Six-membered ring aliphatic compounds: A search for regularities in phase transitions

Nagrimanov, Ruslan N.; Solomonov, Boris N.; Emel′yanenko, Vladimir N.; Verevkin, Sergey P.

doi:10.1016/j.tca.2016.06.014

Cited by 12 publications

(5 citation statements)

References 46 publications

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“…This precondition has been thoroughly followed when selecting experimental data from literature. Again, as in the previous section, the main contribution of experimental sublimation values has been provided by the compendium of 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 [ 59 ].…”

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

Naef

Acree

2017

Molecules

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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.

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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

Naef

Acree

2017

Molecules

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“…Solution enthalpy is precisely measured using solution calorimetry (see Table S3). Solvation enthalpy can be calculated either using molar refraction − ,, or by a group-contribution method. , In the present work the solvation enthalpies were calculated according to the group-contribution method: where Δ soln H m Ai/S is the solvation enthalpy of the aromatic compound in the solvent S ; Δ soln H m ArH/S is the solvation enthalpy of the parent reference molecule in the same solvent S ; Δ soln H m X→H/S is the contribution to the solvation enthalpy related to the substitution of a hydrogen atom in the reference molecule with the substituent X; n is the number of substituents. Solvation enthalpies calculated by group additivity have been shown to be in good agreement with experimental solvation enthalpies available for aromatic compounds and their derivatives …”

Section: Resultsmentioning

confidence: 99%

“…We have shown recently − that solution calorimetry serves as a complementary indirect method for determination of sublimation/vaporization enthalpies of organic molecules by using solution enthalpies measured at the reference temperature 298 K. It has been established that the molar solution enthalpy Δ soln H m A i /S of a solute A i in a solvent S and a molar solvation enthalpy Δ soln H m Ai/S of A i in the same solvent S are connected to the molar enthalpy of sublimation Δ cr g H m ° by eq : This equation is also valid for the determination of vaporization enthalpies . Solution enthalpy is precisely measured using solution calorimetry (see Table S3).…”

Section: Resultsmentioning

confidence: 99%

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Benchmark Thermodynamic Properties of Methyl- and Methoxybenzamides: Comprehensive Experimental and Theoretical Study

et al. 2016

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The enthalpies of formation of 2-, 3-, and 4-CH3-benzamide, as well as for 2-CH3O-benzamide were measured by using combustion calorimetry. Vapor pressures of the isomeric CH3- and CH3O-benzamides were measured by using the transpiration method. The enthalpies of sublimation/vaporization of these compounds at 298 K were obtained from temperature dependencies of vapor pressures. The enthalpies of solution of the isomeric CH3- and CH3O-benzamides were measured with solution calorimetry. The enthalpies of sublimation of m- and p-substituted benzamides were independently derived with help of a solution calorimetry based procedure. The enthalpies of fusion of the CH3-benzamides were derived from DSC measurements. Thermochemical data on CH3- and CH3O-benzamides were collected, evaluated, and tested for internal consistency. A simple incremental procedure has been suggested for a quick appraisal of vaporization enthalpies of substituted benzamides. The high-level G4 quantum-chemical method was used for mutual validation of the experimental and theoretical gas phase enthalpies of formation. A remarkable ability of the G4 based atomization procedure to calculate reliable enthalpies of formation has been established for the set of aliphatic and aromatic amides. An outlook for the proper validation of the G4-AT procedure was discussed.

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“…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

Naef

Acree

2017

Preprint

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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.

show abstract

Six-membered ring aliphatic compounds: A search for regularities in phase transitions

Cited by 12 publications

References 46 publications

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

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

Benchmark Thermodynamic Properties of Methyl- and Methoxybenzamides: Comprehensive Experimental and Theoretical Study

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

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