Vaporization Enthalpies and Vapor Pressures of Some Insect Pheromones by Correlation Gas Chromatography

Goodrich, Sarah; Hasanovic, Jasmina; Gobble, Chase; Chickos, James S.

doi:10.1021/acs.jced.5b00892

Cited by 5 publications

(3 citation statements)

References 11 publications

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“…Experimental data of vaporization enthalpies have essentially been extracted for this work from the large collection of Acree, Jr. and Chickos [ 8 ] and Chickos et al [ 10 , 11 , 12 , 13 , 14 ], supplemented by recent data from a number of further authors publishing experimental vaporization values of several acetophenones [ 23 ], aliphatic tertiary amines [ 24 ], azidomethyl- N -nitrooxazolidines [ 25 ], benzamides [ 26 ], benzocaine [ 27 ], bisabolol and menthol [ 28 ], crown ethers [ 29 ], N , N -dialkyl monoamides [ 30 ], fenpropidin and phencyclidine [ 31 ], flavors [ 32 ], long-chain fluorinated alcohols [ 33 ], whiskey- and metha-lactone [ 34 ], halogenated fluorenes [ 35 ], ibuprofen and naproxen [ 36 ], imidazo[1,2- a ]pyrazine and phthalazine [ 37 ], insect pheromones [ 38 ], morpholines [ 39 ], organo(thio)phosphates [ 40 ], dialkyl phthalates [ 41 ], nitrogen heteroaromatics [ 42 ], phenylimidazoles [ 43 ], 2-acetylthiophene [ 44 ], dicarboxylic n -pentyl esters [ 45 ], and cyclic amines, ethers and alcohols [ 46 ]. The result of the atom-group parameters, based on 3581 compounds, is summarized in Table 1 .…”

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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“…Experimental data of vaporization enthalpies have essentially been extracted for this work from the large collection of W. E. Acree Jr. and J. S. Chickos [8] and J. S. Chickos et al [10][11][12][13][14], supplemented by recent data from a number of further authors publishing experimental vaporization values of several acetophenones [23], aliphatic tertiary amines [24], azidomethyl-N-nitro-oxazolidines [25], benzamides [26], benzocaine [27], bisabolol and menthol [28], crown ethers [29], N,N-dialkyl monoamides [30], fenpropidin and phencyclidine [31], flavors [32], long-chain fluorinated alcohols [33], whiskey-and methalactone [34], halogenated fluorenes [35], ibuprofen and naproxen [36], imidazo[1,2-a]pyrazine and phthalazine [37], insect pheromones [38], morpholines [39], organo(thio)phosphates [40], dialkyl phthalates [41], nitrogen heteroaromatics [42], phenylimidazoles [43], 2-acetylthiophene [44], dicarboxylic n-pentyl esters [45], and cyclic amines, ethers and alcohols [46]. The result of the atom-group parameters, resting on 3581 compounds, is summarized in Table 1.…”

Section: Enthalpy Of Vaporizationmentioning

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.

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“…78 Vapor pressures p GLC for unsaturated FAME subsequently published by Lipkind et al 70 (based on p GLC for FAME 78 ) were found to differ by (27 to 87) percent from Model for the Thermodynamic Properties of a Biodiesel Fuel developed in 2009 in NIST, Boulder, 101 and in case of methyl oleate to differ by 67% from those directly measured in 2017 by another scientific group in NIST, Boulder. 102 There are also other papers reporting p GLC obtained with CGC methodology 27,92,103 based on either vapor pressures for FAME recommended by van Genderen et al 99 or p GLC based on them. 78 Moreover, biased FAME p GLC 78 values were used by other researchers, for example, for parametrization of PC-SAFT EOS, 104 CPA EOS, 105−107 validation of a newly developed force field, 108 development of a group contribution method for estimation of PC-SAFT EOS parameters, 109 and development of a group contribution method for estimation of vapor pressures at 298.15 K. 96 5.1.3.…”

Section: N-alkanesmentioning

confidence: 99%

Estimating Vapor Pressure Data from Gas–Liquid Chromatography Retention Times: Analysis of Multiple Reference Approaches, Review of Prior Applications, and Outlook

et al. 2022

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Reliable methods for determining the vapor pressures of organic materials are of increasing importance as a tool for predicting the behavior and fate of chemicals that are introduced into the environment. In the present work, we analyze the method that relates the gas–liquid chromatography (GLC) retention data, namely, the retention factors (k) of selected organic compounds with their vapor pressures (p 0) using multiple reference standards. Temperature-dependent k values of test chemicals and an adequate number y of reference standard chemicals having directly measured vapor pressure values at temperatures corresponding to GLC measurements are required to apply this method (GLC-RTyS). Retention data of 49 test compounds including a series of alkanes, alkanols, alkyl benzenes, phenols, some (hydro)naphthalene derivatives, and menthol determined on a low-polar dimethylpolysiloxane (HP-1) column at a temperature range from 353 K to (403 or 423) K were used for method validation. We present a first systematic analysis aimed at examining whether and to what extent the selection of experimental conditions might influence/improve the results. Furthermore, we present a review of an alternative multireference correlation gas chromatographic (CGC) method that employs significant extrapolations and is based on the use of adjusted retention time t′ instead of k in order to reveal uncertainties inherent in routine application of this method.

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Vaporization Enthalpies and Vapor Pressures of Some Insect Pheromones by Correlation Gas Chromatography

Cited by 5 publications

References 11 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

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

Estimating Vapor Pressure Data from Gas–Liquid Chromatography Retention Times: Analysis of Multiple Reference Approaches, Review of Prior Applications, and Outlook

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