An Examination of the Thermodynamics of Fusion, Vaporization, and Sublimation of (R,S)- and (R)-Flurbiprofen by Correlation Gas Chromatography

Umnahanant, Patamaporn; Hasty, Darrell; Chickos, James S.

doi:10.1002/jps.23094

Cited by 11 publications

(10 citation statements)

References 24 publications

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“…(6) Tables 5 and 6). The latter values have been in agreement (within the boundaries of experimental uncertainties) with vaporization enthalpies independently derived from the correlation gas-chromatographic method [34,42].…”

Section: Internal Consistency Of the Phase Change Enthalpies Of Benzosupporting

confidence: 67%

Benzoic acid derivatives: Evaluation of thermochemical properties with complementary experimental and computational methods

et al. 2015

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Section: Internal Consistency Of the Phase Change Enthalpies Of Benzosupporting

confidence: 67%

Benzoic acid derivatives: Evaluation of thermochemical properties with complementary experimental and computational methods

et al. 2015

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“…It was previously shown that, if a single fluorine was substituted for hydrogen in hydrocarbons and carboxylic acids, these compounds successfully correlated with the corresponding unsubstituted hydrocarbons and carboxylic acids . To test whether the analogous substitution with the perfluoroalkanes would likewise be successful, 1 H -perfluorooctane was analyzed using C 8 F 18 , C 9 F 20 C 10 F 22 , and C 13 F 28 as standards.…”

Section: Resultssupporting

confidence: 75%

“…Naphthalene is the last compound to elute off the column. The vaporization enthalpies of two of the partially fluorinated aromatics, α,α,α-trifluorotoluene and p -fluoroanisole, are well reproduced by using aromatic hydrocarbons as observed previously . The results for α,α,α-trifluorotoluene is encouraging since it suggests that several fluorine substitutions can be tolerated using hydrocarbons as standards.…”

Section: Resultssupporting

confidence: 61%

“…A goal of this work was to evaluate whether fluorine substitution needed to be treated as a functional group, taking into account both the number of fluorine atoms present and their location or whether fluorine substitution could be treated much like hydrogen. A previous study demonstrated that a single fluorine atom could be substituted for hydrogen successfully and its location on the molecule did not appear to be significant . As is described briefly below, perfluorinated compounds behave in a more complex manner than the corresponding hydrocarbons of similar structure.…”

Section: Introductionmentioning

confidence: 99%

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Applications of Correlation Gas Chromatography and Transpiration Studies for the Evaluation of the Vaporization and Sublimation Enthalpies of Some Perfluorinated Hydrocarbons

et al. 2012

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The fusion, vaporization, and sublimation enthalpies of a series of perfluorinated alkanes have been measured by combining measurements obtained by differential scanning calorimetry (DSC), transpiration, and correlation-gas chromatography and comparing the results to available data in the literature. Additionally, experiments are reported to provide a guide in identifying appropriate structural features of fluorinated compounds suitable for use as standards in correlation gas chromatography measurements. Fusion enthalpies and fusion temperatures by DSC for the following compounds were measured (in kJ•mol −1 ; K): decafluorobiphenyl (20.5 ± 0.6, 339.6), perfluorododecane (24.2 ± 0.6, 346.6), perfluorotridecane (27.9 ± 0.4, 361.7), perfluorotetradecane (31.5 ± 0.3, 375.6), perfluoropentadecane (35.1 ± 0.2, 388.1), perfluorohexadecane (38.7 ± 0.1, 399.7), perfluoroeicosane (50.3 ± 0.3, 436.2), and perfluorotetracosane (63.2 ± 0.6, 461.1). Sublimation enthalpies for the following compounds were measured by transpiration (in kJ•mol −1 ; T = 298.15 K): perfluorododecane (85.8 ± 0.6), perfluorotridecane (94.3 ± 0.5), perfluorotetradecane (102.4 ± 1.0), and perfluoropentadecane (109.4 ± 0.4). Vaporization and sublimation enthalpies, respectively, were also evaluated for the following compounds (kJ•mol −1 ; T/K = 298.15): perfluorohexadecane (88.6 ± 4.0, 117.6 ± 4.9), perfluoroeicosane (113.7 ± 7.4, 148 ± 8.8), and perfluorotetracosane (141.4 ± 2.2, 168.3 ± 11.1). The measured vaporization enthalpies of the perfluorinated alkanes behave linearly as a function of the number of CF 2 groups similar to what is observed with n-alkanes. Correlation-gas chromatography experiments confirmed previous findings that hydrocarbons can be used as standards for compounds containing a few fluorine atoms but otherwise standards need to be chosen with similar fluorine substitution and functionality.

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“…Normal melting temperatures T m and enthalpies of fusion D l cr H o m (T m ) have been reported for fluoro-, 129,165,166 chloro-, 123,125,131,136,167,168 bromo-, 121,125,130,131 and iodobenzoic acids. 122,129,131,169 Most of these results were obtained with a DSC.…”

Section: Validation Of Results Through Trend Analysis For Estimated Ementioning

confidence: 99%

Critical Evaluation of Thermodynamic Properties for Halobenzoic Acids Through Consistency Analyses for Results from Experiment and Computational Chemistry

Chirico

Kazakov

Bazyleva

et al. 2017

Journal of Physical and Chemical Reference Data

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Thermodynamic properties of the twelve monohalobenzoic acids are critically evaluated through the application of computational chemistry methods for the ideal-gas phase and thermodynamic consistency assessment of properties determined experimentally and reported in the literature, including enthalpies of combustion, enthalpies of sublimation, and enthalpies of fusion. The compounds of interest are the 2-, 3-, and 4-halo isomers of fluoro-, chloro-, bromo-, and iodobenzoic acids. Computations were validated by comparison with critically evaluated entropies and heat capacities in the ideal-gas state for benzoic acid, benzene, and some halobenzenes. Experimental enthalpies of formation for 2-and 3-bromobenzoic acids, measured by well-established research groups, are mutually inconsistent and further, are shown to be inconsistent with the computations and assessment in this work. Origins of the discrepancies are unknown, and recommended values for these compounds are based on computations and enthalpies of sublimation validated, in part, by a structure-property (i.e., group-additivity) analysis. Lesser, but significant, inconsistencies between experimental and computed results are demonstrated also for 3-and 4-iodobenzoic acids. The comparison of enthalpies of formation based on the experiment and computation for the ideal-gas state of 1-and 2-chloro-, bromo-, and iodonaphthalenes provides additional support for the findings for halobenzoic acids and also reveals some anomalous results in the experimental literature for chloronaphthalenes. Computations are discussed in detail to demonstrate the approach required to obtain optimal results with modern quantum chemical methods.

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An Examination of the Thermodynamics of Fusion, Vaporization, and Sublimation of (R,S)- and (R)-Flurbiprofen by Correlation Gas Chromatography

Cited by 11 publications

References 24 publications

Benzoic acid derivatives: Evaluation of thermochemical properties with complementary experimental and computational methods

Benzoic acid derivatives: Evaluation of thermochemical properties with complementary experimental and computational methods

Applications of Correlation Gas Chromatography and Transpiration Studies for the Evaluation of the Vaporization and Sublimation Enthalpies of Some Perfluorinated Hydrocarbons

Critical Evaluation of Thermodynamic Properties for Halobenzoic Acids Through Consistency Analyses for Results from Experiment and Computational Chemistry

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