Thermochemical and theoretical study of 2-oxazolidinone and 3-acetyl-2-oxazolidinone

2017

Molecules

The calculation of the standard enthalpies of vaporization, sublimation and solvation of organic molecules is presented using a common computer algorithm on the basis of a group-additivity method. The same algorithm is also shown to enable the calculation of their entropy of fusion as well as the total phase-change entropy of liquid crystals. The present method is based on the complete breakdown of the molecules into their constituting atoms and their immediate neighbourhood; the respective calculations of the contribution of the atomic groups by means of the Gauss-Seidel fitting method is based on experimental data collected from literature. The feasibility of the calculations for each of the mentioned descriptors was verified by means of a 10-fold cross-validation procedure proving the good to high quality of the predicted values for the three mentioned enthalpies and for the entropy of fusion, whereas the predictive quality for the total phase-change entropy of liquid crystals was poor. The goodness of fit (Q2) and the standard deviation (σ) of the cross-validation calculations for the five descriptors was as follows: 0.9641 and 4.56 kJ/mol (N = 3386 test molecules) for the enthalpy of vaporization, 0.8657 and 11.39 kJ/mol (N = 1791) for the enthalpy of sublimation, 0.9546 and 4.34 kJ/mol (N = 373) for the enthalpy of solvation, 0.8727 and 17.93 J/mol/K (N = 2637) for the entropy of fusion and 0.5804 and 32.79 J/mol/K (N = 2643) for the total phase-change entropy of liquid crystals. The large discrepancy between the results of the two closely related entropies is discussed in detail. Molecules for which both the standard enthalpies of vaporization and sublimation were calculable, enabled the estimation of their standard enthalpy of fusion by simple subtraction of the former from the latter enthalpy. For 990 of them the experimental enthalpy-of-fusion values are also known, allowing their comparison with predictions, yielding a correlation coefficient R2 of 0.6066.

Section: Resultsmentioning

confidence: 99%

Calculation of Five Thermodynamic Molecular Descriptors by Means of a General Computer Algorithm Based on the Group-Additivity Method: Standard Enthalpies of Vaporization, Sublimation and Solvation, and Entropy of Fusion of Ordinary Organic Molecules and Total Phase-Change Entropy of Liquid Crystals

2017

Molecules

“…This precondition has been thoroughly followed when selecting experimental data from literature. Again, as in the previous chapter, the main contribution of experimental sublimation values has been provided by the compendium of W. E. Acree Jr. et al [8], supplemented by a number of later publications, referencing the heat of sublimation of acetophenones [23], substituted benzamides [26], crown ethers [29], long-chain fluorinated alcohols [33], halogenated fluorenes [35], tricyclic nitrogen heteroaromatics [42], polyphenylbenzenes [47], adamantylideneadamantane [48], cyclic N,N'-thioureas [49], indole-3-carboxylic acids [50], vanillyl alcohol [51], alkanoylphenols [52], adamantanes [53], six-membered ring aliphatics [54], fluoroquinolones [55], oxazolidinones [56], nitrogen-containing substituted adamantanes [57], 2,7-di-t-butylfluorene [58] and nitroimidazoles [58]. (row B and F at the bottom of Table 2) exhibit a higher scatter of the experimental data in comparison with the heat-of-vaporization data.…”

Section: Enthalpy Of Sublimationmentioning

confidence: 99%

Calculation of Five Thermodynamic Molecular Descriptors by Means of a General Computer Algorithm Based on the Group-Additivity Method: Standard Enthalpies of Vaporization, Sublimation and Solvation, and Entropy of Fusion of ordinary Organic Molecules and Total Phase-Change Entropy of Liquid Crystals

2017

Preprint

Abstract:The calculation of the standard enthalpies of vaporization, sublimation and solvation of organic molecules is presented using a common computer algorithm on the basis of a group-additivity method. The same algorithm is also shown to enable the calculation of their entropy of fusion as well as the total phase-change entropy of liquid crystals. The present method is based on the complete break-down of the molecules into their constituting atoms and their immediate neighbourhood; the respective calculations of the contribution of the atomic groups by means of the Gauss-Seidel fitting method is based on experimental data collected from literature. The feasibility of the calculations for each of the mentioned descriptors was verified by means of a 10-fold cross-validation procedure proving the good to high quality of the predicted values for the three mentioned enthalpies and for the entropy of fusion, whereas the predictive quality for the total phase-change entropy of liquid crystals was poor. The goodness of fit (Q 2 ) and the standard deviation (σ) of the cross-validation calculations for the five descriptors was as follows: 0.9641 and 4.56 kJ/mol (N=3386 test molecules) for the enthalpy of vaporization, 0.8657 and 11.39 kJ/mol (N=1791) for the enthalpy of sublimation, 0.9546 and 4.34 kJ/mol (N=373) for the enthalpy of solvation, 0.8727 and 17.93 J/mol/K (N=2637) for the entropy of fusion and 0.5804 and 32.79 J/mol/K (N=2643) for the total phase-change entropy of liquid crystals. The large discrepancy between the results of the two closely related entropies is discussed in detail. Molecules, for which both the standard enthalpies of vaporization and sublimation were calculable, enabled the estimation of their standard enthalpy of fusion by simple subtraction of the former from the latter enthalpy. For 990 of them the experimental enthalpy-of-fusion values are also known, allowing their comparison with predictions, yielding a correlation coefficient R 2 of 0.6066.

“…A considerable number of experimental combustion and formation data have been published for heterocyclic compounds, including hetarenes, unsubstituted and substituted by functional groups just mentioned. According to the hetero elements in the ring system, they have been subdivided into N x -heterocycles (where x is 1 to 4) , N,O-heterocycles [424][425][426][427][428][429][430][431][432][433], N,S-heterocycles [434][435][436][437][438], O x -heterocycles [439][440][441][442][443][444][445][446][447][448][449][450][451][452], and S x -heterocycles [280,[282][283][284][453][454][455][456][457][458][459][460][461]. A small number of papers contributed data for hetarenes with several element combinations [462][463][464]…”

Section: Sources Of Heat-of-combustion and Formation Datamentioning

confidence: 99%

Revision and Extension of a Generally Applicable Group-Additivity Method for the Calculation of the Standard Heat of Combustion and Formation of Organic Molecules

2021

Molecules

The calculation of the heats of combustion DH°c and formation DH°f of organic molecules at standard conditions is presented using a commonly applicable computer algorithm based on the group-additivity method. This work is a continuation and extension of an earlier publication. The method rests on the complete breakdown of the molecules into their constituting atoms, these being further characterized by their immediate neighbor atoms. The group contributions are calculated by means of a fast Gauss–Seidel fitting calculus using the experimental data of 5030 molecules from literature. The applicability of this method has been tested by a subsequent ten-fold cross-validation procedure, which confirmed the extraordinary accuracy of the prediction of DH°c with a correlation coefficient R2 and a cross-validated correlation coefficient Q2 of 1, a standard deviation σ of 18.12 kJ/mol, a cross-validated standard deviation S of 19.16 kJ/mol, and a mean absolute deviation of 0.4%. The heat of formation DH°f has been calculated from DH°c using the standard enthalpies of combustion for the elements, yielding a correlation coefficient R2 for DH°f of 0.9979 and a corresponding standard deviation σ of 18.14 kJ/mol.