Solvent, salt and high pressure effects on the rate and equilibrium constants for the formation of tri‐n‐butylphosphoniumdithiocarboxylate

Abstract

Solvent, salt and high pressure effects on the rate and equilibrium constants for the formation of tri‐n‐butylphosphoniumdithiocarboxylate at 298.2 K are reported. This equilibrium is shifted to the phosphobetaine in polar solvents, salt solutions and under high external pressure. The reaction volume changes dramatically on going from less polar diethyl ether (−69 cm3 mol−1) and tetrahydrofurane (THF) (−66 cm3 mol−1), to more polar acetonitrile (−39 cm3 mol−1) and acetone (−38 cm3 mol−1). Copyright © 2010 John Wiley & Sons, Ltd.

Aminoxyl (Nitroxyl) Radicals in the Early Decomposition of the Nitramine RDX

“…Molecular volumes were computed at the 0.001 a 0 –3 density contour using the “tight” option for Monte Carlo integration, without any vibrational corrections. These volumes are only approximate, both because of arbitrariness and error in the calculations and because effective volumes depend upon the solvating environment, sometimes dramatically. , …”

“…These volumes are only approximate, both because of arbitrariness and error in the calculations and because effective volumes depend upon the solvating environment, sometimes dramatically. 35,36 The atomic unit of energy, the hartree, is E h ≈ 2625.5 kJ/mol. The symbol E e denotes an electronic energy that does not include ZPE.…”