Kinetics of solvolysis in water of four secondary alkyl nitrates

Abstract

Kinetic data are reported for the solvolysis in water of propane-2-nitrate, butane-2-nitrate, cyclopentyl nitrate, and cyclohexyl nitrate. In each case, the dependence of rate constant on temperature is analysed in terms of two mechanisms for the solvolytic reaction. First it is assumed that the rate constant describes a single step reaction, the analysis leading to estimates of the heat capacity of activation ΔCp≠. Three different analytical methods are discussed in this regard. Second it is assumed that the rate constant describes a two stage mechanism, the first stage being reversible. In this case the explanation of the ΔCp≠ term calculated according to the first mechanism is quite different. We comment on the alternative explanations of trends in activation parameters.

Alkyl nitrates and bifunctional nitrates of atmospheric interest: Henry's law constants and their temperature dependencies

“…Solvolysis of organic nitrates in liquid water must therefore be considered as a potential loss mechanism in the environment and in sampling systems. Solvolysis rate constants ksojv of 2-propyl-and 2-butyl nitrate at elevated temperatures have been reported by Robertson et al (1981). These data extrapolate to kso~v < 10 -7 s I at room temperature, which is by far too slow to affect atmospheric lifetimes of weakly soluble alkyl nitrates.…”

Foliar uptake of atmospheric organic nitrates

“…Organic nitrates are not particularly chemically reactive [ Roberts , 1990] and are only slightly soluble in water (Henry's Law constant is 0.74–1.6 M/atm at 295K for similar nitrates) [ Roberts , 1990]. They hydrolyze in acidic or neutral solutions at a rate of 10 −5 to 10 −3 s −1 at room temperature [ Robertson et al , 1981; Kames and Schurath , 1992]. There are 3 possible pathways for hydrolysis of organic nitrates [ Baker and Easty , 1950; Connon , 1970].…”

NO problem for nitroglycerin: organic nitrate chemistry and therapy

“…as a leaving group in solvolytic studies on the S N 2/S N 1 continuum. 11 No detailed chemical studies of the reaction of nitrate esters with other nucleophiles, such as mercaptans, have been pursued.…”