Predicting Temperature-Dependent Aqueous Henry’s Law Constants Using Group Contribution Methods

Abstract

A first-order temperature-dependent group contribution method was developed to predict Henry’s law constants of hydrocarbons, alcohols, ketones, and formates in which none of the functional groups are attached directly to a benzene ring. Efforts to expand this method to include ester and ether groups were unsuccessful. Second-order groups were developed at a reference condition of 298.15 K and 100 kPa. A second-order temperature-dependent group contribution method was then developed for hydrocarbons, ketones, esters, ethers, and alcohols. These methods were compared to existing literature prediction methods.

Multiphase Ozonolysis of Aqueous α-Terpineol

“…Experimental values have not been measured for the products identified in the current study, however the empirical methods of Brockbank and colleagues can be used to estimate Henry's law constants based on primary and secondary functional group analysis. 44 For example, the geometric average of the two empirical methods predict H = 684 M atm −1 for α-terpineol, in reasonable agreement with the experimental value (429 M atm −1 ). 32 The same methodology predicts lactol and lactone Henry's law constants of 2.73 × 10 7 M atm −1 and 8.70 × 10 6 M atm −1 , respectively, which corresponds to an increase by 4 orders of magnitude.…”

A potential method for comparing instrumental analysis of volatile organic compounds using standards calibrated for the gas phase

“…This approach is reasonable for systems where temperature variations do not exceed 20 K, and for compounds soluble in water. Other predictive models are used to estimate the vapour-liquid equilibrium properties, such as the UNIFAC model or computational methods based on quantum chemical calculations, although some models are designed for 298 K only [16][17][18]. Furthermore, Henry's law constant may be experimentally determined, where dynamic methods (e.g.…”

“…A high counts per second (≤10 7 cps) for H 3 O + at m/ z 19 occurs using PTR-MS, therefore detector saturation follows. For this reason, the isotope of oxygen, 18 O, is commonly used i.e. the, count rates at m/z 21 were measured to assess the counts per second of H 3 O + .…”

Framework for correlating the effect of temperature on nonelectrolyte and ionic liquid activity coefficients

“…The parameter θ i j also can be incorporated directly into an excess Gibbs energy expression. It is a common practice to represent the effect of temperature for a given binary interaction parameter using empirical expressions with 2 or more correlation constants . This is a common option offered by commercially available process simulation software .…”