Thermal decarboxylation of acetate. Part I. The kinetics and mechanism of reaction in aqueous solution

Abstract

In an effort to understand the kinetics of the thermal decarboxylation of acetate and the role of catalysis, a series of laboratory experiments were conducted to measure the rate constants for the decomposition of acetate (acetic acid and sodium acetate) in the presence of titanium, silica, stainless steel, gold, and magnetite. Activation energies for decarboxylation of acetic acid and acetate ion range from about 8 kcal mol −1 in stainless steel vessels to 69 kcal mol −1 in silica tubes. Extrapolated rate constants at 100°C for acetic acid differ by more than fourteen orders of magnitude between the experiments conducted in stainless steel and the catalytically least active titanium vessels. Gold and titanium were the least active catalysts for the acetic acid substrate, while stainless steel, silica, and magnetite showed marked catalytic effects. Methane and carbon dioxide were the predominant reaction products of most of these experiments, although mass spectrometric analyses of the gas phase revealed concentrations of carbon monoxide and hydrocarbons (apparent mass range from 29 to 56) amounting to as much as 55 mole percent of the total volatile products, depending on the catalyst. The reactions were generally first order in acetic acid or acetate ion, except for those involving the acid over silica and magnetite which were zero order. These results and the observed effects of variations in surface area are rationalized in terms of changes in the mode of surface catalysis. The mechanistic assignment is simplified by the existence of three unique straight lines on an isokinetic plot ( i.e., activation enthalpy versus activation entropy) which fit all the respective first- and zeroorder reactions. The results described here provide the nucleus for the discussion in Part II of the role of acetate in the primary migration of methane and the transportation of metals in hydrothermal solutions.