The effects of some catalytic substances to the velocity of azotation of both powdered and “granular” carbide were experimentally determined. 1. There is an optimum quantity of calcium fluoride to be added to the carbide to get the highest velocity of azotation, the quantity of which is a function of both carbide and reaction temperature. 2. The added substances not only have some influence upon the velocity, but also change the characteristics of the velocity curves of azotation. 3. Carbon and carbon containing substances or those which sets carbon free from carbide show strong catalytic action to the azotation of calcium carbide. The opinion that the nascent carbon must be acting as a catalyser is supported.
(1) 0.1–0.7 Per cent. solution of potassium propionate gave neither ethylene nor signs that the solution had undergone any oxidation, when electrolysed by passing a current of DA = 10 A/dm2. at 9–12°C. (2) When 1.0% potassium propionate solution was electrolysed under the same conditions, ethylene was produced, and at the same time oxidizing action of the solution became observable. Hydrogen peroxide was also found present. (3) The presence of ammonium carbonate proved so effective as to produce ethylene even from the most dilute solution. Ethylene formation was always accompanied by oxidizing action of solutions in all cases alike. (4) Electrolyses of a solution containing 5.0 gr. potassium propionate and 2.0 gr. propionic acid and the one containing 5.0 gr. potassium propionate and as much ammonium carbonate, each in 100 c.c, were investigated. (5) The assumption of propionyl peroxide at the intermediate product provides a very satisfactory explanation of Kolbe’s Reaction and also of other reaction related to it in the electrolysis of a propionate; the production of ethylene, hydrogen peroxide and similar oxidizing substances may all be explained to take place according to the following scheme : (C2H5COO)2+H2O = C2H5COOH+C2H5COOOH, C2H5COOOH = CO2+H2O+C2H4 (Ethylene formation), C2H5COOOH+H2O = C2H5COOH+H2O2 (Hydrogen peroxide formation). (6) The difference observed between electrolyses of potassium propionate and potassium acetate will easily be understood, if we take notice of the higher stability of propionyl peroxide in comparison with acetyl peroxide.
Iron and nickel were co-deposited in various proportions electrolytically from their mixed sulphate solutions, and X-ray diffraction patterns were photographed by the Debye-Scherrer and Seemann-Bohlin methods, and the lattice constants were measured by choosing lines of copper as a standard which was mixed with the alloys in the form of powder. The results obtained were as follows. (1) Iron and nickel in the deposit appears as solid solution. The homogeneity of the solid solution thus formed seems not so good as that of the alloy solidified from the melt. (2) The co-existence of α and γ solid solutions is also observed in the deposits the concentration of which ranged from 14% Ni to 58% Ni. In the alloys solidified from the melt this ranges from 25% Ni to 33% Ni. (3) Lattice constant of α or γ solid solution increases slightly at first, reaches maximum and then decreases as the constant of Ni or Fe increases respectively. From these results it has been concluded that when the total or local concentration of the one metal in the deposit is small, two cases may arrise either the metal is forced to deposit among the crystal of the other metal without forming its proper crystal lattice forming pseudo solid solution as a result or the unit mass of the deposited crystal of that metal is small and consequently it easily diffuses into the other after the deposition. This is the reason why the lattice constant-concentration curve runs upward. But when the concentration is fairly large, the unit mass of that crystal also becomes larger and its diffusion into the other takes place not so easily as before leaving some of that crystal undiffused. This tendency becomes greater as the concentration of that metal increases. The existence of the maximum point on the curve above mentioned and the coexistence of α and γ solid solutions in a wider range of the composition of the deposited alloy are explained sufficiently by the process of deposition above supposed.