Showing papers in "Journal of Physical and Chemical Reference Data in 2013"

New Group-Contribution Approach to Thermochemical Properties of Organic Compounds: Hydrocarbons and Oxygen-Containing Compounds

Abstract: A new group-contribution approach involving systematic corrections for 1,4-non-bonded carbon-carbon and carbon-oxygen interactions has been proposed. Limits of the applicability of the method, associated with the highly branched structures, were established. Experimental data for enthalpies of formation in the liquid phase, enthalpies of vaporization, and enthalpies of formation in the gas phase for alkanes, alkenes, alkynes, alkylbenzenes, alkanols, ethers, ketones and aldehydes, carboxylic acids, esters, and carbonates were collected and critically evaluated through dynamic data evaluation as implemented in the NIST ThermoData Engine. An automatic procedure for molecular structure “decomposition” was developed, and algorithms for the assessment of expanded uncertainties for the predicted property values were implemented. The combination of these software tools allows for ongoing improvements of the group-contribution parameter set as new experimental data become available. Fifty-two group-contribution parameters and their variances were evaluated for the proposed schema. Based on comparison of critically evaluated and predicted data for all classes of compounds studied, the performance of the new group formulation and associated parameters is superior to that originally suggested by Benson and the update by Cohen without an increase in the number of required parameters.

Calculation of Physicochemical Properties for Short- and Medium-Chain Chlorinated Paraffins

Abstract: Short- and medium-chain chlorinated paraffins are potential PBT chemicals (persistent, bioaccumulative, toxic) and short-chain chlorinated paraffins are under review for inclusion in the UNEP Stockholm Convention on Persistent Organic Pollutants. Despite their high production volume of more than one million metric tonnes per year, only few data on their physicochemical properties are available. We calculated subcooled-liquid vapor pressure, subcooled-liquid solubility in water and octanol, Henry's law constant for water and octanol, as well as the octanol-water partition coefficient with the property calculation methods COSMOtherm, SPARC, and EPI Suite™, and compared the results to experimental data from the literature. For all properties, good or very good agreement between calculated and measured data was obtained for COSMOtherm; results from SPARC were in good agreement with the measured data except for subcooled-liquid water solubility, whereas EPI Suite™ showed the largest discrepancies for all prope...

Reference Correlation of the Viscosity of n-Heptane from the Triple Point to 600 K and up to 248 MPa

Abstract: This paper contains a new wide-ranging correlation for the viscosity of n-heptane based on critically evaluated experimental data. The correlation is valid from the triple point (182.55 K) to 600 K, and at pressures up to 248 MPa. The estimated uncertainty at a 95% confidence level is 3.5% over the whole range (with the exception of the near-critical region). Along the saturated liquid curve, the estimated uncertainty is 1% below 292 K, 0.6% in the region from 292 to 346 K, rising to 2% between 346 and 363 K, and 0.3% for the low-density gas at temperatures from 317 to 600 K and pressures to 0.3 MPa.

Reference Correlation of the Thermal Conductivity of Toluene from the Triple Point to 1000 K and up to 1000 MPa

Abstract: This paper contains new, representative reference equations for the thermal conductivity of n-hexane. The equations are based in part upon a body of experimental data that has been critically assessed for internal consistency and for agreement with theory whenever possible. In the case of the dilute-gas thermal conductivity, a theoretically based correlation was adopted in order to extend the temperature range of the experimental data. Moreover, in the critical region, the experimentally observed enhancement of the thermal conductivity is well represented by theoretically based equations containing just one adjustable parameter. The correlations are applicable for the temperature range from the triple point to 600 K and pressures up to 500 MPa. The overall uncertainty (considered to be estimates of a combined expanded uncertainty with a coverage factor of 2) of the proposed correlation is estimated, for pressures less than 500 MPa and temperatures less than 600 K, to be less than 6%.

Reference Correlation of the Viscosity of Squalane from 273 to 373 K at 0.1 MPa

Abstract: The paper presents a new reference correlation for the viscosity of squalane at 0.1 MPa. The correlation should be valuable as it is the first to cover a moderately high viscosity range, from 3 to 118 mPa s. It is based on new viscosity measurements carried out for this work, as well as other critically evaluated experimental viscosity data from the literature. The correlation is valid from 273 to 373 K at 0.1 MPa. The average absolute percentage deviation of the fit is 0.67, and the expanded uncertainty, with a coverage factor k = 2, is 1.5%.

Reference Correlation of the Thermal Conductivity of Methanol from the Triple Point to 660 K and up to 245 MPa

Abstract: This paper contains new, representative reference equations for the thermal conductivity of methanol. The equations are based in part upon a body of experimental data that has been critically assessed for internal consistency and for agreement with theory whenever possible. In the case of the dilute-gas thermal conductivity, a theoretically based correlation was adopted in order to extend the temperature range of the experimental data. Moreover, in the critical region, the experimentally observed enhancement of the thermal conductivity is well represented by theoretically based equations containing just one adjustable parameter. The correlation is applicable for the temperature range from the triple point to 660 K and pressures up to 245 MPa. The overall uncertainty (at the 95% confidence level) of the correlation over its range of applicability for the liquid and supercritical phases, excluding the critical region, is estimated to be less than 4.4%. The dilute gas region has an estimated uncertainty of 3%, and the liquid at atmospheric pressure is represented to 2%. Uncertainty in regions where data are unavailable for comparison, such as the dense gas region, may be larger.

IUPAC-NIST Solubility Data Series. 98. Solubility of Polycyclic Aromatic Hydrocarbons in Pure and Organic Solvent Mixtures-Revised and Updated. Part 3. Neat Organic Solvents

Abstract: This work updates Vols. 54, 58, and 59 in the IUPAC Solubility Data Series and presents solubility data for polycyclic aromatic hydrocarbon solutes dissolved in neat organic solvents. Published solubility data for acenaphthene, anthracene, biphenyl, carbazole, dibenzofuran, dibenzothiophene, fluoranthene, fluorene, naphthalene, phenanthrene, phenothiazine, pyrene, thianthrene, and xanthene that appeared in the primary literature from 1995 to the end of 2011 are compiled and critically evaluated. Experimental solubility data for more than 550 different solute-organic solvent systems are included. Solubility data published prior to 1995 were contained in three earlier volumes (Vols. 54, 58, and 59) and are not repeated in this volume.

IUPAC-NIST Solubility Data Series. 99. Solubility of Benzoic Acid and Substituted Benzoic Acids in Both Neat Organic Solvents and Organic Solvent Mixtures

Abstract: Solubility data are compiled and reviewed for benzoic acid and 63 substituted benzoic acids dissolved in neat organic solvents and well-defined binary and ternary organic solvent mixtures. The compiled solubility data were retrieved from the published chemical and pharmaceutical literature covering the period from 1900 to the beginning of 2013.

IUPAC-NIST Solubility Data Series. 98. Solubility of Polycyclic Aromatic Hydrocarbons in Pure and Organic Solvent Mixtures: Revised and Updated. Part 1. Binary Solvent Mixtures

Abstract: This work updates Vols. 54, 58, and 59 in the IUPAC Solubility Data Series and presents solubility data for polycyclic aromatic hydrocarbon solutes dissolved in ternary organic solvent mixtures. Published solubility data for anthracene, phenanthrene, and pyrene that appeared in the primary literature between 1995 to the end of 2011 are compiled and critically evaluated. Experimental solubility data for 119 different solute-ternary solvent systems are included in the volume. Solubility data published prior to 1995 were contained in three earlier volumes (Vols. 54, 58, and 59) and are not repeated here.

IUPAC-NIST Solubility Data Series. 97. Solubility of Higher Acetylenes and Triple Bonded Derivatives

Abstract: Solubility of Ethyne in Liquids was published in 2001 as Vol. 76 of the IUPAC-NIST Solubility Data Series. The current work extends the coverage to the solubility in liquids of higher gaseous and liquid acetylenes and to derivatives that contain a triple carbon-carbon bond. Predictive methods for estimating solubilities in water are summarised and usually give values to within an order of magnitude. The literature has been surveyed to the end of 2010.