A set of 7 Benson group additive values (GAV) together with 15 correction terms for non-nearest neighbor interactions (NNI) is developed to calculate the gas phase standard enthalpies of formation, entropies and heat capacities of monocyclic aromatic compounds containing methyl, ethyl, vinyl, formyl, hydroxyl, and methoxy substituents. These GAVs are obtained through least squares regression of a database of thermodynamic properties of 143 molecules, calculated at the post-Hartree-Fock G4 composite method. Out of the 15 NNIs, which account for several well-known substituent effects in aromatic molecules, 13 have been determined for the first time. All but two group additively calculated standard enthalpies of formation agree within 4 kJ mol 21. The entropies and the heat capacities generally deviate less than 4 J mol 21 K 21 from the ab initio results. Natural bond orbital analysis is utilized to identify the underlying causes of the observed NNIs.

The thermodynamic properties of the unsubstituted and substituted phenyl, phenoxy, anisyl, benzoyl, styryl and benzyl radicals with six substituents (hydroxy, methoxy, formyl, vinyl, methyl, and ethyl) are calculated with the bond additivity corrected (BAC) post‐Hartree‐Fock G4 method. Bond dissociation energies of monocyclic aromatic hydrocarbons are calculated and used to identify substituent interactions in these radicals. Benson's Group Additivity (GA) scheme is extended to aromatic radicals by defining 6 GAV and 29 NNI parameters through least squares regression to a database of thermodynamic properties of 369 radicals. Comparison between G4/BAC and GA calculated thermodynamic values shows that the standard enthalpies of formation generally agree within 4 kJ mol−1, whereas the entropies and the heat capacities deviate less than 4 J mol−1 K−1. © 2016 American Institute of Chemical Engineers AIChE J, 63: 2089–2106, 2017

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Summary In this study, a thermodynamic model of an active direct methanol fuel cell (DMFC) system, which couples in‐house experimental data for the DMFC with the mass and energy balances for the system components (condenser, mixing vessel, blower, and pumps), is formed. The modeling equations are solved using the Engineering Equation Solver (EES) program. This model gives the mass fluxes and thermodynamic properties of fluids for each state, heat and work transfer between the components and their surroundings, and electrical efficiency of the system. The effect of the methanol concentration (between 0.5 and 1.25 M) and air flow rate (between 20 and 30 mL cm−2 min−1) on the net power output and electrical efficiency of the system and the condenser outlet temperature is investigated. The results essentially showed that the highest value for the electrical efficiency of the system is 23.6% when the current density, methanol concentration, and air flow rate are taken as 0.2 A cm−2, 0.75 M, and 20 mL cm−2 min−1, respectively. In addition, the air flow rate was found to be the most significant parameter affecting the condenser outlet temperature.