American Chemical Society
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Transferable Potentials for Phase Equilibria. 7. Primary, Secondary, and Tertiary Amines, Nitroalkanes and Nitrobenzene, Nitriles, Amides, Pyridine, and Pyrimidine

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journal contribution
posted on 2005-10-13, 00:00 authored by Collin D. Wick, John M. Stubbs, Neeraj Rai, J. Ilja Siepmann
The transferable potentials for phase equilibria (TraPPE) force fields are extended to amine, nitro, nitrile, and amide functionalities and to pyridine and pyrimidine. In many cases, the same parameters for a functional group are used for both united-atom and explicit-hydrogen representations of alkyl tails. Following the TraPPE philosophy, the nonbonded interaction parameters were fitted to the vapor−liquid coexistence curves for selected one-component systems. Coupled−decoupled configurational-bias Monte Carlo simulations in the Gibbs ensemble were applied to neat (methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, or triethyl-)amine, nitromethane, nitroethane, nitrobenzene, acetonitrile, propionitrile, acetamide, propanamide, butanamide, pyridine, and pyrimidine. Excellent agreement with experimental results was found, with the mean unsigned errors being less than 1% for both the critical temperature and the normal boiling temperature. Similarly, the liquid densities at low reduced temperatures are reproduced to within 1%, and the deviation for the critical densities is about 4%. Additional simulations were performed for the binary mixtures of methylamine + n-hexane, diethyl ether + acetonitrile, 1-propanol + acetonitrile, and nitroethane + ethanol. With the exception of the methylamine/n-hexane mixture for which the separation factor is substantially overestimated, agreement with experiment for the other three mixtures is very satisfactory.