Thermodynamic properties of 1-naphthol: Mutual validation of experimental and computational results☆
Introduction
The present article is part of a series in which we report studies of experimental and computed thermodynamic properties for aromatic ring systems. Previous work has included an extensive series of azaaromatics (2-methylquinoline [1], 8-methylquinoline [1], 2,6-dimethylquinoline [1], phenazine [2], acridine [2], phenanthridine [3], 1,10-phenanthroline [3], and 7,8-benzoquinoline [3]), 1-phenyl and 2-phenylnaphthalene [4], and 9-fluorenone [5]. All studies included calculations performed at the B3LYP/631+G(d,p) model chemistry with a consistent scaling factor (0.975), with excellent accord demonstrated between computed entropies for the ideal gas and those based on the experimental property measurements. In the present work, this approach is applied for the first time to a hydroxyl-aromatic compound, 1-naphthol (Chemical Abstracts Service Registry Number [90-15-3]).
As we have noted previously [2], the rigid nature of fused-ring systems makes such molecules good candidates for accurate computation of thermodynamic properties for the ideal-gas state with statistical methods. In the present paper, entropies for the ideal-gas state are derived from the reported thermodynamic property measurements and are compared with independently calculated values derived with the methods of computational chemistry. The accord achieved provides a mutual validation of the two methods, and demonstrates a path to the quantification of uncertainties for the computational methods. Derivation of ideal-gas properties from computational methods with reliable uncertainties provides essential data that are, otherwise, impractical or impossible to obtain, such as those for toxic, unstable, or prohibitively expensive materials. Applications of ideal-gas properties in thermodynamics include key roles in property predictions, consistency analyses, constrained property equations, and equation of state formulations.
Here, we report thermodynamic properties of 1-naphthol measured with adiabatic heat-capacity calorimetry, comparative ebulliometry, inclined-piston gauge manometry, and oxygen bomb calorimetry. Standard molar enthalpies, entropies, enthalpies of formation, entropies of formation, and Gibbs energies of formation for the ideal gas state were derived based on the experimental studies. Entropies for the ideal gas state were computed independently at the B3LYP/6-31+G(d,p) model chemistry with the same scaling factor used in previous work [1], [2], [3], [4], [5]. Excellent accord between the computed and experimental entropies is demonstrated. Measured and derived thermodynamic property values are compared with those reported in the literature, where several studies are demonstrated to be of low quality. A summary of the new experimental thermodynamic property measurements reported here is given in table 1.
Section snippets
Materials
The research group of Professor E.J. “Pete” Eisenbraun (retired) of Oklahoma State University purified the sample of 1-naphthol used in this research. A commercial sample was Soxhlet extracted through neutral alumina with hexane, followed by reaction with picric acid in hot methanol. The resulting picrate was triply recrystallized from methanol, filtered, and dried. The picrate was cleaved with basic alumina by Soxhlet extraction with ethyl ether. A mixture of hexanes was added, and the
Heat capacities, enthalpies, triple point temperature, and derived thermodynamic functions for the condensed phases
Measurements of enthalpy increments and derived heat capacities for 1-naphthol were made with adiabatic calorimetry for the temperature range (4.5 < T/K < 445), and included determination of the triple-point temperature Ttp and the molar enthalpy of fusion . The density of liquid 1-naphthol under saturation pressure at temperature T/K = 393 {ρsat = 1063 ± 20 kg · m−3} was determined from the sample mass and volume measured as part of the filling procedure for the sample vessel. Crystallization of
Mutual validation with computational methods
The geometries, energies, and vibrational frequencies for 1-naphthol were calculated at the B3LYP/6-31+G(d,p) model chemistry level using Gaussian 09 software [41]. The hybrid density functional method B3LYP has been demonstrated to predict well molecular geometries and vibrational frequencies, as well as the ideal-gas entropies derived from them, for a range of aromatic and substituted aromatic compounds [1], [2], [3], [4], [5]. Full conformational analysis was performed including optimized
Conclusion
Computational chemistry is a powerful tool for evaluation of thermodynamic properties in the ideal-gas state, and for rigid molecules, such as that studied in this research, relative expanded uncertainties near 0.1% for can be achieved. With the present results, this is now demonstrated successfully for a hyrdroxy-aromatic.
Acknowledgments
We acknowledge the contributions of An (Andy) Nguyen in the vapor-pressure measurements, Norris K. Smith in the combustion study, I. Alex Hossenlopp in vapor-transfer of the samples prior to the physical property measurements, and Stephen E. Knipmeyer for maintenance of all apparatus. The authors gratefully acknowledge the Office of Fossil Energy of the US Department of Energy (DOE) for financial support of the experimental studies. This research was funded within the Processing and Downstream
References (77)
- et al.
J. Chem. Thermodyn.
(2007) - et al.
J. Chem. Thermodyn.
(2010) - et al.
J. Chem. Thermodyn.
(2014) - et al.
J. Chem. Thermodyn.
(2012) - et al.
J. Chem. Thermodyn.
(2004) - et al.
J. Chem. Thermodyn.
(1988) - et al.
J. Chem. Thermodyn.
(1980) - et al.
Anal. Chim. Acta
(1957) Cryogenics
(1973)- et al.
J. Chem. Thermodyn.
(1972)
J. Mol. Spectrosc.
Chem. Phys. Lett.
Spectrochim. Acta A: Mol. Biomol. Spectrosc.
J. Chem. Thermodyn.
J. Chem. Thermodyn.
Thermochim. Acta
Thermochim. Acta
J. Cryst. Growth
Anal. Chim. Acta
Thermochim. Acta
J. Chem. Thermodyn.
J. Chem. Thermodyn.
J. Chem. Thermodyn.
Thermochim. Acta
J. Chem. Thermodyn.
Pure Appl. Chem.
Pure Appl. Chem.
Rev. Sci. Instrum.
J. Chem. Eng. Data
J. Phys. Chem. Ref. Data
J. Sci. Instrum.
J. Chem. Eng. Data
J. Chem. Eng. Data
J. Chem. Eng. Data
J. Phys. Chem.
Cited by (18)
Comments on “measurement and correlation studies of phase equilibria and thermophysical properties of 4-tert-butylbenzaldehyde”
2019, Journal of Molecular LiquidsThermodynamic properties of 2–methylindole: Experimental and computational results for gas-phase entropy and enthalpy of formation
2018, Journal of Chemical ThermodynamicsCitation Excerpt :Future work will include extensions to larger pyrrolic molecules, such as carbazoles, as well as alkyl-substituted and partially saturated multi-ring hydrocarbons, where additional challenges related to low-frequency out-of-plane vibrational modes will need to be addressed. In this series [1–10], we use measurement results of high quality to aid in assessment of uncertainty quantification in computational thermodynamics. Practical application of these results in engineering software, such as the NIST ThermoData Engine (TDE) [11,76–83], can greatly improve upon group-contribution based prediction methods with poorly known uncertainties that remain in wide use today.
Thermodynamic properties of pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, and 2,5-dimethylpyrrole: Experimental and computational results
2018, Journal of Chemical ThermodynamicsCitation Excerpt :This work is a continuation of our investigations [1–9] into quantification of uncertainties for thermodynamic properties derived with computational methods.
Thermodynamic properties of indan: Experimental and computational results
2016, Journal of Chemical ThermodynamicsCitation Excerpt :A description of the basis for scaling factors can be found within the NIST Computational Chemistry and Benchmark DataBase [53].) This same approach was used in our previous publications and was shown to provide good performance in conjunction with B3LYP for a variety of aromatic compounds [1,3–8]. All calculations were performed with Gaussian 09 [54].
- ☆
Contribution of the National Institute of Standards and Technology, not subject to copyright in the United States.