(3) Pure Ammonium Chloride prepared from Ammonium Oxalate. Strength of solution. 2.5 per cent. Description of spectrum. Spectrum continuous to 1/A 4556 (λ 2195), but weak beyond /λ 4422 (λ 2261). Complete absorption beyond / 4422 (A 2261) except for line showing faintly at 1/λ 4656 (a 2148. The spectrum here is practically complete, and photographs of weaker solutions show little or no difference. (4) Ammonium Chloride prepared by the reduction of Hydroxylamine. Solution containing 2·5 grams ammonium chloride in 100 c.c. Spectrum continuous to 1/a 4411 (λ 2267), but weak from 1/λ 3886 (λ 2573). No indication of selective absorption. (5) Pure Ammonium Chloride mixed with Pyridine. Solution containing 2.5 grams ammonia and 0.0001 gram pyridine in 100 c.c. Spectrum continuous to 1à 3521 (λ 2840). Complete absorption beyond. Solution containing 2.5 grams ammonia and 0.00001 gram pyridine in 100 c.c. Spectrum continuous to /A 3638 (λ 2749). Absorption Band from 1/λ 3638 (λ 2749) to 1⁄4λ 4306 (λ 2322). Weak prolongation of spectrum to 1/λ 4555 (à 2195) (6) Pyridine Hydrochloride in Distilled Water. Solution containing 0·0001 gram pyridine in 100 c.c. Spectrum continuous to 1à 3568 (A 2803). Complete absorption beyond. Solution containing 0·00001 gram pyridine in 100 c.c. Spectrum continuous to 1/A 3638 ( 2749). Absorption Band from 1/ 3638 (a 2749) to λ 4306 (λ 2322). Weak prolongation of spectrum to 1/ 4555 (A 2195). (7) Methylamine Hydrochloride. Solution containing 2.5 grams methylamine in 100 c.c. water. Spectrum practically the same as No. 3 (pure ammonia), with the weakening towards the end of the violet somewhat more pronounced, (8) Hydroxylamine Hydrochloride, Solution containing 2.5 grams hydroxylamine in 100 c.c. water. Thickness of layer of solution 150 mm. Spectrum continuous to 1/ 4413 (λ 2266), but very weak from 1/ 3886 (^ 2578). 1.25 grams acetaldoxime in 100 c.c. water. Thickness of layer of solution = 150 mm. Spectrum continuous to 1/λ 3323 (à 3009). Complete absorption beyond. Thickness of layer. 1 mill.-mol. in 20 c.c. water. Description of spectrum. mm. 25 Spectrum continuous to 1/ 3952 (A 2530). Lines showing very (λ 2486). Complete Spectrum continuous to 1/λ 4034 (λ 2479). Complete absorption beyond. Same as 20 mm., but portion of spectrum between / 3921 (λ 2550) and/λ 4034 (a 2479) somewhat stronger. Same as 15 mm., with very faint indication of prolongation to 1/λ 4125 (λ 2424). Spectrum continuous to 1/λ 4125 (λ 2424) with faint indication Spectrum continuous to 1/λ 4176 (λ 2394). Spectrum continuous to 1/λ 4176 (λ 2394). Spectrum continuous to 1/A 4321 (A 2314). Complete absorption Lines showing at 1/λ 4321 (λ 2314). Line showing at 1/λ 4368 (λ 2289) and 1/ 4417 (λ 2264). Complete absorption Same as 2 mm., but somewhat stronger. With further dilution Ketoxime. 1 mill.-mol. in 20 c.c. water. Description of spectrum. There is no in Thickness of layer. mm. 25 Spectrum continuous to 1/λ 3886 (λ 2573). Complete absorption Spectrum continuous to 1/x 3900 (x 2564). beyond. Complete absorption /A 3924 (λ 2548). Complete absorption Same as 10 mm., with faint indications of lines at 1/ 3963 (λ 2523) and 1à 4002 (λ 2499). Spectrum continuous to /A 4039 (x 2476). Same as 4 mm., but stronger. Spectrum continuous to 1/X 4039 (x 2476), with lines showing at 1/λ 4115 (λ 2480) and 1/x 4125 (λ 2424). Spectrum continuous to 1/a 4125 (λ 2424). Strength of solution. Ketoxime-(continued). 1 mill.-mol. in 100 c.c. Description of spectrum. mm. 3 Spectrum continuous to 1/λ 4176 (λ 2394). Complete absorption beyond, except for lines at 1/λ 4245 (λ 2356) and / 4321 (λ 2314). Spectrum continuous to 1/a 4176 (λ 2394), with faint prolonga. tion to 1/λ 4414 (λ 2265). Spectrum continuous to 1/λ 4414 (λ 2265), with lines at 1/a 4540 (λ 2203) and 1/a 4555 (a 2195). We have to express our indebtedness to Mr. Alex. Lauder, of the University College of North Wales, Bangor, for the very valuable assistance which he has rendered us in carrying out a great part of this investigation. XXX.—Ammonium Amidosulphite. By EDWARD DIVERS and MASATAKA OGAWA. THE interaction of such familiar gases as ammonia and sulphur dioxide ceased, sixty years ago and more, to attract the attention of investigators, notwithstanding comparatively nothing had then been definitely made out as to the nature of the product, even the few statements concerning it which occur in some of the best treatises on chemistry having but little experimental foundation. The history of the subject is briefly given on p. 331. Dry Sulphur Dioxide and Ammonia. Although sulphur dioxide and ammonia, even when comparatively well dried, unite at once and with great energy, yet if sufficient care has been taken to exclude moisture they do not combine. It has not been necessary, however, in order to demonstrate this striking phenomenon, to have resort to the elaborate precautions adopted by Brereton Baker in his well known experiments upon the non-union of hydrogen chloride and ammonia (Trans., 1894, 65, 611; 1898, 73, 422). As sulphur dioxide could be dried better than ammonia, using commercial phosphorus pentoxide for the purpose, we were successful in mixing the gases without their combining only on passing the dioxide first. The preparation flask, with its tubes, having been heated and then kept for a time in the desiccator, was placed in ice and salt, and a slow current of sulphur dioxide sent through it, the gas having been dried by passing it first through tubes of sulphuric acid and then of phosphorus pentoxide. The outlet-tube dipped into mercury. Ammonia, dried first by cooling in a freezing mixture and then by passing it through long tubes of freshly fused and crushed potassium hydroxide (but no Stas's mixture) was now also passed into the flask slowly. The result was that the interior of the flask remained clear for some minutes, the mixed gases only combining on their escape through the mercury into the air with the production of white fumes of ammonium pyrosulphite; but after a time, the ammonia having, it is presumed, gradually brought in moisture along with it, through passing more rapidly along the tubes than at first, the walls of the flask became suddenly coated with an orange-coloured deposit, whilst the mercury rose high in the exit tube. Proportions in which Sulphur Dioxide and Ammonia Combine. The proportions in which ammonia and sulphur dioxide combine, or appear to combine, depend largely on the extent to which the temperature is allowed to rise, the heat of union being considerable. They vary also according as one or other of the gases is in excess, unless the temperature is kept very low. But variation in the proportions, as well as apparent condensation of additional sulphur dioxide by a sufficiently ammoniated product, is clearly due to secondary changes (p. 330). If the temperature is kept low, ammonia unites with sulphur dioxide, especially if the ammonia is in excess, in the proportion of two volumes of the former to one of the latter (p. 330), but since, at the ordinary temperature, this union is immediately followed by a decomposition in which ammonia is evolved, the union of the two gases may appear to take place in other proportions than those just mentioned. It is pretty certain that, by proceeding slowly enough and using strong cooling agents, secondary action can be almost entirely prevented, and the statement just made be verified even when working with the gases alone. We have not striven to make a very close approximation to such a result, because a simple modification of the method enabled us to exclude all secondary action. Our experimental work, which is referred to further on (p. 332), has shown that much more nearly two volumes than one volume of ammonia can be made in this way to unite with one volume of sulphur dioxide, the only proportions which Rose met with in his experiments (p. 332), and that the presence of much ammonium amidosulphite in the product can be established with certainty, Preparation and Analysis of Ammonium Amidosulphite. In order to get the primary product of the union of sulphur dioxide with ammonia in an unchanged state, ether was made use of. The ether, freed from alcohol and water by treatment with sodium, was contained in a small flask, fitted with inlet and outlet tubes, which was to serve, not only for the production of the new substance, but for its isolation and its weighing for analysis. The flask was put in a bath of ice and salt, with the outlet tube dipping into a trough of mercury, and the ether was saturated with dried ammonia; having shut off the ammonia, a very slow current of sulphur dioxide was then sent into the solution while the flask was continuously shaken, not only in order to diffuse the heat, but to prevent the product from caking on to the bottom of the flask and enclosing ether. The mouth of the tube containing the sulphur dioxide soon became filled with a yellow, pasty mass (p. 330), and had to be kept open by a platinum rod, manipulated through the rubber tubing above, but the precipitate itself was quite white and powdery. In spite of the external cooling, the heat of combining was sufficient to cause ammonia gas, saturated with ether vapour, to escape through the mercury sealing the exit tube, and when this escape became slight, the passage of sulphur dioxide was stopped. Using about 20 c.c. of ether, more than a gram of the substance was obtained. In order to secure this undecomposed, a second flask was put in connection with the preparation flask, and ammonia again passed to the saturation point. The ammoniated ether was decanted off through the connecting tube into the second flask, which was then detached, and the ether adhering to the precipitate was removed by passing a current of ammonia over the precipitate in the flask for some hours, the whole operation being carried out in the freezing mixture. There was no other means of completely drying the salt, and even this was not altogether successful if the salt had been allowed to cake together. Neither air nor hydrogen could be used in place of ammonia for drying the salt, nor could the flask remain out of the freezing mixture so long as ether still moistened the salt, without the latter acquiring an orange colour. When dry and in an ammoniacal atmosphere, the salt is more stable, but cannot long be kept at the ordinary temperature without becoming discoloured through decomposition. Analysis.—The stopper carrying the gas tubes having been replaced by a plain one, and air allowed to displace most of the ammonia gas, the flask was at once weighed and left for a time inverted with the open mouth dipping into 100 c.c., or more, of water in a beaker. When the salt in it had become damp, it was washed into the water, and its very dilute solution distilled with alkali to determine the ammonia, |