摘要:

750 _. 1 -3922 1 -4022 1-4086 1 -4191 1 -4197 1.4306 1 -3999 1 * 4099 1 4109 1-4211 1 -4234 1. 4377 1- 5640 1.5966 1'5514 1 *5834 1 *4577 1 * 4699 1 '4542 1 *466 1 1-5037 1 -5254 1.3636 1 -3723 1.4315 1'4420 1-3703 1'3809 1 -3805 1'3912 1.3931 1 -4036 1 *3991 1 *4099 1 -4417 1 - 4550 1 -4682 1.4818 1 -3782 1 * 3898 1 -3875 1 -3983 1.3954 1 *4063 1 -3682 1 *3'784 1 -45 577 1 -4708 I I LXIX.-On the Correspondence between the Magnetic Rotdion aihd the Refraction and Dispersion of Light b y Comnpounds contucining Nit?*ogen . By J . H . GLADSTONE. Ph.D. F.R.S. and W . H . PERFIN. Ph.D. F.R.S. The substances containing nitrogen. the magnetic rotation of which was described in Dr . Perkin's recent paper. have been examined by Dr . Gladstone with reference to their refraction and dispersion .The following table contains the refractive indices calculated from the observations . Liquid Substances . Temp . Prop y lamine Dipropg lamine Triprop! 1:imiiie . Isobutylamine . Diisobutylamine . Ally lamine Methyl-aniline Dimethylaniline . Pentamethylenediamine Piperidine . Pyridine Propionitrile Trimethylene cyanide Methyl nitrate . Ethyl . Isobutyl . Ni trog 1 y col . Nitroglycerin . Nitromethane Nitroethane Nitropropane Isobu tylnitrite . C hloropicrin Propy 1 . 6 '5" 4 4 4-4 6 -8 7 *6 5 -2 7 . 8 8 -2 17 *5 7 *o 12 *2 20 . 0 24.2 19.8 20 -4 19 -6 18 *8 18 -5 18.6 17.5 20.5 22 -7 24.2 17 -5 Sp . gr . 0 -7339 0.7530 0 *7703 0 ?437 0 -7546 0 -7587 0 *9983 0 -9675 0.8881 0 *8553 0 '9875 0 -7843 0 *9858 1 *2090 1 -1078 1 *0569 1-0165 1 -4910 1 -5942 1 *1394 1 -0489 1 So022 0 -8638 1 %623 -.P H . 1.4111 1 -4281 1-4408 1 -4188 1 -4301 1 *4502 1 *6324 1.6198 1 *4803 1 -4757 1 *5468 1-3792 1 -4506 1 -3908 1 'n05 1 -4134 1 *4193 1 -4671 1 -4945 1 -4009 1 -4090 1 -4164 1.3838 1 -4829 ~~ ~~~ ~~ In addition to these liquids. the refraction was determined of several gaseous. liquid. o r solid bodies dissolved in water. namely. ethyliimine. ethylamine hydrochloride. diethylatnine hydrochloride. triethylamine hydrochloride. piperidine hydrochloride. hydriodic acid. ammonium iodide. ammonium nitrate.and ammonium sulphate . I n each case the solution was a very strong one. so that the probable error from necessary dilution of the substance was never great CORRESPONDENCE BETWEEN MAGNETIC ROTATION. ETC . 75 1 The following table contains the molecular magnetic rotation. molecular refraction. and the molecular dispersion of the substances in question. together with those of a. few others where the three propei*ties have not been determined from the same specimen ; the latter are indicated by * . Substance . "Ammonia * E thylamine "Diethylamine . Propylamine Dipropylamine Tripropylamine Isobutylamine . "Ammonium chloride Ethylamine hydrochloilde . . Diethylamine . . . . . . Triethylamine . . . . . . Tetretlrylammonium chloride Ally lamine *Aniline Methylaniline .Dimethylaniline Pentamethylene diamine Piperidine Pyridine Propionitrile . Trimethylene cyanide Methyl nitrate . Ethyl . Propyl . Isobutyl . Nitroglycol Nitroglycerin Nitromethane. . Nitroethane . Nitropropane Isobutyl nitrite Chloropicrin Hydrochloric acid (36.5 p . c.) Hpdriodic acid (65.1 p . c.) . . Hydrobromic acid (dilute) . . Ammonium iodide "Nitric acid . "Sulphuric acid Ammonium nit rate . "Triethylamine Diisobutylamine . hydrochloride sulphate . Formula . N H NEtH NEt H NEt XPrH2 NPr2H NPr NBu. H NEtH. HC1 . NEtTH.HC1 NEt.HC1 . NEt. C1 NC.H7 . NC.H. Me NC&. Me. . NBuI3.L NH,.IE.Cl NA11H2 (NH2) d C H2).. NCsHll NC.H HCI NC.H. . NC.H. . (NCMCH.). . ' MeNO. PrNO. . BuNO. C.H.(NO.). ' C.H.(NO.). EtNO. . MeNO. PrNO. . EtNO. B u N O ~ CC13N02 . HCl . HI . HBr . HNO . NH3HI H.SO. . NH.HNO. . (NH3) 2H%S O4 * Mol . mag . rotation . 1-810 3 -609 5 *662 8.518 4.563 7. 549 11 *664 5 -692 9 -936 6 *096 7 -997 9 -896 11 '724 13 * 696 5 '587 16 . I62 19.629 22 -823 7 -493 5.810 10 *034 8.761 3.331 5 '136 2 *057 3 *084 4.085 5 *180 3 968 5 -405 1.858 2.837 3. 819 5 -510 5 -384 4.215 17.868 8 '533 19 -878 1-180 2 -31 5 2 -31 6 4 *980 Molecular refraction . -. 9 -03 24 -47 39 *36 54 -62 31 '57 54 '80 77 '91 39.25 70 * 24 22 '33 37 *18 51.86 65 5'8 80 *70 30 -99 52 -09 60 -45 68 '96 52 *93 44.11 56 -57 40 -30 25 *50 41 *15 23 -59 31-26 39 *05 46 -72 45 -03 66.67 20.25 27 -71 35 -11 43 -90 45 *29 14 -45 31 -87 20 -65 39.66 16 '50 22 '37 25 -23 39 '50 Molecular lispersion .0-50 1.19 1-96 25'6 1-52 2*62 3'92 1-86 3.29 1.52 2-06 2-69 3*26 3"78 1-96 5.96 7.33 8-55 2 -61 2.09 2.96 3 '444 1-09 1'82 1.30 1.64 2-02 2-36 2-59 3*74 1'22 1'53 1-87 2-35? 2*50 1.12 4-19 2*19 4 *88$ 1*13 0.97 1-88 1-78 t. Estimated from pF and p G . $ Estimated from p~ 752 CORRESPONDENCE BETKEEN MAGNETIC ROTATION ETC., The object of this table is to draw attention to the general cor-respondence that exists between tbese three different properties of tbe substances in question ; a correspondence that points to some connec-tion between the rotation Qf the polarised ray under magnetic influence and the retardation of the rays of light im passing through a material substance.The three columns though expressing different properties are really comparable with one another,for in each case the observed value is divided by the density of the substance and it is determined not for equal weights but for an equal number of molecules. This is shown by the formulm employed for reducing the observations. Molecular magnetic rotation = ‘ Mw where r Mw and d represent respectirely the observed rotation molecular weight and density of the substance and x’ and Mw’ the corresponding values for water.Molecular refraction generally called refraction equivalent, T’ x Mw” x d’ - 1 d = M w P A and molecular dispersion or dispersion eqnivalent = -M w P U A where pA and pE are the refractive indices of the lines A and H of the solar spectrum. It has been found that each property is determined in the first instance by the atomic composition of the substance so that it may be laid down as a primary law that the molecular magnetic rotation refraction or diapersion of a compound is the sum of the molecular magnetic rotation refraction or dispersion of its constituents. The values which have been deduced under this primary law mainly iirom the paraffin-group are however subject to large modifications dependent upon differences in the structure of the compound.Thus a change of valency is attended by a marked change of value in these optieal properties and they are apparently affected by some circumstances which are not as yet recognised in our structural form ul 8~ . From the primary law above given, the fdlomiiig values have been deduced by Perkin for the molecular rotation of certain elements in the paraffin-group of carbon-compoundLs and against them have been placed the normal values €or their molecular refmtion and dispersion arrived at by Landoit Briihl and Gladstone. OF LIGHT BY COMPOUNDS CONTAINING KITROGEN. '7'53 CH3 . C H 0 alcoholic . 0 aldehydic . Cl Br . I N in amines. Molecular magnetic rotation. 1 -023 0.515 0.259 0.194 0.261 1 -733 3 '562 '1.757 0.717 I--Molecular refrnction.-'7.6 5 *o 1 -3 2.8 3 -9 9 . 9 15 *3 24 *5 5 -1 Molecular dispersion. 0 34 I) -26 0 -04 '0.10 0 *18 0 5 0 1.22 2 *62 0 *38 A glance at this table will show that the three columns are quite independent. The relative figures for one substame do not corre-spond with those for another although there is a certain analogy between them. Directly however that we tarn to the modifications that are intro-duced by changes in the mode of combination we find that when a change occurs in the one property i t is noticeable also in the other two and these changes are in the same direction though not to the same extent,; in fact the variations in the magnetic rotation are usually greater than those in the dispersion and these again are much more marked than in the refraction.It struck us as a remarkable coincidence that the separate investigations showed two different values for oxygen in alcohols and aldehydes and that there was a very great exaltation of the values in the case of nnsaturat,ed cnrbon-compounds such as those containing allyl. We observed also that the value of CH in the first and second member of the homologous series (such as the alcohols the fatty acids &c.) was different from its value in the higher members of the same series and that these differences were always in the same direction. We have since noticed also that where there was an abnormally large moleculai-rotation as in methylene iodide there is an abnormally large mole-cular refraction and dispersion.Nor have we been the only observers who have been aware of some connection between the two sets of phenomena. H. Becquerel in his " Experimental Reseamhes on Magnetic Rotatory Polarisation," printed in the Ann. Chem. Phys. of 1877 drew up a table which showed a certain rough relationship between that propertg and the refractive index. Rut as he kook no account of differences in density or molecular weight he failed to recognise the connection between these and chemical constitution. This was first observed by us some years ago 754 CORRESPONDENCE BETWEEN MAGNETIC ROTATION ETC., Molecular refraction. Kanonnikoff (J. Russ. Chem. SOL 1888) also has pointed out some curious relations between the specific rotatory and the refractive power of those chemical substances which under ordinary circum-stances exhibit circular polarisation.But this kind of rotation appears t o be a tot'ally different phenomenon &*om that produced by exposure in a magnetic field. The series of compounds contairmiug nitrogen seem to afford a remarkably good opportunity for comparisons and the results have exceeded our expectations. We propose now to consider only the more salient points leaving the smaller questions for future con-sideration. I. Compound Ammodas.-At the commencement of the second table will be found two good series of compound ammonias the one resulting from the successive substitution of ethyl for hydrogen and the other from successive substitution of propyl.The difference for the first is C2H4 and for the second C,H, and the value of these groups is found by subtracting the figures f o r ammonia from those for ethylamine ethyhmine from diethylamine &c. In every instance there is an increase and these are given by the following table :-Molecular dispersion. Molecular magnetic rotation. Ethyl 1st substitution, zna 3rd Normal increase for CzH4 . --------Propyl 1st substitution . 2nd . 3rd . Normal increase for C3Hs . --___ 1 -799 2-053 2-856 2 *046 2 '753 2.986 4-115 3 -069 15 -44 14 *89 15 -26 15 *2 22 -54 23 -23 23 -11 I- -0 '69 0 9 7 0 -80 0 '68 1 -02 1 '10 1 '30 --------22.8 I 1.02 A noteworthy fact here is the rapid augmentation of the molecu1a.r rotation for each additional C2H4 or CIH6.The same is clearly indi-cated also in the molecular dispersion. It is doubtful in the molecular refraction but the irregularities of the numbers are such as may be due t o experimental error. 11. Hydrochlorides of the Compound Ammonias.-The increase for each addition of C2H4 in this series is it^ follows starting from ammonia hydrochloride : OF LIGHT BY COMPOUNDS COKTAININO NITROGEN. '755 Ethyl 1st substitution. 3rd 4th . . . . . . . . . . . . . . Normal increase for C2H,. . 2nd -1 *901 14 -85 0 *54 1.899 14 -68 0 *63 1.888 13 *98 0 -57 1.902 14 '92 0 '52 2 -046 15 '2 0 -68 ----The numbers were obtained from the examination of these salts in aqueous soluhion.I n this series unlike the preceding there is no progression in the increase the additional amounts remaining about the same in regard to the rotation refraction and dispersion. There is also another point of correspondence between the three optical properties. Jn the case of each of them the increase never amounts to the theoretical quantity. 111. Compound AniZiqtes.-The short series of methylanilines gives the following increases for each addition of CH, starting from aniline. 1 s t substitution 2nd Normal increase for CH -I I 3.467 8 *36 1 '37 3 -194 8 -51 1 -22 1 -023 '7-6 0 -34 ---Here the increase in the molecular rotation for each CH is more than three times that which is usually observed in a series belonging to the paraffin group.An equally large augmentation is manifest in the molecular dispersion and a very visible increase occurs in the refraction. This exaltation of the dispersion equivalent of CH in some members of the aromatic group was observed by Gladstone and Dale as far back as 1866. IV. Unsaturated Carbon Compounds.-The table includes three very different examples of unsaturated carbon compounds ally lamine, pyridine and aniline with its substitution compounds. I n each case the observed value is considerably greater than that which would be calculated from the normal values for carbon hydrogen aud ammonia in the paraffin series 756 CORRESPONDENCE BETWEEN MAGNETIC ROTATION ETC., - - ~ 4.040 4.562 5.585 Allylamine. . Pyridine Aniline . 30.99 40-30 52.09 Molecular magnetic Molecular rotation.I refraction. Found. 5 *587 8 -7'61 16 -162 Calculated. -29 -23 36 *63 44 *23 Molecular dispersion. Found. 1 *96 3 -44 5 -96 Calculated. -1 *a 1 *88 2 -22 It will be observed not only that there is a great increase in each case b u t that whilst in allylamine where there is only one pair of double-linked carbon atoms the increase is considerable in aniline, where there are three such pairs the increase in rotation and disper-sion is about seven times as much and in refraction the increase is more tha,n four times as great. V. Nitriles compared with dmmonias.-It was observed many years ago that the refraction equivalent of aitrogen in nitriles and cyanides was smaller than in the nitrogen bwes and this observation was recently extended to the dispersion equivalent.The second table affords two opportunities of testing this in regasd to the molecular magnetic rotation namely propionitril and trimethylene cyanide. By subtracting the normal values for hydrogen and carbon from the observed values for these compounds we obtain the values of nitrogen. Nitrogen. From amines 0 *717 44 -9 0 -38 propionitrile . 0 *516 0 *I1 trimethylene cyanide 1 0.518 1 i'i 1 0.14 VI. Nitric Bther Series.-There is a good homologous series in the second table commencing with methyl nitrate. Assuming nitric acid to be the first member of the series we obtain the following values for each addition of CH, OF LIGHT BY COMPOUKDS CONTAINING NITROGEN. 757 :ular tion.I 1st addition . 2nd . 3rd . 4th (Isobutyl) Molecular dispersion. Kormal increase Molecular rotation. magnetic Molec refrac I 0 '877 1 *027 1 -001 1 -095 1 *023 ~ - - . 7 -1 0 -17 '7 *67 0 -34 7 '79 0 *38 7 -67 0 '34 '7 -6 0 -34 -- -:ular tion. Here there are two points of correspondence to be specially noted. It is evident that neither in the magnetic rotation refraction nor dispersion does the first addition of CH produce the normal increase ; but whilst this normal increase is found in each of the successive additions they are all practically alike and there is no continuous augmentation of the increase as in the case of the compound ammonias. An exception to this last remark is however the increase in molecular rotation (1.095) observable in isobutylic nitrate.This like the iso-compounds in general is somewhat higher than the normal value a difference not perceptible in the refraction and dispersion. VII. Isobutyl Nitrite and Nitrate.-Though there are several NO, compounds in tbe table there is only one true nitrite that of isobutyl. In his paper Dr. Perkin has drawn especial attention to the fact that though this substance contains an atom of oxygen less than the isobutyl nitrate it has a greater molecular magnetic rotation. This is attributed to the fact that the nitrogen is saturated in one case and not saturated in the other. The difference between the two is shown below for each of the optical properties. Molecular dispersion. Molecular magnetic Isobutyl nitrite ) nitrate Difference for 0.Normal difference 5 *510 43 -90 2 -35 5.180 46 9 2 2 '36 -0 *330 -t 2 *82 + 0 -01 + 0 -261 + 3 -4 + 0 *18 - ---_- --I-- I I-- ---Whilst the addition of oxygen has caused an actual diminution in the magnetic rotation i t has given only a doubtful increase in the dispersion and an increase on the refraction considerably below the normal for aldehydic oxygen. The three results though apparently different are in the same direction. YOL. LV. 3 758 CORRESPONDEKCE BETWEEN MAGNETIC ROTATION ETC. Molecular ref ractioxt. The nitro-compounds themselves differ from one another to the usual extent in regard to all three optical properties. VIII. Acids and their Ammonium Salts.-It was among the earliest observations on refraction equivalents that the halogen acids in solu-tion gave abnormal figures far higher than those deducible from the compounds of the halogens with organic radicals.The same is now shown to hold good for their molecular magnetic rotation. It is a.lso found that these values increase with the dilution of the acid up to a certain exteiit ; and in the following tables t,he higher values are used. The calculated values for the magnetic rotations are for the free acids (see p. 739). Molecular dispersion. Moleciilar magnetic rotation. Hydrochloric acid Hgdrobromic acid Hydriodic acid . . 4.412 8 '533 18 *435 Found. Calculated. Found. Calculated. Found. Calculated. I 1 I 1 l l l- I- (-I- 1-1- -2 -187 4.016 8 -211 14 *4.5 20 +65 31 *S7 11.2 16.6 25 -8 1 .I2 2 -19 4 *19 0 *54 1 *26 2 *66 I I I I I I Dr.Perkin has shown that these acids in combining with ammonia or piperidine retain their abnormal values and combine with but little condensation. How far this is true for the other optical properties is shown in the following table. The calculated numbers are the values of the base and acid added together. NH3 + HCI . . . . NH -t HBr . . . Piperidine + HC\ Triethylamine + HC1 } NH3 + HI . Molecular magnetic rotation. Found. 6 -096 10 -177 19.996 10 *034 11 *739 Calculated -6 -230 10 3 5 1 20 '253 10 -222 12 -930 Molecular refraction. Found. -_I 22.33 28 *53 39.66 56.43 65 *78 Calculated. 2 3 *48 29.68 40 *90 58 *56 69 -0'7 Molecular dispersion.Found. 1 -52 2 .49 4 -88 2 -96 3 '26 Calculated. 1 *62 Z *69 4.69 3 *21 3 -88 The correspondence is again seen in these cases and all the three optical properties indicate that although there is but little condensa-tion in the case of ammonia and hydrochloric hydrobroxnic or hydr-iodic acid yet there is considerable condensation in the case of the triethylamine-compound with hydrochloric acid THORPE AND HAMBLY ON PHOSPHORYL TRIFLUORIDE. 759 TX. Hydrochloric Acid in Solution.-Although hydrochloric acid, when dissolved in water has a far greater effect on light than could have been expected it has recently been found that when dissolved in isoamyl oxide it rotates the plane of polarisation to very little more than the theoretical extent.On examining the refraction and dispersion a still closer agreement with theory became manifest. lar Molecular on. dispersion. I I I n water . 4 *412 14 *45 1 -12 In isoamyloxide . 1 2'23A 1 ; P i 6 1 051 By calculation for free acid 2 -187 0.54 Tbese nine cases of comparison all represent different kinds of depart,ure from what we consider the normal values. They have shown a very marked correspondence between the three optical pro-perties of the substances examined. They have also revealed differences in detail and it is only fair to add t,hat other peculiarities in the molecular magnetic rotation exist which are not represented by similar peculiarities in the refraction and dispeisiou. Bnt these exceptions are of such a limited character thatt on a reexamination of the matter with fresh specimens and with varied conditions if is quite conceiv-able that they may disappear.It may therefore be laid down as generally,if not always true that where there is a departure from the normal values in regard to one or other of these properties it is to be found in the other two. The different properties are evidently similarly affected by change in chemical constitution. The general drift of the whole comparison a,ppears to us to lead irresistibly to the conclusion that we have here another close relationship between electro-magnetism and the velocity of light

ISSN:0368-1645    

DOI:10.1039/CT8895500750

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

THORPE AND HAMBLY ON PHOSPHORYL TRIFLUOBIDE. 759 LXX.-On Phosphoryl Tr@uoride. By T. E. THORPE F.R.S. and F. J. HAMBLY. THE existence of oxyfluoride of phosphorus was first definitely estab-lished by Moissan who obtained it by the action of the electric spark upon a mixture of phosphorus trifluoride and oxygen. On passing the induction spark into (?I mixture of 2 vols. of the trifluoride and 1 vol. of oxygen standing over mercury a violent explosion occurs, and the new gas is produced. (Compt. rend. 102 1245.) 3 G 760 DIVERS AND RAGA OXYAMIDOSULPHONATES I n a paper on the Oxidation of Haloid Salts in the Journal fiir praktische Chemie 1880 21,438 Schulze has described tthe behaviour of various oxides upon haloid salts in absence of oxygen and states that on heating fluorides with molybdic oxide and phosphoric oxide, oxyfluoride of molybdenum and oxyfluoride of phosphorus were obtaiued.No description of the properties of these compounds is given nor do any analytical observations appear to have been made. We find that phosphorus oxyfluoride can be easily obtained by heating a n intimate mixture of cryolite and phosphorus pentoxide. The materials in the proportion of 2 parts of the finely-powdered cryolite and 3 parts of phosphoric oxide are placed in a brass tube and gently heated. The gas is readily disengaged and as soon as that which is evolved is wholly absorbed by caustic soda solution the rest may be collected at the mercurial trough. That the gas so obtained is practically pure is shown by the following numbers :-Observed. Calculated. Vapour density. 52.3 52.0 Preparation I . . . 30.136 p. c. 29.81 Determination of phosphorus-Preparation I1 30.06 , -This method of obtaining phosphorus oxyfluoride is analogous to that by which Kolbe and Lautemann prepared the oxychloride (AnnuZen 113 240) namely by heating phosphoric anhydride with common salt : 2P,O5 + 3NaC1 = POCls + 3NaP0,. We had intended to have completed our study of this gas before offering any communication on the subject but as we are no longer in a position to work in concert we have ventured to lay this short preliminary note before the Society. One of us however trusts, in a short time to be able t o present the results of a fuller,investi-gation

ISSN:0368-1645    

DOI:10.1039/CT8895500759

出版商:RSC    

年代:1889

数据来源: RSC

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760 DIVERS AND HAGA OXYAMIUOSULPHONATES 1;XXI.-Oxyamidosulphonates and their Conversion into Hyporiitrites. By EDWARD DIYERS M.D. F.R.S. and TAMEMASA HAGA P.C.S. IN our paper on the Reaction between Sulphites and Nitrites of Metals other than Potassium (Trans. 1887 51 659) we gave notice of our intention to work on the reactions with the sodium salta. This we have done and are already in a position to materially extend an AND THEIR CONVERSION INTO HYPONITRITES. 761 modify our knowledge of the chemistry of the sulphazotised com-pounds contained in the writings of our predecessors in the investiga-tion Fremy (Ann. Chim. Phys. [3] 15 408) A. Claus and Koch, (Annalen 152 336; 158 52 and 194) Berglund (Bull. Soc. Chirn., 25 455 ; Bela. 9 252 and 1896) and Raschig (Annalen 241 161).We propose t o publish our contribution t o this large subject in it few short papers like the present each complete in itself. Oxyarnidosulphonates the subject of the presel=t paper are the sulphazidates of Fremy the sulphydroxylamates of Claus the hydroxyl-amiiae-monosulphoitates of Raschig. Between the one set of terms-&hilo- imido- and amido- oximitlo- and oxyamido-sulphonates-and the other set-amine- and hydroxylarnine- tri. di- and mono-sulpho-nates-there is not much to choose. As however it is desirable on the score of consistency to employ exclusively either one set or the other, the use already prevalent of nitrilo- imido- and amido-sulphonate makes it advisable to employ the term oximido- and oxyamido-sul-phonate rather than hydroxylamine- di- and mono-sulphonate.Oxyamidosulphonic acid known only in solution was first prepared by Fremy who found that potassium oximidosulphonate (neutral sulphazotate) sooner or later decomposed into acid sulphate and the oxyamido salt the change taking place at once when the. solution was boiled. Altering the atomic weights to those now accepted and writing empirically his formula to which he attached no censtitu-tional significance his equation becomes-Claus has shown however that these formulae do not correctly repre-sent the composition of the salts ; and Raschig has confirmed Clam’s statement. The t w o f o r m u h corrected stand as S4018K41110N2 and S20,K2H4N2 or HON(S03K),( OH,) and HONH( S03K) accord-ing t o Claus. The latter formula we find it necessary to modify slightly.To get the oxyamidosulphonic acid pure for the preparation of its salts Fremy neutralised the hydrolysed solution of potassium ox -irnidosulphonate with ammonia added barium chloride filtered off the sulphate and then by the addition of baryta-water threw down a precipitate of a dibarium oxyamidosulphonate. This salt when washed was decomposed by adding just enough sulphuric acid to combine with the barium ; the filtered solution of the new acid being used f o r preparing the salts by combining it with the corresponding bases. The acid appears to be the only sulphoxyazotised acid pas-* He recognised the peculiarity and importance of this first instance of what we now style the hydrolysis of a sulphonate into a sulphate 7 62 DIVERS AND HAOA OXYAlfIDOSULPHONATES sessing any stability.Clam introduced a slight modification in E’remy’s process by omitting the preliminary neutralisation with ammonia As we have discovered a second barium salt which is neutral and soluble we treat the barium precipitate in a different way and thereby avoid the contamination of the salts with sulphite as the latter is always present in Fremy’s barium precipitate (see the sec-tion of this paper headed ‘‘ Decomposition of Oayanaidosulphonates by AZkaZim Bases,” p. 765). The dibnrium salt is as found by Fremy, very alkaline to litmus and we add to it only enough sulphuric acid to remove half the barium as sulphate getting a neutral solution which contains only monobarium oxyamidosulphonate ; from this the acid and its salts can be prepared by adding the equivalent quantity of sulphuric acid or a aulphate.In order to determine the quantity of snlphuric acid requizled it is necessary to estimate the barium in a portion of the solution. Rascbig prepares an impure acid from Fremy ’s solution obtained by boiling potassium oximidosulphonate so as to hydrolyse it into potassium sulphate and oxyamidosulphonate. To do this he removes the potassium snlphate by alcohol and then concentrates the solution of the acid to a syrupy consktence. Sodium oxyamidosulphonate as prepared by Fremy and by us is a clear gummy liquid as viscous as molasses; this when exposed over sulphuric acid under diminished pressure never solidified or showed any sign of crystallisation. Potassium ozyamidosulphonste prepared and analy sed by Fremy by Claus and by us wben crystallised from its hot solution forms six-sided places as stated by Premy but the plates are more often square ; by spontaneous evaporation of the cold solution however, thick tables and bold prisms are obtained.Claus found the crystals to be anhydrons and Fremy’s analysis and formula agree with this observation. Fremy’s analytical resul ts cannot be relied on how-ever and we have already had t o give an instance of this in the present paper md shall have to give others. We differ from Claus, inasmuch as we find t h a t all the crystals of this salt effloresce slowly over sulphuric acid and on analysis give results indicating the presence of 1 mol. H,O. The solutions shorn a great tendency to supersaturate and it often becomes very difficult to crystallise them.When thoroughly dry the crystals can be kept for months without undergoing much change but if moist they are unstable hydrolysing, and becoming acid to litmus. The acidity developed is that of hydroxyammonium sulphate hadly showing with methyl-oramge. When heated they suddenly intumesce below loo” and are com-pletely decomposed. It is neutral in reaction AND THEIR CONVERSION INTO HYPONITRITES. 763 23.45 7-69 19.76 9-29 To determine the sulphur and nitrogen we hydrolped the salt by heating it in a sealed tube with hydrochloric acid at 130" following Raschig's process which however gives somewhat irregular results, as we afterwards found (see the analysis of the dibarium salt).The hydroxylamine thus produced was estimated by iodine after addition of potassium hydrogen carbonate. Water could not be removed by exposure over sulphuric acid at the ordinary temperature and pressure rapidly enough t o be convenient for analytical purposes ; this and other sulphazotised salts retaining according to our ex-perience part of their water of crystallisation with great tenacity. Neither could the water be conveniently driven off in the oven, because of the decomposition of the salt at about 95"; we made a fairly good estimation of it however by moderately heating the salt in a Sprengel-vacuum in a long bulbed tube containing also sulphuric acid The following is a table of our results:-I -7-56 17-50 -HONH(SO,K),OHZ. Potassium. .Sulphur . Oxyamidogen HONH . Water . 23 -08 7'58 18 -94 10 *39 a. -22 '53' 7'34 17 -96 6. f-'--Sample a mas in prisms b in tabular crystals. We have given much consideration to Claus's results apparently carefully obtained, but we are unable to offer any explanation of their difference from ours. We have prepared the salt in winter and in summer (when he found it difficult to work) by evaporation of cold solutions and by cooling hot solutions and have always obtained crystals which slowly effloresced in the desiccator. Dibarium osyamidosulphorcate prepared by Fremy and by us is a crystalline alkaline nearly insoluble salt. It dissolves in hydro-chloric acid and then shows by the odour evolved the presence of sulphite as an impurity varying from a trace only to a considerable quantity.The only analytical datum given by Fremyis that the salt is formed from one equivalent of acid and two equivalents of baryta. We have analysed it and found for it a composition agreeing with the formula given by Fremy less the H by which his formuh generally exceed those now adopted. In this analysis and that of the following salt we slightly modified the method of hydrolysis so as to get uniform and higher numbers * Slight lose of potrtssium sulphate during cooling known to have occurred 7 64 DIVERS AND HXGA OXYAMIDOSULPIIONATES 36.2'7 16-84 for the hydroxylamine. The modification consisted in heating for some time with hydrochloric acid at 100" before raising the tempera-ture to 130". We find that hydroxyammonium sulphate itself may be rapidly heated with acid to 130" or even higher withont getting low results from which it would appear that at the moment of its formation at 130" from its sulphonic-derivative hydroxylamine is less stable than when already formed.The constitution of the 35.88 16-65 - -N( 0 H) *s 0 dibarium salt is expressed by the formuIa Ba<N(olr) ,sO~>Ba,0H2. Calculated. Found. Barium 53.31 53.13 Sulphnr 12.45 12.41 Oximidogen HON 12.06 12.02 Barium oayamidosulphonate prepared by us in solution first as already described in this paper (p. 762) by adding just enough sul-phuric acid to the dibarium salt to remove half its barium. The neutral liquid thus obtained yields crystals of the salt on evaporation over sulphuric acid; it is very soluble and forms small hard bril-liant square tabular crystals intermixed with minute square prisms ; the crystals contain water.When long kept it decomposes. Heated neady to loo" it suddenly and violently decomposes into gases and barium sulphate. In annlysing it the barium was determined in one case by igniting it with sulphuric acid (a) ; in two cases the salt was slowly heated with dry sodium carbonate whereby oxygen was absorbed from the air after which the heat was raised until the mixture fused and the barium and sulphur were then both determined ( b ) ; in another case the salt was hydrolysed by heating with hydrochloric acid the separated barium sulphate (representing all the barium and half the sulphur of the salt) weighed the other half of the sulphuric acid precipitated with barium chloride and lastly the hydroxylamine titrated with iodine (c).The results were the following:-(HONHSO&Ba,OH,. Barium . Sulphur . Oxyamidogen HONH 36 -15 16 -88 16.88 c. 35.53 16 -49 16 -50 The Hydrolysis of Ozy amidosulphonic Acid. Although oxyamidosulphonic acid is relatively stable the fact that Raschig its solution does decompose was fully noticed by Fremy AND THEIR CONVERSION INTO HYPONITRITES 765 has found that the decomposition proceeds sharply and in presence of hot acid rapidly according to the equation-2HONHSO3H + 2H2O = (NEsOH),SOa + HzSOa. With this important observation we fully agree from experience. Fremy stated that when the acid is boiled with water it decomposes wholly into acid ammonium sulphate and oxygen or hydrogen per-oxide.His finding ammonia and oxygen (or any gas) cannot be explained. He appears to have tested for hydrogen peroxide by adding manganese dioxide which would account for his finding it. since an effervescence of nitrous oxide might easily pass for one of oxygen. Claus expressed his hesitation to accept Fremy’s equation (modi-fied)-2H0NH(S03H) + 2H,O = 2(NH4)HSOa + 02-as quanti-tative b u t at the same time admitted that he had also obtained (besides sulphuric acid) ammonia and oxygen (or nitrous oxide). Raschig got other results as already stated and did not find either ammonia or oxygen or nitrous oxide. These inexplicable differences have their parallel in what is contained in the next section of this paper only there the differences noticed arise between ourselves and the other workers.I n presence of hydrogen potassium carbonate oxyamidosulphonaOes react with iodine solution like a hydroxylamine salt only very much more slowly ; so that their amount can be titrated in this way without previous hydrolysis though only with difficulty. Decomposition of Oxyamidosulpbonates by Alkaline Bases. The decomposition of oxyamidosulphonates by a solution of potas-sium hydroxide appeared to have been fairly well worked out when we came to give attention to it. Fremy had observed that when heated with excess of this reagent the potassium salt disengaged ammonia as well as oxygen of which as he says he had established the absolute purity by analysis. Hence it seemed that oxyamido-sulphonates undergo the same decomposition when heated with alkali as when heated with acid.Lossen had just discovered hydroxylamine when work on the sulphazotised compounds was taken up by Clans and this circum-stance led the latter to see in the reaction between potassium hydroxide and Fremy’s sulphazidate as observed by Fremy and by himself most convincing evidence that the salt is constituted as a sulphonic derivative of hydroxylamine and is decomposed by the action of alkali into this base and potassium sulphate. He did not, he admits succeed in isolating the hydroxylamine or any of its salts 766 PIVERS AND HAGA OXYANIDOSULPHONATES but he found all the sulphur of the sulphazidate converted into sul-phate and the other compounds in just the same proportions as Lossen had found when hydroxylamine is decomposed by heating with alkali, namely ammonia equivalent to between a third and a half of the total nitrogen and gases which neither extinguished nor rekindled a glowing match and were therefore not the pure oxygen of Fremy’s finding but might well be nitrogen mixed with nitrous oxide as required on the supposition made.Added to this was the fact of the reducing action which the alkaline mixtnre exerted upon copper and silver salts and the proof seemed complete. Raschig in his recent paper went further in the matter than Claus, and with or without experimental evidence-for we cannot decide from his words-concluded that an (unheated) alkaline solution of oxyamidosulphonic acid is actually a solution of free hydroxylamine, the latter being present in the quantity calculated from the amount of the acid taken and therefore just such a solution of hydroxyl-amine as is wanted for preparing aldoximes and acetoximes.Now with two exceptions namely that nitrous oxide is given off, and that copper and silver salts are reduced-an action to be tzeated of in the following section of this paper-we are unable to confirm any of the observations of these chemists. This decomposition of oxyamidosulphonates by alkali is of another and still more interest-ingcharacter than Claus and Raschig conceived it to be. That the oxyamidosulphonates are hydroxylamine-derivatives which hydro-lyse in acid solutions into hydroxylamine and sulphate is indeed, certain as ascertained by Raschig.But nevertheless in aZkaZine solutions they give neither sulphate nor hydroxylamine nor the decomposition-products of hydroxylamine. Oxyamidosulphonates decompose with potassium hydroxide and similar reagents exclusively into sulphite and hyponitrit,e and the decom position-products of a hyponitrite. No ammonia is formed, neither so far as we could judge any sulphate or any nitrogen or, if any only unimportant quantities of nitrogen and sulphate. The difficulty of keeping a sulphite solution for days free from sulphate, and of detecting small amounts of nitrogen in presence of nitrous oxide are well known and sufficiently explain any uncertainty in oiir results. The total absence of ammonia peremptorily forbids any admission of the generation of hydroxylamine.Cold dilute alkali or alkaline-earth hydroxide suffices to partly effect the change under consideration. Consequently every attempt to form dipotassium or disodium oxyamidosulphonate corresponding with the dibarium salt has failed in our hands because of this re-solution of the salt into simpler ones on the addition of alkali. For the same reason also we find that Fremy’s dibarium salt describe AND THEIR CONVERSION INTO HTPONITRITES. 767 in this paper although insoluble cannot be prepared quite free from sulphite and wheu kept for any considerable time becomes charged with it and also contains traces of hyponitrite. To effect the complete or nearly complete conversion of khese salts into sulphite and hyponitrite they may be either left for days in the cold with the very strongest potassium hydroxide solution or be heated to boiling for a short time with strong alkali.I n both cases, effervescence occurs due t o the decomposition of hyponitrite. The gas evolved is not the feeble supporter of combustion met with by Claus but behaves like oxygen as Fremy had observed; i t is not oxygen however but nitrous oxide soluble in water. The highly alkaline liquid when acidified gives abundance of sulphur dioxide, and if neutralised merely will give with barium chloride a precipitate which might of course be taken for sulphate by a mind prepossessed, as Claus’s almost admittedly was and which does as is well known, rapidly change into sulphate on the filter. When partially or fully neutralised with acetic acid the solution on treatment with sufficient silver nitrate gives much silver hyponitrite together with a very little reduced silver owing to the sulphonic acid not being entirely destroyed.At first the silver nitrate goes to form potassium silver sulphite but this can be avoided if desired either by using the barium salt instead of the potassium salt or by adding barium hydroxide and then filtering o f f the barium sulphite before adding the silrer nitrite. This decomposition actually furnishes by far the most productive method of preparing hyponitrite yet discovered. The following are the results of some trials we have made the silver hyponitrite having been purified by the authors’ method (Trans. 1884 45 Sl) that is by dissolving it in nitric acid and reprecipitatiiig with sodium car-bonate.Generally the silver hyponitrite was directly weighed but in one or two cases it was converted into chloride before weighing :-Digestion of 0.5772 gram of crystals of potassium oxyamido-sulphonate for 24 hours with a saturated solution of potassium hydroxide containing some solid potash. It still contained a very small quantity of the sulphonic salt undecomposed but the yield of hyponitrite in this case was 76 per cent. of the theoretical amount ; Boiling 0.9370 gram of crystals with concentrated potassium hydroxide for a short time was attended with copious efferves-cence of nitrous oxide but still left a little of the salt undecom-posed ; the yield of hyponitrite however was 30 per cent. of the equivalent of the salt taken.In order to prepare hyponitrite from nitrite in this way there is n 768 DIVERS AND HAQA OXTAMIDOSULPHONATES necessity to have the oxyamidosulphonate pure ; a well-prepared solution of either alkali salt safficiently concentrated is all that is necessary if treated with solid potassium hydroxide. Working in this way we found-0.4545 gram of sodium nitrit,e* after conversion into the sulphonic salt and treatment in the cold with the most concentrated potash for 24 hours gave hyponitrite amounting to 40 per cent. of the full yield had all the nitrite been utilised ; 0.5833 gram of sodium nitrate," after conversion was treated first in the cold for 21 hours and then at 100" for a quarter of an hour, and yielded hyponitrite amounting t o 492 per cent.of the cal-culated quantity. In order to get results as good as these however one modification of the process for getting the oximidosulphonate from the nitrite must be followed; we reserve the account of this for the paper on these salts. Here we need only mention that we can get at least 85 per cent. of the calculated quant.ity of oximidosulphonate from the nitrite a proportion far higher than that previously obtained by Raschig the only quantitative worker. In consequence of the decomposition of much of the potassium hyponitrite into hydroxide and nitrous oxide the determination of' the hyponitrite found does not of itself serve to prove that the formation of this salt is the only decomposition of the oxyamido-sulphonate. But it does make this deduction highly probable when taken along with the occurrence of so much nitrous oxide and sulphite and the absence of ammonia nitrogen and sulphate.The determination of the sulphite however seems sufficient of itself to prove that the decomposition is of one kind only although here too, any very close a.pproach to the calculated amount cannot be expected, considering the ready oxidisability of sulphites to sulphates and that the sulphonate is never entirely decomposed. The presence of hypo-nitrite and its reaction with potassium iodide render a volumetric estimation of the sulphite by means of iodine impossible ; in order, therefore to estimate the sulphurous acid we availed ourselves of its reaction with stannous chloride. The latter has no action either upon hydroxylamine (Divers and Haga Trans.1885 47 624) or upon oxyamidosulphonic acid. Our method of procedure was to put into a pressure-bottle the diluted solution of the salt decomposed by alkali and neutralised mix it with excess of stannous chloride and almost fill the bottle with water. The tightly closed bottle was kept in nearly boiling water for an hour and then left to cool. The * Measured off for analysis as oxyamidosulphonate solution produced from a large quantity of nitrite worked upon AND THEIR CONVERSION IXCO HPPONITRITES. 769 washed precipitate of stannous snlphide was heated with hydro-chloric acid and pot,assium chlorate until all the sulphur had been oxidised and the solution after being evaporated to dryness was again evaporated to dryness with hydrochloric acid.Finally after removing the tin by hydrogen sulphide the sulphuric acid in the filtrate was estimated as barium salt. In this way from 0.7470 gram of salt which by long keeping had slightly hydrolysed, we got sulphur equivalent t o 88.63 per cent. of all that was in the original sulphonic salt. This result renders i t clear that sulphite and, therefore hyponitrite are the only two primary products of the change. The reaction by which hyponitrite and sulphite are formed consists probably i n the substitution of potassium for the hydrogen of the oxyamido-radicle and then of spontaneous decomposition of the potassium compound. There is no hydrolysis or saponification, simply dissociation or chemical fission-HONHSO3K + 2KOH = KONKSOSK + 2HzO 2KONKSO3K = (K0N)z + 2KzSO3.Raschig bas observed a decomposition of Fremy’s potassium sulph-azite by strong potash into sulphite and nitrite very similar to this. We would gladly account for. the differences between the results found by other chemists and our own but we are able to do little in this direction. We have to face the fact that Claus’s work was quantitat,ive. The only suggestion we can offer is that Fremy and Claus’s preparations originally pure were not treated with alkali until they had been kept long enough to undergo the decomposition (fully in Claus’s case)-SHONH(S03K),OH = (HONH,)2SO + K2S04 into hydroxylamine and sulphate. Such a mixture would behave exactly in the manner observed. As for oxygen Fremy must have mistaken nitrous oxide for it and in making this supposition we have evidently the support of Claus and Raschig.Lastly as to Claus’s nitrous oxide diluted with nitrogen dilution with air and steam may perhaps have been the cause of the properties of the gas he got differing from that obtained by Fremy and ourselves. Oxyamidosulphonates evaporated to dryness on a water-bath with potassium or sodium carbonate evolve carbon dioxide during the last stages of the evaporation and yield much sulphite. No hypo-nitrite can remain undecomposed under such circumstances. A solution of oxyamidosulphonate left even in the cold for a day with the carbonate shows evidence of the presence of st little snlphite 7 i0 DIVERS AND HXGA OXTAMIDOSULPHONATES After repeated evaporations with potassium acetate an alkaline mixture containing a minute quantity of sulphite is left.Oxidation of 02 yamidosubhonates by Basic Reagents. Fremy observed that manganese dioxide dissolved as manganous salt in oxyamidosulphonic acid with effervescence due to evolution of oxygen also that the same reagent caused it lively effervescence in a solution of the potassium salt. These observations are correct save that he mistook nitrous oxide for oxygen. Finally he found that the potassium salt immediately reduced salts of silver copper and gold. We must however except copper from this statement unless alkali were present. Claus as we have already had occasion to mention found that the potassium salt in the presence of potassium hydroxide reduced ,salts of copper and silver in the cold just like hydroxylamine ; his experiments liowever were qualitative only.Raschig who holds that a1 kalis convert oxyamidosnlphonates wholly in to their equivalent of hydmxylamine records no experimental determinations in support of this point though he quantitatively estimated the hydroxylamine produced by the action of an acid. The reaction which we find takes place is the conversion of the oxyamidosulphonate into sulphite and sulphate and the reduction of a quantity of metaI-oxide equivalent t o the oxidation of the oxyamido-residue and not to that of the hydroxylamine supposed to be pro-duced. That is to say the ouprous oxide obtained is just half what it would be were hydroxylamine first formed as believed by Claus and Raschig. The equation therefore will stand thus :-2HONH(S03K) + 2CuO + 2KOH = KZSO3 + KZSO + CUZO + NZO + 3Hz0, which shows that the potassium hydroxide takes the t w o sulphonic residues to form sulphite sulphate,* and water the copper oxide oxidising to water the two atoms of hydrogen of the two oxyamido-residues the hyponitrous acid left being resoIved finally into nitrous oxide arid water.After the reduction addition of hydrochloric acid liberates much sulphur dioxide. The reaction is not quite complete as it ceases when the solution becomes very dilute. Thus if to an aqueons solution of 1 gram of the oxyamidosulphonate in a litre of water a few drops only of a dilute solution of copper sulphate and then of potassium hydroxide, are added a permanent blue opalescence is produced but no cuprous oxide is deposited even when the solution is kept for hours in a * Hyposulphate waa searched for and could not be found AND THEIR CONVERSION INTO HYPONITRITES.771 closed vessel. This observation may serve to show that although, when very dilute alkalis do not produce much sulphite and nitrite, t h i g is not because hydroxylamine and sulphate are produced instead, for if such were the case the hydroxylamine would act upon the cupric hydroxide. The fact that the alkaline solution contains not hydroxylamine, but a sulphonic-derivative of it which gives sulphite in its reac-tions with reducible compounds and that i t has only half the action of its equivalent of hydroxylamine are serious if not fatal, objections to resorting to it as a reagent in organic research for the purposes suggested by Raschig.This chemist notwithstanding that he has pointed out (see his memoir p. 182) that the reason that oximidosulphonates do not possess any of the reducing powers of hydroxylamine is that in them the two active hydrogens of hydroxyl-amines are replaced by sulphonic radicles and that oxyamidosul-phonates by retaining one of these hydrogens are as easily oxidisahle as hydroxylamine itself has yet failed to see that his contention being well-founded it will be the oxyamidosulphonate and not hydroxylamine which exerts the reducing power in its aIkaline solu-lion. That it is so is shown by the fact determined by us that in the absence of reducible agents alkalis do not completely decompose oxy-itmidosulphonates and for the rest change them into sulpliite and hyponitrite neither of which gives a cnprons precipitate in presence of alkalis.It was unavoidable that the amount of sulphite produced should be imperfectly estimated partly because of the great oxidisability of the very dilute alkaline sulphite by air and partly because the decompo-sition of the oxyamidosulphonate is never complete. To measure it, the mother-liquoib of the copper precipitate was run into excess of half-decinormal iodine solution (mixed with acid enough to more than neutralise the mobher-liquor) and the unconsumed iodine titrated with sodium thiosulphate. The water used was always pre-viously freed from air by boiling. Of the salt 1.0967 grams treated with copper sulphate and potassium hydroxide gave in this way 40 per cent.of the sulphur of the salt as sulphite and that was our best result. Theory as given by us indicates 50 per cent.; whilst on the other view there should be none at all. Other portions of the mother-liquor of the copper precipitate were acidified to promote the hydrolysis of any of the sulphonate yemaining undecomposed and afterwards concentrated by evaporation. One of these then gave a distinct reduction with the copper mixture due t o hydroxylamine ; whilst another measured portion on titration with iodine in presence of hydrogen potassium carbonate also showed the presence of We have yet to supply particulars of our quantitative work 772 DIVERS AND IIAGA OXYAMIDOSULPHOKATES hydroxylamine equivalent however t o only one-twelfth of the whole salt.To measure the amount of copper reduced we added to 0.2913 gram of the salt (already slightly hydrolysed by keeping) dissolved in water a slight excess of a sort of Fehling’s solution much stronger than usual and with less alkali in it heated to boiling collected the cuprous oxide on a filter washed rapidly and weighed the reduced oxide as black oxide. We thus obtained cupric oxide equal to 48 per cent. of the weight of the salt instead of 47 per cent. calculated from our equation. On the other theory twice as much should have been obtained. In alkaline solutions silver and mercuric hydroxides act just like cupric hydroxide qualitatively at least and yield much sulphite. Constitution of Hyponitrites as revealed by the Decomposition of 0 % ~ amidosu lp honnat es.The decomposition of oxyamidosulpbonates in to sulphite and hypo-nitrite sets at rest any doubt as t o the constitution of hyponitrites ; for coming in this case directly from zt substituted hydroxylamine, a hyponitrite must have its oxygen between the nitrogen and metal. Berthelot and Maquenne have recently published papers (Compt. rend. 108 1286 1305) containing analyses of calcium and atrontium hyponitrites. These analyses as they point out establish the accu-racy of the empirical formula given by one of us (Divers) to hypo-nitrous acid upon which doubt had been cast by previous work upon the silver salt by Berthelot himself and Ogier (Cumpt. rend. 96, 30 84). To this salt the latter chemists gave the formula Ag4N405, the correctness of which was afterwards contested by us (Trans,, 1884 45 78).Berthelot now admits that this salt cannot be obtained in a pure state thus confirming our view as against Zorn, van der Plaats and Menke all of whom claimed to have got it in a pure state without difficulty. Zorn’s opinion that the molecule of the acid contains 2 atoms of each of its elements already generally accepted is now endorsed by Berthelot and Maqneune. Lastly, Maquenne is disposed to deiiy that nitrous oxide can be the an-hydride of hyponitrous acid even to the same extent that carbon monoxide is the anhydride of formic acid but on grounds which t o us seem quite insufficient. Even the facts recorded in this paper can leave hardly any doubt that it is so. The formula of hyponitrous acid may now confidently be written as HO*N,*OH or (NOH), that is the acid is hydroximidogen of which NOH is the radicle AND THEIR CONVERSION INTO HYPONITRITES.773 APPENDIX. We have again determined the sulphite produced both when potas-sium oxyamidosulphonate is decomposed by potassium hydroxide alone, and also when it is oxidised by the same reagent and cupric oxide. In these determinations the work was done in closed vessels excluding the air so that no appreciable destruction of sulphite could have occurred through acrial oxidation. Also in measuring the sulphite formed when the salt is oxidised by cupric oxide we employed here for the first time the stannous chloride process described in the paper. The salt was treated with the cupric oxide in an atmosphere of hydrogen in a bottle which was afterwards without opening filled up with stannous chloride and water.Only then and for a moment was the bottle opened in order t o remove the cork and gas tubes and insert the stopper before heating the mixture for an hour in boiling water. We feared that in washing the tin sulphides the copper sulphides mixed with them would give trouble by oxidising on the filter but our fears proved groundless. For the other decomposition by alkali alone we boiled the salt for a few hours with potassium hydroxide in a small tube in connection with a hydrogen-apparatus and when ready quickly dropped this tube with its contents into the bottle of stannous chloride. With the precautions we have taken we have now no longer to admit any imperfection known to us to have existed in our preparations for analysis and can give the new results so far with confidence as being closely accurate.The decomposition of the oxyamidosulphonate by potassium hydroxide into hyponitrite and sulphite using 0.2007 gram of freshly crystallised salt in fine plates gave 89 per cent. (89.05) of the sulphur as sulphite confirming our earlier result cjf 88 per cent. The oxidation of the salt by cupric oxide into sulphite sulphate and nitrous oxide effected on 0.4298 gram of the above-described prepara-tion gave 44 per cent. (43.93) of the sulphur as sulphite a result confirmatory of our theory and better than our best previous result of 40 per cent. It thus appears clear that the sulphite formed when the oxyamido-sulphonate is oxidised by cupric oxide is half what is produced when t.he salt is decomposed by alkali alone. That only nine-tenths of the reckoned sulphite is obtained in either case is partly if not entirely due to two causes. One of them is that as already pointed out in each mode of decomposition a little oxyamidosulphonate (or a body like it) is always left at the end of the reaction. The other and main one is that the tin reaction is incomplete ; for working upon sulphite of a known degree of purity we have got by its mean8 only 91 and again 93i per cent. of the sulphite indicated. VOL. LT. 3

ISSN:0368-1645    

DOI:10.1039/CT8895500760

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

INDEX OF AUTHORS’ NA4MES. T R A N S A C T 1 0 N S. 18 8 9. And to such papers as appeared in Abstracts of Proceedings (Nos. 58-73 December 1888 t o November 1889 inclusive) but not in Transactions. A. Adie R. H. on compounds of arseni-ous oxide with sulphuric anhydride, 157. Armstrong H. E. note on the deter-mination of the moleular weight of substances in solution especially col-loras PROC. 109. -. note on the hydration of cyanides, - note on the interaction of metals and acids PROC. 66. - the constitution of P-naphthol-a-sulphonic acid [Bayer’s acid] PROC., 8. - the sulphonation of naphthalene-8-snlphonic acid PROC. 10. Armstrong H. E. and E. C. Ros-s i t e r action of halogens on P-naph-Lhol PROC. ’71. Armstrong H. E. and W. P. Wynne isomeric change in the naphthalene series No.5 P-iodo-naphthalenesulphonic acid PROC., 119. - nitration of naphthalene-15-sulphonic acid PRO~. 17. - nitro-P-chloronaphthalene, - note on the 1 3-homo- and the isomeric hetero-&-dichloronaph-thalenes melting a t nearly the same temperature PROC. 5. - the determination of the con-stitution of the heteronucleal aB-and BP-di-derivatives of naphthalene. PROC. 122. PROC. 71. PROC. 34 48. B. Bevan E. J. Blackman F. F. See 8. Ruhe-See C. F. Cross. mann. B l y t h A. W.,and B. H.Robertson, notes of experiments on butter fat, B o t t W. method of determining vapour-density applicable at ali tem-peratures and pressures PROC. 1888, 110. B o t t W. and J. B. Miller some de-rivatives and new colonring matters obtained from pyrocresole 51.B r a u n e r B. experimental researches on the periodic law Part 1 tellurium, 382. B r a z i e r J. S. obitua notice of 289. Brown H. T. and 8. H. Morris, amylodextrin of W. Nageli and its relation to soluble starch 449. determination of the molecu-lar weights of the carbohydrates, Part 11,462. Burch G. J. and J. E. Marsh the dissociation of amine vapouw 656. PROC. 5. -C. Carnegie D. J. cupric iodide and the interaction of iodides with cupric Chapman A. C. zinc dextrosate 576. Cohen J. B. Coleman J. J. obituary notice of, Collie N. note on fluoride of methyl, - on some Leadhill minerals 91. - 00me compounds of tribenzylphos-phine oxide 223. Colman H. G. some derivatives of Pr 1 w-methylindole 1.Colman,H. 8. andW.H.Perkin,jun., acetopropyl alcohol and acetobutyl alcohol 352. Coste J. H. Croo kes W. recent researches on the S & h PROC. 2. See T. Ewan. 290. 110. See R. Meldola. 3 ~ 776 INDEX OF AUTHORS. rare earths as interpreted by the spectroscope 255. H. tion. of cellulose PROC. 133. 7- contributions to the chemistry of lignification. Constitution of jute fibre substance 199. - the constituents of flax, Cundall J. T. zinc mineral from a PROC. 155. blast furnace PROC. 67. Cross C. F. and E. J.Bevan acetyla-D. ¶aga,T. See E. Divers. Itrrnblv. F. J. See T. E. Thorpe. D'Arcv R. F. a compound of boric Debray H. obituary notice of 291. D i v e r s E. and T. Haga oxyamido-sulphonates and their conversion into hyponitrites 760.Dixon A. E. contributions to our knowledge of isothiocyanates 300. - further study of the thiocarbimides, 618. Donkin W. F. obituary notice of, 292. Dunstan W. R. and T. S. Dymond, decomposition of nitroethane with alkalis PROC. 1888 117. Dymond,T. 5. See W. R. Dunstan. acid kith sulphur trioxide 155. E. Evans R. E. Ewan T. and J. B. Cohen oxidation-See Meldola R. products of acenaphthene 578. F. Field W. H. W. obituary notice of, 293. G. G l a d s t o n e J. H. and W. H i b b e r t , on the atomic weight of zinc,443. G l a d s t o n e J.H. and W. I€. P e r k i n , sen. on the correspondence between the magnetic rotation and the refrac-tion and diepersion of light by com. pounds containing nitrogen 750. Green A.G. the const,itution of pri-muline and allied sulphur compounds 227. - the isomeric snlphonic acids of p-naphthylaniine 33. G-riffiths A. B. existence of salicylic acid in certain genera of the LiliaceE PROC. 122. I e Ile r,"w. M. formation of sulphones on sulphonating naplithalene-deriva-tives by means of chlorosulphonic acid PROC. 121. genderson G. G. and R.W.Smith, the action of chramium oxychloride on pinene 45. €I ey c oc k C. T. andF. H. N eville the lowering of the freezing point of sodium by the addition of other metals 666. Kibbert. W. See Gladstone. Hopkins F. G. note on a yellow pig-ment in butterflies PROC. 11'7. Houlding W. the acids formed by displacing NH2 in Sronner's p-iiapthylaminesulphonic acid by halo-gens PROC. '74.Hutchinson A. See3I.M.P. Muir. I. I n c e W. H. formation of phenylin-doles by isomeric change PRoC. 90. J. J a p p F. R. and F. Klingemann, condensat,ions of a-diketones wit8h ethyl acetoacetate PROC. 1888 114. 7- aB-nibenzoylstyrolene and the constitution of Zinin's lepiden, PROC. 136. H. Kimmings C. W. on periodates 148. E i p p i n g F. S.and W. H. Perkin, jun. action of dehydrating agents on aw-diacetylpentme formation of di-methylheptamethylene PROC. 143. - - action of reducing agents on aw-diacet,ylpentane formation of di-methylheptamethylene PROC. 145. - aw-diacetylpentane and a w -dibenzoylpentane 330. K i r k l a n d J. B. Klingemann F. See 0. Masson. See F. R. J a p p . L. Lanrie A. P. the alloys of lead tin, zinz and cadmium 677 INDEX OF AUTHORS.777 Lewkowjtsch J. an improved Soxh-let extractor and apparatus for dis-tilling in a vacuum 359. - preparation of glyceric acid PROC., 14. _c sawarri fat PROC. 69. Ling A. R. isomeric change in the - some metallic derivatives of halogen L u n t J. phenol series 583. nitrophenols 56. See Sir H. E. Roscoe. M. Me Leod H. decomposition of po-tassic chlorate by heat in the presence of mangenese peroxide 184. Me M u r t r g G. C. onmercuricchloro-thiocyanate 50. - on thionyl thiocyanate 48. Maiden J. H. the resin of Myoporzcm Marsh J. E. Marshal1,T. R. and W. H. Perkin, jun. [l 21 meth=jlethylpentamethyl-ene PROC. 143. Mason A. T. acetarnide and phen-anthraquinone 107. - action of ethylenediamine on SUC-cinic acid 10.- piazine-derivatives 97. Masson 0.) and J. B. Kirkland ac-tion of bromine and chlorine on salts of tetrethylphosphonium 126. -. - preparation of the salts of triethylsulphine tetrethylphospho-nium and analogous bases 135. M a t t hews F. E. on ethyl cinnamyl-diethacetate 38. Meldola R. synthesis of heteroge-neous mixed alkyldiazoamido-com-pounds 610. Meldola,R.,and J. H. Coste benzyl-derivatives of the phenylenediarnines, 590. Meldola R. and R. E. Evans note on the oxidation of paradiamines, Meldola R. and (3. T. Morgan, contributions to the chemistry of the azo-@-naphthol-compounds 603. - - researches on the constitution of azo- and diazo-derivatives Part V, compounds of the naphthalene series, 114. Meldola R. and I?.W. S t r e a t f e i l d , the isomerism of the alkyl-deriva-tives of mixed diazo-amido-com-pounds 412. platycarpurn 665 See G. J. Burch. PROC. 115. MendelBeff D. the periodic- law of Miller J. B. Morgan G. T. Morris Gt. H. products of the action of sulphur on resin PROC. 102. Morris G. H. See also H. T . Brown. Muir M. M. I?. andA.Hutchimson, on a cubical form of bismubhous oxide 143. the chemical elements 634. See W. B o t t . See R. Meldola. N. Neville 3’. H. See C. T. Heycock. N o r t h B. Gawdowski’s method for the volumetric estimation of sulphuric acid PBOC. 5. 0. Orsman W. J. See W. J. Russell. P. P e r cival J. Bbmethoxynaphthalene-sulphonic acids PROC. 73. P e r k i n A. G. action of nitric acid on anthracene PROC.13. P e r k i n W. H. sen. observations on the melting points of some salicylic and nnisic compounds 549. - the action of the chlorides of pro-pionyl and butyryl on phenol 546. - the magnetic rotatory power of nitrogen-compounds also of hydro-chloric hydrobromic and hydriodic acids and of some of the salts of ammonia and the compound am-monias 680. Perkin W. H. sen. See also J. H. G l a d s tone. P e r k i n W. H. jun. ethylic aal-diace-tyladipate PROC. 141. - on lwrberine (Part I) 63. P e r k i n W. H. jun. and J. B. T i n -gle acetyl carbinol (acetol) PROC., 156. See also H. G. Colrnan F. 8. K i p p i n g and T. R. Marsh a 11. P e r m a n E. P. the boiling points of sodium and potassium 326. Pickering S. U. isolation of a tetr.1-hydrate of sulphuric acid existing in solution YROC.128. - note on the heat of neutralisation of sulphuric acid 323. P e r k i n W. H. jun 778 INDEX OF AUTHORS. Pickering S. U. the expansion of water and other liquids PROC. 89. - the law of the freezing points of solutions PROC. 149. - the nature of solutions as eluci-dated by a study of their densities, electric conductivities heat capacity, and heat of dissolution PROC. 86. - the nature of soldtions as eluci-dated by a study of their freezing temperatures PROC. 106. - the principles of thermochemistry, 14. P r i c e D. S. obituary notice of 294. R. Ramsay W. the molecular weights of the metals 521. Ramsay W. and S. Young mixture of propyl alcohol and water PRO^., 1888,101. Rawson S. Gt.the atomic weight of chromium 213. Reynolds J. E.,researches on silicon-compounds and their derivatives, Part V on silicotetmphenylamides, a- and /3-silicotetranaphthylamides, 4'74. Richardson A. action of light on moist oxygen PROC. 134. Rideal S. the action of ammonia on some tungsten-componnds 41. Robertson G. H. See A. W. Blyth. Rodger J. W. Romanis R. tectoquinone PRoC., 1888,116. Roscoe Sir H E. and J. L u n t on Schutzenberger's process for the estimation of dissolved oxygen in water 552. R o s s i t e r E. C. See H. E. Arm-strong. Ruhemann S. action of chloroform and alcoholic potash on hydrazines, 242. Ruhemann S. and F. F. Black-mann benzophenylhydrazine 612. Ruhemann 5. See also 8. Skinner. Russell W. J. and W. J. Orsman, relation of cobalt to iron as indicated by absorption-spectra PROC.14. See T. E. Thorpe. S. Sindall R. W. P-bromonaphthalene-sulphonic acid PROC. 118. Skinner S. and S. Ruhemann con-tributions to our knowledge of citric and aconitic acids 235. S m i t h J. Denham obituarynotice of, 294. S m i t h R. W. See G. G. Hender-son. S m i t h W. note on /3-phenylnaph-thalene YROC. '70. Storey J. obituary notice of 296. S t r e a t f e i l d F. W. SeeR. Meldola. T. Thorpe T. E. the decomposition of Thorpe T. E. and P. J. Hambly, - - the vapour-density of hydro-Thorpe T. E. and J. W. Rodger, Tingle J. B. See W. H. P e r k i n , carbon disulphide by shock 220. on phosphoryl trifluoride '759. gen fluoride 163. on thiophosphoryl fluoride 306. jun. v. Veley V. H. on a method of inveeti-gating the dissolution of metals in acids 361. W. W a l l a c e W. obituary notice of 296. W a r i n g t o n R. the amount of nitric acid in the rain-water a t Rotham-sted with notes on the analysis of rain-water 537. Werner A. E. benzylammonium suc-cinates and their derivatives 627. Williams J. obituary notice of 298. Wynne W. P. See H. E. Arm-strong. Y. Young S. on the vapour-pressures and specific volume of similar com-pounds of elements in relation to the position of those elements in the periodic table Part 1 486. - the vapour pressures of quinoline, 483. Young S. See also W. Ramsay

ISSN:0368-1645    

DOI:10.1039/CT8895500775

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

INDEX OF SUBJECTS. T R A N S A C T I O N S . 1889. And t o such papers as appeared in Abstracts of Proceedings (Nos. 58-73 November 1888 to November 1889 inclusive) but not in Transactions. A. Acenaphthene action of chromium oxy-- intermediate products of oxidation - ketone 580. - tribromo- and tetrabromo- 581. Acenaphthylene glycol 579. - diacetate 579. - - monacetate 57d. - monobenzoate 500. Acetamide 107. Acetobutyl alcohol 352. - - preparation of 354. - bromide preparation of 332. Acetol PROC. 156. Acetonitrile trichlor- hydration of, Acetophenonebenzophenylhydrazine, Acetopropyl alcohol 352 357. - bromide 357. Acetovalerianic acid w- PBOC. 142. Acetyl carbinol PROC. 156. - osazone of PBOC. 156. Aretylbenzophenylhydrazine 614. Acetylcaproic acid W - 338.Acetyldehydrodiacetylcapronamicie, Acetyldehydrothiotoluidine 230. Acetylorthotolylthiocarbamide 304. Acetylphenylsemithiocarbazide 303. Acids and metals interaction of PROC., 66. - correspondence between the mag-retic rotation and the refraction and dispersion of light by ’751. - method of investigating the disso-lution of metals in 361. Aconitic acid 235. Aconitylanil-anilide 237. chloride on 582. of 578. PROC. 122. 615. 341. Aconitylanil carboxy lic acid 238. Aconityltoluidocarboxylic acid 239. Aconityltoluidotoluidide 239. Adapter for fractional distillation in a AIkyldiazoamido-compounds synthesis Alloys of lead tin zinc and cadmium, - of sodium and gold properties of, Allylamine magnetic rotatory power Allylorthotolylthiocarbamide 622.Alumina phosphorescent sharp line - the phosphorescence of 280. Aluminium molecular weight of 531, Amine vapours dissociation of 656. Amines correspondence between the magnetic rotation and the refraction and dispersion of light by 751. - magnetic rotakory power of 691, 713 728 743. Ammonia estimation of in rain-water, 544. - magnetic rotatory power of solu-tions of 689 728. - magnetic rotatory power of some salts of 680. Ammonias compound correspondence between the magnetic rotation and the refraction and dispersion of light by 754. 7- magnetic rotatory power of some salts of 680. Ammonium bromide magnetic rotatory power of solutions of 716 742. - chloride magnetic rotatory power of solutions of 712 743. - hydrogen mlphate magnetic rota-vacuum 360.of heterogeneous mixed 610. 67’7. 6’70. of 697 732. spectra of 281. 533 780 INDEX OF SUBJECTS. tory power of solutions of 721, 745. Ammonium iodide magnetic rotatory power of solutions of 718 '74'2. - nitrate magnetic rotatory power of solutions of 721 745. - salts correspondence between the magnetic rotation and the refraction and dispersion of light by 751. - sulphate magnetic rotatory power of solutions of 122 745. Amylodextrin action of diastase on, 456. .__ constitution and molecular weight - of W. Niigeli and its relation to soluble starch 449. - properties of 452. Anhydracetonephenonebenzil PBOC., Anilidophenylpyrrole PILOC. 140. Aniline diazotised metanitr- action of, on ethylparabromaniline 428. -- action of on methyl-parabromaniline 425.I_ diazotised parabromo. action of, on ethylmetanitraniline 428. -- action of on ethylpara-nitraniline 423. -- action of on methyl-metanitraniline 426. -- action of on met.hy!-paranitraniline 419. -- action of on methyl-paratoluidine 432. - diazotised parachlor- action of on ~nethylparatoluidine 436. - diazotised paranitr- action of on ethylparabromaniline 423. -- action of on methyl-bromaniline 418. Anilines compouiid correspondence be-tween the magnetic rotation and the refraction and dispersion of light by, 755. Anisic aldehyde melting point of 551. - compounds melting points of, Aiinual General Meeting March 28th, Anthracene action of nitric acid on, - diamido- Paoc. 13. - nitro- and dinitro- PROC. 13.Antimony molecular weight of 532, 533. ,4rsenious oxide compounds of with sulphuric anhydride 157. Atomic weight of chromium 213. of tellurium 382. - of zinc 443. of 454. 136. 549. 1889 250. PROC. 13. -Azo- and diazo -derivatires constitution Azo-p-naphthol-compounds alkyl-deri--- benzoyl-derivatives of, Azo-P-naphthol-derivatives containing Azonaphthols contributions t,o the che-of 114. vatives of 603. 114. acid radicles reduction of 117. mistry of 603. B. Balance Sheet of the Chemical Society from March 21st 1888 to March 18th 1889 286. - of the Research Fund from March 21st 1888 to March 18th, 1889,287. Barium molecular weight of 530 533. - oxyamidosulphonate 764. Benzene boiling point of 487. - bromo- boiling point of 487.- specific gravity of 488 506. - specific volume of 488 506. I__- vapour-pressure of 490 491, - chloio- boiling point of 487. - specific gravity of 488 505. - specific volume of 488 505. - vapour-pressure of 490 495, - expansion of 519. -. fluoro- boiling point of 487. - specific gravity of 488 505. - specific volume of 488 505. - vapour-pressure of 490 493, - iodo- boiling point of 481. - - specific gravity of 488 506. - specific volume of 488 506. - vapour-pressure of 490 498, - specific gravity of 488 504. - specific volume of 488 504. - vapour-pressure of 492 501 508. Benzene-azo-P-naphthol reduction of, Benzene-azo-a-naphthyl acetate nitra-503 509. 503,509. 502,509. 503 510. 122. tion of 609. benzoate 606. - ethylate nitration of 608. Benzene-azo-P-naphthyl acgtate nitra-- reduction of 117 122.- benzoate 115. - - metanitro- 116. - reduction of 124. - ethylate nitration of 608. -tion of 609 INDEX OF SUBJECTS. 781 Benzenediazoamidoparatoluene para-bromo- methrlation of 433. - pal-achloro- methylation of 437. Benzoindole 617. Benzoindolecarboxylic acid 617. Benzo;>henylacetone hydrazine 615. Benzophenylbenzaldehyde hydrazine, Benzophenylhydrazine 612. - action of chloroform and alcoholic Benzophenylhydrazine-pyruvic acid, Benzophenyl-phenylsulphosemicarb-Benzophenylsemicarbazide 614. Benzoylcaproic acid W - 350. Benzoyldiamidohydroxynaphthpl-Benzoylphenylethylthiocarbamide 305. Benzoylphenylsemithiocarbazide 304. Benzylamidobenzene-azo-a-naphthol, Benzylamidobenzene-azo-P-naphthol, Benzylammonium hydrogen succinate, - succinate normal 628.- succinates and their derivatives, Benzjlbenzylidenediamidodiplienyl-Benzylmetaphenylenediamine 597. Benzylmeta- and benzylpara-phenylene-diamines oxidation of a mixture of, 598. Benzylparaphenylenediamine 591. - azo- and diazo-derivatives of 596. - oxidation of in the presence of Berberine 63. I_ action of fused potash on 88. - action of hydrogen iodide on 86. - hydriodide 66. - hydrochloride 70. - nitrate 65. - oxidation of with potassium per-manganate 71. - platinochloride 66. - properties of 68. Beryllium additional proof of the bivalence of 650. Bismuth molecular weight of 532 533. Bismuthous oxide cubical form of 143. Bis-phenylmethylmethylenepyrazolone, Boric acid compound of with sulphur Butter fat nature of PROC.5. 615. potash on 618. 616. azide 615. oxime of 351. --phenyl 125. 596. 596. 628. 627. amine 594. other aromatic amines 592. PROC. 142. trioxide 155. Butterflies yellow pigment in PROC., Butyrylphenol 548. 117. C. Cadmium effect of on the freezing point of sodium 673. - molecular weight of 527 531, 533. periodates 161. Cadmium-lead alloys 679. Cadmium-tin alloys 679. Calamine 96. Calcium niolecular weight of 530 533. - vanado-pyromorphite 94. Caledonite 92. Carbohydrates molecular weights of, 462. Carbon bisulphide decomposition of by shock 220. Carbon-compounds unsaturated corre-spondence between the magnetic rota-tion and the refraction and dispersion of light by 755.Cellulose acetylation of PBOC. 133. Cerotic acid from flax fibre PROC. 155. Ceryl alcohol from flax fibre PROC., Chlorine estimation of in rain-water, Chloropicrin magnetic rotatory power Chromium atomic weight of 213. Citric acid 235. Citryl monochloride chloro- action of -- action of heat on 237. -- action of orthotoluidine - - - action of water on 236. -- constitution of 240. Cobalt relation of to iron as indicated by absorption-spectra PROC. 14. Collo’ids determination of the molecular weight of in solution PROC. 109. Copper dissolution of in acids 361. - periodate 150. Cupric iodide PROC. 2. - salts interaction of with iodides, Cyanides hydration of PROC. 122. -155. 545. of 689. aniline on 237. on 239. PROC. 2. D.Dehydrothiotoluidine 228. - constitution of 232. Dehydrothiotoluidinesulphonic acid, on, 3 H 782 INDEX OF SUBJECTS. Dextrins molecular weights of 469. Diacetylbenzylparaphenylenediamine, Diacetylbutanc aw- PROC. 143. Diacetylcaproic acid aw- 334. Diacetylcapronamide aw- 342. .Diacetylpentane aw- 330 335. - a w - action of dehydrating agents - aw- action of reducing agents on, Diacetylpentanedioxime a-w- 337. Diamines para- oxidation of PROC. 115. Diazoamidobenzene metanitropara-bromo- ethylation of 429. - - methylation of 427. - paradibromo- and its methyl-de-- parametadinitro- and its alkyl-- paranitroparabromo- ethylation of, - methylation of 420. Diazoamido-compounds alkyl synthesis of heterogeneous mixed 610. - mixed isomerism of the alkyl-derivatives of 412.Dibarium oxamidosulphonate 763. Dibenzoylbenzylnietaphenylenediamioe, Dibenzoylbenzylparaphenylenediamine, Dibenzoylcinnamene ap- PROC. 136. Dibenzoylpentane a w - 330 347 348. Dibenzoylpentanedioxime 349. Dibenzoylstyrolene aB- and the con-stitutionof Binin’s lepiden PROC. 136. Dibenzylamidoindamine 598. Dibenzodiamidophenazine 599. Dibenzylidenediamidodiphenylan~ine, Dibenzylindamine 593. Didymium-group absorption-spectra of the elements of 255. Diethylamine hydrochloride magnetic rotatory power of solutions of 713, 743. - magnetic rotatory power of 691, 729. Dihydroxydimethylheptamethylene, Diisobutylamine magnetic rotatory Diketones a- condensation of with Dimethyldehydrothiotoluidine 230. Dimethyldiphenylpiazine tetrahydride Dimethylheptamethylene formation of, - orthodibromo- PROC.145. 592. on PROC. 143. PROC. 145. rivative 435. derivatives 415. 424. 598. 592. 594. ortho- PROC. 145. power of 697 730. ethyl acetoacetate PROC. 1888 114. [l 4 2 31,104. PROC. 145. Diphenyl-P-benzoylpropionic acid a-, Diphenyl-5-phenylpyrrolidone 3-, Diphenyl-5-phenylpyrrolone 3- PROC. Diphenylpiazine [2 31 99. - dihydride 98. - dinitro- 101. - hexahydride cfl-2 3-1 105. - - [a-2 3-1 and its derivatives, Diphenyltetrazine 244. - bromo-derivatives of 246. - methiodide 245. Dipropylamine magnetic rotatory power of 693 730. Dispersion aud refraction of light and magnetic rotation by compounds con-taining nitrogen correspondence be-tween 750.Dissociation of amine vapours 656. Dissolution of metals in acids method of Distillation in a vacuum apparatus for, Ditolyltetrazine para- 247. Dolomite 96. Dvi-tellurium theoretical properties of, Dyes from pyrocresole 54. PROC. 138. PROC. 140. 140. 102. investigating 361. 359. 649. E. Earths rare recent spectroscopic re-searches on 255. Elements chemical periodic law of the, 634. Erbium-group absorption-ppectra of the elements of 265. Ethane nitro- decomposition of with alkalis Pnoc, 1888 117. - magnetic rotatory power of, 68’7. Ethyl acetoacetate condensations of a-diketones with PROC. 1888 114. - acetylsdipate PROC. 142. - anisate melting point of 551. - benzophenylhy drazinepyruvate, - cinnamyldiethacetate 38. - aa,-diacetyladipate €’ROC.141. - aw-diacetylcaproate 333. - action of alcoholic ammonia I_ aw-dibenzoylcaproate 347. - diimidodiacetyladipate PROC., - diphenylhydrazinediacetyladipate, 616. on 339. 141. PROC. 141 INDEX O F SUBJECTS. 7x3 Ethyl methyldel ydrohexonecarboxylate, preparation of 331. - a-methyl-acl -diacetylcaproate, 345. - methyldihyc .ropentenedicarboxyl-ate PROC. 142. Ethyl methyldihydropentenemethyl-ketonecarboxylate PROC. 142. - nitrate magnetic rotatory power of 682 725. - phenanthroxyleneacetoacetate re-actions of PROC. 1888 114. - salicylaldehyde melting point of, 551. E thy lamine hydrochloride magnetic rotatory power of solutions of 713, 743. - magnetic rotatory power of 691, 729. Ethylbenzylthiocarbamide 300. Ethylene nitrate magnetic rotatory Ethylenediamine action of on succinic Ethylenedisuccinamic acid 12.Ethylenerlisuccinimide 11. Ethylmetanitraniline action of diazo-tised parabronianiline on 428. Ethylparabromaniline action of diazo-tised metanitraniline on 4\28. - action of diazotised pwariitraniline on 423. Ethylparanitraniline action of diazo-tised parabromaniline on 423. Ethylphenylsemithiocarbazidc 302. Ethylpiperidylthiocarbamide 624. power of 684 726. acid 10. F. Faraday lecture 634. Fat butter- nature of PEOC. 5. -SSawarri PROC. 69. Ferric chloride absorption-spectra of, Flask for distilling frothing liquids in a Flax constituents of PROC. 155. Formylphenylhydrazine 242 248. Freezing point of sodium lowering of, by the addition of other metals 666.- points of solutions the law of, PROC. 149. -- mechanical physical, and chemical lowering of PRO~. 150, 151. - of sulphuric acid solutions, Furfural preparation of from jute fibre-PROC. 14. racuum 359. PROC. 106. substance 209. G. Galactose molecular weight of 463. Gallium molecular weight of 531, Glyceric acid preparation of PROC., Glycerides of butter-fat PROC. 5. Glycerol nitro- magnetic rotatory Glycol nitro- magnetic rotatolay power Gold effect of on the freezing point of - molecular weight of 532 533. - sodium alloys properties of 670. 533. 14. power of 685,726. of 684 726. sodium 668. H. Heat of dissolution of sulphuric arid, PROC. 88. Heat of neutralisation of sulphuric acid 323. Hydrazines action of chloroform and alcoholic potash on 242.Hydriodic acid magnetic rotatory power of solutions of 708 739. Hydrobromic acid magnetic rotatory power of solutions of 706 739. Hydrochloric acid. in solution corre-spondence between the magnetic rota-tion and the refraction and disper-sion of light by 758. - -- magnztic rotatory power of solutions of 702 739. Hydrofluoric acid pure aqueous pre-paration of' 166. Hydrogen fluoride preparation of 167. - vapour-density of 163. - peroxide formation of by the exposure to light of a mixture of water and pure ether with oxygen, Hydroxylaniinesulphonates conversion of into hyponitrites 760. Hydroxynaphthylphenyl amido-deriva-tives of 124 125. Hyponitrites constitution of as re-vealed by the decomposition of oxyamidosulphonates 772.PROC. 134. I. Inulin molecular weight of 463. Iodides interaction of with cupric Iron periodates 149. salts PROC. 2 784 INDEX OF WBJECTS. Iron relation of cobalt to as indicated by absorption-spectra PROC. 14, Isobutyl nitrate magnetic rotatory power of 683 725. - nitrite and nitrate correspondence beLween the magnetic rotation and the refraction and dispersion of light by, 757. - - magnetic rotatory pow-er of, 686 '727. Isobutylamine magnetic rotatory power of 694 730. -magnetic rotatory power of solu-tions of 695 730 '735. Iso-u/3-dibenzoylcinnamene PROC. 139. Is0 - up-dibenzo ylst yrolene PROC . 139. Isolepiden PROC. 139. Isothiocyanates 300. Isoxylepidenic acid PROC. 139. J, Jute fibre substance action of chlorine -- constitution of 199.-- nitration of 201. -- preparation of furfural on 203. from 209. L. Lanarkite 92. Lead effect of on the freezing point of - molecular weight of 531 533. - periodates 149. Lead-cadmium alloys 679. Leadhillite. 91. Lead-tin alloys 677. Lead-zinc allop 678. Light action of on moist oxygen PROC., 134. - refraction and dispersion of and magnetic rotation by compounds con-taining nitrogen correspondence between 750. sodium 675. Lignification chemistry of 199. Liliacece presence of salicylic acid in Linarite 93. Lithium effect of on the freezing - molecular weight of 530 533. certain genera of the PROC. 122. point of sodium 675. M. Magnesium molecular weight of 531, 533. Magnetic rotation and the refraction and dispersion of light by compounds containing nitrogen correspondence between 750.- rotatory power of hydrochloric, hydrobromic and hydriodic acids, 680. -- of nitrogen-compounds, 680. -- of some salts of am-mania and the compound ammoi:ias, 680. Maltodextrin molecdar weight of, 465. Manganese molecular weight of 532, 533. - peroxide decomposition of potas-sium chlorate in the presence of, 184. Mercuric chlorothiocyanate 50. Mercury effect of on the freezing Metals and acids interaction of 361, - effect of on the freezing point of - method of investigating the disso-- molecular weights of 521. Methane nitro- magnetic rotatory Methoxynaphthalenesulphonic acids p-, Methyl tluoride 110. - action of chlorine on i l l . - nitrate magnetic rotatory power - salicylaldehyde melting points of, Methylacetyltetrahydrobenzene ortho-, Methylbenzylthiocarbamide 619.Methyl-nw-diacetylpentane 346. Methyldihy dropentenedicarboxy lic acid PROC. 142. Methvldioxindole. 8. point of sodium 672. PROC. 66. sodium 666. lution of in acids 361. power of 68'7. PROC 73. of 682 '725. 5 50. PROC. 144. Meth~l-3-diphenyl-5-phenylpyrrolidone, Methyl-3 - diphenyl- 5-pyrrolone 1 -, 1- PROC. 140. PROC. 140. Methylene chlorofluoride 112. Methylethylhexametliylene format,ion Methylethylpentamethylene [l 2j, Methylhexamethylene methyl carbinol, Methylindole Pr. In derivatives of 1. Methy lmetani traniline action of di-azotised paiabromaniline on 426. Met,hylorthotolylthiocarbamide 621.of PROC. 143. PROC. 143. ortho- PROC. 144 INDEX OF SUBJECTS. 785 Methyloxindole 7. - bromo- 7. - dibromo- 3. - dichloro- 4. Methylparabromaniline action of di-- action of diazotised paranitrani-- action of diazotised paratoluidine Methylparachloraniline action of di-Methylparanitraniline action of di-Methylparatoluidine action of di-- action of diazotised parachlor-Methylparatolylthiocarbamide 620. Methylpentamethylene methyl carbinol Methylpaeudoisatin 5. Methylpseudoisatinoxime 6. Methylpseudoisatinphenylhydrazone 5. Methyltetrahydrobenzene methyl car-bind ortho- PROC. 144. - ketone ortho- €'ROC. 144. Minerals from Leadhills 91. Molecular weight determination of the, of substances in solution especially colloyds PROC. 109. azotised metanitraniline on 425.line on 418. on 433. azotised paratoluidine on 436. azotised parabromaniline on 419. azotised parabromaniline on 432. aniline on 436. PROC. 143. - of amylodextrin 455. - weights of the carbohydrates 462. - of the metals 521. Myoporum platycai.pum resin of 665. N. Naphthalene a- and p-cyano- behn-viour of with sulphonating agents, - q-dichloro- constitution of PROC., - heteronucleal up- and Pp-di, derivatives of constitution of PROC.-34 48. - P-iodo- sulphonation of PROC., 75. - nitro-p-chloro- PROC. 71. Naphthalene-derivatives formation of sulphones on sulphonating PROC., 121. Naphthalenes 1 3-homo- and the isomeric hetero-a8-dichloro- PROC. 5. Naphthalene-8-sulphonic acid nitration of PROC. 17. - sulphonation of PROC.10. Naphthalen~sulphonic acids 8-bromo-, PROC. 118. PROC. 122. 49. Nacphthalenesulphonic acids a-chloro-- p- iodo- PROC. 119. Naphthol 8- action of halogens on, - a-amido- identification of 120. - bromo-derivatires of PROC. 71. - chloro- PROC. 72. - clilorobromo- PROC. 72. Naphthol-a-sulphonic acid 8- constitu-tion of PROC. 8. Naphtholsulphonic acid 8- bromo- and chloro-derivatives of PROC. 72. Naphthylnmine p- isomeric sulphonic acids of 33. - 8- products of the sulphonation of a t 100-105" 35. Naphtliylaminesulphonic acid Bronner' s 8- acids formed by displacing NH, in by halogens PROC. 74. Naphthylaminesulphonic acids p- from 8-naphthoisulphonic acids 37. - properties of the four 36. Nickel periodate 151. Nitrates ethereal correspondence between the magnetic rotation and the refraction and dispersion of light by 755.- magnetic rotatory power of, 682 724. Nitric acid amount of in rain-water a t Rothamsted 537. - estimation of in rain-water, 544. - magnetic rotatory power of, 680 724. Nitrites ethereal magnetic rotatory power of 686 727. Nitro-compounds connection between the magnetic rotation and the refrac-tion and dispersion of light by 751. Nitrogen correspondence between re-fraction and dispersion of light and magnetic rotation in compounds con-taining TRANS. 750. Nitrogen-compounds magnetic rotatory power of 680. P-amido- isomeric PROC. 36 48. PROC. 71. 0. Occlusion of oxygen in pure silver 400. Orthonitric acid magnetic rotatory Oxyamidosulphonates and their conver-- decomposition of by alkaline - oxidation of by baPic reagents, power of 681 724.sion into hyponitrit,es 760. bases '765. 770 786 INDEX OF Oxpamidosulphonic acid 761. - hydrolysis of 764. Oxygen dissolved in water estimation - moist action of light on PROC., - occlusion of in pure silver 400. Oxylepidenic acid PROC. 139. Oxylepidens PROC. 137. of 552. 134. P. Pentamethylenediamine magnetic rota-tory power of 698 732. Periodates 148. - constitution of 152. Periodic law experimental researches - - of the chemical elements, Pnenanthrapiazine 98. - dihydride 98. Phenanthraquinone action of acecamide Phenol action of the chlorides of pro-- chlorobromoparanitro- metallic - dibromorthonitro- calcium - de-- dichlororthonitro-.actmion of chlor-- calcium-derivative of 61. - orthochloroparabromo- nitration - orthochloroparabromorthonitro-, - action of nitric acid on 584. - orthochloroparanitro- bromination - orthonitro- action of chlorine on, - parabromorthiodorthonitro- cal-- para bromorthochlurorthonitro-, - parabromorthonitro- action of - parachlororthobromorthonitro-, - calcium-derivative of 60. - nitration of 589. - parachlororthonitro- action of bromine on 588. Phenols halogen-nitro- some metallic derivatives of 56. Phenol-series isomeric change in 583. Phenyl butyrate 547. - propionate 546. on 382. 634. on 107. pionyl and butyryl on 546. derivatives of 57 58. rivative of 61. ine on 586. of 587. action of bromine on 585. of 56. 586.cinm-derivative of 61. nitration of 590. chlorine on 586. action of nitric acid on 584. SUBJECTS. Phenylbenzylthiocarbamide 300. Phenylenediamines benzyl-derivatives Phenylindoles formation of by iso-Phenylnaphthalene 8- PROC. 70. Phenylthiocarbimide action of thialdine Phosphorescence of alumiua 280. Phosphoryl trifluoride preparation of, Piazine-derivatives 97. Pigment yellow in butterflies PBOC., 117. Pinene action of chromium oxychloride on 45. Piperidine hydrochloride magnetic ro-tatory power of solutions of 716 743. -magnetic rotatory power of 699, 733. - magnetic rotatory power of an aqueous solution of 700. Piperidylbenzoylthiocarbamide 623. Plunibo-aragonite 95. Plumbo-calcite 95. Potassium boiling point of 326. - chlorate decomposition of by heat in the presence of manganese per-oxide 184.- effect of on the freezing point of sodium 674. - hydrogen fluoride preparation of, 166. - lowering of the freezing point of, by the addition of other metals 676. - molecular weigltt of 530 533. - oxyamidosulphonate 762. - periodate 151. Primuline base 233. - constitution of 234. - constitution of 227. Propane nitro- magnetic rotatory power Propionitrile magnetic rotatory power Propionylphenol 547. Propyl alcohol and water vapour-pres-sures of a mixture of PROC. 1888, 101. - nitrate magnetic rotatory power of 683 725. Propylamine magnetic rotatory power of 692 5'30. Pyridine magnetic rotatory power of, 70S 734. Pyrocresole a- oxide azo-derivatives of, 54. - diamido- 54. - -.dinitro- 52. - some derivatives and new colouring of 590. meric change PROC. 90. on 627. 759. of 688 '728. of '701. matters obtained from 51 INDEX OF SUBJECTS. 78 7 Pgroeresole tetramido- 53. - trichlor- 52. Pyromorphite 93. Q-Quinoline vapour-pressures of 483. R. Rain-water analysis of 543. - I- a t R othamsted amount of nitric acid in 537. Refraction and dispersion of light and magnetic refraction by compounds containing nitrogen correspondence between 750. Resin hydrocarbon obtained by the action of sulphur on PROC. 102. - of Myoporum platycarpurn 665. - products of the action of sulphur on PROC. 102. S. Saffranine benzylated 595. Salicylic acid presence of in certain genera of the Liliacem PROC. 122. - compounds melting points of 549.Sawarri fat PROC. 69. Silicon-compounds and their deriva-Silicotetra-a-naphthylamide 482. Silicotetra-P-naphthylamicle 481. Silicotetraorthotolylamide 480. Silicotetraparatolylamide 478. Silico te trapheny lamide 4’75. Silver effect of on the freezing point - molecular weight of 532 533. - of M. Stas occlusion of oxygen in 400. - periodates 152. - pure properties of 399. Sodium boiling point of 326. - gold alloys properties of 670. - lowering of the freezing point of, by the addition of other metale 666. - molecular weight of 527 530,53 3. - oxyamidosulphonate 762. Solutions densities heat capacities and electrical conductivities of PROC. 86. - mechanical physical and chemi-cal lowering of the freezing points tives 474. of sodium 674.Of PROC. 150 151. - nature of PROC. 86 106. - study of the freezing temperatures of PROC. 106. Solutions the law of the freezing points of PROC. 149. Soxhlet extractor improved 359. Specific gravities and volumes of ben-zene and its halogen-derivatives 488. - volumes 0f similar compounds of elements 486‘. Spectra absorption of cobalt-con;-pounds PROC. 14. - of ferric chloride PROC. 14. of iron and cobalt relation between YROC. 14. - of the elements of the didy-mium-group 259. - of the elements of the erbium-group 265. - incandescence 267. - of the yttrium-group of elements, - phosphorescence 267. action of different earths on, interference of 2’76. -269. -275. -- reveraion 279. Spectra sharp line of phosphorescent alumina 281.Spectroscope recent researches on the rare earths as interpreted by 255. Spectrum of thiophosphoryl fluoride, 322. Starch soluble action of diastase on 45G. - properties of 450. - relation of W. Nageli’s amylodextrin to 449. Strontianite 95. Succinbenzylamic acid 630. Succinbenzylimide 629. S uccindibenzy lamide 63 1. Succinic acid actioii of ethylenediamine Succinomonobenzylamide 632. SuIphones formation of on sulphona-ting naphthalene-derivatives PROC., 121. Snlphuric acid causes affecting the lowering of the freezing points of solutions of PROC. 150. - estimation of in rain-water, 545. - - heat of dissolution of PROC., 88. heat of neutralisation of 323. - hydrates of PROC. 88 106, 128 151. - tetrahydrate of existing in solution isolation of a ~ R O C .128. - voiumetric estimation of, - anhydride compounds of ar-molecular weight of 465. -on 10. -PROC. 5. senious oxides with 157 785 INDEX OF 7UBJECTS. Sulphuric trioxide compound of boric acid with 155. T. Tetraquinone PROC. 1888 116. - dibromo- PROC. 1888 117. - dinitro- PROC. 1888 117. Tellurium atomic weight of 382. - compound nature of 407 411. - tetrabromide preparation of, Tetrabenzylmetaphenylenediamine 602. Tetrabenzylparaphenylenediamine 600. Tetrahydrophenylmethyl methyl carbi-Tetraphenylcrotolactone PROC. 137. Tetrethylammonium chloride magne-tic rotatory power of solutions of, 715,743. Tetrethylphosphonium dibromiodide, 128. - dichloriodide 130. - heptabromide 131. - salts action of bromine and chlo-- preparation of 135.Tetrethylphosphonium sulphate com-pounds of with chlorine and bromine, 132 133. - tetrachloride 130. - tribromide 131. - trichloride 132. Thallium effect of on the freezing - molecular weight of 531 533. Thermochemistry principles of 14. Thialdine action of orthotolylthiocarb-imide and of phenylthiocarbimide on, 626,627. 396. nol ortho- PROC. 144. rine on 126. point of sodium 671. Thiocarbimides 618. Thionyl thiocyanate 48. Thiophosphoryl fluoride 306. - action of air and of oxygen - - action of alkalis on 318. - action of ammonia on 318. - action of water on 317. - liquefaction of 322. -I_ properties of 311. I_- spectrum of 322. - - vapour-density of 308. Tin lowering of the freezing point of, by the addition of other metals 667.- molecular weight of 531 533. Tin-cadmium alloys 6'79. Tin-lead alloys 677. Tin-zinc alloys 679. Toluidine diazotised para- action of on on 312,313. methylparabromanfiine. 433. Toluidine diazotised para- action of on - para- action of sulphur on 228. Tolylbenzoylthiocarbamide ortho- 622. Tolylhydrazine para- action of chloro-form and alcoholic potash on 247. Tolylthiocarbimide ortho- action of on thialdine 626. Triacet yldiamidoh ydroxynap hthyl-phenyl 124. Tribenzylphosphine oxide action of chlorine on 227. - - action of nitric acid on. 225. - action of sulphuric acid on, - - some compounds of 223. - - trinitro- 225. Triethylamine hydrochloride magnetic rotatory power of solutions of 714, 743. - magnetic rotatory power of 692, 729.Triethylsulphine salts prepamtion of, 135. Trimethylene cyanide magnetic rotatory power of '702. Triphenylbutyrolactone PROC. 138. Triphenylcrotolactone PROC. 137. Triphenylpyrazole PROC. 141. Tripropylsmine magnetic rotatory -.- ignited action of ammonia Tungsten-compounds action of ammo-- hexachloride action of a,mmonia - oxychloride action of ammonia Tungstic anhydride action of ammonium - ignited action of ammonia methylparachloraniline 436. 226. power of 694 730. on 42. nia on 41. on 44. on 43. chloride on 42. on 42. V. Vanadinite 94. Vaponr-density method of determining, applicable a t all temperatures and pressures Paoc. 1888 110. - - of hydrogen fluoride 163. Vapour-pressures of a mixture of props1 alcohol and water PROC.1888 101. - of quinoline 483. - of similar compounds of Volumes specific of benzene and its - of similar compounds of elements 486. haloid-derivatives 488. elements 486 W. INDEX OF SUBJECTS. Y. Water estimation of dissolved oxygen - expansion of PEOC. 89. - oxidation of to hydrogen per-oxide under the influence of light, - rain- analysis of 543. - estimation of ammonia in, 544. - at Rothamsted amount of nitric acid in 537. X. in 552. PROC. 134. Xenylenepyrazine 98. 789 Yttrium-group spectra of 269. Z. Zinc atomic weight of 443. - effect of on the freezing point of - mineral from a blast furnace, - molecular weight of 531 533. Zinc-lead alloys 678. Zinc-tir alloys 6’79. sodium 6’74. PROC. 67

ISSN:0368-1645    

DOI:10.1039/CT8895500779

出版商:RSC    

年代:1889

数据来源: RSC

摘要:

INDEX OF SUBJECTS. 789 ERRATA. VOL. LV. Page. Line. 16 20 from top f o r ‘( enumerate,” read (‘ enunciate.” 17 18 2 from top omit (‘brass.)’ 18 3 , f o r “ braEs,)) read (‘such a compound.” 23 7 & 8 last line after ‘( zinc,” insert ‘‘ in certain proportions.” , for (‘In fact the water at this temperature is continually giving off fundamental molecules (that is has a vapour-tension),” read (‘In the fact that water a t this temperature is continually giving off fundamental molecules (that is has a vapour-tension) we have a proof that.” 430 12 & 13 from topfor “ (m)N0,.C6H~.N,.CloH6.0H(B) . . . . . . (P)B~.C~H,.N~.C~~H,.OH(~). . . . . . . read ‘‘ (m)N0,.C6H4.N2.C,oH6.0H(P) . . . . . . ( p ) Br-C6H4-N2-CloH6-OH @) . . . . . . . 761 5 , f o r ‘( 25 455,” read “ 25 455 and 29 422.” 52 *74 ” 47 *26 I’ 4’7 -26” 52 -7 LONDON : HAPRISOh’ AND SONS PRINTERS IN ORDINARY TO HER MAJESTI, ET. MAETIX’S LANE

ISSN:0368-1645    

DOI:10.1039/CT8895500789

出版商:RSC    

年代:1889

数据来源: RSC