Thermodynamic properties of three-ring aza-aromatics. 2. Experimental results for 1,10-phenanthroline, phenanthridine, and 7,8-benzoquinoline, and mutual validation of experiments and computational methods

Measurements leading to the calculation of standard entropies for 1,10-phenanthroline (Chemical Abstracts registry number [66-71-7]) in the crystal, liquid, and ideal-gas state are reported. Experimental methods were adiabatic heat-capacity calorimetry and comparative ebulliometry. Thermodynamic properties for phenanthridine [229-87-8] and 7,8-benzoquinoline [230-27-3] were reported previously and included those measured with adiabatic heat-capacity calorimetry, comparative ebulliometry (7,8-benzoquinoline only), inclined-piston manometry, and combustion calorimetry. New measurement results for phenanthridine and 7,8-benzoquinoline reported here are densities determined with a vibrating-tube densimeter and heat capacities for the liquid phase at saturation pressure determined with a differential scanning calorimeter (dsc), and vapor pressures by comparative ebulliometry (phenanthridine only). All critical properties were estimated. Molar entropies for the ideal-gas state were derived for all compounds at selected temperatures. Independent calculations of entropies for the ideal-gas state were performed at the B3LYP/6-31+G(d,p) model chemistry for the three compounds studied. These are shown to be in excellent accord with the calorimetric results for 1,10-phenanthroline and phenanthridine. Results for 7,8-benzoquinoline indicate that the crystal state is disordered. All new experimental results are compared with property values reported in the literature.

[1]  R. Chirico,et al.  The thermodynamic properties of 4,5,9,10-tetrahydropyrene and of 1,2,3,6,7,8-hexahydropyrene , 1993 .

[2]  L. Riedel.  Die Flüssigkeitsdichte im Sättigungszustand. Untersuchungen über eine Erweiterung des Theorems der übereinstimmenden Zustände. Teil II , 1954 .

[3]  M. McLinden,et al.  NIST Standard Reference Database 23: Reference Fluid Thermodynamic and Transport Properties-REFPROP, Version 8.0 , 2007 .

[4]  R. Chirico,et al.  Possible precursors and products of deep hydrodesulfurization of gasoline and distillate fuels III. The thermodynamic properties of 1,2,3,4-tetrahydrodibenzothiophene☆☆☆ , 2004 .

[5]  D. Ambrose,et al.  Vapour pressures up to their critical temperatures of normal alkanes and 1-alkanols , 1989 .

[6]  W. Wagner,et al.  The IAPWS Formulation 1995 for the Thermodynamic Properties of Ordinary Water Substance for General and Scientific Use , 2002 .

[7]  M. Wieser.  Atomic weights of the elements 2005 (IUPAC Technical Report) , 2006 .

[8]  R. Goldberg,et al.  Conversion of temperatures and thermodynamic properties to the basis of the International Temperature Scale of 1990 (Technical Report) , 1992 .

[9]  J. Mccullough,et al.  Melting-point purity determinations: Limitations as evidenced by calorimetric studies in the melting region , 1957 .

[10]  F. McCrackin,et al.  Simple calibration procedures for platinum resistance thermometers from 2.5 to 14 K , 1975 .

[11]  W. Waring.  Form of a Wide-Range Vapor Pressure Equation , 1954 .

[12]  R. Chirico,et al.  Thermodynamic properties of methylquinolines: Experimental results for 2,6-dimethylquinoline and mutual validation between experiments and computational methods for methylquinolines , 2007 .

[13]  W. V. Steele,et al.  The thermodynamic properties of the five benzoquinolines , 1989 .

[14]  W. V. Steele,et al.  Thermodynamic properties of tert-butylbenzene and 1,4-di-tert-butylbenzene , 2009 .

[15]  S. Mastrangelo,et al.  Solid Solutions Treatment of Calorimetric Purity Data , 1955 .

[16]  Andrei F. Kazakov,et al.  Thermodynamic properties of three-ring aza-aromatics. 1. Experimental results for phenazine and acridine, and mutual validation of experiments and computational methods , 2010 .

[17]  R. Reid,et al.  The Properties of Gases and Liquids , 1977 .

[18]  F. Emmenegger,et al.  Vapour Pressure Measurements with A Thermobalance , 1999 .

[19]  J. Hales,et al.  Liquid densities from 293 to 490 K of nine aromatic hydrocarbons , 1972 .

[20]  Robert F. Curl,et al.  The Volumetric and Thermodynamic Properties of Fluids. III. Empirical Equation for the Second Virial Coefficient1 , 1957 .

[21]  Robert D. Chirico,et al.  ThermoData Engine (TDE): Software Implementation of the Dynamic Data Evaluation Concept, 2. Equations of State on Demand and Dynamic Updates over the Web , 2007, J. Chem. Inf. Model..

[22]  R. Chirico,et al.  Reconciliation of calorimetrically and spectroscopically derived thermodynamic properties at pressures greater than 0. 1 MPa for benzene and methylbenzene: The importance of the third virial coefficient , 1994 .

[23]  Robert D. Chirico,et al.  ThermoData Engine (TDE): Software Implementation of the Dynamic Data Evaluation Concept. 3. Binary Mixtures , 2009, J. Chem. Inf. Model..

[24]  W. Steele.  Fifty years of thermodynamics research at Bartlesville: The Hugh M. Huffman legacy☆☆☆★ , 1995 .

[25]  Robert D. Chirico,et al.  ThermoData Engine (TDE): Software Implementation of the Dynamic Data Evaluation Concept , 2005, J. Chem. Inf. Model..

[26]  H. Orbey,et al.  Correlation for the third virial coefficient using Tc, Pc and ω as parameters , 1983 .

[27]  Peter J. Mohr,et al.  CODATA recommended values of the fundamental constants , 2001 .

[28]  Wolfgang Wagner,et al.  New vapour pressure measurements for argon and nitrogen and a new method for establishing rational vapour pressure equations , 1973 .

[29]  D. R. Douslin,et al.  Vapor pressure relations of 36 sulfur compounds present in petroleum , 1966 .