The Effect of Hydrogen Peroxide on Nitric Oxide Formation at Combustion of the Vapor/Air/Methane Mixtures

The Corrected Values of ΔrHo(CaHbOd, a≤16) of Atomization of the Aromatic Compounds and Their Uncertainties Determined Using Several Quantum Mechanical Approaches

“…The high error in determination of OH BDE is supported by the values of residual differences, determined in the present work using the corrected values of Δ f H o 298.15 ((H 2 O 2 ) i , CORR) and Δ f H o ((CH 2 (OH) 2 ) i , CORR) (Table 5). The values of H o ((H 2 O 2 ) i , CALC) (n=32, SI, Note 1) and H o ((CH 2 (OH) 2 ) i , CALC) (n=33, SI, Note 1), calculated in the present study using the considered QM i approaches and reported previously, [6–8,9] are demonstrated, respectively, in SI, Notes 2 and 6.…”

“…As it is mentioned above, the extremely high uncertainty is only observed for the values of Δ r H o ((X n ) i , CALC), calculated using the HF/6–311++G(d,p) (SI, Note 5, black dotted line). Thus, the value of the error of the HF scaling dependency ((SE1) 6 =138, i=6) is more than 10 times higher those values ((SE 1 ) i <13 kJ/mol, i≠6), determined in the present and previous works [6–8,9] for all others considered QM i approaches.…”

“…As it is shown previously, [6–8,9] the observed inconsistencies between the values of Δ r H o ((X n ) i , CALC), determined using the different QMi approaches, is due to the systematic errors of calculations which can partially be eliminated using the scaling dependencies, [7,8] determined for the homologues and/or closely related compounds.…”

“…The reference values of Δ r H o 298.15 (X n , TAB) and the values of Δ r H o ((X n ) i , CALC), as well as corrected values of Δ r H o ((X n ) i , CORR) and Δ r H o ((X n ) i , CORRE) of atomization, calculated, respectively, for the main and extended list of compounds within the considered QM i approaches (SI, Note 1), are used for the determination of the values of RMSE i and (SE 1 ) i . The last of these two values are used for the comparison of the accuracy of determination of thermochemical properties of considered compounds, calculated by considered QMi approaches, as well as with those determined previously [6–8,9] using the B3LYP (6–31G(d,p) and 6–311++G(d,p)), M06‐2X (6–31G(d,p) and 6–311++G(d,p)), RO/CBS‐4M and CBS‐QB3 calculations.…”

“…Thus, the values of Δ f H o 298.15 of atoms are very well known, as well as the errors, introduced by their calculations, are systematic and lowest, compared to the polyatomic compounds. However, the uncertainties (root mean squared error (RMSE)) for the values of Δ f H o 298.15 (X), determined from the comparison of the calculated and literature values of Δ r H o 298.15 (X) of the atomization reactions, are often very high and can reach >90 kJ/mol [6] . At the same time, as it is shown in cited work, the significant part of these uncertainties corresponds to the systematic error of calculations of the bond dissociation energy (BDE) of compounds which, according to work, [7] can be corrected using the simple linear correction (scaling, calibration) dependencies.…”