On the Manufacture of Sulphur from Alkali Waste in Great Britain. The author called attention to a new industry-the recovery of sulphur from alkali waste, which had made very rapid progress during the past few years. The importance of the subject had been very ably pointed out in 1861 by Mr. Gossage, in a paper "On a History of Soda Manufacture." Mr. Gossage stated that twofifths of the total cost for raw materials used for the production of a ton of sodaash was incurred for pyrites from which to procure a supply of sulphur; and it was well known that nine-tenths of this sulphur was retained in the material called alkali waste, which was thrown away by the manufacturer. A problem was thus presented for solution, which, if it could be effected, would cause a large reduction in the cost of soda. The author stated that the problem had been very near a satisfactory solution, and called attention to a process with which his name was connected. He took out a patent in 1863 for the process, and its merits had been very fully recognized in this country. The process was carried out in the following way:The first product of Leblanc's famous process for the manufacture of soda, called rough soda or black ash, was now almost universally lixiviated with water in an apparatus which was first used for this purpose in Great Britain, and was composed of a number of iron tanks connected in a very simple manner by pipes and taps, &c., so as to allow the water to enter a tank filled with black ash already nearly spent, and thence to flow through others filled with black ash richer and richer in alkali, until it met fresh black ash in the last tank, thus becoming an almost concentrated solution of alkali before leaving the apparatus. The alkali waste, or insoluble residue of the black ash, remained thus in these tanks deprived of alkali, and as it had been immersed in the liquor throughout the whole time of lixiviation, it was consequently obtained in a very porous cordition. The tanks were always provided with a false bottom. The whole process of oxidation and lixiviation of the waste, though it was repeated three times, was finished in from sixty to seventy-two hours. When the waste left the tanks, all the recoverable sulphur had been taken out of it, and could no more give rise to the dreadful exhalations of sulphuretted hydrogen, or to the formation of those well-known yellow drainage liquors which had hitherto caused the waste to be so great a nuisance, the one poisoning the air and the other the water in the neighbourhood of the vast heaps of waste surrounding many works. Almost all the sulphur left in the waste existed in the form of sulphite and sulphate of calcium, which were both innocuous; and together with the carbonate and hydrated oxide of calcium, as well as with a little soda, alumina, and soluble silica, which were all to be found in the waste, made this waste a very valuable manure for many soils and crops. By other processes which the author explained, he obtained sulphur of a dark colour, the waste from which was turned to advantage and made comparatively harmless. By the author's processes fully one-half of the sulphur contained in the waste was recovered. The cost was small. A plant for the recovery of 10 tons of sulphur per week would be about £800; and the sulphur could be made at £1 per ton. The recovered sulphur being very pure, was not used to replace pyrites in the manufacture of soda; but for purposes where Sicilian sulphur or brimstone had hitherto been employed, this Sicilian sulphur having a much higher value than the sulphur in pyrites, and averaging upwards of £6 per ten. And so large were the quantities of brimstone used, that the British alkali trade, in spite of its enormous extent, could only produce a small portion of the sulphur yearly exported from Sicily, which country had hitherto had the monopoly of the supply of this article. On Chloride of Methylene obtained from Chloroform by means of Nascent Hydrogen. By W. H. PERKIN, F.R.S. From the history of morocarbon derivative, as it stands at present, it would appear that there exist several bodies isomeric with each other; thus we have the description of two bromides of methyl, the one liquid and the other gaseous; two chlorides of methylene, the one boiling at 30°.5 C., and the other at 40° C., &c. Yet it is considered by some chemists that this isomerism is improbable, and that these substances, if reexamined, would be found to be identical. This question being one of considerable importance, and bearing upon the nature of the derivative of not only carbon but probably of all other polyatomic elements, the author commenced a fresh examination of some of these monocarbon derivatives, hoping that an experimental comparison of their properties might in some degree help to a solution of this problem." In this communication only a short account was given of some experiments upon the chloride of methylene, obtained from chloroform by means of nascent hydrogen, and which had been previously used by Dr. Richardson as an anæsthetic. The reagents employed were powdered zinc and ammonia, which react with violence upon chloroform. The chloride of methylene obtained by this method boiled at about 40°5 to 41° C., and would therefore appear to correspond to that obtained by Butlerow from the iodide of methylene. Its formula was determined by combustion and Gay-Lussac vapour-densities, and these gave results showing it to have the composition CH, CÎ2. The author proposes to examine the products of decomposition, and also to prepare a quantity of Regnault's chloride of methylene from chloride of methyl and chlorine, that he may compare these two substances. Note on the Preparation of some Anhydrous Sodium Derivatives of the Salicylic Series. By W. H. PERKIN, F.R.S. In the preparation of salts or other metallic derivatives of organic bodies by means of oxides, there is always an equivalent of water produced, unless the substance acted upon be an anhydride; therefore if the resulting compound has any tendency to form hydrated products, such are nearly sure to be produced, and it often happens that it is difficult or impossible to remove this combined water. Having to prepare a quantity of the hydride-of-sodium salicyl in an anhydrous state, it appeared desirable, if possible, to obtain it anhydrous at once, and thus avoid the blackening and loss which it is subject to unless dried very rapidly. This object was effected by employing sodium-alcohol instead of a solution of hydrate of sodium, alcohol only being liberated when this substance enters into double decomposition with the hydride of salicyl. The hydride-of-sodium salicyl obtained in this manner is perfectly anhydrous, and of a beautiful pale primrose-yellow colour. By treating salicylic acid with sodium-alcohol, a new sodium derivative, crystallizing in needles, was obtained. This product contains two equivalents of sodium, and therefore corresponds to the dimetallic derivatives of Piria. It has the following composition, C, H, Na, O,. Salicine also yields a sodium derivative, when treated with sodium-alcohol, having the formula C1, H, NaO,. This body is but slightly soluble in alcohol, and not very crystalline. It is deliquescent. 13 17 On Sulphocyanide of Ammonium. By Dr. T. L. PHIPSON, F.C.S. In this paper the author alludes, first, to the estimation of sulphocyanogen in a mixture of sulphate, chloride, and sulphocyanide of ammonium. He effects this by precipitating the slightly acid solution by a mixture of equal equivalents of sulphate of protoxide of iron and sulphate of copper. The precipitate dried at 100° C. contains Cu2, C2 NS2. Attention is next called to some properties of sulphocyanide of ammonium. The author finds that this salt produces a great degree of cold in dissolving rapidly in water. Half a litre of water at 96 C., poured on 500 grms. of the impure salt extracted from gas-liquor, caused the thermometer to sink to 2°. In a more exact experiment, 35 grms. of pure sulphocyanide of ammonium, stirred rapidly with 35 cub. centims of water at +26° C., the thermometer descended in a few seconds to 10; the moisture of the atmosphere condensed itself in plates of thin ice on the exterior of the glass vessel. It is next shown that the alcoholic solution of this salt presents the peculiar phenomena of supersaturation in the highest degree. The action of iodine, bromine, and chlorine upon sulphocyanide of ammonium is very remarkable. These bodies are absorbed in large quantities by the concentrated aqueous solution of the salt, and when it is heated the compound called sulphocyanogen is precipitated. This was submitted to analysis, with the following results: which agrees with the formula C H2 N' S O, formerly admitted by Herr Voelkel, and not with that of Laurent and Gerhardt, which demands 24 of N, and nearly 55 of S (C® N3 HIS); these authors, however, estimated only the CH and S; their nitrogen was obtained by difference. In dilute solutions the action of chlorine oxidizes the sulphur of the sulphocyanide, and no precipitate is formed. The crystals of sulphocyanide of ammonium appear to be derived from the right rectangular prism; they are often very fine, and sometimes grouped together in wide crystalline plates several inches broad. General Outline of an original System of Chemical Philosophy, comprising the Determination of the Volume-equivalents, as also a new Theory of the Specific Volumes of Liquid and solid Substances. By OTTO RICHTER, Ph.D. In this paper the author proceeds upon the hypothesis that the chemical elements consist not of individual atoms, but of entire groups of such atoms, in other words, of molecules. The various kinds of elementary molecules agree in being, each and all, built up of precisely the same number of atoms, which are symmetrically disposed with reference to the three axes of space, according to the same fundamental plan of arrangement. The constituent atoms of these elementary molecules are each and all endowed with the same three fundamental properties of gravity, original elasticity, and electrical energy, and these properties vary in range and intensity with each species. In harmony with the common practice, the chemical elements are divided into the two principal classes of the metals and the non-metals, represented respectively by the general formulæ Mt, and Nt. The constituent atoms of the molecules, from the simplest to the most complex, are further supposed to be in a perpetual state of vibration, in which they perform a series of periodical contractions and expansions, and thus, in their final effect, establish between contiguous molecules a permanent tendency to repulsion, the result of which is the formation of a certain space round the centre of each molecule, which constitutes its specific volume, and is always directly proportional to the number of atoms set in motion. The volume-equivalents represent the maximum specific volumes which the elementary molecules are capable of realizing; and the peculiar force, under the influence of which the vibratory movements of the atoms may ad libitum be arrested or restored, is called "the paralytic force.” The order in which this force performs its operations in the complex molecules materially depends upon the particular position which the various constituents occupy in the system relatively to each other. This law of Rankorder is indicated in the table of chemical equivalents, in so far as any chemical element which stands to the left or to the right of any other is supposed to occupy in a certain sense a similar position in comparison with any other with which it happens to be associated as a constituent member of the same type. The science of chemistry is divided into two parts, "Pondo-chemistry and Impondo-chemistry." The former treats exclusively of the molecular arrangement of the constituents, the latter exclusively of their specific volumes. Pondo-chemistry is divided into the two principal sec tions of meta-chemistry, which is subject to the dominion of the principle of polarity, and includes eleven distinct types, and of para-chemistry, which is subject to the principle of parality, and includes three distinct types or forms of molecular grouping. After giving a general description of these various types, the author discusses the law of volume-harmony, according to which the volumes of the constituent members of a given volume-harmonious molecule are always reducible to some simple ratio contained in the volume-harmonious scale: 1: m×1;1:m×2;2: m×3; 3: m×4; 4:m×5; 5:m×6; 6:m×7, where m represents some integral number. The volume-harmonious molecules are divided into two classes. The first class comprises all those compounds where the water of crystallization is excluded, and the second class all those compounds where the water of crystallization is present. As regards the latter class, it is a characteristic peculiarity that in the process of reduction the saline molecule, with every fresh addition of one molecule of water of crystallization, experiences a loss in volume amounting always to a constant quantity. This quantity remains unaltered so long as this loss in volume is caused by the successive paralysation of its envelope-molecules; but when this process of reduction extends to the molecules of the nucleus, the constant quantity in some cases continues the same, but in general it merges into another constant quantity. Further details, in particular as regards the various conditions and rules intended to guide the student in the volume-analysis of the molecules belonging to the parachemical system, are contained in the original paper. Analysis of the Roman Mortar of Burgh Castle, Suffolk. The samples of ancient Roman mortar which form the subject of this memoir, were detached for the purpose of analysis in the years 1863 and 1866. They all had the reddish colour (due to the admixture of pounded brick) which is considered to be characteristic of a Roman origin. The details of construction, dimensions, and other particulars relating to Burgh Castle, the Garianonum of the Romans, were briefly described, and a water-colour sketch of the castrum exhibited. The walls, which are of rubble masonry and about six feet in thickness, are faced with flints and triple layers of red tiles, set with great regularity. Adopting Mr. C. Roach Smith's opinion respecting the antiquity of the castrum, the chemical problem resolved itself into a study of the following leading points in reference to the hardening of the mortar, and changes occurring during a period of about fifteen centuries, viz. : 1st. To what extent the hydrate of lime becomes recarbonated by exposure to air? 2nd. What is the physical condition of the carbonate so produced? and 3rd. Whether in this long interval the silica and lime can directly unite with each other? The conclusion to which the author was led by the chemical examination of the ancient mortars from Burgh, Pevensey, and other Roman castra, is that the lime and carbonic acid are invariably united in monatomic proportions as in the original limestone rock, and that there is no evidence of the hydrate of lime having at any time exerted a power of corroding the surfaces of sand, flint, pebbles, or even of burnt clay, with which it must have been for lengthened periods in contact. Further, that the water originally combined with the lime has been entirely eliminated during this process of recarbonation, and, this stage passed, the amorphous carbonate of lime seems to have become gradually transformed by the joint agency of water and carbonic acid into more or less perfectly crystallized deposits or concretions, by virtue of which its binding properties must have been very considerably augmented. The analytical method was described, and the following results were reported as expressing the composition of the Roman mortar, and also of the red bricks or tiles, which are remarkable for their fine texture and excellent manufacture. Analysis of the Roman Mortar from S.E. Tower, Burgh. Samples II. and III. were taken from the south wall; specimen IV. from the north wall. Red Brick, or Tile, from S. E. Tower, Burgh. On the Absorption of Gases by Charcoal. By Dr. R. ANGUS SMITH, F.R.S. The author said that he had somewhat further extended his inquiries into the laws of absorption of gases, as shown by charcoal. He had some years ago said that he believed the actions were on the border between chemistry and physics, or that physical phenomena were an extension of the chemical. Last year, in a short note, he stated that the gases which he tried were absorbed in whole volumes, or volumes which were multiples of hydrogen. He had now tried other gases, with the following results:-Hydrogen, 1; oxygen, 7.99; carbonic oxide, 6·03; carbonic acid, 22.05; marsh-gas, 1001; nitrous oxide, 12.90; sulphurous acid, 36.95; common air, 40-063. Nitrogen was found to be 4.27; probably this is a little too low, as there is always some nitrogen left in the heated charcoal. These numbers are got by dividing the number of volumes absorbed by each gas by the volumes of hydrogen absorbed. They are an average of many experiments. The numbers in some cases differ considerably; it is supposed that the reason lies in the constitution of the charcoal, but it may be partly owing to the mode of working. He considered that the ultimate particles of gas rested as strata or layers in the charcoal; the outer particles were therefore less forcibly held than the more distant. The latter were also most difficult to remove. If this physical action had an analogy with chemical action, it would probably throw light upon it, and it seemed to point to compounds containing parts held together more or less loosely than other parts. The gas and charcoal form such a compound, which in a sense is not purely chemical Two of the numbers seem to be very remarkable; namely, those of oxygen and carbonic acid, as the volumes are exactly those of the weights of oxygen in water and of an atom of carbonic acid. Eight volumes of oxygen are 128 times heavier than *Found, lime 14.5, carbonic acid 11.25 per cent. |