Indirect Determination of Vapor Pressures by Capillary Gas–Liquid Chromatography: Analysis of the Reference Vapor-Pressure Data and Their Treatment

Růžička, Květoslav; Koutek, Bohumı́r; Fulem, Michal; Hoskovec, Michal

doi:10.1021/je2013186

Cited by 27 publications

(6 citation statements)

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“…[1][2][3] It is usual that the interlaboratory agreement on experimental data on sublimation properties of low volatile species is rather poor. [4][5][6] Moreover, empiric and semi-empiric estimative methods for predictions, based for example on the quantitative structure property relationship (QSPR) models, are not generally reliable or purely predictive, although effort is still exerted in this area. 7,8 On the other hand, the rapid increase of number of known chemical species and corresponding resolved crystal structures does not correlate with the amount of available experimental data on sub ∆ Htypically sublimation data are known for thousands of compounds while millions of crystal structures have been resolved.…”

Section: Introductionmentioning

confidence: 99%

State-of-the-Art Calculations of Sublimation Enthalpies for Selected Molecular Crystals and Their Computational Uncertainty

Červinka

Fulem

2017

J. Chem. Theory Comput.

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A computational methodology for calculation of sublimation enthalpies of molecular crystals from first principles is developed and validated by comparison to critically evaluated literature experimental data. Temperature-dependent sublimation enthalpies for a set of selected 22 molecular crystals in their low-temperature phases are calculated. The computational methodology consists of several building blocks based on high-level electronic structure methods of quantum chemistry and statistical thermodynamics. Ab initio methods up to the coupled clusters with iterative treatment of single and double excitations and perturbative triples correction with an estimated complete basis set description [CCSD(T)/CBS] are used to calculate the cohesive energies of crystalline phases within a fragment-based additive scheme. Density functional theory (DFT) calculations with periodic boundary conditions (PBC) coupled with the quasi-harmonic approximation are used to evaluate the thermal contributions to the enthalpy of the solid phase. The properties of the vapor phase are calculated within the ideal-gas model using the rigid-rotor harmonic-oscillator model with correction for internal rotation using a one-dimensional hindered rotor approximation and a proper treatment of the molecular rotational degrees of freedom in the vicinity of 0 K. All individual terms contributing to the sublimation enthalpy as a function of temperature are discussed and their uncertainties estimated by comparison to critically evaluated experimental data.

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Section: Introductionmentioning

confidence: 99%

State-of-the-Art Calculations of Sublimation Enthalpies for Selected Molecular Crystals and Their Computational Uncertainty

Červinka

Fulem

2017

J. Chem. Theory Comput.

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“…Specifically, the ratio of infinite-dilution activity coefficients of target compounds to co-chromatographed reference standards (γ t /γ ref ) is not equal to unity. 3,15,24,25 As a consequence, the enthalpy of the phase transfer from the GC silicone stationary phase to the gas phase differs somewhat from Δ VAP H/kJ•mol −1 . 17, 25 for calibration compounds.…”

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confidence: 99%

“…3,15,24,25 As a consequence, the enthalpy of the phase transfer from the GC silicone stationary phase to the gas phase differs somewhat from Δ VAP H/kJ•mol −1 . 17, 25 for calibration compounds. The latter can be calculated as the standard prediction error as described.…”

mentioning

confidence: 99%

“…A recent review of the GC-RT method indicates that errors from these sources can be orders of magnitude. 25 Increased accuracy for compounds of differing polarity has been obtained by selecting reference/calibration compounds of the same chemical class as those tested; for example, phenols, 18 phthalates, 17 and fatty acids. 19 While preferable, this approach was not feasible because of the scarcity of well-characterized polar reference/ calibration compounds when screening large numbers of compounds having differing functionalities, as in this paper.…”

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confidence: 99%

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Gas Chromatographic Estimation of Vapor Pressures and Octanol–Air Partition Coefficients of Semivolatile Organic Compounds of Emerging Concern

et al. 2020

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The subcooled liquid-phase vapor pressures (p L 298 /Pa) and octanol−air partition coefficients (K OA 298 ) at T/K = 298, enthalpies of vaporization (Δ VAP H/kJ•mol −1 ), and internal energies of phase transfer from octanol to air (Δ OA U/kJ•mol −1 ) were estimated for synthetic musks, novel brominated flame retardants (N-BFR), organophosphate esters, and ultraviolet filters using the capillary gas chromatographic retention time (GC-RT) method. These compounds, which spanned approximately six and three orders of magnitude for p L 298 /Pa and K OA 298 , respectively, were co-chromatographed with one of three reference compounds to give initial estimates of properties at T/K = 298. The initial GC-RT property estimates were subsequently calibrated using 18 compounds that spanned 6 log units for p L 298 /Pa and 13 compounds covering 4 log units for K OA 298 . The calibrated log 10 p L 298 /Pa values estimated here ranged from 0.14 ± 0.19 to −9.19 ± 0.29 for cyclopentadecanone to syndechlorane plus (syn-DDC-CO), respectively, while the range of log 10 K OA 298 values was 6.59 ± 0.26 to 11.40 ± 0.23 for cyclopentadecanone to 2,2′,4,4′,5-pentabromodiphenyl ether (BDE-99), respectively. The calibrated GC-RT-derived values were highly correlated with, and were within an average of 0.70 log units of, the literature data for compounds with well-established p L 298 / Pa and K OA 298 measured or derived using non-GC-RT methods. Nonpolar compounds were used in this study to estimate the target polar compound data, which may introduce systematic errors. However, the comparison of our GC-RT results against the literature non-GC-RT values shows that the GC-RT methods performed similarly well for estimating both polar and nonpolar target compounds studied in this work.

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“…The vaporization enthalpy (and vapor pressure of supercooled liquid in [15]) was determined using indirect gas-liquid chromatography (GLC) method by Hoskovec et al [16] and by Chickos and coworkers [13,15]. It is outside the scope of this work to analyze the reasons for differences between published values and recommendation of this work (see Table 13); a general analysis of results obtained by the GLC method was recently published by Koutek and coworkers [60,61]. It is however necessary to mention that results of the GLC method are substantially influenced by i) the choice of reference compounds and quality of their reference vapor pressure data and ii) the length of extrapolation since chromatographic measurements are usually performed well above room temperature, while the results are reported down to 298 K. Hoskovec et al [16] [43]).…”

Section: Mutual Consistency Of the Studied Thermodynamic Propertiesmentioning

confidence: 97%

Polymorphism and thermophysical properties of l- and dl-menthol

Štejfa

Bazyleva

Fulem

et al. 2019

The Journal of Chemical Thermodynamics

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The thermodynamic properties, phase behavior, and kinetics of polymorphic transformations of racemic (DL-) and enantiopure (L-) menthol were studied using a combination of advanced experimental techniques, including static vapor pressure measurements, adiabatic calorimetry, Tian-Calvet calorimetry, differential scanning calorimetry (DSC), and variable-temperature X-ray powder diffraction. Several concomitant polymorphs (α, β, γ, and δ forms) were observed and studied. A continuous transformation to the stable α form was detected by DSC and monitored in detail using X-ray powder diffraction. A long-term coexistence of the stable crystalline form with the liquid phase was observed. The vapor pressure measurements of both compounds were performed using two static apparatus over a temperature range from 274 K to 363 K. Condensedphase heat capacities were measured by adiabatic and Tian-Calvet calorimetry in the wide temperature interval from 5 K to 368 K. Experimental data of Land DL-menthol are compared mutually as well as with available literature results. The thermodynamic functions of crystalline and liquid L-menthol between 0 K and 370 K were calculated from the calorimetric results. The thermodynamic properties in the ideal-gas state were obtained by combining statistical thermodynamics and quantum chemical calculations based on a thorough conformational analysis. Calculated ideal-gas heat capacities and experimental data on vapor pressure and condensed-phase heat capacity were treated simultaneously to obtain a consistent thermodynamic description. Based on the obtained results, the phase diagrams of L-menthol and DL-menthol were suggested.

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Indirect Determination of Vapor Pressures by Capillary Gas–Liquid Chromatography: Analysis of the Reference Vapor-Pressure Data and Their Treatment

Cited by 27 publications

References 198 publications

State-of-the-Art Calculations of Sublimation Enthalpies for Selected Molecular Crystals and Their Computational Uncertainty

State-of-the-Art Calculations of Sublimation Enthalpies for Selected Molecular Crystals and Their Computational Uncertainty

Gas Chromatographic Estimation of Vapor Pressures and Octanol–Air Partition Coefficients of Semivolatile Organic Compounds of Emerging Concern

Polymorphism and thermophysical properties of l- and dl-menthol

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