TY  - JOUR
A1  - Awasthi, Neha
A1  - Ritschel, Thomas
A1  - Lipowsky, Reinhard
A1  - Knecht, Volker
T1  - Standard gibbs energies of formation and equilibrium constants from ab-initio calculations covalent dimerization of NO2 and synthesis of NH3
JF  - The journal of chemical thermodynamics
N2  - Standard quantum chemical methods are used for accurate calculation of thermochemical properties such as enthalpies of formation, entropies and Gibbs energies of formation. Equilibrium reactions are widely investigated and experimental measurements often lead to a range of reaction Gibbs energies and equilibrium constants. It is useful to calculate these equilibrium properties from quantum chemical methods in order to address the experimental differences. Furthermore, most standard calculation methods differ in accuracy and feasibility of the system size. Hence, asystematic comparison of equilibrium properties calculated with different numerical algorithms would provide a useful reference. We select two well-known gas phase equilibrium reactions with small molecules: covalent dimer formation of NO2 (2NO(2) reversible arrow N2O4) and the synthesis of NH3 (N-2 + 3 H-2 reversible arrow 2NH(3)). We test four quantum chemical methods denoted by G3B3, CBS-APNO, W1 and CCSD(T) with aug-cc-pVXZ basis sets (X = 2, 3, and 4), to obtain thermochemical data for NO2, N2O4, and NH3. The calculated standard formation Gibbs energies Delta(f)G degrees are used to calculate standard reaction Gibbs energies Delta(r)G degrees and standard equilibrium constants K-eq for the two reactions. Standard formation enthalpies Delta H-f degrees are calculated in a more reliable way using high-level methods such as W1 and CCSD(T). Standard entropies S degrees for the molecules are calculated well within the range of experiments for all methods, however, the values of standard formation Gibbs energies Delta(f)G degrees show some dependence on the choice of the method. High-level methods perform better for the calculation of molecular energies, however, simpler methods such as G3B3 and CBS-APNO perform quite well in the calculation of total reaction energies and equilibrium constants, provided that the chemical species involved do not exhibit molecular geometries that are difficult to handle by the applied method. The temperature dependence of standard reaction Gibbs energy Delta(r)G degrees for the NH3 reaction is discussed by using the calculated standard formation Gibbs energies Delta(f)G degrees of the reaction species at 298.15 K. The corresponding equilibrium constant K-eq as a function of temperature is found to be close to experimental values.
KW  - Equilibrium constants
KW  - Thermochemical properties
KW  - Ab-initio calculations
Y1  - 2013
U6  - https://doi.org/10.1016/j.jct.2013.03.011
SN  - 0021-9614
VL  - 62
IS  - 3
SP  - 211
EP  - 221
PB  - Elsevier
CY  - London
ER  -