Irvine J. Solomon

The decomposition of NF4AsF6

Abstract NF4AsF6 decomposes smoothly at 175° and above, to the starting materials NF3, F2 and AsF5. The decomposition has been followed by total pressure measurements and found to obey the equation P 3 2 = At + B This has been interpreted in terms of an equilibrium dissociation step NF4AsF6 NF5 + AsF5 followed by irreversible decomposition of the unstable NF5 NF5 → NF3 + F2 The latter step is taken to be a 3 2 -order reaction: d P d t = k1PnPa 1 2 where Pn is the partial pressure of NF5 and Pa that of AsF5. Taking the equilibrium into account, the above equation is integrated to yield Pa 3 2 - (P0a 3 2 = 3k1Keqt/2 An attempt to identify NF5 in the products by matrix isolation methods yielded, besides the expected NF3 and AsF5, an unknown minor product which appeared not to contain nitrogen.

Formation of benzene polycarboxylic acids in the oxygen oxidation of solid by-products from coal-conversion processes (CCP) in an alkaline medium

Abstract Solid and liquid carbonaceous by-products have been obtained in both coal gasification and liquefaction processes. A study of the oxidation of the solid by-products was undertaken to determine what commercial chemicals could be derived from these materials. The oxygen oxidation of various coal-conversion-process by-products in 10% aqueous sodium hydroxide was investigated at 250 °C and a total pressure of 8.27 MPa (gauge). The products isolated were carbon dioxide and the organic extract, a complex mixture of aliphatic and aromatic acids. The benzene polycarboxylic acids were the major component of the organic extract.

Gas‐phase electron paramagnetic resonance absorption in nitric oxide. II. The effects of nitrogen‐15 and oxygen‐17 and 18 substitution

The X‐band EPR investigation of the six isotopically related molecules of nitric oxide synthesized from 14N, 15N, 16O, 17O, and 18O has been completed. Perturbation theory applied to Hund’s case (a) representation for nitric oxide yielded excellent agreement with experiment. Linear relationships were found between the g values and the reduced mass, and between the field uncoupling splittings and the reciprocal of the reduced mass, which is indicative of the relationship of these values to the rotational constant, B0. The value of the spin orbit coupling constant was determined to be 123.27 cm−1 in agreement with the value of James and Thibault (Ref. 7), 123.16±0.020 cm−1. The nitrogen‐15 hyperfine splitting constant was found to be 38.41±0.19 G. The oxygen‐17 hyperfine lines revealed a measurable quadrupole effect and the oxygen‐17 hyperfine splitting constant was determined to be 57.6±0.4 G.