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J O U R X A L OF THE CHEMICAL SOCIETY. ABSTRACTS OF CHEMICAL PAPERS PUBLISHED IN BRITISH AND FOREIGN JOURNALS. General and Physical Chemistry. Refraction and Dispersion of Sodium Chlorate. By F; D WSAUD (C'ompt. rend., 113, 291-292).-The measurements were made with several different forms of refractometer, but the diverg- ences between the results obtained with different instruments did not seem to follow any definite law. The following are the indices of refraction at 2 Y :- a. B. C. n. b. F. 1.51097 1.51163 1.51267 1.51510 1.51933 1.52161 Cdg. Cd,@ Cd,,. Cd12. Cd,,. Cd 1s. 1.53883 1.54242 1.54421 1.54700 1.57203 1.58500 The mean variation of the index of refraction is -0*000057 per dtgree, and seems to be practically the same for all the visible rays. C. H. B. Re1 ation between the Index of Refraction, Density, Molecu- lar Weight, and Diathermanous Power of a Substance.By AYsfoPr'KE'r (Compf. Tend., 113, 418--421).-1f A is tho diathermanous conductivity of a certain substance, A = QMV, where M is the mass contained in unit area of substance of thickness kh, and V is the mean relocity. If k is proportional to the thickness a of a molecule, k = CF, where C is a constant. If the molecule is spherical, E = ( e / d j J , e being themolecu- lar weight. Suppose V = n - I , where n is the index of refraction, then where P is a correction applied on account of reflection. M = kXd, d being the densit'y of the liquid. AY = +Ce4 ds (?a - l)", VOL. LXII. b2 ABSTRACTS OF CHEMICAL PAPERS. The author verifies the above formula by observations with water, alcohol, benzene, chloroform, and carbon bisulphide.H. C. Emission Spectra of Neodymium and Praeseodymium Oxides and of Luminous Solids containing Neodymium. By L. HAITINGER (MonLitslL., 12, 362-367) -Welsbach found that prseseo- dymium oxide gives a continuous emission spectrum, and neo- dymium oxide a discont'inuous spectruin similar to that noticed by Bunsen in the case of didymium oxide. The author confirms Wels- hach's obserrntions with neodymium oxide, iising this oxide mixed with aluiniiiium oxide for the production of the spectrum. The liues are found to vary somewhat, both i n intensity and position, oil long-continued heat,ing of the mixed oxides, and also if magnesium is substituted for aluminium oxide. Prsseodymiuni oxide, which alone l i ~ s no emission spectrum, shows one when mixed with alumicium oxide.This behaviour mav, perhaps, be explnined by assuming that a higher oxide is fornied when the salt is heated alone, but not when mixed with other oxides. No emission spectrum was, however, obtained on heating prxwodymium oxide in a reducing atmosphere. The praence of a trace of neodymium i n calcium sulphide causes a phosphorescence, the spectruni of which is similar to the absorption spectrum of concentrated solutions of neodymium salts. Study of the Chemical Neutralisation of Acids and Bases, by means of their Electrical Conductivities. By D. BERTHELOT (Compt. rend., 113, 261-263).-A summary of the results of the researches previously published. Potassium hydn)xide, a strong base, with hydrochloric acid, acetic acid, or phenol gives compounds which have almost identical conductivities, behave as true salts, are stable in solution, and are not decomposed by water.Ammonia. a feebler base, with hydrochloric acid and acetic acid gives stable compounds, b u t with phenol only an unstable compound with a higher resistance than the normal salts, and, to a large extent, dissociated by water. Aniline, a still feebler base, gives with hydrocliloric acid a stable compound that is a goad conductor; with acetic acid an unfitable compound with a considerablj- higher resistaiice ; and u ith phenol only a lion-conducting mixture without any trace of combination. Experiments with the hydroxybenzoic acids. which unite the functions of an acid and A phenol, sliow that, whilst the presence of the two functions call be readily recognised, they affect, one anotheia in a manner more or less marked according to their relative positions; in the molecule.C. H. B. H. C. Calculation of the Specific Heat of Liquids. By G. HIXRICHS (Conzpt. rend., 113, 46x3471) .-In the liquid state, molecules rotate ~ o u n d the natural axis, for which the moment of inertia is a, minimum. Tf .i is the moment of inertia, M the mass of the molecule, and p the indius of gyration, i = Mpz* The total energs, c, of the molecule of a liyiiid is the snm of tlie energy of rotntioii and of the potential energy, which is a function @ of the absolute temperature T, c = liiT + M@(T) = Me,GENERAL AND PHYSICAL CHEMISTRY. 3 wherz c = 7;p?l' + @(T), the tot'al energy of unit mass.The specific heat, c, of unit mass will be obtained by differentiation of e with regard to T, c = K(rZ + @'(T). The author sbows that a formula of this kind holds i n the case of the ethereal salts of the fatty acids, taking Schiff's observations of the specific heats of salts of this series. H. C. Second Law of Thermodynamics and its Application to Chemical Phenomena. By H. LE CHATELIEE (Bull. SOC. Chilit. [3], 5, 837--840).-Carnot's principle is directly applicable to chemical changes, if all restriction as to the natnre of the equilibihm cstablished by the change is removed. Tlie same reasoning which is applied to the eshblishment of heat equilibrium may then be applied TO chemical eqnilibrium. The available energy obtainable from two different states of the sajme system will be the same for all reversible trausformations of the one state into the other, arid independent of the means emploped f o r rendering this energy available, and will be greater for reversible t h a n for non-reversible transformations. The author shows how from this principle mty b e deduced, in a verg sirriple manney, the iaws of isodissociation which he formerly ob- tained by a far more complicated process-starting from the t w o H.c. New Isot3errhal Curves for Carbonic Anhydride. By E. H. AblAGaT (Conyx!. rend., 113, 446--451).-The author has determined the isotliermals f o r carbonic anhydride for every 10" from 0" t o loo", and also for the temperatures 32", 35", 137", 198", and 258'. The pressures were taken up to 1000 atmospheres, and the method em- ployed was that described in former communications.The results are given in t;lbuli\r form, and the isothermal curves for each of the temperatures taken. The following table is given f w the pressures of liquefaction of carbonic anhydride a t the temperatnres under ex- amiriatioii :- cquivalent principles of Clausius. Temperature.. .. .. . . . . .. . . .. 0" 10" 20' 30" Pressure in atmospheres ,. . . . 35.4 44.4 56.4 70.7 The full discussion of the results is reserved for a future paper. Heat of Formation of Platinic Bromide and its principal Compounds. By L. PIGEON (Cornpi. rend., 113, 476--479).-Pla- tinic bromide, prepared hy carefully heating hydrogen platinic brorn- ide, was dissolved in water, 9.86 Cal. being developed.The solution was then reduced by metallic cobalt, the heat developed being i13.59 Cal. By subtracting tlie heat of formation of the cobalt bromide, 145.88 Cal., we get for the heat of formation of dissolved platinic bromide 32.29 Cal., and from this the heat of formation of the solid salt, 42.43 C d . Solid plaqinic bromide dissolved in hydro- biwrnic acid solution (1 mol. in 4 litres; gives rise to a development of 19.27 Cal., from which the heat of formation of a solution r,f H. c. b 24 ABSTRACTS OF CtEEMMICAL PAPERS. hydrogen platsink bromide from platinum, bromine, and hgdro- bromic acid is 60 7 0 Cal. The formation of the crystalline salt H,PtBr, + 9H,O is attended by the development of an additional 2.86 Cal. The author draws attention to the fact that the heats of fornia- tion of the compounds of p7atislnm nzld bromine are, when gaseous hromine is taken, very nearly-equal to the heats of formation of the similar compounds of platinum and chlorine.€3. c. Heats of Combustion and Formation of Nitrobenzenes. By BERTHELOT and MATIGXOX (Compt. ~ e ~ z d . , 113, 246-249) :- ----- Ortbodinit rohenzene. ........... Met,adinitrobenzeiie ............ Paradinitrobenzene ............ Tiinitrobenzene (1 : 3 : 5 ) . ...... Trinitrobenzene (1 : 2 : 4). ...... Heat of combus- tion, conutiint vol urn e . Cnl. + 704 -6 + 698.1 + 696 -5 + 665.9 + 680 -6 -- Heat of combus- tior., constant pressure. Cal. +703 5 + 697 ‘0 + 696.4 + 663 ’8 + 678 ‘5 -- Forma- tion from elements. -- Cal . + 0 . 5 +6.8 +8*4 + 5 . 5 - 9 . 2 Forrna- tion from nitric acid, --- Cal.+ 58 -3 + 64 ’8 + 66 4 + 90.9 t- 76 ‘ 2 It is clear that although the ralucs for t,he various isomerides are very similar, as i s usually the case, there are distinct diflerences, amounting to 1 per cent. in the case of the dinitro-derivatives, and to 2 per cent. in the case of trinityo-derivatives. The differences are also distinct in the case of the formation from nitric acid, and the heat deyeloped becomes less the niore advanced the substitution. The heat of formation of a nitro-derivative is always but slightly dif-ferent from that of the generating hydrocarbon ; and i t follows that the oxygen of the iiitroxyl group has nearly the same combustible power as if it were in the free state. Since the heah of formation becomes less as nitrakiorn advances, it follows that the combustible energy of the ox-j-gen gradually increases.The hearing of this result on the explosibility of nitro-derivatives is obvious. Calorific Value of Food Constituents and their Derivatives. By I!. STOHMAKX’ aiid H. LANGBEIX (J. pr. Chern. [2], 44, 336-399). --Stohmatin is surprised that Berthelot (Ann. Chiin. Phys. [GI, 22, 5) has not, quoted him as an authority on the thermochemistry of protei’ds and made use of his work on the subject (compare Abstr., 1885, 85’7). The authors have already dealt with the calorific values of animal fats (Abstr., 1831, 11) ; in this paper they summarise the calorific values which they obtain for various prote‘ids and the products of their change. Full data for the results, and details as to source of the compounds, are given.The following tables summarise the valiies, C. H. R.*pc---- N l a h i i ................. Vegetable iibi*iii.. ........ Serum albumin .......... Yynlonin.. .............. H ze inoglo hin ............ %[ilk w ~ e ' h , No. 1 . . ...... .. No. 2 . . ...... yolk of egg.. ............ Leguinin ................ Vitellin ................. u albu1nit~ ............ %& Elesh fibre, No. 5 ........ Crystallised dbun\iii.. .... Flesh, No. 3 ............ .. 3 0 . 1 ............ Blood fibrin ............. hwiiack's albumin ....... Wool fibre .............. Conglutin. .............. Skin fibroh.. ............ Yelit one ............... > Cliotidrin ............... Oaaein .................. Fibt.o.:n. ................Chitin.. ................ Calorific value per grain, cal. -- 5961 '3 5941 *6 5917 -8 5907.8 5885 -1 5867 -0 584!) '6 5840.9 5793 *1 5745 '1 5735 '2 5720 -5 5672 0 5662 -6 5640 '9 5637 * 1 5553 *o 5510.2 5479 -0 5355 -1 5298 8 51 30 *6 5039 *!I 4979.6 4 650 '3 Carbon. 55 '03 54 '39 53 *93 53 *64 54 -73 54 *02 5 4 *14 53 -50 53 -32 50 *27 5'5 -95 52.11 51 -48 52.02 58.93 50 -69 50 -20 50.18 49 -92 50.10 49 *14 48 '63 48-63 45 '15 - Hydrogen. 7 '20 6 '98 7-65 7 -4.4. 6.06 7 *33 6 -85 7.31 7 -17 7 .go 7 '50 7 *lo 6-76 7.30 7 '16 6 *68 6 -72 6 *74 5 '76 6 -45 6 -67 6.64 6.08 6 -4 -- - U1 t iinat,e coin posit ion. Nitrogen. 16 -91 15 -39 15 '15 15.76 16 -50 15 *52 15 '61 15 '26 15 '1.8 16'04 15 -19 16 '44 18' 14 16 '38 16 '36 16'72 14.5 1 16 '54 17 '51 18 -01 16'42 15 '37 46.34 18 *97 --- 6 -86(?) Sulpli iir.--- 0.18 1 '02 1 '18 1 -09 0 '46 0.75 0.78 1'11 0 '46 3'09 1'52 1 '03 0.96 1 '09 1'01 1-13 1 '89 3 *70 0 *79 0'30 1-24 1 *26 0 *95 - - Oxjgen. -- 20 -68 22 -28 22 09 22.07 22 -25 23 *38 22 *62 22 -82 23.97 24 *70 28 '85 23 *32 22 -66 23 -31 %2 *06 23 '67 22-84 24 -18 26 '02 25.79 27 -56 2? '44 26 *32 41.59 - Atomic proportiuns.6 LBSTRACTS OF OHlEMICAL PAPEHS. the atomic proport,ions in Table I being calculated to 720 carbon atoms to avoid decimals ; 72 is the proportion of carbon atoms found i n white of egg by Liebci-kuhn. Glycocine . . . . . . Alanine . . . . . . . . Leucine.. . . . . . . Barcosine . . . . . . Hippuric acid.. . Aspartic acid, . . Urea . . . . . . . . . . Asparagine. . . . . Xreatine (cryst.) Kreatine (an- hydrous).. . . . Uric acid . . . . . . Guanine . . . . . . . Caffe’ine . . . . . . . - Mol. weight . 75 89 131 89 1’19 133 60 132 1 49 131 168 151 194 Calorific value. .--- Cul. 234.6 387 ‘7 855 -8 401 -2 1014 ‘5 385 -2 152 -2 463 *5 553 -3 560 -0 460’5 586 *6 1014.9 - Heat of forma- tion. -- Cal. 125 -9 135 8 156.7 122.3 142 -0 232 a 3 79 -8 188 -5 202 -2 126 5 198 -5 55 *9 82.1 Calorific value tic- :ording t o Berthelot Gal. 234.9 389 ‘0 857.1 1012 ‘9 386 .8 151 -5 448.1 --- - - - 461 *4 - - -- B and A. Band A. B and A. B and A. Band A . Band P. B and A. M. B and A = Berthelot and Andr6, B and P = Bertlielot and Petit, M = Matipon. In connection with the first of these tables, the authors give another table showing the results which were obtained by Berthelot and Andre for some of the prote‘ids in the authors’ table; this table appears to be quoted from Ann. Chim.Phys. [S], 22, 25, which con- tains the same table as appears in Abstr., 1890, 937, but the numbers given here do not quite agree with those in the table referred to. If the valnes for elastin, wool-fibre, skin-fibroyn, chondrin, ossein, fibro’in, and chitin be excepted, the mean calorific value for tt e prote‘ids given in the first table is 5730.8 cal. Berthelot (Abstr., 1E90, 938) found 5691 cal. for this number ; the authors regard the mean, 5i11 cal., as representing the real value. This value would be given by the formula C720H11G1NlbiS502L38 ; Lieberkiihn’s formula is From the values given in the second table, the authors deduce the fol- lowiug generslisations :-(1) The substitution of CH, for a hydrogen atom in homologous series increases the calorific value by 156-157 Cal.(2) The calorific r a l ~ i e of a methyl group ahtached to a nitrogen atom is higher than that of one attached to a carbon atom. (3) The displacement of a hydrogen atom in A CH, group hy NH, raises the cnlorific value by 26.9 Crtl. (4) The displacenient of tbe hgdroxyl in a carboxyl group by NH, raises the calorific value by 78.6 Cal. The heat of combustion of carbnnic acid deduced from that of urea by means of this peneralisation is -5.0 Cal. Lnnguinine (Ann. Chia?. Il’hys. [S], 8, 133) found -4.3 Cal. and -10.75 Gal. for this number. GH,iaN,tSOm A. G. B.GENERAL AND PHYSICAL CHEMISTRY. 7 Maximum Density of Water. By H. N.VERSON (PhiZ. MU,^. [ S ] , 31, 337--392).-The author investigated the rate of cooliiig of quantities of water from 30" down to 0". His thermometer was read to 0.01" by means of a cathetometer. When the water waq not Ptirred, there was a sudden break in the cooliiig curve about 4*7", which is therefore to be considerecl tlie point of maximiim density. No bre*ak appeared when the water was stirred, the natural convec- tion currents not then having free play; but from the form of the curve it would seem that the specific heat of water between 0" find 12' is about 3 per cent. greater than between 16" and 30". Both the increased specitic heat and the maximum density are considered by the author to have their cause in an aggregation of (H,O)? molecules to (H20), molectiles about 4" as the water cools.J. W. Expansion of Water. By C. SCHEEL ( C h m . Centr., 1891, ii, 409-410 ; Inaug. Diss., Bedin).-The author has determined the expansion of water between 0" and 33" by means of a glass apparatuu, the volume being read off on a capillary tuhe. (For a complete description of it, see the original paper.) The absolute expansion of water was found to be 0.0408059, tlie minimuni being a t 4~0.38". Dilatation of Phosphorus and its Change of Volume at the Melting Point. By A. LKDUC (Cornpt. rend., 113, 259--%1).- Phosphorus expands almost regularly up to its melting point, which is M.2" on the mercurial theimometer, aiid 44.1" on the normal ther- mometer. A t this point, without any appreciable change OF tempera- ture, there is a considerable expansion, tlie ratio of the volunie of the solid phosphorus to that of.the liquid phosphorus bein:,. 1 : 1.0345. Kopp's number was 1.0:343. The expansion of either solid or liquid phosphorus can only be represented by a formula with three terms, but the abthor is not able to state the coefficients precisely. The value of the mean coefficients on the normal thermometer between 0" and 44.1" is 0*00037:', acll betwoen 26' and 50°, 0.000560, the latter being calculated on ttie volume a t 0". These values differ considerably from those given by KUPP. C. H. B. Capillary Constants of Salts at their Melting Points. By J. '~'RAURE (Ber., 24, 3U74-:3080).-l'he author has determined the capillary constants of a large number of salts at temperat,ures just above their melting points.The method adopted was that of weigh- ing the drops which fell from a single perforation in ft emnll disc that formed the end surface of a short cvliiider let in to the bottom of i L platinum or porcelain crucible. This crucible was so heated, by means of an ordinary gas flame or by the blowpipe, that the flame did not come in contact with the hanging drop. The salts investigated were potassium and sodium salts, and the ratios (T) of the weight of the drops to the weight of the water-drop at 0" from the same vessel are tabulated. From his results, the author deduces the following conclusions :-- Capillarity may be considered a '' colligntive " property. The con- J. W. L.B ABSTRACTS OF CHEMICAL PAPERS. stants for the salts of the fatty acids are unusually small, diminishing rapidly as the series is ascended. For the otheio salts the constants (T) of the potassium salts of monobasic acids lie between 112 and 157; of bibasic and multibasic acids, between 168 and 231.The limits for the constants of the corresponding sodium salts are 123-16!, and 189-325. The difference T,, - T, incveases with the number of cquivalents of the metal in the salts. It is doubtful if tri- and quadri-basic acids can, in this way, be distinguished from bibasic acids, but the author considers it always possible to distinguish between the latter and monobasic acids. The method points to the following formuh as being correct :-K2FZ, KZPZO,, Na3P206, K2 As~O,~. J. W. Mutual Solubility of Salts in Water. By W. W. J. N~cor, (Phil. Mag.[ 5 ] , 31, 369--387).-Uiider the heading '' The Mutual Solubility of Salts," the author groups the phenomena due to tJhe mutual influence of two salts on each other's solubility in water. IIe gives an historical survey of t h e work done on the subject, and pro- ceeds to communicate his own experiments on the chlorides and n ttrates of sodium and potassium taken in all possible combinations of pairs with a common constituent. The method of experiment adopted was as follows :-A salt was taken, ant1 solutions containing 1, 2, &c., gram-mols. of this salt in 100 gram-mols. of water were prepared. These solutions w e i ~ then satuixted ilf a detinite tempera- ture with the other salt added in excess, and the total salt in solution determined. Precisely similar determinations were made with definite niolecular solutions of the other salt. The solnbility of each salt separately i i i water was then determitied, and finally, the solubility of both salts when simultaneously added in excess to water was alao ascertained.'l'he results are presented in the form of tables, formulae, and curves, In general, the presence of one salt diminishes the solubility of the other, but i n the case of the nitrates of potassinm and sodium, t h e presence of the one in solution increases the solubility of the other.. (Compare Nernst, Abstr., 1890, 3 ; Le Blaric and Noyes, Abstr., 18131, 388.) J. W. Cryoscopic Behaviour of Dilute Solutions. By J. TRAURE (Ber., 24, 3071-3074).-Eykrn:tii1i and Arrheriius have pointed out, (Abstx., 1891, 972 and 1148) that the observations of the auihor on the freezing point of dilute.solutions, in particular of those of cane sugar, are not i n accordance with their own experiments, o r w i t h those of Tanimann end Pickering. The author upholds his numbers, and attributes the discrepancy to the other observers having cooled their solutions too far below tne freezing point before making ohser- vations. J. W. Automatic Replacement of Mercury in Sprengel Pumps. By A. VEIINEUIL (ULIIZ. Soc. Chim. [ ; 3 ] , 5, 748---750).-'l'lie mercury is cmntiiiuously and automatically transferred from the lower to the upper reservoir by t h e action of n water-pressure or similar piirnp,GENER1.L AND PHYSICAL CHEMISTRY. 9 tlie suction.tube of which is attached to the upper end t of a small bulb, connected by tubes a, b to both reservoirs, and placed about 40 cm.above the upper one. The contents of the lower reservoir are thus forced into the bulb by atmospheric pressure, and allow-ccl to fnil into the upper reservoir by their own weight. The tube a is 3 mm. in internal diameter, and is recurred at the lower end, the level of the mercury at that poiIit being so adjusted that much air and little mefcury passes up the tube; the tube b is 6 mm. ininternal diameter. It. is not intended to be used at starting, as it is found niorc convenient to transfer any considerable quantity of mercury by hand than to make the apparatus of unnecessarily large dimensions. An incidental advant,age is t h a t the mercury is bronglit into contact with air under conditions favourable to the oxidation of impurities.The a.pparatus is applicable to most existing mercury pumps. JN. W. Block Support for Tubes. By A. GAWALOVSKI (Zeit. anal. CItern., 30, 581-583).-Two elongated blocks of hard wood, laid side10 ABSTRACTS OF CHEMICAL PAPERS. by side, have rectangular grooves ploughed in their contiguous faces, so as to form a channel, the cross section of which corresponds, approximately, with the shape of the bulbs of R P6ligot’s U-tube. The blocks are then united by screws. Upright pieces of wood, of various heights, shaped so as to fit and slide in the channels, can be inserted to give support to the, .U-tubes, or to carry horizontal tubes on their upper, grooved edges. To these pieces the tubes are attached hy spring clips.A trail1 of tube apparatus can thus be held by a single support. M. J. S. Formation of Mixed Crystals. By H. BUHRESS (Bee. TKUZ.. Chim., 10, 57--64).-1. Double Salts of Menm-;c Thiocyanate with Zhc, Cadmium, Cobalt, and Coppel. Yhiocyanates.-The salts having the following compositions, crystallise well :-Hg( CNS)2,Zn(CNS)2 ; Hg( CNS)2,Co(CNS)2 ; 2EIg(CNS)*,Cd(CNS), ; and Hg(CNS),,Cu(CNS), + H,O. The zinc and cobalt double salts are homogeneous c:-ystals, the former colourleis, and the latter deep-blue. The cadmium salts afford analogous, pale-blue crystals, which, in the case of the double salts of zinc and cadmium, are almost identical in forni with those of zinc mercury thiocyanate ; consequently, two double cadmium mercury thiocyanates should exist and correspond with the formuJz 2Hg( CNS),,Cd( CNS), (Nordstrom’s salt) and Hg( CNS,),Cd(CNS ).respectively, which are analogous to the nmmoniiim salts Hg( CNS),,NH,CNS and Hg( CNS)2,!2SH,CNS. Prom the liquid obtained by the addition of mixed solutions of cobalt and cadmium nitrates, or of cobalt and zinc nitratep, to ti very dilute solution of ammonium mercury thiocyana te, colourless needles separate ; these break up on the addition of ammoniuiii thiocyanate, when the mother liquor affords the large, mixed, deep-blue crystals, noted above. No mixed crystals of cobalt and copper compounds could be obtained. With the blue crystals of the cobalt salt, yellowish-green crystals of mercury copper thiocyanate occur, a result the author ascribes to it reaction induced by the water of crystallisation the double copper salt contains.Addition of mercury ammonium thiocyanate to mixed solutions of copper, zinc, cobalt, and cadminm salts, determines the formation of mercury copper thiocyanat,e, and characteristic brown-violet crystals of mercury zinc copper thiocyanate, which contain no cobalt, and are isomorphnus with the zinc compound. These do not alter wbea heated at lYO”, whereas the dark-green needles of mercury copper thiocyauste become dark and opaque. The author concludes that, in presence of much ziiic, meycury copper thiocyanate loses its water of crystallisa- tion yielding mixed cryst~ls with mercury zinc thiocyanate, whereas when mercury copper thiocyanate crystallises alone, it a1 ways con- t:lins a molecule of water of crystallisation.2. Silrer Chromate tcnd Silver SuEphafe.--The small, sed crystaI3, forming the precipitate produced by the addition of potassium dichi-oulate solution to ft silver nitrate solution acidified with nit,&IN0 RGXNIC CHE M ISTR T. It acid belong, like potassium dicliromate, to tht: clinorhombic system. If silver sulphnte he substituted foia silvc r nitrate, the blood-red crystals yielded a t fir4 are monoclinic, but are succeeded by the deposition of oiaange-yellow, orthorhombic crystals of -the mixed salt Ag,S04 + Ag&r04, with liberation of chromic acid. 3. Phosphates a.n.d Arsenates of the type NHdMgPO, + 6H20.- Salts of this type form hcmimorphic ortborhombs. The correspond- ing hemimorphic double phosphates of magnesium, maiignnese, cobalt, and nickel are known, and the anthor has prepared the analogous arsenates of calcium, zinc, and copper.He describes and figures crystals obtained by him in endeavouring to produce mixed crjstnls of these salts: in order to determine if their constitution was of the same type as the magnesium derivative. Although in this resptct his results are not conclusive, ye:f from the developnient of the crystals he concludes thah neither a central point nor a plane of symmetry is necessa1.y to the dovelopmerit of hemimoi-phic crystals, since they originate equally well from a lateral plane or a summit. T. G. N.J O U R X A LOFTHE CHEMICAL SOCIETY.ABSTRACTS OF CHEMICAL PAPERS PUBLISHED INBRITISH AND FOREIGN JOURNALS.General and Physical Chemistry.Refraction and Dispersion of Sodium Chlorate.By F;D WSAUD (C'ompt. rend., 113, 291-292).-The measurements weremade with several different forms of refractometer, but the diverg-ences between the results obtained with different instruments did notseem to follow any definite law. The following are the indices ofrefraction at 2 Y :-a. B. C. n. b. F.1.51097 1.51163 1.51267 1.51510 1.51933 1.52161Cdg. Cd,@ Cd,,. Cd12. Cd,,. Cd 1s.1.53883 1.54242 1.54421 1.54700 1.57203 1.58500The mean variation of the index of refraction is -0*000057 perdtgree, and seems to be practically the same for all the visible rays.C. H. B.Re1 ation between the Index of Refraction, Density, Molecu-lar Weight, and Diathermanous Power of a Substance. ByAYsfoPr'KE'r (Compf.Tend., 113, 418--421).-1f A is tho diathermanousconductivity of a certain substance, A = QMV, where M is the masscontained in unit area of substance of thickness kh, and V is themean relocity. If k isproportional to the thickness a of a molecule, k = CF, where C is aconstant. If the molecule is spherical, E = ( e / d j J , e being themolecu-lar weight. Suppose V = n - I , where n is the index of refraction,thenwhere P is a correction applied on account of reflection.M = kXd, d being the densit'y of the liquid.AY = +Ce4 ds (?a - l)",VOL. LXII. 2 ABSTRACTS OF CHEMICAL PAPERS.The author verifies the above formula by observations with water,alcohol, benzene, chloroform, and carbon bisulphide. H. C.Emission Spectra of Neodymium and PraeseodymiumOxides and of Luminous Solids containing Neodymium.ByL. HAITINGER (MonLitslL., 12, 362-367) -Welsbach found that prseseo-dymium oxide gives a continuous emission spectrum, and neo-dymium oxide a discont'inuous spectruin similar to that noticed byBunsen in the case of didymium oxide. The author confirms Wels-hach's obserrntions with neodymium oxide, iising this oxide mixedwith aluiniiiium oxide for the production of the spectrum. Theliues are found to vary somewhat, both i n intensity and position, oillong-continued heat,ing of the mixed oxides, and also if magnesium issubstituted for aluminium oxide. Prsseodymiuni oxide, which alonel i ~ s no emission spectrum, shows one when mixed with alumiciumoxide. This behaviour mav, perhaps, be explnined by assuming thata higher oxide is fornied when the salt is heated alone, but not whenmixed with other oxides.No emission spectrum was, however,obtained on heating prxwodymium oxide in a reducing atmosphere.The praence of a trace of neodymium i n calcium sulphide causes aphosphorescence, the spectruni of which is similar to the absorptionspectrum of concentrated solutions of neodymium salts.Study of the Chemical Neutralisation of Acids and Bases,by means of their Electrical Conductivities. By D. BERTHELOT(Compt. rend., 113, 261-263).-A summary of the results of theresearches previously published. Potassium hydn)xide, a strong base,with hydrochloric acid, acetic acid, or phenol gives compounds whichhave almost identical conductivities, behave as true salts, are stablein solution, and are not decomposed by water.Ammonia. a feeblerbase, with hydrochloric acid and acetic acid gives stable compounds,b u t with phenol only an unstable compound with a higher resistancethan the normal salts, and, to a large extent, dissociated by water.Aniline, a still feebler base, gives with hydrocliloric acid a stablecompound that is a goad conductor; with acetic acid an unfitablecompound with a considerablj- higher resistaiice ; and u ith phenolonly a lion-conducting mixture without any trace of combination.Experiments with the hydroxybenzoic acids. which unite thefunctions of an acid and A phenol, sliow that, whilst the presence ofthe two functions call be readily recognised, they affect, one anotheiain a manner more or less marked according to their relative positions;in the molecule.C. H. B.H. C.Calculation of the Specific Heat of Liquids. By G. HIXRICHS(Conzpt. rend., 113, 46x3471) .-In the liquid state, molecules rotate~ o u n d the natural axis, for which the moment of inertia is a, minimum.Tf .i is the moment of inertia, M the mass of the molecule, and p theindius of gyration, i = Mpz* The total energs, c, of the molecule ofa liyiiid is the snm of tlie energy of rotntioii and of the potentialenergy, which is a function @ of the absolute temperature T,c = liiT + M@(T) = MeGENERAL AND PHYSICAL CHEMISTRY. 3wherz c = 7;p?l' + @(T), the tot'al energy of unit mass. The specificheat, c, of unit mass will be obtained by differentiation of e withregard to T,c = K(rZ + @'(T).The author sbows that a formula of this kind holds i n the case ofthe ethereal salts of the fatty acids, taking Schiff's observations of thespecific heats of salts of this series. H.C.Second Law of Thermodynamics and its Application toChemical Phenomena. By H. LE CHATELIEE (Bull. SOC. Chilit.[3], 5, 837--840).-Carnot's principle is directly applicable tochemical changes, if all restriction as to the natnre of the equilibihmcstablished by the change is removed. Tlie same reasoning which isapplied to the eshblishment of heat equilibrium may then be appliedTO chemical eqnilibrium. The available energy obtainable from twodifferent states of the sajme system will be the same for all reversibletrausformations of the one state into the other, arid independent ofthe means emploped f o r rendering this energy available, and will begreater for reversible t h a n for non-reversible transformations.Theauthor shows how from this principle mty b e deduced, in a vergsirriple manney, the iaws of isodissociation which he formerly ob-tained by a far more complicated process-starting from the t w oH. c.New Isot3errhal Curves for Carbonic Anhydride. By E. H.AblAGaT (Conyx!. rend., 113, 446--451).-The author has determinedthe isotliermals f o r carbonic anhydride for every 10" from 0" t o loo",and also for the temperatures 32", 35", 137", 198", and 258'. Thepressures were taken up to 1000 atmospheres, and the method em-ployed was that described in former communications. The results aregiven in t;lbuli\r form, and the isothermal curves for each of thetemperatures taken.The following table is given f w the pressures ofliquefaction of carbonic anhydride a t the temperatnres under ex-amiriatioii :-cquivalent principles of Clausius.Temperature.. .. .. . . . . .. . . .. 0" 10" 20' 30"Pressure in atmospheres ,. . . . 35.4 44.4 56.4 70.7The full discussion of the results is reserved for a future paper.Heat of Formation of Platinic Bromide and its principalCompounds. By L. PIGEON (Cornpi. rend., 113, 476--479).-Pla-tinic bromide, prepared hy carefully heating hydrogen platinic brorn-ide, was dissolved in water, 9.86 Cal. being developed. The solutionwas then reduced by metallic cobalt, the heat developed beingi13.59 Cal.By subtracting tlie heat of formation of the cobaltbromide, 145.88 Cal., we get for the heat of formation of dissolvedplatinic bromide 32.29 Cal., and from this the heat of formation ofthe solid salt, 42.43 C d . Solid plaqinic bromide dissolved in hydro-biwrnic acid solution (1 mol. in 4 litres; gives rise to a developmentof 19.27 Cal., from which the heat of formation of a solution r,fH. c.b 4 ABSTRACTS OF CtEEMMICAL PAPERS.hydrogen platsink bromide from platinum, bromine, and hgdro-bromic acid is 60 7 0 Cal. The formation of the crystalline saltH,PtBr, + 9H,O is attended by the development of an additional2.86 Cal.The author draws attention to the fact that the heats of fornia-tion of the compounds of p7atislnm nzld bromine are, when gaseoushromine is taken, very nearly-equal to the heats of formation of thesimilar compounds of platinum and chlorine.€3. c.Heats of Combustion and Formation of Nitrobenzenes. ByBERTHELOT and MATIGXOX (Compt. ~ e ~ z d . , 113, 246-249) :------Ortbodinit rohenzene. ...........Met,adinitrobenzeiie ............Paradinitrobenzene ............Tiinitrobenzene (1 : 3 : 5 ) . ......Trinitrobenzene (1 : 2 : 4). ......Heat ofcombus-tion,conutiintvol urn e .Cnl. + 704 -6 + 698.1 + 696 -5+ 665.9 + 680 -6--Heat ofcombus-tior.,constantpressure.Cal.+703 5 + 697 ‘0 + 696.4+ 663 ’8 + 678 ‘5--Forma-tion fromelements.--Cal .+ 0 . 5+6.8+8*4+ 5 .5- 9 . 2Forrna-tion fromnitric acid,---Cal. + 58 -3 + 64 ’8 + 66 4+ 90.9t- 76 ‘ 2It is clear that although the ralucs for t,he various isomeridesare very similar, as i s usually the case, there are distinct diflerences,amounting to 1 per cent. in the case of the dinitro-derivatives, andto 2 per cent. in the case of trinityo-derivatives. The differencesare also distinct in the case of the formation from nitric acid, andthe heat deyeloped becomes less the niore advanced the substitution.The heat of formation of a nitro-derivative is always but slightlydif-ferent from that of the generating hydrocarbon ; and i t follows thatthe oxygen of the iiitroxyl group has nearly the same combustiblepower as if it were in the free state.Since the heah of formationbecomes less as nitrakiorn advances, it follows that the combustibleenergy of the ox-j-gen gradually increases. The hearing of thisresult on the explosibility of nitro-derivatives is obvious.Calorific Value of Food Constituents and their Derivatives.By I!. STOHMAKX’ aiid H. LANGBEIX (J. pr. Chern. [2], 44, 336-399).--Stohmatin is surprised that Berthelot (Ann. Chiin. Phys. [GI, 22, 5)has not, quoted him as an authority on the thermochemistry ofprotei’ds and made use of his work on the subject (compare Abstr.,1885, 85’7).The authors have already dealt with the calorific values of animalfats (Abstr., 1831, 11) ; in this paper they summarise the calorificvalues which they obtain for various prote‘ids and the products of theirchange.Full data for the results, and details as to source of thecompounds, are given. The following tables summarise the valiies,C. H. R*pc----N l a h i i .................Vegetable iibi*iii.. ........Serum albumin ..........Yynlonin.. ..............H ze inoglo hin ............%[ilk w ~ e ' h , No. 1 . . ...... .. No. 2 . . ......yolk of egg.. ............Leguinin ................Vitellin .................u albu1nit~ ............ %& Elesh fibre, No. 5 ........Crystallised dbun\iii.. ....Flesh, No. 3 ............ .. 3 0 . 1 ............Blood fibrin .............hwiiack's albumin .......Wool fibre ..............Conglutin. ..............Skin fibroh.. ............Yelit one ...............>Cliotidrin ...............Oaaein ..................Fibt.o.:n.................Chitin.. ................Calorificvalue pergrain, cal.--5961 '35941 *65917 -85907.85885 -15867 -0584!) '65840.95793 *15745 '15735 '25720 -55672 05662 -65640 '95637 * 15553 *o5510.25479 -05355 -15298 851 30 *65039 *!I4979.64 650 '3Carbon.55 '0354 '3953 *9353 *6454 -7354 *025 4 *1453 -5053 -3250 *275'5 -9552.1151 -4852.0258.9350 -6950 -2050.1849 -9250.1049 *1448 '6348-6345 '15-Hydrogen.7 '206 '987-657 -4.4.6.067 *336 -857.317 -177 .go7 '507 *lo6-767.307 '166 *686 -726 *745 '766 -456 -676.646.086 -4---U1 t iinat,e coin posit ion.Nitrogen.16 -9115 -3915 '1515.7616 -5015 *5215 '6115 '2615 '1.816'0415 -1916 '4418' 1416 '3816 '3616'7214.5 116 '5417 '5118 -0116'4215 '3746.3418 *97---6 -86(?)Sulpli iir.---0.181 '021 '181 -090 '460.750.781'110 '463'091'521 '030.961 '091'011-131 '893 *700 *790'301-241 *260 *95-6 LBSTRACTS OF OHlEMICAL PAPEHS.the atomic proport,ions in Table I being calculated to 720 carbonatoms to avoid decimals ; 72 is the proportion of carbon atoms foundi n white of egg by Liebci-kuhn.Glycocine .. . . . .Alanine . . . . . . . .Leucine.. . . . . . .Barcosine . . . . . .Hippuric acid.. .Aspartic acid, . .Urea . . . . . . . . . .Asparagine. . . . .Xreatine (cryst.)Kreatine (an-hydrous).. . . .Uric acid . . . . . .Guanine . . . . . . .Caffe’ine . . . . . . .-Mol.weight .7589131891’19133601321 49131168151194Calorificvalue..---Cul.234.6387 ‘7855 -8401 -21014 ‘5385 -2152 -2463 *5553 -3560 -0460’5586 *61014.9-Heat offorma-tion.--Cal.125 -9135 8156.7122.3142 -0232 a 379 -8188 -5202 -2126 5198 -555 *982.1Calorificvalue tic-:ording t oBerthelotGal.234.9389 ‘0857.11012 ‘9386 .8151 -5448.1------461 *4----B and A.Band A.B and A.B and A.Band A .Band P.B and A.M.B and A = Berthelot and Andr6, B and P = Bertlielot and Petit, M =Matipon.In connection with the first of these tables, the authors give anothertable showing the results which were obtained by Berthelot andAndre for some of the prote‘ids in the authors’ table; this tableappears to be quoted from Ann.Chim. Phys. [S], 22, 25, which con-tains the same table as appears in Abstr., 1890, 937, but the numbersgiven here do not quite agree with those in the table referred to.If the valnes for elastin, wool-fibre, skin-fibroyn, chondrin, ossein,fibro’in, and chitin be excepted, the mean calorific value for tt eprote‘ids given in the first table is 5730.8 cal. Berthelot (Abstr.,1E90, 938) found 5691 cal. for this number ; the authors regard themean, 5i11 cal., as representing the real value. This value would begiven by the formula C720H11G1NlbiS502L38 ; Lieberkiihn’s formula isFrom the values given in the second table, the authors deduce the fol-lowiug generslisations :-(1) The substitution of CH, for a hydrogenatom in homologous series increases the calorific value by 156-157 Cal.(2) The calorific r a l ~ i e of a methyl group ahtached to a nitrogenatom is higher than that of one attached to a carbon atom.(3) Thedisplacement of a hydrogen atom in A CH, group hy NH, raises thecnlorific value by 26.9 Crtl. (4) The displacenient of tbe hgdroxyl ina carboxyl group by NH, raises the calorific value by 78.6 Cal. Theheat of combustion of carbnnic acid deduced from that of urea bymeans of this peneralisation is -5.0 Cal. Lnnguinine (Ann. Chia?.Il’hys. [S], 8, 133) found -4.3 Cal.and -10.75 Gal. for this number.GH,iaN,tSOmA. G. BGENERAL AND PHYSICAL CHEMISTRY. 7Maximum Density of Water. By H. N. VERSON (PhiZ. MU,^.[ S ] , 31, 337--392).-The author investigated the rate of cooliiig ofquantities of water from 30" down to 0". His thermometer was readto 0.01" by means of a cathetometer. When the water waq notPtirred, there was a sudden break in the cooliiig curve about 4*7",which is therefore to be considerecl tlie point of maximiim density.No bre*ak appeared when the water was stirred, the natural convec-tion currents not then having free play; but from the form of thecurve it would seem that the specific heat of water between 0" find12' is about 3 per cent. greater than between 16" and 30". Both theincreased specitic heat and the maximum density are considered bythe author to have their cause in an aggregation of (H,O)? moleculesto (H20), molectiles about 4" as the water cools.J. W.Expansion of Water. By C. SCHEEL ( C h m . Centr., 1891, ii,409-410 ; Inaug. Diss., Bedin).-The author has determined theexpansion of water between 0" and 33" by means of a glass apparatuu,the volume being read off on a capillary tuhe. (For a completedescription of it, see the original paper.) The absolute expansion ofwater was found to be 0.0408059, tlie minimuni being a t 4~0.38".Dilatation of Phosphorus and its Change of Volume at theMelting Point. By A. LKDUC (Cornpt. rend., 113, 259--%1).-Phosphorus expands almost regularly up to its melting point, whichis M.2" on the mercurial theimometer, aiid 44.1" on the normal ther-mometer.A t this point, without any appreciable change OF tempera-ture, there is a considerable expansion, tlie ratio of the volunie of thesolid phosphorus to that of. the liquid phosphorus bein:,. 1 : 1.0345.Kopp's number was 1.0:343.The expansion of either solid or liquid phosphorus can only berepresented by a formula with three terms, but the abthor is not ableto state the coefficients precisely. The value of the mean coefficientson the normal thermometer between 0" and 44.1" is 0*00037:', acllbetwoen 26' and 50°, 0.000560, the latter being calculated on ttievolume a t 0". These values differ considerably from those given byKUPP. C. H. B.Capillary Constants of Salts at their Melting Points.ByJ. '~'RAURE (Ber., 24, 3U74-:3080).-l'he author has determined thecapillary constants of a large number of salts at temperat,ures justabove their melting points. The method adopted was that of weigh-ing the drops which fell from a single perforation in ft emnll disc thatformed the end surface of a short cvliiider let in to the bottom of i Lplatinum or porcelain crucible. This crucible was so heated, bymeans of an ordinary gas flame or by the blowpipe, that the flame didnot come in contact with the hanging drop. The salts investigatedwere potassium and sodium salts, and the ratios (T) of the weight ofthe drops to the weight of the water-drop at 0" from the same vesselare tabulated.From his results, the author deduces the following conclusions :--Capillarity may be considered a '' colligntive " property.The con-J. W. LB ABSTRACTS OF CHEMICAL PAPERS.stants for the salts of the fatty acids are unusually small, diminishingrapidly as the series is ascended. For the otheio salts the constants(T) of the potassium salts of monobasic acids lie between 112 and157; of bibasic and multibasic acids, between 168 and 231. Thelimits for the constants of the corresponding sodium salts are123-16!, and 189-325. The difference T,, - T, incveases withthe number of cquivalents of the metal in the salts. It is doubtful iftri- and quadri-basic acids can, in this way, be distinguished frombibasic acids, but the author considers it always possible to distinguishbetween the latter and monobasic acids.The method points tothe following formuh as being correct :-K2FZ, KZPZO,, Na3P206,K2 As~O,~. J. W.Mutual Solubility of Salts in Water. By W. W. J. N~cor,(Phil. Mag. [ 5 ] , 31, 369--387).-Uiider the heading '' The MutualSolubility of Salts," the author groups the phenomena due to tJhemutual influence of two salts on each other's solubility in water. IIegives an historical survey of t h e work done on the subject, and pro-ceeds to communicate his own experiments on the chlorides andn ttrates of sodium and potassium taken in all possible combinationsof pairs with a common constituent. The method of experimentadopted was as follows :-A salt was taken, ant1 solutions containing1, 2, &c., gram-mols. of this salt in 100 gram-mols. of water wereprepared.These solutions w e i ~ then satuixted ilf a detinite tempera-ture with the other salt added in excess, and the total salt in solutiondetermined. Precisely similar determinations were made with definiteniolecular solutions of the other salt. The solnbility of each saltseparately i i i water was then determitied, and finally, the solubility ofboth salts when simultaneously added in excess to water was alaoascertained.'l'he results are presented in the form of tables, formulae, and curves,In general, the presence of one salt diminishes the solubility of theother, but i n the case of the nitrates of potassinm and sodium, t h epresence of the one in solution increases the solubility of the other..(Compare Nernst, Abstr., 1890, 3 ; Le Blaric and Noyes, Abstr.,18131, 388.) J.W.Cryoscopic Behaviour of Dilute Solutions. By J. TRAURE(Ber., 24, 3071-3074).-Eykrn:tii1i and Arrheriius have pointed out,(Abstx., 1891, 972 and 1148) that the observations of the auihor onthe freezing point of dilute. solutions, in particular of those of canesugar, are not i n accordance with their own experiments, o r w i t hthose of Tanimann end Pickering. The author upholds his numbers,and attributes the discrepancy to the other observers having cooledtheir solutions too far below tne freezing point before making ohser-vations. J. W.Automatic Replacement of Mercury in Sprengel Pumps.By A. VEIINEUIL (ULIIZ. Soc. Chim. [ ; 3 ] , 5, 748---750).-'l'lie mercuryis cmntiiiuously and automatically transferred from the lower to theupper reservoir by t h e action of n water-pressure or similar piirnpGENER1.L AND PHYSICAL CHEMISTRY.9tlie suction.tube of which is attached to the upper end t of a smallbulb, connected by tubes a, b to both reservoirs, and placed about40 cm. above the upper one. The contents of the lower reservoirare thus forced into the bulb by atmospheric pressure, and allow-ccl tofnil into the upper reservoir by their own weight. The tube a is3 mm. in internal diameter, and is recurred at the lower end, the levelof the mercury at that poiIit being so adjusted that much air and littlemefcury passes up the tube; the tube b is 6 mm. ininternal diameter.It. isnot intended to be used at starting, as it is found niorc convenient totransfer any considerable quantity of mercury by hand than to makethe apparatus of unnecessarily large dimensions.An incidentaladvant,age is t h a t the mercury is bronglit into contact with airunder conditions favourable to the oxidation of impurities.The a.pparatus is applicable to most existing mercury pumps.JN. W.Block Support for Tubes. By A. GAWALOVSKI (Zeit. anal.CItern., 30, 581-583).-Two elongated blocks of hard wood, laid sid10 ABSTRACTS OF CHEMICAL PAPERS.by side, have rectangular grooves ploughed in their contiguous faces,so as to form a channel, the cross section of which corresponds,approximately, with the shape of the bulbs of R P6ligot’s U-tube.The blocks are then united by screws. Upright pieces of wood, ofvarious heights, shaped so as to fit and slide in the channels, can beinserted to give support to the, .U-tubes, or to carry horizontal tubeson their upper, grooved edges.To these pieces the tubes areattached hy spring clips. A trail1 of tube apparatus can thus be heldby a single support. M. J. S.Formation of Mixed Crystals. By H. BUHRESS (Bee. TKUZ..Chim., 10, 57--64).-1. Double Salts of Menm-;c Thiocyanate withZhc, Cadmium, Cobalt, and Coppel. Yhiocyanates.-The salts havingthe following compositions, crystallise well :-Hg( CNS)2,Zn(CNS)2 ;Hg( CNS)2,Co(CNS)2 ; 2EIg(CNS)*,Cd(CNS), ; andHg(CNS),,Cu(CNS), + H,O.The zinc and cobalt double salts are homogeneous c:-ystals, the formercolourleis, and the latter deep-blue. The cadmium salts affordanalogous, pale-blue crystals, which, in the case of the double saltsof zinc and cadmium, are almost identical in forni with those of zincmercury thiocyanate ; consequently, two double cadmium mercurythiocyanates should exist and correspond with the formuJz2Hg( CNS),,Cd( CNS), (Nordstrom’s salt) and Hg( CNS,),Cd(CNS ).respectively, which are analogous to the nmmoniiim saltsHg( CNS),,NH,CNS and Hg( CNS)2,!2SH,CNS.Prom the liquid obtained by the addition of mixed solutions ofcobalt and cadmium nitrates, or of cobalt and zinc nitratep, to ti verydilute solution of ammonium mercury thiocyana te, colourless needlesseparate ; these break up on the addition of ammoniuiii thiocyanate,when the mother liquor affords the large, mixed, deep-blue crystals,noted above.No mixed crystals of cobalt and copper compounds could beobtained.With the blue crystals of the cobalt salt, yellowish-greencrystals of mercury copper thiocyanate occur, a result the authorascribes to it reaction induced by the water of crystallisation thedouble copper salt contains.Addition of mercury ammonium thiocyanate to mixed solutions ofcopper, zinc, cobalt, and cadminm salts, determines the formation ofmercury copper thiocyanat,e, and characteristic brown-violet crystals ofmercury zinc copper thiocyanate, which contain no cobalt, and areisomorphnus with the zinc compound. These do not alter wbea heatedat lYO”, whereas the dark-green needles of mercury copper thiocyaustebecome dark and opaque. The author concludes that, in presence ofmuch ziiic, meycury copper thiocyanate loses its water of crystallisa-tion yielding mixed cryst~ls with mercury zinc thiocyanate, whereaswhen mercury copper thiocyanate crystallises alone, it a1 ways con-t:lins a molecule of water of crystallisation.2. Silrer Chromate tcnd Silver SuEphafe.--The small, sed crystaI3,forming the precipitate produced by the addition of potassiumdichi-oulate solution to ft silver nitrate solution acidified with nit,IN0 RGXNIC CHE M ISTR T. Itacid belong, like potassium dicliromate, to tht: clinorhombic system.If silver sulphnte he substituted foia silvc r nitrate, the blood-redcrystals yielded a t fir4 are monoclinic, but are succeeded by thedeposition of oiaange-yellow, orthorhombic crystals of -the mixed saltAg,S04 + Ag&r04, with liberation of chromic acid.3. Phosphates a.n.d Arsenates of the type NHdMgPO, + 6H20.-Salts of this type form hcmimorphic ortborhombs. The correspond-ing hemimorphic double phosphates of magnesium, maiignnese, cobalt,and nickel are known, and the anthor has prepared the analogousarsenates of calcium, zinc, and copper. He describes and figurescrystals obtained by him in endeavouring to produce mixed crjstnlsof these salts: in order to determine if their constitution was of thesame type as the magnesium derivative. Although in this resptcthis results are not conclusive, ye:f from the developnient of thecrystals he concludes thah neither a central point nor a plane ofsymmetry is necessa1.y to the dovelopmerit of hemimoi-phic crystals,since they originate equally well from a lateral plane or a summit.T. G. N

ISSN:0368-1769    

DOI:10.1039/CA8926200001

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

IN0 RGXNIC CHE M ISTR T. It I n o r g a n i c C h e mi s t r y. Revised Hydrochloric Acid Tables. By G. LUSGE and L. MARCHLEWSKI ( Z e i t . any. Chem., 1891, 133-1 35).--The author9 have cortstructed a very useful table, giving the specitic gravities (reduced by Kohlrausch's formuln to vacuum and 4" C.), the corresponding degrees of Baume's and l'waddell's hydrometers, the percentage of hydrogen chloride by w-eight, the percentage of weight of 18", 19"' 20°, 21", and 22" acid, and the number of kilograms of the said acids contained in 1 litre. The specific gravities were taken with the utmost care in a specific gravity bottle, provided with art accurate thermometer, and are guaranteed to be accurate witliiu 0.0001. The acid was analgsed by titvation with N/5 solution of sodium hydroxide, which had been staiidardised with N/5 hydrochloric acid. This acid was standardised with pure sodiu tit carbonate, and the results were verified by a gi*nvimetrie estimation as silver chloride.The titrations were done with the greatest care, sud the experimentd error never exceedod 0.02 per cent. with the weaker acids, arid 0.05 per cent. with the stronger ones. The weaker acids were weighed iu a Winkler's stop-cock pipette: the fiiruing ones in sealed glass bulbs. The Place of Fluorine in the Classification of the Elements. By H. h~OlSYhN (Bull. Soc. C h h . [ 3 ] , 5, 8~0--885).-Whilst fluorine in many respects behaves as the most energetic member of the chlorine family, in some ways it is markedly distinguished from chlorine, and seems almost to bear a remote analogy to oxygen ; as instances in point are cited, the ready combustibility of charcoal in flnorine, the dissimilarity of calcium flwoi-ide from the chloride, and its L.D E K.r2 ABSTRACTS OF CHEMICAL PAPERS. resemblance to the oxide, the solubility of silver fluoride in water, and the stability of aluminium fluoride towards water. It is pointed out also that,, whilst the cornpounds of fluorine with the non-metallic elements, including its organic compounds, are uuiformly inore volatile than the corresponding compounds of chlorine, its metallic salts ~equire, a s a rille, a higher temperature for fusion than tlie corrc- spoilcling chlorides. Comparative numerical data are given. Js. W. Action of Fluorine on Phosi7horuS Trifluoride. By H.MOISSAN (Bull. Soc. C h k . [3], 5, 880).-In order to stucly the action or fluorine on other gaseous substances, the two gases were admitted by separate tubes to the central poi.tioii of a platinum tube 15 cm. long, the ends of which were closed by transparent plates of fluor- spar, and the resulting gaseous product was conducted to tlie water or mercury troagh by a third taube near the end. When fluorine comes in contact with phosphorus trifluoride, a yellow tlame of low temperature is seen, and the product of the reaction is mainly phosphorus pentafluoride, the residue consisting of unchanged tri- fluoride. JN. W. Persulphates. By BJEHTIIELOT (Conzpt. rend., 112, I481 -1483 ; see also Berthelot, Gompt. rend., 86, ‘LO, 71, and 277; Marshall, Trans., 1891, 771; MendelAeE, HdZ.Sot; Chirrt., 38, 168; Traube, Her., 22, 1518, and 24, 1764).-The mixture of peraulphuric and sulpliuric acids obtained by electr.ilgsis, when neutralised by baryta- water or potash solution, yields a quantity of the normal persulphate, which is greater when the operation is carried on at a very low temperature. The neutralised solution rapidly becomes acid again, 11m-ticularly on heating; a t the same time losing oxygen. l’he quantity of active oxygen is proportional to the quaiititmy of sulphuric acid formed in the decomposition. Barium persulphate is soluble, and as neutral as the thiosulphate or permanganat’e ; its decomposition proceeds accordiug t o the equation BaS,08 + H,O = BaS04 + II,SO, + 0. In t,iti.ating the active oxygen by the usual reagents,it is necessary to take into account the hydrogen peroxide often coexistent with pei*sulphuric acid, or capable of being formed during the dilutions and other operations. The proportion of hjdiuogen peroxide present has been found to vary from 0 to 2 mols.for each mol. of persuiph- uric acid. Viewing the whole of the active oxygen present in the extreme case as united to the sulphur, the complex acid would have the formula S,O,,nH,O. There is no proof of the existence of a lieu tral and anhjdrous compound, such as the holoxide, SO4, of Trauba. The salts of persulphuric acid are distinct and definite, and com- parable with the permanganates, perchlorates, permolybdates, a i d Thiosulphates. By A. FOCK and I(. KrXss (Ber., 24,3016-3017). --Potassiwn calcium tliiosidphnte, 3K,S20,,CaS20, + 5H20, is obtained in colourless, monosymmetric crystals, by evaporating on the water- bat8h a mixture of potassium and calcium thiosulpbate solutions. pertungstates.NT* 1’.INORGANIC CHEMISTRY. 13 The axial relation of the crptals is a : 5 : c = 1.7610 : 1 : 0.89.31 ; /j = 80" 2'. Potassium sfmitiurn thiosulpnhate, K2S2O3,Si S?Os + 5H20, is pre- pared in a similar manner to the calcium salt ; it is readily soluble in water, and crystallises in slender, lustrous, silky needles, which are not, well adapted for crystallogi*aphic measurements. J. B. T. Ammonium Dithionate Hydrochloride. By A. FOCK and K. Kr,iiss (Ber., 24, 3017--.3018).-0n mixing solutions of ammonium dithiouate and ammonium chloride in molccular proportions, and evaporating, a compound of the formula (NH,)2S,06,H C1, is deposited in rhombic crystals.The axial relation is a : b : c = 0.09827 : 1 : 0.9612. The same substance is also formed in presence of two or more mole- cular proportions of ammonium chloride. J. B. T. Revised Nitric Acid Tables. By G. LUNGE and H. REY (Zeit. any. Cham., 1891, 165-1 70).-The tables are coiistructed on similar lines to the rerised hydrochloric acid tables (compare this POI., p. l l ) , m d similar processes were employed in their construction, but instead of weighing the acid in glass bulbs, or in a Winkler's stop- Q cwk pipette, a new form of weighing pipette, shown in the figure, RW used.14 ABSTRACTS OF CHEMICAL PAPERS. Above the stop-cock a is fixed a bulb b, of about 2 cm.diameter, connected with a second stop-cock c. The lower part of the pipet'te fit,s into a glass tube d, which has n ground neck. When the pipette is wanted for use, the stop-cock a is closed ; suction with the mouth is applied to the top, and the stop-cock c immediately closed, by which nieans R diminished pressure will be obtained inside the bulb / I . The lviint of the pipette is now dipped into the acid, the stop-cock a opened, and the acid allowed t o ascend a s far as the stop-cock, which is then iirimediately turned off. After wiping the pipette, i t is fixed into the tube d and weighed. The pipette is now tnrned round, PO as to open communication between the vhannels e and f . The stop-cock c is opened, water is squirted into the bulb b, and then allowed to flow rhrough cr, into the pipette.The diluted acid runs into the tube d , the air of which escapes through e and f. The acid is finaily emptied into a beaker and titrated. By using this apparatus, any loss of iiitric fumes is avoided. L. r)E K. Compounds of Sulphur and Phosphorus. By J. MAI (Annalcn, 265, 19.L-208).-Th object of these experiments was to ascertain wIiet.her the boiling point of tripbosphorus hexasnlphide, P3S6, was sufficient.ly below that. of stannous chloride (SOSO), and above that of pliosphorus peiitasulpliide (51 So), to allow of its advantageous tdmploymeut as a heating vapour in pyrochemic,zl investigations. When a n intimate rriixtnre of sulphur (2 atoms) and amorphous ~)hcsphorus (1 atom) is cmef rilly heated in an atmosphere of carbonic ;inhydride, and the product theii distilled, a yellow, crystalline sub- stmce (b.p. abont 410°), which seems to contain the cornpound P,&, passes over first; the later fractions consist of a mixture OE tt.iphosphorus hexasulphide and phosphorus pentasulphide, which cannot be separated into its constituents, as they boil at the same temperature (about 508'). Phosphorus pentasulphide boils at 332--340" under a pressure of 10-11 mm. ; triphosphorus hexasulphide, P3Ss, boils a t 335-340" under the sa9e conditions. When the compound of the composition P4S3, prepared from its clements by the usual met,hod, is distilled under a pressure of 11 mm., H yellow liquid passes over between 230" and 240°, and amorphous phosphorus remains i t 1 the flask ; the distillate is almost completely soluble in carbon bisLIphide, from which it is g~adually deposited in ciystals of the composition P4S3.The twiling point of t h i s compound uilder the ordinary pressure would be about 408-418" ; it begins to soften a t 130-135", h u t does not melt completely until the tempers- ture has risen above 160". When phosphorus (2 atoms) is melted with sulphur (3 atoms), and the pyoduct submitted to distillation uiider a pressure of 11 mm., alniost the whole passes over between 285" and 335" ; the distillate slowly solidifies to a yellowish, resinous, pasty mass, which, when digested with carbon bisiilphide under pressure, yields a crystalline compound of the composition PAS, ; the mother liquors from this com- pound contain a crystalline substance, which seems to be a mixture of phosphorus trisclpl~ide with PAS,.I?. s. K.IN0 dGIAS1C CHEMIS rRY. 15 New Method of Preparing Carbon Oxysulphide. 337 J. NuHicsm (Ber., 24, 2967--2974).--Carbon oxysulphide is obtained when cnrbonyl chloride is passed through concentrated sulphuric azid to dry it, and then through a tube 50 cm. long. filled with ignited asbestos well mixed with finely pulverised cadmium eulphide, the tube being placed in a combustion furnace and heated. The author 6nds that even when no external heat; is applied a sin;tll quantity of carbonyl sulphide is formed, but, the most, favouiable teu- yerature for its formation anpears to be 260-28O". The gas thus prodnced was found on analysis to contain COS, 94.87 per cent.; CO, 3.98 per cent.: air, 1.15 per cent.A quantity of crystals, which were identified as cadmiurn chloride, were obsez-ved in a tube previously charged with a layer of cadmium sulp5ide and heated in tt flame during the passage of a current of csarbonrl chloride; the reaction, therefore, appears to be a double decomposition. A. R. L. Allotropic Silver. 111. Blue Silver. By M. C. T ~ E A ( P l d . Uag. [ 5 ] , 31, 497-504 ; compare Abstr., 1891, 803).-When silver nitrate is added to a solution of dextrin made alkaline with sodium 01- potassium hxdroxide, the alkali being kept in moderate excess, the silver is first precipitated as the ordinary brown oxide, but the colour gradually changes to rcddish-chocolate, and the silver begins to di+ solve, and in a few minutes has completely dissolved to form an almost black liquid, a few drops of which.when added to a large quantity of water, give a splendid red liquid, that, spectroscopic clxnmination shows to be a perfect solution. Different specimens of d ~ x t r i n behave differentJy, and the common brown form seems to give the best results. Convenient proportions are 20 grams of sodium Irjdroxidc and 20 grams of dextrin in 1000 C.C. cf water, 14 grams of silver nitrate previously dissolved in a small quantity of water being gradually added. It is interesting to observe that allotropic silver can be formed and can exist in solution in neutrill, acid, and alkaline liquids. The alka- line solution spontaneonsly deposits allotropic silver after some time; and precipitation is immediate on the addition of dilute nitric or sulpll- uric acid.Even with a laige excess of acetic acid, however, precipita- tion is incomplete. When the precipitate has once formed, ~t is almost insolublc, but on washing dissolves to a very small extent, forming a rose-red liquid. A small quantity of sodium phosphate, when added to the alk~.line solution, precipitates the whole of the allotropic silver with a rub?- copper coloui-, which after p~olonged washing changes to deep Nile- #IY~II, and becomes slightly soluble, forming a wine-red solution. The various f o m s of allotropic silver show different body and surface colours, which tend to be complementary. 'The precipitate by sodium phosphate, €or example, when spread thickly on paper, dries with a bright-green, metallic colour, but after it has heen changed to deep green by washing, films dry with a dark gold or cwpper surface-colour. Although the dry substance has a11 the appearance of a metal, it16 ABSTRACTS OF CHEXICAL PAPERS.mRy contain 8 to 10 per cent. OF organic matter that cannot be rcmovetl, even by prolonged washing with hot water under pressure. Four specimens of carefully purified material contained respectively 93.77, 94.27, 92.86, and 96.64 per cent. of metallic silver. When the allo- tropic forms are heated, a vapour is evolved which condenses in small, brownish drops, with an empyreumatic odour. The residue consists of bright white metallic silver, and when dissolved in nitric acid, leaves a residue of black flakes of carbon. When the allotropic silver is dissolved in dilute nitric acid, and the silver precipitated by hydrochloric acid, the filtrate, on evaporation, leaves a small residue of a, yellowish, gummy substance.Tannin reduces silver nitrate to allotropic silver more readily than does clextrin. and gives better results in presence of sodium or potassium carbonate than with the caustic alkalis. 24 grams of anhydrous sodium carbonate are dissolvod in 1200 C.C. of water, and mixed with 72 C.C. of a filtered 4 per cent. solution of tannin. 24 grams of silver nitrate dissolved in a small quantity of water is added gradually, and solution of the silver takes place imme- diately. After standing for a day or two, the intensely dark-coloured liquid may be poured off from a small quantity of black precipitate. On adding a small quantity of dilute acid, the allotropic silver is precipitated, and in films dries with a bluish, steel-grey, surface- colour.Blue allotropic silver (inclnding the green and steel-grey varieties) shows endless variations, and cannot be reduced to one type. Slight dif'ferences in the conditions of formation result in very different products. Of ten products obtained by the action of tannin and sodium carbonate in various proportions, several were easily and completely soluble in ammonia, whilst some dissolved slightly, and others not at all. Some of the specimens, insoluble in water, when treated with phosphoric acid, did not dissolve, but on washing away the acid, were found to have become soluble in water ; other insoluble spacimens did not behave in this way.Some of the solutions were scarcely affected by acetic acid, whilst others were partially, and others almost completely, precipitated. The films OIL paper var.y greatly in their sensitiveness to light, an3 in the ease with which they are converted into the yellow, inter- mediate form. The least sensitive modification is that precipitated by nitric acid ; it dries with a steel-grey colonr. The modifications precipitated by acetic acid tend to have a greenish metallic surface, and are more sensitive. Permanency varies greatly in different speci- mens, and is increased by thorough washing. The blue, grey, and green forms are related to the black, or dark- grey normal silver, and tend to pass into it, whilst the gold-coloured modification tends to change into bright white metallic silver on t h e surface, with dark, or even black, silver underneath.Tannin likewise reduces silver nitrate in prescnce of lithium, ammonium, magnesium, barium, calcium, and strontium carbonates. The product with strontium carbonate is dark-red whilst moist, but dries with a rich, bluish-green, metallic surface-colour in thick films, but is red and transparent in thin films.INORGANIC CHEJILSTRT. 17 The intermediate golden-yellow form produced during the passage of the pold-coloured allotropic form to white normal silver has none of the properties of the original form, except its colour and Instre. It is hard and tough, is not converted into normal silver by friction and high pessure, and offers as much resistance as normal silver to the action of oxidising and chlorinating agents.The difference between the original form and the int,ermediate form lies in the fact that the latter. has a crystallinc structure. which becomes evident on treating the film with ferric chloride solution. When the blue form is gently heated, it also first becomes yellow, and then changes to white normal silver. A film on glass begins&o change from blue to yellow a t about 180", and the same change IS produced by the action of light, some specimens reqniriiig a few hours' exposure to sunlight, whilht others require several days. The author considers that in these allotropic forms the silver exists in a state of atomic divihion, and that this is true also of the pyro- phoric forms of various metals. He points out that there is a differ- ence between cheniical and mechanical division, and that a metal may form N compact mass, and yet be in a state of atomic division, whilst, on the other hand i t may bein a fine state of inechatlical division, and yet possess a high degree of molecular complexity Characteristics of the Alkaline Earths.By G. BHCGELMANP.- (Zsit. anal. Chem., 30, 579--580).-1n his attempts to prepare baryta by igniting the hydroxide in graphite crucibles, the author has been unable to obtain a pure product, the crucible being always attacked. The supposition oE the dimorphism of barium oxide, and the assumed catalytic action of platinum (Abstr., 1890, SSO), must theretorc be Rbandoned, since the substance obtained as a felted mass of needles showing chromatic polarisation c m no longer be regarded as baryta.Since a similar action occurs with lime and strontia, all statements respecting the specitic gra\ ity, &c., of the alkaline earths prepared in other than platinum vessels, must be withdrawn. 'Ylie statements of Fresenius and others, that strontium carbonate fuses while decomposing, cannot be confirmed. Much contraction occurs, but the oxide produced retains the form of the original mass OF car )on- ate, and is, a t most, slightly sintered. Composition of a Boiler Incrustntion. By A. CaR1s.r (Zeit. any. Chem., 1891, 77).-The author communicates an analysis of a curious boiler deposit, which owed its origin partly t o the use of an animal o r a vegetable lubricating oil. CaO, 11-09; MgO? 9.79; Fe,O?,, 5 60 ; A1203, 1.10 ; PbO, 0.98 ; CuO, trace ; SO2, 16.00 ; SO3, 1.71 ; fatty acids, 22.62 ; neutral fats, 25.84 ; moisture, 2.69 ; combined C.H. B. M. J. $, water and organic matter, 5-22 per cent. L. DE K. Action of Hydrogen Peroxide and of Water saturated with Carbonic Anhydride on Magnesium. By G. G~ORGIS (Gazzetta, 21, 510-514) .-According t o Weltzien (dnnalen, 138, 1:32), hydrogen peroxide acts slowly on magnesium, forming an alkaline liquid, which contains the normal hydroxide, Mg(OH),, and on evaporation to dry- VOL. LXlt. C18 ABSTRACTS OF CHEMICAL PAPERS. ness leaves a white, strongly alkaline mass, completely sola\de in waiLr. The author has also observed the slow action of IiTdrogeu peroxide 0 1 1 maqnesiiim and the alkalinity of t.he solution, but fiiidv that, after.remaining for a few days, acicular crystals arc! deposited, which efiervesce on treatment with hydrochloric acid. On treating metallic magnesium in a vacuum w i t h hjdrogen peroxide free from carbonic aiihyclride, the liquid after a time becomes slightly alkaline, and on evaporating to dr-yness in a vacuum, a flocculent precipitate mparates, which is only very sparingly soluble in water free from carbonic anhydride. On the other hand, when magnesium is treated with distilled water saturated with pure carbonic anhydride, the liquid soon becomes strongly alkaline, and the m t k l is energetically attacked with evolution of hydrogen ; the reaction slackens very gradually, and gas ceases to come off after about 10 or 12 hours. The solutioii, after :L time, deposits acicular crystals havirig the composition AJgCO, -t 3H,O.The evolution of hydrogen by the actioii of an aqueous solution of cmbonic anhydride on magnesium is noteworthy ; the reaction also Iwovides nu easy method for the preparation of the normal carboilate of magnesium. Cuprammonium Oxide. By PHuD'HuJi \I (Chem. Centr., 1891, ii, 339-340 ; from Mnn. Sci. [4], 5, ~jt31).--C'upramtrionium oxide is i t more powerful oxidking agent than hydrogen peroxide; it acts i w r e rapidly on cellulose, aud converts it into oxycellulose ; it also decoloriscs indigo-blue mow rapidly than hydrogen peroxide, With " mercerised " cotton wool, i t acis like Ilydrogeo peroxide. I n preparing it, by agitating copper turiiiiip with ammonia and air, both cupric oxide atid nitrous an hycliide are forlt,ed : the Ditrous anhydride is, however, only formed a t a later st,iige of the reaction.Ammonium nitrite oxidises copper, atid nitric peroxide is formed in the tirst instalice; ammonia is also liberated by the reaction, and when this occurs, free nitrogen is formed instead of nitric peroxide, The liquid becomes intensely blue ; an excess of water precipitates cupric hydroxide ; dilute acetic acid ptecipitates cupric oxide as soon S. B. A. A. as the ammonia is exactly neutrdisecl. J. W. 1,. Action of Ferric Chloride on Metallic Sulphides. By CAMMEREK (Chern. Centr., 1891, ii, 370; from Berg. Hutlen Zeit., 50, 2cil-- 664, 282-28-4.).-1n a sealed tube, ferric chloride reacts with both cupric and cuprous sulphides, cupric chloride, ferrous chloride, and mlphur being formed.With pi-ecipii ated ferrous sulphide OF iron pyrites, ferrous chloride and sulphur are the products ; with copper i)yrites, cupric chlo~ide, ferrous chloride, and sulphur are formed. With arsenious sulphide, ferrous chloride, sulphur, and nraeriiouu chloride are tirst formed ; the latter, howevei., is furtlier oxiclised to arsenic anhydride by the continued action of t-xcess of ferric chloride. With eitliey precipitated or native antimony trisulphide, antinronious iAloride, ferrous cliloride, and sulphur are formed. With stannous -;ulphide, staiiiiic chloride, ferrous cliloI*ide, aid sulphur are formed. J. IV, 1 1 .IXL?ROXNlC CHEMISTRY. 19 Manganese Tetraahloride. By H. M. VERNON ( P l i i l . LMCLg. [ 5 ] , 31, 469-484).--Pisher (Trans., 1878, 409) endeavoured to show thab t,he dark-brown liquid obtained on dissolving manganese dioxide in hydrochloric acid contains manganese tetrachloride.Picker-ing, who repeated Fisher's experiments, aiid made, in addition, a number of his own (Tram., 1879, 6.54), thought that the evidence was in fayour of the existenre of Mn,Cl, in the solution, and not of MnCII. The author now attempts to decide between these views by experi- ments on the rate a t which the " available " cliloi*iiie is evolved at different, temperatures. If Mn2C16 is really formed in the solution, half the available chlorine should be much rno1.e easily removed by means of a current of air passed through the solution than the other half, whereas. if MnCI, is present, the rate of removal should be more ~egular.The curvt s obtained from the experimental results at various temperaturt-s sliow no break a t the point where half the available chlorine has been driven out, so the author concludes that when MrisOr, Mn,03, OY MnO, is dissolved in hydrochloric acid, the onlF higher chloride formed is MnC14. The brown solution is much more stable at -26" than at ordiiiary temperatures. Pickeriug found that the presenceoF MnC1, in the solutioii from the beginning rendered it more stable. This the author accounts for on the supposition that the MnC14 dissociates directly into illnC1, and CI,, so that the presence in excess of MnCl,, one of the products of dissociation, would diminish the actual amount of disso iation. Calorimetric Researches on the Condition of Silicon and of Aluminium in Cast Iron.By F. OSMOND (Cornpt. ~d., 113, 474 -476).-The heat developed on dissolving 1 gram of cast ii.or.i con- taining different amounts of :;ilicon in a saturated solution of the double chloride of copper and ammoniuni was measured. From the results, i t appears that when the silicon is present in sufficient quan- tity,. it conrbines with the iron with the development of heat and formation of a cotupound which is dissociated by an excess of iron, and therefore only exists wlieii the amount of silicon i n the alloy is sufficiently great. Hence the difference between the quantities of heat found and those calcolated in the above experiments changes sign when the amount of silicon present reaches a percentage some- where betwecn 4.1 and 7.3.Samples of c,ast iron containing aluminium were also examined in the above manner. The results show that alumiiiiuni dissolves ill cast iron with the absorptioii of heat. Attempts to Prepare Metallic Chromium from Chromic Fluoride. By W. P. EVASS (Zeit. any. C h e w , 1891, 18-2Oj.-Tht. mthor tried the effect ot' nwtallic sodium, metallic zinc, aiid mixed carbon and silica on chromic fluoride a t a very high temperature, in the hope of getting metallic chromium. 1. Action of Sodium.-The metal was heated a t 400' in a porce- lain tube, and the fluoride passed over it. The latter was prepttrzd by distilling a mixture of lead chwnictte, calcium fluoride, and snlph- uric acid. A very &ong reactiun-tcok place and the bube becarns i .2 J. W. H. C.20 ABiTRACTS OF CHEJllCAL PAPERS. red-hot, but was soon stopped up. After cooling, the excess of sodium was dissolved out by water, and the residue examined for metallic chromium. But very little was found, and this was chiefly in combination with silicon. The experiment was repeated in an iron apparatus, in which tile va1)our of about 70 grams of metallic sodium was brought in contact, at R temperature of 900-1000°, with the fluoride. The chief products obtained were amorphous, green chromic oxide, bright-green particles of sodium-chromic fluoride, and a grey- i S l l , Lritrtle, spongy mass, which was chiefly located near the fluoride clelivery tube. On analysis, i t proved to be an alloy of sodium witli %bout 25 per cent. of chromium intermixed with a little chromic oxide and a trace of iron.The experiment was repeated, and, t h i s time, to avoid contamination with iron, in a Hessian crucible. The crucible and the delivery tubes were well lined inside with a mixture of 6 parts of alumina and 1 part of potassium chloride. After being. kept red-hot for balf an hour, the experiment came to ;i prc- iilttture end through the tube gettiag stopped up. After cooling, there was found adhering to the tube a greyish, stalactitic mixss, which foy the greater part dissolved in hot water. The insoluble por- tion consisted of fairly pure, crystalline, metallic chromiurn. 2. Action of Zinc.-About 2010 griims of zinc was heated to boiling under a layer of salt, and the fluoride M'HS passed in through a porcelain delivery tube.'l'he greater part of the fluoride was taken up by the salt with formation of sodiiini chromate. The zinc: regulus dissolved slowly in nitric acid, which gradually acquired a greenish tinge. No chromium could be detected in the insoluble residue. There was, however, good reason to believe that. an alloy of zinc with about 0*67-1*60 per cent. of chromium had been formed. In the porcelain tube, however, a lustrous, steel-like substance wls found, which on analysis proved to be practically pure metalli chromiii m. 3. Action of Carbon and Silica -The fluoride was passed through a strongly heated porcelain tube containing small granules of a mix- ture of 9 parts ot' amorphous silica and 4 parts of powdered char- coal. Abundant vapours of silicon fluoride made their escape, and on openiiig the tube, sharp, shining, hexagonal crystals of chromic oxide were foiind; besides this, an almoht black, hrittle mass, wllich on analysis yielded Cr, 30.13 ; SiO:, 48.53 ; C, 11-39; 0, 9-95, COU- taining, therefore, 8.39 per cent.of metallic chromium. From these experiments, it seems that although there is not the slightest doubt atbout the reduction of the chromic fluoridn by the piocesses described, it is not possible to prepare the metal 011 the large scale in t h i s way. Pure Bismuth. By A. CLASSEN (J. p r . Chem. [2], 44, 411- 514 ; compare Abstr., 1891, 271, 525,1324).--This is another chapter in the controversy between Schneider and Classen as to pure bismuth. Against Schneider's aualyses of commercially pure bismuth (Abatr., 1891,1524), the author puts in two analyses, the one of '' chemically llnre bismuth for scientific investigations," which gave sonle 10 grarll,s lead chloride from 500 grams of the metal, the other of '' bismuth L.DE K.,\.XISERALOGICAL CHENISTRT. 21 pnrissimnm,” from the same factory, which contained, besides lead (ufidetermined), 1-56 per cent. of copper and 0.45 per cent. o.f iron. The nnthor’s electroljtic bismuth melts at 264” ; “bismuth puriss.” from Tromsdorff melted at 272.8’. and another sample at 273”; ‘‘ absolutely pure bismuth ” from Tromsdorff melted a t 265-266” ; ‘‘ bismuth pnriss.” from Schering melted a t 269-270”. This is further evidence of the impurity of commercial “ pure b.ismuth.” The rest of the paper deals with Marignac’s method and material, and is purely polemical.A. G. B.IN0 RGXNIC CHE M ISTR T. ItI n o r g a n i c C h e mi s t r y.Revised Hydrochloric Acid Tables. By G. LUSGE and L.MARCHLEWSKI ( Z e i t . any. Chem., 1891, 133-1 35).--The author9 havecortstructed a very useful table, giving the specitic gravities (reducedby Kohlrausch's formuln to vacuum and 4" C.), the correspondingdegrees of Baume's and l'waddell's hydrometers, the percentage ofhydrogen chloride by w-eight, the percentage of weight of 18", 19"'20°, 21", and 22" acid, and the number of kilograms of the said acidscontained in 1 litre. The specific gravities were taken with theutmost care in a specific gravity bottle, provided with art accuratethermometer, and are guaranteed to be accurate witliiu 0.0001.Theacid was analgsed by titvation with N/5 solution of sodium hydroxide,which had been staiidardised with N/5 hydrochloric acid. This acidwas standardised with pure sodiu tit carbonate, and the results wereverified by a gi*nvimetrie estimation as silver chloride. The titrationswere done with the greatest care, sud the experimentd error neverexceedod 0.02 per cent. with the weaker acids, arid 0.05 per cent. withthe stronger ones. The weaker acids were weighed iu a Winkler'sstop-cock pipette: the fiiruing ones in sealed glass bulbs.The Place of Fluorine in the Classification of the Elements.By H. h~OlSYhN (Bull. Soc. C h h . [ 3 ] , 5, 8~0--885).-Whilst fluorinein many respects behaves as the most energetic member of thechlorine family, in some ways it is markedly distinguished fromchlorine, and seems almost to bear a remote analogy to oxygen ; asinstances in point are cited, the ready combustibility of charcoal inflnorine, the dissimilarity of calcium flwoi-ide from the chloride, and itsL.D E Kr2 ABSTRACTS OF CHEMICAL PAPERS.resemblance to the oxide, the solubility of silver fluoride in water, andthe stability of aluminium fluoride towards water. It is pointedout also that,, whilst the cornpounds of fluorine with the non-metallicelements, including its organic compounds, are uuiformly inore volatilethan the corresponding compounds of chlorine, its metallic salts~equire, a s a rille, a higher temperature for fusion than tlie corrc-spoilcling chlorides.Comparative numerical data are given.Js. W.Action of Fluorine on Phosi7horuS Trifluoride. By H.MOISSAN (Bull. Soc. C h k . [3], 5, 880).-In order to stucly the actionor fluorine on other gaseous substances, the two gases were admittedby separate tubes to the central poi.tioii of a platinum tube 15 cm.long, the ends of which were closed by transparent plates of fluor-spar, and the resulting gaseous product was conducted to tlie wateror mercury troagh by a third taube near the end. When fluorinecomes in contact with phosphorus trifluoride, a yellow tlame of lowtemperature is seen, and the product of the reaction is mainlyphosphorus pentafluoride, the residue consisting of unchanged tri-fluoride. JN. W.Persulphates. By BJEHTIIELOT (Conzpt.rend., 112, I481 -1483 ;see also Berthelot, Gompt. rend., 86, ‘LO, 71, and 277; Marshall,Trans., 1891, 771; MendelAeE, HdZ. Sot; Chirrt., 38, 168; Traube,Her., 22, 1518, and 24, 1764).-The mixture of peraulphuric andsulpliuric acids obtained by electr.ilgsis, when neutralised by baryta-water or potash solution, yields a quantity of the normal persulphate,which is greater when the operation is carried on at a very lowtemperature. The neutralised solution rapidly becomes acid again,11m-ticularly on heating; a t the same time losing oxygen. l’hequantity of active oxygen is proportional to the quaiititmy of sulphuricacid formed in the decomposition.Barium persulphate is soluble, and as neutral as the thiosulphate orpermanganat’e ; its decomposition proceeds accordiug t o the equationBaS,08 + H,O = BaS04 + II,SO, + 0.In t,iti.ating the active oxygen by the usual reagents,it is necessaryto take into account the hydrogen peroxide often coexistent withpei*sulphuric acid, or capable of being formed during the dilutionsand other operations.The proportion of hjdiuogen peroxide presenthas been found to vary from 0 to 2 mols. for each mol. of persuiph-uric acid. Viewing the whole of the active oxygen present in theextreme case as united to the sulphur, the complex acid would havethe formula S,O,,nH,O. There is no proof of the existence of a lieu traland anhjdrous compound, such as the holoxide, SO4, of Trauba.The salts of persulphuric acid are distinct and definite, and com-parable with the permanganates, perchlorates, permolybdates, a i dThiosulphates. By A.FOCK and I(. KrXss (Ber., 24,3016-3017).--Potassiwn calcium tliiosidphnte, 3K,S20,,CaS20, + 5H20, is obtainedin colourless, monosymmetric crystals, by evaporating on the water-bat8h a mixture of potassium and calcium thiosulpbate solutions.pertungstates. NT* 1’INORGANIC CHEMISTRY. 13The axial relation of the crptals is a : 5 : c = 1.7610 : 1 : 0.89.31 ;/j = 80" 2'.Potassium sfmitiurn thiosulpnhate, K2S2O3,Si S?Os + 5H20, is pre-pared in a similar manner to the calcium salt ; it is readily soluble inwater, and crystallises in slender, lustrous, silky needles, which arenot, well adapted for crystallogi*aphic measurements. J. B. T.Ammonium Dithionate Hydrochloride. By A.FOCK and K.Kr,iiss (Ber., 24, 3017--.3018).-0n mixing solutions of ammoniumdithiouate and ammonium chloride in molccular proportions, andevaporating, a compound of the formula (NH,)2S,06,H C1, is depositedin rhombic crystals. The axial relation is a : b : c = 0.09827 : 1 : 0.9612.The same substance is also formed in presence of two or more mole-cular proportions of ammonium chloride. J. B. T.Revised Nitric Acid Tables. By G. LUNGE and H. REY (Zeit.any. Cham., 1891, 165-1 70).-The tables are coiistructed on similarlines to the rerised hydrochloric acid tables (compare this POI.,p. l l ) , m d similar processes were employed in their construction,but instead of weighing the acid in glass bulbs, or in a Winkler's stop-Qcwk pipette, a new form of weighing pipette, shown in the figure,RW used14 ABSTRACTS OF CHEMICAL PAPERS.Above the stop-cock a is fixed a bulb b, of about 2 cm.diameter,connected with a second stop-cock c. The lower part of the pipet'tefit,s into a glass tube d, which has n ground neck. When the pipetteis wanted for use, the stop-cock a is closed ; suction with the mouthis applied to the top, and the stop-cock c immediately closed, by whichnieans R diminished pressure will be obtained inside the bulb / I . Thelviint of the pipette is now dipped into the acid, the stop-cock a opened,and the acid allowed t o ascend a s far as the stop-cock, which is theniirimediately turned off. After wiping the pipette, i t is fixed intothe tube d and weighed. The pipette is now tnrned round, PO as toopen communication between the vhannels e and f . The stop-cock cis opened, water is squirted into the bulb b, and then allowed to flowrhrough cr, into the pipette.The diluted acid runs into the tube d ,the air of which escapes through e and f. The acid is finaily emptiedinto a beaker and titrated. By using this apparatus, any loss ofiiitric fumes is avoided. L. r)E K.Compounds of Sulphur and Phosphorus. By J. MAI (Annalcn,265, 19.L-208).-Th object of these experiments was to ascertainwIiet.her the boiling point of tripbosphorus hexasnlphide, P3S6, wassufficient.ly below that. of stannous chloride (SOSO), and above thatof pliosphorus peiitasulpliide (51 So), to allow of its advantageoustdmploymeut as a heating vapour in pyrochemic,zl investigations.When a n intimate rriixtnre of sulphur (2 atoms) and amorphous~)hcsphorus (1 atom) is cmef rilly heated in an atmosphere of carbonic;inhydride, and the product theii distilled, a yellow, crystalline sub-stmce (b.p. abont 410°), which seems to contain the cornpoundP,&, passes over first; the later fractions consist of a mixture OEtt.iphosphorus hexasulphide and phosphorus pentasulphide, whichcannot be separated into its constituents, as they boil at the sametemperature (about 508').Phosphorus pentasulphide boils at 332--340" under a pressure of10-11 mm. ; triphosphorus hexasulphide, P3Ss, boils a t 335-340"under the sa9e conditions.When the compound of the composition P4S3, prepared from itsclements by the usual met,hod, is distilled under a pressure of 11 mm.,H yellow liquid passes over between 230" and 240°, and amorphousphosphorus remains i t 1 the flask ; the distillate is almost completelysoluble in carbon bisLIphide, from which it is g~adually deposited inciystals of the composition P4S3.The twiling point of t h i s compounduilder the ordinary pressure would be about 408-418" ; it begins tosoften a t 130-135", h u t does not melt completely until the tempers-ture has risen above 160".When phosphorus (2 atoms) is melted with sulphur (3 atoms), andthe pyoduct submitted to distillation uiider a pressure of 11 mm.,alniost the whole passes over between 285" and 335" ; the distillateslowly solidifies to a yellowish, resinous, pasty mass, which, whendigested with carbon bisiilphide under pressure, yields a crystallinecompound of the composition PAS, ; the mother liquors from this com-pound contain a crystalline substance, which seems to be a mixture ofphosphorus trisclpl~ide with PAS,.I?. s. KIN0 dGIAS1C CHEMIS rRY. 15New Method of Preparing Carbon Oxysulphide. 337 J.NuHicsm (Ber., 24, 2967--2974).--Carbon oxysulphide is obtainedwhen cnrbonyl chloride is passed through concentrated sulphuricazid to dry it, and then through a tube 50 cm. long. filled with ignitedasbestos well mixed with finely pulverised cadmium eulphide, thetube being placed in a combustion furnace and heated. Theauthor 6nds that even when no external heat; is applied a sin;tllquantity of carbonyl sulphide is formed, but, the most, favouiable teu-yerature for its formation anpears to be 260-28O".The gas thusprodnced was found on analysis to contain COS, 94.87 per cent.;CO, 3.98 per cent.: air, 1.15 per cent. A quantity of crystals,which were identified as cadmiurn chloride, were obsez-ved in a tubepreviously charged with a layer of cadmium sulp5ide and heated intt flame during the passage of a current of csarbonrl chloride; thereaction, therefore, appears to be a double decomposition.A. R. L.Allotropic Silver. 111. Blue Silver. By M. C. T ~ E A ( P l d .Uag. [ 5 ] , 31, 497-504 ; compare Abstr., 1891, 803).-When silvernitrate is added to a solution of dextrin made alkaline with sodium01- potassium hxdroxide, the alkali being kept in moderate excess, thesilver is first precipitated as the ordinary brown oxide, but the colourgradually changes to rcddish-chocolate, and the silver begins to di+solve, and in a few minutes has completely dissolved to form analmost black liquid, a few drops of which.when added to a largequantity of water, give a splendid red liquid, that, spectroscopicclxnmination shows to be a perfect solution. Different specimens ofd ~ x t r i n behave differentJy, and the common brown form seems togive the best results. Convenient proportions are 20 grams of sodiumIrjdroxidc and 20 grams of dextrin in 1000 C.C. cf water, 14 grams ofsilver nitrate previously dissolved in a small quantity of water beinggradually added.It is interesting to observe that allotropic silver can be formed andcan exist in solution in neutrill, acid, and alkaline liquids.The alka-line solution spontaneonsly deposits allotropic silver after some time;and precipitation is immediate on the addition of dilute nitric or sulpll-uric acid. Even with a laige excess of acetic acid, however, precipita-tion is incomplete. When the precipitate has once formed, ~t is almostinsolublc, but on washing dissolves to a very small extent, forming arose-red liquid.A small quantity of sodium phosphate, when added to the alk~.linesolution, precipitates the whole of the allotropic silver with a rub?-copper coloui-, which after p~olonged washing changes to deep Nile-#IY~II, and becomes slightly soluble, forming a wine-red solution.The various f o m s of allotropic silver show different body andsurface colours, which tend to be complementary.'The precipitateby sodium phosphate, €or example, when spread thickly on paper,dries with a bright-green, metallic colour, but after it has heenchanged to deep green by washing, films dry with a dark gold orcwpper surface-colour.Although the dry substance has a11 the appearance of a metal, i16 ABSTRACTS OF CHEXICAL PAPERS.mRy contain 8 to 10 per cent. OF organic matter that cannot be rcmovetl,even by prolonged washing with hot water under pressure. Fourspecimens of carefully purified material contained respectively 93.77,94.27, 92.86, and 96.64 per cent. of metallic silver. When the allo-tropic forms are heated, a vapour is evolved which condenses in small,brownish drops, with an empyreumatic odour.The residue consistsof bright white metallic silver, and when dissolved in nitric acid,leaves a residue of black flakes of carbon. When the allotropicsilver is dissolved in dilute nitric acid, and the silver precipitated byhydrochloric acid, the filtrate, on evaporation, leaves a small residueof a, yellowish, gummy substance.Tannin reduces silver nitrate to allotropic silver more readily thandoes clextrin. and gives better results in presence of sodium orpotassium carbonate than with the caustic alkalis. 24 grams ofanhydrous sodium carbonate are dissolvod in 1200 C.C. of water, andmixed with 72 C.C. of a filtered 4 per cent. solution of tannin.24 grams of silver nitrate dissolved in a small quantity of water isadded gradually, and solution of the silver takes place imme-diately.After standing for a day or two, the intensely dark-colouredliquid may be poured off from a small quantity of black precipitate.On adding a small quantity of dilute acid, the allotropic silver isprecipitated, and in films dries with a bluish, steel-grey, surface-colour.Blue allotropic silver (inclnding the green and steel-grey varieties)shows endless variations, and cannot be reduced to one type. Slightdif'ferences in the conditions of formation result in very differentproducts. Of ten products obtained by the action of tannin andsodium carbonate in various proportions, several were easily andcompletely soluble in ammonia, whilst some dissolved slightly, andothers not at all.Some of the specimens, insoluble in water, whentreated with phosphoric acid, did not dissolve, but on washing awaythe acid, were found to have become soluble in water ; other insolublespacimens did not behave in this way. Some of the solutions werescarcely affected by acetic acid, whilst others were partially, andothers almost completely, precipitated.The films OIL paper var.y greatly in their sensitiveness to light, an3in the ease with which they are converted into the yellow, inter-mediate form. The least sensitive modification is that precipitatedby nitric acid ; it dries with a steel-grey colonr. The modificationsprecipitated by acetic acid tend to have a greenish metallic surface,and are more sensitive.Permanency varies greatly in different speci-mens, and is increased by thorough washing.The blue, grey, and green forms are related to the black, or dark-grey normal silver, and tend to pass into it, whilst the gold-colouredmodification tends to change into bright white metallic silver on t h esurface, with dark, or even black, silver underneath.Tannin likewise reduces silver nitrate in prescnce of lithium,ammonium, magnesium, barium, calcium, and strontium carbonates.The product with strontium carbonate is dark-red whilst moist, butdries with a rich, bluish-green, metallic surface-colour in thick films,but is red and transparent in thin filmsINORGANIC CHEJILSTRT. 17The intermediate golden-yellow form produced during the passageof the pold-coloured allotropic form to white normal silver has noneof the properties of the original form, except its colour and Instre.Itis hard and tough, is not converted into normal silver by friction andhigh pessure, and offers as much resistance as normal silver to theaction of oxidising and chlorinating agents. The difference betweenthe original form and the int,ermediate form lies in the fact that thelatter. has a crystallinc structure. which becomes evident on treatingthe film with ferric chloride solution.When the blue form is gently heated, it also first becomes yellow,and then changes to white normal silver. A film on glass begins&ochange from blue to yellow a t about 180", and the same change ISproduced by the action of light, some specimens reqniriiig a fewhours' exposure to sunlight, whilht others require several days.The author considers that in these allotropic forms the silver existsin a state of atomic divihion, and that this is true also of the pyro-phoric forms of various metals.He points out that there is a differ-ence between cheniical and mechanical division, and that a metal mayform N compact mass, and yet be in a state of atomic division, whilst,on the other hand i t may bein a fine state of inechatlical division, andyet possess a high degree of molecular complexityCharacteristics of the Alkaline Earths. By G. BHCGELMANP.-(Zsit. anal. Chem., 30, 579--580).-1n his attempts to preparebaryta by igniting the hydroxide in graphite crucibles, the author hasbeen unable to obtain a pure product, the crucible being alwaysattacked.The supposition oE the dimorphism of barium oxide, andthe assumed catalytic action of platinum (Abstr., 1890, SSO), musttheretorc be Rbandoned, since the substance obtained as a felted massof needles showing chromatic polarisation c m no longer be regardedas baryta. Since a similar action occurs with lime and strontia, allstatements respecting the specitic gra\ ity, &c., of the alkaline earthsprepared in other than platinum vessels, must be withdrawn. 'Yliestatements of Fresenius and others, that strontium carbonate fuseswhile decomposing, cannot be confirmed. Much contraction occurs,but the oxide produced retains the form of the original mass OF car )on-ate, and is, a t most, slightly sintered.Composition of a Boiler Incrustntion.By A. CaR1s.r (Zeit.any. Chem., 1891, 77).-The author communicates an analysis of acurious boiler deposit, which owed its origin partly t o the use of ananimal o r a vegetable lubricating oil. CaO, 11-09; MgO? 9.79;Fe,O?,, 5 60 ; A1203, 1.10 ; PbO, 0.98 ; CuO, trace ; SO2, 16.00 ; SO3,1.71 ; fatty acids, 22.62 ; neutral fats, 25.84 ; moisture, 2.69 ; combinedC. H. B.M. J. $,water and organic matter, 5-22 per cent. L. DE K.Action of Hydrogen Peroxide and of Water saturated withCarbonic Anhydride on Magnesium. By G. G~ORGIS (Gazzetta, 21,510-514) .-According t o Weltzien (dnnalen, 138, 1:32), hydrogenperoxide acts slowly on magnesium, forming an alkaline liquid, whichcontains the normal hydroxide, Mg(OH),, and on evaporation to dry-VOL.LXlt. 18 ABSTRACTS OF CHEMICAL PAPERS.ness leaves a white, strongly alkaline mass, completely sola\de inwaiLr. The author has also observed the slow action of IiTdrogeuperoxide 0 1 1 maqnesiiim and the alkalinity of t.he solution, but fiiidvthat, after. remaining for a few days, acicular crystals arc! deposited,which efiervesce on treatment with hydrochloric acid. On treatingmetallic magnesium in a vacuum w i t h hjdrogen peroxide free fromcarbonic aiihyclride, the liquid after a time becomes slightly alkaline,and on evaporating to dr-yness in a vacuum, a flocculent precipitatemparates, which is only very sparingly soluble in water free fromcarbonic anhydride.On the other hand, when magnesium is treatedwith distilled water saturated with pure carbonic anhydride, the liquidsoon becomes strongly alkaline, and the m t k l is energetically attackedwith evolution of hydrogen ; the reaction slackens very gradually, andgas ceases to come off after about 10 or 12 hours. The solutioii, after:L time, deposits acicular crystals havirig the composition AJgCO, -t3H,O.The evolution of hydrogen by the actioii of an aqueous solution ofcmbonic anhydride on magnesium is noteworthy ; the reaction alsoIwovides nu easy method for the preparation of the normal carboilateof magnesium.Cuprammonium Oxide. By PHuD'HuJi \I (Chem. Centr., 1891,ii, 339-340 ; from Mnn. Sci. [4], 5, ~jt31).--C'upramtrionium oxide isi t more powerful oxidking agent than hydrogen peroxide; it actsi w r e rapidly on cellulose, aud converts it into oxycellulose ; it alsodecoloriscs indigo-blue mow rapidly than hydrogen peroxide, With" mercerised " cotton wool, i t acis like Ilydrogeo peroxide.I n preparing it, by agitating copper turiiiiip with ammonia andair, both cupric oxide atid nitrous an hycliide are forlt,ed : the Ditrousanhydride is, however, only formed a t a later st,iige of the reaction.Ammonium nitrite oxidises copper, atid nitric peroxide is formed inthe tirst instalice; ammonia is also liberated by the reaction, andwhen this occurs, free nitrogen is formed instead of nitric peroxide,The liquid becomes intensely blue ; an excess of water precipitatescupric hydroxide ; dilute acetic acid ptecipitates cupric oxide as soonS. B.A. A.as the ammonia is exactly neutrdisecl. J. W. 1,.Action of Ferric Chloride on Metallic Sulphides. By CAMMEREK(Chern. Centr., 1891, ii, 370; from Berg. Hutlen Zeit., 50, 2cil--664, 282-28-4.).-1n a sealed tube, ferric chloride reacts with bothcupric and cuprous sulphides, cupric chloride, ferrous chloride, andmlphur being formed. With pi-ecipii ated ferrous sulphide OF ironpyrites, ferrous chloride and sulphur are the products ; with copperi)yrites, cupric chlo~ide, ferrous chloride, and sulphur are formed.With arsenious sulphide, ferrous chloride, sulphur, and nraeriiouuchloride are tirst formed ; the latter, howevei., is furtlier oxiclised toarsenic anhydride by the continued action of t-xcess of ferric chloride.With eitliey precipitated or native antimony trisulphide, antinroniousiAloride, ferrous cliloride, and sulphur are formed.With stannous-;ulphide, staiiiiic chloride, ferrous cliloI*ide, aid sulphur are formed.J. IV, 1 1 IXL?ROXNlC CHEMISTRY. 19Manganese Tetraahloride. By H. M. VERNON ( P l i i l . LMCLg. [ 5 ] ,31, 469-484).--Pisher (Trans., 1878, 409) endeavoured to show thabt,he dark-brown liquid obtained on dissolving manganese dioxide inhydrochloric acid contains manganese tetrachloride. Picker-ing, whorepeated Fisher's experiments, aiid made, in addition, a number ofhis own (Tram., 1879, 6.54), thought that the evidence was in fayourof the existenre of Mn,Cl, in the solution, and not of MnCII.The author now attempts to decide between these views by experi-ments on the rate a t which the " available " cliloi*iiie is evolved atdifferent, temperatures.If Mn2C16 is really formed in the solution,half the available chlorine should be much rno1.e easily removed bymeans of a current of air passed through the solution than the otherhalf, whereas. if MnCI, is present, the rate of removal should be more~egular. The curvt s obtained from the experimental results at varioustemperaturt-s sliow no break a t the point where half the availablechlorine has been driven out, so the author concludes that whenMrisOr, Mn,03, OY MnO, is dissolved in hydrochloric acid, the onlFhigher chloride formed is MnC14. The brown solution is much morestable at -26" than at ordiiiary temperatures.Pickeriug found that the presenceoF MnC1, in the solutioii from thebeginning rendered it more stable.This the author accounts for onthe supposition that the MnC14 dissociates directly into illnC1, andCI,, so that the presence in excess of MnCl,, one of the products ofdissociation, would diminish the actual amount of disso iation.Calorimetric Researches on the Condition of Silicon and ofAluminium in Cast Iron. By F. OSMOND (Cornpt. ~d., 113, 474-476).-The heat developed on dissolving 1 gram of cast ii.or.i con-taining different amounts of :;ilicon in a saturated solution of thedouble chloride of copper and ammoniuni was measured. From theresults, i t appears that when the silicon is present in sufficient quan-tity,. it conrbines with the iron with the development of heat andformation of a cotupound which is dissociated by an excess of iron,and therefore only exists wlieii the amount of silicon i n the alloyis sufficiently great.Hence the difference between the quantities ofheat found and those calcolated in the above experiments changessign when the amount of silicon present reaches a percentage some-where betwecn 4.1 and 7.3.Samples of c,ast iron containing aluminium were also examined inthe above manner. The results show that alumiiiiuni dissolves illcast iron with the absorptioii of heat.Attempts to Prepare Metallic Chromium from ChromicFluoride. By W. P. EVASS (Zeit. any. C h e w , 1891, 18-2Oj.-Tht.mthor tried the effect ot' nwtallic sodium, metallic zinc, aiid mixedcarbon and silica on chromic fluoride a t a very high temperature, inthe hope of getting metallic chromium.1.Action of Sodium.-The metal was heated a t 400' in a porce-lain tube, and the fluoride passed over it. The latter was prepttrzdby distilling a mixture of lead chwnictte, calcium fluoride, and snlph-uric acid. A very &ong reactiun-tcok place and the bube becarnsi . 2J. W.H. C20 ABiTRACTS OF CHEJllCAL PAPERS.red-hot, but was soon stopped up. After cooling, the excess ofsodium was dissolved out by water, and the residue examined formetallic chromium. But very little was found, and this was chieflyin combination with silicon. The experiment was repeated in an ironapparatus, in which tile va1)our of about 70 grams of metallic sodiumwas brought in contact, at R temperature of 900-1000°, with thefluoride.The chief products obtained were amorphous, green chromicoxide, bright-green particles of sodium-chromic fluoride, and a grey-i S l l , Lritrtle, spongy mass, which was chiefly located near the fluorideclelivery tube. On analysis, i t proved to be an alloy of sodium witli%bout 25 per cent. of chromium intermixed with a little chromic oxideand a trace of iron. The experiment was repeated, and, t h i s time,to avoid contamination with iron, in a Hessian crucible. Thecrucible and the delivery tubes were well lined inside with a mixtureof 6 parts of alumina and 1 part of potassium chloride. Afterbeing. kept red-hot for balf an hour, the experiment came to ;i prc-iilttture end through the tube gettiag stopped up. After cooling,there was found adhering to the tube a greyish, stalactitic mixss,which foy the greater part dissolved in hot water. The insoluble por-tion consisted of fairly pure, crystalline, metallic chromiurn.2. Action of Zinc.-About 2010 griims of zinc was heated to boilingunder a layer of salt, and the fluoride M'HS passed in through aporcelain delivery tube. 'l'he greater part of the fluoride was takenup by the salt with formation of sodiiini chromate. The zinc: regulusdissolved slowly in nitric acid, which gradually acquired a greenishtinge. No chromium could be detected in the insoluble residue.There was, however, good reason to believe that. an alloy of zincwith about 0*67-1*60 per cent. of chromium had been formed.In the porcelain tube, however, a lustrous, steel-like substance wlsfound, which on analysis proved to be practically pure metallichromiii m.3. Action of Carbon and Silica -The fluoride was passed througha strongly heated porcelain tube containing small granules of a mix-ture of 9 parts ot' amorphous silica and 4 parts of powdered char-coal. Abundant vapours of silicon fluoride made their escape, and onopeniiig the tube, sharp, shining, hexagonal crystals of chromicoxide were foiind; besides this, an almoht black, hrittle mass, wllichon analysis yielded Cr, 30.13 ; SiO:, 48.53 ; C, 11-39; 0, 9-95, COU-taining, therefore, 8.39 per cent. of metallic chromium.From these experiments, it seems that although there is not theslightest doubt atbout the reduction of the chromic fluoridn by thepiocesses described, it is not possible to prepare the metal 011 thelarge scale in t h i s way.Pure Bismuth. By A. CLASSEN (J. p r . Chem. [2], 44, 411-514 ; compare Abstr., 1891, 271, 525,1324).--This is another chapterin the controversy between Schneider and Classen as to pure bismuth.Against Schneider's aualyses of commercially pure bismuth (Abatr.,1891,1524), the author puts in two analyses, the one of '' chemicallyllnre bismuth for scientific investigations," which gave sonle 10 grarll,slead chloride from 500 grams of the metal, the other of '' bismuthL. DE K,\.XISERALOGICAL CHENISTRT. 21pnrissimnm,” from the same factory, which contained, besides lead(ufidetermined), 1-56 per cent. of copper and 0.45 per cent. o.f iron.The nnthor’s electroljtic bismuth melts at 264” ; “bismuth puriss.”from Tromsdorff melted at 272.8’. and another sample at 273”;‘‘ absolutely pure bismuth ” from Tromsdorff melted a t 265-266” ;‘‘ bismuth pnriss.” from Schering melted a t 269-270”. This isfurther evidence of the impurity of commercial “ pure b.ismuth.”The rest of the paper deals with Marignac’s method and material,and is purely polemical. A. G. B

ISSN:0368-1769    

DOI:10.1039/CA8926200011

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

MISERALOGICAL CHENISTRT. M i n e r a l 0 g i c a l Chemistry. 21 Asphalt in Utsh and Colorado. By G. H. STOXE (Amel.. J. Sci., 42,148--159) .-In western Colorado and north-eastern Utah, asphalt deposits of four classes are represented : (1) asphaltic sand-rock, known also as sand-asphalt and bituminous rock, the most abundaiit of all the asphaltic deposits; (2) bituminous shales or mark; ( 3 ) bituminous limestones ; and (4) outflow or overflow asphalt,, in- cluding all forms of asphalt that have oozed out of the rock that originally contained them. These deposits are described in detail by the author, and the various theories t h a t have been propounded to explain the origin of petroleum and asphalt are fully discussed. T h author intends t o complete a map of the asphalt exposures, and to publish a more complete account of them.Gmelinite from Nova Scotia. 3 y L. V. PIRSSON (Amel.. J. Sci., 42, 57-&3).--The zeolites of Nova Scotia have long been noted for the size and perfection of their crystals, and arriongst them gmeliriite has held a prominent place. The author has consequently made a careful investigation of the crystalline form and physical properties of this mineral. The material employed was collected at Pinnacle Island, Nova Scotin. I n order to control the crystallographic work, two analyses were made. In I the outer shell WAS aualysed, anti in €I tlie inner nucleus, the results being as follows :- B. H. B. SiO,. A1203. Fe20,. CaO. K20. N%O. H20. Total. I. 509.5 18-33 0.26 1-01 0.15 9.76 20.23 100.d9 IJ. W 6 7 18-50 0.15 1.05 0 16 9.88 20.15 10@*56 In considering the bearing of these results on the identity of this mineral with chabazite, there is an ampparent discordance. The re- sults of the crystallographic work point to a difference in axial ratio:, and there is also a different habit and cleavage.On the other hand, t,he twinning and the chemical coiistitution indicate the identity of the species. These appaxent discrepancies trhe author explains by the hypothesis that the effect of sodit is to lengthen tliu vertical axis; the analyses of chabazite and gmelinite showing that soda arid lime may22 ABSTRACTS OF CHEJIICAL PAPERS. replace each other t o any extent. According to this view, gmelinite would bear much the same relation to chabazite as enstatite does t o hypersthene. Whether i t should be considered a distinct Apecies would be largely a matter of choice or convenience.Newtonite and Rectorite, two new Minerals of the Kaolin Group. B y R N. BRACKETT and J. F. WILLIAMS (Amer. J. &i., 42, 11-21 j .-The authors describe two hydrous silicates of aluminium which they believe have not before been obsewed. The mineral, which they term newtode, is found on Sneed’s Creek, Newton Co., Arkansas: in R dark-grey clay, of lower carboniferous age. It is a plire white, soft, compact, liomogeneous snbstance, having a sp. gr. of 2-37. B. H. B. Analysis gave the f’ollowing results :- SiO,. AbO, Loss on ignition. Fe,O,,. CaO. K,O. Pu’a,O. Total. 40.28 35.27 22.89 0.21 0.54 0.99 0-73 100.85 These results ane in accord with the formiila AI2O3,2SiO2,4H2O. Under the microscope, the rriineral is seen to be entirely made up of minute rhombs.The second hydrous silicake of aluminium, rectorite, which is also to be regarded as new, is found in the Blue Mountain mining district, Arkansas. When pure, i t is a soft, white mineral occurring in large leaves. Analysis gave the followiug results :-- SiO?. A1.10,. Loss on ignition. Total. 54.32 37-69 7-99 100~00 I n this analysis, small pi*oportione, of ferric oxide, lime, magnesi:], and alkalis have been disregarded. The formula of the mineral is AI2O3,2SiO2,H20 + Aq. From the authors’ reseamhes it is probable that three members of the kaolin series out of the possible four are known ; and the present status of the series may be concisely stated as follows :- 1.Rectorite.. . . . . . . . 2. Kaoiin and members A1203,2Si02.2 t1,O Monoclinic or 0. of the kaolin group Ai2O3,2SiO2,2H20 + Aq 0. 3. - A120,,2Si0,,3H,O - 4. Newtonite . . . . . . . . Al2O3,2SiO2,H20 + Aq Monoclinic (?). A120,,2Si0,,4H20 + Aq Rhombohedral. B. H. B. New Analyses of Astrophyllite and Tscheffkinite. By L. G. EAK~KS (Amer. J . Sn’., 42, 34-373.--1. Ast.l.oPhi/ZZile.-Piaom a dis- cussion of the xnaljses published by Hiickstrom m d by Konig, Brogger deduces the general fortnula R”,R’,Ti( Si04)r for this mineral. The new analysis made by the author closely confirms this formula, agreeing with it better than those from which it was derived. Cal- culating the small amount, of ferric oxide present in with the R” group, the molecular ratios of the author’s analysis give the following elementary proportions :- Si,,0,9T i (Zr) 15qR’t33GR t231H,a.If ISERALOGICA L CHENISTRY.23 which reduces to Si,O,,.,Ti 1.Ji''3.65( RH)4.7. 2. !lk&efkin;fe -A fragment of this rare mineral from Bedford Co., Virgiiiia, analysed by the author, showed a distinctly banded structure of lustrous black and dull-black material. The analyses-, however, show that tliesc two bands are practically identical, the dull being somewhat more hydrated. The molecular ratios seem to lead to no definite or satisfactory formula, a result quite i n accordance with the eyidence furnished 1))- the microscopic examination of sections. B. H. B. Minerals in Hollow Spherulites of Rhyolite. By J. P. IDDINGS and S. L. PENFIELD (rln~er. .J. Lvc?., 42, 39--46).--The o c ~ ~ r r e n c e of fayalite with other mirierals in the litbophysae and hollm spherulites a t Obsidian Clig has been described by the authors (Abstr., 1891,26), and they have also called attention to the occurrence of faj'tlite in obsidian a t Lipari and Vulcano (Abstr., 1891, 1.58).In the prment paper, they contribute further to the knowledge of these aqneo-igneous products in siliceous lsvas by describing a somewhat different develop- ment of hollow spherulites in rhyolites at Glade Creek, Wyoming. In this rhyolite, as in the obsidian of Ohsidian Cliff, fayillite occurs i n atssoc*i;i tiort witli abundant quartz, B S the result of the mineralising action of vapours in the cooling acid lavas. The qiiartz in both localities has an unusual, simple, and pedect development, and is accompanied by an uncommon form of smidine and by tridymite.11 oreoi-w, in certain hollow spherulites the fayalite is replaced by himbleride arid biotite. R. H, B. Siliceous Sand of Monte Soratte. By G. GIORGIS (Gnazetta, 21, 514--516).-At St. Orest,e, near Monte Soratte, there is a deposit of qunrtzose sand of the pliocetie age lying unconfoi*mably on the jurrlwic limestone of the district. Microscopically it is seen to consist of quartz, orthoclasic felspar, and small quantities of mica. Its corn- position is as follows :-- Water at 100" = 0.20 per ceiit. SiO,. AI20,{. FePO,. CaO. MgO. Alkalis. Dry residue.. . . . . 93.50 3.6'2 traces traces - 2.88 Ditto aftel. lcviga- tion.. . . . . . . . . . 94.41 2.99 0.11 - - 2.42 S.B. A. A . Reproduction of Acid Rocks. By H. IJE CBATETJEII (Cowpf. rpnc?., 113.370- SCS).-'l'he distinctness, purity, and uniform devPlop- rnent of felspxr crystals show undoubtedly that they have heen formed within a f l u i d mass and not from nt solid mass under the influerice of mineralising agents;, or from the devitrification of a glass The grent pressure under which crystallismtion takes place has prevented ihe felspnr from becoining vitreous or amorphous, as it does wlim hented under atmospheric pressure. Kxperiments made nnder a pressure of24 ABSTRACTS OF CHEMICAL PAPERS. 5000 stmos. gave ouly glasses, probably because cooling took place much too rapidly. C. H. B. Kctmacite, Taenite, and Plessite, from the Welland Meteoric Iron. By J. M. DAVlSON (Amer.J. Sci., 42, G&ti6).-The WeI- land siderolite was described by E. E. Howell (PTOC. finchester Acnd. Sci., 1890, 86--87). Its analysis gave 91.17 per cent. of iron, and 8-54 per cent. of nickel. I t is singularly free from troilite and schreibersite, and thus offered a good opportunity for the analysis of its separated nickel-iron alloys. Between the decomposed ou hide and the compact centre there was a zone in which the oxidatinn was super- ficial, and confined to the planes of contactof the diffewnt alloys that form the Widmanstatten figures. It thus became possible to separate the kamacihe and tamite in quantities sufficient for analysis. It was intended to analjse the plessite as a whole ; bnt, on examination, its fine layers were SO suggestive of kamacite and of tcenite that an attempt was made to analyse them separately. The analytical iTesults were as follows, the analyses of knmacite and taenite being givcn, each next to its correspondtiig part of- the plessite :- Plessite.rI.-h----- 7 li nmwi tc. haiiiscit e-like part. 'I'uenite-like part. Tsenite. Pe.. . . 93-09 92-81 72.98 75. i 8 'Ni ... 6.69 6.9 7 25.87 24 32 Co.. . . 0.25 0.19 0.83 0.33 c * . .. 0.02 0.1'3 0-91 0.S) 100.03 100.16 100*39 The physical and chemical correspondences appear to justify the concliision that in the Welland meteoric iron there are but two dis- tinct nickel-iron alloys-kamacite and taenite, and that the so-called plessite consists merely of thin, alternating lamella3 of these two alloys. It is unsafe to generaiise on a single analysis; but an ex- aminatioii of the markings of other meteoric irons suggests the thought that in them also there may be but two distinct alloys. A Gold-bearing Hot-spring Deposit.By W. H. WEISD (Amei.. J: Xci , 42,166-169).--The author has examined a series of speci- mens from the Moant Morgan gold mine, Queensland, with a view to cornpace ttieir~ with the siliceous sintcrs from the hot-spring region of the Yellow,tone Park. These specimens possess unustial interest, inasmuch as the observations of the Government Geologist of Queens- land show that the Mount Morgan mine, which paid a dividend of S1,200,000 in 1889, works a depcsit of a hot spring, the ore being a siliceous sinter impregnated with auriferous hematite (compare Abstr., 1886, 21). The Steamboat Springs of Nerada are surrounded by deposits of sinter, in the fissnres of which ore dcposition is now taking place, L hmall amourit of gold being found in these contem- poraneous mineral reins.The Mount Morgan deposit is, however, the only hot-spring deposit known that has been found to contain B. H.B.ORQANZC CHEMISTRY. 25 gold in workable qiiantities. A careful search for such deposits has been inade for the past eight years in the Yellowstone Park, the most remarkable hot-spring district of the world, without bringing to light a single caseof the sort. Hot-spring waters and deposits have been most carefully analysed, without indicating the presence of even a trace of the precious metals. Note by Abstractw.-In discussing the origin of the Mount Morgan deposit, the author accepts Mr.H. L. Jack's theory, that the deposit is that of a geyser, without pointing out that the origin of this ore- deposit has been the therue of much controversy. According to some, the deposit is thought to be an auriferous zone traversed by a series of quartz veins of auriferous qundic. Others think that it is the decomposed cap of a large pyrites lode. The last contribntion to the discussion i s afforded by a paper read before the American Iristitute of Mining Engineers, in June, 1891, by Mr. T. A. H,icknrd, who adro- cates the theory of metamorphosis and replacement. The ore-deposit, he thinks, represents a n altered portion of shattered country rock, which, by reason of i t s crushed condition, was readily acted on by miiieral solutions, and t h a t these solntions replaced the basic and felspathic with acid and quartzose material, which was also anriferous.I t is its quartzose and pei*meable c4iamcter which bas saved from dis- integrntiou the mass t h n s affected, and has preserved it as an ore- body on the summit of the hill. Analysis of a Hot Mineral Spring at Sclafani. By E. PATERK~ (Gazzetta, 21, ii, 4~J--.51).--This water issues at, a temperature of 32-9", and has a sp. gr. of 1.0074 compared \kith water a t Uo. It con- tains 0.1982 gram per litre of free carbonic anhydride, 0.0171 gram of free liydrogen sulphide, and 16.9 C.C. of nitrogen per litre. The total weight of carboiiic anhydride per litre is 0.3527 gram, and of hydrogen sulphide 0.0185 gram. The residue from a litre, when dried at 110", weighs 12.510 grams.B. H. B. One litre of the water contains in grnms : SiO,. so,. c1. R 1. I. CaO. Sr0. 0.0746 0-0790 G 6900 0.0148 0.0062 0.4720 0.1145 MgO. NaJ3. K,O. Fe,O, and A1,03. 0.3550 5-5512 0.0170 0.001 5 togebher with 0*0003 gram of organic matter and traces of phosphoric acid, lithiurn. barium, arid manganese. The results obtained differ considerably from those published by Cappa in 1847. W. J. P.MISERALOGICAL CHENISTRT.M i n e r a l 0 g i c a l Chemistry.21Asphalt in Utsh and Colorado. By G. H. STOXE (Amel.. J. Sci.,42,148--159) .-In western Colorado and north-eastern Utah, asphaltdeposits of four classes are represented : (1) asphaltic sand-rock,known also as sand-asphalt and bituminous rock, the most abundaiitof all the asphaltic deposits; (2) bituminous shales or mark;( 3 ) bituminous limestones ; and (4) outflow or overflow asphalt,, in-cluding all forms of asphalt that have oozed out of the rock thatoriginally contained them.These deposits are described in detail bythe author, and the various theories t h a t have been propounded toexplain the origin of petroleum and asphalt are fully discussed. T hauthor intends t o complete a map of the asphalt exposures, and topublish a more complete account of them.Gmelinite from Nova Scotia. 3 y L. V. PIRSSON (Amel.. J. Sci., 42,57-&3).--The zeolites of Nova Scotia have long been noted for thesize and perfection of their crystals, and arriongst them gmeliriite hasheld a prominent place. The author has consequently made a carefulinvestigation of the crystalline form and physical properties of thismineral.The material employed was collected at Pinnacle Island,Nova Scotin. I n order to control the crystallographic work, twoanalyses were made. In I the outer shell WAS aualysed, anti in €Itlie inner nucleus, the results being as follows :-B. H. B.SiO,. A1203. Fe20,. CaO. K20. N%O. H20. Total.I. 509.5 18-33 0.26 1-01 0.15 9.76 20.23 100.d9IJ. W 6 7 18-50 0.15 1.05 0 16 9.88 20.15 10@*56In considering the bearing of these results on the identity of thismineral with chabazite, there is an ampparent discordance. The re-sults of the crystallographic work point to a difference in axial ratio:,and there is also a different habit and cleavage.On the other hand,t,he twinning and the chemical coiistitution indicate the identity ofthe species. These appaxent discrepancies trhe author explains by thehypothesis that the effect of sodit is to lengthen tliu vertical axis; theanalyses of chabazite and gmelinite showing that soda arid lime ma22 ABSTRACTS OF CHEJIICAL PAPERS.replace each other t o any extent. According to this view, gmelinitewould bear much the same relation to chabazite as enstatite does t ohypersthene. Whether i t should be considered a distinct Apecieswould be largely a matter of choice or convenience.Newtonite and Rectorite, two new Minerals of the KaolinGroup. B y R N. BRACKETT and J. F. WILLIAMS (Amer. J. &i., 42,11-21 j .-The authors describe two hydrous silicates of aluminiumwhich they believe have not before been obsewed.The mineral,which they term newtode, is found on Sneed’s Creek, Newton Co.,Arkansas: in R dark-grey clay, of lower carboniferous age. It is aplire white, soft, compact, liomogeneous snbstance, having a sp. gr. of2-37.B. H. B.Analysis gave the f’ollowing results :-SiO,. AbO, Loss on ignition. Fe,O,,. CaO. K,O. Pu’a,O. Total.40.28 35.27 22.89 0.21 0.54 0.99 0-73 100.85These results ane in accord with the formiila AI2O3,2SiO2,4H2O.Under the microscope, the rriineral is seen to be entirely made up ofminute rhombs.The second hydrous silicake of aluminium, rectorite, which is also tobe regarded as new, is found in the Blue Mountain mining district,Arkansas. When pure, i t is a soft, white mineral occurring in largeleaves.Analysis gave the followiug results :--SiO?. A1.10,. Loss on ignition. Total.54.32 37-69 7-99 100~00I n this analysis, small pi*oportione, of ferric oxide, lime, magnesi:],and alkalis have been disregarded. The formula of the mineral isAI2O3,2SiO2,H20 + Aq.From the authors’ reseamhes it is probable that three members ofthe kaolin series out of the possible four are known ; and the presentstatus of the series may be concisely stated as follows :-1. Rectorite.. . . . . . . .2. Kaoiin and members A1203,2Si02.2 t1,O Monoclinic or 0.of the kaolin group Ai2O3,2SiO2,2H20 + Aq 0.3. - A120,,2Si0,,3H,O -4. Newtonite . . . . . . . .Al2O3,2SiO2,H20 + Aq Monoclinic (?).A120,,2Si0,,4H20 + Aq Rhombohedral.B.H. B.New Analyses of Astrophyllite and Tscheffkinite. By L. G.EAK~KS (Amer. J . Sn’., 42, 34-373.--1. Ast.l.oPhi/ZZile.-Piaom a dis-cussion of the xnaljses published by Hiickstrom m d by Konig,Brogger deduces the general fortnula R”,R’,Ti( Si04)r for this mineral.The new analysis made by the author closely confirms this formula,agreeing with it better than those from which it was derived. Cal-culating the small amount, of ferric oxide present in with the R” group,the molecular ratios of the author’s analysis give the followingelementary proportions :-Si,,0,9T i (Zr) 15qR’t33GR t231H,aIf ISERALOGICA L CHENISTRY. 23which reduces toSi,O,,.,Ti 1.Ji''3.65( RH)4.7.2. !lk&efkin;fe -A fragment of this rare mineral from BedfordCo., Virgiiiia, analysed by the author, showed a distinctly bandedstructure of lustrous black and dull-black material.The analyses-,however, show that tliesc two bands are practically identical, the dullbeing somewhat more hydrated. The molecular ratios seem to leadto no definite or satisfactory formula, a result quite i n accordancewith the eyidence furnished 1))- the microscopic examination of sections.B. H. B.Minerals in Hollow Spherulites of Rhyolite. By J. P. IDDINGSand S. L. PENFIELD (rln~er. .J. Lvc?., 42, 39--46).--The o c ~ ~ r r e n c e offayalite with other mirierals in the litbophysae and hollm spherulitesa t Obsidian Clig has been described by the authors (Abstr., 1891,26),and they have also called attention to the occurrence of faj'tlite inobsidian a t Lipari and Vulcano (Abstr., 1891, 1.58).In the prmentpaper, they contribute further to the knowledge of these aqneo-igneousproducts in siliceous lsvas by describing a somewhat different develop-ment of hollow spherulites in rhyolites at Glade Creek, Wyoming.In this rhyolite, as in the obsidian of Ohsidian Cliff, fayillite occurs i natssoc*i;i tiort witli abundant quartz, B S the result of the mineralisingaction of vapours in the cooling acid lavas. The qiiartz in bothlocalities has an unusual, simple, and pedect development, and isaccompanied by an uncommon form of smidine and by tridymite.11 oreoi-w, in certain hollow spherulites the fayalite is replaced byhimbleride arid biotite. R. H, B.Siliceous Sand of Monte Soratte. By G.GIORGIS (Gnazetta, 21,514--516).-At St. Orest,e, near Monte Soratte, there is a deposit ofqunrtzose sand of the pliocetie age lying unconfoi*mably on the jurrlwiclimestone of the district. Microscopically it is seen to consist ofquartz, orthoclasic felspar, and small quantities of mica. Its corn-position is as follows :--Water at 100" = 0.20 per ceiit.SiO,. AI20,{. FePO,. CaO. MgO. Alkalis.Dry residue.. . . . . 93.50 3.6'2 traces traces - 2.88Ditto aftel. lcviga-tion.. . . . . . . . . . 94.41 2.99 0.11 - - 2.42S. B. A. A .Reproduction of Acid Rocks. By H. IJE CBATETJEII (Cowpf.rpnc?., 113.370- SCS).-'l'he distinctness, purity, and uniform devPlop-rnent of felspxr crystals show undoubtedly that they have heen formedwithin a f l u i d mass and not from nt solid mass under the influerice ofmineralising agents;, or from the devitrification of a glass The grentpressure under which crystallismtion takes place has prevented ihefelspnr from becoining vitreous or amorphous, as it does wlim hentedunder atmospheric pressure.Kxperiments made nnder a pressure o24 ABSTRACTS OF CHEMICAL PAPERS.5000 stmos. gave ouly glasses, probably because cooling took placemuch too rapidly. C. H. B.Kctmacite, Taenite, and Plessite, from the Welland MeteoricIron. By J. M. DAVlSON (Amer. J. Sci., 42, G&ti6).-The WeI-land siderolite was described by E. E. Howell (PTOC. finchester Acnd.Sci., 1890, 86--87). Its analysis gave 91.17 per cent. of iron, and8-54 per cent. of nickel. I t is singularly free from troilite andschreibersite, and thus offered a good opportunity for the analysis ofits separated nickel-iron alloys.Between the decomposed ou hide andthe compact centre there was a zone in which the oxidatinn was super-ficial, and confined to the planes of contactof the diffewnt alloys thatform the Widmanstatten figures. It thus became possible to separatethe kamacihe and tamite in quantities sufficient for analysis. It wasintended to analjse the plessite as a whole ; bnt, on examination, itsfine layers were SO suggestive of kamacite and of tcenite that anattempt was made to analyse them separately. The analytical iTesultswere as follows, the analyses of knmacite and taenite being givcn,each next to its correspondtiig part of- the plessite :-Plessite.rI.-h----- 7 li nmwi tc.haiiiscit e-like part. 'I'uenite-like part. Tsenite.Pe.. . . 93-09 92-81 72.98 75. i 8'Ni ... 6.69 6.9 7 25.87 24 32Co.. . . 0.25 0.19 0.83 0.33 c * . .. 0.02 0.1'3 0-91 0.S)100.03 100.16 100*39The physical and chemical correspondences appear to justify theconcliision that in the Welland meteoric iron there are but two dis-tinct nickel-iron alloys-kamacite and taenite, and that the so-calledplessite consists merely of thin, alternating lamella3 of these twoalloys. It is unsafe to generaiise on a single analysis; but an ex-aminatioii of the markings of other meteoric irons suggests thethought that in them also there may be but two distinct alloys.A Gold-bearing Hot-spring Deposit.By W. H. WEISD (Amei..J: Xci , 42,166-169).--The author has examined a series of speci-mens from the Moant Morgan gold mine, Queensland, with a view tocornpace ttieir~ with the siliceous sintcrs from the hot-spring regionof the Yellow,tone Park. These specimens possess unustial interest,inasmuch as the observations of the Government Geologist of Queens-land show that the Mount Morgan mine, which paid a dividend ofS1,200,000 in 1889, works a depcsit of a hot spring, the ore being asiliceous sinter impregnated with auriferous hematite (compareAbstr., 1886, 21). The Steamboat Springs of Nerada are surroundedby deposits of sinter, in the fissnres of which ore dcposition is nowtaking place, L hmall amourit of gold being found in these contem-poraneous mineral reins.The Mount Morgan deposit is, however,the only hot-spring deposit known that has been found to containB. H.BORQANZC CHEMISTRY. 25gold in workable qiiantities. A careful search for such deposits hasbeen inade for the past eight years in the Yellowstone Park, themost remarkable hot-spring district of the world, without bringing tolight a single caseof the sort. Hot-spring waters and deposits havebeen most carefully analysed, without indicating the presence of evena trace of the precious metals.Note by Abstractw.-In discussing the origin of the Mount Morgandeposit, the author accepts Mr. H. L. Jack's theory, that the depositis that of a geyser, without pointing out that the origin of this ore-deposit has been the therue of much controversy.According to some,the deposit is thought to be an auriferous zone traversed by a seriesof quartz veins of auriferous qundic. Others think that it is thedecomposed cap of a large pyrites lode. The last contribntion to thediscussion i s afforded by a paper read before the American Iristituteof Mining Engineers, in June, 1891, by Mr. T. A. H,icknrd, who adro-cates the theory of metamorphosis and replacement. The ore-deposit,he thinks, represents a n altered portion of shattered country rock,which, by reason of i t s crushed condition, was readily acted on bymiiieral solutions, and t h a t these solntions replaced the basic andfelspathic with acid and quartzose material, which was also anriferous.I t is its quartzose and pei*meable c4iamcter which bas saved from dis-integrntiou the mass t h n s affected, and has preserved it as an ore-body on the summit of the hill.Analysis of a Hot Mineral Spring at Sclafani. By E. PATERK~(Gazzetta, 21, ii, 4~J--.51).--This water issues at, a temperature of32-9", and has a sp. gr. of 1.0074 compared \kith water a t Uo. It con-tains 0.1982 gram per litre of free carbonic anhydride, 0.0171 gramof free liydrogen sulphide, and 16.9 C.C. of nitrogen per litre. Thetotal weight of carboiiic anhydride per litre is 0.3527 gram, and ofhydrogen sulphide 0.0185 gram. The residue from a litre, whendried at 110", weighs 12.510 grams.B. H. B.One litre of the water contains in grnms :SiO,. so,. c1. R 1. I. CaO. Sr0.0.0746 0-0790 G 6900 0.0148 0.0062 0.4720 0.1145MgO. NaJ3. K,O. Fe,O, and A1,03.0.3550 5-5512 0.0170 0.001 5togebher with 0*0003 gram of organic matter and traces of phosphoricacid, lithiurn. barium, arid manganese. The results obtained differconsiderably from those published by Cappa in 1847. W. J. P

ISSN:0368-1769    

DOI:10.1039/CA8926200021

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

Organic Chemistry.25Constitution of Mercuric Fulminate. By A. F. HOLLEMAK'N(Rec. Trav. Chirn., 10,65-84 ; compare Abstr., 189 I , 64) .-In order todetermine whethcr mci*curic fu!minate contained the same empirica26 ABSTRACTS OF CEEMICAL PAPEHF.group, C2K20?, as the ‘‘ diriitrosacyls” (Abstr., 1889, 49), the authorstudi d the action of benzoic chloride on dry mercuric fulminate, andfound that a dibenzoylcnrbamide was formed. I n the course offurther experimental work, which is here described a t some length, hehas determined this to be symmetrical and t o be identical in meltin:point (19i” j and physical characters with the dibenzoylcnrbamideobtained by the actioii of guauidine carbonate on anhydrous benzoicacid (Creath, Beis., 7, 1739), and with that described by Riidd&ns(Abstr., 1890, 12:3).Schmidt’s s’atement that dibenzoylcarbamideyields benzamide when boiled with pot rssium hydroxide solution(this Journal, 1872, p. 718) is incorrect. The author has preriviifil~~-pointed ouh the alialogy which this formation of a substituted carb-arnid(a presents to the conversion of isocynnic acid into an analogoussnbstaiicc, whilst Scholl (Abstr., 1891, 282) obtained acctylisocyanicacid by the action of acetic chloride on mercuric fulminate. Fromthis it would seem that the formation of dibenzoylcarbamide is alsodue to the formation of a n isocyanic derivative. Kekulb’s formula,CNCH,.NO,, neither explains these results nor the fact tbat carb-amitle is formed on the decomposition of coppcr ammonium fulminateby hycli-ogen sulphide (Gladstoile, Quart.Journ. C‘henz. Soc., 1, 228),nor Steiner’s observation (this Journal, 1875, p. 1382), that urea Rndguanidine result from the action of ammonia on mercuric fulminate.Steiner’s formula, OH*N:C:U:N*OH, explaiiis these reactions, but notthe formation of chloropicrin and of cyanogen chloride by the actionof chlorine water on mercuric fulminate. Regarding fulminic acid asa desrnotropic compound, the author suggests the following tautomericfoi.innla, which he thinks Divers’ results (Trans., 1884, 13) support :To demonstrate the preseixe of the nitro-group in the molecule, anattempt was made to sycthesise mercuric fulminate by the actionof monobromonitroethane (1 mol.) on a solution of mwcuric oxide( I mol.) and mercuric cyanide (1 mol.), but R red precipitate ofthe compound CHgBr,N02 was alone obtained, wbich neither deton-ated on percussion nor on heating, and yielded with potanaium cyanidethe salt RBr,HgCg, + 2H20.-4 further attempt to prove thepresence of a nitro-group by the action of chlorine-water led to nodefinite result, a very complicated reaction ensuing.Mercuric fulminate (1 niol.) absorbs dry chlorine (4 atoms) withoutevolntioii of anygrtseous product, and i s converted into a yellow massof pungent odour which is soluble in cold water, and is probablydichloronitroncetonitrile. Bromine vapour is absorbed by the fnlmin-ate in the same rz,tio, and steam distillation of the resulting yellowmass affords a liquid of irritating odour, which soon solidities toyield crystals of dibromacetonitrile melting a t 60”; the latter canalso be separated from a slight residue of mercuric bromide byexhausting the crude product of the reaction with light petroleum.Scholl and the auth-w consider dinitroacet,onitrile to be a nitro-derivntive.Provided no oxidation occnrred in the action of drORGAXIC CBEMISTRT. 27chlorine on mercuric fulminate, the study o€ dinit~oacetotliCIeshould determine the validity or otherwise of Kekuld's fornau1;c.T. G. W.Constitution of Ally1 Cyanide. By F. LIPPMAKN (iMonafsh., 12,402--409).--The sn-called R l l v l cyanide was prepared according tothe directions of Riiine and Tollens (Annalen, 159, lO5), exceptingthat ally1 brornidc was substituted for ally1 iodide in the process;$0 per cent.of the tlieorcticnl yield of cjanide boiling at 118"was obtained. In o ~ d e r to prepare the dibromo-additive product,a quantity of the cyanidf. u-as cooled in ice, and gradually treatedwith a molecular proportion of bronline. After 1-2 days, the pro-duct, which no longer hnd the odour of bromine, was mixed withfuming hydrochloric acid, arid allowed to remain for 2-3 days, untilthe liquid assumed it reddish-brown colour. It wits then decomposedwith water, and the crystalline precipitate thus formed recrystallised,first from ether atid afterwards from. hot chlorofoi-m, when silkyscales of ap-dihrornob?Lt7JI.nmir7e, CHMeBr-C H BrC O N B?, were ob-tained. It melts at 147-148", is readily soluble in cold ether and inhot alcohol and chloroform, but loses hydrogen bromide whm heatedwith water.The acid solution from which the rtmide was separated by waterwas shaken with ether. The ethereal extract, on evaporation, gave Bcrystalline residue, p r t of which was insoluble in water, and con-sisted of a further quantity of the amide, whilst the rem:iinder wasreRdily soluble.The aqueous solution, on evaporation i n a vncunm,gave white, needle-shaped crjwtals of ap-diLromoh?dyric arid,C EIMeBr*CHBr*COOH. This acid may be recrystallised from etherand water, in both of which it is readily soluble; it melts a t88-89", and differs considerably in physical properties from norrnrildibromobutyric acid, CH,Me*CBr2*C00H, wliich is liquid at ordin-ary temperatures.The amide. melting at 147-148", is readily con-verted into a@-dibromobutyric acid when heated with fuming hydro-chloric acid for five hours a t 120".The formation of ap-dibromobutyyic acid from the so-called alljlcyanide shows that the constitpution of the latter must beCHMe:CH*CN. This is in harmony with the view of Kekule and ofRinne (Ber., 6, :38t;), bvt does not agree with that of Pinner (Ber.,12, 2053). G. T. M.Direct Synthesis of Primary Alcohols. By P. HENRY (C~n?pt.ven,d., 113, 368--370).-Monochloromethyi ether, CH,Cl*OMe, and thecorresponding ethyl compnund CH.,CI*O E t, react energetically withthe organo-zinc compounds. Zinc chloride separates, and, on treatingt h e product with water and distilling, the primayy alkyl oxide can beis0 1 at ed .The following ethers were prepared :-Primary methyl props1ether boiling at 41" under a pressure of 761 mm.; sp. gr. = 0.7381a t 20", by the action of zinc ethyl on inoriochloroniethyl ether.Normal primary butyl methjl ether, by the action of zinc propF1 onmonochloiwmethyl ether; i t is a colourless liquid with an agrzeabl28 ARSTRXCTS OF CBENICAL PAPERS.odour, insoluble in water, and boiling at 71" under a pressure of7.59 mm. ; sp. gr. nt20" = 0.7593. Normal ethyl propyl ether, by theaction of monochloromethyl ethyl ether ; it boils a t 63-64' ; sp. gr.a t 20" = 0.7474. l4t,kiyl butyl ether, by the action of zinc propylon monochloromethyl ethyl ether; it boils at 9d0 under a pressureof 753 mm.Zinc prcpyl is produced as easily as zinc ethyl by means ofGladstone and Tribe's zinc-copper couple, biit the yield is only 90t o 75 per cent., propylene and propane being liberated.Oxidation of Tertiary Almhols. By G.WAGXER ( J . p ~ . C'hem.[2], 44, 308--312).--TL\e oxidation of the tertiary alcohols has here-tofore always been eflectcd by chromic acid mixture, which, however,is acknowledged to convert them, by denydration, into correspondingolefines, so that the products of t h e oxidation have been those derivedfrom the olefines, ratlier than true oxidation products of the tertiaryalcohols (compme Abstr., 1883, 566 ; 1886, 4:{7). E'or this reasonthe author lias experimented with a neutral solution of potassiumpermanganate as an oxidising agent for tertiary alcoliols.He findsthat trimethylcarbinol is scarcely ;ittacked by an alkaline 4 per cent.solution of potasssiurn permanganate even when warmed ; and thattertiary amyl alcohol is oxidised by the same solution at the ordinarytemperature, but even after a month, the reaction is not complete.Dimethylisopropylcarbinol (b. p. 117-118"), howevey, is readilgoxidised to pinacone by a neutral aqueous solutim of potassium per-mangauate, aud the process adopted is fully described in the paper.This is the first case in which a saturated monhydric alcohol hasbeen directly converted into the corresponding dihydric alcohol.From this result, the author concludes that the oxidation of tertiaryalcohols results in the hydroxpli+iug of oiie of the carbon atoms whichare directly linked to ttie C(0H) graup, a reaction similar to thatobserved in the oxidation of the ketones, and probably conforming t othe same rules (compare this vol., p.35).c. H. R.A. G. B.Xylose. By G. BERTRAKD (Bull. SOC. Chim. [ S ] , 5 , 554--557).-Xylose may be obtained from wheat or oat straw by the followingpi*ocess, which is stated t o be less laborious than that used byWheeler and Tollens (Abstr., 1889, 847) in preparing i t from pinewood. The straw is extracted witli tepid water, and is then boiledfor several hours witli dilute (1-2 per cent.) siilphuric acid. Theliquor, after removal of the sulptiuiic acid by barium hydroxide, is con-centrated on the water-bath, and treated witti nlcoliol, thus yielding anextract from which xylose is obtained as a yellow syrup on removingthe solvent.The syi*up crptallises oil the addition oF a crystal ofxylose, arid the product is recrjstallised from hut alcohol. Ttie yieldfrom wheat< btr<tw is 2 per cent., from oitt straw 4 per cent.When xylose is treated with sodium amalgam, xylitol is obtainedas a syrup, whiclt, like sorbitol and perse'itol, and unlike arabitol,gives, with benzaldehgde iu the presence of sulphuric acid anabnndaiit precipitate, which appeilrs to have the compositionC5H80,(CHPh),. The xglitol mty be recovered fmm the compounORG ASIC CHEW ST RY. 29by hydrolysis, and, as thus obtained, is a rather sweet, faintly dextro-rotatory syrup. PentacetyExyZitoZ is obtained as a syrup, whenanhrdrous sylitol is treated with acetic anhydride in the presence ofzinc chloride.Xylose is farther distinguished from nrabinose by the fact that thecadmium salt of it's first.oxidation product, xylonic acid, forms well-defined, crystalline, double salts with cadmium bromide and chloride ;the react-ion is very sensitive, as it is visible when only a few milli-grams of the sugni. is present. The xylose (1 part) dissolved inwater (5 parts) is treated with brom.;ne (1 part), and, after 24 hours,the excess of bromine is evaporated oft'. If the bromine compound isrequired, the residue is now saturated with cadmium carbonate, con-centrated, and precipitated with alcohol ; whilst, if the chlorine com-pound is wanted, the hydi-ogen bromide i~ removed by means of leadcarbonate.cadmium carbonate and chloride are ndded to the imDurexybonic uckd thus obtained, and the operation is completed as befire.JN. W.Constitution of Xylitol and Xylose. By G. BERTitAh'D (7l1dZ.Soc. Chim [3], 5, 740-742 ; compare preceding abstract).-Whenxylitol is treated with a mixture of nitric imd sulphuric acids, it yieldsa pentanitrate, C,H,( NOg)5, as a colourless, irisoluble syrup, which i8lieitvier. t'han water, cati he exploded by percussion, and burns rapidlywithout leaving auy residue.By hentirig xylitol with amorphous phosphorus and iodine in astteam of nai*bonic anhydride, i t is converted into a secotidary amyliodide, which boils at 146', and yields, on prolonged heating withlead hydroxide and water, methylpropjlcarbinol, boiling a t 116O.Xylitol is thus an open-chain pentabjdric alcohol, of which xylnseis the aldehyde; the two substances being represented by the forffiuls0 H*C H2.[ C H-OH],*C H:,.O H and OH*CH2.[ C H-OH] ,.C 110.Js, W.Epichlorminel By R. SCHIFF (Gazxettc, 21, ii, 1-ti).-Equiva-lent weights of epichlorhydrin and ethyl acetoacetate are mixed withexcess ot' alcoholic ammonia solution and left for some houi*s ; there isa slight development of heat, and the reaction is completed by heat.ing on the water-bath for 15 minutes ; on the addition of water,colourless oil is obtained, which soon solidifies to aciculnr crjstals.When recrystallised from dilute alcohol, the new compound has thecomposition C,H,,NO,Cl, melts a t 95" without decomposition, mid isnot altered by beating for some time at 100-110".It dissolves inacids to form salts, and is precipitated unchanged from the solutionby alkalis; it is moderately soluble in absolute alcohol, less so iuether, and very sparingly in cold water; it separates from its hotaqueous solution in long needles. The solution is not precipitated bysilver salts or by picric acid and sodium carbonate, arid does notyield a platinochloride.If, in the preparation of this substance, the heating on the water-bath be too prolonged, a whitish, slightlg crjstailine substance isdeposited, wliich is insoluble in all ordinary solvents, aud has theNo ncetyl derivative could be prepared30 ABSTRACTS OF OHE3lICAL PAPERS.composition C12H1'IN3CILOP ; it appears to be identical with the chlor-hydrinimide of Claus (Abstr., 1875, 1121).When the eubstance C'9H16N03C1, is dissolved in hot alcohol, andtreated with oxalic acid in alcoholic solution, Ppichloramine oxalate,( C,H,NOCl)2,H2C201, is obtained as a voluminous.white precipitate,and is puritied by solution in water and precipitation by absolutealcohol. I t melts a t 193-184" with evolution of carbonic anhydride,is moderately soluble in warm water, and almost insoluhle in alcohol.I n a similar manncr. epich/ommiwe l ~ ~ ~ ~ ~ ~ o c h Z o ~ ~ i t Z e , C..H,NOCI,HCI, isobtained by treating the coiidet:satdun product with hot dilute hydro-chloric acid; on evaporating the solution in a vacuum, the salt isobtained colourlesd atid well crystallised ; it is very soluble in water.Free epichlorsrnine is verv soluble in water, atid is decomposed bysteam distillation with evolution of ammonia ; it seems to be veryrendily converted info condensation products.The a n tlior regards itas formed hy tile condensation of a niolecnle each of ammotiia, epi-clilor~hjdriii, arid ethyl nceto;wet:tle M it11 eliiiiination of wiLter, aud cou-d e r s that it has p i ohably the conhtitutionC H,CI-CH( OH).CI€,.N:CMe*CH,.CO~~~t.W. J. P.Unsaturated Fatty Amines. Hy C. PAAL and A. HELPEI, (Be]..,24, 3035-3048 ; con~pare Abstr., 1889, 116, and 1890, 399).-Dihromopropy Zctu L t r I I I idp, NH**CO*NH*CH2-CH Br*CH,Br, is preparedby mixing a conccntricted aqueous solution of the hyd~ocliloride ofdibrornopropylsmiiie (compare Henry, Ber., 8, 39!1) with potassiumcyanate.It melts a.t lt;3", and dissdves easily in alcohol and hotwater, sparingly in ether and cold wnter. An attempt t o prepare theartalogous thiocat*haniide from the hydi olnmide of the base andpo t,assium t hiocpnate was unsuccessf'u 1.By acting on an alcoholic: solution of free propargylamine wit11e t h j l iodide, and allowing th mixturw to evaporate i t 1 the absence oflight, ti crystalline wsidue is obtained, which is separated by treat-ment with alcohol into propurgy1arrz;ne hydr-ioditle, C.,H,*NH,,HI,which forms lustrow, large, white plates, melting a t 205" andsparingly so1 uble in alcohol, and diet Izylp1.opa,.~u?llcL~~i~~~ hydriod ide,C,+,H,*NNt,,HI, which is easily soluble in alcohol.The silvei- com-pound of propargylamine previously prepared was found tt) have avariable constitution, but undoubtedly contains oxygen. PI opargyl-amine itself, when boiled with sodium nitrite atld a little hyclrocliloricacid, jieldv propargyl alcohol ; Chis can be distilled with Btea~n, a n di f the distillate is collected in an ammoniacal silver solution, a white,explosive silver compound, C,H,Ag*OH, is formed.Propa,.~?/l~Zithiocar.Damic acid, C3H3.NH*CSSH, is obtained by boil-ing ail alcoholic so1utio:i of free propargyiamine with excew of carboubisulphid: in a reflux apparatus. J t melts a t 115", has a feeble, un-pleasant odour, and, when heated, smells like a thiocarbimide. Itdissolves eaily in aqueous alkalis, mineral acids, hot water, ether,alcohol, and benzene, sparingly in light petroleum and cold water.Piom dilute alcohol, it crysfallisc s in white needles ; from a mixtwORQAKlC CKKXISTHT.31of benzene and ligbt petroleum in long plates. Acetic acid and dilutemineral acids precipitate it from solutions of its alkali salts. Thebarium salt forms a white, flocculent, the stannic B white, gelatinous,the copper a preen, flocculent, the lead a white, granular, and thesilver salt R white, flocculent precipitate. The silver salt yields silversulphide wheu boiled with water. The acid itself is completelyoxidised by silver or mercuric oxide.Propargy lpheny Zcnrbumide, NHPh*CO*NH*C,H,, is prepared bymixing an aqueous solution of propargylamiiie oxalnte with ratherless than the theoretical amount of phenyl cjanate, mid adding to thecooled mixture a slight excess of a concentrated solution of potassiumcarbonate.After shaking for a time, a crystalline product is obtainedcontaining a small quantity of symmetrical diphenylcarbarnide, whichis easily soluble in hot water, mixed with very spzringly soluble proy-ai.gylphenSlcai.bamide ; the lntt,er crystallises from water in radiatinggroups of needles, melts at 133". and dissolves easily in ether, alc;ohol,and benzene, sparing1.y in light petrolenm and cold water.Isobuty ZalZylamine, CsH5*KH*CH2.CHMez, is prepared by digestingequivalent quantities of allylamine and isobutyl bromide for two o rthree days at first a gentle heat, finally on the water-bath.The pro-duct is diluted with water, acidified, separated from unattackedisobutyl bromide, and treated with caustic soda, and the bases thusliberated are dried with d i d potakh and fractionally distilled.Some diisobutyZaZl!/Zanziiir, C,H,.N (C,H,)?, boiling a t about lti5", wasisolated, but the main product is isobutylallylaiuine, a coloui~lees, vola-tile liquid boiling at 123" (uncorr.), and having a penetmting odourresembling that of allylamine. The hydro-chloride, C,HlaN,HC1, crystallises i n white, lustrous, hygxmopicplates whichmelt a t 216", and are fatty to the touch. The aiirocltloride,C,Hl,N,HAuC14, cryst allises from hot water ill splendid, yellowneedks which ue!t at 140", and slowly decompose wiien boiled withwater. '1' 11 a plat hr oc: hloride, (C,H,,N) 0,H2 P t C: 1.1, crys t allises fromalcohod in splendid, red needles, melts at 18Y, and dissolveseasily in alcohol and water.The AydroLromzde, C7H,5N,HBr, crystal-lises from a mixture of alcohol and ether in white plates whichhave a silky Instie ; it melts at 222" and dissolves rt adily in waterand alcohol. The acid oxalate, C7Hl5N,CZHZO4, crystallises from alcoholin small, white plates, inelts at 221", and dissolves fairly easily inwater, sparingly i i i alcohol.Isu but y la1 l p lp heny Zcarbanzide, C4H9*N (CJ&)*C 0 *NHPh, is formed bythe nriioii of isobut~lallylarnine with phenyl cyauate at the ordinarytemperature. A viscid, colourless oil i s obtained, which very slowlybecomes crystalline. It is insoluble iu water, but soluble in alcohol,benzene, and light; petroleum, and crystallises from the last solventis aggregates with a radial structure which melt at 37-39".I~oh~tylallylphtn~lthiocarbamide, CdH ?ON( CsH5).CS*NH Ph, is ob-tained by mixing equivalent quantities of isobutylallylamine andphengltliiocarbimide. It forms a viscid colourless oil which slowlycrystallises in long, colourlem needles grouped like ice- flowers.I tmelts at 41-43', and dissolves readily in ether, ethyl acetate, alcohol,md benzene, sparingly in light petroleum and not at all in water.It is soluble in water32 ABSTRACTS OF CHEXICXL PAPERS.lsobut?/Zpropargylanzine, CrH9-NH*C3B3, was prepared bv gradual I yadding isobutyldi bromopropylamine hydrobromide, CaH,*NH*C3B,Br,,to a well-cooled alcoholic solution of sodium ethoxide, and finallyheating the mixture in well-corked bottles in the water-bath.Thecontents were then diluted with water md distilled with steam untilan oily base tjhat w-as also forrned began to come over. The distil-late was concentrated, treated with a large excess of potassiumcarbonate, and the bases extracted wihh ether. The ethereal solutionwas dried with solid potash and fractionally distilled ; by thismeans, isobutylpropargylamine was isolated AS ~1 colourless, volatileliquid, boiling a t 134-136" (uncorr.), miscible in all proportionswith water and having an odour which recalls that of ammoilia, and atthe same trime tha&of camphor. Its aqueous solution precipitatesiron hydroxide from a solution of the chloride, has no effect on anammoniacal copper solution, and with an ammoniacal silver solutionyields a silver compound as a white precipitate which is fairlystable while moist, but explodes easily when dry.The oxulate,C7H,3N,C2HZOd, forms lustrous, white needles or plates melting at210" ; i t can be crystallised from alcohol or from water. It reducesa solution of gold chloride only very slowly (ullylamine oxalateitself, C3Ks.NH2,CzHzO4, which forms radiating groups of whiteneedles melting a t 120", effects this reduction even more slowly).The hydrochloride, C7H13N,HCI, crystallises from a mixture of alcoholand ether in large, lustrous, white plates melting a t 148" anddissolving readily in water and alcohol.The platiiiochloride,(CiH,,N)2,H,PtC16, separates from alcohol in ill-defined, red, crystal-line aggregates which iiielt a t 172", and are decomposed when keptfok a short time at 100".Isobut!/ZproljyZcrmine, C4H,*NHPp, is obtained by reducing isobutyl-propargylamine in alcoholic solution with metallic sodium, tbemixture being heated on the water-bath. The product formed wasdiliited with water and distilled with steam ; the distillate acidifiedwith hydrochloric acid, evaporated to a small bulk, and treated withpotash; the oily layer was removed, dried with solid potash, andfractionally distilled, finally over metallic sodium. The base is a.colourless, volatile liquid boiling at 123-125", miscible with water i nall proportions, and very similar to isobutylallylamine. The hydro-chloride, C,H,,N,HC'l, dissolves easily in water and alcohol, andcrystallises from a mixture of alcohol and ether in Rmall plates whichmelt at 135".The oxalate, C7H1,N,C2H2O4, crystallises from alcoholin small, white needles melting a t 224". c. I?. B.Crotonaldoxime. By T. SCHINDLER (Illonatsh., 12, 410-418). -This componnd is obtained when 2 mols. of crotonaldehyde (compareLieben and Zeisel, Monntsh., 1, 20) is slowly added during continuedagitation to a cold solution of 3 mob. of hydroxylamine hydrochlor-ide which has betm carefully neutralised with sodium carbonate, andthe resulting carbonic anhydride conipletely removed by shaking.The product is extracted with ether, and the ethereal solution dis-tilled until the greater portion of the cther is removed.The con-centrated solution is allowed t o evaporate spontaneously, when an oiORGANIC CHEMISTRY. 33having a characteristic odonr separates, and in this oil a number ofstout, closely striated prisms of crotorraldoxime, CJH,ON, slowly form.The compound is insoluhle in water, but readily dissolves in ether,alcohol, chloroform, and hot benzene, and may be best recrystallisedfrom the last-nariied solvent, when it forms colourless, odourless,volatile crystals which melt at 119-120". On heating mith aceticanhydride for two hours in a ~eflnx apparatus, the aldoxime isconverted into crotononitrile, C,H,N, a product which boils at117*4-118*4"; has a sp. gr. of 0.8468 a t 0" cornpiired with water a t4", and is apparcntly identical with that, obtained by Rinne anctTollens (A~znaletz, 159, 105) from ally1 iodide and potusiiim cyanide.Tollens (loc.cit.) and Pinner (Ber., 12, 2053) have erroneouslyatti ibuted the formula CHz:CH*CHz*CN to this compound, which, asshown by its prridiiction from crotonaldoxime, CHMe:CH*CH:NOH,must really be CHMe:CH*CN (compare KekulB, Ber., 6, 386). Onthe additlion of bromine and subsequerit digestion with concentratedhydrochloric acid, the nitrile is converted into a mixture of dibromo-butyramide, CHMeBr:CHBr*CONH,, which melts a t 148-149", anda/3-d;bromobutyric acid, CHMeBr.CHBr,*COOH, which melts a t87-90" (compare Lippman, this vol., p. 27). When the aldoximeis reduced by Goldschmidt's method (Abstr., 1887, 568), crotylamine,CiH,NHz, which boils a t 81-85', i s obtained.The oil from which the crotonnldoximc separates is a very inactivesubstance, and does not readily lend itself to purification. Since, O I Lelernen tar7 analysis, it gives numbers which w r y ciosely correspondwith tliose required for the formula of crotonsldoxime itself, the authorsuggests thnt it may possibly be the stereoisomeride of the formulaC,d,*CH:N.OH (compare Hantzsch, Abstr., 1891, 439).G.T. M.The Oximes of Chloral and Butyl Chloral. By R SCH~FF andN. TARU(;T (Gazzetta, 21, ii, 6--12).-Nageli (Abstr., 1883, 728) pre-pared a dichloroglyoxime, OH.N:CCl-CCl:NOH, in small quantities bythe action of free hydroxylamine on chloral hydrate. The autborsfiticl t h a t chZwaldosinze is easily prepared by boiling an aqueous solu-tion of equivalent proportions ot' chloral hydrate and hydroxylaminehydrochloride (compare V.Meyer, ,Qbstr., 1891, 1181). On cooling,a yellowish or greenish oil separates, having an odour closely re-semiding that of free chlorine. It could not be obtained in a statesutiiciently pure for analjsis; if left to itself, or treated with hotwater, it decomposes with evolution of hydroyen chloride andhydrogen cyanide, probably in accordance with the following equa-tion:--CCl,*CH:NOH = HCN + COC1, + HCl.BufyZchlornZdoxime, CHMeCl-CCl,*CH:NOH, is readily prepared bypouring boiling water on a dry mixture of equivalent proportions ofbntyl chloral hydrate and hydrox~lamine hydrochloride ; the oximeseparates as an oil which solidifies on cooling.A still better methodof preparation is to pour the cold solution of the hydroxyln-minehydrochloride on the i r y butyl chloral hydrate, and allow i t t oremain for some days; the theoretical yield of pure oxime is thusobtained. Butyl chloraldoxirne is fairly soluble in all the usualsolvents excepting water ; it crystnllises from light petroleum in veryFOL. LXII. 34 ABSTRACTS OP CBEMICAL PAPERS.largr, opaque odahedm, and melts at 65' without drcomposit,ion. It.dissolves in cold. concentrated sulphuric acid, and is precipih tedunaltered by water ; on heatinc the solntion, however, hpdroyenchloride is evolved. Tt i8 extremely sensitive towards aIkalis, andeven when washed with ordinary tap-maim.rapidly turns yellow andgreen. AcetyZbiityE ahZoraMoxhne, C6HSC1:302, is obt,ained bv Cent.1-yheating the oxime in wetic a.nhvdride snlution ; it is a whit8e sub-stance melting at 63-64". If the heating be too prolonged, decom-pnsition occurs with evoIution of hydrogen chloride and hydrogencyan i de.On henting with alkalis or alkali carbonates. hutvI chloraldoximebecomes first green Rnd findly bright ycllov, hypoahlorous acid beingformed. If the reactinn is arrested a t the preen stage, R yellowpowder is obtained having tJhe covpnsition C,H,,Cl,N,O,.When a few drops of glacid ncet,ic acid a m added to an alcnholicsolution of the oxime (1 mol.) containing Iit,hnr(re (2 mols.), leadchloride is formed, and a CoIourless, well crpstallised subst,nnce isobtained which melts wit,h dwnmposition at 158".This is probablyd.i~:hZo?.ncrotonaZdlnxime, CMeCl:CCI*CH:NOR.The study of butyl chloraldoxime is being continued.Sulph inic Derivatives and their Analogies to Compoundsof Organic Amines. By R. NAPIXI and T. COSTA (Gnzzetta. 21,554--565).-1t WRS previously shown hy t,he aut,hors (Ahstr., 1891,1305) that the mnlecnlar refractive energv of sulphur in t,he deriva-tives of triethylsulphine is extremely high. and especial attentionwas drawn to the iodide, the molecular refractive energy of whichremains const,ant when the concent'ration is varied, but varies whenthe solvent is chmged. Similarly, aqnenns snlntions of trimethyl-sulphine bromide and iodide give very high results for the molecnlarrefrwtive energy of sulphur.The authors consider that the theoryoE electric dissociation affords a simple explanation of these facts.I)et>erminations of the molecular weights of the above-med%medcompounds by the crposcopic method yield approximately normalnumbers in aqueous soluticms, but the acetic solut,ions of the chlorideand bromide of t,riethylsulphine yield abnormal results. It is, how-ever, noticenhle that the hydrak, chloride, and iodide, which yieldsuccessivcly incressing values for the molerular refractive energy ofsulphur. also appear to be successively less dissociated in their solu-trions. Similarly the iodide of trimethylsulpbine appears t o he lessdissociated than that of triethglsalpbine, and the sulphiir in theformer compound a.ccordingly appears t.0 have a smaller molecularrefractive energy. The alcoholic solution of triethylsulphine iodide,in which electrical dissociation cannot.take place. in like manner yieldsthe highest value for the molecular refractive energy of sulphur. I nacetic acid solutions, the molecule of triethplsulphine iodide appearsto be more complex. The moleculnr weight of triethylsulphinebromide calculated from the rise of the boiling point of an alcoholicsolution gave approximately normal resul ts.The molecula~r depression of tetrethylammonium iodide in aqueoussolution is almost equal to that of the corresponding sulphinic de-W. J. PnRQANIC CHEMISTRY. 35rivative. The refractive enerpy of tetrethylnmmonium iodide is greaterthan the sum of the refractive energies of triethylamine and ethT.1iodide, exactly as the refractive energy of triethylsulphine iodideexceds that of its constituents. The determination of t>he molecularweight of tetrethylammonium iodide from the rise of the boilingpoint of an alcoholic solution also yields a normal result.S .B. A. A.Oxidation of Mixed Ketones of the Fatty Series. By G.WAGNER (J. pr. Chem. [2], 44, 257--308).-0f Popoff's seven rulescwcerning the oxidation of ketones (Annulen, 161, 299-301 : J. ETLSS.Chpm. Soc.. 4, 67), the fourth, or that which is commonly knowh as" Popoff's rule," asserts thah when a ketone whose alcohol radiclesare of t'he mme series, bnt not isomeric, is oxidised, the carbony1remains linked to the alcohol radicle which is lowest in the series;the fifth states that in a ketone whose alcohol radicles are of the sameseries and are isomoric, that alcohol radicle in which the leasthydrogenised carbon atom is attached to the carboiiyl will be thefirst oxidised.In this paper, the author details several experiments which are notin accordance with the above rules, and disciisses them hy'the lightof t'he work which has been done on the subject by various chemists.The experiments, some of which have already hem puhlished in.J.Russ. Chem,. rcCoc., 16, 645 and 695 (compare Abstr., 1885,1197),b u t have not been copied into other journais, may be summarisedbere.Ethyl propyl ketone (b. p. 122-123" a t 745 mm.), from the actionof zinc ethyl on butyric chloride (b.p. 98--102"j, yields butyric.propionic. and acetic acids when oxidised by potassium dichromateand sulphuric acid. The formation of butyric and acetic acidsappears to be the pyimary reaction, the propionic acid resulting froma secondary one; two distinct reactions take place in this way inthe oxidation of most mixed ketones, and the proportion of theprimary to the secondary reaction approaches 2 : 1, as in this case.Popoff (AunaZen, 161, 289) and Volker (Wien. Acad. [el, 73, 335)found that propionic acid was the only product of the oxidation ofethyl propyl ketone ; the author can only conclude that they workedwith too small quantities of the ketone, and failed to separate theacids.EthyZ hexyl ketonp, obtained by the oxidation of tbe correspondingsecondary alcohol, itself obtained from the action of zinc ethyl oncenanthaldehydc, is a clear, refractive liquid with a sharp, aromaticodour; it crystallises at -8" i n long prisms, and boils st 190"(752 mm.) ; its sp.gr. at 0" = 0.840, a t 20°/00 = 0,825. The pro-ducts of the oxidation of this ketone are mnanthylic and acetic acidsfrom the primary reaction, and caproic and propionic acids from thesecondary, the proportion between the two reactions being nearly 3 : 1.Propyl hexyl ketone, obtained by the oxidation of the correspondingalcohol (b. p. 210-211" at, 759 mm.), boils a t 206-207" (753 rnm.),and solidifies in a freezing mixture to clusters of needles which melta t -9.5" to -9"'. Its odour is similar to that of ethyl hexvl ketone ;d 8 6 ABSTRACTS OF CHEMICAL PAPEHS.its sp, gr.at 0' = 0.839, a t 20*5"/0" = 0.8'24. Only cenanthplic andpropionic acids could be separated from the product of the oxidationof this ketone.The above experiments disprove Popoff's fourth rule ; the followingconcern the fifth rule :-3 i h y 7 isobafyl lrafone is formed by the action of zinc ethyl on iso-propplacetic chloride (b. p. 116-116*.5"). It i s a reFr;wtive liquidwith an odonr like peppermint ; i t boils a t 134.5-135" (735 mm.) ;its sp. gr. a t 0" = 0.829, at 17"jO" = 0.815. Isopropylacetic acidboils a t 175" (749 mm.). When oxidised, the ketone yields, from theprim8ry reaction, isopropy1;icetic acid and acetic acid ; and from thesecondory reaction, isobutyric acid and propionic acid, the pyimaryreaction exceediiig the secondary ; acetone and dimethacrylic acid(?) are also obtained, probably R S secondary oxidation products of theacids.This behaviour shows that the fifth rule is fallacious.Propyl isobutyl ketone (b. p. 154-156" at 755 mm.) yields iso-propylacetic acid, propionic acid, ncetone, and acetic acid, when oxi-dised.Ethyl isopropyl ketone is prepared from isobutyric chloride (I). p.92-93") and zinc ethyl ; it boils at 11375-114" (745 mm.), not117-119" (Pawloff, J. Buss. Chem. Soc., 8, 242) ; its sp. gr. at, 0" L=0.S30, a t 18"/0" = 0.814. It yields on oxidation acetone, propionicacid, isobutyric acid, and acetic acid (compare PawlofY, Zoc. cit.).Methyl isobutyl ketone boils a t 115.5" (745 mm.; Frankland,Aniialen, 145, 8 3 , gives 114" at $58"), and has a sp.gr. at 0" = 0.8195(Frankland gives 0-81892), a t 19"/0" = 0.8034. When oxidised, ityields isobutyric and acetic acids from the primary reaction, and iso-propylacetic acid and formic acid from the secondary.Methyl isoamyl ketone (b. p. 144-144.5" a t 752 mm.) yields iso-propylacetic acid and isobutylacetic acid on oxidation ; PopoE obtainedvaleric and acetic acids.Methyl butgl ketone yields butyric acid and normal valeric acid onoxidation,The author deduces the following generalisations From the resultsof hisand of other experimenters' work on this subject :-1. When a ketone of the fatty series is oxidised, the hydrogenatom attached to one of the carbon atoms linked to the carbonyl ishjdroxylised : the molecule of hytlroxyl compound thus formed issplit u p by further oxidation, 2 mols.of fatty acids, or 1 mol. of afatty acid and 1 mol. of a ketone, being formed.2. If only onr of t h e carbon atoms linked to the carbon71 behydrogenised, only this will be oxidised .and detached. If, however,both be hydrogenised, chromic acid mixture at 100" will generallycrluse oxidation in two directions, so that in some molecules of theketone the one, arid in others the other, of these carbon atoms will beoxidised, and theye will rewlt a primary and a secondary reactionregulated by the following conditions. 7;3. If the carbon atoms linked to the carbonyl be unequallyhydrogenised, the one which has less hydrogen will be oxidised andeliruinated in the primary reaction, and the one which is more hydro-genised, in the secondary reactionORGANIC CHEMISTRY, 374.If tbe carbon atoms be equally hydrogenised but combined,t h e one with a secondary (or tertiary ?), the other with a primary,alcohol radicle, the latter will be oxidised and eliminated.5. If the carbon atoms linked to the carbongl be eqnally hydrogen-.ised and combined with radicles of the same series, but of diffprentmolecular weight, that which is combined with the radicle haviirg lesscarbon will be preferably oxidised and eliminated.These generalisations allude to the oxidation of ketones a t 100"with chromic acid mixture. Experiments made w i t h methyl butylketone showed that (1) the course of the oxidation of methyl butylketone is influenced by the temperature ; (2) a t low temperatures, theoxidation proceeds in one direction only, and the less hydrogeuisedcarbon atom attached to the carbonyl is oxidised and eliminated ; (3)at higher temperatures, the oxidation extends to both these carbonntonls ; (4) it is thus probable that a t vei-y high temperatures, if theketone could withstand such, the coiirse of the oxidation mould be inone direction only, and that would be the reverse of (2).A.G. R.Determination of the Affinity of Organic Acids by means ofLacmoid. By F. ROHMANN and W. SPITZRR ( B e y . , 24, 3010-301.5).-During the titration of organic avids with soda, the authors haveobserved that a drop of the liqnid brought into contach with redlacmo'id paper produces a blue colour before sufficient soda has beenadded to form the norrrinl salt; the solution will turn blue Iacmoi'dpaper red, but t,his red colour disappears before the acid is cntirelyneutralised. This reaction depends on the fact that the alkali isdivided between the Iacmoid arid the organic acid in a definite pro-portion, which varies according to the nature of the acid ; a methodis thus afforded of determining the relat'ive affinities of acids for alkali.Experiments have shown that the coefficient of neutrality s/s' of twoacids is in inverse proportion to their affinity for alkali: s = thequantity of acid which is necessary to bring about the change incolour of the lavmoid paper, and s' represents the amount of normalsalt present.For the full details of calculation the original papershould be consulted.The affinities of the following nionobasic acids, compared withformic acid, agree closely with the values given in Ostwald's tables :-Acetic, propionic, butyric, isobu tjric, valeric, hydmxypropionic, andIiydroxyisobutyric. The method is also applicable to the bibasicacids, a similar agreement i n the results, as compared with othermethods, beinc obtained.It is desirable t o always deterniine the quantity of alkali which isrequired to be added to the acid in order to produce a blue colour onred lacmo'id paper, since the inverse procedure is more liable toexperimental error. J. B. T.Behaviour on Dry Distillation of the Silver Salts of OrganicAcids. By J.KACHLER (Monafsh., 12, 3 3 8 4 4 9 ) .-Silver acetate, CIILdry distillation. is decomposed according to the equation 4AgC,H,O,= 4Ag + 3C,H,02 + C + C02, the reaction being complete a t a tem-perature of 220-240'. The compound furnishes the same products38 ABSTRACTS OF OHEMICAL PAPERS.and in practically the same proportions, when it is heated to a hightemperature with water in sealed tubes.Silver formate decomposes in accordance with the equationSAgCHO, = CH,02 + CO, + 2Ag, when heated with water in sealedtubes.The silver salts of isovaleric, normal caproic, and oenanthylic acids,on dry disdlation, are approximately decomposed according t o theequation 2n(AgC,H2,-102) = (an - 1)(C,,H2,0,) + (n - l ) C + C 0 2 + 2nAg; in fact, this equatioti appears to indicate tlhe manner inwhich the silver salts of fatty acids are generally resolved under suchconditions.Silver palmitate, on distillation under reduced pressure (430 mm.),gives a considerable quantity of palmitic acid, aud, similarly, thesilver salts of lactic:, 01- hydroxy iso bu tyric, phenylacetic, and beuzoicacids decompose with formation of the respective free acids.The author confirms the statement of Klirnenko (J.Rus.s. Chem.SUC., 12, 97), that silver lactate, when air-dried, crystallises with 8 4101. H,O (compare Engelhardr, and hladdrell, Amalen, 63, 90).G. T. ill.Action of Hydriodic Aoid On Amido-auids. By A. KW~SDA(-Monatsh., 12, 4 1 9 4 3 0 ) .- l'lie author finds that the readiness withwhich .hydrogen is substituted for amidogen, on treatiug the amido-i~olcls with hydsiodic acid, varies considerably with the constitutionof the acid (see original).In his investigations, the acids utlderexamination, namelj, glyc;ociiie, u- and p-alauine, leucine, asparticacid, glutamic acid, aud oi*tho-, meta-, and para-amidobenzoic acids,were heated in sealed tubes with excess of Iiydriodic acid of sp. gr..1.96. Monobasic, Eattj acids, ot' the formula NH2.C,H2,z*COOH, arethereby decomposed, accordiiig to the equation NH2*CnH2rl*CO0 H -+-3HI = C,H2H+lCOOH + NklJ + 12, whilst such bibasic acids asaspartic and glutaniic acids are converted into monobasic acids,NH,I + 1,; ortho-, nieta-, and pal-d-amidobenzoic acids are llotdeconiposed in the ssme way as the monobasic acids of the fattyseries, for, in addition to the chief product, benzoic acid, smadyuautities of carbonic anhydride and of free hydrocarbons are ob-tained.The author has not been able to confirm the observation ofRosenstiehl ( Z e d . fiir Chem., lb69, 471) that toluidines are formedon heating amidobenzoic acids with hydriodic acid.6- Trimekhyle thylidenelactic Acid. By C . G L ij c KSM ANK (Monatsh. ,12, 356-361 ; compare Abstr., 1890, 237). - A more convenientmethod of preparing trimethyllactic acid than that previously de-bcribed is as follows :-20 grams of pinacone is suspended in 100 C . C .of 20 per cent. sodium hydroxide solution, and 63 grams of potassiulnpermauganate in a 4-5 per cent. aqueous solution is slowly addedt o the well-cooled mixture. When the oxidation is complete, theproduct is filtered, neutralised with sulpliuric acid, and evaporated todryness on the water-bath.The residue is dissolved in the leastpossible quantity of water, and treated with 250 grams of 4 per cent.sodium amalgam, added a little at a time. 'l'h solution ib filtered,thus:--NH,.C,H,,-,(COOH), + 3HI = C,B2,+1*COOH + COZ +G. T. MORGANIC CHEMISTRY. 39acidified with sulphuric acid, extracted with ether, the ethereal solu-tion evaporated, and the residue steam distilled, until the distillateceases to be acid. The residue, dried in a vacuum over sulphuricacid, consists of trimethyllac t ie acid.On heating the acid (1 part) with 98 per cent. snlphuric acid( 3 - 4 parts) in a reflux apparatiis at SO", it is resolved into carbonmonoxide, water, and tri.methylacetaIdehyde, CMe3*COH (yield 80 percent.).The new aldehyde boils ah 92-94', reduces a solution ofsilver, restores the colour to magenta, which has previously beentreated with sulphurous anhydride ; and, on oxidation with chromicacid, appears to be converted into acetic acid.By M. CONRAD andC. BK~;'CKNEK. (Ber., 24, 2993---3005). - h'thyl clichloromalonate,CCl,(COOEt),, is prepared by treating ethyl chloromalonate withchlorine a t 12U", removing t'he excess of the latter and the hydrogenchloride, first by heating on the water-bath, and subsequently byallowing the product to remain over soda-lime in n vacuum, and dis-tilling, when the compound passes over at 231-234" with only slightdecomposition as a colourless liquid, having a sp.gr. 1.268 at 17"compared with water at 15". Treated with an excess of cold alcoholicpotash, a niixt ure of potassium dichloromalouate and meaoxalateappears to be formed; whilst on mixing it with 6-10 times itsvolume of concentrated alcoholic ammonia, dichloromalonamide,melting at WiY (see Zincke an3 Kegel, Abstr., 1890, 49Oj, separatesafter two days, arid dichloracetamide (m. p. 98") is obtained fromthe filtrake.Ethyl chlorobromomalonate, CClBr( COOEt),, is obtained by bromin-ating ctliyl chloroniaionate ; it distils at 1.36-139" under a pressureof 35 mm., and boils a t the ordinary pressure af, 239--241" witlipa~tisl.deconiposition ; its sp.gr- is 1.467 a t 16" compared with watera t 13". Treated with four times its volume of concentrated alcoholicammonia, a compouud melting ah lC;O--ltj5" separates, which ie,perhaps, a mixture of chlorobromomalonaniide and amidochloro-malonnmide ; whilst chlorobromacetawide melting at 117" is obtainedfrom the filtrate. Chlorobromacetauiide has already been preparedby Cech and Steiner (this Journal, 1876, 1, 373), and as i t differs inmeltiug yoiiit from the authors' compound, they have repeated Cechand Steiner's experiments, and find that neither chlorobromaceticwid nor the amide described by these chemists are homogeneous sub-stances, but are contaminated with the dibromo-derivatives. Xthylbromornalomte, CHBr(COOMt), (Knoevenagel, Abstr., 1888, 707),lias A sp.gr. of 1.426 a t 15" cornpared with watein a t the same tem-perature.&thy1 acetyltwtronate, OAc-CH(COOEt),, is produced togetherwith the cowzpound C(COOEt),:C(COOEt),, by heating ethyl bromo-ma1on:tte (88 grams) arid potassium acetate (40 grams) dissolved in;tbsolute alcohol, a t 40-50' ; tlie formek is zlr bright yellow oil, boilingat 1S8--163' (60 min.), and has a sp. gr. la1;3l at 1.95" comparedwith water a t 15", whilst the latter is a solid compound melting a t 56".LVLcu etlrgl u c e t ~ Itartrunate i:, dissulved iu e t k i aid treated withG. T. M.Halogen Derivatives of Malonic Acid40 ABSTRACTS OF CHEMlCAL YAPEltS.sodium (1 eq.j,and then heated for 10 seconds on the wntein-bathwith ethyl iodide, the ethyl derivatice, OAc*CEt(COOEt),, boiling a t151-153" (30 mm.) is formed.Ethyl mesoxalate, C(OH),(COOEt),, described by Petrieff as anoil, is obtained by treating ethyl acetyltartronate w i t h somewhat morethan one molecular proportion of bromine a t 110" : i t boils at 140-145"(50 min.), solidifies after a time, and when crystallised from ethermelts atl 57".Ethyl phenyltartronate, OPh-CH(COOEt),, is prepared by dissolvingsodium (2.3 grams) in alcohol (35 c c.), adding phenol (9.4 grams)and ethyl bromomalonatr~ (24 grams), heating, distilling off thegreater portion of the alcohol, adding water, and extracting the pre-cipitated oil with ether ; it distils under a pressure of 60 mm.at,'2:30--'240". The acid obtained on hydrolysis with hydrochloric acidyields phenglglycollic acid (ni.p. 96') when heated a t 180".Ethyl dibromomalonate, CBr,( COOEt), (J. W isliceiius, Abstr.,1888, 151), is obtained by brominating ethyl mnlonate in direct sun-light ; it distils a t 145-155" under a pressure of 25 mm. ; when dis-solved in half i t s volume of cooled, concentrated, alcoholic ammonia,crystals separate, after a time, of a compound which probahly consistsof dinmidomalonarnide, C (NH2)2( CONH,), ; t h i s darkens at 150",dissolves in water with decomposition, and loses ammonia when care-fully heated a t 90-100",. yielding i?)zidoma!onarnide, NHI:C(CONH,),,a compound dissolving in water t o a neutral solution, from whichammonia is evolved on heating. When ethyl di bromomalona te i.;Iieated with benzene and sodium in the form of wire, i t yields thecornpowad C(COOEt),:C(COOEt), (see above) ; if digested with analcoholic solution of potassium acetate, ethyl mcsoxalate is formed ;whilst whcn heated with a mixture of plienol and sodium ethoxide,ethyl diphenoxymalonate, C(OPh,) (COOEt),, is obtained distilling a t250-260" under a pressure of 60 mm., and this, on boi1in.g withalcoholic potash, yields the corresponding acid, which, after beingcrgstnllised from water, melts a t 173".Brornethylrrialonic neid, Cfi;tBr(COOH),, is obtained in theoreticalyield when ethylmalonic acid is heated on the water-bath with a11excess of bromine ; i t melts a$ 104" with the evolution of carbonicanhydride and the formation of bromobutyric acid.A.R L.Action of Zinc on Ethyl Dibromosucciiiate. By A. MICHAEL(J. pr. Chem. [el, 44, 399403).-In this paper t.he author repliest o the criticisms of Claus (Abstr., 1891, 1338) on the work whichMichael and Schulthess published on the subject (Abstr., 1891,1184).The discussion is now closed as far as the author is concerned.A. ti. l5.Decomposition of Glutaric Acid at a High Temperature.By A. CLAUS (Annalen, 265, 247--253).-1n reply t o Wisbar (Abstr.,1891, l o l l ) , the author states that a careful repetition of his previou.;experiments has proved conclnsively t h a t carbonic anhydride isevolved on heating glutaric acid under the conditions already de-scribed. When the acid is kept for a long time a t 180-210°, it isconverted into i t s anhydride ; this compound is then cornpletelORGASIC CHEMtSTRS.41decomposed 'with evolution of carbonic anhydride, and there rcmainsa pornus, carbonaceous mass; the liquid distillate contains a con-siderable quantity of a n acid, which is not butyric acid, as was firststated ; the investigation of this product will be continued.Synthesis of Polybasic Fatty Acids. By K. AUWERS, E.K~~BKER, and F. V. MKYENBURG (Ber., 24, 2887--2901).--Tn a previouspaper (Abstr., 1891, 307), Auwers has published a preliminaryaccount of the synthesis of polybasic acids ; the present commuiiica-tion gives a detailed account of the acids already prepared. Theprocess employed is the same in all cases, and consists in warming amixture of a solution or emulsion of the sodium compound of ethylnialonate or one of its nlkyl derivatives with the ethyl salt of anunsaturated acid.The product is mixed with water and dilutesiilphuric acid, and the oily, ethereal salt which separates washed,dried, fractionated under reduced pressure, and hydrolysed by boilingwith a niixture of equal volumes of concentrated hydrochloric acidand water.The preparation of symmetrical ax-dimethylglutaric acid hasalready been described (luc. cit.).F. S. K./3-2l.;Crdhylgluturic acid,CO OH*C]H,*CHMe*CH,* C OOH,is formed by the action of ethyl crotonate on ethyl sodiomalonate,a~id hydrolysis of the crude ethyl salt, first obtained ; after crjstallisa-tion from ether and benzene, it nielhs a t 86". Ethyl sodiorrialoriate andethyl fumarate yield as t,he first product ethyl pro~nnetefracarboxylate,CH(COOEt),.CH(COOEt).CH,.COOEt, which boils a t 200--220"under a pressure of 25 mm., and on hydrolysis yields tricarballplicacid, COOH*CH2*CH(COOHj*CH2.COOB, melting a t 162 -164".The authors confirm Emery's statement that this acid, on treatmentwith acetic acid, yields an CLil7Lydrot).icai,ballylic acid, c;j6HG05, meltingat 131" (Abstr., 1891, 689).The product of the reaction of ethyl fumarate and ethyl sodio-niethylmalonate is an ethyl salt which boils a t 196-198O under apressure of 'LO mm., and has a sp.gr. of 1.1158 a t 38"/4". On hydro-lysis, i t yields two acids of the composition C7Hln06, which must,from t heiv mode oE formation, both be a-metl~yltI.icrzrball!/lic acid,COOH*CHMeCH(COOH)*CHL*COOH, and represent stereometrici>omerides, an acid of this formula having two asymmetrical cilrbonatoms. The acids are separated by crystallisation from water ; theless soluble compound crjstallises in compact, lustrous prisms, meltsa t 180", is readily soluble i n alcohol and acetone, but alrnost insolubleiii benzene and light petroleum ; its siluer salt, C7H7Ag3O6, is a heavy,white precipitate.The more soluble pcid is contained in the motherliqaor of the previons acid, and is separated by repeated crystallisa-t,ion from water ; it still, however, contains ammonium chloridederived from the ethyl cyanacetate present in commercial ethylmalonate, and may be separated from it by treatment with anhydr-ous ether.It then melts a t 134", and in its other properties closelyrcsembles the isomeric acid, into which it is partially converted byheating with hjdrochloric acid at 200"42 ABSTRACTS OF CHEMICAL PAPERS.The action of ethyl sodiomalonate on ethyl cit,raconate mightFroceed in two different ways, giring rise either to an a- or a /3-methyl-tricarballylic acid. The intermediate ethereal salt boils a t 226" undera pressure of 39 mm., and on hydrolysis yields i n small quantity anacid which has the composition C7HidOs, forms beautiful, transpareid,Crystals, and ruelts at 164". It is not identical with either of the fore-going acids, and mu.& therefore be ~-methyltricsrbccElylic &,id,COOHCH,-CMS( COOH).CH2*C00 H. If ethyl itaconat,e be substi-tuted for ethyl citracorinte, two reactions are also possible.leadingto the formation of either P-methyltricarballylic acid or butanetri-carboxylic acid. The iuterutediate ethyl salt was found t o boil at200-240" under 37 mm. pressure, whilst the acid formed from itcrystallises in rosette-shaped aggregates of prisms, and melts at116-120". It differs, therefore, csrripletely from /3-mehliyltricarb-allylic acid, and must be bzLtanet~i.'carbox~lic acid,C OOH-C H2*C H,.CH( COO H) *CH2C OOH.The two stereoisomeric a-eth~ltricarballylic acids,COOH*CHEt*CH( COOH)-CH,*COOH,may be prepared in a manner exactly similar to the correspondingmethyl compounds, TI be. intermediate ethyl ethylpropnnetetracarb-oxylate boils at 207-212" under a pressure of 25 nirri.The lemsoluble acid forms spherical aggregates of thin, lustrous obliqueprisms, and riielts a t 147-148"; its silver salt, CdH9Ag306, is a volu-minous, white precipitate, very susceptible to bhe action of light.The more soluble acid was not obtained in auffiicieut quantiky for COLU-plete purification.Yropy Ztricarhally Zic acid, CO OH-CH Pra* CH (C 0 OH) *ClH,*C OOH,and isvyropy ltricarballylic acid,C 0 OH- C H Prp* C H ( C 0 0 H j - C H,. C 0 0 H,are readily obtained by heating ethyl fumarate with ethyl propyl- orisopropyl-sodiomalonate. The former crystallises from water onspontaneous evaporntion in cumpact, lustrous prisms which containwater of crystmallisation and melt below 100" ; when rapidly crystal-lised, however, i t forms nodules consist,ing of anhydrous plates,melts at 151-152", and is soluble in alcohol and ether, but alnio,stinsoluble in benzene and light petroleum.The mother liquors con-tain lower melting products which could not be isolated. Isoprupyltri-carballylic acid crystallises in anhydrous nodules formed of platesor compact prisms, meits a t 161-162", and behaves towards solventsin the same manner. as the previous acid.Determinations of the conductivities of these acids have been madeby Walden, and it appears that, as j11 the case of succiriic acid, theilltrod uction of alkyl groups into t,ricarhallylic acid raises the toll-ductivity t o a cousideruble extent.An attempt W H S made to bring about the combination of ethylsodiomalonate and t h e ethyl salt of A'-tetrnhydroplithxlic acid, HYthe lat,tor beh;~vea in many rospects its an uus'tturilted fatty acidORGANIC CHEIIISTRI'.43No reaction, however, was found to take place on digesting the mix-ture for six hours at 100". H. G. C .Furfurylamine. By A. DEUTZMANN (Chew. Centr., 1591, ii, 295-296 ; from Dim. BerZiiL).-The following compounds are described :-Furfurylamine furfury~ditlai~arbamate,C40 &* C H2.NH.C SSH,NH2* CH2*CaOH3,is prepared from 6.8 grams of carbon bisulphide dissolved in dryether and 18 gmms of furfurylamine; i t is soluble in alcohol, ether,benzene, and light petroleum; when exposed to the air, it becomesyellow. ~urfiec9.ylthiocarbimide, CS:N.CH2-C40H3 is prepared fromthe last-named salt by the action of mercnric chloride, which mustnot be in excess.D~iL.1.fu?.ydthioca1.barrLide, CS (KH-CH2*C40H,),, prc-pared by heating the dithiocarbamate at loo", melts a t 85-86".MethyIfurfurllZthio~rEamide, prepared from methylthiocarbimide andfurfurylamine, melts at 85". Etl~ylfur~ury7thiocarbnmide melts at 67".AllyQurfuryIthiocarbamide melts a t 42-43'. Y?~eny~u~fui.?Jlthioccxrb-amidc! melts at 128" ; the paratolglmrbarnide melts at 165" ; the metu-z y iy lcarbamide at 12 1-3".f~brfur~lcarhnnzide, NHz0CO*NH-CH2-C@H,, prepared from f u r -furylamine and potassium cyanate, melts a t 110-111" ; difurfuryl-carbantide, prepared from furfurylamine, potassium h-j-droxide, andcarbouyl chloride dissolved in benzene, melts at 128". E'thyI;fiir-u~yl-carbaniide melts at 95 -96" ; a~~lj~L1j:u?.y1cal.lramide at 120-1.'1".These were prepared by the aid of ethyl- and aniyl-carbimide respec-tively.PhenylfurfurylcarEa~aide melts at 124" ; the orthotolylcarh-amidP at ltjS-16t3*5° ; the metnxylyQluarbamide a t 178". From di-fur~~ryltl~iocarbarnide, by the action of mercuric oxide, cyanamide andfurfurylamine are obtained, but not the corresponding guanidine.The hydrochloi-ide of jurfurylguanidine, C( NH,)2:N*CH2*C40H,, maybe prepared by heating cyanamide and furfurylamine hydrochlorideat 100" in a sealed tube. Both it and the platinum salt were analyseti.Dipheng Vurf u ~ ! / lguanidine, C (NH Ph) , X * C H ,.C,OH 3, is preparedfrom the last-named compound by heating i t with aniline a t 80-81".By treating the aniine with methyl iodide, t l .i m e t h y ~ u ? f u r y l a n ~ ~ ~ o ~ ' i u iodide, C,0H,*CH2*NMe31, is obtained,By distilling f urfurylamine hydrochloride, a liquid was obtainedwhich probably contained furfuryl chloride. Nitroj"urfu,ylami?/e isprepared by acting with nitric acid on acetylfurfusylauiine in glacialacetic acid, and then distilling with steam. J. W. 11.Intramolecular Change of the Propyl Group. By 0. WID-MAN ( J . pr. Chew.. [ a ] , 44, 414-415; compare Abstr., 1891, 686,1344).--Fileti (Abstr., 1891, 1,344) quotes Widman as having pointedout that the nitration of cumenylacrylic acid produces paranitrociii-namic acid, orthonitroparisopropylcinnamic acid, and an isonieride oftile latter which he called orthonitroparapropylcinnamic acid.Wid-man now points out that Fileti has missed the publications (Abstr-.,1891, 69, 45) i n which i t is shown that this " orthonitroparapropyl-cinuamic;" acid is really a mixture of about one-third ruetanitlo32 ARSTRACTS OF GHEMIOAL PAPERS.cumenylacrylic acid and two-thirds orthonitrocumcnylacrylic acid,the mixture having a constant melting point and crystnllisinq in adefinite form. A. G. B.Isomeric Change in the Synthesis of Aromatic Amines andPhenols. By M. SET~KOWSKI (Ber., 24, 2974--3977).-It is wellknown t,hat the higher homologues of aniline, produced by heating itsalkjl derivat,ives or the corresponding alcohols with its hydrochlorideor stannochloride, invariably belong to the para-series ; the sameapplies to the homolopes of phenol obtained by the action of zincchloride on a mixture of phenol and the alcohol.The experimentsto he descrihed were instituted to ascertain whether in these casesintramolecular changes occur similar to those observed in the syn-thesis of aromatic hydrocarbons by means of aluminium chloride.Paratertiarybutylplienol (Abstr., 1890, 1296) is obtained by theaction of zinc chloride and isobutyl alcohol on phenol in the mannerdescribed by A. Liebmann (Abstr., 1882, lil, 72'7).Paramidophenyltrimethylmethane (7oc. cit., 1890j is formed byheating auiliiie hydrochloride with isobutyl alcohol in a sealed t,ubea t 230"; it yields trimethylphenylmethane (Zoc. cit., 189U) by thediazo-reac tion.The so-called isobutylbenzene boiling a t 165-1'70" (Goldschmidt,Ab$tr., 1882,952) is a mixture.When treated with bromine in directsunlight until the colour of the bromine persists for several minutes,and, after wasliing the product with potash and drying, it is distilledover sodium, a small quantity of a bydrocarbon passes over at167-168", apparently identical w i t h trimethylphenylrnethane.1soam.ylnniline (Hofmann, this Journal, 1874,807 ; Merz and Weith,Abstr., 1882, 179), when treated with one molecular proportion ofbromine in sunlight, and with a second, in the dark, at the temyera-ture of the water-bath, yields Schramm's isoainylbenzene dibromidemelting a t 129" (Abstr., 1883, 977), and is, therefore, a normalproduct. A. R. L.Action of Nitrous Acid on Resorcinol Diethyl Ether and onTriethylresorcinol.By A. KRAUS ( M o ~ L u ~ s ~ . , 12, 368-378) .-When a solution of resorcinol dietliyl ether (1 part) in acetic acid(10 parts) is saturated with hydvogen chloridc, and treated in thecold with a large excess of alkaline nitrite, a very considerable quan-tity of a dark-green precipitate separates. The product is dilutedwith water and filtered, and the solid thus obtained treated with cold,dilute potash, whereby the greater portion dissolves, forming a dark-red solution, f rorn which hydrochloric acid separates nitrosoreso~-c.inoZethyl, sthey, NO*C,H,(OH)*OEt, in the form of a voluminous, light-yellow precipitate. The ether may be readily recrystallised from hotwater and from hot alcohol (compare Aronheim, Ber., 12, 30).when it forms thiu, pale-yellow scales which decompose at 150"without having previously melted.That part of the above-mentiouedproduct which is insoluble in cold dilute potash is washed with coldalcohol, and dried in a vacuum. On elementary analpsis, it giveORGANIC CHEMISTRY. 45numbers correspondirtg with t h e formula for nitrosoreso&noZ diet7,yzether, NO*CaH,(O13t)2. It melts at 122--123", is soluble in cold chloro-form, benzene, and ether, but is decomposed when warmed with thosesolvents ; i t has a pale-rose colonr, and givcs a n intense blue colorationwith concentrated sulphuric arid hydrochloric acids. The benzoyZderivative of nitrosoresorcinol et h j 1 ether, NO.C,H,( OEt)*OBz, isobtained i n the form of yellow flocks on sbaking a solution of theether i n soda with an excess of benzoic chloride.When recrystal-lised from alcohol, i t forms beautiful, jellow crystals which melt at155".Xitrosoethy Zresorcinol ethyl ether, KO*C,H2Et (OH)*OEt, is obtninedwhen triethylresorcinol (compare Herzig and Z ( isel, Abstr., 18!& j,1404) is dissolved in ten titnes its weight of absolute alcohol, aild thesolution mixed with slightly more than the molecular equivalent ofsodium nitrite, and decomposed with concentrated hydrochloric aciduntil the whole assumes a brownish-yellow colour. On the additioilof v\ ater, a green, flocculent pi-ecipitate is formed, the colour of whichgradually changes t o reddish-yellow. The precipitate is dissolved inpotash, and the solution exhausted with ether; the ethereal extrac.tis acidified, and the yellow precipitate thus obtained crystallisedfrom hot benzene, which furnishes the compound in the form ofheautif'ul, yellow prisms.I t dissolves when warmed with ordiuaryFolvertts, and decomposes a t 150', without having previously melted ;it gives a stable base on treatment with reducing agents, is oxidised bynitric acid, first to a nitro-compound, and eveiitually to oxalic acid,and forms a well chara eterised hrnzoyl drricatice,NO*C,H,Et( OEt)*OBz,which is insoluble in potash, and melts at 141-142'. G. T. M.Hydroxyquinones. By KOWALSKI (Chem. Cenfr., 1891, ii, 377 ;from Schweiz. Wochewsc7ir. Yhurin., 29, 265).-The author hasobserved the formatioil of hydroxyquinones from quinones, when thelatter are left exposed to the action of aqueous alkali and air.Fronla-naphthaquinone and from thyruoquiiione the corresponding hydl--oxy q ui n ones were obtained .Isoeugenol, Diisoeugenol, and their Derivatives. By E.TTEM.4SN (bey., 24, 2870---2877).-1n his researches 011 the productsof oxidatiori of acetyleugenol (tliis vol., p. 59), the author was ledto suppose that t h e eugenol enipIoyed might contain a hithertounknown isomeride, or that such a cornpound might be formed as a11intermediate product during its oxidation. H e therefore examinedthe action of various reagents on eugenol, but only succeeded in con-vertiiig it into the already known isotneride, isoeugenol,CHMe:CH*C6H3(OMe)*OH [l : 3 : 41.This molecular interchange proceeds best when carried out asfo1lows:--12-5 parts of potash a r e dissolved in 18 parts of amylalcohol, 5 parts of eugenol added, the mixture heated for 16-20J-. W.L46 ARSTRACTS OF CHEJITCAL PAPERS.hours at 140", and the nmyl alcohol removed by distillation in acnrrent of steam. Snlphiiric acid is then added, the isoeugenolseparated, washed with Podiiim carhnnnte solution, and distilled ina current, of steam. It then boils at 261" (uncorr.), and hfis all theproperties assigned to it by Kmaz and Tiemann (Abstr., 1583, 201) ;in alcoholic solution, it is coloured olive-green bv ferric chloride, andif left it becomes yellow, bnt mnch less rapidly than engenol. Itscoefficient of refraction is 1.5728, that of en pen01 being 1.5438.The substance described by Kraaz and Tiemann as Inenzopliso-eiigenol is in reality a derivative of diisoeugenol, and not of iso-euyenol.The monomolecular acetyl and benzoyl componnds can onlybs obtained under certain conditions. Acetylisoeugenol, Cl,,H,,02Ac, isprepared by boiling the phenol with acetic anhydride, and separates inlustrous, white needles on the addition of l i g h t petroleum to its benzenesolution; it melts a t 79-40", boils at 282-283" (uncorr.), and isreconverted in to isoeugenol hy alkalis. Benzoylisoevgenol, CloHI1O2Bz,is formed by the action of benzoic chloride on a solution of isoeugenolin dilute soda, provided the liquid never becomes acid ; it crystallisesfrom alcohol in white prisms melting at 103-104".Dia,cety ZdiisoeugenoI, C~~HZ,O~AC~, is obtained by adding acetylchloride to isoeugenol previously warmed to 54", and raising thetemperature to 80°, heating as long as hydrogen chloride is evolved.The product solidifies on coolinq, and may be separated from adheringoil by means of ether ; the rcsidue is crystallised from boiling alcoliol,and then forms white needles which melt at 150-151", and arealmost, insolnhle in water and ether.Dihenzoy ZdiisoeugenoZ, CzoHZOdBZ2,is the compound previously described by Kraaz and Tiemann (Zoc. cit.)as beneoylisoeugenol. Both these substances on hydrolysis yielddiisoeugenol, which may also be obtained by the action of mineralacids or acid Halts on isoeugenol; it crystallises from 50 per cent.alcohol in slender needles, melts at 180-181°, is readily soluble inether and chloroform, less easily in alcohol, and almost insoluble inwater and light petroleum.Its alcoholic solution is coloured olive-green by ferric chloride.The molecula~ weight of diisoeugenol, as found by Rnoult'smethod, agrees with the above formula, but no evidence as to i t sconstitution has yet been obtained. It might possibly be a tetra-methylene derivative of a formula such as~HMe*~H*C6H3(OMe)-OHCHMe*CH*C6H3( OMe)*OH'or it may be a diphenyl derivative. Further investigation of thiscompound is in progress.Oxidation Products of Safrole. By F. TIEMANN (Ber., 24,2'379-2886).-The results given in the preceding abstract and on p S 9show that acetyleugenol and acetylisoeugenol are compounds whichreadily undergo decomposition.and that in their oxidation several pro-cesses occur simultaneously ; the exact investigation of these processeshas been rendered still more difficult by the fact that in thesecondaryreactions the benzene nucleus itself has been attacked. The authorH. G. CORQANIC CHEMISTRP. 47therefore wished to follow out the oxidation pi'ocwses in a phenyl-allylene derivative, i n which the action of the oxidising agent wouldbe confined to the carbon side chnJn. Such a derivative has heenfound in sifrole, which has been shown by Eykman (Abstr., 1886,95) and Poleck (Abstr., 18E4, 1339 ; 1886, 697) t o have the constitu-(3)tion CH2<o>C,H,.CH,*CN:C12 0 (1).(4)On carefully oxidising safrole wit'h 14 per cent,.prmanganate solu-tion at 70--80", it takes up two hydroxyl groups, forminq mefhylene-3 : 4-dihydroxybenz?/ 1 glycol, CH2< o> C6H3*CH2*CH(OH) *C H2*OH,which crystdlises from henzene in white needles, melts at, 82-83',and is readily soluble in boiling water and ether, less eRsily in alcohol.Its diacetate. ClnHlo04Ac2, is a pale-vellow oil boiling at 240" undera pressure of 15-20 mm. ; and the diphenylcarbarnate,obtained by the action of phenyl isocyanate on the glycol, crystallisesin plates, and melts a t 127".If 5 parts of safrole be warmed at 70-80" with 12.5 parts of per-manganate, 5 parts of acetic acid, and 1000 parts of water. piperonal,piperonic acid, and a-homopipwonic acid are obtained. The f i i a s t isremoved hy extracting the alkaline solntion with ether, and the alkalinesolution is then concentrated.acidified, amd exfracted with ether.The residue obtained from this extract, which contains piperonic and01- homopiperonic acids, is boiled with ma,gne&-im carbonate, resinousmatters being removed by ether, the solution again acidified and takenup with etrher, the latter evaporated, and the residual mixture of thet w o acids separated by fractional crystallisation from hot water,0Cl~H~oO~ (CO*NH Ph) 2,2-Homopiperonic acid, CH2<O>CJ13*CH2*COOH, 0 c~ystallises inwliite needles, melts a t 127--128", and dissolves readily in boiling water,alcohol, ether, and hot benzene, scarcely a t all in light petroleum.The calciuriz salt contains 2 mols. H?O, which are given off sit 100"; thecopper salt, (CgH,04)2Cu, forms a pale-green, crystalline powder ; thesilver salt, C9H,04Ac, a white, crystalline powder, which may becrystallised from hot water ; the zinc salt, (C,H704)2Zn, is also whiteand crystalline.The methyl salt, C4H704Me, and ethyl salt, C9H7O4Et,are yellow oils boiling at 278-280" and 291" respectivelg, and thearnidr, C,H,O,.CON H2, crystallises in needles melting at 172-173".On treatment with nitric acid, a-homopiperonic acid yields a, nitro-cninpouv.d, CgH,04*N02, which ~rysta~llises in yellow plates, andmelts a t 188". Further oxidation converts the acid into piperoaicacid and piperonal.From these remlts, it appears that the allenyl group of safroleundergoes oxidation in a normal manner ; the intermediate homo-0 piperonal, CH2< > CsH3*CH2*CH0, has not been isolated, owing 0probably to its instability; so far also no indication of a compoundcorresponding with acetovanillone has been observed.H. G. C45 ABSTRACTS OF CHEMICAL PAPERS.Action of Benzyl Chloride on Orthotoluidine. By C.R,ARAUT (Bull. Xoc. Chim. [$I, 5, 742--743).-Benzylnrthotoluidine,C,H,Me*NHPh, is formed when benzjl chloride (1 mol.) is heated wit,liorthotoluidine (2 mols.) in a n open vessel for 4U hours at 175". Thecrystalline product of the reaction is treated with aqueous sodiumcarbonate. and gieltls a dark, chestnut-coloured oil, which, on puri-fication, becomes almost colourl~ss. Benzylorthotoluidine boils a t210' under a pressure of 25 mm., cryst'alliees from alcohol in tuft+,melts a t 56-57", and is soluble in the ordinary menstrua.Thehydrochloride forms white crystals, is soluble i n alcohol and hotwater, and unites with platinum chloride to form a jellow, crystal-line platinochloride. The acetate, sulphate, nitrate, and oxalute arewhite.When henzylorthotoluidine is treated with ethyl iodide, henzyl-ethylorthotoluidine, C,H,Me*NEt*CH,Ph, is obtained as a yellowislr,neutral oil boiling at 230" under 25 HIM. pressure.AcelyZbenzllZorthot(,luidine is solid z t ordinary temperatures, andboils at 289-285" under a pressure of 20 mm. JN. W.Oxidation of Azo-compounds. By C. LAUTH (Compt. rend., 112,1 512-1514) .-Azo-compounds, when oxidised by various reagents inthe cold, yield diazo-compounds together with quinones.Acid andalkaline reagents give similar results; the author has chiefly eni-ployed lead dioxide in the presence of sulphuric acid.The sodium salt of henzeneazo-/3-napht~holdisulphonic acid is dis-Folved i n 30 parts of water ; to the solution, 2 parts of sulphuric acid(66") and 1 part of the lead dioxide are added; the red-orange solu-tion rapidly becomes lemon-yellow, and there i s no evolution of gasi n the cold. Kitrogen is rapidly evolved on heating, and, when dis-tilled, phenol comes over in tlhe first portions of the distillate. Thediazo-solution, on treatment with a n alkaline solution of phenol,yhenolsulphonates, o r amines, gives azo-colouring matters ; foroxnmple, the addition of ~-naphtholdisulphonic acid regeneratesl~enzene-azo-~~-naphtholdisulplionic acid.Conipounds substituted int h e diazo-group react equally well: Orange I (the sodium salt ofsulphobenzeneazo- a-iiaphthol) yields, similarly, a diazo-solutiou ,giving, on distillation, phenylparasulphonic acid. Again, snlpho-henzenenzo-phenol, by oxidation, yields a diazo-solution, u hich, ont h e addition of an alkaline solution of a-naphthol, gives Orange I.The reaction has been applied to a large number of azo-compounds,including unsubstituted compounds, such as azobenzene, as well ascompounds containing amido-, hydroxg-, or carboxyl-groups. Noexception has been found to the general course of the reaction in-dicated above. The reaction may be considered to be characteristicof the azo-compounds.When the liqnid, after oxidation, is filtered from t h e lead sulphateformed, it yields a yuinone in the case of sulphobenzeneazo-phenol ;in other cases the residue contains most of t h e oxidation products.The general reaction for the oxidation is of the type ofC6$&,.Nz*CJ€G*OH + H2SO4 + 0, = C,III,.N,*SO,H + CIUHGO, + H2OORQANLU C KEXISTR Y.4)intermediate products may be obtained at tohe same time, if thooxidising agent is noto present in sufficient quantity, as well as tetrazo-compounds. W. T.Action of Phenylhydrasine on Phenols. By A. SEYEWETZ(Compt. retad., 113, 264--267).--Phetiol, the cresols, and thenaphthols do noh yield compounds with phenylhydrazine in presenceof various solvents, and under various conditions.Dihrdric phenols behave differently, and readily combine withphenylhydrazine, the reaction being so distinct in the case oforcinol that it would almost seem to indicate the presence of a ketonicor aldehydic group in this compound.A concentrated aqueous solution of the phenol is mixed with asolution of phenylhydrazine in water slightly aciditied with aceticacid.After agitating for some minutes, the compound separates, iswashed with water containing a little acetic acid, and then recrystal-lised from benzene.Q uinol yields the compound C,H,( OH),, 2NHP h*NH?, which crystal-lises from boiling benzene in small, white, nacreous plates melting a t70-71". It gradually alters when exposed to the air, and becomesyellow, is slightly soluble in cold water, somewhat soluble in warmwater, alcohol, chloroform, ether, and benzene, very slightly soliiblein light petroleum.Alkalis liberate phenylhydrazine, even in thecold ; acids liberate the phenol.Resorcinol yields the compound described by Baeyer and Kochen-doerfer.Orcinol readily yields the compound C,H3Me(0H),,2NHPh-NB,,which forms white crystals melting at 61-62", and similar in generalproperties to the yuinol derivative.Catechol seems not to form a corresponding compound, and this istrue also of pyrogallol.Salicylic acid, in presence of toluene, yields R compound crystal-lisiug in slender, white needles, and melting a t 122-123". In manycases, however, the finding of a suitable solvent constitutes a greatdifficulty.C. H. B.Combination of Phenylhydrazine with Ethyl Oxalacetate.By W. WISLICENUS and M. SCHEIVT (Bsr., 24, ~~006--3010).-0nmixing together ethereal solutions of phenylhydrnzine and ethyloxalacetate in molecular proportion, and cooling, an additive corn-pouiid is deposited in coloiirless, lustrous plates ; it may be crystal-Jised from absolute alcohol, and melts at 105-106". This substanceis distinguished from the hydrazone (m. p. 76-78') by its colour,and by its insolubility i n ether arid in light petroleum. The adclitivecompound is readily converted into the hydrazone by filsion, or byheating it in solution ; a t ordinary temperatures the change is moregradual. The constitution of this compound may be represented bythe formula CoOEtC(3H)(NH*NHPh)CH2.CO0 Et, which wouldreadily exp'lain its conversion into the hydrazone ; from the generalproperties of the substance, however, as well as from tho fact thatall efforts hitherto made to prepare similar substances from ot,herVOL.LXII. 50 ABJTRACTS' OF OHEMCCAL PAPERS.less acid, ketonic, etheraal salts have failed, t,he authors consider i tt o be an analogue of the ammonium salts, with the formulaCOOEt-CO-C H(NH,.NHPh)*COOE t orC0OEt.C ( O*NH3*N HP h) :C: H*COOEt.The same substance is alsn formed bv the action of phenplhydr-azine hydrochloride on ethyl sodoxalacetate in cold, concentrated,aq 11 eou 8 solution.Mrthyl oxalacetate and ethyl et,hoxyoxnlacetate yield additive com-pounds with phenylhydrasine similar to the one described above,whilst et(hp1 methyloxnlacets,te, et'hgl oxalsnccinate, ethyl acetoacetate,ethyl benzoylacetate, and ethyl levulinate do not react in this manner.J.B. T.Oximes and so-called Stereochemistry. By A. CLAUS (J. pr.Chem. [2], 44, 312--385).-This paper deals with the isomerism ofthe hgdroxylamine derivatives of benzile. and esp~cially with theI-ecent work of Anwers and Meyer on ths subject (Abstr., 1889, 403,609, 611, 713). The author concludes by claiming that he has in-c mtrovertibly proved that all mnnifesta tions of isomeri,sm amongthe products of the reaction of hpdroxylnmine with benzile can beefficiently and easily explained as caqes of isnmerism in Rtructure,without having recourse to any stereochemical hypothesis.A. G. B.Intramolecular Change of some Isoaldoxime Derivatives.Ry R.BEHREND (Annmlen., 265, 238-246).- When pure benzpliso-1)aranitrohenzaldoxime (m. p. 118") is dissolved in alcohol (9-10parts), and the solution warmed with a few drops of a dilutealcoholic solution of sodium ethoxide, it is partially converted intolwranitrobenzy lisobenxaldoxime ; this change is expressed by theeq urttionand is, to st certain extent, reversible, as when para,nitrobenzyliso-benzaldoxime is treated with sodium ethoxide under the sameconditions, it is in part transformed into beneylisoparanitrobenzald-oxime.When benzylisometmit rohenzaldoxime, prepared by the con densa.tion of metanitrohenzaldehyde with B benzylbydroxrlan~ine, is warmedwith a dilute alcoholic solution of sodium ethoxide, it is partiallyconverted into the isomeric metanitrobenzylisobenzaldoxime, and onevaporating the solution, amixture of the two isonierides is left ; this isdissolved in alcohol (about 10 parts), and on keeping the solution forabout 24 hours, the greater part of the unchanged benzylisonitro-benzaldoxime is deposited in crystals, whilst most of the isomerideremains in solution; the latter is obtained i n a pure condition byrepeated fractional crystnllisation from alcohol.Metanitrobenzylisobenzaldoxime, C,J€12N203, purified in the mannerjust described, crystallises from hot alcohol and benzene, in both oORGANIC CHEMISTRT.51which i t i s readily soluble, in lustrous, pale-yellow needles, melts at114-115", aiid is only sparingly soluble in ether, and almost insolp-hle in light petroleum.It seems t o he unchanged by a warm solutiono€ sodium ethoxide, but when heated with hydrochloric acid, it isdecomposed into benzaldehyde and p-me~anitrobenzylhydrox:ylamineh~d?-ochlo~ide; the latter is readily soluble in water, but moresparingly in alcohol, from which it is precipitated OR the addition ofetlikr, as a colourlesa, crystalline powder, melting at 145-146",with previous softening; the melting point of the salt which hagonce been melted is much higher. The free base crystallises fromhot water in needles, melts at 79*5-80*5", and reduces Fehling'ssolution,Renzylisoanisaldoxime is not acted on by sodium ethoxide underthe conditions described above. F. S. I(.Amidines. By W.LOSSEN (Annalen, 265, 129--178).-Theinteresting results obtained on treating benzeaylamidine and otherItmidines with nitrous acid (Abstr., 1891, 103%-1042) have Ied t h eauthor and his pupils (Mierau, Kobbert, Neubert, C. Lossen, Kiimh-nick, and Umbowski) to subject the amidines to a somewhat ex-tended investigation, in order to determine (1) which of thesecompounds form dioxytetrazotic acids and stable nitrites, and (2) howthe properties of the amidines compare with those of the amid-o xi rfi es .Benzmylamidine sidphafe, (C7H8Na),H2SOa + H,O, is easily ob-tained by evaporating a solution of the nitrite with the theoreticalquantity of sulphuric acid, and extracting the residue with aicoholland ether successively; the insoluble sulphate is then dissolved inwater and reprecipitated by the addition of alcohol ; it loses its watera t 80--81", and decomposes into benzonitrile and ammonium sulphateon further heating.The formate, C,H8N2,CH20a + H70, prepared bydecomposing the sulphate with barium formate, orystallises well, isreadily solnble in alcohol and water, and loses its water over sulph-uric acid. The acetate, C7H8N2,C2H,0a, forins monoclinic crystah,a : b : c = 1.099 : 1 : ?, p = 120" lS', and is readily soluble in waterand alcohol. The n.itrite, C7HsN2,HNO2 + HzO, can be obtained byevaporating a solution of equivalent quantities of benzenylamidinehydrochloride and sodium nitrite ; it crystallises from alcohol innionoclinic (01- rhombic ?) plates, a : b : c = 3.467 : 1 : 3.425, /3 =94" 32'.and decomposes below 70" with formation of benzonitrile ; itis readily soluble in water and alcohol, but insoluble in ether.Pbenylbenzenylaniidine can be prepared by triturating benzimido-ethyl ether hydrochloride (1 mol.) with warm aniline (1 mol.), andalso by treating benzanilide imidochloride with aiihjdrou; ammonia inlight petroleum solution ; i t melts at 112", and is identical with thecompouud obtained by Bernthsen (Annulen, 184, 348; 192, 29)by treating aniline hydrochloride with tbiobenzamide, or withbenzonitrile ; its constitution is probably exprewed by the formnlaNH,*CPh:NPh. When thifi amidine is treated with nitrous acidunder various conditions, it yields benzanilide a8 the sole product, afact which shows that the nitrite of the base is very unstable.e 52 ABSTRAC l'S OF CHEMICAL PAPERY.Phenylbenzin~idoethyl ether, NPh:CPh.OEt, is formed in preparing~,henylbenzenylanidine by the action of aniline on benziniidoethylether hydrochloride ; it is an oily liquid, the hydrochloride of whichdecomposes at about 60" into henzanilide and ethyl chloride.Whenthe oil is heated ato about 70" with phosphorus pentachloride, i tundergoes decomposition into eth-jl chloride and Lenzxnilideimidochloride, CC 1 P h:N P h.Metanitrobenzimidocthy3 ether hvdrochloride, identical with thecompound described by Tafel and Enocli (Abstr., 1890, 973), can beprepared by passing hydrogen chloride into a well-cooled, alcoholicbenzene solution of metanitrobenzonitrile ; the pZatJnochloi.ide,is a reddish-yellow compound.When met:mitrobenzimidoetbyl ether hydrochloride is treated withalcoholic ammonia, it is converted into nietani trobenzetiylamidinehydrochloride (compare Tafel and Enoch, Zoc.cit.). The correspond-ing sulphate, [NO,C,H,*C (NH >):NH],,H,SO,, prepared from thenitrite, is soluble in water and alcohol.N0,*C6H,*C (N H,) : NH,HN O,,is obtained when a concentrated solution of the hydrochloride istreated with d y e r nitrite, and the filtrate evaporated a t 30-40" ; i tcrystallises in prisms. and decomposes when heated, yielding meta-nit robenzoni trile, water, R TI d nitrogen.Metanitrobenzo y Zbenzamide, N 02*CsH4* C O*N H *CO P h, is formedwhen metmitrobenzenylamidine is treated with bcnzoic chloride andpotash ; it crystallises from alcohol i n plates, and nielts at 133--134O.An ethyl derivative of metanitrohenzenylamidiiie can be obtained bytreating the amidine with ethyl iodide in ethereal solution; itsplutiizochloride has the compo-ition ( NO,G H,-N,H,Et),,H ,PtCI,.When iiretatiitrobenzenylamidine is treated with hydroxplamine, it isconverted into the corresporiditig amicloxirne.PheTrylmetanitroherLzimiclo ether, N0,.C6H,*C( :NPh)*OH, is formed,together with phenylmetanitrobenzenylamid~ne, when metanitro-benzirriido ether.hydrochloride is warmed with aniline ; i t crystallisesi n yellow prisms, melts a t 55-56", and is readily soluble in colcihydrochloric acid ; when heated with alcoholic ammonia a t 100°, it isdecomposed into aniline and metanitrobenzonitrile.Yhen~lm~tanitrohenzen!~lumidine, rc'0,-C6H4C(:NPh).NH, + HzO,can also be obtained by heating metanitrobenzonitrile w i t h anilineliydrochloride ; it crystallises from ether in yellow prisms, melts a ti2-73", and deconiposes a t 100".nielts a t about 251".When an ethereal solution of the amidine isheated a t 100" with ethyl iodide, :: yellow, crystalline salt ot' thccomposition N 02*C6H4*CN2 HPhEt,HT is formed.Symmetrical diuhenylbenzenylamidine is not acted on by nitronsacid ; when anhydrous asymmetrical di phenylbenzenylanlidine iswarmed with amy1 nitrite, or treated with nitrous ncid in aqueoussolution, it is couvcited into diphenylbenzamide (m. p. 175").(C,H,UN?O,)Z,H!2PtC16,The nitrite,The hydrochloride,NOzoC6H4*CN2H2P h ,HCIORGANIC CHEMISTRY.53EthyZhenzenyEamifli//e, CN,K2PhEt, is for tied when b3tizimido etherhydrochloride is treated with a 25 Fer cent. solution of ethylatnine,but it, cannot be obtained i n a pure condition. The hydrochEoride.CN,H,PhEt,HCI, crystallises from alcoholic ether in needles, melts rtt161", and decomposes above 200" with formation of beneonitrile andethylamine hydrochloride; i t is very readily soluble in water andalcohol. The platinochloride, ( CN2H2PhEt),,H2PtC16, crystallises fromalcohol in microscopic, reddish-yellow prismg. The nitrate,CN,H,P h E t ,HN03,is deposited in long needles when a. solution of the nitrite in fuminqnitric acid is evaporated at the ordinary temperatuve; i t is veryreadily soluble in water.The nitrite, CN2H2PhEt,HN0,, prepared bytreating an aqueous solution of the hydrochloride with silver nitrite,crystallises from alcohol in slender needles, melts tit 12T, and is veryrertdily soliible in wRter and alcohol, but almost insoluble in ether ; it isonly slowly decomposed by boiling water, and it, is stable in pre-sence of tiitrous acid. The henzoyE derivative, C,,H,,N20, crystallisesfrom dilute alcohol in needles, melts at 88", and is only moderatelyeasily soluble in ether. The diethyl derivative is formed when theamidine is heated at 100-110" with an ethereal solution of ethyliodide ; its hydriodde, C,,H,,N,,HT, is a coloudess, crystalliiie com-pound, but turns yellow on keeping.Acetarnidine nitrite, CN,H,Me,HNO,I prepared by treating a con -centrated aqueous solution of acetamidiiie h i drochloride with silvernitrite, melts a t 148" with decomposition, and is soluble in water andalcohol, but insoluble in ether.Propioimnzidine nit?.de, CN2HJEt,HN02, obtained in like manner,separates from alcohol in crystals, melts a t lit?, and is readily solu-ble in water and alcohol.PaTatoleny lamidine nitrite, CsH,MeCN,H,,HNOZ, cr.ystallises inneedles, melts at 133", and is readily soluble in alcohol and wafer,but insoluble in ether.Imp h t hulamidine nitrite, C,H, ( CN2 H ,3) z , 2 H N Oz, cry s t a1 1 i ses f roniwater in lustrous needles.Succinimidine nitrite, C2H4<C C ( N H ) > ~ ~ , ~ ~ ~ , (NH) + +H,Q, ic;formed when a solution of a mixture of the hydrochlorides of snccin-amidine and succinimidine is treated with silver nitrite ; i t crystallisesin small, yellow plates.Guunidine nitrite, CH5N3,HN02, can be obtained by evaporating asolution of guanidine sulpbate with sodium nitrite, and extracting theresidue with alcohol, from which the nitrite is deposited in crystals ;it melts a t 76-78.5", decomposes at about 120", and is readily solublein water and alcohol, but insoluble in ether.Froin the results of the experiments described above, the authorconcludes that the substituted amidines cannot be converted intodioxytetrazotic acids.The sti*ongly basic amidines combine mi-changcd with nitrous acid, but when. b.7' the substitution of a phenylgroup for hydrogen, they are converted into feeble bases, they becomeless stable towards nitrous acid.F. S. K54 ABSTRACTS OF CHEMIOAL PAPERS.Thio-derivatives of Orthamidobenaamide. By A. STEWART<,J. pr. Chem. [2], 44, 415-416) -The compound CIIR~oNzSO isbtained by beating oi*tjhamidobenzamide with allylthiocarbsmide(equivalent proportions) in benzene for several hours. It crys-tallises from hot alcohol, ether, or benzene in colourless needlesNnd tables, and niclts with decomposition a t 198-199". It dissolvesin alkalis, and is reprecipitated by acids unchanged ; its solution inbenzene has a blue fluorescence.A compound which ci-jstallises i n colourless, silky tables is formedwhen phenylthiocarbimide is substituted for the ally1 compound inthe above reaction.By heating orthamidobenzamide with thiocarbamide i n an oil-bathat 180-200", until no more ammonium sulphide is given off, thecompound C,H,N,SO is formed; it crystal!ises from alcohol increamy-white nodules, dissolves in ether and benzene, and melts at280--281".It dissolves in alkalis, and is reprecipitated by acids.When heated for 2-3 hours with methyl iodide (2 mols.) and sodium(2 mols.) in a tube a t about 130°, a, smell of mercaptan is perceived,and beautiful, colourless, six-sided priems crystttllise out ; they containsulphur, dissolve in alkalis, nild are unchanged at 300'.A colourless, crystalline substance is obtained when thiocarbamideis heated with anthranilic acid.The author suggests constitutional formulm for some of the abovecompounds, but does not support them.The investigation is pro-ceeding. A. G. B.Condensation of hilpyruvic Acid. By C. BOTT~KGER(Annulen, 265, 253-256).--ln hhe conversion of anilpyruvic acidinto aniluvitonic acid by treatment with concentrated sulphnric acid,a very small quantity of a compound, which is insoluble in alkalis, isdormed; t h i s substance has the composition C17H16N20, melts a t194-195", and is identical with t.he compound obtained by LaznrusFy t,renting aniline with pyruvic acid a t a high temperature. Thecondensation product of paratohidine and pyruvic acid has con-sequently the composition C19HZONZ0, and not ClaHz0N20, as given byLazams. F. 8. K."tranilide. By H. POLIKTER (Rer., 24, 2959-296.2) .-Tnrtr-aailide is obtained in almost theoretical yield by gradually addingtartaric acid (1 part) to boiling aniline ( 5 parts), and after a timedistilling off the excess of aniline from the solution, waslling the solidresidue successively with dilute hydrochloric acid, boiling water, anda little alcohol, and finally crystallising from alcohol ; it melts above250" with decomposition.C2H2(0Ac),(CO*NHPh),,is formed when tartranilide is boiled in a reflux apparatus with aceticanhydride until the solution commences to darken ; i t cryetallises inlieedles, melts a t 227", and is more soluble in alcohol, ether.andchloroform than tartranilide. The triucetyl derkntive, CnHZ20;Ns, isThe diacetyl deriratiseORGANIC CHEYISTRY. 55produced by heating tartranilide with acetic anhydride in a sealedtube at 150" for two hours ; i t forms delicate, liistrous, white needles,melts a t 216", and is readily soluble in alcohol, ether, and &.cia1acetic acid. The tetracetyl derivative, C2H2(OAc),( CO*NAcPh)2, isobtained when tartranilide (3 grams) is heated with acetic chloride( 5 grams) in a sealed tube a t 140" tor two hours, the product beirigwashed with a little glacial acetic acid, and repeatedly crystallisedfrom alcohol ; it forms colourless needles, melts at 137", and is moreeasily soluble in all solvents than the di- and tri-derivatives.When tartranilide is submitted to dry distillation, 01' better, when amixture of tartaric acid (1 part) and aniline (4 parts) is heated forhalf an hour a t the boiling point of aailine, then distilled over n freeflame until nothing but a carbonaceous mass remains, the distillateagain treated with tartaric acid, and the same operation repeatedseveral times, on adding dilute hydrochloric acid to the last distillate,dianilidosuccinaiiilide, GHZ( NHPh),(CO*NHPh),, melting at 220", isprecipitated, the yield being at most 20 per cent.It is very stable,beirlg attacked neither by acids nor alkalis, and boiling at about 300".The acetyl derivative,NPhAc*C EI( CO*NHPh)*CH(NHPh) GO*NHPh,is prepared by boiling dianilidosuccinanilide with acetic anhydride in a1.etlux apparakus for two hours ; it crystallises in large, yellow leaves,arid melts at 252". A. R. L.Aromatic Dithiocarbarnates. By S. M. LOSANITSCH (Ber., 24,3021--3028).-Ammonium phenylditbiocarbamate, NHPh*CS*SNH,,is prepared by the interaction of aniline, carbon bisulphide, andammonia o r ammonium sulphide, in dilute alcoholic solution a t ordi-nary temperatures ; it crystallises in large, yellow, transparent prisms,and is soluble in aqueous ammonia or ,zmuionium sulphide, but de-composes when dissolved in alcohol or water.Ammonium sulphide,ammonium thiocarbonate, carbon bisulphide, thiocarbanilide, andaniline are formed on heating the compound a t 100". Ammoniumphenyldithiocarbamate appears t o be identical with the " phenyl-ammonium thiouramate " of Hlasiwetz and Kachler.Yhenyl~i~hiocLIrbamic thioanhydride, ( CS*NHP'h)2S, is obtained bythe action of iodine in excess on animonium phenyldithiocarbamate ;i t crystallises from benzene in yellow, lustrous needles, melts1:36-138", and i s not affected by acids, but is converted into thiocn.:b-rtnilide on treatment with potash.Barium phenyldithiocarbamate,(LVHPh-CSS),Ba, is insoluble in alcohol 01' water at ordinary tem-peratures, and crgstallises in yellow plates. The pntussium salf,NHPh*CSSK, is deposited in long, t h i n , colourless needles ; the nickelstdt forms yellow, lustrons plates. The remaining salts are sparinglysoluble, and on heating are decomposed qudntitatively into themetallic sulyhide and phenylthiocarbimide.Methyl phenyldithiocarbamnte, NHPh*CSSRle, prepared frommethyl iodide and ammonium phenyldithiocnrbamate, crystallisesfrom alcohol in large, white needles ; it melts a t 93*5", not at 87-88",as stated by Will, The ethyl salt melts a t 59.5"5 1; ABSTRACTS OF CHEMICAL PAPERS.By the iutemction of carbon bisulyhide, aniline, and tetmmethyl-ammonium hydroxide in dcoholic solulion, a compound is obtainedwhich crystallises in yellow needles and melts a t 152-1.53" ; this ~111)-stance is not a phenyldithiocarbamate, and is being further invest; -gated.Ammonium pnratoluyldithiocarbamate, C,H4Me-PU'H*CS*SNH4, isprepared in a similar manner to the phenyl derivative, and crystal-lises in large, yellow prisms.The harium salt is deposited i n colour-less needles ; the nickel salt forms brown needles. The observationsof Will and Rilschowski on the methyl and ethyl salts of the abovecompound are confirmed.Barium rrzetatol7Lyldithiocarbamlnte resembles the para-compound ; i tis soluble in wafer, h u t not in alcohol.The wickel salt crystallisesin yellowish-brown, lusti*oiis plates. The methyl salt,C6H, Me-NH-CSSMe,crystallises from alcohol in colourless needles, and melts a t 89".Barium orthotolisyldithioca6amate is obtained i n colourless plates,which are insoluble in water or alcohol ; the nickel salt forms browiineedles. The methyl salt crystallises from alcohol in colourlessneedles, and melts a t 132".Ruriurn cc-naphth?yldithiocnrbamate is prepared in a manner similart,o the preceding compounds, and is deposited in colourless, insolubleneedles ; the nickel slrlt crystallises in yellowish-brown needles.Bayiurn /J-naph thyli7ithiocarb~imate forms yellow, crystalline plates ;the nickel salt resembles that of the a-derivative.The difference in behaviour between aliphatic and aromatic aminestowards carbon bisulphide appears t o be due t o the extremely feeblebasic properties of the aromatic ammonium gronp (NH,X), since, i i ipresence of a base, the aromatic amines react i n a manner similar tothe aliphatic amines, yielding dithiocarbaruates.J. B. T.Ethyl Acetoacetate Aldehydeuramides. By P. BIGINELLI (Ber.,24, 2962-2967 ; compare Abstr., 1801, YOS).-When salicyldiurelde(Xchiff, Annulen., 151, 199) which has been previously dehydrated,first in a vacuum, and then by heating a t 90-100", is boiled withabfiolute alcohol and ethyl acetoacetate ('2 mols.), ethyl /j-ui-amido-crotonat,e, and a subdance having tlie composition CilH16N20i, areobtained ; the lattcr is also formed when carbamide, salicylaldehyde,avd ethyl acetoacetate are boiled together, in molecular proportion,with a little alcohol ; it appears to be a mixttiire of two isomerides,aiid separates from alcohol in small needles melting at 199-200",and large prisms melting at 203-201", these having probably theconstitutions OH-C,H,*CHE:N*CO*N:CMe~CH,*COOEt andOH*C,H,.CH: N*CO.NHCMe*CH.COOEt 'respectively.If the prisms are dissolved in hot alcohol. the needlesseparate out on cooling, whereas if the latter are allowed tto remain incontact with this solvent they change by degrees into thc former. Thcsubstance is insoluble in water, and decomposes when boiled with it ; itORGANICJ CEEhlISTKY.57however, dissolves in dilute potassium hydroxide, but, the solution be-conies yellow after ;t time, o w i n g to decomposition. When a currentof carbonic anliydride is passed through the alkaline solution until thesubstance commeiiceo to separate out, hydrochloric acid precipitatesthe compound Ci,H,,N,02, which crystallises from alcehol in whiteiieedles,' decomposes a t 260-270" without niclting, and is insolubleNH*CO*PU':$IH , in alkalis ; it probably has the constitution CHMe< CH2---0- C6H, 'it is formed more readily from the iqomeride of lower melting point.Cumiiidiurei'de, CsH4Pr13*CH (NH-CO-NH,),, is prepared by addingsuficient alcohol to a concentrated aqueous solution of carbamideto enable i t to dissolve cumaldehyde, allowing the mixture to remainl o r two days, collecting the precipitated compouiid, drying, and wash-ing with ether; it is a colourless, crystalline powder, insoluble inwater, only slightly soluble in boiling alcohol, and melts att175-176".The compound C,,H,:N,03 is obtained when a solutionof ciimindiureide and ethjl acetoacetate in absolute alcohol, or one ofcarbamide, cuniilldehyde, and ethyl acetoacetate in the same solvenl,is boiled ; it crystallises from alcohol in delicate needles, and melts at161-162"; if left for some days in contact with the solvent, or ifrepeatedly fused, it changes its form to octahedra, and then melts a tCi.rinnmdizcreide, CHPh:CH*CH(NH-CO.NH,),,'separates as a white,crystalline substance, when a concentrated aqueous solution of carb-amide is shaken with cinnamaldehyde ; it melts a t 172" with decom-position.TricirLnanztet?.aurei'de, C,H,(NH-CO*NH*C,H,.NH.CO.NH,),, isobtained by gently heating a solntion of carbamide and cinnnm-aldehyde in alcohol ; i t is a yellowish powder, and melts at 183-184"with decomposition. Both urei'des are decomposed on boiling withwater, or more quickly by dilute acids ; nitrous acid occasions com-plete decomposition, and when suspended in ether they absorbbromine.When cinnamaldellyde is shaken with a very dilute solu-tion of carbamide at a moderate temperature for a long time, a urejidemelting at 212" is formed; but if an excess of cinuamitldehgdeis digested mith a concentrated solution of carbamide a t 50-60" foi-an hour, a urei'de meltirg a t 115-116" is produced.When either ofthe cintiamure'ides is heated with ethyl acetoacetate, the coinpountlC16H18NZ03, crystallisirig from alcohol in needles, and melting a t243-244", is obtained; this appears also to exist in two forms, theinelting points of which are very close. Althongh, as- Schiff hasshown, fiirfurnldehyde does not yield a urei'de, when this aldehyde isheated with carbamide and ethyl acetoacetate, ethyl P-furfwainido-crotoiiate, C40H3*CH:N.CO*NH*CMe:CH*COOEt, is formed. Whenthe benzurzmide derivative (m. p. 207-208" ; Abstr., 1891, 908) iscrystallised from hot alcohol, needles are obtained having the meltingpoint 206-206.5". A. R. L.164-165".Ethylation of Salicylaldehyde.By M. Liiw (Monatsh., 12,39S-4Ol).-T he author has ethylated salicylaldehyde by slowl55 ABSTRACTS Ol!' CHEMICAL PAPERS.adding a mixture of it (1 mol.) with ethyl iodide (3 mols.) to a boilingsolution of alcoholic potash (3 mols.), exhausting the product w i t h ether,and distilling the residue from the ethereal extract under a pressurrof 25 mm. The ethyl compound t h u s obtained (yield 54 per cent. oftheory) boiled at 143-147" (25 mm.), and melted a t 20-22".OrthethoxyEenzaZdoxime, OE t*C6H,*CH:NOH, is formed when ethyl-salicylaldehyde is heated w i t h hydrox~lamine hydrochloride andexcess of soda, It is readily soluble i n alcohol, ether, aud benzene,sparingly so in water, slightly volatile in a current of steam, hasa, characteristic odour, and crystallises from light petroleum in colour-less, compact prisms which melt at 57-59'.The hydrochloride, OEt.C6H4*CH:NOH,HCI, separates in the formof small, yellow needles, when the base is dissolved i n ether and thesolution treated with dry hydrogen chloride. I t melts a t 123-125",and is reconverted into orthethoxybenzaldoxime on warming withwater .Orthethoayb~nz!/Zamine, OEt-C6H4.CH2.NH2, is obtained on dissolvingthe aldoxime in a little alcohol, and reducing with 4 per cent.sodium amalgam, keeping the solution always slightly acid withacetic acid. The ylatinochloride, OE t*C,H,.CH,*NH,,H,PtC16, is acrystalline, yellow precipitate, and melts at 182".Orthethoxybenzonifrile, OEt.C,H,*CN, is formed on Heaking i n areflux apparatus a mixture of orthethoxybenzaldoxime (1 mol.) andacetic anhydride (4 mols.).The product is neutralised with soda,extracted with ether, and the ethereal solution distilled, when thecompound separates as a colourless oil which boils at 252-254"(260.7" corr.). On heating 4 t h alcoholic potash in sealed tubes, it isconverted into a mixture of orhhethoxybenzoic acid, OE t*C6H4*COOH,and orthethoxybenzamide, OEt*C,H,*CONH,. The latter crystttlliaesfrom hot water in flat, silky needles, and melts at 132-135".With phenylhydrazine, ethylsalicylaldehjde forms a ver-y unstablecompound, which is readily oxidised, even by atmospheric oxygen.The formation of the above-described compounds confirms Perkin'sview ( A n d e n , 1868, 306) t h a t the product of ethylation ofsalicylaldehyde is really orthetboxybeiizaldehyde, a n d shows that theeth)l is not directly attached to a, carbon atom (compare Hersig andZeisel, Abstr., 1888, 882 ; 1889, 247 and 966). G.T.,M.P ~ O I l O l . B y W. N. NAGAt (Bw., 24, 2847--2853),-Paeonol wasfirst obtained by Martin and Yagi ( d ~ c h . I'?xzrm., lo), from thebark of the root of Ptaonia rnoutan, a drug frequently used i n Japanand China. In order to prepare it, the finely-powdered bark isextracted with ether, the extract shaken with sodium carbonate solu-tion to remove impurities, and then with aqueous soda, which takesup the psonol : the alkaline solut,ion is acidified with sulp'huric acid,again extracted with ether, and the residue obtained on evaporatingthe latter is recrystallised from alcohol.Peon01 is thus obtainedin colourless, lustrous needles, having the composition C9HloOs, andmelting a t 50" ; it bas an aromatic odour and burning taste, is spar-ingly soluble in cold water, readily in alcohol, ether, and benzene.It gives a reddish-violet coloration with ferric chloride, but dissolveORGANIC OHE3fISTRY. 59in sulphuric acid without alteration of colonr ; i t rllso dissolvesreadily in caustic alkalis, but not in ammonia or solutions ofalkRli carbonates, which agrees with the supposition that it is aphenol.When fused with potash, it yields 1 : 2 : 4-dihydroxracetophenonejresacetophenone), CsH3Ac( OH),, a-resorcyl ic acid, COOH*C,H,( OH),[l : 2 : 41, and resorcinol ; tbe first is probably the primary product,the other compounds being formed from i t by the further action ofalkali.Hydriodic acid converts i t into methyl iodide and resrtceto-pbenone, of which it must therefore be the methyl ether. To ascer-tain which of t.he hydroxyl groups is methylnted, the acetyl derivativewas prepared by boiling pmnol with acetic anhydride for 30 honrs,extracting any unaltered paeonol with light petroleum (b. p. 55-57"),and recrystallking the residue from alcohol. AcetyZpceot/oZ, C9H9O3Ac,is thus obtained in flat, lustrous needles melting a t 46.5". If insteadof acetic anhydride a mixture of this compound with anhydroussodium acetate is employed, two condensation products are obtained,melting at 180" and 160" respectively; these are being furtherexamined.By oxidation with alkaline potassium permanganate, acetylptzonolyields parame thoxyace ty lsalicylic acid, COOH*C,H., (0 Ac).OMe[1 : 2 : 41, which, on treatment with strong aqueous potash, is con-verted into paramethoxysalicylic acid, COOH-(:,H,(OH)*OMe[l : 2 : 41, the properties of which were found to agree with previousstatements (Abstr., 1881, 270; Ber., 14, 847), except as regards themelting point, which the author finds to be 156".The formation ofthis acid shows conclusively that the methoxyl group occupies thepara-position with respect to the acetyl group, and hence pseonolmay be termedparumet h o q o r t h 07~ydrmyacetopheno ite, OH* CsH3Ac*0 Me[ = 2 : 1 : 4 ] . H. G. C.Pzeonol Phenylhydrazone and Oxirne. Bp F. TIEMANN (Bey., 24,2854-2853).-Although paeonol, according to Nagai, does not form ;Idouble compound with sodium hydrogen sulphite, i t readily combineswith pheny lhydrazine atid hydroxy lamine.Pworwl phenylhydrazone,C9H,002:N2HPh, is prepared by the addition of phenylhydrazinehydrochloride and sodium acetate t o an aqueous s o h tion of p8eono1,a.nd crystallises from alcohol in pale-yellow needles, melts at 107", isreadily soluble in ether and benzene, sparingly in alcohol and1 ight petroleum, and almost insoluble in water. PceonoZoxinw,CgHloO2:N*0H, separates in needles when its dcoholic solution ispoured into water; it is almost insoluble iri cold, readily solublein hot water, and in akohol, ether, &c.Paeonol itself may be readily purified by distillation in a curroit ofsteam and recrvstsllisation from hot water. It then melts at 48".and not at 50°, is stated by Nagai (see preceding abstract).H. G.C.Acetovanillone. By F. TIEMANN (Ber., 24, 2855--2862).-Inthe course of his researches on the members of the protocstechuicseries, the author, in conjunction with Nagai (this journal, 1877, itGO ABSTRACTS OF GEIEMICAL PAPERS.3W), showed that acetylengenol, on oxidation and subsequent. hydro-lysiq, gives a product from which a-homovanillic acid, vanillic acidand vanillin, may be isolated ; in addition to these, a large quantityof a i*esinous maw is obtained, which, on dry distillation, givesguaiacol aq tlie sole recognisable product. Further investigation ofthis resin in larger quantity has shown that a crystalline compoundmag he obtained from it, by neutralking the free acid present withcalcium or magnesium carbonate, repeatedly Pxtracting with boilingwater, and shaking the extract with ether.The ethereal solution isthen treated with sodium hydrogen sulphite to removevanillin, the etberevaporated, and the oily residue repeatedly washed with water, anddistilled under a pressure of 50 mm. The distillate solidifies on cooling,and may be purified by dissolving it in aqueous soda, reprecipitatingwith carbonic anhydride, extracting again with ether, evaporatingtho latter, and recrystallising the residue from boiling water, alcohol,or benzene. The new compound then forms long prisms, melts at115", boils a t 295--300", and may be readily sublimed.The analysisand molecular weight determinations lead t o the formula C9HI0OJ,and it is termed metovanilbone for the reasons stated below.Acetovanillone has the properties of a phenol, yields protocatechuicacid wlien fused with potash, and contains one methoxyl group, asfound by Zeisel's method. It therefore contains the residueiC*C6H3( OMe)*OH. The remniniiig atoms, CzH30, must be present asan met71 group, for acetovanillone yields an oxime and phenyl-hydrazone, and is also formed, although only in small qumtity, bydistilling a mixture of calcium acetate and vanillate. On boilingwith acetic anhydride, it yields an acetyl compound, which may bereadily oxidised to acetovanillic acid and vanillic acid, showing thattile hydroxyl and methoxyl groups occupy the same positions as inthe last-named compound.Hence, acetovanillone has the constitutionCsH3Ac(OMe)*OH [l : 2 : 41, aud stands in the same relation tovanillin as acetophenone does to benzaldehyde. Acetovanillone givep,with an excess of ferric chloride, exactly the same reaction as vanilliii(Abstr., 1886, 238); tlie liquid assumes first a deep, bluish-violetcolour, and on warming gives a precipitate of insoluble dehydrodi-ace tovani llone.The presence of acetovamillone among the products of oxidation ofacetlyleugenol, CHz~CH~CH,CsH,(OMe)-OAc, is not capable of readyexplanation. The simplest way of explaining it would be to supposet h a t it is present ready formed in the eugenol, or that it isobtained by the oxidation of an isomeride of eugenol, of the formulaCH,:CMe*C,H,(OMe).OH, either present i n the liquid or formedduring the reaction ; no evidence has, however, been found in favourof these views.To explain its formation from acetoeugenol, ono mightsuppose that the latter first takes up the elements of water, formingthe compound OH-CH2-C;H2*CH2*C,H3( OMe).OAc, and then undergoesoxidation in the w- and /&carbon atoms of the side chain, FieldingCOOH*CH2*COoC6H,(OMe).0Ac, which loses carbonic anhydride,forming acetovanillone.The properties of the substances obbained in this research are givenin the following abstract. H. G. CORQANIC CHEMISTRY. t; 1Derivatives of Acetovanillone. By E. NETTZEL (Rer., 24,2863--2868).-Acet~ovanillone yields a series of phenol salts wit,h theirietals of the alkalis and alkaline earths, the former having :in:Ilkaline reaction, and all readily undergoing decomposition.Thecopper salt is a yellowish-green, amorphous powder.By the action of an alcoholic solutirm of methyl iodide on analkali salt of acetovanillone, t h e methyl ether, or acdoveratrone.C,H,AC(OM~)~, is obtained ; i t forms rhomboidal crystals, melts at48-49", boils a t 2 ~ 7 ' under 15 mm. pressure, is soluble in hotwater, alcohol, ether, and benzene, and is converted by 1 otasFiuiiiIwrrnRnganate int,o veratric acid. The corresponding eth?/Zaceto-yaniZEone forms radial groups of needles, and melts at 78". Acetyl-acetovanillone, OMe*C6H2Ac*OAc, prepared bay boiling acetovanillonewith acetic anhydride, crystallises from alcohol, on the addition ofwater, in long needles melting a t 58O, and yields vrtriillic acid on oxid-ation.Henzoylucefovanillone, OMe*C&&'O~Z, obtained frl jm analkaline solution of acetovanillorie by the action of benzoic chloride,melts at 106".Acetoprotocatechone. CsH3Ac( OH),, is formed in small quantity bpthe action of hydrochloric acid on acetornnillone a t 140-1 Xi", andseparrtt es from chloroform solution, on t.he addition of light petroleum,in crystals which melt a t 96-98'. The same compound appears to beformed by the action of zinc chloride on a mixture of catecbol andacetic acid, but could not be separated from the excess of catechol.zlcetovaniZEoneplien?/Zl~ y d rami e, N? H Ph: CMe*C6H3 ( 0 Me) *OH, form swell-developed crystals, melts a t 125", and is soluble in alcohol aridether ; the oxime, OHoN:CMe.(=,H,(OMe~*0H, melts a t 95", is fairlysoluble in water, and cryntallises best from henzene.Ethylaceto-.ca~zillor:oxiirre, NOH:CMe*C,H,(OM~)-OEt, c-rystallises fi om alcohol inlustrous prisms melting a t 116-118". As already mentioned in thepi-eveding abstract, ferric: chloride converts acetovanillone into dehydw-diacetocanillone, C18H which is almost insuluble in the usualsolvents, and melts above W O " .When a mixture of calcium acetate and vanillate in rnoleculiu. pro-portions is distilled, acetovanillone passes over in small quantitytogether with acetone, guniacol, &c. These are removed by distillingi n n cutarent of steam, and the residue purified by repeatediy Iirecipi-tating the benzene solution with light petroleum.Synthesis of Acetovanillone from Guaiacol and Acetic Acid.By T.Owo ( B e T . , 24, 2869-2S70).-Acetovanillone may be oh-tained synthetically by dissolving 60 parts of guaiacol in 120 parts ot';Lcetic acid, and gradually adding 30-40 parts of a niixtrire of zincand aluminium chlorides i n equal proportions ; the whole is warmed onthe water-bath after the frotliing has moderated, and finally heilted a t14&-150" until hydrogen chloride is no ioriger evolved. The productis then poured into water, the unaltered guaiavol renioved by distilla-tion i n a current of steam, the solution filtered from resinous matters,;\nd extracted with ether; the residue from the ethereal sulutioii istreated with fioda, the aqueous solution saturated with carbonicanhydride and again extracted with ether, the latter distilled off,H.G. Cti 2 ABSTRACTS OF CHEXICAL PAPERS.the residue fractionated, and finally recrgskallised from boiling water.The acetovanillone thus obtained crystallihes in white needles, meltsat 115", and hns all the properties ascribed to it in the previousabstracts ; the yield of the pure compound is, however, verv small.H. G. C.Aromatic Hydroxyketones. Ry P. CRlhEux (Chem. Centr., 1891,ii, 377 ; from Schweiz. Woc7masclw. Pharm., 29, 255-256).-AppIy-ing the same method as Nencki used to produce hgdroxyketones, theauthor has obtained from resacetophenone, a substance of the formulrCaHzAc2(OH)2, and from gallacetophenone, a compound,C6HA~( OH),*OAc.The latter is hydrolysed by potash, one acetyl group beinqeliminated, and the compmud C,HAcz(OH), formed.By the actionof glacial acetic acid and fused sodium acetate on propionyl-p benol, resacetop henone, gallacetoph en one, the acetyl derivativesA cetyl propioph enone, diacetylgal lace to-phenone are formed. Where more than one hydroxyl group waspresent, one remained intact, the others becoming acetjlated.Constitutents of Paracoto Bark. By G. CrmIcIm and P.STLBER ( n e r . , 24. 2977- 2990).-The authors find that hydrocotoin,to which they assigned the formula OH*C,H,(OMe),*COPh (Ber., 24,299; Ahstr., 1891, 578), yields neither an oxime nor a hydrazone:many ketonic compounds are, however, indifferent towards h~droxyl-amine and phenylhydrazine (compare Hantzsch, Abstr., 1891, 36),arid in the case under discussion, this behaviour is perhaps explained bythe position of the methoxyl groups in the molecule.The compoundis not attacked by aqueous alkalis, but when hekted with alcoholicpotash under pressure, benzoxc acid and a phenolic compound, appa-rently a mixture, are formed. When hydrocotoln (10 grams) isintimately mixed with phosphorus pentachloride (60 grams), and themixture slowly distilled uiitil all the phosphorus trichloride and oxy-chloride hat*e passedover, the residue and the distillate being then mixedwith water, united, and steam distilled, benzotrichloride first passesover, and then very slowly a solid compound, C,H,CI,O, ; this crystal-lises from alcohol i n colourless needles, melts at 174".and is imolublein alkalis : it yields methyl chloride when heated with\ hydrochloricacid at 140", and i8 probably a dimethoxy-derivative. When methyl-hydrocotoh (2oc. cit.) is treated in a similar manner with phosphoruspentachloride, benzotrichloride, together with a compound, C9H9ClJ03,probably a trimethoxg-derivative, is obtained : the latter formxdelicate, white needles, and melts at 130-131"; benzo'ic acid isfound in the aqueous portion of the Tesidue from the steam distilla-tion, whilst by treating the solid portion of the latter with glacialacetic acid and adding water to the solution, a compound, C16H14C1204,separates, which crystnllises from alcohol in colourless prisms, meltsat @1--82", and is perhaps dichloroniethylhydroco~~n.Protocotozn, ClsHldOs, is another constitnent of prrracoto bark, andoccurs AB an impurity in crude hydrocotoh, from which, by reason of itsmuch smaller solubility in alcohol.i t may be separated by fractionalcrystallisation from that liquid. It forms bright-yellow, monoclinicm onacety lresaceto phenone,J. W. LORGANIC OHEMISTHY. 68prisms, a : b : c = 2'930.3 : 1 : 2.0558; p = '79" 06', melts a t 141-142",iq soluble in most solvents, hut insoluble in water; it dissolves inalkalis, and is reprecipitated by carbonic anhydride : its solutioIl indilute alcohol gives a reddish-brown colour with ferric chloride ;whilst on treating it with dilute nitric arid, a bluish-green cnlour isproduced.and on heatinv the solution a reddish-brown precipitat,e isformed. When its solution in alkali., is reduced with sodium amalgamand acidified, ether extracts a compound cryshllising from alcohol inwhite. amorphous flocks, and melting a t 215-220". A determinationbv Zeisel's method showed that protocotoin contains two methoxplgroups. The acetyl derivative, C,,H,,O,, p,repnred by heating it withan equal weight of anhydrous sodium acetate and four time8 itsweight of acetic anhydride i n R reflux apparatus for six hours, formscolourless crystals, melts at 10:-3", and is insoluble in water andalkalis, but readily soluble in ether, hot alcohol, and chloroform: itdiwolves in cold nitric acid to a yellow solution. which.on heatinp,becomes bluish-green, and finally red ; its solution in dilute alcoholgives no coloration with ferric chloride ; on hoiliiig with alkalis,protocoto5n is regenerated ; i t contains one methoxyl group.MethyZprotiIcotoin, C14H703(OMe)3, is obtained by heating togetheri n n sealed tube, protocotoin (10 grams), a little methyl alcohol. potash(3 grams), and methyl iodide (15 grams), evaporating the alcohol,washing with water, and crvstallising from dcnhol ; i t forms colonrlessprisms, melts at 134-135", and is insoluble in water and in alkalis.Protocoto'in does not react with hydroxylarnine.The hydrazone, C22H20N206, is obtained by heating protwotoynwith an excess of pheny!hy?razine, dissolving the melt inglacial acetic acid, pouring I t into water, and crystallising tl:eprecipitated compound from alcohol ; i t forms small, colourlesnprisms, melts at 211".m d is sparingly soluble in rtlcohol andglacial acetic acid. Dihromoprdocotoin, CI6Hl2Br2O6, is preparedby treating protocotoyn dissolved in chloroform with m excem ofbromine, evaporating the sdvmt, and crystallising from dcohol ; i tcrystallises in silky scales, melts R t 170°, and dissolves in alkalifc, inh4)t dilute nitric acid, and in d p h u r i c acid with a yellow colou1-.BromacetyZ~rotr,cotoi'n, CI6Hl5BrO,,, is obtained in a similar mannerfrom acetrlprotocotoh ; it forms smdl, delicate, white needles, meltsat 175", and is insoluble in water and cold alkalis, b u t dissolves inhot alkalis with a yellow colour. Protocatechuic acid is producedwhen protocotoin is fused with potash or heated with concentratedhydrochloric acid in a, sealed tube at 130"; whilst the compoundCRH7C1302, melting a t 174", and identical with that obtained fromhydrocotoin (see above) is produced by treating protocotoh withphosphorus pentachloride in the manner already described underhydrocotoin.Methylprotocotoln, treated in a similar manner, yieldsthe compound melting at 131° identical with that obtRined frommethylhydrocotoin. Taking all these facts into consideration, it isprobable that protocotoh has the constitution3CH2<~>CaH3*CO*G,EI,( OMe),*OH,4: 4 ABSTRACTS OF CHEMICAL PAPERS.which is, however, given under reservation, as the presence of n,inethylene group has notl yet been demonstrated.When protocotoin is oxidised in alkaline solution with potasqiumpermanganate, a11 acid, which is being investigated, together with Jobst;~nd Hesse's paracouniarhydrin (Abstr., 1880, 3271, is formcd ; ittaontains a carboxyl group, as it yields a, hydrazone, C,,H,,N,O,,melting at 114".A. R. L.Vanilloylcarboxylic Acid (Parahydroxymetamethoxybensoyl-carboxylic Acid). By F. TIEMANN (Her., 24, 287$--28i9).--Tbeclimethoxyphenylglyoxylic 'acid [I : 3 : 41 recently obtained byCiarnician and Silber by the oxidation of methyleugenol (Abstr.,189 1, 966) has already been described by the author and Matsmotounder the nume veratroylcarboxylic acid (hbstr., 1878, 503). Thecorresponding ketonic acid of the vanillin series, or vaniZloyZcarboxylicmid, COOH.CO*C6H,(OMe)-OH [l : 3 : 41, has been found in certainvanillin preparations obtained by the oxidation of acetyleugenol, andacecylisoeugenol, and distinguished by their yellow colour.I t may bebeparated from vanillin by shaking with water containing magnesium(.arbonate in suspensioii, the vanilloylcarboxylic acid passing into theaqueous solrition as a magnesium salt. This is aciditied with snlph-uric acid, extracted with ether, the latter distilled off, the residue heatedat 50-60" in R vacuum and crystitllised from benzene. It then formsprisms containing benzene of crystallisation, which is rapidly givenoff on exposure to the a i r ; after dryingat loo", it meltsat 233-134 ,and dissolves readily in waitel., alcohol, ether, and benzene, sparinglyi n light petroleum.When heated above its melting point, i t isresolved into vanillin and carbonic anhydride. H. G. C.Benzenesulphamides and Mixed Secondary Amines. By 0.HINSBERG ( A ~ w l e n , 265, 178--192).-1n a previous paper (Abstr.,1891, 491, i t has been stated that phcnylsulphoiiic chloride reactsvery readily both with secondary and with primary amines; thecompounds obtained from the primary amines are soluble iu potash,yielding stable salts, which react .readily with fatty and (sotlie)aromatic halogen derivatives, being thereby converted into trisub-stituted amines (or disubstituted alliides). Various new compoundsobtained in this manner are described below.l'enzerLesulphonernethylethylcLmide, SO,Ph*NMeEt, is easily obtainedby warming a solntioir of benzenesulphonemethylamide in excess ofpotash with a, little alcohol and excesb of ethyl iodide; the yield isquantitative. It is a thick oil, distils under reduced pressure(50 mm.) with only slight decomposition, and is only sparingly solublein water, acids, and alkalis, but readily in alcohol and ether.Ethylmethyluniine, NHMeEt, is produced when the preceding corn-pound is heated with conceritrated hydrochloric acid a t 150-160" ; itboils a t 33-34.", and has properties similar to those of its nexthomologues.The hydrochloride, C3HqN,HCI, separates from a mix-ture of chloroform and ether i n coXourless, hygroscopic crystals, andis very readily soluble in alcvliol ; d l the other salts are very readilsoluhle in water and alcohol, hut the platinochloride crystallises fromthe former in moderately large plates.Renzene.szilphonepiperidine, SO,Ph.C,NH,,, mii be prepared by re-peatedly adding stiiall quantities of a mixture of phenylsulphonicchloride and coiicentrnted potash to an aqueous solution of piperidine,and shaking vigorously until the reaction is complete.It crystallisesin colourless prisms, melts a t 93-94", and is readily soluble in alc I -hol and ether, but only sparingly in water ; it is decomposed into itscomponents by concentrated hydrochloric acid a t 150".Re~~zenesul-phoneben~ylamide, SO,Ph*NH*CH,Ph, prepared fromben zylamine and phe ny lsulphonic chloride, crptall ises from dilutealcohol in colourless needles, melts a t 88", and is readily soluble inalcohol and ether, but only sparingly in water.The methyl deriva-tive, SO,Ph-NMe*CH,Ph, is obtained when the aniide is warmed withmethyl iodide and alcoholic soda; i t is a colourless, crystallinecompound, melts at !)4", and is decompo:,ed into benzenesulphonicacid and methrlbenzylamine by concentrated hydrochloric acid at160-1 go".ill'ethylbenzylamine, CH2Ph*NHMe, is a colourless liquid, boils at184", and has a slight amine-like odour ; i t is more readily soluble incold than in hot water. The sulphnte and the hydrochloride are veryreadily soluble in watei-. The platinochloride, (C,H,,N),,H,PtCl,,crystallises in long, yellowish-red needles, melts a t about 199, and ismoderately easily soluble in water.Benzenesulp honeortho to1 uid ide, S 02P h* N H*Cs H4Me, crystal 1 i ses fromdilute alcohol in colourless needles, melts at 125--126', and is readilysoluble in alcohol and ether, but only sparingly in water: i t is in-soluble in mineral acids, but it forms stable, readily soluble salts withalkalis.Brtrzenesulp honeparaphenetidin e, S 0,P h*NH.C6H4.0Eh, cry stsllisesfrom alcohol in coloui*less needles melting at 142" ; its methyl deriva-tive, C,5H1,NSOJ, crystallises from ether in large plates, and melts a t79".nibeiizenesulphonediphenetidine, CzsHz8F2S2O6, can be obtained bygradually adding it Concentrated solution of iodine in potassiumiodide to a hot, concentrated solution of benzenesulphonephenetidinein sodium carbonate.It crystnllises from alcohol i n colourlessneedles, melts a t 168", and is more sparingly soluble in alcohol, ether,and glacis1 acetic acid than the simple sulphone from which i t isobtaiued ; i t gives a blue coloration with hot, concentrated sidphuricacid, and forms a crystalline potctssiurn derivative of the compositionC,,H,,N,S,C),K, which is only sparingly soluble in water, but itrorereadily in alcohol. When heated with concentrated hydrochloric acidat 170", it yields ethyl chloride, benzenesulphonic acid, and a bluesubstance which is soluble in alkalis; its constitution is probablyexpressed by the formula S02Ph*NH*CsH,(OEt).N( d02Ph)*C,H*.0 Et.A bertzyl derivative of the composition C35Y34N,S2O, is formed whenthe potassium derivative just referred to is treated with benzylchloride ; it crystallises from alcohol in slender, colourless needlee,and melts a t 158".Dibenzrnesulphonepnraphenylenediamine, C,H1(NH*S02Ph),, crystal-The nitrnsamirie is a n oil.VOL.LXII. 66 ARSTR ACTS OF Cki EMICAL PAPERS.lises in colourless, 1ust8i*ous plates, melts a t 247', and is re:idily soluhlein alkalis, but only nioclerntrly easily in hot alcohol, and almost i i r -soluble in water. The diethgl derivative, C22H21N2S20,, crystallisesfrom dilute alcohol, in which it is moderately easily soluble, incolourless needles melting a t 197" ; on hydrolysis, i t yields diethyl-phenylenediamine, the diacetyl derivn tive of which crystallises fi-omhot water or dilute alcohol in colourless needles, melts a t 186-18i0,and has the composition C,,H,,N,O,.Di benzenesulp ho ti eort hot0 iw y lenediamine, C, H,Me ( N H* S 0,Ph) 2, cr7s-tallises from alcohol in plates, melts a t 178--1i9", and is readilysoluble in alkalis ; its solution in ammonia gives a blue, amorphousprecipitate on the addition of copper sulpbate.The diethyl deriva-tive, C-,H&N2S,04, crystallises f rowL alcohol in coloui~less needles tion-taining 4 mol. C,H,O, and melting at ahout 117" with previoussoftenirig; it loses its iilcohol at about 120", and solidifies on cooliiigt o a vitreous mass, which melts at 62-70".DiethyZtuZuyle?,ec?iu~~n~, C,B,Me(NHEt),. is obtained v hen thepreceding componnd is hydrolysed with concentrated hydrochloricacid ; it isa colourless oil, boils at 265" (uncorr.), and rapidly darkenson exposure to the air.I t gives a reddish-brown coloration withplatinic chloride aud also with ferric chloride i n presence of hydro-chloric acid ; in its concentrated aqueous solution, potassinni ferro-cyanide produces a colourless precipitate. Its salts are readily solublein water, and seem not to cr.1 stallise ; when tlle diamine is warmedwith phenanthraquinonc and acetic acid, it yields a reddish-yellowsolntion, from which, on evaporation, only amorphous substances areobtained. I?. S. K.Synthesis of Indole from Tartaric Acid and Aniline. By H.POLIKIER (Bw., 24, 2954-295!)).-- 'l'artrai\ilide (30 grams) is fusedi n a retort, and, after heating a t 260-270" for t w o hours, slowlydistilled over a tree flame, until nothing more passes over ; the productis then redistilled in ;I current of steam, when a mixtiire of aiiilineand indole passes over, fibom which the 1att8cr Ciin be isolated as picrate,0.74 pram being obtaiued ; whilst a yellowish residue weighing 4.8grams remains.which, on crystallisation from alcohol, melts a t 220",;tiid proves to be dianilidosuccinanilide (compare t h i s vol., p. 5,5). Byhclating tnrtranilide (20 grams) with an equal weight of zinc chloride at270-280" for an hour, diaiiilidosiiccii~anilide (1.32 grams) and indole( ~ 2 2 gram) may be isolated ; whilst, if a mixture of tartaric acid,aniline, and zinc chloride is heated in a sealed tube at 280°, theproduct extracted with alcohol, and the solution distilled, indole isobtained from the portion of the distillate pausiQg over last, and ispurified as described above.When tartaric acid is added b? degrees to boiling orthotoluidine i tdissolves after a time, and, on now distilling, the tempwature quicklyrises to 300", carbonic anhydride is eyolved, and orthotoluidine, nietlyl-indole, and a white, crystalline compound melting at 247" pass over ;the methylindole is formed in much larger quantity than is indole bythe methods described above.When dianilidosuccinanilide is heated in a sealed tube with a littlORG .%SIC UHEMISTEZT.(i iw.nfer at 200", R isesinous mass, tozether with aniline and traces ofindole is obtained ; whilst, if etliyldianilidosnccinic acid (Abstr.,1888, 951) is heated with zinc chloride, a compound melting a t about62", and giving all the reactions of indole, is produced. It wonldappear, therefore, that bv the action of aniline on tartiaanilide, di-anilidosuccinanilide is initially formed, and this, by the action of water,yields indole, aniline, carbonic anhydride, and carbonic oxide.Furtherexperiments are promised. A. R. L.Molecular Weight of Nitrosoindole. By C. ZATTI and A.FERRATINI (Gazzettn, 21, ii, 19--25).--The authors have already notedtbe comparatively hiEli melting point of the nitrosoindole describedby them (Abstr., lt390, lag?), and suggested that its empiricalformula might, have t o be doubled to give the tru2 inoleoular weight.'1'11~ moleanlar nreicht could not be determined by the cryoscopiomethod, owing t o the very sparing solubility of the substttnce i n thecold, but by observing the elevation of the bailing point of its solu-tion in acetone, numbers were obtained showing that the moleculavformula of nitrosoindole is C,,HI2N,O2.Nitrosodimethylindole behaves normally in i t s solution in acetone,the formula of the molecule being C,,,HloN20.When nitrosoindole is treated with nitric acid, i t dissolves, yieldingail intensely red solution, and on pouring thin into water, a flocculent,blood-red substance wparates, which agrees in properties with the so-called nitrosoindole nitrate prepared by Nencki (Abstr., 1875, l.LO.j),W. J.P.Indazole Derivatives. By C. PAAL (Ber., 24, 3058-3065;compare Abstr., 1891,723).-Phenylindazole, C,H,< 1- >NPh [l : 21,was dissolved in glacial acetic acid, treated with rather more thanthe theoretical amount of chromic acid, and boiled in a reflux appa-ratus until the solution acquired a pure green tint.On diluting themass with water, azobe?izeneorthoi.ar.Eozylic: acid, N2Ph*CGH4*COOH,separates out, the yield being 70 per oeut. of the theoretical. It dis-solves easily in ether, alcohol, glacial acetic acid, ethyl acetate, andbeuzene, very sparinqly i n hot light petroleum, and riot a t all in water.It crystallises from alcohol slowly in large, dark-red crj stals, or quicklyin small needles of the colour of azobenzene. It melts a t 9S0, and ata higher temperature decomposes with evoliition of red fumes, azo-benzene being formed.The alkali salfs and thc barium salt are easilysoluble i n water ; the lead salt forms a n orange-coloured, granular,amorphous precipitate which melts in hot water ; the silver salt formsan unstable, yellowish precipitate, which decomposes when heated,yielding azo ben zene, carbonic anhydride, s i 1 v er, and carbonaceousproducts. The acid itself is converted into h2/drazobsnzenerll.thocarb-ozylic acid, NHPh:NH-C,H,*COOH, when it is dissolved in alcoholand treated with zinc-dust and a few drops of acetic acid. The newacid separates on pouring the mixture into water. It dissolveseasily in mineral acids, ether, alcohol, glacial acetic acid, and ethylacetate, sparingly in benzene and light petroleum, scarcely at all inN-LHf 68 ABSTRACTS OF CHEJITCAI.PAPERS.w,atpr, It crptallises in yellowish, ill-defined pi isms which melt at.16,?-1B6 , aud, in the air, quickly darken in colour, hec*oming oxidisedto t h e azo-acid. The white sodiu,m. salt dissolves readily in water ;the barium salt, (Ci3HllNzOz)2Ba, forms lorig, white, hair-like crystnlsgrouped as in wavellite ; i t oxidises 1'ea.dil.y in the air.BenziJiltemetacarbozy Eic acid, N Ht2*CcHt.C6H3( NHz)*COOH, is formedto the extent of 60 per cent. of the t,h(,oreticalyield, whet1 ambenzene-orthocarboxplic acid is reduced by dissolving i t in absolute alcohol,excess of tin added, and then IiTdrochloric acid in snccessive smn.11proportions, the niixture being heated. On cooling the solution, theI-lihydrochlovide, C18H12N'L02,2HClr crjstnllises out in white, lustrousneedles which melt at a very high temperature, and do not dissol\.ei n alcohol, but do so in water, iindergoing dissociation and forminqthe rnonohy~lrochloride, C1:,H12N202,HC1, which separates in short, dull-white needltbs ; this melts i j t a very high temperature, and is only spar-ingly soluble even in hot, water.This salt; may also be obtained hy boil-i rig a hydrochloric acid sol u t ion of h y drazobenzen eorthoc.nrboxylic acid.The acid itself is ohtained by dissolving either of the hydrochloridesin aqueous ammoiiia and adding acetic acid. I t dissolves sparinglyin I ot wat,er, hard!y a t all in absolute alcohol; from dilute alcoliol, it,crystallises in crusts formed of white needles which melt at 210",decomposing into carbonic anhydride and benzidine.The allcLzZi saZt,<are soluble in water, but insoluble in concentrated alkalis. T h abarium salt forms short,, white prisms, almost insoluble in cold waterThe silrer salt, C&TlIN2OzAg~ is a white, amorphous substance, fairlysfable in the light, aiid almost insoluble in hot water.Pa,.nchZoi.~rzobenzeneorthocarb/,zyZic m i d , C6H4Cl0N2*C6H4-COOH, isobtained by midising parachlorophenylindazole in acetic acid snlrl-tion with chromic acid, cooling the solution, and diluting i t withwater. It dissolvcs readily in hot, alcohol, glacial acetic acid, ant1benzene, scarcely a t all in light petroleurn. It forms small, 0i.ang.e-coloured, dendritic needles, mid melts at, 166".Reduced w i t h zinc-dust and acetic aci(1, it yields p~rrachl~~rhydraa~~benzeneol.thocarhoxyl~icacid, C6H,CI*NH*NH.C6H,.COoH~ which is precipitated in whiteflakes on the addition of water. 'J'ht: yellow sodium sdZt of t h e azo-acid is soluble in water, but insoluble in concentrated alkalis. Thebariiim salt forms lustrous, orange-coloured needles illsoluble in watey.The copper salt forms a briglit,-green, amorphous, the silcer salt, areddish, amorphous, granular, and t,he ferric salt, a bulky, reddish,precipitate.YarlLbrornnzobenzeneol.thocarboxylic acid, C6H4Br.Nz.C6H4.COOH, isprepared by oxidising par,zbromophenylindazole with chromic acid inacetic acid solution. It crjstallises from alcohol in small, lust,rous,orange-red needles, melts at 176", and dissolves readily in glaciaiacetic acid, ethyl acetate, and benzene, b u t not i n light, petroleum.It,is redneed by zinc-dust 2nd acetic acid to parabromh~jilrazoben2ene-carboxy lir: acid, C,H,Br*NH*NH*C,H,*COOH. which forms white,crystalline flakes insoluble in water. The salts of the bromazo-acidresemble those of the chlorazo-acid, except that. they are redder, andthat t h e cnpper and ferric salts are, respectively, bright-green a,n(1rusty coloured . C. F. BORGANIC CHEMISTRY. 69Synthesis of Indigodisulphonic Asid. By B. HEY.II~YN(Bey., 24, 3066--3070).-A reply t,o Kuiet,sch (Abstr., 1891, 1231). 1tis sliown t h a t when indigocarmine is obtained from phenylglycocint!by dissolving the latter i n funiing sulphuric acid (containiug 80 percent.of t h e anhydride) and removing the excess of anhydride by t h eaddition of concentrated sulphuric acid, the oxygen of the a i r plays nooxidising part in the reaction, for in an experiment, during whicha i r was carefullv excluded, as good a yield was obtained as i n otherexperimeuts. The author is of opinion that the 1euco.compound atfirst formed has a constitution similar to HSO~*C,H,<~~so3H)~CH,and that, when t h e concentrated sulphuric acid is added, this com-pound either splits u p into indigo-carmine, sulphurous acid, and water,the sulphuric acid residue furnisbing the necessary oxygen, or, as ismore probable, breaks u p into the sulphonic acid and the leuco-com-pound, which is then oxidised to indigo-carmine by sulphuric niihydr-ide still present in the solution.C. 17. B.Diphenyltetraketone. By P. W. ABENIGS and H. G. SODELRAUU(ljer,, 24, 3033--3034).-The yellow substance melt.ing at 170"(Abstr., 1891, 1043) obtained when the acetyl derivative of w-isonitro-soacetophenone (benzoylformoxime) is dissolved i n a dilute soIution ofsodium carbonate is shown to be in reality diphenylhydroxytriketone(phenylglyoxalbenzoh), OLI-CHBz-COBz, for i t is identical with thesubstance obhained by treating ben~oylformaldehyde~ COPh-CHO,with potassium cyanide in alcoholic solution. When treated withstrong nitric acid, i t is oxidised t o a tetraketone, COPh*CO*CO*COPh,a red substance which easily takes up 1 mol. of water, formkg ayellow hydrate which melts at 86- 88"-and crystallises weil.C.F. B.Constitution of Naphthalene. By G. ClawcrAN (Gnzzetta, 21,ii, 101--108).-The author considers Bamberger's hypothesis of theconstitution of naphthalene to be erroneous, and believes that the in-ternal structnre of the molecule is better represented by employingBaeper's conception of five double bonds of mean solidity 01- resistaim.The author is of opinion that the internal structureof thenaphtha-lene iiiolecule is well represented by considering the carbon atomsplaced at, the ceritree of the sides of two intersecting equilateral b u tnot equiangular hexagons, the two ceritral carbon atoms being commont o both hexagons. I n the orthogonal projection of such a system asthis, six of the straight lilies joining pairs of carbon atoms will belonger than the remaining five ; these latter represent the f i v e doublebonds in Bweyei*'s conception of tlie ring, whilst t h e longer ones repre-sent the single bonds.The hydrogen atoms are disposed in two])lanes parallel to that of the carbon atoms, the plane of the hydrogenatoms belonqing to one hex:igon being above, that of the other.hexagon below, the carbon plane. Such a, s.vstem as this is perfectlysgrnmetrical and may be considered to explain t h e seeming proximityof the peri-h~drogen atoms i n the naphthalene molecule.W. J. P70 ABSTRACTS OF CHEMICATA PAPER,!?.Azines of the Uric Acid Group. By 0. K ~ H L I S G (Ber., 24.alloxantin with a-naphthylenedinmine hydrochloride in aqueous solu-tion ; i t crystallises from a mixture of glnciat acetic acid and alcoholin small, slender, yellow needles, melts a t 285", and is insoluble in sodaor in sodium carbonate solution.N:C*NMe.COIlIethyZal2oznzine, C6H4<N:b.co. kH, is obtained from ortho-phenylenediimine hydrochloride and dimethylalloxantin, arid crys-tallises from a mixture of alcohol and glacial acetic acid in small,pale-yellow needles, melting att 250". The conipoulici is soluble insodium carbdnate solution at the ordinary temperature, and is reprc-diuitated anchanged bv acids.1 : 3 : 4-ortliotolnylencdiamine hydrochloride and dimethylalloxantin ;i t resembles thepreceding compound in properties, and blackens when-heated above 250".N:C.N.Me-COilIethylnay7~thaZloxazi~ze, C,oHs<N:A .co *.&H, is deposited onheating a-naphthylenedi~mine hvdrochluride with dimethylalloxantinin aqueous solution; i t is iriaoluble i n water, very spariugly so inalcoliol, and ciystallises from glacid acetic acid in sletider, yellowneedles. The azine dissolves in scjdaor in sodium carbonate solutionon gently warming, and is piwci~tatecl unchanged by acids ; i t is uri-altered by heating atgabout ROO". On boiling aqueous solutions oforthodiamine .hydrochlorides witli parabanic acid, spwingly solulllecompounds are obtaivrd, which proved on analysis to be dihydi-oxy-quinoxalines ; thesejcoqounds are formed h 7 t h e resolution of theparabanic acid into cvlibamide arid oxalic acid, and the condensationof the latter cornpovrncl with the orthodiamine.Nnphthndih!/droxy/-:s prepared by heating parabanic acid N :COO H' q ctinozaZine, >C,,H,.<Lvith a-naph~~ylenedinmine hydrochloi-ide f o r several hours in aqueoussolution ; i t is,purified by dissolving in dilute potash and pwcipitatitlgwith hydrochloric acid, and forms slender, coloui.less needles whicllmelt above NO". l l i e compound dissolves iu glacial acetic acid, and+paringJy in aicohol, but is in>olublc: in water. The Larium salt is+isoluble in water a n d is decomposed by acids.The substituted pai*abnnic acids appear to be morc stable towardsorthodiamines ; cholestrophane is unaffected by orthotoluylerledi-aniine hydrochloride, and allantoin does not rcact at all witli ortho-diamines.J. B. T.N:y'oHA Volatile Oil from Aristolochia reticulata. By J. C.PEACOCK (C'htm. Ctwtr., 1891, ii, 379 ; from Amw. .I. Yhawn., J u n e ,l890).--From the rhizomes of this plant, a s they are obtained COIUORGANIC C HEMISTltS'. 51.mercially, the author separated 0 61-0.94 per cent. of a golden-yellow oil. It has a camphor-like odour and taste, dries slowly whenexposed to the air, does not solidify a t -17", and has a sp. gr. of0*9i45-0-9785 at 15*5", and 0*971+-0*9758 at 20". I t is misciblewith alcohol, et,her, chloroform, benzene, and light petroleum ; i texhibits no a!dehyde readion, and rotates the polarised ray -4 in100-mm. tube. By fractional distillation, 10 per cent. passed over at74-75' under a pressure of 43 mm., 60 per cent.between 122-124",under a pressure of 43 mm., and 20 per cent. between 147-150" undera pressure of 47.7 mm. ; the residue in t h e retort possessed a blue andgreen fluorescence, and contained tawy matters.This first distillate boiled at 157" under a pressure of 769.6 mm. ; i t ssp. gr. was 0.865 a t 13.5" ; its formula is C,,H,,, wihh which its vapoiirdensity corresponded ; it absorbs bromine very readily, and is charac-terised as a member of Wallach's pinene group.The secoud fraction boils a t 211" under 763.6 mm. pressure; itsformula is CI5Hz5O2, wit,h which the vapour density corresponds. Onhydrolysis with potash, a camphor, CloHi80, is produced, which is verysimilar to borneol ; it boils a t 199*5-200". A n acid is also sept-rated of tlie probable formula C,H,O, ; melting point about 65" ; itforms a red precipitate with ferric chloride ; its odour is unpleasant.The third fraction, boiliiig a t 239-240", under 762.1 mm.pressure,is a greenish-yellow oil; sp. gr. 0.938d at 15-5"; its formula isCl9HZ90, with wliich the vapour density corresponds; i t is a n e u t r ~ ~ l ,indifferent substance. J. W. L.Bergapten, the Stearoptene of Bergamot OiL By C. 'POMERANZ(JIorLatslL., 12, 379--396).--Tliis subsharice separates as a crystalliiiemagma when the ethereal oil obtained from the rind of the fruit oECitrus Zlergamia is kepc for some time. It may be purified by s ~ h -limation 01- by recry stallisation from alcohol, when i t forms hard,white, silky needles, whitah are tasteless and odourless at ordinarytemperatures, but evolve aromatic vnpours when heated.It issliglitlg soluble in cold alcohol and in hot water; dissolves in hotalcohol, acetic acid, chloroform, benzene, and phenol, and melts at188', with partial sublimation. Elementary analysis and a determina-tion of its molecular weight by observing the depression of thefreezing point of a solution in phenol show t h a t i t has the moiecularformula C,zH,O,. Aqueoiis and alcoholic potash, acetic anhydride,pheiiylhydrazine, and boiling hydrochloric acid are all without actionon the compound, which, however, as shown by the action of hyclriodicacid and acetic arihydride (compare Herzig, Xonatsh., 9, 544), con-t<iins three rnettioxyl groups.On heating bergapten with potash, methyl alcohol, and methyliodide in a reflux app3ratus €or five hours, two new compounds areobtained.One of these has the formula C,,H,,O,; crystsllises fromalcohol in microscopic prisms, which are far more soluble in alcohol,chloroform, arid ether than i s bergapten, and melts a t Y,iL". Theother, which the authw has named iriethylberqaptic acid, contains CHless than tlie precediug cunipound, which is prohably its rnethjl sali 2 ABS I'HACTM OF UHEMICAL PAPERS.since, on hjdrolysis with potash, it furnishes the lree acid. Itcrystallises from dilute alcohol in small, rhombic plates, dis-solves readily in alkaline hydroxides and carbonates, and melts at138'. When, in the above described operation, ethyl iodide is sub-stituted for methyl iodide, ethylberguptic acid is ohtained ; this crys-tallises in acute-angled prisms or in twinned or clustered needles, andmelts at 142".From its behaviour with methyl and ethjl iodides,nbergapten must be regarded as the anhydride, C1,H,O,<Y and it,CO'tlierefore, closely resembles coumarin in constitution.Wlien fused with potash, bergapten gives rise to phluroglucinol,and on treiit,u\ent with two moledi~l* proportions of bromine, the an-hydride is converted into monobromobeygapten dihroriride, Cl2H,O4Br,,formed froni bergapten, whicbh has two double linkages in the sidecI\ains, by the addition of four atoms of bromine, one of which isafterwards eliminated in the form of EydroLrornic acid.On reduction wit,h sodium amalgam, methylbergaptic acid is con-verted i n to methy Ihy dmbergaptic acid, C,,H,,O,, which crystallisesfrotn dilute alcohol in small, white needles, and melts at 122".Thisproduct is analogous to the hydro-acids obtained on the reduction ofmethyl- and ethyl-coumaric acids.The above-described reactions of bergapten point to its having oneO F the following constitutions :-$H--y:C(OMe)*g*C'H:yH, ~ H . O . ~ . C H : C ( G M e ) . ~ * C ~ : ~ H ; orCH*O.CH --- C-0-CO ' CH-C--C-0-GO$ €I - C 0-0 $ *CHIC( OMe)$ -- 9 HCH----C ---C*O.CHG. T. M.Action of Sodium Alkyloxides on Caxnphor. Preparation ofAlkylcamphors. By A. HALLEK (Compt. rend., 112, 1490-1494).-Action Oj'Sodium a'thoxide o n C!untphor.-At 100" there is no reaction.5 grams oE camphor and 30 c'c.of absolute alcohol to which 0.75gram of sodium has been added are heated in sealed tubes for 24hours a t 200". A great pressure is observed on openirig the tubes, dueto the disengagement of large quantities of bydrogen. The productis treated with water, and the separated, coloured, viscous mass dis-solved in ether, from which it separates on spontaneous evaporat.ionof the solveut. Repeatedly crystallised from a mixture of ether andlight petroleum, it forms white, hexagonal crystals. melting a t208-210". This substance i s a niixture of dextro- and hvo-borneol,the proportions varying with the preparation. The rotatory powel-sof t w o preparations were [.In = +125" and [ a ] D == +16".15 grams of camphor yield 8-10 grams of pure borneol.Thejield is better than with Berthelot's method ; the product is riot mixedwith camphor, and only contains traces of campbic acid, small quan-tities of a liquid produut insoluble in water and alkalis, and sodiumacetateORGANIC CHEBILS'L'HY. 73Sodium propoxide, isobutoxide, and amyloxide yieid borneol, thequctiitity decreasiug with the rise in the molecular weight of thealcobol employed. Secoudary liquid products intermediate i n com-position between alk-jlcampliors and alkylborneols increase in the sameyatio.Bemylcnvip7)oT.-Dry dextrocamphor (1 mol.) is heated with sodium henzyloxide(1 mol.), dissolved in excess of benzyl alcohol, a t 220-225" for 24liours. There is no disengagement of gas. L)ist,illation of the etherealextract at 220-225" (H = 70 mm.) yields SL s*yrupy, very I-efractivesubstance, which, a t first, has a slight empyreumatic odour, becomingsimilar to the odour of benzaldehyde on exposure to the air.Boilingalcoholic potash, glacial acetic acid, 01' hydrochloric acid does notattack t h i s substance. It ct-ystallises on cooling, after the addition ofa crystal of benzylcamphor, in small crystals which, when recrystal-lised from alcohol, yield fine, large crystals melting a t 51-52', solublei n alcohol, ether, benzene, and toluene, aiid insoluble in water and thealkalis. The formation of benzylca~nphor is accompanied by the pro-duction of an equivalent amount of sodium benzoate and the libera-tion of hydrogen, which, doubtless, acts on a part of the benzyl-camphor yielding reduction products which remain in the uncrystal-lisable oil.Benzylcamphor may also be obtained by the action of benzyl chlorideon sodiumcamphor when heated.l'he reaction is finished when aportion of the material, diluted with water, does not give an alkalinereaction. When distilled a t 110 mm. prcssiire, a mixture of camphorand oily products passes over below 'LOO' ; from 2L5-22Oo, benzyl-borneol passes over; whilst from 220--250", a fraction distils as at liick oil, crystallising on cooling. The crystals, purified by recrys-t:illisation from alcohol, correspond in properties with the benzyl-camphor prepared from sodium benzyloxide.Benzalcamphor also yields benzylcamphor on reduction with sodiumaiualgnm.Action of Sodium Benxytoxide .o n Dextrocarn.phor.aBenzylcamphoroxime, C,H,,< I is obtained by heating forCH*CH,Ph'two days benzylcnmphor, mixed with the theoretical amount of thedouble chloride of ziric and hjdroxylamine and a little alcohol. l'hepiboduct crystallises from alcohol in long, flat prkms melting at12';-128", soluble in ether, benzene, and light petroleum, insolublein alkalis. The oily liquid separated from the oxime solidifies intime ; it has not been examined, but is, doubtless, an isomeride.Lrlevobenzylcamphor may be prepared fi*om Iaxocawphor by themethods given above. The crystals melt a t 50-52". Benzplb, rneolsare formed, together with benzylcnmpbors, when t h e camphor iodidesare treated with benzpl chloride. They are separated from the benzyl-camphors with some dificulty, owing to the approximation of theboiling points. They are oily liquids, having the odour of bitteralmonds, and distillinq a t 215-216" under a pressure of 80 mm.The oily products obtained by treating camphor a t R high tempera-t u r e with sodium propoxide, butoxide, and amyloxide are held tocontain the propjl-, butyl-, and amyl-camphors.W. Ti 4 ABSTRACTS OF CEEJlICAL PAPERS.Action of Sodium Benzyloxide on Ethyl Camphocarboxyl-ate. By J. MINGU~N (Compt. rend., 112, 1454-1455).-20-30 C.C.of benzyl alcohol to which has been added 0.5 gram of sodium ishetited with 10 grams of ethyl camphocarboxylate a t 1.50" for24 hours. The resulting pasty mass yields an oil on treatment withwater. On evaporating the ethereal solution, the residne yielclsbcnzyl alcohol and a viscous liquid distilling a t 260-290" under10 mm.pressure. This is benzyZ hydroxlycamphocarboxylate,The yield is about 30 grams from 40 grams of ethyl camphocarh-oxylate. Hydrolysis with alcoholic potash in sealed tubes givesbenzyl alcohol and hydroxycamphocarbox3lic acid. Tbe rotatorypower in alcohol is [ a ] D = +35.5".The wash waters, on nentralisation with an acid, yield an oil whichdistils at, 250-275" a t a pressure of 10 mni. This acid is veryviscons a t the ordinary temperature, On hydrolysiy it gives benzj Zalcoliol and hydroxjcamphocarboxylic acid. It may be considered tobe beti zy 1 hydroxycnm ph ocarboxylic acid, C 0 OH.C,H,,.(=H,*COOC?H,.Its rotatory power in alcoholic solution is [aID = 52-62'.New Method for Determining the Constitution of Homo-logues of Pyrroline. By C.U. Z A N w r r (Gaxzerta, 21, ii, 25-32).-Cismician arid Zanetti (Abstr., 1890, 1155) showed that hydroxyl-amine reacts with members of the pyrroline series, yielding dioximes,which are oximes either of dikrtones or of ketoalclehydes, accordingt o the constitution of the pyrroline. By boiling the resnlting oxinlewith 30 per cent. potash, the author finds that the correspondingbibasic o r keto-acid is obtained. This reaction furnishes a means ofdetermining the constitutioii of the pyrrolino homologue employed.Hydroxj laniine and pyrroline react to form succindialdoxime ;when this is boiled with 30 per cent. caustic potash there is ariabuiiclant evolution of nmmonia, and succinic acid, amounting to70 per cent.by weight of the oxitne employed, may be extractedfromthe solution.2 : 4-lXmethylpyr~oline, on treatment with hydroxylamine, yieldsa-methjllevulindioxime, which, when boiled f o r 2+ hours with causticpotash, gives the /3-acetoisobutyric acid prepared by Bischoff (Abstr..1881, 4Lc)). The hydm,-.o?ie of this acid crystallises from alcoholin splendid, yellowish scales melting at 122O, with evolution of gas,to a yellow liquid ; it is solnble in glacial acetic acid, alcohol, ether,benzene, and ethyl acetate, sparingly so in cold dilute alcohol, aridirisoluble i n water or light petroleum. It dissolves in solutions oftlie alkaline carbonetes with effervescence, and is precipitated un-altered by acids.On exposnre to air wid light, i t is converted into aheavy, reddish. brown liquid. &thy 1 /3-acetoitsobutyrafe is obtained asa liquid of fruity odour. on passing dry hydrogen chloride through astrongly cooled sollition of the acid in absolute alcohol. I t s hydrazonr,which heparates from dilute alcohol in yellowish scales, riielts a t 105",arid is soluble in alcohol, ether, etlijl acetate, and acetic acid, spiir-ingly so it1 cold, dilute alcohol, ant1 insolnble iu water and alkaliueW. TOHQANlC CHEIJIETRY. 75cmbonntes.exposure to air and light.Methyldipyridyls. By A. HEUSER and C. STOEHR ( J . pr. Chem.[Z], 44, 404-410).--aa-Dimethyldipyridyl (Abstr., 1891, 80) isbetter isolated by extracting the base, which separates from theaqueous solution of the reaction mass, with ether, drying the ethercia1solution over pot,assium hydroxide, distilling off the ether, re-dissolv-in$ in absolute alcohol, and converting the base into hydrochlorideby a stream of dry hydrogen chloride.When aa-dimethj ldipyridj 1 is oxidised with permanganate, threeacids are obtained, namely, a-methyldipyridyl-a-carboxylic acid, di-pSridyl-aa-dicar~oxylic acid, and lutidinic acid, in the proportion of10, %, and 2 grams respectively, from 20 grams of the base.Five gramsof the base are introduced into a solution of 32 grams of potahsiumperniang:inate in 1200 grams of water, and the solution is kept a t40" for about 14 days. The manganese dioxide is then filtered off,the filtrate evapoiwated in a stream of carbonic anhydride, andiieutralised with nitric acid.By evaporation with alcohol, most ofthe potassium nitrate is separated, and the acids are then precipitatedwith silver nitrate; the silver salts are decomposed by hydrogensulphide, when a jellow precipitate separates as the hot filtrate coolr ;this contains the mono- and di-carboxylic acids, which can be separ-ated by the greater solubility of the former in hot water; tlrelutidinic acid is extracted from the filtrate from the yellow precipitateby evaporation with animonia and extraction with ether.a-Methy Idipyri yl-z-carboxylic acid has been already described(Abstr., 189L, $1). When heated with glaci~l acetic acid at 180",it, is converted i n b methyldipyridyl with evolution of carbonic:anhydrideD ~ ~ y r i t l y I-rxa-dicarboxylic acid, C,,,H,N,(C@OH), + H,O, crystallisesin colonrless needles, melts at 247*j", decomposes a t a slightly highertemperatnm, and dissolves sparingly in water and glacial acetic: acid.It is colourecl retidish-yellow by ferrous snlphate when in aqueoussolution, and violet when crystalline.The silver and bariuob saits wereobtained, and also an easily soluble plafirmhlorids. When this acid isheated with glacial acetic acid in a sealed tube at 180", it yields+/-/-dipyritiyl, which melt,s a t ~ l ~ - - I l ~ * (Weidel gives 114", Abstr.,18K3, 483) ; the ylcttiaoc,hlnride of this base was obtained, and it, isnoted t h a t potassium ferrocvanide gives a red-brown solution withthe base, from which tramparent, six-sided tables gradually separate(compare Abstr., 1891, SO).L?itidinic acid, C,H,N(COOH), + H,O [(COOH), = a : -11, c y s t n l -lises in aggregates of mlourless needles, melts a t 232-233" withrapid evolution of gas, and dissolves easily in hot water.Like the hydrazone of tlre free acid, it liquefies onW.J. P.A. G. B.Preparation of g- and p- Pyridyllactic Acid from a-Picoline.By A. EINHORY (Airden, 265, ZO8-23tS).-Pj-ridyl-w-trichloro-=r-hJdroxypropane (Abstr., 1887, 845) is best prepared by heating asolution of a-picoline (50 c.c.) and cliloral (45 c.c.) in amyi acetate(175 c.c.) for 10 t o 1 2 hours a t 140-1.50"; the product is extracteARSTRSCTS OF CHEMICAL PAPERS. n a4from the solution by shaking with dilute hydrochloric acid.Theyield of the hydroclrloride is a t least 125 grams from 100 g r a m sof picoline ; this salt crystallises from alcohol i n lotig, prismaticneedles, and melts at '201-202". The free base crystallises fromdilute alcohol in hexagonal plates melting at 86-87". The hydro-bromide, C8H9NOC13,HBr, forms well-defined crystals, and melts at20i-206".P!/ridyl-w-trirhZoro~~o~~Ze~~e, C5NH,*C H:CH*CCl,, can be obtainedby gradually aciding phosphorus pen tnchloride to a boiling mixtureo f py~~idyltrichloroliydroxypropane hydi-uchloride and chloroform, anddeconiposing the salt thus produced w i t h sodium carbonate ; i tcrystallises from alcohol in prismatic iiedlee, melts at 97", andpadually decom ~ O S W on keeping.a-PyTidylZaclic acid, C,NH,*C H,~CH(OHj*COOH, is formed whenNn aqueous solution of pyridy Itrichlorotiydrox-~ propane hydrochlorideis gradually added to boiling sodium carbonate, and the heating con-tinued until the reaction is a t an end ; it is isolated by means of itsbasic copper salt.It ct*ystallises from alcohol in transparent, seem-i n g l y iriotloclinic prisms, melts a t 124 -125", and is only sparinglysoluble in ethyl acetate, but more readily in cliloroform. The basiccoppier salt, ( CRH,N03)2Cu,Cu0. crystallises from hot water and am-monia in slender, green needles. The silver salt, CHHsNOJAg, crys-tallises from dilii te ammonia in colourless needles. The hydrochloride,C'8H9NC)3,HC1, separates from alcohol i n crystalline aggregates, andmelts a t 85-86'.The hydrobromide, CsHgNOJ, H Br, crystallises fromglacial acetic acid and alcohol in large, well-defined needles meltinga t 125-126". The ylatinochloi-id?, ( C6H9NO,),,H2PtCI6, is moderatelyeasil7 soluble, and inelta a t 202-204". The aiwocldoride forms com-))act, yellow prisms, and melts a t 177". When pyridyllnctic acid isheated at 130-140" under reduced pressure, i t is converted intopyridglacrylic acid with elimination of 1 mol. H20 ; on oxidation withexcess of very dilute potassiurn permanganate, it yields picolinic acid.BeiLzoyZ-31-pyI.idyZZactic acid, C:,NH[,.CH,*CH( OBz)*Ci>OH, is bestprepared by gradually adding bmzoic anhydride (4 grams) in smallportions a t a time to a solution of a-pyridyliactic acid (2 grams) inwater (4 grams), heated a t a temperature just below 90" ; it crystal-lises from hot water in lustrous needles, and melts at 145" withd ecom position. The platinochlr ir ide, (C ,5H ,,NO,) 2, H,PtC 16, crystal -lises from water or dilute alcohol i n yellow, transparent, prismaticneedles melting at 179" with decomposition.The barium salt is acoloiirless, crgstalline compound, readily soluble i n water and alcohol ;tlie silcsr salt crystallises in cdourless needles. The methyl salt, pre-pared by treating the silver salt with methjl iodide, is an oil, but itsp!atinoctiloride, ( C16H1,N0,),,H,PtC16, crystallises from hot water anddilnte alcohol in yellow needles melting a t 193" with decomposition.Methyl a-pyyidyliactate, C5NH,*C:H2*CH( 0 H)*COOMe, prepared bytreating a methyl alcoholic solution of the acid with hydrogen chloride,is a colourless, crystalline compound melting at about 34O ; its aura-chloride, C9HI1XO3,HAuCl4, separates from water in crystals, and meltsat about 119" ; its benzoyl derivative crystnllises in transparent needles,iiielts a t 41°, and is identical with the methjl benzoylpj ridyl-cc lactatOR OhNIC CHEJIISTRT.77just described (as an oil), as was proved by converting it into thecrystalline platinocliloride (m. p. 193-194").Pyridylacrylic acid, C5NH4-CH:CH*COOH (Zoc. cit.), is best prc-pared by adding pyridyltrichloropropane hydrochloride (60 grams),in Rmall portions (3 to 4 grains) a t a time, to a boiling solution ofpotassium hydroxide (132 prams) in alcohol (400 grams), air heiilgexcluded fts much as possible.After boiling for six hours, the filteredsolution is evaporated with hydrochloric acid, tho residue extractedwith alcohol, the extract decolorised with animal cbarcoal and con-centrated ; on cooling, pyridylacrjlic acid hydrochloride is depositedi n crystals, and the mother liquors contain pyridyllactic acid hydro-chloride, which can be isolated by means of its copper salt ; the yieltlof the former is 20 grams, and of the copper salt, 5 grams. Pyritlyl-acrylic acid crystallises from hoiling water in small, transparentneedles, melts at 202-203' with decomposition, and is almost in-eoluble in cold water, butl readily soluble in alcohol. The hydrochlor-ide crystallises from alcohol in colourless needles melting a t 220" withdecomposition.The hydrohromide, C8H,N02,HBr, forms spear-shapedcrystals, and melts a t 222-223". The aurocbloi-ids, C8H7N 02,HAuC11,crystallises from hot watey in small, light-yellow needles, and meltsa t 194-195". The plntinochloride, (C, H,NO2),,H,PtCl6, is moderatelyeasily soluble in water, from which it crystallises in reddish-yellowprisms melting a t 209-210". The barium salt and the salts of theaikalis do not crystnllise, but the cczlciiim salt, (C8H6N0,),Ca, separatesfrom dilute alcohol in slender needles ; the silver salt, C,H,NO,Ag,. isalso crystalline. Tbe methyl salt, prepared by treating the acid wlthhydrogen chloride in methyl alcoholic solution, is a solid, very hygro-scopic substance ; its hydrrch Zoride, CgH9NOz,HC1, sepiwates frommethyl alcohol in small, colourless crystals melting at 185-1 86".The Pthyl salt crystallises in lonp, transparent needles.The meth-iodid.-, C8HiN02,MeI, separates from dilute :tlcohol in amber-yellow,prismatic needles, and melts at 219-220" with decomposition. Themethobromide, C,H7N02,MeBr, separates from water in colourlesscrystals, melts at 242" with decomposition, and is almost insoluble inalcohol, and only sparingly soluble in glacial acetic acid.Yyricly Mibromoproioionic acid, C5NHEI*C HBr-CHBrGOOH, preparedby warming pyridglacrylic acid (1 part) with a glacial acetic acidsolution of bromine (1.3 parts), separates from water ill yellowishcrystals melting at 127", and from glacial acetic acid in grey crystals,which retain some of the solvent, and melt at 146.5".p- Pyricly 1 bromcpropionic acid lqdro byomide,C5NH,*C HBrC H,.CO 0 H, HBr,is formed when pyridylacrylic acid is heated a t 100" with a solutionof hydrogen bromide in glacial acetic acid, saturated a t 0" ; it crys-tallises i n colourlcss needles or plates, and melts a t 163-164".Pyridyler hylene is produced, together with pyridylacrylic acid andp-pyridyllactic acid, when an aqueous solution of the preceding corn-pound is warmcd with a slight excess of sodium carbonate; it isa colourless oil, boils a t 159-160" with partial decomposition, andis identical wi t,h Lad enburg's viny Ipyridine.The platinochloride78 ARSTRACTS OF CHEllICAL PAPERS.(C,H,N),,H2PtCl,, separates from W R ter in crvstals, and melts at 174"with decomnosit,ion.The nwrochloride, C,H,N, A.uC13, crystallises inyellow needles, and melts at 244".fl-.PyridyZZnctic u.cid, C,NH,.CH(OH).CH,.COOH, is isolated fromthe red solut.ion which remains after distilling the pyridylethjlcnewith steam, by first acidifyinr wit,h dilute hvdrochloric acid to pre-cipitate the pyridylacrylic acid, and thon adding an ammoniacal solu-tion of conper sulphate to the filtrate ; after a time, the bwic coppersalt, (CRH,N0,),Cu.CnO, is deposited i n blue crpstals. and can bepurified by recrystallisation from dilute ammonia. Thp free acid is acrystalline compound meltinq at 86". The hy&ocl/~loride, CsHnNO3,HC1,crpstnllises from alcnhol in colourless prisms, and melts a t 147".ThepZat;nochloride, ( C,E,NO:,),,H2PtC16. separates from dilute alcohol insmall, yellow crvstals meltin,q a t 191". The methyl salt, prepared bytreating a methyl alcoholic solution of the acid with hydrogenchloride, is a light. yellow oil ; its pZntinochZoridz, (C,KllNO3),,H2PtC1,,crystallises from dilute alcohol in lustrous, yellow plates, and meltsa t 178.5". The ethyl salt is also a pale-,vellow oil, but its hydro-chloride crvstallises from alcnholic ether in lustrous plates.Renzo?lZ-~-p~ridyZlacfl:c acid. C ,,H13NOC, is formed when ethyl B-pvridyllactate is warmed with benzoic chloride on the water-bath ;the benzoic acid is separated in the nsual wa.7, the product theti dis-solved in hydrochloric acid.the solution kept for some days, and thecrvAt8alline hydrochloride thus obtained decomposed with water : thefree a,cid crystallives from hot water in lustrous prisms, and melts a t135.5". The silver salt is a colonrless, crystlalline compound. ThemethyZ salt, C,,H,,NO,. prepared from the silver salt, crystallises intrmsparent prisms, and melts a t 79".The relationship between some of the compounds described zboveand certain derivatives of coca'ine is shown with the aid of graphicformulae. F. S. K.Synthesis of Quinoline Derivatives by means of Alkyl Aceto-acetates. By M. CONRAD and L. LIMPACH (Ber., 24, 2990-2992).--An extension of the method previously described by the authors(Abstr., 1888, 593) to the synthesis of other quinoline derivatives.Methyl phenylamidomethylcrotonate is obtained by mixing methylmethylacetoacetate and aniline in equivalent proportions, and allowingthe mixhure to remain for some days, or by dissolving methyl phenyl-amidocrotonate in benzene, and treating it first with sodium and thenwit.h mc thy1 iodide.nim,efhyZhydro~~yquinoZine, C9NHiMe2*OH [Me2 : OH = 2' : 3' : 4'1,is obtained by quickly heating methyl phenylamidomethylcrotonate(30 grams) to 240°, withdrawing the source of heat as soon as thetemperature reaches 260", dissolving in dilute hydrochloric acid,treating the solution with animal charcoal, and rendering it faintlydkaline with ammonia or soda, when it separates as a white, crystal-line mass ; the yield is 10 grams.It crystallines from boiling waterin lustrons prisms containing 1 mol.H20, sublimes at 300", meltsabove 305", and is only sliglitly soluble in alcohol ; it has not a bittetaLste. The platinorh7oride, (C,,H~lNO)21)-12PtC16 + 2H,O, forms long,orange-yellow needles.Methylethylhyclroxyquil70;ine, C,NH4'iLIeEt.0H, is prod {iced in xsiniilar manner to the dimethyl derivative, 1)y lieatinq uicithyl phenyl-smidoethylcrotonate ; it melts a t 290", and is only sparingly solublei n boiling water and alcohol. A. R. L.Action of Hydroxvlamine on Ketonic Nitriles. By HANRIOT(null. 15'oc. C71im. [ 3 ] , 5, 773-779).-When ethyl sc-cynnet.hy1 ketone,COEt-CHMe.CN (Abst'r., 1889, 841) (100 grams) is dissolved in con-centrated potash (200 c.c.), a potassium compound is formed, whichmay be crystnllised in brilliant, plates ; but if the solution is heatedon the water-bath for half an hour with a solution of hvdroxvlaminehydrochloride (100 grams) in the minimum quantity of baterr amido-?net lay 1 e t h y lisox az o 1 e , >0, separates as an oily liquid,FMe:C( NH?)CEt=Nwhich, on purification, becomes crystalline.It forms highly refrac-t i v e prisms, melts a t 44", and boils a t 180' under a pwssure of20 nlm. ; a t a higher temperature, it changes into an isonieric sub-stance melting at 280". It is soluble in the usual menstrua, with theexception of petroleum, and is not affected by alkalis. The hydro-chloride, CsH,,N,O,HC1, crystallises i n long needles, and is soluble inwater and alcohol, but insoluble in ethw.The acefyl derivative,C,H,N20Ac, crystallises in colourless plates, melts a t 16L", and isSOl-able in alcohol and acetone, sparingly soluble in water, and in-soluble in ether.When an et)hereal solution of the isoxazole is saturated withbromine, a yellow, viscous mass is obtained, which is decomposed bywater into ammonium chloride and rnethyZethylbromazolone,YMeBt-COCEt E N > 0 ,a crystRlline substance which melts a t 41", and dissolves in the usualmprtstrua. If, however, the bromination is effected in chloroformsolution, a substance melting a t 92" is obtained.When t,he isoxazole is oxidised with nitrous acid (sodium nitriteand hydrochloric acid), yellow crystals of the corresponiiing azoxy-compound are obtained. Azoxyrnet hyleth ylisoxneole,melts at 65-66", and explodes at a somewhat higher temperature.Itis soluble in al(:ohol, ether, and alkalis ; the alkaline solution is red,and is decolorised by acids, the compound being reprecipitated. Itdoes not unite with bromine.When hydrogen sulphide is passed through an ammoniacal alcoholicsolution of the azoxg-compound, the colour disappears, and on eva-poration crystal B of h!ldrazornet?L y 1 eth y 1 isoxy azoleFO ABSTRACTS OF CHRJIICAL PAPERS.are deposited. When pure, it foi*ms felted needles, melts a t 150", anddissolves in the usual menstrua. It is easily oxidised to the aizoxy-compound, and f o r m an oily compound with bromine.When ethyl a-cyanisopropyl ketone, COKt.CMe,*CN (Zoc. cit.),IS treated with hydroxylaniine hydrochloride, the ring conderisatioiican no longer take place, as tho hydrogen previously available forthat purpose is replaced hy metliyl.Consrquciltly, ethyl a-cyan-isopropyl hetoxiwe, OH*S :C Et*CMe,.CN, is obtained, instead of anisoxazole. I t crystallises it1 plates, melts a t 61-62', and is soluble in theusual menstrua with tlie exception of petroleum. It differs from thei,soxazole in t h a t it forms a cryshallhe potassium derivative whentreated with potash, that it does not unite with bromine, and that it isnot oxidised with nitrous acid. JN. W.Methylphenyldihydroquinazoline and its Derivatives. ByC. PAAL Nncl P. KKECKE (Ber., 24, 3049-3058; compare Absti..,1890, 144:3).-After orthoniti.obenzylacetanilide,has been reduced with tin and hydrochloric acid, and the stanno-chloride of methylphenyldihydroquinazoline, c61i4< hasbeen removed by crystallisation, there remains in the mother liquor avarying qnantity, never exceeding one-third of the theoretical, ofo rthamido benz?jlacetanilide, N H2* C6H ,*NP h Ac.This subs tan ce is . notforn~ed when the reduction is carried out with zinc-dust and aceticacid. It can be obtained from the mother liquor by removing the tinwith sulphuret ted hydrogen, and extracting the filtered solution withether, after previously making i t alkaline. It crystallises fronlalcohol or water in Iustroiis, white prisms melting at, 126-127", anddissolving easily in alcohol, benzene, carbon bisulphide, ethyl acetate,and glacqial acetic acid, moderately in ether, arid sparingly in IigIitpetroleum and hot water.When oxidised with alkaline permangall-ate at loo", it yields, besides a small quantity of azobenzene, a, sub-stance of undetermined constitution which crystallises irom water illbvoad, yellowish needles melting at 178", and from ethyl acetate incrossed crystals ; this dissolves sparingly in benzene, easily in alcohol,ethyl acetate, glacial acetic acid, concentrated hydrochloric acid,alk;jlis, and alkaline carbonates.Ort hanaido benzy Zacetan ilide hy drnchlcrid e, c 1,H,6'N,0, H C1, is bcs tobtained by adding a little concentrated sulphuric acid and ethcr toiin alcoholic solution of the base. It crystallises in white needles,melts at 170", and is readily soluble in water and alcohol.The,~tannochluride, C15H,6N20,HSnC13. does not crystallise readily; it meltsbetween 110-115", and dissolves easily in water and alcohol. Theacid subhate, C,5H16E20,H,SO*, crgstallises in stellate groups ofcolourless needles, which become green on the surface when kept,melts at 163", and dissolves readily in water. The oxalate and thepicrate are both easily solnble in water and alcohol.When the base is boiled for a short time with excess of aceticanhydride, arid the product treated with a dilute solution of sodiumNO,*C~H~*CH~*NP~AC (1 : 2),N= ?MeCH,*NP hOHQANIC OHEMISTRY. 81cerbonate, orthmetnrnidobenrylacetanilide, NHAc*C,H,NPhAc, sepa-rates. It crystallises from alcohol in four-sided plates, melts at 1 2 1 O ,and dissolves readily in most organic solvents and in dilute mineralacids, but very sparingly in w;i ter.Met h y l p hen y I d i hydro g n i v ~ azoline, pre v io us1 y obtained by red 11 cingorthonitrobenzylacetanilide with tin and hydrochloric acid, is betterobtained by using zinc-dust and acetic acid, the solution being keptcool.The solntion is then filtered from excess of zinc, and treatedwith excess of soda ; the base is extracted wihh ether, and convertedinto the sparingly soluble hydrochloride, which is purified by crystal-Iisation from water. It may also be obtained by distillinq orth-amidobenzylacetanilide, which loses water and gives almost a quanti-tative yield of methylphenyldihydroquinazoline. The arid sulphateC,,H,,N,,H,SO, + H,O, obtained by adding sulphuric acid in slightexcess and then some ether to an alcoholic solution of the base,crvqtallises from water in colourless, interwoven needles.It melts a t78" ; when anhydrous, at 201". When methylphenyldihydroquin-azolitie is oxidised with alkaline permanganate, the filtered solutioncontains pI~eny1l;etodihycEropuinazolinecurboaylic acid,This can be seprlrated as a crystalline precipitate by adding hydro-chloric acid to the solution ; when fresh, i t is soluble in hydrochloricacid, alkalis, and alkaline carbonates, but it readily loses carbonicN:CHanhydride, yielding phenyll;etodih2ld?.opui?zaxoline, C6&<C0.&ph.The manganese precipitate contains rnetiLylphe.rLylTcstodihydropuin-azoline, C6H,< which may be extracted with alcohol; it crys-tallises from that, solvent in long, yellowish prisms, melts at 143", anddissolves readily in ether, alcohol, benzene, and light petroleum, ye1-ysparingly in hot water.The hydyochlorids forms bunches of whiteneedles, melts a t a, very high temperature, and dissociates in water., was obt,ainedby reducing a hot concentrated alcoholic solution of the dihydlmo-compound with sodium in large excess, and then diluting the mixturewith water. It crystallises from dilute alcohol in broad ncedlep,melts a t 94-95", and dissolves easily in most organic solvents and i nmineral acids, but not in water. The hjdrochloride and oxalate wereN C;MeC 0 -N P h 'NH-YHMeMet hy lp hen y 7 tet rahy dropuinazoline, CGH, < CH,*NPhprepared.NAc-Y HMephenyltetrahydroquii~azoline, C6H4<CH,.NPh ,When heated with acetic anhydride, it yields acetylnzethyl-which crystallisesfrom dilute alcohol in colourless, rhbmlboidal plates, melts a t 120.5",and dissolves readily in the usual organic solvents. C. F. B.Action of Hydriodic Acid on Quinine. Isoquinine. By E.LIPPMANN and F. PLEISSNER (Monatsh., 12, 327-337 ; compare Zorn,9 VOL. LXII82 ABSTRACTS OF CHEMICAL PAPERS.Amden, 8, 201; Skraup, ,T. pr. ChPm. [a], 8: and Comstock andKoenigs, Abstr., 1887, 1122, and 1888, 7 1) .-Hydyiodoquiiiinc hydr-iodide, HZC2,,HzrN2O2,2H1, is obtained a s a heavy, yellow, crystallinepowder on warming quinine with hydriotlic acid of sp. gr. 1.7--.7 -8.T t is sparingly soluble in cold water; dissolves in hot water withpartial decomposition ; crystallises from hot alcohol in bright-yellowprisms, melts at 2 15-2SO" with decomposition, and, on treatmelitwith dilute ammonia, gives the compound hydyiodnquitrine,C,,H2,N,Oz,HI.This snbstance crystallises in slender needles, softens a t 95' andcommences to melt a t a higher temperature : gives silver iodide onheating with silver nitrate solution ; is insoliible in wntm, dissolves inalcohol and in ether, and forms solulile salts with acids.ffydy;ndo-quinine platinochloride, HI,C2,H2,N,0,,HzPt C1, + 2H20, is nb+aiiiedas a light-brown, crystalline precipitate on adding platinum chlorideto a cold solution of hydriodoquinine hjdrioilide in hydi*ochloricacid.Hydrindo-upoqitinine is prepared hy heating liydriodoqninine hydr-iodide with a solution of hydriorlic acid, saturated at, 0" for severalhours under pressure ?t 100".Methyl iodide is evolved, and, oncnoling, the new compound, HIC1YH22N202rZH'I, separates as a yellow,crystalline mass, which, after recrystallisation from alcohol, com-mences to darken in colour a t 120", and melts with decomposition at237". On the addition of ammonia, 2 mols. of hydriodic acid meremoved with formation of hydriodo-apoqninine, of which the platino-chloride, C19H22N20,,H1 ,H,PtC16 + H20, is a heavy, brown, crjsfallinepowder.Iso-upoquinine, C1RHZ2N202, is formed on warming hydriodo-apo-quinine in alcoholic solution with potash. It melts at 176" (Hessestates that the compound decomposes at lSOo), and dissolves readilyi n dilute potash ; the plafinochloride, C,,H?2N2c~2,H2PtC& + H20, isa crystalline powder, only sparingly soluble in water.Isoqitinine.--This base is obtained when hpdriodoqninine is boilcdwith alcoholic potash.After repeated crystallisations from ether anddilute alcohol, i t melts a t 186" (uncorr.). Hesse and Lenz have giventhe melting point as 174.4-175' and 170*4-174*4" respectively.The base is levorotatory, [aID = -186.75" being the rotation of analcoholic solution containing 0.9644 gram in 100 c c . , and [aIn =-1180.8" for a solution containing 3.9936 grams i n 100 C.C. Jso-quiiiine crystallises in small needles containing 2 mols. H,O ; thesulphacte, [C2,,H24N202]2,H2S04 + 10H20, forms characteristic groupsof slender needles readily soluble in water, giving a ready means of dis-tinguishing between the base and quinine.The no?-mal hydrochloride,CdLNzOZ,BC1 + 2H20, crystallises in needles, and is readily solublein water ; the acid hydi*uchZoride, C2nH20NzOz,2HC1, is not so easilysoluble ; the platinochloride may be obtained as a crystalline, yellowprscipitate ; and the compound with silver nitrate, C2,1H24KZ02,AgN03,precipitated a s a gelatinous mass on addiilg an alcoholic solutionof the ba,ge to a solution of silver nitrate. G. T. 31ORQANIC CHEMISTRY. 83Compounds of the Cinchona Alkalo'ids with Hydriodic Acid.Ry Z. H. SKRAUP (Moiiatslt , 12, 431-434) -Quinine, quiaidine,einchonidine, and cinchonine are all dissolved slowly by cold, andmore quickly by warm, hydriodic acid, with the formation of yellowor orange-red coloured compounds, which contain 1 mol.of the base to:$ mols. of the acid ; the quinine and yuinidine solutions, if kept, furtrherexchange methyl for hpdrogen, giving compounds of the formula,C19H,,N,0,(HI),, which are readily solub!e in caustic potash. Alithese substances crystallise well ; they are alrllost insoluble in water,slightly soluble in absolute alcohol, and dissolve to) a moderateextent in dilute alcohol, from which, with care, they may be recrys-tallised (compare Lippmann and Fleissnnr, preceding abstract), Thecompounds from isomeric alkaloids differ in appearance, solubility,and melting point, and are analogous in comlposition to the corre-s pondiiig compounds with hydrochloric and hgd robromic acids (com-p r e Comstock and Koenigs, Abstr., 1887, 11122 ;.and Zorn, AniiaEen,When the compounds CzoHziN20a,3 H I and C,,H,N,O,S HI whichare fortned from quinine and cinchonidine respectively, are gent'lywarmed with caustic alkalis, they lose 2 mols. of hydrogen iodide,and furnish the compounds C?,H,NzOzI and CigHJTZOI respec*-tively. These are analogous in composition to the couipounds withhydrochloric acid, which are obtained in a similar way (Corn-stock and Koenivs, Znc. cit.). The compounds C20H2,NzOz.SHIand C19H,N,0,3HI. formed from quinidine and cinchonine respec-tively, lose only 1 niol. of hydrogen iodide when treated with excess ofalkali, the bases Cz,, B26N202T2 and C1, H2AN2012, respectively, beingproduced.The mono- and di-iodine compounds are almost colonrlesF.and must not be regarded as periodid-s, the hydrogen iodide evidentlybeing held within the molecule. The compounds of the formulnC,9Hz2Nz02,3HI, obtained from quiuine and quinidiue, and which aresoluble in potash, behave in a preciselysimilar way when treated withalkalis, the compound from the former bme losing 2 mols. of hydriod cacid, whilst tliat from the latter loses only I mol. This differentliehaviour of the products of the action of hydriodic acid with potashforms a convenient means of distinguishing betweeri the isomericcinchona alkaloi'ds ; and it is also remarkable t liat those alkaloidswhich are decomposed in the same way hiive a similar effect on cir-cularly polarised light.Attempts to displace the iodine of the mono- and di-iodine com-pounds with alkyl groups or other radicles by heatiiig with sodiumt thoxide, potash, silver nitraite, &c., invariably led to the eliminationof hydrogen iodide.The base C ,9Hz~Nz012, obtained from cinchonine,Iiomever, gave, with sodium etlzoxide, in addition t o cinchonine, asmall quantity of a base which was readily soluble i n ether, refused tocrystallise, and was probably isocinchoninc. The quinidine compoundC20H26NZ0212, on similar treatment? did not give the original base, but,an isomeride, which is only slightly soluble, and gives salts whichcrystallise badly. The isomeric quinine compound behaves in anaudogous way, biit also gives some quinine; whilst the quinine8,20)84 ABSTRACTS OF CHEMICAL PAPERS.compound that is soluble in potash does not give rise to cuprejine,but forms an isomeride.The compounds with hydriodic acid are easily reduced with zinc-dust, and the products appear to be different from those obtained by thereduction of the cinchona alkaloids.They are semi-liquid, volatile insteam, and very rich in hydrogen.Quinoliiie, paramethoxyquinoline, chit enine, and cinchotenine do notcombine with hydriodic acid. The author therefore supposes that itis the C,H,J'TO porticn of the quinine molecule that attaches thebydriodic acid, but cannot explain the absorption of 2 rnols. of hydro-gen iodide, as, even if the oxygen were originally held to a carbonatom by a double bond, only one of the two molecules is accountedfor To explain the addition bg assuming a molecular ~earmngernentof the qainoline nucleus is unsatisfactory, as the hydriodic acid istaken y~p G t ordinary temperatnres.Full particulars of the compounds of the cinchonla alkalo'ids withhjdriodic acid will be giveu in a future paper.A new Alkaloi'd from Chrysanthemum Fbwers. By F.MARINO Zuco (Gazzetta, 21, 516--554).--'l'kie author has previouslyextracted from chi*ysanthemum flowers a new cholesterol (Abstr.,1890, 757), a glucoside, arid an aikalo'id (fiend.Acad. Lincei, 6, ii, 572 ;7, i, 121). The latter is prepared in quantity by boiling about10 kilos. of the flowers in distilled water (:3 parts) for 2 or 3 hours,filtering through cloth, pressing the residue, and trpatihg it again inthe same msnuer.The extracts are evaporated down to 30 litres,treated with.neutra1 lead acetate and basic acetate of lend, nentralisedwith soda, filtered, and the excess of lead removed'by passing sulphur-etted hydrogen. After filtration, the liquid is concentrated to about2 litres, boiled for some t'me with dillate sulphnric acid, filtered, andagain boiled until no more resinous matters are formed. The liquid isthen decdlorised withanimal black and an excesq of the double iodideof potassium and bismuth added, when a heavy, bright-red, crystallinepowder containing the whole of the alkaloi'd is deposited.The pure alkalo'id chrysmtthemine, C,*HnaN2Oj, is a colourless syrupwhich, when kept in a vacuum, partially crystalhes 'in tufts of silkyneedles, and may be heated without decomposition to 1 0 0 " ~ but notbeyond that temperature.It dissolves i n water forming alkaline solu-tions whichabsorb cal-bonic anhydride from the air ; it is also soluble inethyl and methyl alf,ohuls, b u t not in ether, chloroform, or benzene.Salts of chrysantheinine yield, wlth the double iodide of potassiumand bismuth, orange-red, flocculent precipitates which become crystal-line and bright-red on agitation ; with the double iodide oi' mercuryand potassium, a yellowish-white precipitate ; with the iodide ofplatinum and sodium,#& brown precipitate ; with auric trichloride, ayellow, crystalline precipitate which dissolves 011 heating and is re-deposited on cooling ; no pi-ecipitate is formed with platinic chloride,picric acid, tannin, or mercuiic chloride. The base is optically in-active and physiologically innocuous. Its salts are for the most partsoluble i n water and even deliquescent; the aurochloride and thedouble iodide of bismuth and chrysanthemine are insoluble, It is ilG. T. MORGAKIC CHEMISTRY. 85biacid base, but in dilute solutions it behaves towards acids as if i twere monacid. Both the hydrochlorides crjst:illise in small, colour-less, deliquescent needles, very readily soluble in water and alcohol,but only moderately in hot water. The azwochloride,crjstallises in minute, golden-yellow prisms T pry readiIy soluble inhot water and in absolute alcohol ; M hen pure, it is not much affectedby light. The platinochloride, Claf€?aN,03,HtPtC16, crystallises inorange-coloured prisms, and is extremely soluble i n water.On heating chrysiinthemine with an excess of methyl iodide for twodays a t 100". trio mcxtliyl groups are taken: up. and it is partly con-verted into a new base in which both nitrogen atoms are combinedwith hydrogen. The two baseq can be separated by taking advantage ofthe great difference in the solubility of their platinochlorides inwater. l h e pZutinochZol-ide o€ the new base, C16H,,N20,,H2P tCl,,crystallises in small, orange-coloured needles, dissolves very sparinglyin water, but moderately in hot water slightly acidified with hydro-chloric atilt ; i t is insolnble in absolute alcohol. The hydrochloride isa deliquescent compound which crystallises in a vacuum in tufts ofsmall needles. It is freely soluble in water and in hot absolutealcohol. The free base is a syrupy liquid which becomes partiallycrystalline after being kept for a long tinie in a vacuum.Oxychrysanthcmine, C1J32fiN201, prepared by oxidising chrysanth-emine with sodinm hypobromite, yields a doiible iodide with bismuth,crjsta11is;ng in orange-colourcd needles readily soluble in hot water.The alkaloid is a syrupy liquid which, if kept in a vacuum, isslowly con\-erted into a very deliquescent, crystalline mass. It hasan acid rcnction, but combines with both acids and alkalis. It formstwo hydrochlorides : the dihydrorhloyide is a deliquescent, crystallinemass very soluble in absolute alcohol ; the ?,ro,iuhydl.ochlorid~, is ;Icolourless, crystalline mass composed of very slender, brilliant needle-,very soloble in tiater, but only spmingly in absolute alcohol. Theaul-ochlwide, C,,H2,N20,Au,CI,, crptallises in brilliant, golden-yellow,Iiexagonal laminae freely soluble in hot water. Chrysantheminestrongly resists the 'action of oxidising agents ; on heating a sutph-uric acid solution of the base with potassium dichromate andsulphuric acid, it is almost quantitatively converted into oxychrys-antheinine ; a solution of potassiurri permanganate, on the other hand,only part idly converts i t into oxyclirysanthemine, carbonic anhydride,ammonia, and traces of trimethy lamine being evolved, whilst a portionof the base is conipletely broLen up. Oxychrysanthemine is completelydisintegrated by a hot solution of potassium permanganate. Dilutesolutions of alkalis have no action on chrysantheniine even after pro-longed boiling : very concentrated solutlions decompose it into tri-methylamiue, y-hydroxybutyric acid, and hexahydropiperidinecarb-oxylic acid with evolution of hydrogen according to the equationK2C03 + 4H2. The hexahydropiperidinecarboxylic acid obtained in thisway yields a very stable aurochloride, crystallising in golden-yellowscales very soluble i n hot water, but only very sparingly in cold, hiC1,H,,N2O, + 4KOH + HZO = C6H,,NO2K + (>~HTO~K + NMea 86 ABSTRACTS OF CHEMICAL PAPERS.melts at 150-1.51" without decomposition. The hydrochZo?.ide crystal-lises in plates, and melts a t 184-185". The acid corresponds, there-fore, neither with Ost's pipecolinic acid (Abstr., 1883, 791) nor withLadenburg's nipecotitiic acid (Abstr., 1891, 735) but is probably ar,-pjperidinecarboxy lic acid (hexahydroisonicothic acid). If chrysan th-cmine is tzeatcd with a- moderately concentrated solution o€ potash,the decomposition takes place more slowly and a small quantity of aproduct intermediate between chrysanthcmine and hexahydropyr-idinecarboxylic acid is obtained. This cornpound yields an a~~7-9-chloride, CllH,I0.,NAuC13, crjstallising in tufts of reddish-yellowneedles. Oxychrysanthcmine is deco I t 1 posed by very Concentratedsolutions of potash into EvexFthydroppridinecarboxylic and snccinic:acids, carbonic anhydride, trimethylatnine, and hydrogen. Fuminghjdrochloric acid has no action on chrysanthemine even after pro-longed heating ; concentrated sulphui.ic acid merely resinities a verysmall proportion on boiling. A glac'al acetic acid solution ofchrpanthemine (1 mol.) dissolves iodine (10 atoms), and on distillingoff the solvelit in a vacuum, a brown oil is lefb which does not loseiodine on heating a t 150". Chrysanthemine may be boiled with waterfor days wiihoiit change; if, however, a solution of the base i n anequal weight of water is fract,ionally distilled, water alone passes overuntil the temperature exceeds 150" ; trimethylnmine then begins tocome off, and continucs to do so until the temperature reaches ZOO",when an oily product accornpanies it. If the apparatus is nowexhausted, the residue distils over between 200" arid 230", the dis-tillate consisting of a mixture of aqneous solntions of hexahydro-pyridinecarboxy lic acid , amyl glycol, dihpdroxyarnylpiperidin e, tri-methylamine, and traces of pyridine bases. The amyl glycol isseparated from the mixture in the form of benrocr.te, C,Hl,(OBz),, acolourless, crystalline powder melting a t 40" ; the hexahydropJ-ridine-carboxylic acid is then removed a s aurochloride, and the residue cou-tains dihydroxyum ylpiperidine auroclzloi*ide, CloH,,O2NAuCl3, a yellow,crystalline salt which 1-eadily loses a molecule of hydrogen chloi*ideand decomposes at 100".From a consideration of all the above reactions, the author arrivesa t the conclusion that the structure of chrysanthemine is best re-presented by the formularMe,*CH,*y A1 e.CH,-C HI,.OH0- CO -CSNHg8. B. A. A.A new AIbumin from Protoplasm. By W. DEMME (Cltem.Cen.fr., 1891, ii, 257 ; from Centr. med. Wiss., 1891, 483).-Cyto3Eobii,,obtained from the lymphatics, liver, spleen, &c., by pressing, extract-ing the deposit with alcohol, dissolving the residue in water, andreprecipita ting with absolute alcohol, is readily soluble in water, isreprecipitated without coagulation from this solution by absolutealcohol, and may be again dissolved in water. I t decomposeshydrogen peroxide. Addition of a mineral acid to the nqueous soln-tion converts it into a n albuniin, prceglobulin, which is insoluble inwater, and into a substance soluble in water. ; the same change beingeffected by ljeatiilg to boiling. Cytoglohili and prceglobulin are buPHYSIOLOGICAL CHE3fISTRT. 87little soluble in the gastzic juice, and still less so i n the pancreaticjuice. Cytoglobiri contains : carbon, 52.4 ; hydrogen, 6.9 ; nitrogen,16.7 ; sulphur, 3.5 ; and phosphorus, 4.5 per cent. ; preeglobulin :carbon, 51.4 ; hydrogen, 7.6 ; nitrogen, 23.9 ; sulphur, 3.4 ; phos-phorus, 3.7 per cent. J. W. L

ISSN:0368-1769    

DOI:10.1039/CA8926200025

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

PHYSIOLOGICAL CHE3fISTRT. P h y s i o l o g i c a l C h e m i s t ry. 87 Influence of Wine on Peptic Digestion. By L. HUGOTJNENQ (Bull. 8oc. (?him. [3], 5, 849--855).--Fibrin was digested with dilute hydrochloric acid in the presence of various colouring matters and wines. It was found that peptic digestion is considerably hindered by colouring matters, whether occurring naturally in the wine, or added fraudulently, and in the latter case, whether artificial, such as magenta, azotlavine, and methylene blue, or natural, such as the colouring matters of elder and mallow. Plastered wine was found to exercise a less injurious iufluenoe than wine containing the f u l l aniount of tartrates. JN. W. Coagulation of the Blood. By C. A. PEKELHARING (Virchow’s Festschrift, 1891, Bd.l).-Recently, a number of observations on the importance of calcium salts in the process of blood coagulation have been published. Rriicke first showed that the ash of fibrin always contains calcium. In 1875, Haammarsten found that calcium chloride can take the place of seruiii globulin in tibriu formation. I n 1887, Green (Abstr., 1888, 306) found that in magnesium sulphate plasma, and also in other forms of plasma, coagulation is hastened if small quantities of calcium sulphate is added iu addition to fibrin ferment. Later, Ringer and Sainsbury (Abstr., 1890, 1176) found that t,his result can be brought about by other calcium salts, such as the chloride, and also, but not so vxdily, by means of soluble strontium and barium salts. Freund ( M d . ,Jahrb., 1888, 259) who also noted the hastening of coagulation by calcium salts, considered that the blood corpuscles, as soon as the blood is shed, yield alkaline phosphates t9 the plasma ; meeting with the calcium salts there, tricalciurn phosphate is precipitated, and herein lies the cause of fibrin formation.Latschenberger (Meed. Jnhrb., 1888, 479), and voii St.rauch (Ilissert. Dorpat, 1889) showed certain fallacies in this hypothesis; tlius the addition of alkaline phosphates and calcium salts resulting in the precipitation of tri- oalciuui phosphate does not always lead to the formation of fibrin in filwinogenous liquids ; also the fii+t portions of fibrin formed were found to contain calcium, but no phosphoric acid, and further, in the piaesent research, it is shown t h a t injection of disodium phosphate into the circulation of a liviilg animal is not followed by thrombosis.Arthus and Pages (Arch. de Pliysiol., 1890, No. 4) found that blood coagulation may be entirely prevented i f , immediately on being shed, the blood is mixed with small quantities of subdauces, like oxalates88 ABSTHACTS OF CHEMICAL PAPERS. or flnorides, which precipitate calcium salts as very insoluble com- pounds. On adding to the plasma obtained from this blood a slight excess of calcium chloride, coagulation immediately ensues. Fibrin ferment is, however, essential for the process ; and the action of this agent is considered to be t h e bringing together of fibrinogen and the calcium compound, and thus t h e formation of fibrin. It1 this, they draw a close analogy between fibrin formation and the formation of casein in milk under the influence of t h e rennet ferment.Green attempted to answer t h e question, Does t h e fibrin ferment exist as zymogen in the plasma, arid is such zjmogen converted into the ferment by t.he action of t h e calcium salt ? H e was unable to find a, positive answer ; and thvrefore considered t h a t the calciiim acts in assisting the ferment much as hydrochloric acid in tlit! gastric juice favours the activity of pepsin. This question is again taken lip i n t h e present investigation, and i t was found possible to prepare from plasnia (such as oxalate plasma which contains no ferment) a globulin which has no fibrinoplastic properties, which, however, after contact with calcium chloride, is converted into the ferment,.The zymogen yields an ash contairiiiig little or no calcium, whilst the ferment is rich i n calcium. The material in question arises from t,he formed elements of the blood, and is identical with what is called cell- globulin by Halliburton (Abstr., 1888, 574). Fibrin, moreover, is a calcium compound, and the main a.ction of t h e ferment appears t o be t o transfer the calcium to the fibrinogen. Granting this hypothesis, i t is possible to explain several facts hitherto but little understood in connection with blood coagulation, and to reconcile certain conflicting theo~ies. The action of oxalates in hindering coagulation is explained on the supposition that tlie pre- cipitate of calcium oxalate, on account. of its insolubility, is not avail- able for the conversion of zymogcri into ferment.The action of neutral sa1t.s in restniinitig clotting is explained o n t h e assumption that the ferment is a globulin, and, although the amouut of salt added is not sufficient to precigitate the globulin, yet i t is sufficient. t o lessen those intramolecular r lovements which, i n the end, produce its specific action. The acriop of peptone in hindering coagulation can be explained by t h e affinity betwcen peptone and calciiim couipoulids. It thus pre- vents ttieae from coiivertiiig ',he zyniogeri into ttie fwrnent. This view is suppo~ted b j the fact, thitt other substances, like soaps, which combine with calcium compounds, produce similar symptoms to those set up by yeptoiie (MuII~).Thus, there is loss of coagulability of the blood, low blood pressu :e, suppression of secretions, and wen death. The toxic eflecis app,:ar to tx due to the removal of calcium gaits, which are necessaty, H S Ringer has shown, for all vital processes. A further support to the theory IS obtained from ttie fact t h a t injec- tion into the circulatioir of c:alcicm chloi-ide simultaneonslg with the peptone, or after the peptone, (~L\iates tlle poisolions eflects of the latter ; peptone is then 11o Jonge'r capable of rendering t h e blood un- coagulable. Peptone alsc i*estrairis coagulittion in intrsvascular plasma (or solutions of Ha?nmarsten's filwinogeri), provided t h a t it is added so rapidly that tlie zj-niogeii has not had time to combine withPHYSIOLOGICAL CHEMISTRY.89 the calcium to form the ferment. After the ferment has been once formed in the plasma, or added to the solution of fibrinogen, peptone has no longer any hindering, influence on coagulation. Wooldridge's tissue fibrinogens appear to consist of prote'id, nuclei'n, and lecithin. They contain no fibrin ferment unt,il t,hey have been digested for some time with a litkle calcium chloride ; i t is, therefore, considered that they contain the zymogen of fibrin ferment, and their action in producing intravascular coagulation is explicable on the theory that, in the blood, they come into contact with calcium compounds, so that the zyrnogen is then converted into the ferment. W. U. H. Hematic Glycolysis. Estimation of Glycogen in the Blood. By R. LAPINE and BARRAL ( C o ~ ~ p f .rend., 112, 1414--1416),-The sugar present in the blood of a starving dog was estimated after destroying the glycolytic ferment a t 90'. Four portions of the same blood were maintained a t 39" for 15, SO, 4.5, and 60 minutes respec- t i vel y . Taking the initial sugar at 100, the sugar present at each interval would be represented by 88, 81, 76, and 72, indicating losses foraeach successive 15 minutes of 12, 7, 5, and 4 respectively. Treating the blood of a well-nourished dog in the same manner, the loss of sugar for the first 15 minutes was hardly measurable. There is frequently an augmentation of the quantity of sugar present after the first 15 minutes; this is more frequently the case with serum. The glycolytic ferment is contained in the white corpuscles and not in the serum.Sugar is doubtless produoed a t the expense of the glycogenic matter. To estimate the amount thus formed, blood is raised to 58' to destroy the glycolytic ferment and the sugar titrated as above, yielding for successive periods of 15 minutes, a gain of 18, 2, 0, and 0 respectively. The addition of saliva to the blood did not increase the gain. The glycolytic power of the blood of a starving dog is given by deducting the quantity of su,car obtained after an hour a t 39" from. the initial quantity, the apparelit power only is given for the blood of a well-fed dog; to obtain the real power in the latter case, it is necessarg to add the quantity of sugar produced during the same time to the apparent gljcolytic power. A t 58", the traosformstion of glycogen into sugar is rapid ; after a n hour a t this temperature, the whole of the glycogen of the biood may be estimated as sugar.W. T. Mechanism of the Production of Urea i n the Animal Organism. By POPOFF (Bull. Scc &WL. [ 3 ] , 5, 551-554).--To determine whether the transformation of ammonium salts into urea is effected by an unorgamsed ferment, or by the living cell, portions of liver, spleen, and kidney, removed from recently-killed dogs and guinea-pigs, were digested, with antiseptic precautions, f o r mang hours with warm, dilute (0.5-1.0 per cent.), sterilised solutions of various ammonium salts. In no case was any trace of urea formed. The author concludes, therefom, that the formation o€ urea from90 ABSTRACTS OF UHEMIOAL PAPERF.ammonium salts is due to the direct action of the living cells of the various organs, and not to that of soluble ferments secreted by them. JN. W. The Action of Azoimide on Living Organisms. By 0. LOEI\- (Ber., 24, 2!~47-2953).-Expei.iments were made to test the action of xxoimide (N,H) on l i ~ i n g plants and animals. Sodium azoimide WRS found to be a powerful poison in all cases; seedlings died irl about hhree days if attenipts were made t o grow them iu a nutritive Puid containing 0.1 per cent. of the poison. A l p were not affected so readily, but did not grow. Bacteria were killed, aud thus the material in question acts as an antiseptic. Bxxperiments with yeast, penicillium, and other fongi were en tirely confirmatory of the above. To animal life, as tested on infusiorians, various invertebrates, and mammals (mice and rabbits) this substance is equally inimical.There is, first, loss of movement, preceded in mammals by muscular twitch- ings and finally death. ‘l’lie imide is thus not available as a nitrogenous food; and t h e ca,iise of its toxicity is considered to be its sudden decomposition when it comes into relation with the cells and the aldehyde contain- i n g radicles of prote’icl within them. This, occurring within the nerve cells, produces first, stimulation, hence the spasmodic movements, and then kills them. Probably the deccmposition t h a t occurs, may be represented thus, N:,H + H 2 0 = N20 + NH3. It certainly yields aiumonia when acted on by platinizm black. \Y. D. H.PHYSIOLOGICAL CHE3fISTRT.P h y s i o l o g i c a l C h e m i s t ry.87Influence of Wine on Peptic Digestion.By L. HUGOTJNENQ(Bull. 8oc. (?him. [3], 5, 849--855).--Fibrin was digested withdilute hydrochloric acid in the presence of various colouring mattersand wines. It was found that peptic digestion is considerablyhindered by colouring matters, whether occurring naturally in thewine, or added fraudulently, and in the latter case, whether artificial,such as magenta, azotlavine, and methylene blue, or natural, such asthe colouring matters of elder and mallow. Plastered wine was foundto exercise a less injurious iufluenoe than wine containing the f u l laniount of tartrates. JN. W.Coagulation of the Blood. By C. A. PEKELHARING (Virchow’sFestschrift, 1891, Bd.l).-Recently, a number of observations on theimportance of calcium salts in the process of blood coagulation havebeen published.Rriicke first showed that the ash of fibrin always contains calcium.In 1875, Haammarsten found that calcium chloride can take the placeof seruiii globulin in tibriu formation. I n 1887, Green (Abstr., 1888,306) found that in magnesium sulphate plasma, and also in otherforms of plasma, coagulation is hastened if small quantities of calciumsulphate is added iu addition to fibrin ferment. Later, Ringer andSainsbury (Abstr., 1890, 1176) found that t,his result can be broughtabout by other calcium salts, such as the chloride, and also, but not sovxdily, by means of soluble strontium and barium salts. Freund( M d .,Jahrb., 1888, 259) who also noted the hastening of coagulationby calcium salts, considered that the blood corpuscles, as soon as theblood is shed, yield alkaline phosphates t9 the plasma ; meeting withthe calcium salts there, tricalciurn phosphate is precipitated, andherein lies the cause of fibrin formation. Latschenberger (Meed.Jnhrb., 1888, 479), and voii St.rauch (Ilissert. Dorpat, 1889) showedcertain fallacies in this hypothesis; tlius the addition of alkalinephosphates and calcium salts resulting in the precipitation of tri-oalciuui phosphate does not always lead to the formation of fibrin infilwinogenous liquids ; also the fii+t portions of fibrin formed werefound to contain calcium, but no phosphoric acid, and further, in thepiaesent research, it is shown t h a t injection of disodium phosphateinto the circulation of a liviilg animal is not followed by thrombosis.Arthus and Pages (Arch.de Pliysiol., 1890, No. 4) found that bloodcoagulation may be entirely prevented i f , immediately on being shed,the blood is mixed with small quantities of subdauces, like oxalate88 ABSTHACTS OF CHEMICAL PAPERS.or flnorides, which precipitate calcium salts as very insoluble com-pounds. On adding to the plasma obtained from this blood a slightexcess of calcium chloride, coagulation immediately ensues. Fibrinferment is, however, essential for the process ; and the action of thisagent is considered to be t h e bringing together of fibrinogen and thecalcium compound, and thus t h e formation of fibrin.It1 this, theydraw a close analogy between fibrin formation and the formation ofcasein in milk under the influence of t h e rennet ferment. Greenattempted to answer t h e question, Does t h e fibrin ferment exist aszymogen in the plasma, arid is such zjmogen converted into theferment by t.he action of t h e calcium salt ? H e was unable to find a,positive answer ; and thvrefore considered t h a t the calciiim acts inassisting the ferment much as hydrochloric acid in tlit! gastric juicefavours the activity of pepsin. This question is again taken lip i nt h e present investigation, and i t was found possible to prepare fromplasnia (such as oxalate plasma which contains no ferment) a globulinwhich has no fibrinoplastic properties, which, however, after contactwith calcium chloride, is converted into the ferment,.The zymogenyields an ash contairiiiig little or no calcium, whilst the ferment isrich i n calcium. The material in question arises from t,he formedelements of the blood, and is identical with what is called cell-globulin by Halliburton (Abstr., 1888, 574).Fibrin, moreover, is a calcium compound, and the main a.ction oft h e ferment appears t o be t o transfer the calcium to the fibrinogen.Granting this hypothesis, i t is possible to explain several factshitherto but little understood in connection with blood coagulation,and to reconcile certain conflicting theo~ies. The action of oxalatesin hindering coagulation is explained on the supposition that tlie pre-cipitate of calcium oxalate, on account.of its insolubility, is not avail-able for the conversion of zymogcri into ferment. The action ofneutral sa1t.s in restniinitig clotting is explained o n t h e assumptionthat the ferment is a globulin, and, although the amouut of saltadded is not sufficient to precigitate the globulin, yet i t is sufficient.t o lessen those intramolecular r lovements which, i n the end, produceits specific action.The acriop of peptone in hindering coagulation can be explained byt h e affinity betwcen peptone and calciiim couipoulids. It thus pre-vents ttieae from coiivertiiig ',he zyniogeri into ttie fwrnent. Thisview is suppo~ted b j the fact, thitt other substances, like soaps, whichcombine with calcium compounds, produce similar symptoms to thoseset up by yeptoiie (MuII~).Thus, there is loss of coagulability ofthe blood, low blood pressu :e, suppression of secretions, and wendeath. The toxic eflecis app,:ar to tx due to the removal of calciumgaits, which are necessaty, H S Ringer has shown, for all vital processes.A further support to the theory IS obtained from ttie fact t h a t injec-tion into the circulatioir of c:alcicm chloi-ide simultaneonslg with thepeptone, or after the peptone, (~L\iates tlle poisolions eflects of thelatter ; peptone is then 11o Jonge'r capable of rendering t h e blood un-coagulable. Peptone alsc i*estrairis coagulittion in intrsvascularplasma (or solutions of Ha?nmarsten's filwinogeri), provided t h a t it isadded so rapidly that tlie zj-niogeii has not had time to combine witPHYSIOLOGICAL CHEMISTRY.89the calcium to form the ferment. After the ferment has been onceformed in the plasma, or added to the solution of fibrinogen, peptonehas no longer any hindering, influence on coagulation.Wooldridge's tissue fibrinogens appear to consist of prote'id,nuclei'n, and lecithin. They contain no fibrin ferment unt,il t,heyhave been digested for some time with a litkle calcium chloride ; i t is,therefore, considered that they contain the zymogen of fibrin ferment,and their action in producing intravascular coagulation is explicableon the theory that, in the blood, they come into contact with calciumcompounds, so that the zyrnogen is then converted into the ferment.W.U. H.Hematic Glycolysis. Estimation of Glycogen in the Blood.By R. LAPINE and BARRAL ( C o ~ ~ p f . rend., 112, 1414--1416),-Thesugar present in the blood of a starving dog was estimated afterdestroying the glycolytic ferment a t 90'. Four portions of the sameblood were maintained a t 39" for 15, SO, 4.5, and 60 minutes respec-t i vel y .Taking the initial sugar at 100, the sugar present at each intervalwould be represented by 88, 81, 76, and 72, indicating losses foraeachsuccessive 15 minutes of 12, 7, 5, and 4 respectively. Treating theblood of a well-nourished dog in the same manner, the loss of sugarfor the first 15 minutes was hardly measurable. There is frequentlyan augmentation of the quantity of sugar present after the first15 minutes; this is more frequently the case with serum.Theglycolytic ferment is contained in the white corpuscles and not in theserum. Sugar is doubtless produoed a t the expense of the glycogenicmatter. To estimate the amount thus formed, blood is raised to 58'to destroy the glycolytic ferment and the sugar titrated as above,yielding for successive periods of 15 minutes, a gain of 18, 2, 0, and0 respectively. The addition of saliva to the blood did not increasethe gain.The glycolytic power of the blood of a starving dog is given bydeducting the quantity of su,car obtained after an hour a t 39" from.the initial quantity, the apparelit power only is given for the blood ofa well-fed dog; to obtain the real power in the latter case, it isnecessarg to add the quantity of sugar produced during the sametime to the apparent gljcolytic power.A t 58", the traosformstionof glycogen into sugar is rapid ; after a n hour a t this temperature, thewhole of the glycogen of the biood may be estimated as sugar.W. T.Mechanism of the Production of Urea i n the AnimalOrganism. By POPOFF (Bull. Scc &WL. [ 3 ] , 5, 551-554).--Todetermine whether the transformation of ammonium salts into ureais effected by an unorgamsed ferment, or by the living cell, portionsof liver, spleen, and kidney, removed from recently-killed dogs andguinea-pigs, were digested, with antiseptic precautions, f o r manghours with warm, dilute (0.5-1.0 per cent.), sterilised solutions ofvarious ammonium salts. In no case was any trace of urea formed.The author concludes, therefom, that the formation o€ urea fro90 ABSTRACTS OF UHEMIOAL PAPERF.ammonium salts is due to the direct action of the living cells of thevarious organs, and not to that of soluble ferments secreted by them.JN.W.The Action of Azoimide on Living Organisms. By 0. LOEI\-(Ber., 24, 2!~47-2953).-Expei.iments were made to test the actionof xxoimide (N,H) on l i ~ i n g plants and animals. Sodium azoimideWRS found to be a powerful poison in all cases; seedlings died irlabout hhree days if attenipts were made t o grow them iu a nutritivePuid containing 0.1 per cent. of the poison. A l p were not affectedso readily, but did not grow. Bacteria were killed, aud thus thematerial in question acts as an antiseptic. Bxxperiments with yeast,penicillium, and other fongi were en tirely confirmatory of the above.To animal life, as tested on infusiorians, various invertebrates, andmammals (mice and rabbits) this substance is equally inimical. Thereis, first, loss of movement, preceded in mammals by muscular twitch-ings and finally death.‘l’lie imide is thus not available as a nitrogenous food; and t h eca,iise of its toxicity is considered to be its sudden decompositionwhen it comes into relation with the cells and the aldehyde contain-i n g radicles of prote’icl within them. This, occurring within the nervecells, produces first, stimulation, hence the spasmodic movements, andthen kills them. Probably the deccmposition t h a t occurs, may berepresented thus, N:,H + H 2 0 = N20 + NH3. It certainly yieldsaiumonia when acted on by platinizm black. \Y. D. H

ISSN:0368-1769    

DOI:10.1039/CA8926200087

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

90 ABSTRACTS OF UHEMIOAL PAPERF. Chemistry of Vegetable Physiology and Agriculture. A Bacterium which Ferments Starch and Produces Amy1 Alcohol. By L. PERDHIX (Clzem Centr., 1891, ii, 252-253 ; from Aun. Ir8st. Pasteur, 1891, No. 5).-The author has separated from Paris water a bacillns, B. arnylozylnzicus, which ferments starch, with production of amyl alcohol. It is separated by cultivation on pota- toes, and finally on gelatin. The bacillus is 2-3 p long, and 0.5 p thick; the rods are joined i n pairs and chains, and in the absence of oxygen are motile, like Vibrio bufyricus, Pusteur. The rods are readily stained ; the spores are set free through the dissolution of the walls of the mother cell. The bacillus flourishes only in the absence of oxygen, readily, however, either in a vacuum or in hgdro- gen, nitrogen, or carbonic anbydride.The optimum temperature is 3.5" ; i t grows quite well at 20-25" ; at 16-17", fermenthtion com- mences a t the end of four days. Its "maximum" temperature is 42-43'. It will grow in all the usual cultivating media, ferments the sugars and starch, but does not attack cellulcse o r calcium lactate, differing in t h i s respect from Vibrio butpicus, Pasteur, Acids are produced during the fermentations which it, causes, and the presence of acidity, equivalent to 0.055 gram sulphuriu anhydride, or of'VEOETBBLE PHYSIOLOGY ASD AGRICULTURE. 91 nlkali equivalent to 0.08-0.11 gram in 100 c.c., is suficient to arrest the process ; the addition of ca.lcium carbonate to the liquid enables the fermentation to become perfect.Glucose ferments to hjdrogen, carbonic anhydride, acetic and butyric acids during the first three dpys ; from the third t o the ninth day, no acetic acid is forined. From saccharose and lactose, acetic acid is formed during the first five days. The greater the amount of oxygen present, the more acetic acid is produced; it was also observed that a t the time of t.he butyric acid formation, all the cells coiitained spores. From the fei5mentation of starch a distillate was obtained, of which one-third was amyl alcohol, and from 100 grams of potatoes, 2-3-2.5 C.C. of alcohols were sepa- rated. The sugar obtained from starch is vr1.y siiiiilar to glucose, but has a less imotatory action, and its phenylglucosazone mvlts 10" lower tlian that from glucose ; 94 per cent.of the starch is coiiverted into sugar, carbonic anh;pdride, ethyl and amyl alcohols, acetic and butJyric acids, arid 6 per. cent. is coiiverted into dextriii. The sngzr formed by the bacillus from starch may be fermented perfectly wlth beer-yeast, either after sterilisation, or in the presence of the bacillus. If either the sugar obtained by fermentation of starch with this bacillus, or a stei.ilised mash, be fermented with a pum cultivation of yeast, no f'usel oil is formed, and the autlior concludes that the fuse1 oil found in commercially prepared alcohol, is tormed by the action of bacteria. The 8. urripZozyrriictis remains uninjured f u r 10 days a t 30-5.5". J. W. Ti. Action of the Bacillus of Malgnant CEdema on Carbo- hydrates, and on Lactic Acid.By 8. KERRY and S. FKAENKEL (Momtsh., 12, 350-355 ; compare Abstr., 18W, 1454).-When lactic acid, in the form of its calcium salt, is dissolved in bouillon containing peptone and Kernmerich's meat extract, and the solution, placed in an atmosphere of hydrogen, is inoculated wit8h the bacillus of malig- nant cedenia, fermentation occurs. After remaiiiing 8-10 days, the solution contains props1 alcohol and formic: and butyric acids, but no ethyl alcohol. Milk sugar, cane sugar, and starch, in presence of substances con- taining the materials necessary for building up the organism, are i l l 1 fermentable by the bacillus, and yield variable quantities of butjric, formic, and inactive lactic acids, and ethyl alcohol. The formation of the last-named pyociuct on long-contiuiied anaiirohic fermentatioii of the carbohydrates is most probably to be ascribed to a further change induced in the propjl alcohol derived from the lactic acid. The authors have succeeded in fermenting the wood pulp obtained from fir, and have recognised the presence of volatile alcohols and fixed acids in the product; all attempts to induce decomposition iii pure cellulose have, however, led to negative results.Influence of Carbohydrates on the Accumulation of Aspara. gine in Plants. By MOSTBFERDE (Ann. Agrm., 17, 376-377j.- Branches of lilac, plunged in distilled water, mid i n 4 per cent. solution of glycerol, and kept, in the dark, contained abundance of aspartigine a t the end of 15 days, but neither starch nor mannitol. Branches of G.T. M.92 ABSTRACTS OF CHEMICAL PAPERS. the same plant kept iu solutions of glucose, cane sugar, or mannitol formed no asparagine in a month, but contained much starch and mannitol. Peas, vetches. and monkshood, which do not stand the dark well, were kept in the light in an atmosphere deprived of carb- onic anhydride ; when plunged in solutions of' glucose or cane sugar, they were completely deprived of asparagine in 10 days. J. M. 13. 11. Diastase. By G. KRABRE ( A m . Agroiz., 17, 381j.-T11e author believes that diastase attacks the starch of mslt, not by gradual per- colation through the entire maw, but by local action. Diastase is not dialysable, and the anthor consitlers its pal-ticles to consist of groups of m~lecules, and chaiiis of group.j too large to pass from one cell to another; it will not even traverse biscuit ware.By P. LESAGE (Cotnpt. rend., 113, 3i3--3iS).--The radish contains little or no starch, even when exiimined in different degrees of development. If watered with solutions of sodium chloride containing 1 to 20 grams per litre, starch appears in the endoderm, and also in some cases i r i the corticdl parenchyma. The results were a s follows :--No starch with pure water. or water containing 1, 2, or 20 grams of salt per lit1 e ; very little starch with 3 and 5 grams per litre ; a little starch with 10 grams per litre ; a considerable quantity with 4 grams pzr l i t r e ; 20 grams of salt per litre kills the plant. I n other cases the maximum amount of starch was fonnd with proportions of salt tiniounting to 5 grams and 10 grams per litre.Oil of Lime Seed. By C. MCELLER (Awn. dgron., 17, 431- 432) -The seeds of Tilin phirtyphylla, or grandifolia ; II'. ulmi;folia, or p~rrvifolia; and !Z'. intewiedia, contain little starch, and about 58 per cent. of oil. It is a yellow, bland oil, resembling the best olive oil, not bitter or aromatic, and non-drying. I t does not become rancid, or resinify on exposure to air. Mixed with sulphuric acid, the liquid becomes de2p brown-red, and the rise in temperatiire is considerable. The oil solidifies under the action of nitric acid and mercury. I t s soda soap crystxllises from alcohol in long, yellow needles. The oil does not solidify a t -21.5". J. M. H. 31. Quantity of Starch in the Tuberzles of the Radish. C. H. B.J. 11. H. M. Earth-nut Meal. Rg A. EMMGRLING (Bied. Centr., 20, 606-607). -The author has :Llrcudy called attention to the adulteration of food with the husks of earth-nuts. Attempts are now being made to introduce the latter. in the form of meal, as a food. The com- mercial product, is a dirty-jellow powder with a slightly bitter taste, and contains sand. It is prepared from the onter covering of the earth-nut,, but contains portions of the skin of the seeds. The ana- Ijsis of six samples gxve the following results :- Cnide Crude Carbo- Crude Minimum., 7.26 3.83 7 64 48.87 1-5-88 3.46 Average . . 7.9.5 10.15 8-23 53.66 16%3 4.11 Maximum . 8.58 14-31 8.97 58.9tj 16 85 5-65 UTatcr. Ash. prote'in. fibre. hydrates. fat. ,VEGETABLE PHYSIOLOGY AND AGRlCULTURE.93 The digestibility of the prote'ids was determined in two samples :- Total Coeficient of prot ei'ds, Digestibility, digestibilif y, per cent. per cent. per cent. 7.87 4.20 53.3 8-66 4.01 46.3 The name given to the meal is misleading, as it denotes the skin of the seed. whereas it, i s prepared maiIlly from the outer covering, the nutritive value and digestibility of which is less than that, of the skin. N. H. M. Behaviour of Strontium Tartrate with Plastered Wines. By M. SYICA (Guzzetta, 21, ii, 12--19).-When a wine is plastered or treated with plaster of Paris iri order t o preserve it, a certain amount of potassium sulphate goes into solution and may be deleterious to the lrealth of the consumer. nreyfus (&iron. v h i d l e , 1890, 66) has described a method for the i-emoval of the potassium sulphnte, which coiisists in treating th? -v\rine with strontium tartrate.The author gives complete analyses of three samples of wines both before and after treatment witli strontium tartrpte, which dhow that the quantity of potassium sulphate is not sufficiently reduced, as from a third 'to a hrtlf of the salt originally present remains in the wine. The quantiby of hydrogen potassium tartrate in solution is incpeasrd 'from less than 1 gram to betaecll 2 and 3 grams per litre. The.amount of ffree'tartaric acid is COR- siderably'dirniiiished, but the total acidity notably increases and the weight of ash is diminished to abont one-half, whilst a quantity of strontiuni hydrogen tni'trate vaq'ing from half a gram to more ttlall 1 gram per litre goes into solution and may be injurious to health.Tile wine is also rendered somewhdt insipid by the treatment. Presen'ce of Boric Acid in Products of the Soil. W. J. P. By A. GASSEND (Ann. A g r m . , 17, 352-354).-Having bad his attention directed toiaertain samples of wine by the Custom House authorities,' the author hasexamined a great number of sainples of French, Greek, Italian, Spanish, .Algerian, and Corsican wines, and finds boric acid to be a nornial constituent of them all, in the proportion of 5-1r) miliigrains per litre. I n this proportion the ash of 10 C.C. of wine will not give the green flame with alcohol and sulphuric acid, but the boric acid is easily recognised by the turmeric paper test and by the spectroscope. Wheii the spectroscope is employed, the ash should be moistened with l0idrops of pure hydrofluosilicic acid.The author finds similar traces of boric acid in grapes, apples, potatoes, radishes, lettuce, and in some pears, not in all. He does not find it in tea, saffron, or cow's milk. Hotter also has found boric acid in some plailts. J. M. H. &I. Action of Lime as a Manure, With Special regard to Paddy By 0. KELLNEB, H. SAKANO, D. SATO, and S. SHIXJO Fields.94 BUSTRACTS OF CHEMICAL PIPERS. Univ. ColZ. Agric. Tokyo B d Z , 9,1891,1-23).-The excefisive amount of lime (11360 kilos. per hectare) npplied to rice in the paddy fields in manly districts of Japan causes injury to the soil and crops. The mineral constituents uf the soil are liable to become cemented together, either a t the surface or a few feet helow, rendering the treatment and cultivation of the soil difficult, for this reason, as well as owing to the consequent staglintion of water on it.Potash and ammonia are, moreover, liberated from the soil and are liahle to he washed away hy the irrigating water ; in fact, complete infertility from over-liming has occurred in several parts. Besides the injurious effect on the soil, both physicially and horn loss of valuable constituents, the crop itself suffers, the stems becoming tnore fragile and the grain acquiring an inferior taste and lustre, and becoming lighter. An examination of several samples of hulled rice (all exceedingly brittle) from different soils showed no great difference in corn position from ordinary hulled rice, grown withoiit l i m e ; but i t pi-oved to be somewhat poor in crude protei'ds.This result was unexpected, as i t was thought that something in the compoGition of the seed, as in the amount, of carbo- hydrates, would throw some light on the action of lime. Lower per- centage of protejids has already been thought to be the reason of the glassy condition of barley and wheat, but this has never been known t o arise from over-liming. Experiments made to ascertain the relation of the hardness of the grain to the percentage of crude protein in tLe dry matter showed tbat the proportion of nitrogenous compounds plays an important part in the resistibility of rice grains to pressure or impact. The brittleness caused by over-limiug, is due to the destruction of nitrogenous matter in the soil by the lime.The mealy condition of the rice may be diminished by early cutting.' The liming of over-limed fields should be stopped and large amounts o f nitrogenous manure applied for the first, year to compensate for the loss of nitrogen ; and tlie manui es should be thoroughly fermented, before being mixed with the soil. Paddy rice prefers ammonia as nitrogenous food, and does not thrive well, as long as it is irrigated, if supplied with nitrates alone. In order to investigate the actinn of lime on soils, experiments were made in which several kilograms of dry and paddy earth, after being dried and mixed, were treated with slaked lime and kept in closed bottles. The dry land soil (containing 200 grams of dry matter) was previously mixed with air-dry soy bcans (containing 10 grams of dry matter) and 50 C.C.of water. The paddy soil w~ similarly treated, but had 300 C.C. of water. The amount of lime added corresponded with 10 grams of CaO. The results, which are given in tables, show that lime accelerates the decomposition of 01'- ganic matter in both dry-land and irrigated soils, and that the action IS much greater in dry land than in irrigated land. Thus, whilst the drj-land soil lost, iii six weekfi, 13.58 per cent. of its organic matter, tlie paddy soil lost only 5-85 per ceiit. ; the same soils, but without the addition of lime, lost respectively 3-24 and 2.21 per cent. of their organic matter. Experiments are next described which were made on the formation of nitricacid and ammonia from nitrogenous manures in dry-land and-VEGETABLE PHYSIOLOGY AND AGRICULTURE.9 5 paddy soils. was as follows :- The percentage cmiposition of the partly dried soils Hypo- Hamiis and scopic combined Total Nitric Organic water. water. nitrogen. acid. Ammonia. nitrogen. Drycland soil.. 41.12 14-06 0.231 0.098 0.009 0.198 Paddy soil . . . . 42.12 21-61 0.4S5 0,048 0.024 0.418 Glass jars were filled with the soils (1400-1600 grams), which were only so far dried as not to destroy the micro-organisms contained in them. The soils were manured with ammonium sulphate, fish inttnure, and in some cases with calcium carbonate, and the jars then taken to the respective fields, where they were let into the ground ; the paddy soil was watered with distilled water, the level of which was kept about 2 cm.above the surface of the soil. It was found that in dry-land soil the nitrogenous manures were quickly converted into nitric acid, whilst nitrification did not take place in the irripited paddy soil, in which ammonia seemq to be amonq the principal pro- d u d s of the decompoqi tion of the nitrogenous organic manure. The applicat,ion of lime distinctly favours, on the one liand, nitrification i n the dry land, and, on the other hand, the formation of ammonia in the paddy soil. The fact that nitrification does not take place in paddy soils was observed by Kellner and Sawano in 1832 (Abstr., 1884, 674 ; vompare Bmrnann, Abstr., 1887, 82, and Muntn, Abstr., 1890, 1183). Many organic and inorganic constituents of soils have the power of retaining ammonia, rind protect it very well from being washed away, Init lime (as oxide or hydroxide) will disperse the ammonia, and may thus give rise to considerable loss of nitrogen.The action o f lime on the phosphates in the two soils was next in- vestigated. The first soil wris taken from the surface of the paddy field ; the other was from the subsoil of a dry-land field. Bottles were filled with the soils (10 grams each) Containing 0.0, 0 25, 0.5, 1.0, 2.5, and 5.0 per cent. of quicklime. Each bottle received 20 C.C. o€ water, and two weeks later a solution of potassium dihrdrogen phoqphate (containing 0.0.5 gram of phosphoric acid) was added t o each bottle. The first set of soils examined one mont'h after the application of. the phosphate showed. that in the paddy soil only 12.7 per cent.of tho phosphoric acid remained in the soluble form, and that the addition of lime was decidedly henr?.fic:iaI, the maximum effect bein? obtained with an application of 1 to 2.5 per cent., the amount of soluble phos- phate beicg in both these cases 22.6 per cent. of the total phosphate added. After two months, there was still more soluble phosphate (27.2 per cent.) in t8he soil which had 2.5 per cent. of lime. This. slight after-effect is attributed to the action of calcium hydrogen carbonate on ferric phosphate, converting a part of it into free ferric hydroxide and calcium phosphate. This view is verified by direct experiments with ferric phosphate and lime-water saturated with carbonic anhydride. The beneficial egect of lime was not obseryed i n the case of the dry-field subsoil, and inasmuch as the two soils have the same geological origin there is nG doubt that the humus of the paddy soil9 l; ABSTRACTS OF CHEMICAL PAPERS.played an important part in bringing about the action of lime on superphosphates. With regud to the frequent application of large amoniits of lime it is shown that the exhaustive action of lime is not confined to nitrogen and potash but also favours the consumption of the phos- phatic ingredients of the soil by the crops. The Value of Animal DBbris as Nitrogenous Dressing. By A. M ~ N T Z and A. C. GIRARD (Compf. Tend., 112, 1458-1460).- Nitrogenous materials require that their nitrogen be transformed into the state of nitrate before plants can avail themselves of them as aliment).Hence the aptitude of organic manures to undergo nitrifica- tion under the influence of organisms present in the soil may be taken as a measure of their activity as dressings. KO practical value can be assigned to the ordinary laboratory methods of comparing the relative values of animal mnnnres. A numher of substances hnve been compared 5.y the authors by ascertaining the proportion of nitrate formed i n ft given time by in- trodncing quantities of the substances containing an equivalent amount of nitrogen into a, nitrifying soil and maintaining the same conditions in each case. Commercial manures may be divided into three classes: the first, undergoing nitritication rapidly, comprises dried blood, dried flesh, horn refuse, and guano : these substances are nearly as active, and have nearly the same effect on the crop, a s t h e mineral manures, sodium nitrate and ammonium ~ulphate ; the second comprises burnt leather, woollen waste, and dried night, soil, of which the nitrification is slower; these consequently do not give their whole effect in one season.but have some influence on the followinq crop ; the third includes unburnt leather waste, the nitrification of which is so slow that the yield of the crop is not sensibly augmented. This classification has been confirmed by careful practical agri- cultural experiments. With manures ot’ the first class, 60 per cent. of the nitrogen has been utilised in two years; with those of t h e second class, 40 per cent. ; and with that in the third class, 20 per cent.only. The unburnt leather refuse should only be used in compost heaps, as its nitrification proceeds too slowly for it to be directly available €or the crops. The unit of weight of nitrogen often costs more when purchased as organic manure than when obtained as saline manures ; i t would be more logical to pay the higher price for it in the latter case, as it could then be immediately 11 tilised, and its applicaf ion regnlated according to the needs of the crops. N. €3. M. W. T.90 ABSTRACTS OF UHEMIOAL PAPERF.Chemistry of Vegetable Physiology and Agriculture.A Bacterium which Ferments Starch and Produces Amy1Alcohol. By L. PERDHIX (Clzem Centr., 1891, ii, 252-253 ; fromAun. Ir8st. Pasteur, 1891, No. 5).-The author has separated fromParis water a bacillns, B.arnylozylnzicus, which ferments starch, withproduction of amyl alcohol. It is separated by cultivation on pota-toes, and finally on gelatin. The bacillus is 2-3 p long, and 0.5 pthick; the rods are joined i n pairs and chains, and in the absenceof oxygen are motile, like Vibrio bufyricus, Pusteur. The rodsare readily stained ; the spores are set free through the dissolution ofthe walls of the mother cell. The bacillus flourishes only in theabsence of oxygen, readily, however, either in a vacuum or in hgdro-gen, nitrogen, or carbonic anbydride. The optimum temperature is3.5" ; i t grows quite well at 20-25" ; at 16-17", fermenthtion com-mences a t the end of four days. Its "maximum" temperature is42-43'. It will grow in all the usual cultivating media, fermentsthe sugars and starch, but does not attack cellulcse o r calciumlactate, differing in t h i s respect from Vibrio butpicus, Pasteur, Acidsare produced during the fermentations which it, causes, and the presenceof acidity, equivalent to 0.055 gram sulphuriu anhydride, or ofVEOETBBLE PHYSIOLOGY ASD AGRICULTURE.91nlkali equivalent to 0.08-0.11 gram in 100 c.c., is suficient to arrestthe process ; the addition of ca.lcium carbonate to the liquid enablesthe fermentation to become perfect. Glucose ferments to hjdrogen,carbonic anhydride, acetic and butyric acids during the first threedpys ; from the third t o the ninth day, no acetic acid is forined. Fromsaccharose and lactose, acetic acid is formed during the first five days.The greater the amount of oxygen present, the more acetic acid isproduced; it was also observed that a t the time of t.he butyric acidformation, all the cells coiitained spores.From the fei5mentation ofstarch a distillate was obtained, of which one-third was amyl alcohol,and from 100 grams of potatoes, 2-3-2.5 C.C. of alcohols were sepa-rated. The sugar obtained from starch is vr1.y siiiiilar to glucose,but has a less imotatory action, and its phenylglucosazone mvlts 10"lower tlian that from glucose ; 94 per cent. of the starch is coiivertedinto sugar, carbonic anh;pdride, ethyl and amyl alcohols, acetic andbutJyric acids, arid 6 per. cent. is coiiverted into dextriii. The sngzrformed by the bacillus from starch may be fermented perfectly wlthbeer-yeast, either after sterilisation, or in the presence of the bacillus.If either the sugar obtained by fermentation of starch with thisbacillus, or a stei.ilised mash, be fermented with a pum cultivation ofyeast, no f'usel oil is formed, and the autlior concludes that the fuse1 oilfound in commercially prepared alcohol, is tormed by the action ofbacteria.The 8. urripZozyrriictis remains uninjured f u r 10 days a t30-5.5". J. W. Ti.Action of the Bacillus of Malgnant CEdema on Carbo-hydrates, and on Lactic Acid. By 8. KERRY and S. FKAENKEL(Momtsh., 12, 350-355 ; compare Abstr., 18W, 1454).-When lacticacid, in the form of its calcium salt, is dissolved in bouillon containingpeptone and Kernmerich's meat extract, and the solution, placed inan atmosphere of hydrogen, is inoculated wit8h the bacillus of malig-nant cedenia, fermentation occurs.After remaiiiing 8-10 days, thesolution contains props1 alcohol and formic: and butyric acids, but noethyl alcohol.Milk sugar, cane sugar, and starch, in presence of substances con-taining the materials necessary for building up the organism, are i l l 1fermentable by the bacillus, and yield variable quantities of butjric,formic, and inactive lactic acids, and ethyl alcohol. The formation ofthe last-named pyociuct on long-contiuiied anaiirohic fermentatioiiof the carbohydrates is most probably to be ascribed to a furtherchange induced in the propjl alcohol derived from the lactic acid.The authors have succeeded in fermenting the wood pulp obtainedfrom fir, and have recognised the presence of volatile alcohols andfixed acids in the product; all attempts to induce decomposition iiipure cellulose have, however, led to negative results.Influence of Carbohydrates on the Accumulation of Aspara.gine in Plants.By MOSTBFERDE (Ann. Agrm., 17, 376-377j.-Branches of lilac, plunged in distilled water, mid i n 4 per cent. solutionof glycerol, and kept, in the dark, contained abundance of aspartiginea t the end of 15 days, but neither starch nor mannitol. Branches ofG. T. M92 ABSTRACTS OF CHEMICAL PAPERS.the same plant kept iu solutions of glucose, cane sugar, or mannitolformed no asparagine in a month, but contained much starch andmannitol. Peas, vetches.and monkshood, which do not stand thedark well, were kept in the light in an atmosphere deprived of carb-onic anhydride ; when plunged in solutions of' glucose or cane sugar,they were completely deprived of asparagine in 10 days.J. M. 13. 11.Diastase. By G. KRABRE ( A m . Agroiz., 17, 381j.-T11e authorbelieves that diastase attacks the starch of mslt, not by gradual per-colation through the entire maw, but by local action. Diastase is notdialysable, and the anthor consitlers its pal-ticles to consist of groupsof m~lecules, and chaiiis of group.j too large to pass from one cell toanother; it will not even traverse biscuit ware.By P.LESAGE (Cotnpt. rend., 113, 3i3--3iS).--The radish contains little orno starch, even when exiimined in different degrees of development.If watered with solutions of sodium chloride containing 1 to 20 gramsper litre, starch appears in the endoderm, and also in some cases i r ithe corticdl parenchyma.The results were a s follows :--No starchwith pure water. or water containing 1, 2, or 20 grams of saltper lit1 e ; very little starch with 3 and 5 grams per litre ; a little starchwith 10 grams per litre ; a considerable quantity with 4 grams pzrl i t r e ; 20 grams of salt per litre kills the plant. I n other cases themaximum amount of starch was fonnd with proportions of salttiniounting to 5 grams and 10 grams per litre.Oil of Lime Seed. By C. MCELLER (Awn. dgron., 17, 431-432) -The seeds of Tilin phirtyphylla, or grandifolia ; II'. ulmi;folia, orp~rrvifolia; and !Z'.intewiedia, contain little starch, and about 58 percent. of oil. It is a yellow, bland oil, resembling the best olive oil,not bitter or aromatic, and non-drying. I t does not become rancid,or resinify on exposure to air. Mixed with sulphuric acid, the liquidbecomes de2p brown-red, and the rise in temperatiire is considerable.The oil solidifies under the action of nitric acid and mercury. I t ssoda soap crystxllises from alcohol in long, yellow needles. The oildoes not solidify a t -21.5".J. M. H. 31.Quantity of Starch in the Tuberzles of the Radish.C. H. B.J. 11. H. M.Earth-nut Meal. Rg A. EMMGRLING (Bied. Centr., 20, 606-607).-The author has :Llrcudy called attention to the adulteration offood with the husks of earth-nuts.Attempts are now being madeto introduce the latter. in the form of meal, as a food. The com-mercial product, is a dirty-jellow powder with a slightly bitter taste,and contains sand. It is prepared from the onter covering of theearth-nut,, but contains portions of the skin of the seeds. The ana-Ijsis of six samples gxve the following results :-Cnide Crude Carbo- CrudeMinimum., 7.26 3.83 7 64 48.87 1-5-88 3.46Average . . 7.9.5 10.15 8-23 53.66 16%3 4.11Maximum . 8.58 14-31 8.97 58.9tj 16 85 5-65UTatcr. Ash. prote'in. fibre. hydrates. fat. VEGETABLE PHYSIOLOGY AND AGRlCULTURE. 93The digestibility of the prote'ids was determined in two samples :-Total Coeficient ofprot ei'ds, Digestibility, digestibilif y,per cent. per cent.per cent.7.87 4.20 53.38-66 4.01 46.3The name given to the meal is misleading, as it denotes the skinof the seed. whereas it, i s prepared maiIlly from the outer covering,the nutritive value and digestibility of which is less than that, of theskin. N. H. M.Behaviour of Strontium Tartrate with Plastered Wines.By M. SYICA (Guzzetta, 21, ii, 12--19).-When a wine is plastered ortreated with plaster of Paris iri order t o preserve it, a certain amountof potassium sulphate goes into solution and may be deleterious to thelrealth of the consumer.nreyfus (&iron. v h i d l e , 1890, 66) has described a method for thei-emoval of the potassium sulphnte, which coiisists in treating th?-v\rine with strontium tartrate. The author gives complete analyses ofthree samples of wines both before and after treatment witli strontiumtartrpte, which dhow that the quantity of potassium sulphate is notsufficiently reduced, as from a third 'to a hrtlf of the salt originallypresent remains in the wine.The quantiby of hydrogen potassiumtartrate in solution is incpeasrd 'from less than 1 gram to betaecll2 and 3 grams per litre. The.amount of ffree'tartaric acid is COR-siderably'dirniiiished, but the total acidity notably increases and theweight of ash is diminished to abont one-half, whilst a quantity ofstrontiuni hydrogen tni'trate vaq'ing from half a gram to more ttlall1 gram per litre goes into solution and may be injurious to health.Tile wine is also rendered somewhdt insipid by the treatment.Presen'ce of Boric Acid in Products of the Soil.W.J. P.By A.GASSEND (Ann. A g r m . , 17, 352-354).-Having bad his attentiondirected toiaertain samples of wine by the Custom House authorities,'the author hasexamined a great number of sainples of French, Greek,Italian, Spanish, .Algerian, and Corsican wines, and finds boric acidto be a nornial constituent of them all, in the proportion of 5-1r)miliigrains per litre. I n this proportion the ash of 10 C.C. of wine willnot give the green flame with alcohol and sulphuric acid, but theboric acid is easily recognised by the turmeric paper test and by thespectroscope. Wheii the spectroscope is employed, the ash should bemoistened with l0idrops of pure hydrofluosilicic acid. The authorfinds similar traces of boric acid in grapes, apples, potatoes, radishes,lettuce, and in some pears, not in all.He does not find it in tea,saffron, or cow's milk. Hotter also has found boric acid in someplailts. J. M. H. &I.Action of Lime as a Manure, With Special regard to PaddyBy 0. KELLNEB, H. SAKANO, D. SATO, and S. SHIXJO Fields94 BUSTRACTS OF CHEMICAL PIPERS.Univ. ColZ. Agric. Tokyo B d Z , 9,1891,1-23).-The excefisive amountof lime (11360 kilos. per hectare) npplied to rice in the paddy fieldsin manly districts of Japan causes injury to the soil and crops. Themineral constituents uf the soil are liable to become cemented together,either a t the surface or a few feet helow, rendering the treatment andcultivation of the soil difficult, for this reason, as well as owing to theconsequent staglintion of water on it.Potash and ammonia are,moreover, liberated from the soil and are liahle to he washed awayhy the irrigating water ; in fact, complete infertility from over-liminghas occurred in several parts. Besides the injurious effect on the soil,both physicially and horn loss of valuable constituents, the crop itselfsuffers, the stems becoming tnore fragile and the grain acquiring aninferior taste and lustre, and becoming lighter. An examination ofseveral samples of hulled rice (all exceedingly brittle) from differentsoils showed no great difference in corn position from ordinary hulledrice, grown withoiit l i m e ; but i t pi-oved to be somewhat poor incrude protei'ds. This result was unexpected, as i t was thought thatsomething in the compoGition of the seed, as in the amount, of carbo-hydrates, would throw some light on the action of lime.Lower per-centage of protejids has already been thought to be the reason of theglassy condition of barley and wheat, but this has never been knownt o arise from over-liming. Experiments made to ascertain the relationof the hardness of the grain to the percentage of crude protein in tLedry matter showed tbat the proportion of nitrogenous compoundsplays an important part in the resistibility of rice grains to pressureor impact. The brittleness caused by over-limiug, is due to thedestruction of nitrogenous matter in the soil by the lime. Themealy condition of the rice may be diminished by early cutting.'The liming of over-limed fields should be stopped and large amountso f nitrogenous manure applied for the first, year to compensate for theloss of nitrogen ; and tlie manui es should be thoroughly fermented,before being mixed with the soil.Paddy rice prefers ammonia asnitrogenous food, and does not thrive well, as long as it is irrigated,if supplied with nitrates alone.In order to investigate the actinn of lime on soils, experiments weremade in which several kilograms of dry and paddy earth, afterbeing dried and mixed, were treated with slaked lime and kept inclosed bottles. The dry land soil (containing 200 grams of drymatter) was previously mixed with air-dry soy bcans (containing10 grams of dry matter) and 50 C.C.of water. The paddy soil w~similarly treated, but had 300 C.C. of water. The amount of limeadded corresponded with 10 grams of CaO. The results, which aregiven in tables, show that lime accelerates the decomposition of 01'-ganic matter in both dry-land and irrigated soils, and that the actionIS much greater in dry land than in irrigated land. Thus, whilst thedrj-land soil lost, iii six weekfi, 13.58 per cent. of its organic matter,tlie paddy soil lost only 5-85 per ceiit. ; the same soils, but withoutthe addition of lime, lost respectively 3-24 and 2.21 per cent. of theirorganic matter.Experiments are next described which were made on the formationof nitricacid and ammonia from nitrogenous manures in dry-land andVEGETABLE PHYSIOLOGY AND AGRICULTURE.9 5paddy soils.was as follows :-The percentage cmiposition of the partly dried soilsHypo- Hamiis andscopic combined Total Nitric Organicwater. water. nitrogen. acid. Ammonia. nitrogen.Drycland soil.. 41.12 14-06 0.231 0.098 0.009 0.198Paddy soil . . . . 42.12 21-61 0.4S5 0,048 0.024 0.418Glass jars were filled with the soils (1400-1600 grams), which wereonly so far dried as not to destroy the micro-organisms contained inthem. The soils were manured with ammonium sulphate, fishinttnure, and in some cases with calcium carbonate, and the jars thentaken to the respective fields, where they were let into the ground ;the paddy soil was watered with distilled water, the level of which waskept about 2 cm. above the surface of the soil.It was found that indry-land soil the nitrogenous manures were quickly converted intonitric acid, whilst nitrification did not take place in the irripitedpaddy soil, in which ammonia seemq to be amonq the principal pro-d u d s of the decompoqi tion of the nitrogenous organic manure. Theapplicat,ion of lime distinctly favours, on the one liand, nitrification i nthe dry land, and, on the other hand, the formation of ammonia in thepaddy soil. The fact that nitrification does not take place in paddysoils was observed by Kellner and Sawano in 1832 (Abstr., 1884, 674 ;vompare Bmrnann, Abstr., 1887, 82, and Muntn, Abstr., 1890, 1183).Many organic and inorganic constituents of soils have the power ofretaining ammonia, rind protect it very well from being washed away,Init lime (as oxide or hydroxide) will disperse the ammonia, and maythus give rise to considerable loss of nitrogen.The action o f lime on the phosphates in the two soils was next in-vestigated. The first soil wris taken from the surface of the paddyfield ; the other was from the subsoil of a dry-land field.Bottles werefilled with the soils (10 grams each) Containing 0.0, 0 25, 0.5, 1.0, 2.5,and 5.0 per cent. of quicklime. Each bottle received 20 C.C. o€ water,and two weeks later a solution of potassium dihrdrogen phoqphate(containing 0.0.5 gram of phosphoric acid) was added t o each bottle.The first set of soils examined one mont'h after the application of. thephosphate showed. that in the paddy soil only 12.7 per cent.of thophosphoric acid remained in the soluble form, and that the additionof lime was decidedly henr?.fic:iaI, the maximum effect bein? obtainedwith an application of 1 to 2.5 per cent., the amount of soluble phos-phate beicg in both these cases 22.6 per cent. of the total phosphateadded. After two months, there was still more soluble phosphate(27.2 per cent.) in t8he soil which had 2.5 per cent. of lime. This.slight after-effect is attributed to the action of calcium hydrogencarbonate on ferric phosphate, converting a part of it into free ferrichydroxide and calcium phosphate. This view is verified by directexperiments with ferric phosphate and lime-water saturated withcarbonic anhydride.The beneficial egect of lime was not obseryed i n the case of thedry-field subsoil, and inasmuch as the two soils have the samegeological origin there is nG doubt that the humus of the paddy soi9 l; ABSTRACTS OF CHEMICAL PAPERS.played an important part in bringing about the action of lime onsuperphosphates.With regud to the frequent application of large amoniits of limeit is shown that the exhaustive action of lime is not confined tonitrogen and potash but also favours the consumption of the phos-phatic ingredients of the soil by the crops.The Value of Animal DBbris as Nitrogenous Dressing.ByA. M ~ N T Z and A. C. GIRARD (Compf. Tend., 112, 1458-1460).-Nitrogenous materials require that their nitrogen be transformed intothe state of nitrate before plants can avail themselves of them asaliment). Hence the aptitude of organic manures to undergo nitrifica-tion under the influence of organisms present in the soil may be takenas a measure of their activity as dressings. KO practical value canbe assigned to the ordinary laboratory methods of comparing therelative values of animal mnnnres.A numher of substances hnve been compared 5.y the authors byascertaining the proportion of nitrate formed i n ft given time by in-trodncing quantities of the substances containing an equivalentamount of nitrogen into a, nitrifying soil and maintaining the sameconditions in each case.Commercial manures may be divided into three classes: the first,undergoing nitritication rapidly, comprises dried blood, dried flesh,horn refuse, and guano : these substances are nearly as active, andhave nearly the same effect on the crop, a s t h e mineral manures,sodium nitrate and ammonium ~ulphate ; the second comprises burntleather, woollen waste, and dried night, soil, of which the nitrificationis slower; these consequently do not give their whole effect inone season. but have some influence on the followinq crop ; the thirdincludes unburnt leather waste, the nitrification of which is so slowthat the yield of the crop is not sensibly augmented.This classification has been confirmed by careful practical agri-cultural experiments. With manures ot’ the first class, 60 per cent.of the nitrogen has been utilised in two years; with those of t h esecond class, 40 per cent. ; and with that in the third class, 20 per cent.only. The unburnt leather refuse should only be used in compostheaps, as its nitrification proceeds too slowly for it to be directlyavailable €or the crops.The unit of weight of nitrogen often costs more when purchased asorganic manure than when obtained as saline manures ; i t would bemore logical to pay the higher price for it in the latter case, as itcould then be immediately 11 tilised, and its applicaf ion regnlatedaccording to the needs of the crops.N. €3. M.W. T

ISSN:0368-1769    

DOI:10.1039/CA8926200090

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 97 An a l y t i c a1 Chemistry. Estimation of Hydrochloric Acid in the Gastric Juice. By J. BOAS (Chem. Centr., 1891, ii, 357; from Centr. med. Wiss., 1891, 509).-The author has adopted Bourget’s method (evaporation and incineration with barium carbonate, extraction with water, and pre- cipitation of the barium chloride formed by sodium carbonate), with the slight modification that, after dissolving the precipitate in decinormal acid, the liquid is boiled until all carbonic anhydride is expelled, and the excess of acid is then neutralised with decinormal alkali ; the indicator is phenolphthalei’n. Estimation of Free Oxygen by means of Nitric Oxide. By L. L. DE KONINCK (Zeit. ang. Chem., 1891, 78--80).-The author’s attention was drawn to an article by Wsnklyn and Cooper on the estimation of oxygen by means of nitric oxide.These chemists con- sider that this process, which was originated by Priestley, but which now only possesses a,n historical interest, is not only verj accurate but even one of the best methods known, and they communicated a few satisfactory test analyses. The author some time ago had occasion to try the process, but his experience agreed with the results obtained by Berthelot, Lunge, and Winkler, which were very irregular and unsatisfactory. He therefore thought it advisable to once more thoroughly investigate the matter. The modus operandi was practically identical with that employed by Wanklyn and Cooper, except, perhaps, as regards the preparation of the nitric oxide, which was obtained by the action of nitric acid (sp.gr. 1.1) on a, spiral of sheet-copper contained in an old-fashioned Hempel’s hydrogen pipette. On account of its simplicity and easy execution, the following plan was adopted :-The gas (oxygen or air) was introduced into a Winkler-Hempel burette, the nitric oxide introduced into a like apparatus, and thoroughly shaken with the water to saturate this with the gas, and also to remove traces of nitric peroxide. After a few minutes rest, the two volumes of gas were respectively recorded, and after connecting the two burettes with a capillary tube filled with water, the oxygen mixture was forced into the nitric oxide (not the reverse way), and the burettes were now disconnected. After thoroughly shaking t o facilitate the ab- sorption, and waiting for twelve or fifteen minutes, the volume of the gas was read off with the usual precautions, and the contraction noted.The results obtained once more proved the process to be absolutely useless, as the quantity of oxygeii found varied between 77.5 and 122.j per cent. of the amount operated on. From a scien- tific point of view, however, the results were not uninteresting. The ratio between the volume of the oxygen and the contraction after the action of the nitric oxide may theoretically vary between 1 : 2.33 and 1 : 5, as shown by the following equations :- VOL. LXII. h J. W. L.98 ABSTRACTS OF 0 dEMIOAL PAPERS. 4N0 + 30, + 2Hz0 = 4HNO; ratio, 1 : 2.33, 2N0 + 0 2 + R2O = HNOZ + RON,; ,, 1 : 3, 4N0 + 202 + H20 = 4HN0 ,, 1 : 5. A good deal depends on the celerity with which the gases have been mixed and shaken with the water.As a rule, a large excess of nitric oxide or admixture with an inert gas, such as nitrogen, seems to favour the formation of nitrous acid. L. DE K. Estimation of Free Oxygen dissolved in Water. By W. KISCH (Zed. ang. Chem., 1891, 105-108) .-The author compared the various processes in use for the estimation of free oxygen in water. (a,.) Bunsen-Tiemann’s process.-The water is boiled, and the gases collected over hot solution of caustic potash. The oxygen is then estimated by explosion with hydrogen or by absorption with alkaline pyrogallol. ( b . ) Mohr’s process -The sample is mixed with an acld solution of ferrous sulphate of known strength, then with aqueous soda to throw down the ferrous hydroxide.After remain- ing for a few hours (air, of course. being rigidly excluded), the -precipitate is redissolved in sulphuric acid, and the ferrous sulphate titrated with permanganate. (c.) The Schiitzenberger-Itisler process. -The water is allowed to act on a solution of sodium hydrindigotin- disulphonate, which then passes into the blue compound. Standard solution of sodium hyposulphite is then run in till the liquid is again decolorised. ( d . ) Winkler’s process.-T he water is mixed with a solution of manganous chloride, and then with potassium iodide and potassium hydroxide. The precipitated rnanganous hydr- oxide rapidly absorbs the oxygen, and passes into a higher oxidised state. On adding hydrochloric acid, iodine is liberated, which is then estimated by a solution of sodium thiosulphate.On applying these processes to the same sample of water, the results obtained by Bunsen-Tiemann’s process were decidedly lower than those ob- tained by Winkler’s process, whilst those obtained by both Mohr’s and the Schutzenberger-Rider methods corresponded very well with Winkler’s figures. The author, however, strongly recommends the latter process as being the safest, most trustworthy, and the easiest Schiltzenberger’s Process for the Estimation of Free Oxygen. By T. ‘K~NIG (Zeit. ang. Chem., 1891, 108, llO).-The author, not always getting satisfactory results with this process, investigated the cause. Success depends in a great measure on the quality of the indigo solution employed. If the sample is poor in quality, it does not absorb the oxygen rapidly enough, and a portion of this is swept away by the current of hydrogen. Indigo-carmine is obtained by precipitating a solution of purified indigo in sulphuric acid with salt, If simply collected, a pasty mass is obtained which forms the commercial indigo-carmine ; but, if well washed and dried, solid sodium indigodisulphonate is obtained.These preparations vary, however, considerably in strength, sometimes from 79.08 to 91.58 per cent. in the so-called crystallised and sublimed product, whilst ot.her in manipulation. L. DE K.ANALYTICAL CHEMISTRY. 99 samples vaaied in strength from 9.41 to 72.42 per cent. It is no use to increase the quantity of indigo solution when dealing with poor samples. The colour will generally be very dirty, and it will be almost impossible to notice the change from blue to a yellow or pale yellow.Analysts wishing t o use the process must, therefore, get the best quality of indigo-carmine. L. DE K. Analysis of Phosphates. By R. JONES (Zeit. ang. Chem., 1891, 3-41) .-The author is very satisfied with Giaser’s alcohol process, but thinks it may be much improved by lessening the amount of sulph- uric acid. Glaser recommends 45 grams of the strongest acid ; but even if the sample consisted solely of calcium oxide, 2 grams would be quite sufficient. The author also thinks that the quantity of the sample actually used for the analysis (0.4 gram) is far t,oo small, and that at least 1 gram should be taken. He finally recommends the following process :- 10 grams of the sample, which must be free from organic matter, is dissolved in nitro-hydrochloric acid, and diluted to 500 C.C. 50 C.C.of the solution (= 1 gram of the sample) is evaporated t o 25 C.C. and, while still hot, mixed with 10 C.C. of dilute sulphuric acid (1 : 5). After adding 150 C.C. of alcohol, the mixture is allowed t o remain for a t least three hours (Glaser thought half an hour sufficient). The calcium sulphate is collected and washed with alcohol until the washings, after being diluted with water, do not show the faintest acidity with methyl-orange. I f it is desired to estimate the amount of calcium (the process is really devised for the accurate estimation of theiron and nluniiiiium), the filter is put into a platinum dish, the alcohol burnt off, and the calcium sulphate finally ignited and weighed, Tho alcoholic filtrate is distilled, the residue rinsed into a beaker, and a slight excess of ammonia added, but it must again be completely boiled off. This is of particular importance when the phosphate con- tains magnesia ; the precipitate at first almajs contains magnesia, but this is redissolved on boiling. In order to get a clear filtrate, it is as well to wash the precipitate, consisting of ferric arid aluminic phos- phates, with water containing a little ammonium nitrate.If it is pre- ferred to weigh the iron and aluminium as pure oxides, the precipitate may be treated according to Stutzer’s plan, namely, removal of the phosphoric acid by ammonium molybdate and precipitation of the filtrate with ammonia.L. DE K. Physiological Detection of Carbonic Oxide in a Medium containing only 1 part in 10,000. By N. GRBHANT (Compt. rend., 113, 289--X90).-When air containing only 1 part of carbonic oxide in 10,000 is passed for half an hour through 50 C.C. of defibrinated, filtered dog’s blood, the respiratory power falls from 23.7 to 23.0. Under a pressure of 5 atmospheres, with the same gas and the same blood, the respiratory power falls to 17.2. This fact may be utilised for the detection of minute quantities of carbonic oxide. It is clear that the absorption of carbonic oxide by the blood is not determined by the percentage of this gas by volume, but by the mass of the gas present in a given Tolume. C. H. B.100 ABSTRAOTS OF OHEMICAL PAPERS. Separation of Barium from Calcium.By R. FRESENIUS (Zeit. anal. Chem., 30, 583-595).-Methods based on th)e Diferential Action of Alkaline Carbonates on the mixed Sulphates.-Boiling the freshly- precipitated sulphates with a mixture of potassium carbonate and sulphate, and subsequent treatment with hydrochloric acid, gives fairly accurate results, the comparatively small errors compensating one another. The errors are milch larger when cold ammonium carbonate solutioa is used for the decomposition of the calcium sulphate, the barium sulphate being also attacked to a considerable extent, whilst weighable amounts of calcium are left undissolved. Fleischer’s method gives results sufficiently accurate for most pur- poaes. The solution is precipitated by a mixture of 3 parts of potas- sium sulphate and 1 part of potassium carbonate.Since this at once throws down the calcium as carbonate, there is no tendency for the barium sulphate to retain calcium sulphate. After 12 hours’ diges- tion, the precipitate is washed with ammonium carbonate, then dried, weighed (burning the filter and treating the ash with ammonium carbonate), and treated with a measured excess of standard hydro- chloric acid, the excess being titrated with alkali. To complete the action of the acid on the calcium carbonate, prolonged digestion is necessary. Sidersky’s process likewiee affords serviceable results. The solution is precipitated by a mixture of ammonium sulphate and oxalate (200 grams of the former and 30 grams of the latter in a litre). The washed precipitate, consisting of bariiim sulphate and calcium oxalate, is dissolved in dilute hydrochloric acid, and the oxalic acid titrated by permaaganate.The barium sulphate can then be collected (after partially neutralising the acid by ammonia), or the joint amount of the two metals may be found in a separate portion. Rose’s proposal to separate calcium sulphate from strontium sulpliate by digestion with concentrated solution of ammonium sulphate, ap- peared likely to succeed with a mixture of barium and calcium sulph- ates, but prolonged digestion leaves much of the calcium undissolved, whilst the portion dissolved cannot be. accurately estimated by am- monium oxalate, since the ammonium sulphate solution (whether concentrated or dilute) is capable of dissolving a very notable amount of calcium oxalate.M. J. S. Combination of Wet and Dry Methods in Chemical Analysis. By W. E. ADENEY and T. A. SHEGOG (Chem, News, 64, 174-175, 185-187, and 192--193).-The problems which the authors wished to solve by direct experiments were : 1. Whether, when fused in the reduc- ing flame on charcoal with borax and sodium carbonate, the metals anti- mony, tin, lead, arsenic, silver, tismut,h, copper, nickel, and zinc could be completely reduced from their salt,s containing either volatile or non-volatile acids. ‘2. Whether, when sirnilurly treated, aluminium, chromium, manganese, cobalt, and iron are wholly non-reducible from their compounds; the cobalt and iron more especially from their arsenates and phosphates. 3. Whether, when a mixture of salts is similarly treated, the constituent metals thereof respectively behave as in simple co~ripounds, or whether their behaviour is modified in any way.In their present paper, the authors mainly deal with theANALYTICAL CHEMISTRY. 101 problems Nos. 1 and 2. The details of manipulation are as fol- lows :- The Charcoal Support.-The pieces should be about 15 inches in length, and about 1s inches in diameter, and should be tolerably free from fissures. The cavity into which the substance is to be intro- duced should be bored conical, the sides being slightly curved. The size, of course, varies with the quantities of the materials used in the experiment ; but, in the authors’ assays, the diameter was l h inches, and the greatest depth If inches. The Source of Heat.-Although an ordinary paraffin oil lamp, or one burning solid paraffin, may be ad- vantageously used, titill, when coal gas is procurable, it is by far the most convenient source of heat, as it can be burnt at the end of a flattened tube; and, if this be pivoted so that it can rotate in a vertical plane, it will be found of advantage in dealing with readily oxidisable met,allic beads.Phe blowpipe used was an ordinary mouth- blowpipe, furnished with a platinum jet, and fixed in a clip on a retort-stand. An india-rubber hand-blower was used for obtaining the blast. The boi-ax used was fused in a platinum dish, powdered, and kept in a dry aud well-stoppered bottle. The silver was at first used in the form of nitrate, but, this not answering well, it was re- placed by a, mixture of argentic chloride arid borax.In some cases it was used in the form of wire, or a butkon, after the substance and the fluxes had been first fused in the oxidising flame. The s o d i m carbojtafe, which the authors now only employ in the analysis of silicates, was the ordinary dried and powdered commercial article. Quantities.-The most convenient quantities to work on generally are 0.3 gram of substance and 1.2 grams of borax; but, when dealing with ores rich in nickel or zinc, not tilore than 0.1 gram should be taken. While the fusion is proceeding, the charge must be worked round and round the cavity, the metallic bead being made t9 run ‘round the glass and pick up the metals as reduced. ‘1’0 prevent oxidation, a stream of coal gas is directed into the cavity while the melt is cooling. As regards the first problem, the authors found that when fusing oxygenated compounds of antimony, tin, lead, arsenic, bismuth, and copper, or nickel chloride (mixed.with metallic arsenic), with a mix- kure of borax, sodium carbonate, and argentic chloride, the reduction of the metals was practjically complete, the glass bead being free from metal. Zinc, however, was foutid in both beads, showiug the incom- pleteness of the reduction. Auother series of experiments was now made. The ores and fluxes were fused together in a shallow cavity in charcoal with the aid of the oxidising flame. After cooling, the beads were transferred to a cavity of the usual shape a n d size, and, after the addittori of a button of metallic silver, hetted in the rsducing flame.Satisfactory result3 were obtained with antimony, lead, arsenic, copper, and nickel; but in the case of tin and bismuth the reduction was incomplete. As regards the ditficultly reducible metallic oxides, th3 authors operated as follows :-O*S gram of the substance was fused with 1.2 grams of borax or charcoal in the oxidising dame, 0.9 gram of silver button (1.2 grams when dealirig with cobalt) was added, and .the fusion102 ABSTRACTS OF CEIEMIOAL PAPERS. repeated i n the oxidation flame. The results were qualitatively satis- factory with cobalt, aluminium, chromium, and manganese ; of iron, only a mere trace passed into the silver button. The investigation as regards mixed metallic compounds will ba carried on by one of the authors, L.DE K.. Assay of Commercial Aluminium. By F. REGELSBERGER (Zeit. ung. Chem., 1891, 20, 52).--Klemp has proposed to measure the volume of hydrogen which is evolved by dissolving the metal in potash-ley ; but as commercial aluminium invariably contains silicon, which also evolves hydrogen, his process cannot give the exact amount of pure metal. A sample submitted to the author contained 98 per cent. of aluminium, but as it also contained 1.5 per cent. of silicon, it showed 99.9 per cent. of metal by Klemp’s process. The author thinks it by far the best plan to carefully estimate the percent- age of impurities in the sample and take the aluminium by difference ; but if a direct estimation of the metal is desired, he proceeds as follows :- Two grams of the sample is dissolved in a platinum basin, in water containing 15 grams of Fotassium hydroxide, and the whole is finally made up t o 200 C.C. 50 C.C.of the alkaline solution (= 0.5 gram of the sample) is now boiled with a slight excess of neutral ammonium nitrate which throws down the alumina with more or less silica. After washing, igniting, and weighing, any silica must be estimated in the usual way by fusion with potassium hydrogen sulphate, and if there is any reason to believe that t h e reagenta used contain alumina or silica, the usual check mnst be made. L. DE K. Direct Estimation of Aluminium in Iron and Steel. By T. M. DROWN and A. G. MCKENNA (Chem. News, 64,19+196).-The alumina obtained dur.ing a quantitative analysis often contains ferric oxide and phosphoric acid.As the direct estimation of the alumina is as yet very unsatisfactory, the analyst, as a rule, contents himself with estimating the iron and phosphoric acid, and taking the alumina by difference. This is a very good plan when the iron and phosphorus are present in relatively small quantities, but when, as in the modern alloys of aluminium and iron, the aluminium may be present only to the extent of a fraction of I per cent., nothing short of the isolation of the alumina can satisfactorily prove its presence. The authors, after many experiments, finally adopted the following electrolytic process :-About 5 t o 10 grams of the iron or steel is dissolved in sulphuric acid, and the solution heated until white fumes of aulphuric anhydride begin to come off, Boiling water is added to dissolve the iron salt, and the liquid filtered off from the silica and carbon, which are washed with acidified water.The filtrate is nearly neutralised with ammonia, and, if necessary, diluted to 300-500 C.C. The beaker in which the electrolysis is to be made contains from 500 to 1000 grams of mercury, which consti. tutes the cathode, It is connected with the battery or dpamo current in such a manner that about 2 amperes may pass through theANALP l‘ICAL CHEMISTRY. 103 solntion over night, which is best accomplished by using three lamps of 32-candle power, arranged in parallel on an Edison circuit. After, as far as possible, neutralising the acid which has been set free, the electrolysis is continued until the liquid gives no reaction for iron.It generally turns reddish from the formation of permanganic acid. When all the iron has amalgamated, the liquid is removed by means of a pipette while the cnrrent is still passing, and the mercury is repeatedly washed. The platinum anode, which will generally be slightJy coated with manganese dioxide, is now taken out, and the mercury again washed with water until the last traces of solution have been removed from it. After filtering to remoFe any suspended manganese dioxide, excess of sodium phosphate is added, and also 10 grams of sodium acetate. After boiling for at least 40 minutes, the aluminium phosphate is collected, washed, ignited, and weighed. The formula is not, as generally believed, AlzP20a, but 7AlZO3,6 P,O,. It should, of course, have a pure white colour, but it must, be remem- bered that the presence of even 4 per cent.of ferric oxide will give a, decidedly reddish product. In case of doubt, it may be fused with potassium hydrogen sulphate, and the solution once more submitted to electrolysis, but the authors hare always found this t o be super- -8uous. The test analyses are satisfactory. L. DE K, Separation of Iron from Cobalt, Nickel, and Manganese. By A. C. CAMPBELL (&it. anal. Chern., 30, 616-617; from J. arbaZ. Chem., 2, 291 ).-Ferric salts are precipitated by lead carbonate, whilst those of cobalt, nickel, manganese, and ferrous iron are not decomposed. Some lead chloride should be present to neutralise any traces of alkali. Warming promotes the reaction, and as oxida- tion of the cobaltous, manganous, and ferrous salts must be prevented, nitrates should be absent.The washed precipitate is treated with sulphuric acid, whereby the iron is redissolved and separated from the lead. To test the iron precipitate for cobalt and nickel, it is dissolved in hydrochloric acid and the concentrated solution reduced by tin foil. Traces of cobalt or nickel can then be recognised by the colour they communicate to the colourless ferrous chloride solution. M. J. S. New Methods of Quantitative Analysis. Part I. By A, BAUMANN (Zeit. ang. Chenz., 1891, 135--142).-When chromic acid is dissolved in dilute sulphuric acid and mixed with hydrogen peroxide, oxygen is evolved. According to some investigators, the reaction is not quantitative, but the author’s experiments prove that 1 mol.of chromic acid liberates exactly 2 mols. of oxygen and 1 mol. of potassium dichromate 4 mols. of that gas. The most suit- able apparatus is a Wagner’s azotometer, or a Knop’s apparatus con- nected with a Wagner’s gas flask, which is an ordinary flask into which a small glass cylinder has been sealed. Estimation of Chromic Acid.-The liquid, which must not be too concentrated and not exceed 50 C.C. in bulk, is mixed with 10 C.C. of dilute sulphuric acid (1 : 5) in the outer chamber of the flask. The104 ABSTRACTS OY CHEMCCAL PAPEHB. little gl~ss cylinder is filled with 5 to 10 C.C. of commercial hydrogen peroxide. After allowing the hydrogen peroxide to run into the chromate, the liquid will at first assume a fine blue colour, and then gradually evolve oxygen. The bulk of this gas will be given off in a few minutes, but the remainder will be only expelled after five minufeB’ brisk agitation.When shaking, the operator must open the stopcock about every half minute to let the oxygen gradually escape into the measuring tube. The liquid i n the non-graduated tube ought to stand a little lower during the evolution of the gas. When no more gas is given off, the apparatus is put, for about 15 minutes, into water of the temperature of the room ; the water in the tubes is levelled, and the volume of the gas is read off; 1 C.C. of oxygen at norms1 temperature and pressure = 0.002246 gram of chromic acid (Cr03). It is not advisable to work with hydrochloric instead of sulphuric acid, as there is always a risk of chlorine being evolved. Traces of free nitric acid do not interfere, but when the liquid contains more than 0.2 gram the oxygen found will be some- what too low.Acetic and succinic acids do not affect the results, but other organic acids or organic substances decidedly interfere. In standardising a solution of potassium dichromate, it must be remem- bered tha,t only three-eighths of the oxygen evolved is derived from the chromic acid. Estimation of Chromic Oxide.-This is very readily converted into a chromate by treating its alkaline solution with hydrogen peroxide, the excess of which may be driven off by boiling. After neutralising the solution with sulphuric acid, the chromic acid is determined as directed, and calculated to Cr203. In the assay of chrome-iron ore by this process, the use of nitre as an oxidising flux must be avoided, and 0.3 gram of the finely powdered mineral must be fused with a mixture of 3 prams of sodium carbonate and 3 grams of barium peroxide for half an hour.The mass must afterwards be decomposed with sulphuric instead of hydrochloric acid, Estimation of Combined Sulphuric Acid.-The liquid, which should contain no excess of hydrochloric acid and but traces of nitric acid or nitrates, is put into a 100 C.C. measuring flask, and precipitated in the cold with a solut’ion of pure barium chromate in hydrochloric acid. As the commercial salt often contains alkali chromate, it must before use be thoroughly washed with water until the filtrate is practically colourless. The residue i s then dissolved in an insuffici- ency of hydrochloric acid containing 3 per cent.HC1, and, after filtering, preserved for use. After diluting with water to about 90 c.c., the liquid is rendered faintly alkaline with ammonia, made up t o the mark, and filtered. An aliquot part of the filtrate, say 25 or 60 c.c., is then treated in the apparatus with sulphuric acid and hydrogen peroxide. 1 C.C. of oxygen = 0.001787636 gram of sulphuric anhydride. The various test analyses are very satisfactory. L. DE K.ANALYTICAL CHEMISTRY. 97An a l y t i c a1 Chemistry.Estimation of Hydrochloric Acid in the Gastric Juice. ByJ. BOAS (Chem. Centr., 1891, ii, 357; from Centr. med. Wiss., 1891,509).-The author has adopted Bourget’s method (evaporation andincineration with barium carbonate, extraction with water, and pre-cipitation of the barium chloride formed by sodium carbonate),with the slight modification that, after dissolving the precipitate indecinormal acid, the liquid is boiled until all carbonic anhydride isexpelled, and the excess of acid is then neutralised with decinormalalkali ; the indicator is phenolphthalei’n.Estimation of Free Oxygen by means of Nitric Oxide.By L.L. DE KONINCK (Zeit. ang. Chem., 1891, 78--80).-The author’sattention was drawn to an article by Wsnklyn and Cooper on theestimation of oxygen by means of nitric oxide. These chemists con-sider that this process, which was originated by Priestley, but whichnow only possesses a,n historical interest, is not only verj accuratebut even one of the best methods known, and they communicated a fewsatisfactory test analyses.The author some time ago had occasion totry the process, but his experience agreed with the results obtainedby Berthelot, Lunge, and Winkler, which were very irregular andunsatisfactory. He therefore thought it advisable to once morethoroughly investigate the matter.The modus operandi was practically identical with that employedby Wanklyn and Cooper, except, perhaps, as regards the preparationof the nitric oxide, which was obtained by the action of nitric acid(sp. gr. 1.1) on a, spiral of sheet-copper contained in an old-fashionedHempel’s hydrogen pipette. On account of its simplicity and easyexecution, the following plan was adopted :-The gas (oxygen or air)was introduced into a Winkler-Hempel burette, the nitric oxideintroduced into a like apparatus, and thoroughly shaken with thewater to saturate this with the gas, and also to remove traces ofnitric peroxide. After a few minutes rest, the two volumes of gaswere respectively recorded, and after connecting the two buretteswith a capillary tube filled with water, the oxygen mixture was forcedinto the nitric oxide (not the reverse way), and the burettes werenow disconnected.After thoroughly shaking t o facilitate the ab-sorption, and waiting for twelve or fifteen minutes, the volume of thegas was read off with the usual precautions, and the contractionnoted. The results obtained once more proved the process to beabsolutely useless, as the quantity of oxygeii found varied between77.5 and 122.j per cent.of the amount operated on. From a scien-tific point of view, however, the results were not uninteresting.The ratio between the volume of the oxygen and the contractionafter the action of the nitric oxide may theoretically vary between1 : 2.33 and 1 : 5, as shown by the following equations :-VOL. LXII. hJ. W. L98 ABSTRACTS OF 0 dEMIOAL PAPERS.4N0 + 30, + 2Hz0 = 4HNO; ratio, 1 : 2.33,2N0 + 0 2 + R2O = HNOZ + RON,; ,, 1 : 3,4N0 + 202 + H20 = 4HN0 ,, 1 : 5.A good deal depends on the celerity with which the gases havebeen mixed and shaken with the water. As a rule, a large excessof nitric oxide or admixture with an inert gas, such as nitrogen,seems to favour the formation of nitrous acid.L. DE K.Estimation of Free Oxygen dissolved in Water. By W.KISCH (Zed. ang. Chem., 1891, 105-108) .-The author compared thevarious processes in use for the estimation of free oxygen in water.(a,.) Bunsen-Tiemann’s process.-The water is boiled, and the gasescollected over hot solution of caustic potash. The oxygen is thenestimated by explosion with hydrogen or by absorption with alkalinepyrogallol. ( b . ) Mohr’s process -The sample is mixed with anacld solution of ferrous sulphate of known strength, then withaqueous soda to throw down the ferrous hydroxide. After remain-ing for a few hours (air, of course. being rigidly excluded), the-precipitate is redissolved in sulphuric acid, and the ferrous sulphatetitrated with permanganate. (c.) The Schiitzenberger-Itisler process.-The water is allowed to act on a solution of sodium hydrindigotin-disulphonate, which then passes into the blue compound.Standardsolution of sodium hyposulphite is then run in till the liquid isagain decolorised. ( d . ) Winkler’s process.-T he water is mixedwith a solution of manganous chloride, and then with potassiumiodide and potassium hydroxide. The precipitated rnanganous hydr-oxide rapidly absorbs the oxygen, and passes into a higher oxidisedstate. On adding hydrochloric acid, iodine is liberated, which isthen estimated by a solution of sodium thiosulphate. On applyingthese processes to the same sample of water, the results obtainedby Bunsen-Tiemann’s process were decidedly lower than those ob-tained by Winkler’s process, whilst those obtained by both Mohr’sand the Schutzenberger-Rider methods corresponded very well withWinkler’s figures.The author, however, strongly recommends thelatter process as being the safest, most trustworthy, and the easiestSchiltzenberger’s Process for the Estimation of Free Oxygen.By T. ‘K~NIG (Zeit. ang. Chem., 1891, 108, llO).-The author, notalways getting satisfactory results with this process, investigated thecause. Success depends in a great measure on the quality of theindigo solution employed. If the sample is poor in quality, it doesnot absorb the oxygen rapidly enough, and a portion of this is sweptaway by the current of hydrogen. Indigo-carmine is obtained byprecipitating a solution of purified indigo in sulphuric acid withsalt, If simply collected, a pasty mass is obtained which formsthe commercial indigo-carmine ; but, if well washed and dried, solidsodium indigodisulphonate is obtained.These preparations vary,however, considerably in strength, sometimes from 79.08 to 91.58 percent. in the so-called crystallised and sublimed product, whilst ot.herin manipulation. L. DE KANALYTICAL CHEMISTRY. 99samples vaaied in strength from 9.41 to 72.42 per cent. It is no useto increase the quantity of indigo solution when dealing with poorsamples. The colour will generally be very dirty, and it will bealmost impossible to notice the change from blue to a yellow or paleyellow. Analysts wishing t o use the process must, therefore, get thebest quality of indigo-carmine. L.DE K.Analysis of Phosphates. By R. JONES (Zeit. ang. Chem., 1891,3-41) .-The author is very satisfied with Giaser’s alcohol process, butthinks it may be much improved by lessening the amount of sulph-uric acid. Glaser recommends 45 grams of the strongest acid ; buteven if the sample consisted solely of calcium oxide, 2 grams wouldbe quite sufficient. The author also thinks that the quantity of thesample actually used for the analysis (0.4 gram) is far t,oo small, andthat at least 1 gram should be taken. He finally recommends thefollowing process :-10 grams of the sample, which must be free from organic matter,is dissolved in nitro-hydrochloric acid, and diluted to 500 C.C. 50 C.C.of the solution (= 1 gram of the sample) is evaporated t o 25 C.C.and,while still hot, mixed with 10 C.C. of dilute sulphuric acid (1 : 5).After adding 150 C.C. of alcohol, the mixture is allowed t o remain fora t least three hours (Glaser thought half an hour sufficient). Thecalcium sulphate is collected and washed with alcohol until thewashings, after being diluted with water, do not show the faintestacidity with methyl-orange. I f it is desired to estimate the amountof calcium (the process is really devised for the accurate estimation oftheiron and nluniiiiium), the filter is put into a platinum dish, the alcoholburnt off, and the calcium sulphate finally ignited and weighed, Thoalcoholic filtrate is distilled, the residue rinsed into a beaker, and aslight excess of ammonia added, but it must again be completelyboiled off.This is of particular importance when the phosphate con-tains magnesia ; the precipitate at first almajs contains magnesia, butthis is redissolved on boiling. In order to get a clear filtrate, it is aswell to wash the precipitate, consisting of ferric arid aluminic phos-phates, with water containing a little ammonium nitrate. If it is pre-ferred to weigh the iron and aluminium as pure oxides, the precipitatemay be treated according to Stutzer’s plan, namely, removal of thephosphoric acid by ammonium molybdate and precipitation of thefiltrate with ammonia. L. DE K.Physiological Detection of Carbonic Oxide in a Mediumcontaining only 1 part in 10,000. By N. GRBHANT (Compt.rend.,113, 289--X90).-When air containing only 1 part of carbonic oxidein 10,000 is passed for half an hour through 50 C.C. of defibrinated,filtered dog’s blood, the respiratory power falls from 23.7 to 23.0.Under a pressure of 5 atmospheres, with the same gas and the sameblood, the respiratory power falls to 17.2. This fact may be utilisedfor the detection of minute quantities of carbonic oxide. It is clearthat the absorption of carbonic oxide by the blood is not determinedby the percentage of this gas by volume, but by the mass of the gaspresent in a given Tolume. C. H. B100 ABSTRAOTS OF OHEMICAL PAPERS.Separation of Barium from Calcium. By R. FRESENIUS (Zeit.anal. Chem., 30, 583-595).-Methods based on th)e Diferential Actionof Alkaline Carbonates on the mixed Sulphates.-Boiling the freshly-precipitated sulphates with a mixture of potassium carbonate andsulphate, and subsequent treatment with hydrochloric acid, givesfairly accurate results, the comparatively small errors compensatingone another.The errors are milch larger when cold ammoniumcarbonate solutioa is used for the decomposition of the calciumsulphate, the barium sulphate being also attacked to a considerableextent, whilst weighable amounts of calcium are left undissolved.Fleischer’s method gives results sufficiently accurate for most pur-poaes. The solution is precipitated by a mixture of 3 parts of potas-sium sulphate and 1 part of potassium carbonate. Since this at oncethrows down the calcium as carbonate, there is no tendency for thebarium sulphate to retain calcium sulphate.After 12 hours’ diges-tion, the precipitate is washed with ammonium carbonate, then dried,weighed (burning the filter and treating the ash with ammoniumcarbonate), and treated with a measured excess of standard hydro-chloric acid, the excess being titrated with alkali. To complete theaction of the acid on the calcium carbonate, prolonged digestion isnecessary. Sidersky’s process likewiee affords serviceable results.The solution is precipitated by a mixture of ammonium sulphate andoxalate (200 grams of the former and 30 grams of the latter in alitre). The washed precipitate, consisting of bariiim sulphate andcalcium oxalate, is dissolved in dilute hydrochloric acid, and theoxalic acid titrated by permaaganate.The barium sulphate can thenbe collected (after partially neutralising the acid by ammonia), or thejoint amount of the two metals may be found in a separate portion.Rose’s proposal to separate calcium sulphate from strontium sulpliateby digestion with concentrated solution of ammonium sulphate, ap-peared likely to succeed with a mixture of barium and calcium sulph-ates, but prolonged digestion leaves much of the calcium undissolved,whilst the portion dissolved cannot be. accurately estimated by am-monium oxalate, since the ammonium sulphate solution (whetherconcentrated or dilute) is capable of dissolving a very notable amountof calcium oxalate. M. J. S.Combination of Wet and Dry Methods in Chemical Analysis.By W.E. ADENEY and T. A. SHEGOG (Chem, News, 64, 174-175,185-187, and 192--193).-The problems which the authors wished tosolve by direct experiments were : 1. Whether, when fused in the reduc-ing flame on charcoal with borax and sodium carbonate, the metals anti-mony, tin, lead, arsenic, silver, tismut,h, copper, nickel, and zinc couldbe completely reduced from their salt,s containing either volatile ornon-volatile acids. ‘2. Whether, when sirnilurly treated, aluminium,chromium, manganese, cobalt, and iron are wholly non-reducible fromtheir compounds; the cobalt and iron more especially from theirarsenates and phosphates. 3. Whether, when a mixture of salts issimilarly treated, the constituent metals thereof respectively behaveas in simple co~ripounds, or whether their behaviour is modified inany way.In their present paper, the authors mainly deal with thANALYTICAL CHEMISTRY. 101problems Nos. 1 and 2. The details of manipulation are as fol-lows :-The Charcoal Support.-The pieces should be about 15 inches inlength, and about 1s inches in diameter, and should be tolerably freefrom fissures. The cavity into which the substance is to be intro-duced should be bored conical, the sides being slightly curved. Thesize, of course, varies with the quantities of the materials used in theexperiment ; but, in the authors’ assays, the diameter was l h inches,and the greatest depth If inches. The Source of Heat.-Although anordinary paraffin oil lamp, or one burning solid paraffin, may be ad-vantageously used, titill, when coal gas is procurable, it is by far themost convenient source of heat, as it can be burnt at the end of aflattened tube; and, if this be pivoted so that it can rotate in avertical plane, it will be found of advantage in dealing with readilyoxidisable met,allic beads.Phe blowpipe used was an ordinary mouth-blowpipe, furnished with a platinum jet, and fixed in a clip on aretort-stand. An india-rubber hand-blower was used for obtainingthe blast. The boi-ax used was fused in a platinum dish, powdered,and kept in a dry aud well-stoppered bottle. The silver was at firstused in the form of nitrate, but, this not answering well, it was re-placed by a, mixture of argentic chloride arid borax. In some casesit was used in the form of wire, or a butkon, after the substance andthe fluxes had been first fused in the oxidising flame.The s o d i mcarbojtafe, which the authors now only employ in the analysis ofsilicates, was the ordinary dried and powdered commercial article.Quantities.-The most convenient quantities to work on generallyare 0.3 gram of substance and 1.2 grams of borax; but, when dealingwith ores rich in nickel or zinc, not tilore than 0.1 gram should betaken. While the fusion is proceeding, the charge must be workedround and round the cavity, the metallic bead being made t9 run‘round the glass and pick up the metals as reduced. ‘1’0 preventoxidation, a stream of coal gas is directed into the cavity while themelt is cooling.As regards the first problem, the authors found that when fusingoxygenated compounds of antimony, tin, lead, arsenic, bismuth, andcopper, or nickel chloride (mixed.with metallic arsenic), with a mix-kure of borax, sodium carbonate, and argentic chloride, the reductionof the metals was practjically complete, the glass bead being free frommetal. Zinc, however, was foutid in both beads, showiug the incom-pleteness of the reduction. Auother series of experiments was nowmade. The ores and fluxes were fused together in a shallow cavityin charcoal with the aid of the oxidising flame. After cooling, thebeads were transferred to a cavity of the usual shape a n d size, and,after the addittori of a button of metallic silver, hetted in the rsducingflame.Satisfactory result3 were obtained with antimony, lead,arsenic, copper, and nickel; but in the case of tin and bismuth thereduction was incomplete.As regards the ditficultly reducible metallic oxides, th3 authorsoperated as follows :-O*S gram of the substance was fused with 1.2grams of borax or charcoal in the oxidising dame, 0.9 gram of silverbutton (1.2 grams when dealirig with cobalt) was added, and .the fusio102 ABSTRACTS OF CEIEMIOAL PAPERS.repeated i n the oxidation flame. The results were qualitatively satis-factory with cobalt, aluminium, chromium, and manganese ; of iron,only a mere trace passed into the silver button.The investigation as regards mixed metallic compounds will bacarried on by one of the authors, L. DE K..Assay of Commercial Aluminium.By F. REGELSBERGER (Zeit.ung. Chem., 1891, 20, 52).--Klemp has proposed to measure thevolume of hydrogen which is evolved by dissolving the metal inpotash-ley ; but as commercial aluminium invariably contains silicon,which also evolves hydrogen, his process cannot give the exactamount of pure metal. A sample submitted to the author contained98 per cent. of aluminium, but as it also contained 1.5 per cent.of silicon, it showed 99.9 per cent. of metal by Klemp’s process. Theauthor thinks it by far the best plan to carefully estimate the percent-age of impurities in the sample and take the aluminium by difference ;but if a direct estimation of the metal is desired, he proceeds asfollows :-Two grams of the sample is dissolved in a platinum basin, inwater containing 15 grams of Fotassium hydroxide, and the whole isfinally made up t o 200 C.C. 50 C.C.of the alkaline solution(= 0.5 gram of the sample) is now boiled with a slight excess ofneutral ammonium nitrate which throws down the alumina withmore or less silica. After washing, igniting, and weighing, any silicamust be estimated in the usual way by fusion with potassiumhydrogen sulphate, and if there is any reason to believe that t h ereagenta used contain alumina or silica, the usual check mnst bemade. L. DE K.Direct Estimation of Aluminium in Iron and Steel. By T.M. DROWN and A. G. MCKENNA (Chem. News, 64,19+196).-Thealumina obtained dur.ing a quantitative analysis often containsferric oxide and phosphoric acid.As the direct estimation of thealumina is as yet very unsatisfactory, the analyst, as a rule,contents himself with estimating the iron and phosphoric acid, andtaking the alumina by difference. This is a very good plan whenthe iron and phosphorus are present in relatively small quantities,but when, as in the modern alloys of aluminium and iron, thealuminium may be present only to the extent of a fraction of I percent., nothing short of the isolation of the alumina can satisfactorilyprove its presence. The authors, after many experiments, finallyadopted the following electrolytic process :-About 5 t o 10 grams ofthe iron or steel is dissolved in sulphuric acid, and the solutionheated until white fumes of aulphuric anhydride begin to come off,Boiling water is added to dissolve the iron salt, and the liquid filteredoff from the silica and carbon, which are washed with acidified water.The filtrate is nearly neutralised with ammonia, and, if necessary,diluted to 300-500 C.C.The beaker in which the electrolysis is tobe made contains from 500 to 1000 grams of mercury, which consti.tutes the cathode, It is connected with the battery or dpamocurrent in such a manner that about 2 amperes may pass through thANALP l‘ICAL CHEMISTRY. 103solntion over night, which is best accomplished by using three lampsof 32-candle power, arranged in parallel on an Edison circuit. After,as far as possible, neutralising the acid which has been set free, theelectrolysis is continued until the liquid gives no reaction for iron.Itgenerally turns reddish from the formation of permanganic acid.When all the iron has amalgamated, the liquid is removed bymeans of a pipette while the cnrrent is still passing, and the mercuryis repeatedly washed. The platinum anode, which will generally beslightJy coated with manganese dioxide, is now taken out, and themercury again washed with water until the last traces of solutionhave been removed from it. After filtering to remoFe any suspendedmanganese dioxide, excess of sodium phosphate is added, and also10 grams of sodium acetate. After boiling for at least 40 minutes,the aluminium phosphate is collected, washed, ignited, and weighed.The formula is not, as generally believed, AlzP20a, but 7AlZO3,6 P,O,.It should, of course, have a pure white colour, but it must, be remem-bered that the presence of even 4 per cent.of ferric oxide will give a,decidedly reddish product. In case of doubt, it may be fused withpotassium hydrogen sulphate, and the solution once more submittedto electrolysis, but the authors hare always found this t o be super--8uous.The test analyses are satisfactory. L. DE K,Separation of Iron from Cobalt, Nickel, and Manganese.By A. C. CAMPBELL (&it. anal. Chern., 30, 616-617; from J.arbaZ. Chem., 2, 291 ).-Ferric salts are precipitated by lead carbonate,whilst those of cobalt, nickel, manganese, and ferrous iron are notdecomposed. Some lead chloride should be present to neutraliseany traces of alkali. Warming promotes the reaction, and as oxida-tion of the cobaltous, manganous, and ferrous salts must be prevented,nitrates should be absent.The washed precipitate is treated withsulphuric acid, whereby the iron is redissolved and separated from thelead. To test the iron precipitate for cobalt and nickel, it is dissolvedin hydrochloric acid and the concentrated solution reduced by tinfoil. Traces of cobalt or nickel can then be recognised by the colourthey communicate to the colourless ferrous chloride solution.M. J. S.New Methods of Quantitative Analysis. Part I. By A,BAUMANN (Zeit. ang. Chenz., 1891, 135--142).-When chromic acidis dissolved in dilute sulphuric acid and mixed with hydrogenperoxide, oxygen is evolved. According to some investigators, thereaction is not quantitative, but the author’s experiments prove that1 mol.of chromic acid liberates exactly 2 mols. of oxygen and1 mol. of potassium dichromate 4 mols. of that gas. The most suit-able apparatus is a Wagner’s azotometer, or a Knop’s apparatus con-nected with a Wagner’s gas flask, which is an ordinary flask intowhich a small glass cylinder has been sealed.Estimation of Chromic Acid.-The liquid, which must not be tooconcentrated and not exceed 50 C.C. in bulk, is mixed with 10 C.C. ofdilute sulphuric acid (1 : 5) in the outer chamber of the flask. Th104 ABSTRACTS OY CHEMCCAL PAPEHB.little gl~ss cylinder is filled with 5 to 10 C.C. of commercial hydrogenperoxide. After allowing the hydrogen peroxide to run into thechromate, the liquid will at first assume a fine blue colour, and thengradually evolve oxygen.The bulk of this gas will be given off in afew minutes, but the remainder will be only expelled after fiveminufeB’ brisk agitation. When shaking, the operator must openthe stopcock about every half minute to let the oxygen graduallyescape into the measuring tube. The liquid i n the non-graduatedtube ought to stand a little lower during the evolution of the gas.When no more gas is given off, the apparatus is put, for about15 minutes, into water of the temperature of the room ; the water inthe tubes is levelled, and the volume of the gas is read off; 1 C.C. ofoxygen at norms1 temperature and pressure = 0.002246 gram ofchromic acid (Cr03). It is not advisable to work with hydrochloricinstead of sulphuric acid, as there is always a risk of chlorine beingevolved. Traces of free nitric acid do not interfere, but when theliquid contains more than 0.2 gram the oxygen found will be some-what too low. Acetic and succinic acids do not affect the results, butother organic acids or organic substances decidedly interfere. Instandardising a solution of potassium dichromate, it must be remem-bered tha,t only three-eighths of the oxygen evolved is derived fromthe chromic acid.Estimation of Chromic Oxide.-This is very readily converted intoa chromate by treating its alkaline solution with hydrogen peroxide,the excess of which may be driven off by boiling. After neutralisingthe solution with sulphuric acid, the chromic acid is determined asdirected, and calculated to Cr203. In the assay of chrome-iron ore bythis process, the use of nitre as an oxidising flux must be avoided,and 0.3 gram of the finely powdered mineral must be fused with amixture of 3 prams of sodium carbonate and 3 grams of bariumperoxide for half an hour. The mass must afterwards be decomposedwith sulphuric instead of hydrochloric acid,Estimation of Combined Sulphuric Acid.-The liquid, which shouldcontain no excess of hydrochloric acid and but traces of nitric acid ornitrates, is put into a 100 C.C. measuring flask, and precipitated inthe cold with a solut’ion of pure barium chromate in hydrochloricacid. As the commercial salt often contains alkali chromate, itmust before use be thoroughly washed with water until the filtrate ispractically colourless. The residue i s then dissolved in an insuffici-ency of hydrochloric acid containing 3 per cent. HC1, and, afterfiltering, preserved for use.After diluting with water to about 90 c.c., the liquid is renderedfaintly alkaline with ammonia, made up t o the mark, and filtered.An aliquot part of the filtrate, say 25 or 60 c.c., is then treated inthe apparatus with sulphuric acid and hydrogen peroxide. 1 C.C. ofoxygen = 0.001787636 gram of sulphuric anhydride.The various test analyses are very satisfactory. L. DE K

ISSN:0368-1769    

DOI:10.1039/CA8926200097

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

105 G e n e r a l a n d P h y s i c a l Chemistry. Apparent Variability of the Electro-chemical Equivalent of Copper. By J. VAN" (Ann. Phys. Chem. [el, 44, 214--221).-Gray (Plzil. Mag. [ 5 ] , 22, 389 ; 25, 179), in his researches on the electro- chemical equivalent of copper, found that this magnitude at 12' varied from 0.0003287 with a current density of 20 milliampAres per square centimetre at the cathode, to 0.00032713 with a density of 3.3 mi%- amphres; and at 35" sank so low as 0.0003245. He advances RS a probable explanation of this variability the fact, observed by Gore, that the solution of copper sulphate dissolves up a quantity of copper varying with different conditions. The object of the present investi- gation was to test the validity of this explanation, and to determine the true electro-chemical equivalent.Two copper voltameters with plates of different surface (4 : 1) were placed in the same circuit ; and it was found, for instance, that with a solution of copper sulphate containing 1 per cent. of free sulphuric acid, 0.1903 gram of copper was deposited on the larger cathode, while 0.1960 gram was deposited on the smaller cathode, in the course of three hours. After interruption of the current, the cathodes were allowed to remain three hours longer in the solutions, when i t mas observed that the larger cathode had lost weight to the extent of 9.2 milligrams, and the smaller cathode only 3.2 milli- grams. These weights, added t o the former pair, give 0.1995 gram and 0.1992 gram respectively-results sufficiently close. The author found that when the copper sulphate solution em- ployed contained merely a trace of sulphuric acid (about 5 milligrams per litre), there was no perceptible quantity of copper dissolved in two hours.With such solutions, the electro-chemical equivalents of copper and of silver were compared ; and, taking that of silver as equal to 0.001118, the author gives, as a mean value of 12 concordant ex- periments, the electro-chemical equivalent of copper in cupric salts as equal to 0.0003284. J. W. New Method of Measuring Electromotive Forces and Electrical Resistances. By S. PAGLIBNI (Gnxzettu, 21, 449-454). -A standard wire of known resistance is joined in circuit with the current generator whose electromotive force is to be measured. A branch circuit containing a voltameter is also established, having one terminal fixed to one end of the standard wire and the other fixed to 8 key which slides along the standard wire. The voltameter consists of a glass tube, closed by two taps, containing a 25 per cent.solution of potassium iodide to which has been added a little starch solution. Platinum and copper wires are used for the cathode and anode respectively. The width of the tube is 10 mm. ; the distance between the electrodes 120 mm. The resistance of the standard wires must be so great as to render negligible thc internal resistance of the VOL. LXII. i106 ABSTRACTS OF CHEMIOAL PAPERS. current generator. At the commencement of the determination, the branch circuit is so arranged that the difference of potential at its terminals is insufficient for the electrolysis of the potassium iodide solution: the key ia now moved along the standard wire until it reaches a point at which a violet coloration is observable a t the surface of the platinum wire.The position of the key is then noted, and the electromotive force of the current generator can be calculated in terms of the electromotive force necessary to decompose the potas- sium iodide solution (0.610 volt). Electrical resistances may be measured by employing a current generator of kfiown electromotive force, and inserting the unknown resistance in eit,her the main o r the branch circuit. The author states that this method gives very concordant results. W. J. P. Characteristic Difference between the Substituted Alcohol Radicles directly united with Carbon or with Nitrogen.By C. MATIGNON (c‘ompi. rend., 113, 550--55l).-h the course of a therniochemical study of t h e ureides, the author has arrived at the law, “The substitution of an alcohol radicle directly united with nitrogen increases the heat of combustion more than when the same radicle is directly united with carbon.” The publication of a paper by Stohmann and Langbein (this vol., p. 4), enunciating the same law, rendered necessary the imrnediate production of the author’s r e su 1 t s . Caffeine, theobromine, cholestrophane, and ethylcarbamide were purified and analysed ; their heats of combustion at constant preSsure, together with those of parebanic acid and carbamide, are given below, cal. cal. Caffe’ine(methy1theobromine) C702N4H7Me, 1016.0 Theobromine .............C50,N4H, 845.9) 170.1’ Ethylcarbamide. .......... CON2H3Et, 472.2 320.7 Carbamide ............... CON2H4, Cholestrophane ........... CJ03N,Me,, 538*6 326 Parabanic acid.. .......... C303N2H2, r i 1 he. introduction of a methyl group united with carbon never increases the heat of combustion of the substance by more than 157 cal. ; in the above cases, this number is exceeded by an amount far beyond the limits of experimental error. Ethylcarbamide is con- sidered as derived from urea by two successive methyl substitutions ; takiug 155 cal. as the mean for a substitution of methyl united with carbon, 165.7 cal. is the increase caused by the introduction cf a methyl group combined with nitrogen. The application of this law confirms the suggestion of Grimaux, that pyruvile is a methjl derivative of allantdin, and that it is a true homologue of that substance ; the increase in heat of combustion i n this case is 153 cal.W. T. 151.5 } (= 155 + 165.7). 2 W 6 } (=163 x 2). Expansion of Water. By W. MARRK (Ann. Php. C’hem. [ a ] , 44, 171- 172).--This paper contains a table of the densities of water con-GENERAL AND PHYSICAL CEEMISTRY, 107 taining air for every tenth of a degree from 0" to 31". experimental method will be given in a subsequeni communication. H. C . Details of the Molecular Weights of Liquids as evinced by their Boiling Points. By H. M. VERNOS (Chem. News, 64, 54--58).--The author endeavours to show that from the boiling point of liquids s3me indi- cation as t o the probable value of their molecular weights may be obtained.Hydrogen iodide boils at --So, hydrogen bromide at - 7 3 O , and hydrogen chloride at -loo", from which a boiling point of about -120" might be predicted for hydrogen fluoride. But since hydrogen fluoride actually boils at 19.4", we must assume a more complex molecule for this substance in the liquid state than that represented by the formula HF. This result agrees with Thorpe and Hambly's conclusion that at the boiling point the hydrogen fluoride molecule is probably H,F,. In like manner, comparing the boiling point of water with those of the similar compounds SH2, SeH2, and TeH,, which are gaseous at temperatures far helow O", we should have to assign t p liquid water a molecular weight not smaller than that cor- responding with the formula (H,O)a. The following table illastrates the striking regularity in increase of boiling point which is always observed on the substitution of bromine for chlorine :- Chloride.1 B-P. I-- --- I PC1, ........... -76 -0' POC!, .......... ' 107 '2 AsC13 .......... ~ 134.0 BCI, ............ 18.2 SiCl, ..... ......I 59.6 CHCI,.. ........ I 61.0 CCl, ............ '76 *5 TiC14.. ......... ' 136.1 CH,Cl.. ........ i -22 *O i Bromide. PBr,.. .......... POBr3.. ........ AuBr, .......... BBr, ........... SiBr., ........... CHBr, .......... CBr,. ........... CH3Br.. ........ TiBr, ........... B. p. 175 '0" 195 -0 220.0 90.5 1.54 -0 151 -0 189 '0 4 -5 230 -0 Increase for each atom of Br. ~ ~- 33 *oo 29.3 28.7 24 *1 23 -6 30 *O 28 '1 26 ' 5 23 -5 Other cases are discussed, and the author argues, from a study of the boiling points, that i n all probability all compounds, both organic and inorganic, containing one or more hydroxyl groups, have in the liquid state molecular weights double those expressed by their ordin- arily received formulx?.H. c. Solubility of Gases in Water. By C. BOHR and J. BOCK (Ann. Phys. Chevn. [2], 44, 318--343).-The authors have made fresh determinations of the solubility of oxygen, hydrogen, and nitrogen in water, partly by means of a Bohr's absorptiometer, and parbly by means of two new instruments-a differential absorptiometer and a pumping-out apparatus-which are fully described and figured in the paper. The differential absorptiometer was used for femperatures from 0" to 60"; from 60" to 100" the other apparatus was em- ployed. The mean coefficient of absorption of oxygen in water was found to i 2108 ABSTRACTS OF CHEMIOAL PAPERS.be 0.03497 at 15" ; at 100" it is 0.01679. The agreement with the values obtained by Dittmar and Winckler is good. For nitrogen, the absorption coefficient is 0.01667 at 19", and 0.01046 at 100". The coefficient remains practically constant between 60" and 100'. The authors' numbers agree well with those of Petterson and SondQn, Dittmar, and Hamberg, but diverge considerably from those of Bunsen and of Hiifner. In the case of hydrogen, the author finds that the coefficient of absorption is not independent of the temperature, as Bunsen stated, but falls t o a minimum at about 60", after which it rises until at the boiling point it becomes equal to the coefficient of absorption of oxygen at the same temperature.The numerical values are- a , ~ = 0.0203, a150 = 0.0183, a600 = 0.0144, alm~ = 0.0166. The authors further made two dcteyminations of the solubility of carbonic anhydride, and found a for 37.39' to be 0.5629, and for 100" to be 0-2438. J. W. Nature of Solution. By J. A. WANKLE" and W. JOHNSTONE (Chem. News, 64, 39, 51, and 146 ; compare Abstr., 1891, 1412).- When a solid is dissolved, the volume of the solution is not, as a rule, ,equal to the sum of the volumes of the solid and solvent. The authors have determined the amount of the change for a considerable number of substances which dissolve in water. The alteration, which is usually that of contraction, is expressed in terms of a quantity, which they name the condensate, and obtain by subtracting the mass of solvent displaced by unit mass of dissolved substance from the ratio of the excess of the density of the solution over that of the solvent to the solution-density of the dissolved sub- stance :- .. c = 2 - 21, ____ Density of solution - density of solvent No. of grams of dissolved substance per C.C. of solution ' where i = - - 1 and il = 1 - I Density of dissolved substance The condensate, which, it is stated, may be regarded as the amount of solvent which enters into combination with, or is condensed by, the dissolved substance, appears in several cases to bear a simple molecular ratio to the amount of the latter. Thus, with potassium nitrate, the number is 0.058, whilst the ratio H,O : 3KN0, is 0,059, and with barium hydroxide the number is 0.320, whilst the ratio 3H,O : Ba(OH), is 0.316.I n other cases, however, the agreement is not so close, and the numbers can only be expressed by more complex ratios. With cane sugar, the condensate is zero, whilst with certain am- monium salts it appears to be negative. JN. W. Strong Solutions and the Dissociation Hypothesis. By S. U. PICKERING (Ber., 24, 317-3327) .-The author states that the factQENERAL A:d D PHYSICAL CHEMISTRY. 109 established by him (Abstr., 1891, 972), that weak solutions of sulph- uric acid and other substances contain less, instead of more, acting units than the acid and water separately, caiinot be brought into harmony with the dissociation hypothesis, as Arrhenius considers (Abstr., 1891, 1148), by admitting that complex aggregates of similar molecules exist in pure liquids and strong solutions. After answering some recent criticisms of Arrhenius, he gives a preliminary statement of numerous results obtained in a study of the freezing points of strong solutions.Very weak solutions of electrolytes, as is well known, exhibit an abnormally large molecular depression ; this de- creases as the strength is increased up to a certain point, but after- wards it again increases, and often attains values which are abnorm- ally large in a very high degree. Non-elect'rolytes appear to behave in the opposite manner; in every case investigated, the molecular depression decreases with the strength of the solution, although in a few cases this abnormally small depression is preceded by a com- paratively slight and temporary increase.Although so- called dis- sociation may offer some explanation of the behaviour of very weak solutions, it appears to be incapable of explaining that of strongel- solutions, for here the molecular depression increases, while the amount of dissociation, as measured by the electric conductivity, diminishes. The abnormally high values obtained by Perkin for the magnetic rotation of many salts, &c., in strong solution, and by Gladstone for their refractive indices, is probably due to the same causes as those owing to which these solutions exhibit an abnormally large depression. A table is given in which the rotation values are compared with the amount of dissociation existing, and there appears to be no connection whatever between the two.The Cryoscopy of Cane Sugar Solutions. By S. U. PICKERING (Bey., 24, 332%-3341) .--Numerous determinations, both with very weak solutions, and with solutions up to 64.5 per cent., are quoted, and the results examined in detail, partially by the bent-lath method and partially by the application of parabolas deduced from the experi- mental values. In all the instances where both methods were applied to the same series of results, they have led to precisely the same con- clusions respecting the nature of the figure formed, that is, whether it is a continuous curve or whether it contains changes of curvature. With very weak solutions-0 to 1.2 mols. to lOOH,O, with an actual depression extending up to l*4"-the molecular depression increases from 1.050" to 1.105" at a strength of 0.1 mol., then diminishes to 1.102 at 0.3 mol., and finally increases again till it reaches 1.156" at 1.2 mols.From 0.06 to 1.2 mols. canbe represented by two curves meeting at about 0.6 mol., so as t o give the apparent error of the points very nearly the same value as the known experi- mental error, whereas when the same portion is drawn as one con- tinnous curve the apparent emor is twice the experimental error, and there is such a bad arrangement of error of like signs, that such a drawing could not be accepted as a legitimate representation of the results. Hence the author concludes that a " break " exists at about 0.6 mol. to 100HzO.There appears to be some further irregularity in s. u. P.110 ABSTRAOTS OF OHEMICAL PAPERS. &he region of much weakcr solutioiis, but the position of a break here cannot well be determined. With the freezing points of stronger solutions, the figure is sensibly a straight line as far as about 2.5 mols. ; it then bends downwards as far as 5.5 mols., when i t begins to bend in the opposite direction. The molecular depression for the strongest solution, 9.5 mols., is 1.445, the maximum molecular depression being reached a t 8 mols., where it amounts t o 1.455. The author considem that there is a change of curvature at 2.5 or 2 mols., but not at 5.5 mols., where the inflection of the figure occurs : a representation, either by bent-lath curves or by parabolas, which shows a break at the former point, gives a mean apparent error for the points agreeing very closely with the experimental error, whereas a one-curve representation, which makes no break at this point, gives an apparent error 2.4 times larger than the known experimental error, or taking into account indications of error other than the mean error-such as arrangement of like signs into groups, and the occurrence of errors of improbable ma@- tude-the total apparent error, and, therefore, the improbability, of the one-curve drawing, is estimated by the author to be 100 times greater than that of the two-curve drawing.Representing the figure by three curves, instead of two, produces no appreciable diminu tion in the apparent error of the points. s. u. P.Existence of Acid or Basic Salts of Monobasic Acids in very Dilute Solutions. By D. BERTHELOT (Compt. rend., 113, 641--643).-1f a dilute solution of an alkali is added, in gradually increasing proportion, to an equivalent solution of a monobasic acid, the phenomena can be represented in a very simple manner by means of a curve, the abscissae being the electrical conductivity of the mixture, and the ordinates the proportion of one of the constituents. The curve consists mainly of two right lines (one corresponding with excess of acid, and the other with excess of base), inclined at an acute angle, and connected by a short curved portion, part of which repre- sents the effect of a slight excess of acid, whilst the remainder repre- sents t,he influence of a slight excess of base.A slight escess of base has a greater effect than an equivalent excess of acid, but the effect disappears rapidly as the quantity of acid or base in excess is increased. These results are very distinctly shown by solutions of barium chloride, hydrochloric acid, and barium hydroxide, aud they indicate that acid or basic salts are not completely decomposed by dilution, but exist in minute quantities even in very dilute solutions. C. H. B. Catalytic Influence of Acids on the Velocity of the Reaction between Hydrogen Peroxide and Hydriodic Acid. By G. MAGMANINI (Gaxzetta, 21, 476-490).-l'he author has studied the effect of hydrochloric, nitric, nitro-hydrochloric, sulphuric, hydr- iodic, oxalic, acetic, monochloracetic, and phosphoric acids on the velocity of the reaction between hydrogen peroxide and hydriodic wid, in a similar manner to that employed in his study of the re- action between bromic and hydriodic acids (Abstr., 1891, 144).As in the case of the latter reaction, the velocity of the action is acceler-INORGANIC CHEMISTRY. 111 ated by the addition of acid. When hydrochloric or sulphuric acid is employed, the accelerations are not rigorously proportional to the amount OE acid added, the ratio of the acceleration to the quantity of foreign acid present decreasing slightly, but senei bly, as the amount of acid is increased ; this constitutes a marked difference from the case of bromic and hydriodic acids, in which this ratio increases rapidly with increase of acid. The quantity of iodine set free when nitric acid is used is practically the same as with hydrochloric acid.The accelerating effect of hydriodic acid is very great. Optical Proof of the Existence of Suspended Matter in Flames. By G. G. STOKES (Chenz. Nezus, 64, 167-168 ; compare G. J. Burch, Abstr., 1885, 466).-When a bean1 of sunlight, condensed by a Izns, is passed through a candle-flame, the area of intersection of the double cone of light with the luminous envelope is marked by two brighter patches of light of inappreciable thickness, which exhibit the polarisation of light scattered by fine particles -that is to say, when viewed in a direction perpendicular t o the incident light, it was polarised in a plane passing through the beam and the line of sight. They can be made more conspicuous by viewing the whole through a.cell containing copper ammonium sulphate solu- tion, or through cobalt glass. The same phenomenon is shown by a luminous gas or ether flame, but not by the blue base of a candle flame, or by a Bunsen flame, even when rendered luminous with sodium chloride, or by an alcohol flame, or by an ether flame, j u s t expiring for want of air. The separation of carbon, or carbon associated with hydrogen, thus rendered evident by its polarising effect on light, is due to the actioii on the volatile carbon compounds, in the absence of a sufficient supply of oxygen t o effect complete combustion, of the heat evolved by the more complete combustion at the base of the flame. I n the case of the dying ether flame, the heat is probably distributed over too large a mass of inert gases to effect the decomposition.The thinness of the stratum of glowing carbon is probably due to the combined attack of oxygen on the outside, and carbonic anhydride on the inside (compare Smithells, Proc., 1891, 159). W. J. P. JN. W.105G e n e r a l a n d P h y s i c a l Chemistry.Apparent Variability of the Electro-chemical Equivalent ofCopper. By J. VAN" (Ann. Phys. Chem. [el, 44, 214--221).-Gray(Plzil. Mag. [ 5 ] , 22, 389 ; 25, 179), in his researches on the electro-chemical equivalent of copper, found that this magnitude at 12' variedfrom 0.0003287 with a current density of 20 milliampAres per squarecentimetre at the cathode, to 0.00032713 with a density of 3.3 mi%-amphres; and at 35" sank so low as 0.0003245.He advances RS aprobable explanation of this variability the fact, observed by Gore,that the solution of copper sulphate dissolves up a quantity of coppervarying with different conditions. The object of the present investi-gation was to test the validity of this explanation, and to determinethe true electro-chemical equivalent.Two copper voltameters with plates of different surface (4 : 1)were placed in the same circuit ; and it was found, for instance, thatwith a solution of copper sulphate containing 1 per cent. of freesulphuric acid, 0.1903 gram of copper was deposited on the largercathode, while 0.1960 gram was deposited on the smaller cathode, inthe course of three hours. After interruption of the current, thecathodes were allowed to remain three hours longer in the solutions,when i t mas observed that the larger cathode had lost weight to theextent of 9.2 milligrams, and the smaller cathode only 3.2 milli-grams.These weights, added t o the former pair, give 0.1995 gramand 0.1992 gram respectively-results sufficiently close.The author found that when the copper sulphate solution em-ployed contained merely a trace of sulphuric acid (about 5 milligramsper litre), there was no perceptible quantity of copper dissolved in twohours. With such solutions, the electro-chemical equivalents ofcopper and of silver were compared ; and, taking that of silver as equalto 0.001118, the author gives, as a mean value of 12 concordant ex-periments, the electro-chemical equivalent of copper in cupric saltsas equal to 0.0003284.J. W.New Method of Measuring Electromotive Forces andElectrical Resistances. By S. PAGLIBNI (Gnxzettu, 21, 449-454).-A standard wire of known resistance is joined in circuit with thecurrent generator whose electromotive force is to be measured. Abranch circuit containing a voltameter is also established, having oneterminal fixed to one end of the standard wire and the other fixed to 8key which slides along the standard wire. The voltameter consists ofa glass tube, closed by two taps, containing a 25 per cent. solution ofpotassium iodide to which has been added a little starch solution.Platinum and copper wires are used for the cathode and anoderespectively. The width of the tube is 10 mm. ; the distance betweenthe electrodes 120 mm.The resistance of the standard wires mustbe so great as to render negligible thc internal resistance of theVOL. LXII. 106 ABSTRACTS OF CHEMIOAL PAPERS.current generator. At the commencement of the determination, thebranch circuit is so arranged that the difference of potential at itsterminals is insufficient for the electrolysis of the potassium iodidesolution: the key ia now moved along the standard wire until itreaches a point at which a violet coloration is observable a t thesurface of the platinum wire. The position of the key is then noted,and the electromotive force of the current generator can be calculatedin terms of the electromotive force necessary to decompose the potas-sium iodide solution (0.610 volt).Electrical resistances may be measured by employing a currentgenerator of kfiown electromotive force, and inserting the unknownresistance in eit,her the main o r the branch circuit.The author states that this method gives very concordant results.W.J. P.Characteristic Difference between the Substituted AlcoholRadicles directly united with Carbon or with Nitrogen. ByC. MATIGNON (c‘ompi. rend., 113, 550--55l).-h the course of atherniochemical study of t h e ureides, the author has arrived at thelaw, “The substitution of an alcohol radicle directly united withnitrogen increases the heat of combustion more than when the sameradicle is directly united with carbon.” The publication of a paperby Stohmann and Langbein (this vol., p.4), enunciating the samelaw, rendered necessary the imrnediate production of the author’sr e su 1 t s .Caffeine, theobromine, cholestrophane, and ethylcarbamide werepurified and analysed ; their heats of combustion at constant preSsure,together with those of parebanic acid and carbamide, are given below,cal. cal.Caffe’ine(methy1theobromine) C702N4H7Me, 1016.0Theobromine ............. C50,N4H, 845.9) 170.1’Ethylcarbamide. .......... CON2H3Et, 472.2 320.7Carbamide ............... CON2H4,Cholestrophane ........... CJ03N,Me,, 538*6 326Parabanic acid.. .......... C303N2H2,r i 1 he. introduction of a methyl group united with carbon neverincreases the heat of combustion of the substance by more than157 cal. ; in the above cases, this number is exceeded by an amountfar beyond the limits of experimental error.Ethylcarbamide is con-sidered as derived from urea by two successive methyl substitutions ;takiug 155 cal. as the mean for a substitution of methyl united withcarbon, 165.7 cal. is the increase caused by the introduction cf amethyl group combined with nitrogen.The application of this law confirms the suggestion of Grimaux,that pyruvile is a methjl derivative of allantdin, and that it is a truehomologue of that substance ; the increase in heat of combustion i nthis case is 153 cal. W. T.151.5 } (= 155 + 165.7).2 W 6 } (=163 x 2).Expansion of Water. By W. MARRK (Ann. Php. C’hem. [ a ] , 44,171- 172).--This paper contains a table of the densities of water conGENERAL AND PHYSICAL CEEMISTRY, 107taining air for every tenth of a degree from 0" to 31".experimental method will be given in a subsequeni communication.H. C .Details of theMolecular Weights of Liquids as evinced by their BoilingPoints.By H. M. VERNOS (Chem. News, 64, 54--58).--The authorendeavours to show that from the boiling point of liquids s3me indi-cation as t o the probable value of their molecular weights may beobtained. Hydrogen iodide boils at --So, hydrogen bromide at - 7 3 O ,and hydrogen chloride at -loo", from which a boiling point of about-120" might be predicted for hydrogen fluoride. But since hydrogenfluoride actually boils at 19.4", we must assume a more complexmolecule for this substance in the liquid state than that representedby the formula HF.This result agrees with Thorpe and Hambly'sconclusion that at the boiling point the hydrogen fluoride molecule isprobably H,F,. In like manner, comparing the boiling point ofwater with those of the similar compounds SH2, SeH2, and TeH,,which are gaseous at temperatures far helow O", we should have toassign t p liquid water a molecular weight not smaller than that cor-responding with the formula (H,O)a. The following table illastratesthe striking regularity in increase of boiling point which is alwaysobserved on the substitution of bromine for chlorine :-Chloride. 1 B-P.I-- ---IPC1, ........... -76 -0'POC!, .......... ' 107 '2AsC13 .......... ~ 134.0BCI, ............ 18.2SiCl, ..... ......I 59.6CHCI,.......... I 61.0CCl, ............ '76 *5TiC14.. ......... ' 136.1CH,Cl.. ........ i -22 *OiBromide.PBr,.. ..........POBr3.. ........AuBr, ..........BBr, ...........SiBr., ...........CHBr, ..........CBr,. ...........CH3Br.. ........TiBr, ...........B. p.175 '0"195 -0220.090.51.54 -0151 -0189 '04 -5230 -0Increase for eachatom of Br.~ ~-33 *oo29.328.724 *123 -630 *O28 '126 ' 523 -5Other cases are discussed, and the author argues, from a study ofthe boiling points, that i n all probability all compounds, both organicand inorganic, containing one or more hydroxyl groups, have in theliquid state molecular weights double those expressed by their ordin-arily received formulx?. H. c.Solubility of Gases in Water.By C. BOHR and J. BOCK (Ann.Phys. Chevn. [2], 44, 318--343).-The authors have made freshdeterminations of the solubility of oxygen, hydrogen, and nitrogen inwater, partly by means of a Bohr's absorptiometer, and parbly bymeans of two new instruments-a differential absorptiometer and apumping-out apparatus-which are fully described and figured in thepaper. The differential absorptiometer was used for femperaturesfrom 0" to 60"; from 60" to 100" the other apparatus was em-ployed.The mean coefficient of absorption of oxygen in water was found toi 108 ABSTRACTS OF CHEMIOAL PAPERS.be 0.03497 at 15" ; at 100" it is 0.01679. The agreement with thevalues obtained by Dittmar and Winckler is good. For nitrogen,the absorption coefficient is 0.01667 at 19", and 0.01046 at 100".The coefficient remains practically constant between 60" and 100'.The authors' numbers agree well with those of Petterson and SondQn,Dittmar, and Hamberg, but diverge considerably from those of Bunsenand of Hiifner.In the case of hydrogen, the author finds that the coefficient ofabsorption is not independent of the temperature, as Bunsen stated,but falls t o a minimum at about 60", after which it rises until at theboiling point it becomes equal to the coefficient of absorption ofoxygen at the same temperature.The numerical values are-a , ~ = 0.0203, a150 = 0.0183, a600 = 0.0144, alm~ = 0.0166.The authors further made two dcteyminations of the solubility ofcarbonic anhydride, and found a for 37.39' to be 0.5629, and for 100"to be 0-2438.J. W.Nature of Solution. By J. A. WANKLE" and W. JOHNSTONE(Chem. News, 64, 39, 51, and 146 ; compare Abstr., 1891, 1412).-When a solid is dissolved, the volume of the solution is not, as arule, ,equal to the sum of the volumes of the solid and solvent. Theauthors have determined the amount of the change for a considerablenumber of substances which dissolve in water.The alteration, which is usually that of contraction, is expressedin terms of a quantity, which they name the condensate, and obtainby subtracting the mass of solvent displaced by unit mass of dissolvedsubstance from the ratio of the excess of the density of the solutionover that of the solvent to the solution-density of the dissolved sub-stance :- .. c = 2 - 21,____ Density of solution - density of solventNo. of grams of dissolved substance per C.C. of solution ' where i = - -1and il = 1 - IDensity of dissolved substanceThe condensate, which, it is stated, may be regarded as the amountof solvent which enters into combination with, or is condensed by,the dissolved substance, appears in several cases to bear a simplemolecular ratio to the amount of the latter. Thus, with potassiumnitrate, the number is 0.058, whilst the ratio H,O : 3KN0, is 0,059,and with barium hydroxide the number is 0.320, whilst the ratio3H,O : Ba(OH), is 0.316. I n other cases, however, the agreement isnot so close, and the numbers can only be expressed by more complexratios.With cane sugar, the condensate is zero, whilst with certain am-monium salts it appears to be negative.JN. W.Strong Solutions and the Dissociation Hypothesis. By S. U.PICKERING (Ber., 24, 317-3327) .-The author states that the facQENERAL A:d D PHYSICAL CHEMISTRY. 109established by him (Abstr., 1891, 972), that weak solutions of sulph-uric acid and other substances contain less, instead of more, actingunits than the acid and water separately, caiinot be brought intoharmony with the dissociation hypothesis, as Arrhenius considers(Abstr., 1891, 1148), by admitting that complex aggregates of similarmolecules exist in pure liquids and strong solutions. After answeringsome recent criticisms of Arrhenius, he gives a preliminary statementof numerous results obtained in a study of the freezing points ofstrong solutions.Very weak solutions of electrolytes, as is wellknown, exhibit an abnormally large molecular depression ; this de-creases as the strength is increased up to a certain point, but after-wards it again increases, and often attains values which are abnorm-ally large in a very high degree. Non-elect'rolytes appear to behavein the opposite manner; in every case investigated, the moleculardepression decreases with the strength of the solution, although in afew cases this abnormally small depression is preceded by a com-paratively slight and temporary increase. Although so- called dis-sociation may offer some explanation of the behaviour of very weaksolutions, it appears to be incapable of explaining that of strongel-solutions, for here the molecular depression increases, while theamount of dissociation, as measured by the electric conductivity,diminishes.The abnormally high values obtained by Perkin for themagnetic rotation of many salts, &c., in strong solution, and byGladstone for their refractive indices, is probably due to the samecauses as those owing to which these solutions exhibit an abnormallylarge depression. A table is given in which the rotation valuesare compared with the amount of dissociation existing, and thereappears to be no connection whatever between the two.The Cryoscopy of Cane Sugar Solutions. By S. U. PICKERING(Bey., 24, 332%-3341) .--Numerous determinations, both with veryweak solutions, and with solutions up to 64.5 per cent., are quoted, andthe results examined in detail, partially by the bent-lath method andpartially by the application of parabolas deduced from the experi-mental values. In all the instances where both methods were appliedto the same series of results, they have led to precisely the same con-clusions respecting the nature of the figure formed, that is, whether itis a continuous curve or whether it contains changes of curvature.With very weak solutions-0 to 1.2 mols.to lOOH,O, with anactual depression extending up to l*4"-the molecular depressionincreases from 1.050" to 1.105" at a strength of 0.1 mol., thendiminishes to 1.102 at 0.3 mol., and finally increases again till itreaches 1.156" at 1.2 mols.From 0.06 to 1.2 mols. canbe representedby two curves meeting at about 0.6 mol., so as t o give the apparenterror of the points very nearly the same value as the known experi-mental error, whereas when the same portion is drawn as one con-tinnous curve the apparent emor is twice the experimental error,and there is such a bad arrangement of error of like signs, that sucha drawing could not be accepted as a legitimate representation of theresults. Hence the author concludes that a " break " exists at about0.6 mol. to 100HzO. There appears to be some further irregularity ins. u. P110 ABSTRAOTS OF OHEMICAL PAPERS.&he region of much weakcr solutioiis, but the position of a break herecannot well be determined.With the freezing points of stronger solutions, the figure is sensiblya straight line as far as about 2.5 mols.; it then bends downwards asfar as 5.5 mols., when i t begins to bend in the opposite direction.The molecular depression for the strongest solution, 9.5 mols., is1.445, the maximum molecular depression being reached a t 8 mols.,where it amounts t o 1.455. The author considem that there is achange of curvature at 2.5 or 2 mols., but not at 5.5 mols., where theinflection of the figure occurs : a representation, either by bent-lathcurves or by parabolas, which shows a break at the former point,gives a mean apparent error for the points agreeing very closely withthe experimental error, whereas a one-curve representation, whichmakes no break at this point, gives an apparent error 2.4 times largerthan the known experimental error, or taking into account indicationsof error other than the mean error-such as arrangement of likesigns into groups, and the occurrence of errors of improbable ma@-tude-the total apparent error, and, therefore, the improbability, ofthe one-curve drawing, is estimated by the author to be 100 timesgreater than that of the two-curve drawing.Representing the figureby three curves, instead of two, produces no appreciable diminu tionin the apparent error of the points. s. u. P.Existence of Acid or Basic Salts of Monobasic Acids invery Dilute Solutions. By D. BERTHELOT (Compt. rend., 113,641--643).-1f a dilute solution of an alkali is added, in graduallyincreasing proportion, to an equivalent solution of a monobasic acid,the phenomena can be represented in a very simple manner by meansof a curve, the abscissae being the electrical conductivity of themixture, and the ordinates the proportion of one of the constituents.The curve consists mainly of two right lines (one corresponding withexcess of acid, and the other with excess of base), inclined at an acuteangle, and connected by a short curved portion, part of which repre-sents the effect of a slight excess of acid, whilst the remainder repre-sents t,he influence of a slight excess of base.A slight escess ofbase has a greater effect than an equivalent excess of acid, but theeffect disappears rapidly as the quantity of acid or base in excess isincreased. These results are very distinctly shown by solutions ofbarium chloride, hydrochloric acid, and barium hydroxide, aud theyindicate that acid or basic salts are not completely decomposed bydilution, but exist in minute quantities even in very dilute solutions.C. H.B.Catalytic Influence of Acids on the Velocity of the Reactionbetween Hydrogen Peroxide and Hydriodic Acid. By G.MAGMANINI (Gaxzetta, 21, 476-490).-l'he author has studied theeffect of hydrochloric, nitric, nitro-hydrochloric, sulphuric, hydr-iodic, oxalic, acetic, monochloracetic, and phosphoric acids on thevelocity of the reaction between hydrogen peroxide and hydriodicwid, in a similar manner to that employed in his study of the re-action between bromic and hydriodic acids (Abstr., 1891, 144).Asin the case of the latter reaction, the velocity of the action is accelerINORGANIC CHEMISTRY. 111ated by the addition of acid. When hydrochloric or sulphuric acidis employed, the accelerations are not rigorously proportional to theamount OE acid added, the ratio of the acceleration to the quantity offoreign acid present decreasing slightly, but senei bly, as the amountof acid is increased ; this constitutes a marked difference from thecase of bromic and hydriodic acids, in which this ratio increasesrapidly with increase of acid.The quantity of iodine set free when nitric acid is used is practicallythe same as with hydrochloric acid. The accelerating effect ofhydriodic acid is very great.Optical Proof of the Existence of Suspended Matter inFlames. By G. G. STOKES (Chenz. Nezus, 64, 167-168 ; compareG. J. Burch, Abstr., 1885, 466).-When a bean1 of sunlight,condensed by a Izns, is passed through a candle-flame, the area ofintersection of the double cone of light with the luminous envelopeis marked by two brighter patches of light of inappreciable thickness,which exhibit the polarisation of light scattered by fine particles-that is to say, when viewed in a direction perpendicular t o theincident light, it was polarised in a plane passing through the beamand the line of sight. They can be made more conspicuous by viewingthe whole through a. cell containing copper ammonium sulphate solu-tion, or through cobalt glass. The same phenomenon is shown by aluminous gas or ether flame, but not by the blue base of a candleflame, or by a Bunsen flame, even when rendered luminous withsodium chloride, or by an alcohol flame, or by an ether flame, j u s texpiring for want of air.The separation of carbon, or carbon associated with hydrogen,thus rendered evident by its polarising effect on light, is due to theactioii on the volatile carbon compounds, in the absence of a sufficientsupply of oxygen t o effect complete combustion, of the heat evolvedby the more complete combustion at the base of the flame. I n thecase of the dying ether flame, the heat is probably distributed overtoo large a mass of inert gases to effect the decomposition.The thinness of the stratum of glowing carbon is probably due tothe combined attack of oxygen on the outside, and carbonic anhydrideon the inside (compare Smithells, Proc., 1891, 159).W. J. P.JN. W

ISSN:0368-1769    

DOI:10.1039/CA8926200105

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 111 I n o r g a n i c C h e m i s t r y . Sulphur Tetroxide. By D. CARNEGIE (Chem. News, 64, 158- 159).-A criticism of Traube’s work on the electrolysis of 40 per cent. aqueous sulphuric acid (Abstr., 1891, 978). The author, whilst admit- ting that the substance formed cannot be a heptoxide of sulphur, comments on the absence of direct evidence in favour of the existence of a tetroxide. The ratio 1 : 5 of active oxygen to sulphuric anhydride, which Traube considers t o prove the existence of the tetroxide SO, in the electrolysed solution, would be equally well112 ABSTRAOTS OF OEEMIOAL PAPERS. explained on the hypothesis of the existence of a substance having the composition S207,H20.,,xH20. The existence of such a substance would not only accord with Berthelot’s results (Abstr., 1878, 469), but would harmonise with the known existence of tungsten and molybdenum heptoxides, and with the tendency of peroxides of the type M20, to form stable compounds with hydrogen peroxide. Moissmn’s perchromic acid (Abstr., 1884, 20 ; comparo Berthelot, Abstr., 1889, 350) might then be regarded as a compound, Cr207,H202,H20, of the same type. With regard to the low amount of active oxygen shown by the iodometric method, the author points out that this cannot be accountJed for by the presence of sodium hydrogen carbonate, since the latter has practically no action on iodine, but that it can be accounted for by the presence of free alkali in the potassium iodide, and that this supposition accords with the higher results which were obtained on working with acid instead of neutral solutions.JN. W. Azoimide. By T. CURTIUS (Bey., 24, 3341-3349; compare Abstr., 1891, 56).-Ethereal salts of benzoic acid react with hydrazinc hydrate accordiiig to the equation PheCOOR + N2H4,H20 = COPh*NH.NH2 + ROH + H20. The benzoylhydrazine, when treated with nitrous acid, yields benzoylazoimide, and on digesting this with sodium ethoxide it IS decomposed quantitatively into sodium nitride, NaN3, and ethyl benzoate. The salts of azoimide may also be prepared from hippurylhydrazine, by the action of nitrous acid; in this case, a compound is formed which was previously termed nitrosohippurylhydrazine ; it is, however, n diazo-compound with the formula COPh*NH*CH,*CO*NH*N:N*OH (see below) ; it cannot be converted into hippurylnzoimide by elimin- ation of water, but on treatment with ammonia in alcoholic solution, it is decomposed into hippuramide and ammonium nitride ; the hip- puramide combines with hydrazine hydrate to form hippuryl- hy drazine. Argentic nitride, AgN,, has been previously described; it is soluble in ammonia, from which it crystallises in long, colourless needles ; i t is exceedingly explosive.Mercurous nitride, HgN,, is precipitated in microscopic needles which are insoluble in water ; it is more stable than either the silver or lead salts, becomes yellow on exposure to light, and yields a black, insoluble compound with aqueous ammonia. Plztmbic nitride, PbN6, is prepared by adding plumbic acetate to a solution of the sodium or ammonium salts ; it is soluble in excess of the precipitant, but insoluble in water in the cold, and more sparingly soluble in boiling water than plumbic chloride, which it closely resembles. It crystallises from water in long, colourless, lustrous needles, which explode violently on gently warming and decompose gradually when heated with water o r acetic acid.Sodium nitride is most readily prepared in the manner described above, but may also be obtained by adding soda to solution of the free acid or of the ammonium salt; it is readily soluble in water, in- soluble in alcohol or ether, has a slight alkaline reaction and aINOROANIO CHEMISTRY. 113 saline taste, The compound is neit,her ~olatile nor hygroscopic ; its solution may be evaporated to dryness without undergoing any change, and i t only explodes when heated to a comparatively high temp- erature.Ammonium nitride, N4Hi, obtained as above, is rea,dily purified by adding ether to the alcoholic solution, or it may be crystallised from alcohol, irom which it is deposited in plates closely resembling am- monium chloride, but not belonging to the regular system. It is excessively volatile, and explodes violently when heated in a combus- tion tube with cupric oxide in a current of air; it may, however, be sublimed by cautiously heating at a little aboye loo", although violent explosions occur if it is rapidly heated, Hydrazine nitride, NsH5, is prepared by adding hydrazine hydrate to ammonium nitride or to the free acid; it crystallises i n long, lustrous prisms, or in plates, and is sparingly soluble in alcohol. By detonation, or on rapidly heating, the compound explodes violently, but it will burn quietly with a smoky, slightly yellow flame ; if the combustion takes place on a metallic surface, every trace of oxide on it will be reduced arid the metal will appear bright and polished.The formation of diazohippuramide, COPh*NH*CH,-CO*NH*N:OH, has already been described ; it combines with ammonia. aniline, hydr- azine, and similar compounds with elimination of axoiniide, whilst the action of water, alcohol, aldehydes, or acidyl hydrazines causes nitrogen to be evolved ; for example, the action of aniline on diazo- bippurlylamide gives rise t o hippurylanilide, aniline nitride, and water ; the reaction with alcohol is represented by t.he equation, NHBz~CH2*CO*NH*N2*OH + EtOH = N2 + NHBz*CH2*CO*NH*OEt + HzO.On treating diazohippurylamide with benzoylhydrazine, nitrogen and water are eliminated, and a compound is formed which has the formula NHBz*CH,*CO*NH*NH*NH.Bz ; this is exceedingly stable towards acids and alkalis, and attempt8 to hydrolyse it have hitherto been unsuccessful; its properties and mode of formation prove it to be a derivative of trinmide, NH2*NH*NHz, which has not as yet been obtained in the free state. J. B. T. The Colour of Nitric Acid. By L. M~CHLEWSKI (Ber., 24, 3271--327G).-It is well known that as water is added to red fuming nitric acid, the colour changes through green to blue and finally dis- appears. I n explanation of this, it has always been assumed that the red acid i s a solution of nitrogen peroxide, N204, in nitric acid, and that the water added decomposes the peroxide with formation of nitric and nitrous acids.The solution of nitrous acid in nitric acid is blue, and this, with the red solution of still undecomposed peroxide, gives a green colonr. As more water is added, this excess of peroxide is decomposed, and nothing is then left but a blue solution of nitrous acid. The author has investigated the matter experimentally in the follow- ing manner :-The gases contained in the coloured acid were expelled by means of carbonic anhydride and collected i n concentrated sulph- uric acid, with which nitrous acid forms nitrosyl hydrogen sulphate,114 ABSTRACTS OF CHEMICAL PAPERS. but with nitrogen peroxide forms a mixture of nitrosyl hydrogen gulphate with nitric: acid in moiecular proportion.The total nitrogen was determined with the nitrometer, and the reducing power by titra- tion with permanganate. Both results were calculated to trioxide, and from the ratio of the second to the first a conclusion could be drawn as to the constitutlion of the mixture of gases absorbed. I f the gas were pure trioxide, the ratio would of course be 1 ; if it were pure peroxide, 0.5, since the reducing power of the peroxide is only half that of the trioxide. The results obtained were astonishing, for although they showed that the blue acid contained pure trioxide, yet they also showed that the green acid did not contain more than a t most mere traces nf the peroxide. The author was consequently led to suspect that his results were vitiated by the presence of nitric oxide, NO, in the coloured acids examined; and in fact when the experiments were repeated, the gases that escaped absorption in the strong sulphuric acid being passed through a strongly acid per- manganate solution, the permanganate was perceptibly reduced.The reduction was, of course, due to nitric oxide, and a great deal of this gas must have been present originally, for had only a small quantit>y been there, i t would have formed nitrosyl hydrogen sulphate wit.h the peroxide also present and the concentrated snlph- uric acid, and would thus have been absorbed. The solutions investigated were made by passing the gaseous oxide into pure nitric acid. Solutions obtained by mixing pure liquid peroxide with nitric acid of different strengths are now being in- vestigated.C. F. B. Boron Phosphoiodides. By H. MOISSAN (Conz-pt. rend., 113, 624--627).-Melted phosphorus acts with great energy on boron triiodide, and if red phosphorus is heated in the vapour of the iodide, decomposition takes place with incandescence. If, however, a solution of the iodide in carbon bisulphide is mixed with a similar solution of phosphorus, great care being taken t o avoid the presence of moisture, the reaction takes place more slowly. The mixture is sealed up in a flask and kept a t the ordinary temperature of the laboratory ; it is at first clear, but has a red colour. I n a few minutes a brown precipi.- tate begins to separate, and the reaction is complete in about three hours.The product is filtered through glass wool, washed with carbon bisulphide, and dried in a vacuum, the apparatus being filled with carbonic anhydride until the latter is removed by the pump, The product is boron phosphodiiodide, BPI,, an amorphous, homo- geneous, deep-red powder. When heated in a vacuum, it melts at 190-200", and will remain in superfusion a t the ordinary temperature for a long time ; in a vacuum, it begins to volatilise at 170-200", and condenses on the cold part of the tube in distinct red crystals. It is only very slightly soluble in carbon bisulphide, and seems t o he com- pletely insoluble in benzene, phosphorus trichloride, and carbon tetrachloride. It is extremely hygroscopic, and decomposes very rapidly in moist air. In presence of a large excess of water, it be- comes yellow, without, apparent development of heat, and hydriodic, phosphorous, and boric acids are formed, a small quantity of phosphineINORGANIC CHEMISTRY.115 being evolved, and a small quantity of a yellow substance with an odour of phosphorus being deposited. With a very small quantity of water, the yellow precipitateis produced i n larger quantity, and a distinct quantity of phosphonium iodide is formed. Boron phosphodiiodide, wheir heated in hydrogen sulphide, yields boron sulphide, phosphorus sdphide, and hydrogen iodide without any free iodine. Dilute nitric acid yields phosphoric acid and boric acid, whilst strong nitric acid produces the same result, but with in- candescence. Siilphuric acid (even Nordhausen) has 110 action in the cold, b u t , on heating, free iodine, hydrogen iodide, and sulphurous anhydride are evolved.Phospliorous trichloride and carbon tetra- chloride have no action even in sealed tubes at 100". Chlorine pro- duces incandescence, with formation of boron chloride, iodine chloride, and phosphorus pentschloride. When heated in oxygen, the compound burns and yields iodine, boric anhydride, and phosphoric anhydride. Sodium has no action in the cold, but decomposition takes place at t>he melting point of the metal. Powdered magnesium reacts with incandescence. When thrown into mercury vapour, the phosphodiiodicle takes fire a t once. I n presence of carbon bisulphide the behaviour of metals is different; magnesium or sodium a t the ordinary temperature produces a red compound, PBT, whilst silver or mercury in the cold, or more rapidly a t loo", yields a maroon- coloured compound with the properties of boron phosphide, BP.Boron phosphoiodide, BPI, is obtained by heating the preceding compound in hydrogen, and is an amorphous, red powder, somewhast less hygroscopic than the diiodide. It volatilises in a vacuum a t 210-250" without previous fusion, and condenses in orange-yellow crystals. Strong nitric acid decomposes i t with development of heat and without incandescence, iodine being liberated. Concentrated sulphuric acid has no action in the cold, but, OIL heating, iodine, sulphurous anhydride, and boric acid are formed. When heated out of contact with air, it decomposes a t a temperature below dull redness with evolution of Fapours of iodine and boron phosphide.Mercury in excess, in presence of dry carbon bisulphide, yields mercuric iodide and boron phosphide a t the ordinary temperature. Boron phoThide, BP, resembles the phosphoiodide B P I in its general properties. It can be obtained by heating the phosphoiodide in hydrogen, and if the heating is continued, a residue of the composi- tion B,P, is left. C. H. B. Reducing Action of Graphitoidal Silicon. By H. N. WARREN (Chenz. News, 64, 75).-When the oxides of easily reducible metals, such as lead, copper, and silver, are heated to dull redness with powdered graphitoydal silicon, they are reduced to the metal, and if the silicon is in excess, a metallic silicide is formed. The oxides of chromium, tungsten, and molybdenum may also be reduced in thia way.In some cases, the reduction takes place with explosive violence ; when, for instance, a small quantity of a mixture of equal paxts of finely-divided silicon, aluminium, and litharge was melted before the blowpipe, the explosion was so violent as to indent the supporting brick. JN. W.116 ABSTRACTS OF CBEMICAL PAPERS. Solubility of Sodium Carbonate and Sodium Hydrogen Carbonate in Solutions of Sodium Chloride. By K. REICR (Monatsh., 12, 464--473).-The solubility of sodium carbonate a t 15" in a solution of sodium chloride of gradually increasing concentration at first diminishes and then increases. The solubility y as a function of the quantity x of sodium chloride in 100 parts of water is expressed by the formula y = 61.406 - 2.091077~ + 0.0554932 - 0*00029'7357~~. Accordingly, the minimum lies near cc = 23.15 where y = 39.05. On passing carbonic anhydride through the saturated solution, the amount of bicarbonate precipitated increases with the quantity of sodium chloride in solution ; but a maximam cannot be recognised.G. T. M. Allotropic Silver. By M. C. LEA (Phil. Mag. [ 5 ] , 32, 337-3421. -The blue form of allotropic silver is capable of change into an intermediate yellow form which seems t o be identical with that, into which the gold-coloured form passes under the influence of various causes (Abstr., 1891, 803). The change takes place at about B O O , both with lumps of the blue silver and with films. By the action of sulphuric acid, however, blue silver can be converted into yellow silver at the ordinary temperature, and consequently with retention of all its active properties.40 grams of sodium hydroxide and 40 grams of yellow or brown dextrin are dissolved in 2000 C.C. of water, and 28 grams of silver nitrate is added in successive very small quantities, with frequent -agitation. The solution is slightly turbid. and is deep-green by re- flected' light, red by transmitted light. The precipitate tbat forms spontaneously or is produced by the addition of acetic acid, dilute nitric acid, and many neutral substances, consists of blue silver, but if sulphuric acid is added, the precipitate, when dried in films, is blue, green, yellowish-green, or yellow, according to the proportion of acid used. When the silver solution is mixed with an equal volume of a mixture of i s 5 C.C. of sulphuric acid and 92.5 C.C.of water, the precipitate consists wholly of yellow silver, bnt with higher propor- tions of acid the product dries with a coppery shade. The lustre of )the product, diminishes as the proportion of acid used for precipitation is increased. Conversely, it solution which would yield yellow silver under or- dinary circumstances can be made to yield blue silver by the addition of an alkali, and it is immaterial whether the alkali is added to the ferrous tartrate or the silver mixtnre or to a mixture of the two. There is, therefore, a tendency for acids to produce the yellow pro- .duct, and alkalis the blue product., but it is a tendency only, and both forms can be obtained from neutral solutions ; for instance, ferrous tartrate and silver tartrate yield gold-coloured silver, but ferrous citrate and silver citrate produce the blue variety.When sodium hypophosphite is added to silver nitrate, there is no recluction, but if phosphoric acid is added so that hypophosphorous .acid is liberated, it transient red colour appears, and red and blueINORGANIC CHEMISTRY. 117 stains are formed on the side of the vessel. Phosphorous acid gives similar though somewhat less distinct results. The blue silver obtained by adding the soda-dextrin silver solution to an equal volume of water containing 4 per cent. of sulphuric acid is not only constant in character but is one of the forms most sensi- tive to light. When this form is exposed to light, it first becomes more distinctly blue, then yellowish-brown, and finally is converted into the golden-yellow intermediate or crystalline form, with great brilliancy and lustre.It is noteworthy that the action of light on this blue varietyat first. increases its sensitiveness to reagents such as potassium ferricpanide, and afterwards reduces it. This is well shown if one part of a film is covered with an opaque substance, another part with a translucent substance, whilst the third is left uncovered, and the three are ex- posed simultaneously to bright sunlight for about five hours and afterwards treated with dilute ferricyanide solution. The author regards this phenomenon as analogous to the reversing action ob-- served with gelatinobromide plates. The production of reduced silver is direct when an ordinary silver.compound is converted into metal without formation of a sub-salt, and indirect when the silver compoufid is first reduced to a, sub-salt, and the latter is afterwards reduced to the metal. It would seem that only under the latter conditions is there any formation of allo- tropic silver. If, in any of the three principal methods of producing allotropic silver, the action is interrupted by the addition of hydro- chloric acid, a dark, chestnut-brown or purple-brown mixture of the subchloride with the photochloride is obtained, and from it beautiful rose-red photochloride can be obtained by treatment with cold dilute nitric acid after complete removal of the hydrochloric acid. This result is only obtained by interrupting the reaction before it is c v - .plete, and if the hydrochloric acid is added after complete reduction, only grey, normal silver is precipitated. Ifi every case examined, silver subchloride is obtained as one of the products when a reaction resulting in the formation of allotropic silver is interrupted by the addition of hydrochloric acid before reduction is complete. The rich and varied colour of silver sub-salts would seem to indi- cate that in these compounds the metal existls in an allotropic form, but, on the other hand, the greater activity of allotropic silver and its lower sp. gr. would tend to show that the allotropic form has a simpler molecular structure than the normal metal. Colloidal Silver. By E. A. SCHNEIDER (Ber., 24, 3370-3373).- Collo'idal silver prepared according to Carey Lea's method, by the reduction of silver nitrate with ferrous citrate, cannot be purified by dialysis alone ; the better plan is to separate the solid colloid from the mother liquor as completely as possible by filtration, then to dissolve the silver in a little water and allow this solution to dialyse.On adding hydrochloric acid to aqueous collojdal silver solutions, silder and argentic chloride are precipitated, the proportion of the latter being greater with increasing quantities of hydrochloric acid ; the mixed precipitate is extracted with ammonia, the argentic chloride * C. H. B.118 ABSTRAOTS OF OEIEMIOAL PAPERS. precipitated by acidification with nitric acid, and hydrochloric acid added t o the filtrate ; if the quantity of hydrochloric acid originally employed was small, a further precipitate is produced, showing tho presence of a silver snbchloride.The mixed precipitate of silver and argentic chloride was always rose-red. Nitric and sulphuric acids react with colloydal silver solutioiis in a similar manner. No evolution of hydrogen could be detected even when sutlicient hydrochloric acid was added to the silver solution to produce a considerable precipitate of argentic - chloride ; this may indicate the presence of nrgentous oxide : neither was oxygen evolved when, in consequence of the small quantity of hydrochloric acid em- ployed, t.he precipitat,e consisted of almost pure silver. J. B. T. Direct Combination of Chlorine and Bromine with Metals, By H. GAUTIER and G. CHARPY (Compt.rend., 113, 597-600).-Well cleaned wires of various metals, 2 mm. in diameter, were kept in the dark in contact with dry bromine for a definite length of time at 15" and 100". The percentage loss of weight in each case is given in the following table :- At 15' in At 15' in At 100' in 8 days. 4 months. 8 days. Magnesium ...... 0.0 0.0 0.19 Copper .......... 0.371 1- 740 6.62 Zinc ............ 0.289 0.48 7 0.63 Iron ............ 0.210 0.440 23.27 Silver. .......... 0.003 0.540 - Aluminium under similar conditions combines energetically with bromine and becomes incandescent, a burning fragment running about on the surface of the bromine like potassium on water. With liquid chlorine in sealed tubes at the ordinary temperature, the results are similar, the percentage losses being : magnesium, 0.0 ; zinc, 0.0 ; iron, 0.740 ; copper, 3.241 ; silver, 0.673.Potassium, sodium, and aluminium seem to be unaffected by liquid chlorine at its boiling point, but a t -20" aluminium combines with the halogen with incandescence. Magnesium and aluminium, when placed in bromine-water, produce a regular evolution of hydrogen, and, after some time, an oxybromide separates, the reactions being analogous to the decomposition of water by iodine in presence of aluminium. With zinc, iron, and copper, there is no evolution of gas, and a wire 2 mm. in diameter and 50 mm. in length disappears in seven t o eight hours in excess of bromine-water. It seems probable that in these cases the decomposition of water by the halogen is accelerated by the presence of' the metal, the latter being converted into an oxide which is attacked by the hydracid formed. C.H. B. I n presence of water, the results are very different. Lithium Copper Chloride. By A. CHASSEVANT (Compt. rend., 113, 646-648) .-When a concentrated solution of lithium chloride isINORGANIO OHEMISTRY. 119 added to 8 cancentrated solution of an equivalent quantity of cupric chloride, a magma of crystals of the latter salt is formed, but if the midurc is evaporated in a vacuum over phosphoric acid or on a water-bath at loo", the ci-ystals dissolve, the liquid acqnires a, brownish-red colour and deposits transparent, gzrnet-red crystals of the double chloride 2CuClZ,2LiC1,5H,O. When exposed to the air, they decompose, and become opaque, crystals of cupric chloride separating, whilst the lithium chloride deliquesces.If heated rapidly to 130", they melt in their water of crystallisation arid form a deep-brown, almost black, solution. A t tt higher temperature, the salt, like lithium chloride under similar conditions, decomposes and evolves chlorine. When heated slowly i n an oven, or in a current of dry ail-, the crystals become anhydrous a t 100-120", but some hydrochloric acid is likewise given off, and, on treatment with water, a residue of cupric oxychloride is left. The double salt can be obtained as an anhydrous, chamois-coloured powder by heating it a t 120" in a current of dry air mixed with dry hydrogen chloride. It is decomposed by water, but can be recrystallised from a concentrated solution of lithium chloride.C. H. B. Formation of Saline Hydrates at High Temperatures. By G. ROUSSEAU (Conzpt. Tend., 113, G43--648).---When the hydrated sodium ferrite obtained a t 800", and previously described, is allowed t o remain in contact with glycerol for several days, and is washed first with this liquid and afterwards with absolute alcohol, the dried residue contains only 9-68 per cent. of water, instead of the 14.5 per cent, that it contains when water is used for washing. The ferrite, 14Fe,0,,13H20,Naz0, when treated with glycerol in a similar manner, loses 2.79 per cent. of water. If either of these compounds is heated at 100" with glycerol, its colour rapidly becomes darker, and if diges- tion is prolonged, the whole of the water and alkali is removed, and anhydrous ferric oxide remains.The sodium manganites, such as 12Mn02,4H,0,Na,0, are not affected i n a similar way by glycerol. The author considers that these results establish. his previous con- clusions and support the view that the alkaline oxide replaces part of the water. C. H, B. Crystallised Ferric Oxychlorides. By G. ROCSSEAU (Compt. rend., 113, 542-5444 .-Very concentrated solutions of ferric chloride, containing ahout 80 per cent. of Fe2Cls, maintained at a temperature of lW--220" for some time, yield a crystallised feryic oxychloride, 2Fe,03,Fe2Cl, + 3H,O. By prolonged boiling with water, this compound is gradually converted into a ferric hydroxide, (Pe,O, + H20)3, which retains the same crystalline form as the oxgchloride. Solutions containing 85 to 911 per cent.of the anhydrous ferric chloride have been heated in sealed tnbes, together with a fragment of marble or giobertite. Between 225" and 280", red-brown lamella: of the oxychloride 2Fe,03,1?e2C16 are obtained. Between 300" and 340°, large plates of a brownish-black oxychloride 3Fe2O3,Fe2Cl6 are formed.120 ABSTRAOTS OF CHEMICAL PAPERS. The author has been unable to study the reaction at higher tem- peratures, but believes that a, series of oxychlorides of the type (Fe,O3),,Fe,CI6 would be formed, in which the proportion of EeZO, would increase with the temperature. The anhydrous oxychlorides are very sparingly soluble in dilute mineral acids. When boiled with water i n presence of marble for 150-200 hours, they lose all their chlorine as hydrochloric acid, ferric oxide of a fine brownish-red colour remaining. The optical properties of these oxychlorides have been determined by Fouqu6. They occur in prisms giving longitudinal extinction.The plans of their optic axes is transverse, and the bisectrix is positive. It would be interesting to observe whether the rhombic oxychlor- ides retain their form during the concentration of ferric oxide in the molecule, or whether they assume, at a temperature near a red heat, the hexagonal form characteristic of ferric oxide. On the latter hypothesis, the hydrolysis of the hexagonal oxychloride, by boiling with water, should give a new method for the synthesis of hzmatite, allowing the determination of the degree of polymerisation of this mineral oxide. W. T. Action of Water on Glass.By E. PFEWFER (Ann. Phys. Chein. [ Z ] , 44, 239-264) .--The author has taken advantage of electrolytic conductivity for the purpose of determining the amount of substaiice dissolved from glass by water at low temperatures. Ordinary chemical methods give very uncertain numerical results, on account of the difficixltg in determining the exact magnitude of the large surface which must be exposed to the action of water, and even these results are obtained ander conditions diverging considerably from those of laboratory practice. Water first of all dissolves practically pure alkali (potassium or sodium hydroxide) out of the glass, and this afterwards exerts its own influence by dissolving silica. The author estimates the amount of alkali dissolved by determining the electrical conductivity of the solution, to which it is proportional. As the molecular conductivities of potassium hydroxide and sodium hydroxide lie close together (220 x 10-7 and 200 x according to Kohlrauschj, no great error is comrnitted in estimating the total amount dissolved on the assumption that each alkali dissolves proportionately to the extent to which i t is contained in the glass.When silicates are formed in the solution, the conductivity falls. The experiments were made by exposing cylinders of good Thuringian glass with known surface to the action of water contained in glazed porcelain vessels; the temperature in the three series of observations made being lo", 30", and 30". For one sort of glass at a given temperature, it was found that A0 = A w / o is a constant, A being the increase in conductivity per hour, w the volume of water, and o tbe surface of the cylinder.When the glass has been exposed for some time to the action of water at a temperature of 60", the value of A,, for 2G" falls considerably. Aha("") for the first day is muchINORGANIC CEEMISTRY. 122 greater than A,-,(2o) afterwards. With the specimen of glass examined, it was found that a t 20" one to two millionths of a milligram were dissolved out by 1 C.C. of water per square centimeter in an hour. No silica is dissolved a t 10" or 20". Ati 30°, however, a considerable falling off of A. with the time is observed, due in all probability to this cause. The values of AL, (reduced to go*) for the various tern- peratures are as follows :- 10".20". 30". A. .... .. .. 25 100 673 Prolonged treakment of the glass at a low temperature does n o t appreciably affect its solubility a t a higher temperature. J. W. Stannibromides. By LETEUR (Compt. rend., 113, 540-542).- The stannibromides of the alkali metals and magnesium are yellow, well-crystallised substances. Concentrated solutions have the same colour, but a t a certain state of dilution, the colour disappears. The anhydrous stnnnibromides of potassium and ammonium only suffer change in very moist a i r ; others are very deliquescent. Concen- trated solutions may be heated without decomposition ; on dilution, decomposition occurs with the formation of hydrobromic acid and the deposition of hydrated tin dioxide. Alcohol decomposes these corn- pounds, slowly in the cold, more rapidly on heating ; benzene has no action on them.The general method for the preparation of the stannibromides consists in mixing concentrated solutions of the two bromides and evaporating the mixture in R vacuuni or in dry air. The ammonium salt, (NH4)2SnBr6, forms sulphur-yellow ocka- hedra belonging to the cubic system; it decrepitates when heated, and volatilises with partial decomposition. The sodium salt, Na,SnBr, + 6H20, for.ms yellow prisms of the monoclinic system, having a position of extinction in polarised light at lFjo to the longer axis. It is very deliquescent, but effloresces rapidly over sulphuric acid OY in a vacuum. It decomposes, when heated, with evolntion of water and stannic bromide. The lithium salt is probably Li,SnBr, + 6H20, but the water cannot be accurately determined owing to the extreme deliquescence of the compound.It forms small, yellow, prismatic needles whicli act on polarised light, and appear to belong to the monoclinic system. Over sulphnric acid, these crystals effloresce. giving a citron-yellow, crystalline powder tending towards the composition Li2SnRr, + 5H,O. The magnesium salt, MgSnBr, + 10H20, gives small, sulphnr- yellow, monoclinic crystals. The ordinary form is a prism showing the faces q1 and h, with modifications on the angle a. Macles are frequent. The study of the alkaline earthy stannibromides is being nolv carried on. W. T. VOL. LX1I. 72 Extinction occurs a t an angle of 60".122 ABSTRACTS OF CIHEMICAL PAPERS. Dissolution of Bismuth Chloride in a Saturated Solution of Sodium Chloride : Basic Bismuth Salicylate.By H. CAUSSE (Compt. rend., 113, 547-549) .-Sodium chloride, like ammoniiiin chloride, may be employed instead of free acid to prevent the dis- sociation of bismuth salts by water. Hence, in presence of sodium chloride, hydrochloric acid may be completely neutralised by bismuth carbonate or oxide. 100 C.C. of hydrochloric acid solution containing 3.0775 grams HC1 is left in contact with 3 grams of bismuth oxide until no further solution takes place ; the remaining oxide is collected and weighed. 1.50 grams of the oxide are dissolved, requiring 0.4775 gram of the acid t o form BiCI,; the remaining 2.60 grams of the hydrochloric acid are required to maintain the equilibrium in the solution.With 100 C.C. of acid containing 6.155 grams HCl, 6.00 grams of oxide are dissolved, and 3.117 grams of free acid remain. With 100 C.C. of acid containing 9.2325 grams HCI, 10 grams of oxide are dissolved, and 4.557 grams of acid remain. Each of these solutions is saturated with common salt, and then treated with bismuth oxide. The quantities of bismuth oxide dissolved as compared with the quantities required to neutralise the hydrochloric acid present with production of bismuth trichloridc are respectively 6.80 : 6.584, 13.25 : 13.160, and 20.25 : 19.70. The numbers given above do not show that any definite relation exists between the free acid and the amount of bismuth chloride formed. To ascertain whether such a relation exists at the experi- mental limit, the author treats 50 grams of oxide with 50 C.C.of saturated hydrochloric acid containing 22.80 grams of acid. 47.50 grams of oxide are dissolved, and 5.18 grams of free acid remain. 5.40 grams of acid would be uncombined if the reaction were as follows: Bi,O, + 8HC1 = S(BiCl,,HCl) -l- 3H?O ; helice tRe author concludes that under these circumstances a definite salt is formed. To obtain basic bismuth salicylate, 40 C.C. of conccritrated hydrochloric acid is saturated with bismuth oxide in presence of 500 C.C. of saturated sodium chloride solution ; to another SO0 C.C. of brine are added 9 grams of soda and 22 grams of sodium salicylate, the two solutions are mixed, and the precipitate formed is washed with water containing a few drops of nitric acid.The basic sali- cylate, C,H,BiO4,IIZO, obtained, forms microscopic prisms, and has properties similar to those of the normal salicylate previously described. It is decomposed by heat with loss of the whole of its salicylic acid, which may also be completely eliminated by boiling concentrated alcohol. The constitution of t h i s salt may be represented by the formula OH*CsH~*COO*Bi(OH)z, which accounts for its ready hydrolysis. W. T.INORGANIC CHEMISTRY. 111I n o r g a n i c C h e m i s t r y .Sulphur Tetroxide. By D. CARNEGIE (Chem. News, 64, 158-159).-A criticism of Traube’s work on the electrolysis of 40 per cent.aqueous sulphuric acid (Abstr., 1891, 978). The author, whilst admit-ting that the substance formed cannot be a heptoxide of sulphur,comments on the absence of direct evidence in favour of theexistence of a tetroxide.The ratio 1 : 5 of active oxygen to sulphuricanhydride, which Traube considers t o prove the existence of thetetroxide SO, in the electrolysed solution, would be equally wel112 ABSTRAOTS OF OEEMIOAL PAPERS.explained on the hypothesis of the existence of a substance having thecomposition S207,H20.,,xH20. The existence of such a substancewould not only accord with Berthelot’s results (Abstr., 1878, 469),but would harmonise with the known existence of tungsten andmolybdenum heptoxides, and with the tendency of peroxides of the typeM20, to form stable compounds with hydrogen peroxide. Moissmn’sperchromic acid (Abstr., 1884, 20 ; comparo Berthelot, Abstr., 1889,350) might then be regarded as a compound, Cr207,H202,H20, of thesame type.With regard to the low amount of active oxygen shown by theiodometric method, the author points out that this cannot beaccountJed for by the presence of sodium hydrogen carbonate, sincethe latter has practically no action on iodine, but that it can beaccounted for by the presence of free alkali in the potassium iodide,and that this supposition accords with the higher results which wereobtained on working with acid instead of neutral solutions.JN. W.Azoimide.By T. CURTIUS (Bey., 24, 3341-3349; compareAbstr., 1891, 56).-Ethereal salts of benzoic acid react with hydrazinchydrate accordiiig to the equation PheCOOR + N2H4,H20 =COPh*NH.NH2 + ROH + H20. The benzoylhydrazine, when treatedwith nitrous acid, yields benzoylazoimide, and on digesting this withsodium ethoxide it IS decomposed quantitatively into sodium nitride,NaN3, and ethyl benzoate.The salts of azoimide may also be prepared from hippurylhydrazine,by the action of nitrous acid; in this case, a compound is formedwhich was previously termed nitrosohippurylhydrazine ; it is, however,n diazo-compound with the formula COPh*NH*CH,*CO*NH*N:N*OH(see below) ; it cannot be converted into hippurylnzoimide by elimin-ation of water, but on treatment with ammonia in alcoholic solution,it is decomposed into hippuramide and ammonium nitride ; the hip-puramide combines with hydrazine hydrate to form hippuryl-hy drazine.Argentic nitride, AgN,, has been previously described; it is solublein ammonia, from which it crystallises in long, colourless needles ; i tis exceedingly explosive.Mercurous nitride, HgN,, is precipitated in microscopic needleswhich are insoluble in water ; it is more stable than either the silveror lead salts, becomes yellow on exposure to light, and yields a black,insoluble compound with aqueous ammonia.Plztmbic nitride, PbN6, is prepared by adding plumbic acetate to asolution of the sodium or ammonium salts ; it is soluble in excess ofthe precipitant, but insoluble in water in the cold, and moresparingly soluble in boiling water than plumbic chloride, which itclosely resembles.It crystallises from water in long, colourless,lustrous needles, which explode violently on gently warming anddecompose gradually when heated with water o r acetic acid.Sodium nitride is most readily prepared in the manner describedabove, but may also be obtained by adding soda to solution of thefree acid or of the ammonium salt; it is readily soluble in water, in-soluble in alcohol or ether, has a slight alkaline reaction and INOROANIO CHEMISTRY.113saline taste, The compound is neit,her ~olatile nor hygroscopic ; itssolution may be evaporated to dryness without undergoing any change,and i t only explodes when heated to a comparatively high temp-erature.Ammonium nitride, N4Hi, obtained as above, is rea,dily purified byadding ether to the alcoholic solution, or it may be crystallised fromalcohol, irom which it is deposited in plates closely resembling am-monium chloride, but not belonging to the regular system.It isexcessively volatile, and explodes violently when heated in a combus-tion tube with cupric oxide in a current of air; it may, however, besublimed by cautiously heating at a little aboye loo", although violentexplosions occur if it is rapidly heated,Hydrazine nitride, NsH5, is prepared by adding hydrazine hydrateto ammonium nitride or to the free acid; it crystallises i n long,lustrous prisms, or in plates, and is sparingly soluble in alcohol. Bydetonation, or on rapidly heating, the compound explodes violently,but it will burn quietly with a smoky, slightly yellow flame ; if thecombustion takes place on a metallic surface, every trace of oxide onit will be reduced arid the metal will appear bright and polished.The formation of diazohippuramide, COPh*NH*CH,-CO*NH*N:OH,has already been described ; it combines with ammonia. aniline, hydr-azine, and similar compounds with elimination of axoiniide, whilst theaction of water, alcohol, aldehydes, or acidyl hydrazines causesnitrogen to be evolved ; for example, the action of aniline on diazo-bippurlylamide gives rise t o hippurylanilide, aniline nitride, and water ;the reaction with alcohol is represented by t.he equation,NHBz~CH2*CO*NH*N2*OH + EtOH = N2 + NHBz*CH2*CO*NH*OEt + HzO.On treating diazohippurylamide with benzoylhydrazine, nitrogen andwater are eliminated, and a compound is formed which has theformula NHBz*CH,*CO*NH*NH*NH.Bz ; this is exceedingly stabletowards acids and alkalis, and attempt8 to hydrolyse it have hithertobeen unsuccessful; its properties and mode of formation prove it tobe a derivative of trinmide, NH2*NH*NHz, which has not as yet beenobtained in the free state.J. B. T.The Colour of Nitric Acid. By L. M~CHLEWSKI (Ber., 24,3271--327G).-It is well known that as water is added to red fumingnitric acid, the colour changes through green to blue and finally dis-appears. I n explanation of this, it has always been assumed that thered acid i s a solution of nitrogen peroxide, N204, in nitric acid, andthat the water added decomposes the peroxide with formation ofnitric and nitrous acids. The solution of nitrous acid in nitric acidis blue, and this, with the red solution of still undecomposed peroxide,gives a green colonr.As more water is added, this excess of peroxide isdecomposed, and nothing is then left but a blue solution of nitrous acid.The author has investigated the matter experimentally in the follow-ing manner :-The gases contained in the coloured acid were expelledby means of carbonic anhydride and collected i n concentrated sulph-uric acid, with which nitrous acid forms nitrosyl hydrogen sulphate114 ABSTRACTS OF CHEMICAL PAPERS.but with nitrogen peroxide forms a mixture of nitrosyl hydrogengulphate with nitric: acid in moiecular proportion. The total nitrogenwas determined with the nitrometer, and the reducing power by titra-tion with permanganate. Both results were calculated to trioxide, andfrom the ratio of the second to the first a conclusion could be drawn asto the constitutlion of the mixture of gases absorbed.I f the gas werepure trioxide, the ratio would of course be 1 ; if it were pure peroxide,0.5, since the reducing power of the peroxide is only half that of thetrioxide. The results obtained were astonishing, for although theyshowed that the blue acid contained pure trioxide, yet they alsoshowed that the green acid did not contain more than a t mostmere traces nf the peroxide. The author was consequently ledto suspect that his results were vitiated by the presence of nitricoxide, NO, in the coloured acids examined; and in fact when theexperiments were repeated, the gases that escaped absorption inthe strong sulphuric acid being passed through a strongly acid per-manganate solution, the permanganate was perceptibly reduced.The reduction was, of course, due to nitric oxide, and a great deal ofthis gas must have been present originally, for had only a smallquantit>y been there, i t would have formed nitrosyl hydrogensulphate wit.h the peroxide also present and the concentrated snlph-uric acid, and would thus have been absorbed.The solutions investigated were made by passing the gaseous oxideinto pure nitric acid.Solutions obtained by mixing pure liquidperoxide with nitric acid of different strengths are now being in-vestigated. C. F. B.Boron Phosphoiodides. By H. MOISSAN (Conz-pt. rend., 113,624--627).-Melted phosphorus acts with great energy on borontriiodide, and if red phosphorus is heated in the vapour of the iodide,decomposition takes place with incandescence.If, however, a solutionof the iodide in carbon bisulphide is mixed with a similar solution ofphosphorus, great care being taken t o avoid the presence of moisture,the reaction takes place more slowly. The mixture is sealed up in aflask and kept a t the ordinary temperature of the laboratory ; it is atfirst clear, but has a red colour. I n a few minutes a brown precipi.-tate begins to separate, and the reaction is complete in about threehours. The product is filtered through glass wool, washed withcarbon bisulphide, and dried in a vacuum, the apparatus being filledwith carbonic anhydride until the latter is removed by the pump,The product is boron phosphodiiodide, BPI,, an amorphous, homo-geneous, deep-red powder.When heated in a vacuum, it melts at190-200", and will remain in superfusion a t the ordinary temperaturefor a long time ; in a vacuum, it begins to volatilise at 170-200", andcondenses on the cold part of the tube in distinct red crystals. It isonly very slightly soluble in carbon bisulphide, and seems t o he com-pletely insoluble in benzene, phosphorus trichloride, and carbontetrachloride. It is extremely hygroscopic, and decomposes veryrapidly in moist air. In presence of a large excess of water, it be-comes yellow, without, apparent development of heat, and hydriodic,phosphorous, and boric acids are formed, a small quantity of phosphinINORGANIC CHEMISTRY.115being evolved, and a small quantity of a yellow substance with anodour of phosphorus being deposited. With a very small quantityof water, the yellow precipitateis produced i n larger quantity, and adistinct quantity of phosphonium iodide is formed.Boron phosphodiiodide, wheir heated in hydrogen sulphide, yieldsboron sulphide, phosphorus sdphide, and hydrogen iodide withoutany free iodine. Dilute nitric acid yields phosphoric acid and boricacid, whilst strong nitric acid produces the same result, but with in-candescence. Siilphuric acid (even Nordhausen) has 110 action in thecold, b u t , on heating, free iodine, hydrogen iodide, and sulphurousanhydride are evolved. Phospliorous trichloride and carbon tetra-chloride have no action even in sealed tubes at 100".Chlorine pro-duces incandescence, with formation of boron chloride, iodinechloride, and phosphorus pentschloride. When heated in oxygen, thecompound burns and yields iodine, boric anhydride, and phosphoricanhydride. Sodium has no action in the cold, but decompositiontakes place at t>he melting point of the metal. Powdered magnesiumreacts with incandescence. When thrown into mercury vapour, thephosphodiiodicle takes fire a t once. I n presence of carbon bisulphidethe behaviour of metals is different; magnesium or sodium a t theordinary temperature produces a red compound, PBT, whilst silveror mercury in the cold, or more rapidly a t loo", yields a maroon-coloured compound with the properties of boron phosphide, BP.Boron phosphoiodide, BPI, is obtained by heating the precedingcompound in hydrogen, and is an amorphous, red powder, somewhastless hygroscopic than the diiodide.It volatilises in a vacuum a t210-250" without previous fusion, and condenses in orange-yellowcrystals. Strong nitric acid decomposes i t with development of heatand without incandescence, iodine being liberated. Concentratedsulphuric acid has no action in the cold, but, OIL heating, iodine,sulphurous anhydride, and boric acid are formed. When heated outof contact with air, it decomposes a t a temperature below dull rednesswith evolution of Fapours of iodine and boron phosphide. Mercuryin excess, in presence of dry carbon bisulphide, yields mercuric iodideand boron phosphide a t the ordinary temperature.Boron phoThide, BP, resembles the phosphoiodide B P I in its generalproperties.It can be obtained by heating the phosphoiodide inhydrogen, and if the heating is continued, a residue of the composi-tion B,P, is left. C. H. B.Reducing Action of Graphitoidal Silicon. By H. N. WARREN(Chenz. News, 64, 75).-When the oxides of easily reducible metals,such as lead, copper, and silver, are heated to dull redness withpowdered graphitoydal silicon, they are reduced to the metal, and ifthe silicon is in excess, a metallic silicide is formed. The oxides ofchromium, tungsten, and molybdenum may also be reduced in thiaway. In some cases, the reduction takes place with explosiveviolence ; when, for instance, a small quantity of a mixture of equalpaxts of finely-divided silicon, aluminium, and litharge was meltedbefore the blowpipe, the explosion was so violent as to indent thesupporting brick.JN. W116 ABSTRACTS OF CBEMICAL PAPERS.Solubility of Sodium Carbonate and Sodium HydrogenCarbonate in Solutions of Sodium Chloride. By K. REICR(Monatsh., 12, 464--473).-The solubility of sodium carbonate a t 15"in a solution of sodium chloride of gradually increasing concentrationat first diminishes and then increases. The solubility y as a functionof the quantity x of sodium chloride in 100 parts of water is expressedby the formulay = 61.406 - 2.091077~ + 0.0554932 - 0*00029'7357~~.Accordingly, the minimum lies near cc = 23.15 where y = 39.05.On passing carbonic anhydride through the saturated solution, theamount of bicarbonate precipitated increases with the quantity ofsodium chloride in solution ; but a maximam cannot be recognised.G. T.M.Allotropic Silver. By M. C. LEA (Phil. Mag. [ 5 ] , 32, 337-3421.-The blue form of allotropic silver is capable of change into anintermediate yellow form which seems t o be identical with that, intowhich the gold-coloured form passes under the influence of variouscauses (Abstr., 1891, 803). The change takes place at about B O O ,both with lumps of the blue silver and with films. By the action ofsulphuric acid, however, blue silver can be converted into yellow silverat the ordinary temperature, and consequently with retention of allits active properties.40 grams of sodium hydroxide and 40 grams of yellow or browndextrin are dissolved in 2000 C.C.of water, and 28 grams of silvernitrate is added in successive very small quantities, with frequent-agitation. The solution is slightly turbid. and is deep-green by re-flected' light, red by transmitted light. The precipitate tbat formsspontaneously or is produced by the addition of acetic acid, dilutenitric acid, and many neutral substances, consists of blue silver, but ifsulphuric acid is added, the precipitate, when dried in films, is blue,green, yellowish-green, or yellow, according to the proportion ofacid used. When the silver solution is mixed with an equal volumeof a mixture of i s 5 C.C. of sulphuric acid and 92.5 C.C. of water, theprecipitate consists wholly of yellow silver, bnt with higher propor-tions of acid the product dries with a coppery shade. The lustre of)the product, diminishes as the proportion of acid used for precipitationis increased.Conversely, it solution which would yield yellow silver under or-dinary circumstances can be made to yield blue silver by the additionof an alkali, and it is immaterial whether the alkali is added to theferrous tartrate or the silver mixtnre or to a mixture of the two.There is, therefore, a tendency for acids to produce the yellow pro-.duct, and alkalis the blue product., but it is a tendency only, and bothforms can be obtained from neutral solutions ; for instance, ferroustartrate and silver tartrate yield gold-coloured silver, but ferrouscitrate and silver citrate produce the blue variety.When sodium hypophosphite is added to silver nitrate, there is norecluction, but if phosphoric acid is added so that hypophosphorous.acid is liberated, it transient red colour appears, and red and bluINORGANIC CHEMISTRY.117stains are formed on the side of the vessel. Phosphorous acid givessimilar though somewhat less distinct results.The blue silver obtained by adding the soda-dextrin silver solutionto an equal volume of water containing 4 per cent. of sulphuric acidis not only constant in character but is one of the forms most sensi-tive to light. When this form is exposed to light, it first becomesmore distinctly blue, then yellowish-brown, and finally is convertedinto the golden-yellow intermediate or crystalline form, with greatbrilliancy and lustre.It is noteworthy that the action of light on this blue varietyat first.increases its sensitiveness to reagents such as potassium ferricpanide,and afterwards reduces it.This is well shown if one part of a film iscovered with an opaque substance, another part with a translucentsubstance, whilst the third is left uncovered, and the three are ex-posed simultaneously to bright sunlight for about five hours andafterwards treated with dilute ferricyanide solution. The authorregards this phenomenon as analogous to the reversing action ob--served with gelatinobromide plates.The production of reduced silver is direct when an ordinary silver.compound is converted into metal without formation of a sub-salt,and indirect when the silver compoufid is first reduced to a, sub-salt,and the latter is afterwards reduced to the metal.It would seemthat only under the latter conditions is there any formation of allo-tropic silver. If, in any of the three principal methods of producingallotropic silver, the action is interrupted by the addition of hydro-chloric acid, a dark, chestnut-brown or purple-brown mixture of thesubchloride with the photochloride is obtained, and from it beautifulrose-red photochloride can be obtained by treatment with cold dilutenitric acid after complete removal of the hydrochloric acid. Thisresult is only obtained by interrupting the reaction before it is c v - .plete, and if the hydrochloric acid is added after complete reduction,only grey, normal silver is precipitated.Ifi every case examined,silver subchloride is obtained as one of the products when a reactionresulting in the formation of allotropic silver is interrupted by theaddition of hydrochloric acid before reduction is complete.The rich and varied colour of silver sub-salts would seem to indi-cate that in these compounds the metal existls in an allotropic form,but, on the other hand, the greater activity of allotropic silver and itslower sp. gr. would tend to show that the allotropic form has asimpler molecular structure than the normal metal.Colloidal Silver. By E. A. SCHNEIDER (Ber., 24, 3370-3373).-Collo'idal silver prepared according to Carey Lea's method, by thereduction of silver nitrate with ferrous citrate, cannot be purified bydialysis alone ; the better plan is to separate the solid colloid fromthe mother liquor as completely as possible by filtration, then todissolve the silver in a little water and allow this solution to dialyse.On adding hydrochloric acid to aqueous collojdal silver solutions,silder and argentic chloride are precipitated, the proportion of thelatter being greater with increasing quantities of hydrochloric acid ;the mixed precipitate is extracted with ammonia, the argentic chloride*C.H. B118 ABSTRAOTS OF OEIEMIOAL PAPERS.precipitated by acidification with nitric acid, and hydrochloric acidadded t o the filtrate ; if the quantity of hydrochloric acid originallyemployed was small, a further precipitate is produced, showing thopresence of a silver snbchloride.The mixed precipitate of silver andargentic chloride was always rose-red.Nitric and sulphuric acids react with colloydal silver solutioiis in asimilar manner. No evolution of hydrogen could be detected evenwhen sutlicient hydrochloric acid was added to the silver solution toproduce a considerable precipitate of argentic - chloride ; this mayindicate the presence of nrgentous oxide : neither was oxygen evolvedwhen, in consequence of the small quantity of hydrochloric acid em-ployed, t.he precipitat,e consisted of almost pure silver.J. B. T.Direct Combination of Chlorine and Bromine with Metals,By H. GAUTIER and G. CHARPY (Compt. rend., 113, 597-600).-Wellcleaned wires of various metals, 2 mm.in diameter, were kept in thedark in contact with dry bromine for a definite length of time at 15"and 100". The percentage loss of weight in each case is given in thefollowing table :-At 15' in At 15' in At 100' in8 days. 4 months. 8 days.Magnesium ...... 0.0 0.0 0.19Copper .......... 0.371 1- 740 6.62Zinc ............ 0.289 0.48 7 0.63Iron ............ 0.210 0.440 23.27Silver. .......... 0.003 0.540 -Aluminium under similar conditions combines energetically withbromine and becomes incandescent, a burning fragment runningabout on the surface of the bromine like potassium on water. Withliquid chlorine in sealed tubes at the ordinary temperature, the resultsare similar, the percentage losses being : magnesium, 0.0 ; zinc, 0.0 ;iron, 0.740 ; copper, 3.241 ; silver, 0.673.Potassium, sodium, andaluminium seem to be unaffected by liquid chlorine at its boilingpoint, but a t -20" aluminium combines with the halogen withincandescence.Magnesiumand aluminium, when placed in bromine-water, produce a regularevolution of hydrogen, and, after some time, an oxybromide separates,the reactions being analogous to the decomposition of water by iodinein presence of aluminium. With zinc, iron, and copper, there is noevolution of gas, and a wire 2 mm. in diameter and 50 mm. in lengthdisappears in seven t o eight hours in excess of bromine-water. Itseems probable that in these cases the decomposition of water by thehalogen is accelerated by the presence of' the metal, the latter beingconverted into an oxide which is attacked by the hydracid formed.C.H. B.I n presence of water, the results are very different.Lithium Copper Chloride. By A. CHASSEVANT (Compt. rend.,113, 646-648) .-When a concentrated solution of lithium chloride iINORGANIO OHEMISTRY. 119added to 8 cancentrated solution of an equivalent quantity of cupricchloride, a magma of crystals of the latter salt is formed, but if themidurc is evaporated in a vacuum over phosphoric acid or on awater-bath at loo", the ci-ystals dissolve, the liquid acqnires a,brownish-red colour and deposits transparent, gzrnet-red crystals ofthe double chloride 2CuClZ,2LiC1,5H,O. When exposed to the air, theydecompose, and become opaque, crystals of cupric chloride separating,whilst the lithium chloride deliquesces.If heated rapidly to 130",they melt in their water of crystallisation arid form a deep-brown,almost black, solution. A t tt higher temperature, the salt, likelithium chloride under similar conditions, decomposes and evolveschlorine. When heated slowly i n an oven, or in a current of dry ail-,the crystals become anhydrous a t 100-120", but some hydrochloricacid is likewise given off, and, on treatment with water, a residue ofcupric oxychloride is left. The double salt can be obtained as ananhydrous, chamois-coloured powder by heating it a t 120" in a currentof dry air mixed with dry hydrogen chloride. It is decomposed bywater, but can be recrystallised from a concentrated solution of lithiumchloride. C.H. B.Formation of Saline Hydrates at High Temperatures. ByG. ROUSSEAU (Conzpt. Tend., 113, G43--648).---When the hydratedsodium ferrite obtained a t 800", and previously described, is allowedt o remain in contact with glycerol for several days, and is washedfirst with this liquid and afterwards with absolute alcohol, the driedresidue contains only 9-68 per cent. of water, instead of the 14.5 percent, that it contains when water is used for washing. The ferrite,14Fe,0,,13H20,Naz0, when treated with glycerol in a similar manner,loses 2.79 per cent. of water. If either of these compounds is heatedat 100" with glycerol, its colour rapidly becomes darker, and if diges-tion is prolonged, the whole of the water and alkali is removed, andanhydrous ferric oxide remains.The sodium manganites, such as 12Mn02,4H,0,Na,0, are notaffected i n a similar way by glycerol.The author considers that these results establish.his previous con-clusions and support the view that the alkaline oxide replaces part ofthe water. C. H, B.Crystallised Ferric Oxychlorides. By G. ROCSSEAU (Compt.rend., 113, 542-5444 .-Very concentrated solutions of ferric chloride,containing ahout 80 per cent. of Fe2Cls, maintained at a temperatureof lW--220" for some time, yield a crystallised feryic oxychloride,2Fe,03,Fe2Cl, + 3H,O. By prolonged boiling with water, thiscompound is gradually converted into a ferric hydroxide, (Pe,O, +H20)3, which retains the same crystalline form as the oxgchloride.Solutions containing 85 to 911 per cent.of the anhydrous ferricchloride have been heated in sealed tnbes, together with a fragmentof marble or giobertite. Between 225" and 280", red-brown lamella:of the oxychloride 2Fe,03,1?e2C16 are obtained. Between 300" and340°, large plates of a brownish-black oxychloride 3Fe2O3,Fe2Cl6 areformed120 ABSTRAOTS OF CHEMICAL PAPERS.The author has been unable to study the reaction at higher tem-peratures, but believes that a, series of oxychlorides of the type(Fe,O3),,Fe,CI6 would be formed, in which the proportion of EeZO,would increase with the temperature.The anhydrous oxychlorides are very sparingly soluble in dilutemineral acids. When boiled with water i n presence of marble for150-200 hours, they lose all their chlorine as hydrochloric acid,ferric oxide of a fine brownish-red colour remaining.The optical properties of these oxychlorides have been determinedby Fouqu6.They occur in prisms giving longitudinal extinction.The plans of their optic axes is transverse, and the bisectrix ispositive.It would be interesting to observe whether the rhombic oxychlor-ides retain their form during the concentration of ferric oxide in themolecule, or whether they assume, at a temperature near a red heat,the hexagonal form characteristic of ferric oxide. On the latterhypothesis, the hydrolysis of the hexagonal oxychloride, by boilingwith water, should give a new method for the synthesis of hzmatite,allowing the determination of the degree of polymerisation of thismineral oxide.W. T.Action of Water on Glass. By E. PFEWFER (Ann. Phys. Chein.[ Z ] , 44, 239-264) .--The author has taken advantage of electrolyticconductivity for the purpose of determining the amount of substaiicedissolved from glass by water at low temperatures. Ordinarychemical methods give very uncertain numerical results, on accountof the difficixltg in determining the exact magnitude of the largesurface which must be exposed to the action of water, and even theseresults are obtained ander conditions diverging considerably fromthose of laboratory practice.Water first of all dissolves practically pure alkali (potassium orsodium hydroxide) out of the glass, and this afterwards exerts itsown influence by dissolving silica.The author estimates the amountof alkali dissolved by determining the electrical conductivity of thesolution, to which it is proportional. As the molecular conductivitiesof potassium hydroxide and sodium hydroxide lie close together(220 x 10-7 and 200 x according to Kohlrauschj, no greaterror is comrnitted in estimating the total amount dissolved on theassumption that each alkali dissolves proportionately to the extent towhich i t is contained in the glass. When silicates are formed in thesolution, the conductivity falls.The experiments were made by exposing cylinders of goodThuringian glass with known surface to the action of water containedin glazed porcelain vessels; the temperature in the three series ofobservations made being lo", 30", and 30".For one sort of glass ata given temperature, it was found that A0 = A w / o is a constant, Abeing the increase in conductivity per hour, w the volume of water,and o tbe surface of the cylinder. When the glass has been exposedfor some time to the action of water at a temperature of 60", thevalue of A,, for 2G" falls considerably. Aha("") for the first day is mucINORGANIC CEEMISTRY. 122greater than A,-,(2o) afterwards. With the specimen of glass examined,it was found that a t 20" one to two millionths of a milligram weredissolved out by 1 C.C. of water per square centimeter in an hour.No silica is dissolved a t 10" or 20". Ati 30°, however, a considerablefalling off of A. with the time is observed, due in all probability tothis cause.The values of AL, (reduced to go*) for the various tern-peratures are as follows :-10". 20". 30".A. .... .. .. 25 100 673Prolonged treakment of the glass at a low temperature does n o tappreciably affect its solubility a t a higher temperature. J. W.Stannibromides. By LETEUR (Compt. rend., 113, 540-542).-The stannibromides of the alkali metals and magnesium are yellow,well-crystallised substances. Concentrated solutions have the samecolour, but a t a certain state of dilution, the colour disappears. Theanhydrous stnnnibromides of potassium and ammonium only sufferchange in very moist a i r ; others are very deliquescent. Concen-trated solutions may be heated without decomposition ; on dilution,decomposition occurs with the formation of hydrobromic acid and thedeposition of hydrated tin dioxide.Alcohol decomposes these corn-pounds, slowly in the cold, more rapidly on heating ; benzene has noaction on them.The general method for the preparation of the stannibromidesconsists in mixing concentrated solutions of the two bromides andevaporating the mixture in R vacuuni or in dry air.The ammonium salt, (NH4)2SnBr6, forms sulphur-yellow ocka-hedra belonging to the cubic system; it decrepitates when heated,and volatilises with partial decomposition.The sodium salt, Na,SnBr, + 6H20, for.ms yellow prisms of themonoclinic system, having a position of extinction in polarised lightat lFjo to the longer axis. It is very deliquescent, but efflorescesrapidly over sulphuric acid OY in a vacuum.It decomposes, whenheated, with evolntion of water and stannic bromide.The lithium salt is probably Li,SnBr, + 6H20, but the watercannot be accurately determined owing to the extreme deliquescenceof the compound. It forms small, yellow, prismatic needles whicliact on polarised light, and appear to belong to the monoclinic system.Over sulphnric acid, these crystals effloresce. giving a citron-yellow,crystalline powder tending towards the composition Li2SnRr, +5H,O.The magnesium salt, MgSnBr, + 10H20, gives small, sulphnr-yellow, monoclinic crystals. The ordinary form is a prism showingthe faces q1 and h, with modifications on the angle a. Macles arefrequent.The study of the alkaline earthy stannibromides is being nolvcarried on. W. T.VOL. LX1I. 72Extinction occurs a t an angle of 60"122 ABSTRACTS OF CIHEMICAL PAPERS.Dissolution of Bismuth Chloride in a Saturated Solution ofSodium Chloride : Basic Bismuth Salicylate. By H. CAUSSE(Compt. rend., 113, 547-549) .-Sodium chloride, like ammoniiiinchloride, may be employed instead of free acid to prevent the dis-sociation of bismuth salts by water. Hence, in presence of sodiumchloride, hydrochloric acid may be completely neutralised by bismuthcarbonate or oxide. 100 C.C. of hydrochloric acid solution containing3.0775 grams HC1 is left in contact with 3 grams of bismuth oxideuntil no further solution takes place ; the remaining oxide is collectedand weighed. 1.50 grams of the oxide are dissolved, requiring 0.4775gram of the acid t o form BiCI,; the remaining 2.60 grams of thehydrochloric acid are required to maintain the equilibrium in thesolution.With 100 C.C. of acid containing 6.155 grams HCl, 6.00 grams ofoxide are dissolved, and 3.117 grams of free acid remain. With100 C.C. of acid containing 9.2325 grams HCI, 10 grams of oxide aredissolved, and 4.557 grams of acid remain. Each of these solutionsis saturated with common salt, and then treated with bismuth oxide.The quantities of bismuth oxide dissolved as compared with thequantities required to neutralise the hydrochloric acid present withproduction of bismuth trichloridc are respectively 6.80 : 6.584,13.25 : 13.160, and 20.25 : 19.70.The numbers given above do not show that any definite relationexists between the free acid and the amount of bismuth chlorideformed. To ascertain whether such a relation exists at the experi-mental limit, the author treats 50 grams of oxide with 50 C.C.of saturated hydrochloric acid containing 22.80 grams of acid.47.50 grams of oxide are dissolved, and 5.18 grams of free acidremain. 5.40 grams of acid would be uncombined if the reactionwere as follows: Bi,O, + 8HC1 = S(BiCl,,HCl) -l- 3H?O ; helice tReauthor concludes that under these circumstances a definite salt isformed.To obtain basic bismuth salicylate, 40 C.C. of conccritratedhydrochloric acid is saturated with bismuth oxide in presence of500 C.C. of saturated sodium chloride solution ; to another SO0 C.C. ofbrine are added 9 grams of soda and 22 grams of sodium salicylate,the two solutions are mixed, and the precipitate formed is washedwith water containing a few drops of nitric acid. The basic sali-cylate, C,H,BiO4,IIZO, obtained, forms microscopic prisms, and hasproperties similar to those of the normal salicylate previouslydescribed. It is decomposed by heat with loss of the whole of itssalicylic acid, which may also be completely eliminated by boilingconcentrated alcohol. The constitution of t h i s salt may be representedby the formula OH*CsH~*COO*Bi(OH)z, which accounts for its readyhydrolysis. W. T

ISSN:0368-1769    

DOI:10.1039/CA8926200111

出版商:RSC    

年代:1892

数据来源: RSC

摘要:

MINERALOGICAL CHENISTRY. M i n e r a l o g i c a1 Chemistry. 123 Boleite, a New Mineral. By MALLARD and E. CUMENGE (Coinpt. renid., 113, 5 19--524).-This mineral occurs in cubical crystals of a fine indigo-blue colour in an argillaceous matrix, termed jctboncillo, next above the true copper-bearing bed of Boleo, near Santa Rosalia, Lower California. The crystals are accompanied by anglesite, phosgenite, cerussite, and atacamite. They are not decom, posed by water ; they melt in a candle flame, and, when heated in a closed tube, decompose with evolution of water. Two analyses of clean samples yield the numbers :- a I. 11. Calculated. Silver ........... 8.85 8.70 8.50 Lead.. .......... 48.45 49.75 48.90 Chlorine ........ 19.98 19.00 19.55 Water. .......... 4.77 4-00 4.28 Copper.......... 13.95 14-50 15.00 Oxygen (by diff.) . 4.00 4.05 3.77 The calculated percentages correspond with the formula 3[PbCl*OH,CuC1-OH] + AgC1. Metallic copper is obtained by re- duction in a current of dry hydrogen without the liberation of hydro- chloric acid: this would seem to indicate that the chlorine is not combined with t,he copper, but, in reality, the hydrochloric acid formed immediateiy reacts on the lead oxychloride, producing lead chloride and water. The formula given best shows the relationships of this mineral to laurionite, PbC1-OH, and atacamite, CuCl*OH,Cu( OH),. Brooke’s percylite, from Sonora, may possibly be the same mineral, although it,s imperfect analyses do not indicate the presence of silver. I n hardness, the mineral is a little superior to calcite, and its density is 5.08.The common form is the cube without modifying faces. Some crystals show very sharp and brilliant octahedral faces ; more rarely, dodecahedra1 faces are met with. Some small crystals have been observed with the edges replaced by re-entering angles formed by faces of the hexakistetrahedron. The cleavage is distinct and easy, parallel to the faces of the cube, the octahedral cleavage being less distinct. The observed optical properties are those of very birefringent, negative, uniaxial crystals ; the index of refraction could not be accurately determined; for a, prism formed by the cubical and dodecahedral faces, its approximate value is 2.07. Bol6ite belongs to the tetragonal system, though pseudo-cubic in habit. Along with the cubical crystals, octahedral crystals occur in pecu- liar groupings, showing the octahedml faces brilliant, but generally formed of three facettes, composing a low pyramid.k 2124 ABSTRACTS OF CHEMICAL PAPERS. The angular measurements are dificult, aud only yield approxi- mately the values f o r the parameters, a : c = 1 : 1.645. The com- position of the octahedral crystals is the same as that of the cubical crystals :- Silver ........ 9.2 9.4 8-5 Copper.. ..... 14.8 L5.0 15.0 Lead. ........ 50.2 50.7 48.9 Chlorine.. .... 19.4 19.7 19.5 Cubic cryst. Octahedral cryst. Calculated. Their densities appear to be about t,he same, a small specimeu of the octahedral crystals giving 5.0. W. T. Polydymite, Ullmannite, and Wolfsbergite. By H. L-4SPEI’RES (Zeit.Kryst. Min., 19, 417-436).;1. Po1ydymite.-The author brings forward fresh evidence in support of the formula Ni,S, he pro- pounded 15 years ago for polydgmite and nickel-bismuth glance, minerals which he regards as identical. The accuracy of this formula is confirmed by the a,nalysis of the polydymite from Sudburj, in Canada, as well as by the examination of some excellent crystals of this mineral from the Griineau mine, in the Siegen district. 2. UZEmannite.-The author describes some crystals of ullmannite, from the Landeskrone mine, near Siegen. Although this mineral is of frequent occurrence in the Siege11 mines, it has never before been found in crystals. 3. Wolfsbergite.-Of the crystalline form of the copper-antimony glance (Wolfsbergite), from Wolfsberg, in the Harz, all that is known is the brief account given by G.Rose in 1835. A discovery of a well-crystallised specimen in the Bonn Museum has enabled the author to give a detailed description of the crystallography of this mineral. The forms he has observed are:-OP, +Pw, Pm, 2 P a , pm, ;-Pa, QP+, ;P3. The axial ratio is cc : b : c = 0.52830 : 1 : 1.62339. B. H. B. Some New Chilian Minerals : Darapskite, Lautarite, Iodo- chromate. By A. DIETZE (Zeit. Kryst. &Fin., 19, 445-451).- 1. Darapskite.-This is the name given by the author to a new double salt of the cornposition repyesented by the formula NaNO, + Na,SO, + H,O. It is colourless, transparent, and occurs in square tablets bevelled by tetragonal pyramids. The new mineral is found at the Pampa del Toro, and is named after Dr.L. Darapsky, the well-known mineralogist, of Santiago. 2. I;autarite.-Although it has long been known that the iodine contained in the caliche or raw nitrate is due to the presence of iodates, no iodate has hitherto been found as a distinct mineral species. The new mineral described by the author is calcium iodate, the analytical results being in accord with the formula Ca(IO&. It occurs at the “ Pampa del Pique III?” in the form of large, monoclinic prisms, having the sp. p. of 4.59. I t is transparent, and of a yellow- ish colour. 3. Iodochromate.--Near the chief locality of lauterite, small, yellow It is very slightly soluble in water,YINERALOQICAL OHEMISTRY. 125 crystals occur in the caliche. These prove on analysis to be a double iodate and chromate of calcium, of the formula 7Ca(IO&,8CaCrOa.The accuracy of this formula is shown by the results of seven analyses. B. H. B. Formula of Axinite. By A. KENNGOTT (Jahrb. f. illin., 1891, ii, Mem. 335--336).-1n a recent paper (Abstr., 1891,1168), the author published a formula for axinite calculated from two analyses given by Whihefield. This result he now compares with three analyses given by 3'. A . Genth (Amer. J. Xci., 41, 394). These analyses refer to axinite from Franklin, New Jersey, in crystals and in lamelle, and from Guadalcazar, in Mexico. The analyses of axinite from Franklin give results closely approaching those obtained from White- field's analyses. The axinite from Guadalcazar, however, wag appa- rently admixed with white felspar partially converted into kaolin, and, consequently, cannot be considered suficiently pure to serve as the basis for the calculation of a formula.B. H. B. Constitution of certain Micas, Vermiculites, and Chlorites. By F. W. CLARKE and E. A. SCHKEIDER (dnzer. J. Xci., 42,242-251). -In a previous paper (Abstr., 1891, 529), the authors considered the constitution of the mica and chlorite groups. The present paper is a continuation of the same research. Throughout the investigation the fundamental hypothesis that the minerals studied are substitution derivatives of normal salts has been amply justified. Of the so-called vermiculites, two only, jefferisite and kerrite, were considered in the former paper, and these wcre shown to be tri- hydrated micas in which the original alkalis had been replaced by hydrogen. The examination of other varieties shows that kerrite is essentially a t,rihydrated hydrophlogopite.Protovermiculite, from Magnet Cove, Arkansas, is the same substance mixed with an equal proportion of trihydrated hydroclintonite. Jeff erisite is a similar mixture of hydrobiotite and hydroclintonite, also trihydrated. An altered biotite, from Henderson Co., North Carolina? is found to be essentially a biotite, about half way changed into a. vermiculite, and is interesting as a transition product. All the vermiculites are not so simple as the above-named minerals. I n some members of the group, there seems to be a small admixture of chloritic molecules, and it is even probable that many interme6iate stages between mica and chlorite may exist.As bearing on this question, the authors give analyses of the ballite from Nottingham, Chester Go., Pennsyl- vania, and of the vermicixlites from Lennie, Delaware Go., Pennsyl- vania. They also give the results of their examination of vermiculites from Newlin, Chester Go., and from Middletown, Delaware Co., in both of which Tschermak's view, that some of the vermiculites are probably chlorites, is partly sustained. A very interesting example of the way in which the chloritic vermiculites approach the serpen- tines in composition has been furnished by a specimen found at Old Wolf Quarry, Chestnut Hill, Easton, Pennsylvania, an analysis of which is given by the authors. Lastly, there is one other mineral examined during this investigation, a pale, yellowish-green mica, from126 ABSTRAOTS OF OHEMIOAL PAPERS.Aubum, Maine, where it occurs in direct contact with ordinary mus- covite. Analysis shows that it has the composition of muscovite, The case is interesting as showing a secondary growth of muscovite on muscovite, with a marked difference in outward appearance between the two formations. 13. H. B. Genesis of Iron Ores by Replacement of Limestone. By J. P. KIMRALL (dmer. J. Xci., 42, 231-241).-The object of this memoir is to show that the well-recognised products of epigenesis, like siderite and ferrocalcite, are, as a rule, also products of direct psendomorphous replacement of isomorphous calcium carbonate. From this it follows that secondary o r indirect replacement of calcium aarbonate by ferric hydroxide is wrought through alteration of pseudo- morphons siderite or ferrocalcite, and also, through progressive alteration, by ferric oxide and even by magnetic oxide.As the result of his investigations, the author advances the proposition that de- posits of concentrated iron ores occur far more extensively a s pseudo- morphons replacements than has hitherto been made to appeal., and far more extensively than by original sedimentation of ferric hydr- oxide. B. H. B. The Basalt of the Stempel, near Marburg. By M. BAUER (Jahrb. f. Min., 1891, ii, Mem. 2:31-271).-This is the concluding instalment of an elaborate monograph (compare Abstr., 1891, 1440) on the basalt occurring at the hill known as the Stempel, which rises above the sandstone of the Lahn plateau.This section deals with the inclusions met with in the rock. These inclusions consist of limestone, quartz, apatite, nepheline, felspar, amphibolite, titanite, and zircon. 13. H. B.MINERALOGICAL CHENISTRY.M i n e r a l o g i c a1 Chemistry.123Boleite, a New Mineral. By MALLARD and E. CUMENGE(Coinpt. renid., 113, 5 19--524).-This mineral occurs in cubicalcrystals of a fine indigo-blue colour in an argillaceous matrix, termedjctboncillo, next above the true copper-bearing bed of Boleo, nearSanta Rosalia, Lower California. The crystals are accompanied byanglesite, phosgenite, cerussite, and atacamite. They are not decom,posed by water ; they melt in a candle flame, and, when heated in aclosed tube, decompose with evolution of water.Two analyses of clean samples yield the numbers :-aI.11. Calculated.Silver ........... 8.85 8.70 8.50Lead.. .......... 48.45 49.75 48.90Chlorine ........ 19.98 19.00 19.55Water. .......... 4.77 4-00 4.28Copper. ......... 13.95 14-50 15.00Oxygen (by diff.) . 4.00 4.05 3.77The calculated percentages correspond with the formula3[PbCl*OH,CuC1-OH] + AgC1. Metallic copper is obtained by re-duction in a current of dry hydrogen without the liberation of hydro-chloric acid: this would seem to indicate that the chlorine is notcombined with t,he copper, but, in reality, the hydrochloric acidformed immediateiy reacts on the lead oxychloride, producing leadchloride and water. The formula given best shows the relationshipsof this mineral to laurionite, PbC1-OH, and atacamite,CuCl*OH,Cu( OH),.Brooke’s percylite, from Sonora, may possibly be the same mineral,although it,s imperfect analyses do not indicate the presence of silver.I n hardness, the mineral is a little superior to calcite, and itsdensity is 5.08.The common form is the cube without modifyingfaces. Some crystals show very sharp and brilliant octahedral faces ;more rarely, dodecahedra1 faces are met with. Some small crystalshave been observed with the edges replaced by re-entering anglesformed by faces of the hexakistetrahedron. The cleavage is distinctand easy, parallel to the faces of the cube, the octahedral cleavagebeing less distinct. The observed optical properties are those ofvery birefringent, negative, uniaxial crystals ; the index of refractioncould not be accurately determined; for a, prism formed by thecubical and dodecahedral faces, its approximate value is 2.07.Bol6itebelongs to the tetragonal system, though pseudo-cubic in habit.Along with the cubical crystals, octahedral crystals occur in pecu-liar groupings, showing the octahedml faces brilliant, but generallyformed of three facettes, composing a low pyramid.k 124 ABSTRACTS OF CHEMICAL PAPERS.The angular measurements are dificult, aud only yield approxi-mately the values f o r the parameters, a : c = 1 : 1.645. The com-position of the octahedral crystals is the same as that of the cubicalcrystals :-Silver ........ 9.2 9.4 8-5Copper.. ..... 14.8 L5.0 15.0Lead. ........50.2 50.7 48.9Chlorine.. .... 19.4 19.7 19.5Cubic cryst. Octahedral cryst. Calculated.Their densities appear to be about t,he same, a small specimeu ofthe octahedral crystals giving 5.0. W. T.Polydymite, Ullmannite, and Wolfsbergite. By H. L-4SPEI’RES(Zeit. Kryst. Min., 19, 417-436).;1. Po1ydymite.-The authorbrings forward fresh evidence in support of the formula Ni,S, he pro-pounded 15 years ago for polydgmite and nickel-bismuth glance,minerals which he regards as identical. The accuracy of this formulais confirmed by the a,nalysis of the polydymite from Sudburj, inCanada, as well as by the examination of some excellent crystals ofthis mineral from the Griineau mine, in the Siegen district.2. UZEmannite.-The author describes some crystals of ullmannite,from the Landeskrone mine, near Siegen.Although this mineral isof frequent occurrence in the Siege11 mines, it has never before beenfound in crystals.3. Wolfsbergite.-Of the crystalline form of the copper-antimonyglance (Wolfsbergite), from Wolfsberg, in the Harz, all that is knownis the brief account given by G. Rose in 1835. A discovery of awell-crystallised specimen in the Bonn Museum has enabled theauthor to give a detailed description of the crystallography of thismineral. The forms he has observed are:-OP, +Pw, Pm, 2 P a ,pm, ;-Pa, QP+, ;P3. The axial ratio is cc : b : c = 0.52830 : 1 : 1.62339.B. H. B.Some New Chilian Minerals : Darapskite, Lautarite, Iodo-chromate. By A. DIETZE (Zeit. Kryst. &Fin., 19, 445-451).-1.Darapskite.-This is the name given by the author to a new doublesalt of the cornposition repyesented by the formula NaNO, + Na,SO,+ H,O. It is colourless, transparent, and occurs in square tabletsbevelled by tetragonal pyramids. The new mineral is found at thePampa del Toro, and is named after Dr. L. Darapsky, the well-knownmineralogist, of Santiago.2. I;autarite.-Although it has long been known that the iodinecontained in the caliche or raw nitrate is due to the presence ofiodates, no iodate has hitherto been found as a distinct mineral species.The new mineral described by the author is calcium iodate, theanalytical results being in accord with the formula Ca(IO&. Itoccurs at the “ Pampa del Pique III?” in the form of large, monoclinicprisms, having the sp.p. of 4.59. I t is transparent, and of a yellow-ish colour.3. Iodochromate.--Near the chief locality of lauterite, small, yellowIt is very slightly soluble in waterYINERALOQICAL OHEMISTRY. 125crystals occur in the caliche. These prove on analysis to be a doubleiodate and chromate of calcium, of the formula 7Ca(IO&,8CaCrOa.The accuracy of this formula is shown by the results of sevenanalyses. B. H. B.Formula of Axinite. By A. KENNGOTT (Jahrb. f. illin., 1891, ii,Mem. 335--336).-1n a recent paper (Abstr., 1891,1168), the authorpublished a formula for axinite calculated from two analyses givenby Whihefield. This result he now compares with three analysesgiven by 3'. A . Genth (Amer. J. Xci., 41, 394). These analyses referto axinite from Franklin, New Jersey, in crystals and in lamelle,and from Guadalcazar, in Mexico.The analyses of axinite fromFranklin give results closely approaching those obtained from White-field's analyses. The axinite from Guadalcazar, however, wag appa-rently admixed with white felspar partially converted into kaolin,and, consequently, cannot be considered suficiently pure to serve asthe basis for the calculation of a formula. B. H. B.Constitution of certain Micas, Vermiculites, and Chlorites.By F. W. CLARKE and E. A. SCHKEIDER (dnzer. J. Xci., 42,242-251).-In a previous paper (Abstr., 1891, 529), the authors considered theconstitution of the mica and chlorite groups. The present paper is acontinuation of the same research.Throughout the investigationthe fundamental hypothesis that the minerals studied are substitutionderivatives of normal salts has been amply justified.Of the so-called vermiculites, two only, jefferisite and kerrite, wereconsidered in the former paper, and these wcre shown to be tri-hydrated micas in which the original alkalis had been replaced byhydrogen. The examination of other varieties shows that kerrite isessentially a t,rihydrated hydrophlogopite. Protovermiculite, fromMagnet Cove, Arkansas, is the same substance mixed with an equalproportion of trihydrated hydroclintonite. Jeff erisite is a similarmixture of hydrobiotite and hydroclintonite, also trihydrated. Analtered biotite, from Henderson Co., North Carolina? is found to beessentially a biotite, about half way changed into a.vermiculite, andis interesting as a transition product. All the vermiculites are notso simple as the above-named minerals. I n some members of thegroup, there seems to be a small admixture of chloritic molecules,and it is even probable that many interme6iate stages between micaand chlorite may exist. As bearing on this question, the authorsgive analyses of the ballite from Nottingham, Chester Go., Pennsyl-vania, and of the vermicixlites from Lennie, Delaware Go., Pennsyl-vania. They also give the results of their examination of vermiculitesfrom Newlin, Chester Go., and from Middletown, Delaware Co., inboth of which Tschermak's view, that some of the vermiculites areprobably chlorites, is partly sustained.A very interesting exampleof the way in which the chloritic vermiculites approach the serpen-tines in composition has been furnished by a specimen found at OldWolf Quarry, Chestnut Hill, Easton, Pennsylvania, an analysis ofwhich is given by the authors. Lastly, there is one other mineralexamined during this investigation, a pale, yellowish-green mica, fro126 ABSTRAOTS OF OHEMIOAL PAPERS.Aubum, Maine, where it occurs in direct contact with ordinary mus-covite. Analysis shows that it has the composition of muscovite,The case is interesting as showing a secondary growth of muscoviteon muscovite, with a marked difference in outward appearancebetween the two formations. 13. H. B.Genesis of Iron Ores by Replacement of Limestone. ByJ. P. KIMRALL (dmer. J. Xci., 42, 231-241).-The object of thismemoir is to show that the well-recognised products of epigenesis,like siderite and ferrocalcite, are, as a rule, also products of directpsendomorphous replacement of isomorphous calcium carbonate.From this it follows that secondary o r indirect replacement of calciumaarbonate by ferric hydroxide is wrought through alteration of pseudo-morphons siderite or ferrocalcite, and also, through progressivealteration, by ferric oxide and even by magnetic oxide. As the resultof his investigations, the author advances the proposition that de-posits of concentrated iron ores occur far more extensively a s pseudo-morphons replacements than has hitherto been made to appeal., andfar more extensively than by original sedimentation of ferric hydr-oxide. B. H. B.The Basalt of the Stempel, near Marburg. By M. BAUER(Jahrb. f. Min., 1891, ii, Mem. 2:31-271).-This is the concludinginstalment of an elaborate monograph (compare Abstr., 1891, 1440)on the basalt occurring at the hill known as the Stempel, which risesabove the sandstone of the Lahn plateau. This section deals withthe inclusions met with in the rock. These inclusions consist oflimestone, quartz, apatite, nepheline, felspar, amphibolite, titanite,and zircon. 13. H. B

ISSN:0368-1769    

DOI:10.1039/CA8926200123

出版商:RSC    

年代:1892

数据来源: RSC