Studies on the Discharge Reaction in Liquid Ari. II : On the Thermal Secondary Reaction

The thermal reactions under discharge and reactions between the discharge reaction products during the rise of temperature after discharge were discussed from the following thermal reactions : 1) between NO and (NO_2)_2 above -85℃, 2) between nitrogen trioxide and oxygen above -80℃, 3) between NO and oxygen at temperatures slightly above the boiling point of oxygen and very violent reaction at -165℃, 4) explosive reaction between nitrogen trioxide and ozone at -100℃, 5) explosive reaction between (NO_2)_2 and ozone at -40℃. The reactions 4) and 5) sometimes proceeded nonexplosively forming N_2O_5 and oxygen. The green product of the discharge reaction was compared with the product of the similar colour obtained by passing NO into liquid oxygen, and the difference between them was ascertained. The compound such as NO_3 or N_3O_4, which had been believed by other authors to be a product of the latter reaction was not detected

Studies on the Discharge Reaction in Liquid Air. I : On the Discharge Reaction Products

Applying high tension from an induction coil or from a transformer, discharge reactions in liquid air were studied. The reaction products were examined by vapor pressure method, that is, by comparing the vapour pressure curves of the products with those of the known compounds. The results varied with the kinds of high tension sources and were very different from those of other authors ; especially, the yield of ozone varied markedly with the current intensity and type of discharge. By raising the temperature after discharge, reactions and products were investigated. NO_2 or (NO_2)_2, nitrogen trioxide and N_2O_5 were ascertained. An explosion due to decomposition of ozone often occurred at about -100℃. The green coloured solid product was supposed to be a mixture of (NO_2)_2 and nitrogen trioxide. A higher oxide of nitrogen such as NO_3 was not obtained in the reaction

Studies on the Discharge Reaction in Liquid Air. III : On the Mechanisms of Nitric Oxide- and Ozone-Formation

The emission spectra and the current-wave forms were obtained from the discharge in liquid oxygen, liquid nitrogen and liquid air. From the results obtained, the mechanisms of NO- and ozone-formation were discussed. It was concluded that NO was produced by the reaction between N_2 (B^3II_g) and O_2 (ground), and that ozone was formed by the reaction between O (ground) and O_2 (ground) at a very early stage of the spark discharge characterized by the emission of the continuous spectrum, being hardly formed through the exothermic arc discharge

On the Explosion of Air-Rectifying Apparatus. II

Following reactions at very low temperatures were tried which may be possible to become a cause of explosion of an air-rectifying apparatus : (1) reactions between acetylene and products of discharge reaction in liquid air, (2) reactions between ethylene and ozone, (3) reactions between nitric oxide and ozone. Explosions occurred in these several experiments. It is discussed that an explosion of an air-rectifying apparatus may occur from ozone or atomic oxygen formed by electric discharge of particles which are charged through streaming in the apparatus

Note on the Free Volume of a Liquid

Assuming the Hildebrand\u27s relations concerning the internal energy of liquid and using the Clausius\u27 virial theorem, a general equation of state of liquid was obtained. Combining this equation and the partition function of liquid, the free volume was derived as the function of molal volume of liquid. This results were compared with the Eyring\u27s free volume of liquid in the case of ethyl ether. The disagreement between the two kinds of the free volumes is due to the neglect of dependency of the dimension of molecule upon the molal volume of the liquid. In conclusion, the author wishes to express his hearty thanks to Prof. E Kanda for his helpful advices and kind guidance through this work and also to T. Sugawara and T. Haseda for their valuable discussions