The ThermoML Archive is a subset of Thermodynamics Research Center (TRC) data holdings corresponding to cooperation between NIST TRC and five journals: Journal of Chemical Engineering and Data (ISSN: 1520-5134), The Journal of Chemical Thermodynamics (ISSN: 1096-3626), Fluid Phase Equilibria (ISSN: 0378-3812), Thermochimica Acta (ISSN: 0040-6031), and International Journal of Thermophysics (ISSN: 1572-9567). Data from initial cooperation (around 2003) through the 2019 calendar year are included. The archive has undergone a major update with the goal of improving the FAIRness and user experience of the data provided by the service. The web application provides comprehensive property browsing and searching capabilities; searching relies on a RESTful API provided by the Cordra software for managing digital objects. JSON files with a schema derived from ThermoML are provided as an additional serialization to lower the barrier to programmatic consumption of the information, for stakeholders who may have a preference of JSON over XML. The ThermoML and JSON files for all available entries can be downloaded from data.nist.gov (https://data.nist.gov/od/id/mds2-2422).

Combustion calorimetry is the predominant method for determination of enthalpies of formation for organic compounds. Both initial and final states of the calorimeter deviate significantly from the standard conditions. Correction of the obtained results to the standard state must be applied as accurately as possible to determine the combustion energy with an acceptable uncertainty, which is typically a few hundredths of a percent. The correction procedures in their current form were introduced in 1956 with simplifications to allow application in a pre-computer era. In this work, the procedures have been updated with respect to both the equations and reference values. The most reliable data sources are identified, and the updated algorithm is presented in the form of a Web-based tool available through the NIST TRC Web site.

Thermophysical properties of Fe-Cr-Ni melts are studied using electrostatic levitation and rapid solidification techniques. Six hypoeutectic FeCr Ni alloys with a Cr/Ni ratio of around 0.8 were melted and solidified at different degrees of undercooling. From the observed relationship between the undercooling and thermal plateau time, the hypercooling limit and heat of fusion of FeCr Ni melts are determined as a function of Cr mass fraction. A ratio of specific heat and total hemispherical emissivity of the Fe-Cr-Ni melts is calculated using the time-temperature profiles. A new method is presented to evaluate the temperature dependence of specific heat for undercooled melts and applied to this alloy family.

In this review, results of the studies of thermodynamic properties of organic substances conducted at the Chemistry Department of the Belarusian State University (Minsk, Belarus) over a period of more than 50 years are summarized. Emphasis is made on precise measurements (both calorimetry and equilibria) and prediction methods, including group-contribution, quantum chemical, and statistical mechanical, for a broad range of thermodynamic properties of various classes of chemical substances. The principal purposes of these studies were to establish relationships between thermodynamic properties of organic substances and their molecular structure, develop methods of extrapolation and prediction of the properties of substances lacking experimental data, and provide thermodynamic background for innovative energy- and resource-saving technologies.

Measurements leading to the calculation of thermodynamic properties in the ideal-gas state for 2-methylindole (Chemical Abstracts registry number [95-20-5]) are reported. Experimental methods were adiabatic heat-capacity calorimetry, differential scanning calorimetry (d.s.c.), comparative ebulliometry, inclined-piston manometry, and oxygen bomb calorimetry. The critical temperature of 2-methylindole was determined experimentally with d.s.c. Molar thermodynamic functions for the condensed and ideal-gas states were derived from the experimental results. Statistical calculations were performed based on molecular geometry optimization and vibrational frequencies using B3LYP hybrid density functional theory with the def2-TZVPPD basis set. Excellent accord between computed and experimentally-derived ideal-gas entropies is shown. The enthalpy of formation for 2-methylindole in the gas phase was computed with an atomization-based protocol described recently, and excellent agreement with the experimental values is seen. The experimental literature for enthalpies of formation in the gas phase for 1- and 2-ring pyrrollic compounds is reviewed, and comparisons with computed values further support the findings here. All experimental results are compared with property values reported in the literature, where possible.

The feed wastes and waste water treatment plants are the major sources for the entry of N-oxides into the soils then to aquatic life. The complexation of actinides with potentially stable anthropogenic ligands facilitate the transportation and migration of the actinides from the source confinement. The present study describes the determination of thermodynamic parameters for the complexation of Th(IV) with the three isomeric pyridine monocarboxylates (PCNO) namely picolinic acid-N-oxide (PANO), nicotinic acid-N-oxide (NANO) and isonicotinic acid-N-oxide (IANO). The potentiometric and isothermal calorimetric titrations were carried out to determine the stability and enthalpy of the formations for all the Th(IV)-PCNO complexes. Th-PANO complexes are more stable than Th-NANO and Th-IANO complexes which can be attributed to chelate formation in the former complexes. Formation of all the Th-PCNO complexes are endothermic and are entropy driven. The geometries for all the predicted complexes are optimized the energies, bond distances and charges on individual atoms are obtained using TURBOMOLE software. The theoretical calculation corroborated the experimental determinations.

We report precise experimental values of the enthalpy of sublimation (Δ ) of quenched condensed films of neon (Ne), nitrogen (N), oxygen (O), argon (Ar), carbon dioxide (CO), krypton (Kr), xenon (Xe), and water (HO) vapor using a single consistent measurement platform. The experiments are performed well below the triple point temperature of each gas and fall in the temperature range where existing experimental data is very limited. A 6 cm and 400 µm thick double paddle oscillator (DPO) with high quality factor (Q ≈ 4 × 10 at 298K) and high frequency stability (33 parts per billion) is utilized for the measurements. The enthalpies of sublimation are derived by measuring the rate of mass loss during temperature programmed desorption. The mass change is detected due to change in the resonance frequency of the self-tracking oscillator. Our measurements typically remain within 10% of the available literature, theory, and National Institute of Standards and Technology (NIST) () values, but are performed using an internally consistent method across different gases.

The equilibrium solubility of ribavirin in solvent mixtures of {methanol (1) + water (2)}, {-propanol (1) + water (2)}, {acetonitrile (1) + water (2)} and {1,4-dioxane (1) + water (2)} was determined experimentally by using isothermal dissolution equilibrium method within the temperature range from (278.15 to 318.15) K under atmospheric pressure (101.1 kPa). At the same temperature and mass fraction of methanol (-propanol, acetonitrile or 1,4-dioxane), the mole fraction solubility of ribavirin is greater in (methanol + water) than in the other three solvent mixtures. The preferential solvation parameters were derived from their thermodynamic solution properties by means of the inverse Kirkwood-Buff integrals. The preferential solvation parameters for methanol, -propanol, acetonitrile or 1,4-dioxane ( ) were negative in the four solvent mixtures with a very wide compositions, which indicated that ribavirin was preferentially solvated by water. Temperature had little effect on the preferential solvation magnitudes. The higher solvation by water could be explained in terms of the higher acidic behaviour of water interacting with the Lewis basic groups of the ribavirin. Besides, the solubility of the drugs was mathematically represented by using the Jouyban-Acree model, van't Hoff-Jouyban-Acree model and Apelblat-Jouyban-Acree model obtaining average relative deviations lower than 1.57% for correlative studies. It is noteworthy that the solubility data presented in this work contribute to expansion of the physicochemical information about the solubility of drugs in binary solvent mixtures and also allows the thermodynamic analysis of the respective dissolution and specific solvation process.

We explore a novel method for determining the dew-point density and dew-point pressure of fluid mixtures and compare it to traditional methods. The () behavior of three (methane + propane) mixtures was investigated with a two-sinker magnetic suspension densimeter over the temperature range of (248.15 to 293.15) K; the measurements extended from low pressures into the two-phase region. The compositions of the gravimetrically prepared mixtures were (0.74977, 0.50688, and 0.26579) mole fraction methane. We analyzed isothermal data by: (1) a "traditional" analysis of the intersection of a virial fit of the ( vs. ) data in the single-phase region with a linear fit of the data in the two-phase region; and (2) an analysis of the adsorbed mass on the sinker surfaces. We compared these to a traditional isochoric experiment. We conclude that the "adsorbed mass" analysis of an isothermal experiment provides an accurate determination of the dew-point temperature, pressure, and density. However, a two-sinker densimeter is required.

The speed of sound of two (argon + carbon dioxide) mixtures was measured over the temperature range from (275 to 500) K with pressures up to 8 MPa utilizing a spherical acoustic resonator. The compositions of the gravimetrically prepared mixtures were (0.50104 and 0.74981) mole fraction carbon dioxide. The vibrational relaxation of pure carbon dioxide led to high sound absorption, which significantly impeded the sound-speed measurements on carbon dioxide and its mixtures; pre-condensation may have also affected the results for some measurements near the dew line. Thus, in contrast to the standard operating procedure for speed-of-sound measurements with a spherical resonator, non-radial resonances at lower frequencies were taken into account. Still, the data show a comparatively large scatter, and the usual repeatability of this general type of instrument could not be realized with the present measurements. Nonetheless, the average relative combined expanded uncertainty ( = 2) in speed of sound ranged from (0.042 to 0.056)% for both mixtures, with individual state-point uncertainties increasing to 0.1%. These uncertainties are adequate for our intended purpose of evaluating thermodynamic models. The results are compared to a Helmholtz energy equation of state for carbon capture and storage applications; relative deviations of (-0.64 to 0.08)% for the (0.49896 argon + 0.50104 carbon dioxide) mixture, and of (-1.52 to 0.77)% for the (0.25019 argon + 0.74981 carbon dioxide) mixture were observed.

This paper reports the thermal, thermodynamic, thermophysical and surface properties of eight ionic liquids with fluorinated alkyl side chain lengths equal or greater than four carbon atoms. Melting and decomposition temperatures were determined together with experimental densities, surface tensions, refractive indices, dynamic viscosities and ionic conductivities in a temperature interval ranging from 293.15 to 353.15 K. The surface properties of these fluorinated ionic liquids were discussed and several thermodynamic functions, as well as critical temperatures, were estimated. Coefficients of isobaric thermal expansion, molecular volumes and free volume effects were calculated from experimental values of density and refractive index and compared with previous data. Finally, Walden plots were used to evaluate the ionicity of the investigated ionic liquids.

Polycyclic aromatic hydrocarbons (PAH) are common components of many materials, such as petroleum and various types of tars. They are generally present in mixtures, occurring both naturally and as byproducts of fuel processing operations. It is important to understand the thermodynamic properties of such mixtures in order to understand better and predict their behavior (, fate and transport) in the environment and in industrial operations. To characterize better the thermodynamic behavior of PAH mixtures, the phase behavior of a binary (anthracene + phenanthrene) system was studied by differential scanning calorimetry, X-ray diffraction, and the Knudsen effusion technique. Mixtures of (anthracene + phenanthrene) exhibit non-ideal mixture behavior. They form a lower-melting, phenanthrene-rich phase with an initial melting temperature of 372 K (identical to the melting temperature of pure phenanthrene) and a vapor pressure of roughly ln/Pa = -2.38. The phenanthrene-rich phase coexists with an anthracene-rich phase when the mole fraction of phenanthrene () in the mixture is less than or equal to 0.80. Mixtures initially at = 0.90 consist entirely of the phenanthrene-rich phase and sublime at nearly constant vapor pressure and composition, consistent with azeotrope-like behavior. Quasi-azeotropy was also observed for very high-content anthracene mixtures (2.5 < < 5) indicating that anthracene may accommodate very low levels of phenanthrene in its crystal structure.

A literature overview of enthalpy of mixing data for liquid Co-Sn alloys shows large scattering but no clear temperature dependence. Therefore drop calorimetry was performed in the Co-Sn system at twelve different temperatures in 100 K steps in the temperature range (673 to 1773) K. The integral enthalpy of mixing was determined starting from 1173 K and fitted to a standard Redlich-Kister polynomial. In addition, the limiting partial molar enthalpy of Co in Sn was investigated by small additions of Co to liquid Sn at temperatures (673 to 1773) K. The integral and partial molar enthalpies of the Co-Sn system generally show an exothermic mixing behavior. Significant temperature dependence was detected for the enthalpies of mixing. The minimum integral enthalpy values vary with rising temperature from approx. -7820 J/mol at  = 1173 K to -1350 J/mol at  = 1773 K; the position of the minimum is between (59 and 61) at.% Co. The results are discussed and compared with literature data available for this system. X-ray studies and scanning electron microscopy of selected alloys obtained from the calorimetric measurements were carried out in order to check the completeness of the solution process.

The heat capacities of two samples of a fcc Cu-Zn alloy with the composition CuZn15 and CuZn34 were measured from  = 5 K to 573 K using relaxation and differential scanning calorimetry. Below ∼90 K, they are characterised by negative excess heat capacities deviating from ideal mixing by up to -0.20 and -0.44 J · mol · K for CuZn15 and CuZn34, respectively. The excess heat capacities produce excess vibrational entropies, which are less negative compared to the excess entropy available from the literature. Since the literature entropy data contain both, the configurational and the vibrational part of the entropy, the difference is attributed to the excess configurational entropy. The thermodynamics of different short-range ordered samples was also investigated. The extent of the short-range order had no influence on the heat capacity below  = 300 K. Above  = 300 K, where the ordering changed during the measurement, the heat capacity depended strongly on the thermal history of the samples. From these data, the heat and entropy of ordering was calculated. The results on the vibrational entropy of this study were also used to test a relationship for estimating the excess vibrational entropy of mixing.

The heat capacity of one Na-rich and two K-rich samples of the NaCl-KCl (halite-sylvite) crystalline solution was investigated between 5 and 300 K. It deviated positively from ideal behaviour with a maximum at 40 K. The thereby produced excess entropy at 298.15 K was described by a symmetric Margules mixing model yielding [Formula: see text] = 8.73 J/mol/K. Using enthalpy of mixing data from the literature and our data on the entropy, the solvus was calculated for a pressure of 10 Pa and compared with the directly determined solvus. The difference between them can be attributed to the effect of Na-K short range ordering (clustering).

Integral molar enthalpies of mixing were determined by drop calorimetry for Cu-Li-Sn at 1073 K along five sections / ≈ 1:1, / ≈ 2:3, / ≈ 1:4, / ≈ 1:1, and / ≈ 1:4. The integral and partial molar mixing enthalpies of Cu-Li and Li-Sn were measured at the same temperature, for Li-Sn in addition at 773 K. All binary data could be described by Redlich-Kister-polynomials. Cu-Li shows an endothermic mixing effect with a maximum in the integral molar mixing enthalpy of ∼5300 J · mol at  = 0.5, Li-Sn an exothermic minimum of ∼ -37,000 J · mol at  ∼ 0.2. For Li-Sn no significant temperature dependence between 773 K and 1073 K could be deduced. Our measured ternary data were fitted on the basis of an extended Redlich-Kister-Muggianu model for substitutional solutions. Additionally, a comparison of these results to the extrapolation model of Chou is given.

The thermodynamic properties of liquid (Au-Sb-Sn) alloys were studied with an electromotive force (EMF) method using the eutectic mixture of KCl/LiCl with addition of SnCl as a liquid electrolyte. Activities of Sn in the liquid alloys were measured at three cross-sections with constant molar ratios of Au:Sb = 2:1, 1:1, and 1:2 with tin in the concentration range between 5 at.% and 90 at.% from the liquidus of the samples up to 1073 K. The integral Gibbs excess energies and the integral enthalpies at 873 K were calculated by Gibbs-Duhem integration. Additionally liquid Au-Sb alloys have been measured at 913 K with the EMF method as no reliable data for the Gibbs excess energies have been found in literature. The eutectic mixture of KCl/LiCl with addition of SbCl has been used as an electrolyte for the measurements. The Gibbs excess energies from the (Au + Sb) system were necessary for the integration of the thermodynamic properties of the ternary (Au + Sb + Sn) system.

Accurate enthalpies of formation of hydrofluoric acid in the gas and liquid states as well as in aqueous solutions are critical for reduction and interpretation of combustion calorimetry data for fluorinated compounds. Analysis of current recommendations reveals inconsistencies with the existing literature that can significantly affect experimental values derived using these recommendations. Through thorough and comprehensive analysis of available experimental data, including the sources not considered before, we provide recommendations that substantially improve consistency with these results. However, the scatter in the existing data also prevents further improvements and uncertainty reduction. New experimental data, particularly for aqueous HF solutions, are needed to advance.

Based on room-temperature densities measured in this research for ionic nanofluids (INFs) with four ionic liquids (ILs), we conclude that evacuation is a necessary step to maximize the IL penetration into multiwalled carbon nanotubes (MWCNT). An improved procedure for reproducible preparation of INFs is proposed. Thermal behavior of five (1-butyl-3-methylimidazolium hexafluorophosphate + MWCNT) samples was studied by adiabatic calorimetry over the temperature range (78 to 370) K. The samples contained from 0.11 to 0.92 mass fraction of the nanophase. Their appearance changed from the fluid to the powder with increasing the MWCNT content. For the fluid samples, the specific heat capacity was found be an additive quantity of the specific heat capacities of the components for the crystal and liquid phases, and the temperatures of phase transitions did not change relative to the bulk values. For the powder-like sample with the highest IL content, a sigmoidal heat capacity curve was observed. Thus, the internal diameter of the studied MWCNT was small enough to switch from the isothermal melting process to the gradual transition from the crystal-like structures to the liquid-like ones.

High quality thermophysical property data are essential to many scientific and engineering applications. These data are produced at a high rate and are affected by a range of experimental and reporting error sources that often exceed stated uncertainties. As a result, critical evaluation is required to establish the limits of reliability in a quantified way. The present work describes reporting recommendations and property data validation methods developed and applied at the Thermodynamics Research Center at NIST through the use of the ThermoData Engine (TDE; SRD 103a/b) software. Examples are provided with an emphasis on various consistency checks, which may include the use of equations of state (EOS).

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 (, , , and forms) were observed and studied. A continuous transformation to the stable 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. Condensed-phase heat capacities were measured by adiabatic and Tian-Calvet calorimetry in the wide temperature interval from 5 K to 368 K. Experimental data of L- and 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.