Good Reporting Practice for Thermophysical and Thermochemical Property Measurements (IUPAC Technical Report).

Scientific projects frequently involve measurements of thermophysical, thermochemical, and other related properties of chemical compounds and materials. These measured property data have significant potential value for the scientific community, but incomplete and inaccurate reporting often hampers their utilization. The present IUPAC Technical Report summarizes the needs of chemical engineers and researchers as consumers of these data and shows how publishing practices can improve information transfer. In the Report, general principles of Good Reporting Practice are developed together with examples illustrating typical cases of reporting issues. Adoption of these principles will improve the quality, reproducibility, and usefulness of experimental data, bring a better level of consistency to results, and increase the efficiency and impact of research. Closely related to Good Reporting Practice, basic elements of Good Research Practice are also introduced with a goal to reduce the number of ambiguities and unresolved problems within the thermophysical property data domain.

The general phase behavior of mixtures of 1-alkyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide ionic liquids with n-alkyl alcohols.

The liquid-liquid equilibrium (LLE) phase behavior of mixtures of 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]amide (C(2)mimNTf(2)) with the n-alkyl alcohols (C(n)OH; 3≤n≤8) is described. By applying the cloud-point method, the LLEs were determined over a temperature range of 275-423 K at ambient pressure. Partial miscibility with upper critical solution temperatures (UCST) was observed. The UCST increase with increasing chain length of the alcohols. The phase diagrams were analyzed numerically by presuming Ising criticality. Concepts for the description of the asymmetry of the phase diagram by presuming the validity of the rectilinear diameter rule or a nonlinear diameter requested by the theory of complete scaling were applied. The results (UCST, critical composition, width and diameter of the phase diagrams) are compared with similar systems and discussed in terms of the corresponding state behavior; they map on a single curve. From at least 45 individual phase diagrams, general aspects of the behavior of this ionic liquid-alcohol mixture type were extracted. A simple empirical relationship was formulated to allow the description of the UCST with an accuracy of about 10 K when taking the ratio of the molar volumes of the alcohol and the 1-alkyl-3-methylimidazolium cation of the ionic liquid into account.

Revisiting the Liquid-Liquid Phase Behavior of n-Alkanes and Ethanol.

Mixtures of alkanes and ethanol are important in many areas, for example, as fuel blends. This paper describes new experimental data obtained for the liquid-liquid equilibrium phase behavior of normal alkanes (n-alkanes; CnH2n+2; 9 ≤ n ≤ 24) with ethanol. The results were obtained by applying the cloud point method in a temperature range of T = 230-423 K at ambient pressure. All systems are partially miscible with an upper critical solution point. The two phase regions of the phase diagrams show no indication of any obvious optical irregularities, like birefringence, coloring, formation of schlieren, or remarkable turbidity, except critical opalescence. With increasing length of the molecular chain of the n-alkanes, the (liquid-liquid) critical point is shifted to higher temperatures and higher ethanol content. The data are analyzed numerically implying Ising criticality. The nonsymmetric shape of the phase body is considered in different approaches for describing the diameter by presuming (a) the validity of the rectilinear diameter rule, (b) a nonlinear diameter predicted in the theory of complete scaling, and (c) combining both concepts. The numerical analysis yields the critical temperature, the critical composition, the width, and the diameter of the phase diagrams. The results are compared with literature data sets from similar mixtures; these data are also evaluated in terms of the models applied here. Phase diagrams of 13 different sets of mixtures are measured and analyzed to extract general aspects of the behavior of the normal alkane-ethanol mixtures. A simple Flory-Huggins-like approach allows a semiquantitative description of the experimental results of the critical temperatures. Therefore, it confirms the picture of molecular ordering within the solutions.

Lower critical solution temperature in the metastable region of an ionic solution in a non-polar solvent.

Previous studies of the critical behavior of ionic solutions in nonpolar solvents showed mainly upper critical solution temperatures. Now, we report for the solution of tetra-n-butyl ammonium bromide (N4444Br) in toluene a nearly closed miscibility loop, where the lower critical solution temperature (Tc=297.75+/-0.05 K, xc=0.0270+/-5x10(-4)) is located in the region, which is metastable in respect to crystallization of the salt. The new observation is in variance to the former findings according to which the phase separation of ionic solutions in nonpolar solvents is similar to that of the model of charged hard spheres in a dielectric continuum, termed restricted primitive model (RPM), which has an upper critical solution point.

Vapor Liquid Equilibria of 1-Ethyl-3-methylimidazolium Triflate (C2mimTfO) and n-Alkyl Alcohol Mixtures.

The isobaric vapor liquid equilibria (VLE) of different binary mixtures of the ionic liquid (IL) 1-ethyl-3-methylimidazolium trifluoromethanesulfonate (C2mimTfO) with the n-alkyl alcohols, methanol, ethanol, propan-1-ol, and butan-1-ol, are studied at the pressures of p = 500, 700, and 1000 mbar, covering a composition range 0.25-0.35 ≤ x(solvent) ≤ 1.0. Complementarily, the experimental results are compared with calculations by the perturbed-chain statistical associating fluid theory (PC-SAFT) equation of state (EoS). For deriving suitable PC-SAFT parameters, experimental liquid densities were determined for the neat IL C2mimTfO and its longer homologues, 1-butyl-3-methylimidazolium trifluoromethanesulfonate (C4mimTfO) and 1-hexyl-3-methylimidazolium trifluoromethanesulfonate (C6mimTfO), in a temperature range of 288.15 K ≤ T ≤ 363.15 K (C2mimTfO) and 293.15 K ≤ T ≤ 363.15 K (C4mimTfO and C6mimTfO), respectively. The PC-SAFT EoS is found to be suitable for describing the VLEs under study with good accuracy (AARDVLE ≤ 0.4%).

Vapor Liquid Equilibria of Binary Mixtures of 1-Butyl-3-methylimidazolium Triflate (C4mimTfO) and Molecular Solvents: n-Alkyl Alcohols and Water.

Isobaric vapor liquid equilibria (VLE) of binary mixtures of the ionic liquid (IL) 1-butyl-3-methylimidazolium trifluoromethanesulfonate (C4mimTfO) with either water or short chained n-alkyl alcohols (methanol, ethanol, propan-1-ol, and butan-1-ol) are described in this study. Two different microebulliometers and a classical VLE apparatus were compared and the VLEs were determined in the composition range 0.4 ≤ x(solvent) ≤ 1 at three different pressure levels ( p = 500 mbar, 700 mbar, and 1000 mbar). The experimental data were modeled using the soft-SAFT equation of state, which was able to accurately describe the nonideal behavior of these mixtures. The combined experimental-modeling results obtained contribute to establish the structure-property relationship between the C4mimTfO and n-alkyl alcohol molecules and to infer about its influence on the phase behavior of these solvents.

Nature of Mesoscopic Organization in Protic Ionic Liquid-Alcohol Mixtures.

The mesoscopic morphology of mixtures of ethylammonium nitrate, a protic ionic liquid, and n-pentanol is explored for the first time using small angle X-ray scattering as a function of concentration and temperature. Both compounds are amphiphilic and characterized by an extended hydrogen bonding network; however, though macroscopically homogeneous, their mixtures are highly heterogeneous at the mesoscopic spatial scales. Previous structural studies rationalized similar features in related mixtures proposing the existence of large aggregates or micelle- and/or microemulsion-like structures. Here we show that a detailed analysis of the present concentration and temperature resolved experimental data set supports a structural scenario where the mesoscopic heterogeneities are the due to density fluctuations that are precursors of liquid-liquid phase separation. Accordingly no existence of structurally organized aggregates (such as micellar or microemulsion aggregates) is required to account for the mesoscopic heterogeneities detected in this class of binary mixtures.

The ion speciation of ionic liquids in molecular solvents of low and medium polarity.

The ion speciation of ionic liquids dissolved in molecular liquids of low and medium polarity is studied experimentally and theoretically. The ion speciation in some representative systems is characterized by dielectric relaxation spectroscopy and electrical conductance measurements. A corresponding-states approach is used to compare the experimental results with predictions for a reference system of charged hard spheres in a dielectric continuum. Topics of special interest are the formation of ion pairs and larger ion clusters in dilute solutions and their fate at high concentrations, where they have to redissociate in the excess ionic liquid to form the charge-ordered structure of the fused salt. In solvents of low polarity this transition leads to electrical conductance minima and liquid-liquid immiscibilities.

Anomalous corresponding-states surface tension of hydrogen fluoride and of the Onsager model.

In a corresponding-states analysis of the liquid-vapor surface tension originally suggested by Guggenheim, we study the behavior of different simple (i.e., nonpolar), polar and ionic fluids. The results are compared to the corresponding ones for model fluids of each of the three types. For simple and weakly polar fluids (both real and model), the data map onto a master curve, as demonstrated by Guggenheim. For strongly dipolar, associating fluids, which also exhibit hydrogen bonding, one finds deviations from the master curve at low temperatures and, thus, observes the characteristic sigmoid behavior of the reduced surface tension as a function of temperature. The same is obtained for the model ionic fluid, the restricted primitive model. Truly exceptionally low values of the reduced surface tension are found for hydrogen fluoride and for the Onsager model of dipolar fluids, the surface tension of which we evaluate using an approximate hypernetted chain relation to obtain the square-gradient term in a modified van der Waals theory. Remarkably, in the corresponding-states plot, the surface tensions of HF and of the Onsager model agree very closely, while being well separated from the values for the other fluids. We also study the gradual transition of a model fluid from a simple fluid to a strongly dipolar one by varying the relative strength of dipolar and dispersion forces.

Liquid-vapor interface of square-well fluids of variable interaction range.

Properties of the liquid-vapor interface of square-well fluids with ranges of interaction lambda=1.5, 2.0, and 3.0 are obtained by Monte Carlo simulations and from square-gradient theories that combine the Carnahan-Starling equation of state for hard spheres with the second and third virial coefficients. The predicted surface tensions show good agreement with the simulation results for lambda=2 and for lambda=3 in a temperature range reasonably close to the critical point, 0.8