52 , 21-43 ,, Two distinct reactions therefore take place when C2sHl,0 is fused In the first place the elements of water are taken up 1 mol. of with potash. C28H1407 splitting up into 2 mols. of alizarin thus :-whereas at the same time a certain amount of reduction takes place, some of the C28H1407 being reduced to the original red substance, thus :-C28H1407 + H = C,~Hiio + J%O. Action of Chromic Acid on C28H1407. In the first paper ori these anthraqninone-derivatives (Zoc. cit., p. 683) we showed that when the red substance C,6Hl,06 is oxidised with chromic acid in acetic solution it is converted into a white sub stance of the formula CI4H6O4 thus :-C28HuO6 + 0 = 2 0 4 + J&O SOME DERITBTIVES OF ANTHRAQIJIKONE. 837 On considering the results just described it appeared likely that thc substance CZ8H,,O7 was really the first product of the action of oxidising agents on C2PH1406 and that this therefore on further oxidation should yield the same substance C1,H604 as is obtained direct by the action of chromic acid on C28H1406.In order to decide this point a small quantity of the substance C,,H1407 was dissolved i n hot glacial acetic acid and treated with chromic acid until the violent reaction which set in a t first had subsided. On allowing the green solution to cool a white crystalline powder wzs deposited. This was collected washed dried and several times recrystallised from glacial acetic acid. In this way the product was easily separated into two portions, one of which was considerably more soluble i n acetic acid than the other.The less soluble portion on analysis gave the following numbers :-0.1583 gram substance gave 0.0385 gram H,O and 0.4100 gram c 0 2 . Theory. o 4 . Found. C 70.59 per cent. 70.63 per cent. H . 2.52 , 2.70 ,, 0 26.89 , 26-67 ,, The substance therefore has the formula Cl4H6O4 arid a careful comparison showed that it is without doubt identical with that pro-duced by the direct oxidation of the red substance C,8H1r06 with chromic acid. Attempts to produce the subst,ance C,8H,,07 by cautious oxidation of C28H1406 with chromic acid were unsuccessful the reaction in all cases going as far as the formation of the compound C,,H,O,. The more soluble substance cbt'ained in the above oxidation was found on examination to consist of unchanged substance as the following analysis shows :-0.1699 gram substance gave 0.0490 gram HzO and 0.4520 gram co,.Theor?. C?sH1407. Found. C 72.72 per cent. 72.51 per cent. H . 3-03 , 3.20 ,, 0 24-25 , 24-29 ,, Action of Hydriodic Acid on C28H1406. Experiments were next made with the object of removing some of the oxygen-atoms from the molecule Cz,H140e in the hope of thn 838 A. G. AND W. H. PERKIN JUN. ON obtaining some well-known compound the formation of which might tlirow additional light on the iiature of the red substance. I f Cz8Hl4O6 is suspended in hot glacial acetic acid and fuming aqueous hydriodic acid added drop by drop the crystals rapidly dissolve forming a deep red solution which contains free iodine ; this is filtered and poured into water when a lemon-yellow precipitate is deposited which is collected well washed dried and purified by recrystallisation from a mixtiire of hot aniline and alcohol ; on cooling it is deposited as a yellow crystalline powder.Two different samples dried a t 110" were analysed with the following resnlts :-I. 0.1457 gram substance gave 0.0470 gram H,O and 0.4160 gram 11. 0.0659 gram substance gave 0.0212 gram H,O and 0.1880 gram CO,. co,. Found. Theory. /-+ (-A-I. 11. C?SHIQOS. C?,H16$. C . . . . 77.86 77.80 p. c. 78-14 77-77' p. c. H . . . . . 3.58 3.57 , 3-26 3 i O ,, 0 . . . . 18.56 18-53 , 1S.60 18.52 ,, The nunibers obtained agree therefore better with the formula C,,H,,O than with C2,Hl6O5 and i t is probable that this new com-pound is formed from the red substance simply by eliniination of oxygen thus :-C,,H1406 + H = Cz,H,,O5 t H,O.This substance C2sH1105 which is insoluble in aqueous potash dis-solves in a strong hot solution of potash in methyl alcohol with an intense orange-brown coloiir which on long boiling does not change. If the alcohol is evaporated the colour becomes intenser as the solution becomes stronger until a t last a dark-brown residue is left ; this dissolves in water with an orange-red colour which how-ever alniost disappears on shaking with air. Wheii boiled with zinc-dust and potash C,,HI4O5 gives scarcely any coloration but it dissolves in concentrated sulphuric acid forming an intense reddish-brown solution. The ease with which the red substance C,,H,,O loses 1 atom of oxygen and is reduced to C28H1105 led us to think that it would be interesting t o study the further action of hydriodic acid on this substance.For this purpose a mixture of 0.5 gram of the pure red substance 5 grams of fuming hydriodic acid and 5 grams of glacial acetic acid were heated in a sealed tube for about half an hour t o 160". The dark-red liquid thiis obtained was gently evaporated to get rid of most of the acetic acid the residue freed from iodine b SOME UERIVATIVES O F AXTHRAQUXXONE. 839 boiling with dilute aqueous sulphurous acid. The precipitate which separated on cooling was collected filtered washed with water and dried on a porous plate. On extracting the product with alcohol, nearly the whole dissolved leaving a small quantity of a yellow substance behind.This residue after careful drying and sublimation in a test-tube formed microscopic yellow needles melting at about 260-265" and which on boiling with potash solntion and zinc-dust gave a red solution becoming colourlcss again on shaking with air. This substance was therefore probably anthraquinone. The alcoholic solution on evaporation deposited a considerable quantity of a somewhat sticky yellow substance which especially when boiled with water possessed in a marked degree the peculiar odour of dihydroanthracene. In order to determine whether the reduction really had gone as far as this the crude substance was distilled in a test-tube the solid distillate washed with a little alcohol, and then recrjstallised from this solvent.I n this way small crystals were obtained which melted at 104-106" and otherwise showed all the properties of dihydroanthracene. Action of S d p h u ~ i ~ Acid o n C,sH,407. I n studying this action a small quantity of the substance was heated with fuming sulphuric acid at 180". The reddish-brown solution first formed became gradually darker and eventually after 20 minutes' heating of a hluish-red colour. At this stage the decom-position was evidently complete the product dissolving completely in water sliowing that a sulphonic acid had been formed. On adding acetic acid t o the strong hot solution and allowing it to cool a small quantity of a crystalline precipitate separated. I t was however, found inipracticable t o purify the sulphoriic acid by this method as it was too soluble in acetic acid to admit of sufficient washing.The mixture of the sulphonic acid and sulphuric acid dissolved in water forming a greenish solution with which lead or barium carbonate yielded insoluble compounds only. 111 order if possible t o determine the nature of the sulphonic acid ihus formed resort was had t o fusion with potash. The solution was mixed with a considerable excess of concentrated aqueous potash and heated in closed iron tubes at 180" for about 12 hours. The product dissolved in water formiiig a red-violet solution and on the addition of acids a brownish-yellow precipitate was thrown down which was collected and well mashed with water. This substance dyed mordanted cloth shades intermediate be tween those given by anthrapurpurin and flavopurpurin and therefore, probably consists of a mixture of these two substances 840 A.G . AND TT. H. PERKIN JUN. OX Fusion of C,,H,O with PotasJh. This substance the preparation of which was given in the previous paper (Zoc. cit. p. 683) is formed by the oxidation of the red substance, C28H1406 with chromic acid in act tic acid solution. Considering the interesting constitution previously assigned to this substance and its mode of formation from the red substance it was thought that valuable results might be obtained from the further study of its properties. The first decomposition which was studied was the action of caustic potash a t high temperatures on this substance. Two grams of pure CldH607 were heated with concentrated potash solution for about 12 hours a t l80" the dark-coloured product extracted with boiling water and filtered.A small quantity of lime was then added to the bluish-violet filtrate the lime compound thus precipitated collected, washed with water and decomposed with dilute hydrochloric acid. This caused the precipitation of an orange-red compound which after collecting washing with water drying and recry stallising once 01' twice from benzene was obtained in long red needles ; i t melts a t about 285" and possesses all the properties of alizarin. The analysis gavs the following numbers:-0.1175 gram substance gave 0.0391 gram H20 and 0.1175 gram GO,. Theory. ~14Ht304. Found. C 70.00 per cent. 69.98 per cent. H . 3-33 , 3.69 >, 0 20.67 , 20.43 ,, The portion of the product insoluble in water obtained during the fufiion of C,H,O with potash was extracted several times with glacial acetic acid and boiling water added to the filtrate.On cooling long orange-coloured needles were deposited which on analysis gave numbers corresponding with the formula CI4H,O2. I. 0.1235 gram substance gave 0.0465 gram H,O and 11. 0.1285 gram substance gave 0.0466 gram H,O and Theory. F - - 7 Cl4H802. I. 11. 0.3648 gram CO,. 0.3800 gram CO,. Found. C 80.i7 p. c . 80.60 80.65 p. c. 0 15.39 , 15.23 15-32 ,, H 3.84 , 4.17 4.03 ,, This compound obtained by the fusion of C,4H60 with potash did not a t all resemble anthraquinone outwardly as however often it wa SOME DERIVATIVES OF ANTHRAQUINONE.841 recrg-stallisecl it was always deposited in flat silky needles of an orange colour. It melted however at 275" the melting point of anthraquinone and when heated strongly it sublimed much in the same way as ordinary anthraquinone so that there can be no doubt as to its identity with that substance. The action of caustic potash on CI4HGO4 appears therefore to be entirely a reducing action alizarin and anthraquinone being formed according t o the equations-1. cI~Htjo* + RZ = C14H801, 11. ClaHGOi + 3H ClaHSOZ + 2Hz0. Action of Sulpliuric Acid on ClaH6Oi. I n studying this reaction the substance CI4H6O4 was heated with three or four parts of Nordhansen sulphuric acid at 200" until a sample taken out dissolved entirely in water. As soon as this was found t o be the case the product was poured into glacial acetic acid drop by drop the whole being constantly stirred during the operation.This caused the separation of a white substance which when examined under the microscope was seen to consist of R mass of small crystals. When the precipitation was complete, about twice the bulk of glacial acetic acid was added the mixture thrown on a filter washed with glacial acetic acid till free from sulphuric acid and then well drained. The product was dissolved in a little water and alcoholic soda added to the solution until the white crystalline salt thus formed had been completely precipitated. After collecting well washing with alcohol and drying at loo" tliis salt gave the following numbers on analysis :-0.1963 gram substance gave 0,0333 gram HzO.0.3540 gram CO,. 0.0415 gram N&301. Theory. C14H50,.S0,Na. Found. C 49.41 per cent. 49.18 per cent. H . 1.47 , 1.88 ,, Na 6.76 , 6-84 ,, 0 32-95 ,, S - 9-41 ,, Solutions of this salt give precipitates with salts of copper lead, barium and other metals. On fusion with potash this sulphonic acid yields a reddish-violet solution which on addition of acids, deposits a yellow precipitate. This after being collected and washe 842 A. G. AND IT. H. PERICIY JUN. ON with water was found to dye niordanted cloths shades vcry closely resembling those produced by flavopurpurin. As the substance also gave the same absorption-bands as flavopurpurin there can be no doubt of its identity with this substance. In order to examine more completely the action of snlphuric acid on CIIHBOI the acetic acid filtrate from the precipitated sulphonic acid was next experimented on thus :-After distilling off the acetic acid the residue was dissolved in potash fused with an excess of strong potash solution in an iron tube and the product isolated in the usual way.The yellowish-brown flocculent precipitate thus obtained dyed mordanted cloth with shades slightly yellower than but otherwise exactly similar to those produced by anthrapurpurin and a careful examination of the substance showed that it agreed with this compound in all its reactions. By the action of Nordhausen sulphuric acid on CI4H6O4 it would appear therefore that two suiphonic acids are formed, of which one is insoluble and the other soluble in glacial acetic acid.On fusion with potash the former yields flavopurpurin and the latter anthrapnrpurin. Theoretical Remarks. On considering the results described in the body of this paper it appears very doubtful whether the red substance C,,H,,O can have the formula first assigned to it (loc. cit. p. 684) namely-co co /\ /\ ,CO-C CH-CH C-CO CcH4\ 11 I I 11 )C6H*? GO-C CH CH C-CO x v/ CH as this formula does not in any way explain the formation of the oxidation compound C'28H140i or the decomposition into alizarin by fusion with potash. A reaction of this kind would involve the severing of the two anthraquinone molecules which would hardly take place so easily if they were joined simply carbon to carbon as shown above. I n order t o be a3le to explain the formation of its various deriva-tives it is necessary to suppose that the two anthraquinone molecules are linked together in a much more feeble way as for instance with the intervention of an oxygen-atom.The most probable formula f o r the red substance CzsHI4O6 and one which would explain all its decompositions would be SOME DERIVATIVES O F ANTHRAQUIKONE. 843 co C H /\ CO-C”CH-0-4 C-CO C6H4’ )I I 1 I/ )C,H4. >g 2.6 ‘CO-C C H CH C-CO By the action of nitric acid this substance is converted into C,,H,,O,, which would be represented by the formula-co co /\ /\ CO-C CH-0-CH C-CO C H C-CO \/ \/ CH HC I 11 >c6=4* C6H4’ 11 I \CO-C CH On further oxidation this substance is converted into 2 mols. of CI4H6O4 a change which is easily understood if we assume that the latter substance has the constitution which was previously assigned to i t ; that is-co /\ co-c co ‘CO-C C H CsH4’ )I I There is every reason to believe that this substance has the simde formula C&,O; and not the double formula C2sH1208.The cornpaia-tively low melting point of this substance (about 300°) and the fact that it sublimes easily and completely when heated almost exclude the possibility of its having the double molecular weight C,,H,,O,. The constitutional formula given above for this substance easily explains the reduction to alizarin and anthraquinone by the action of potash at a high temperature. Lastly the substance CzsH1405 produced by the action of hydriodic acid on C,H,,06 would be represented by t,he formula-CH CH /\ co-c c-0-CPC-co C6H4< 11 I I II ‘CGHL, CO-C CH C H C-CO 844 TURNER THE IKFLUESCE OF SILICON which in its turn would easily explain the formation of anthraquinone and dihydroanthracene by the further reducing action of hydriodic acid

ISSN:0368-1645    

DOI:10.1039/CT8885300831

出版商:RSC    

年代:1888

数据来源: RSC

摘要:

844 TURNER THE IKFLUESCE OF SILICON LXX.-The Injluencs of Silicon o n the Properties of Iron and Steel. Part 11. .By THOMAS TURKER Assoc. R.S.M. P.T.C. Lecturer on Metallurgy, Mason College Birmingham. l x the first part of this paper (Trans. 1887 51 129) a brief re'sume' was given of previous experiments on this subject and observations were described connected with the influence of silicon on the purest form of iron which can be obtained commercially in considerable quantities and in the fluid condition viz. the metal produced in the basic process at the end of the blow and before any addition of carbon o r manganese has been made. From this material ingots were prepared containing gradually increasing proportions of silicon, 2nd by combined chemical and mechanical testing the following con-clusions were arrived at.The metal being as above stated very low in manganese was originally rather red short and this red shortness was increased by the presence of silicon so much so that all ingots containing over 0.13 per cent. of silicon crumbled to pieces in the rolls. Silicon increased the tensile strength and limit of elasticity ; i t also rendered the metal quiet in the mould; the elongation and contraction of area were both considerably diminished however and the fracture changed in character from finely silky to crystalline. On khe other hand silicon had no apparent influence on the welding pro-perty of the iron. At the same time it was pointed out that these iysults were only true under the circumstances of the experiments, and that in the presence of larger quantities of other elements the influence of silicon would doubtless be considerably modified.The results of the above experiments differ in one or two important par-ticulars from what is observed commercially with ingot iron con-taining about half a per cent. of manganese which is one of the purest forms of metal produced by steel works. The results differ in the same way from those of the experiments now to be described. The present series of experiments was undertaken i n order to deter-mine the effect produced by silicon 0x1 ingot iron that is the " mild steel " now so largely used and which differs from the mctal employed in the previous experiments chiefly i n containing about one-tenth pe ON THE PROPERTIES OF IRON -4SD STEEL.845 cent. more carbon and a half per cent. moremanganese. The experi-ments were conducted as before at the works of the South Stafford-shire Steel and Ingot Iron Company Bilston and the general method of procedure was very similar to that described in Part I though a few alterations in detail were necessary. A weighed quantity of the same siliceous iron (10.3 per cent. silicon) as had been previously used was placed in a covered clay crucible which was heated in a small rever-beratory furnace t o the melting point of cast iron ; at the same time a second and exscbly similar crucible was heated in the same way and to the same temperature. The crucibles were capable of holding about 4Olbs. of metal. .At the conclusion of the blow after the addition of ferromanganese had been made and the metal teemed into the ladle the crucibles were rapidly brought from the furnace and the one contain-ing the siliceous iron was filled up with ingot iron from about the middle of the cast.After standing for about a minute and while the contents of the crucible were st'ill thoroughly fluid the metal was poured into the other red-hot crucible so as to ensure as nearly as possible perfect mixture. I n the second crucible the metal was allowed to solidify and the ingots so obtained were examined as in the previous experiments. I have again gratefully to acknowledge the important assistance received in conducting these experiments. The rolling of the specimens and the works tests were superintended by Nr. F. W. Harbord of Rilston ; the mechanical testing was per-formed by Professor A.B. W. Kennedy with the University College testing machine ; whilst the whole of the chemical analyses were cou-ducted by Mr. J. P. Walton of Wishaw. The author's part lias been merely the preparation of the ingots and the general arrangement of the experiments and of the results. Works Tests. (See Table A.) The ingots were reheated and rolled by workmen accustomed to the macipidation of mild steel ; no special care was given so as t o humour the metal the desire being to give all the ingots as fair a test as possible. In each case the ingots rolled satisfactorily and the required round bar of l+ inch diameter was obtained. I n each case also the hot test was satisfactory. These results are quite different from what was noticed when manganese was absent but they accord with obser-vations of experienced steel makers.It may be mentioned that the hot test employed was that commonly used at the works the bar being plated out hot doubled flat upon itself across the middle of the platcd portion and the doubled part bent again at right angles to the first bend. In the cold or bending test all thesamples behaved well with the single exception of No. 11 which contained not only 0.504 per VOL. LIII. 3 -No I 1 2 3 4 5 6 7 8 9 10 11 -Chemical Analyses. (By J. P. Wnlton.) Xi. 0 *010 0 *061 0.070 0.092 0 *lo2 0,121 0.135 0 *247 0 *320 0.382 0.504 C. -0 -16 0 -16 0 -15 0 -21 0 '18 0.19 0 *13 0 -19 0 -15 0.16 0 *18 8.-. 0.050 0,028 0 '084 0 *084 0 *028 0 -064 0 -028 0 *028 0 -040 0 -042 0 *094 P. -0.060 0 *058 0.051 0.064 0 -066 0 * 068 0.057 0.07'4 0,081 0 *087 0 9121 Mn. -0 -550 0 *619 0 *500 0 *634 0 '662 0 '576 0.480 0 ,642 0 -490 0 -533 0.455 -Worlis Tests. (By 3'. W. IIarbord.) Rolling. -Rolled well. >> 7 ) 7) > ) 7) > ) > 9 9) 7 7 >> 7 7 7) 7 ) 77 7 7 97 7 7 )) 7 ) 7) Hot. Good. ) ) 7 7 > > 7 ) Good but rather red-shori st weld-ing heat. Good. 7 ) 7 7 ) J 7) Cold. --Perfect . 9 ) Good. Perfect. Good. 9 ) Y7 7 9 9 9 Perfect. Broke short off at 50". flelding. --Perfect,.J ) 7) 7 ) J) 7 ) > > >> )7 )) 9 9 -Limit of elas-ticity. tons. 22 * 22 -21 21 * 22 -43 21 '26 22 -70 21 '29 22.23 22 '32 24.72 26 - 3 ON THE PROPERTIES OF IRON AND STEEL. 847 cent. of silicon bnt also 0.121 of phosphorus. It is not at all certain that the sample would ha-ve proved quite so brittle in the absence of phosphorus. It is to be regretted that the comparatively small scale on which tlie experiments were performed precluded accurate tests as to resistance to shock but so far as these experiments have gone they appear t o show that there is certaiiily no appreciable brittleness in ingot iron until the proportion of silicon reaches 0.25 per cent. Beyond that proportion the character of the other tests would lead us t o expect more or less brittleness.The welding tests as in the previous experiments were all perfect and silicon appears t o be without influence in this respect. C'hemicnZ Composition.-An examination of the results of chemical analysis (given in Table A) shows that the silicon gradually increases throughout the series. It should be explained that Sample No. 1, which is given for comparison represents ingot iron to which no silicon has been added. The composition shown is about what may be expected in good quality ingot iron of this kind whilst the niechanical values are derived from four separate tests made by Professor Kennedy on metal which had been produced on two separate occasions by treating ingot iron in precisely the same way as in the other cases when silicon was added.I n experiments of this kind it is of course extremely difficult to keep all the other con-stituents quite constant while silicon varies and in the deductions which are drawn from these experiments I have endeavoured as f a r as possible to make allowance for the known effect of the variations observed before drawing any cpnclusion as to the influence of silicon. The mxxinizcrn variations observed are as follows :-Carbon 0.08 per cent. ; sulphur 0.056 per cent.; phosphorus 0.036 per cent. (in a single instance previously mentioned this is exceeded) ; and man-ganese 0.207 per cent. JIechanlcaZ Tests.-These were performed in duplicate the actual results being given in Table B ; the mean values deduced from these experimental data being given in Table A.It ail1 be seen from Table A that the two experiments with each sample generally gave values which agreed very fairly well with each other. The greatest variations are noticed in the elongation and contraction of area where, in a few cases very considerable differences are noticed. Some allowance must of course be made on account of the small scale on which the experiments were conducted; but it may be pointed out that in the previous series of experiments as in the present case the samples low in silicon are distinctly more regular than those contain-ing a larger proportion of this element ; hence the results support the views of M. Pourcel that silicon renders tlie contraction of area and the elongation irregular.(Compare Trans. 1887 51 141.) 3 ~ TABLE B.-iVechanical Tests. Pyofessor A. B. IV. Ii'fmaecly's -NO, -1 2 3 4 5 6 7 8 0 10 11 II University College No. -Original metal, mean of 4 12,296 12,297 12,284 12,285 12,280 12,281 12,292 12,293 12,278 12,279 12,288 12,289 12,294 12,295 12,290 12,291 12,282 12,283 12,286 12,287 -3ilicon per cent. -. 0.01 0 -061 0 *07 0.092 0 *lo3 0.121 0 *135 0 -247 0 '320 0'382 0 -504 Limit of elasticity per sq. inch. Pounds. 49,280 49,400 50,100 45,480 48,800 48,860 Ei 1,600 45,550 49,750 51,570 50,100 47,330 48,060 46,490 53,110 51,280 48,720 54,300 56,420 59,120 58,930 -Tons. 22.00 22 -06 22 *37 20 '31 21 -79 21 *82 23.04 20 -33 22 '21 23 *02 22 '37 21 -13 21 *46 20 -75 23 * 71 22 -89 21.75 2-4-25 25 -19 26 -40 26-31 7 Breaking load ?er square inch.Pounds -66,385 70,040 71,580 65,000 66,270 76,000 74,020 76,160 71,640 74,769 71,100 67,120 64,630 79,700 75,470 73,380 79,800 80,000 81,300 83,180 75,780 -Tons. -29 '64 31.26 31 *96 29 '43 29 '59 33.38 33.94 33'04 34 *01 31 *98 31 9 5 29 *96 28 *88 33 -83 35 *58 33 -70 32 *76 35 *63 35 9 2 36 '30 37 -14 --Ratio of limit to break. 0 *743 0 906 0 -700 0 *690 0 -736 0.654 0 -679 0 ,615 0 -653 0 '720 0 a 705 0 '705 0 '743 0 .G13 0 *666 0 -679 0 *664 0.681 0.705 0.727 0 * 70s --Exten-sion per cent.on 10 inches. 23 *1 23.0 17 -8 22 *1 23 ' 8 20 '1 18 a 8 22 -7 18 *6 21 *2 22 *6 24 - 3 25 '3 20'3 15 ' 0 17 .O 16.5 12.7 23 * 4 18 *5 20 *3 --Reduc-tion of area a t fracture per cent 43 -8 48 -4 33 *1 49 *3 53 -7 42 *2 46 -1 52.0 60.9 42 *7 44 -8 57 a2 56 -0 45 -4 50 *0 28 *8 43.8 10 *7 50.8 34 '0 35 -6 --Work done in fracture ,er cubic inch. hi. tons. -6 -25 6-43 5.12 5 '83 6.42 5 -94 5.70 6 *54 5 *59 6 *15 6 -47 6 -56 6 *6S 5 *98 4 *74 5 *12 4 '80 4 -04 7.54 6 -10 6 -81 OX THE PROPERTIES OF IRON AND STEEL. 849 Limit of Elasticity.-This is rather high (22 tons) in the original metal and in the mean results (Table A) varies over a maximurn range of 1.65 tons in the six following samples (Nos.2 to 7). These small differences are precisely of the kind which can be accounted for by the observed variations in the other constituents present and the addition of 0.135 per cent. of silicon does not appear to have produced any important alteration in the limit of elasticity. The limit is however distinctly raised with more silicon, Breaking Load.-This varies in a manner almost exactly like that of the elastic limit. It is high in the original metpal (29.64 tons), and in the six following samples shows a maximum range of 4.1 tons, due apparently to circumstances other than the proportion of silicon. With more silicon however the breaking load is distinctly raised.Extet~sion.-The extension is rather below the average for such metal in the original sample and in the first six specimens but is about what would be anticipated from the other mechanical properties of the metal. The average of the values for the extension of these six samples is rather lower than that of the original metal so that the influence of silicon though slight is probably not beneficial. The irregular and lower results are more marked with larger proportions of silicon. Beduction of Area.-This as would be expected follows closely in the order of extension and is distinctly low and irregular with the larger percentages of silicon. Appearance cf Fracture.-In the first specimen the fracture is almost entirelg silky in appearance the intermediate specimens show greater tendency to granular or crystalline structure while the specimens with most silicon were most crystalline 01' granular and the fracture in several instances showed considerable irregularity.These results tend to show that the influence of several tenths per cent. of silicon is not beneficial. Ingct iron containing silicon in all proportions up to 0.5 per cent. (and with about 0.5 per cent. of manganese) rolls well and does not show any signs of red shortness ; i t welds perfectly wit.h a11 pro-portions of silicon and with the somewhat doubtful exception of the 0.5 per cent. specimen is not brittle when cold. With less than about 0.15 per cent. of silicon the limit of elasticity the breaking load the extension and the reduction of area are but little if at all, affected by the proportion of silicon present. The fracture though not much altered shows rather greater tendency to a crystalline or granular appearance. With upwards of 0.15 per cent. of silicon th 850 RUHEMANN AND ELLIOTT THE limit of elasticity and breaking load are increasd though the effect of silicon in this respect is not nearly so marked as that of carbon. The reduction of area and extension (that is the ductilit'j) are dis-tiiictly reduced and rendered more irregular by the presence of much silicon. The fracture is also rendered more granular or crystallinc, 2nd is less regular in character

ISSN:0368-1645    

DOI:10.1039/CT8885300844

出版商:RSC    

年代:1888

数据来源: RSC