Henry’s law constants (IUPAC Recommendations 2021)

Henry’s law states that the abundance of a volatile solute dissolved in a liquid is proportional to its abundance in the gas phase. It applies at equilibrium and in the limit of infinite dilution of the solute. For historical reasons, numerous different definitions, names, and symbols are used in the literature to express the proportionality coefficient, denoted the “Henry’s law constant”. Here, a consistent set of recommendations is presented. An important distinction is made between two new recommended reciprocal quantities: “Henry’s law solubility constant” (H s) and “Henry’s law volatility constant” (H v). Eight recommended variants of H s and H v are described and relations among them presented.

Diffusion Coefficients at Infinite Dilution of Carbon Dioxide and Methane in Water, Ethanol, Cyclohexane, Toluene, Methanol, and Acetone: A PFG-NMR and MD Simulation Study

Diffusion coefficients at infinite dilution are important basic data for all processes involving mass transfer. They can be obtained from studying samplesin equilibrium using nuclear magnetic resonance spectroscopy with pulsed field gradients (PFG-NMR), a technique which is widely used in chemistry but isonly rarely applied in engineering studies. This advantageous technique was employed here to measure the self-diffusion coefficients of diluted solutions ofcarbon dioxide and methane in the pure solvents water, ethanol, cyclohexane, toluene, methanol, and acetone at 298.15 K. For the systems (carbon dioxide +water) and (carbon dioxide + ethanol), measurements were also carried out at 308.15 K, 318.15 K and 333.15 K. Except for (methane + water) and (methane +toluene), no literature data for the methane-containing systems were previously available. At the studied solute concentrations, there is practically no differencebetween the self-diffusion coefficient and the mutual diffusion coefficient. The experimental results are compared to experimental literature data as well as toresults from semi-empirical methods for the prediction of diffusion coefficients at infinite dilution. Furthermore, molecular dynamics simulations were carried outfor all systems to determine the diffusion coefficient at infinite dilution based on force fields that were taken from the literature, and the results are compared tothe experimental data and those from the classical prediction methods.

Thermodynamic Solution Properties of a Biodegradable Chelant (L-glutamic-N,N-diacetic Acid, L-GLDA) and Its Sequestering Ability toward Cd2+

The thermodynamics of the interaction of L-glutamic-N,N-diacetic acid (GLDA) with protons was studied potentiometrically at different temperatures, ionic strengths and ionic media. Four protonation constants and corresponding enthalpy changes occurred at infinite dilution together with temperature and ionic strength coefficients. The medium effect was also interpreted in terms of the formation of weak complexes between the ligand and the cations of supporting electrolytes, resulting in a greater tendency of GLDA to chemically interact with Na+ rather than K+ and, in turn, (CH3)4N+. Formation constants of GLDA with Cd2+ were determined in NaCl(aq) at different ionic strength values. Five complex species were found, namely CdL2−, CdHL−, CdH2L0(aq), Cd2L0(aq), and Cd(OH)L3−, whose formation constant values at infinite dilution were log β = 12.68, 17.61, 20.76, 17.52, and 1.77, respectively. All the species results were relevant in the pH range of natural waters, although the Cd2L0(aq) was observed only for CCd ≥ CGLDA and concentrations of >0.1 mmol dm−3. The sequestering ability of GLDA toward Cd2+, evaluated by means of pL0.5, was maximum at pH~10, whereas the presence of a chloride containing a supporting electrolyte exerted a negative effect. Among new generation biodegradable ligands, GLDA was the most efficient in Cd2+ sequestration.

Solutions, in Particular Dilute Solutions of Nonelectrolytes: A Review

The liquid state is one of the three principal states of matter and arguably the most important one; and liquid mixtures represent a large research field of profound theoretical and practical interest. This topic is of importance in many areas of the applied sciences, such as in chemical engineering, geochemistry, the environmental sciences, biophysics and biomedical technology. First, I will concisely present a review of important concepts from classical thermodynamics of nonelectrolyte solutions; this will be followed by a survey of (semi-)empirical approaches to representing the composition and temperature dependence of selected thermodynamic mixture properties, and finally the focus will be on dilute binary nonelectrolyte solutions where one component, a supercritical solute, is present in much smaller quantity than the other component, called the solvent. Partial molar properties in the limit of infinite dilution (indicated by a superscript ∞) are of particular interest. For instance, activity coefficients (Lewis–Randall (LR) convention) are customarily used to characterize mixing behavior, and infinite-dilution values $$\gamma_{i}^{{{\text{LR,}}\infty }}$$ γ i LR, ∞ provide a convenient route for obtaining binary parameters for several popular solution models. When discussing solute (j)—solvent (i) interactions in solutions where the solute is supercritical, the Henry fugacity $$h_{j,i} \left( {T,P} \right)$$ h j , i T , P , also known as Henry’s law (HL) constant, is a measurable thermodynamic key quantity. Its temperature dependence yields information on the partial molar enthalpy change on solution $$\Delta H_{j}^{\infty } \left( {T,P} \right)$$ Δ H j ∞ T , P , while its pressure dependence yields information on the partial molar volume $$V_{j}^{{{\text{L,}}\infty }} \left( {T,P} \right)$$ V j L, ∞ T , P of solute j in the liquid phase (superscript L). I will clarify issues frequently overlooked, touch upon solubility data reduction and correlation, report a few recent high-precision experimental results on dilute aqueous solutions of supercritical nonelectrolytes, and show the equivalency of results for caloric quantities (e.g. $$\Delta H_{j}^{\infty }$$ Δ H j ∞ ) obtained via van ’t Hoff analysis of high-precision solubility data with directly measured calorimetric data.

Hybridizing Physical and Data-driven Prediction Methods for Physicochemical Properties

We present a generic way to hybridize physical and data-driven methods for predicting physicochemical properties. The approach ‘distills’ the physical method's predictions into a prior model and combines it with sparse experimental data using Bayesian inference. We apply the new approach to predict activity coefficients at infinite dilution and obtain significant improvements compared to the physical and data-driven baselines and established ensemble methods from the machine learning literature.

QSPR modeling of selectivity at infinite dilution of ionic liquids

The intelligent choice of extractants and entrainers can improve current mixture separation techniques allowing better efficiency and sustainability of chemical processes that are both used in industry and laboratory practice. The most promising approach is a straightforward comparison of selectivity at infinite dilution between potential candidates. However, selectivity at infinite dilution values are rarely available for most compounds so a theoretical estimation is highly desired. In this study, we suggest a Quantitative Structure–Property Relationship (QSPR) approach to the modelling of the selectivity at infinite dilution of ionic liquids. Additionally, auxiliary models were developed to overcome the potential bias from big activity coefficient at infinite dilution from the solute. Data from SelinfDB database was used as training and internal validation sets in QSPR model development. External validation was done with the data from literature. The selection of the best models was done using decision functions that aim to diminish bias in prediction of the data points associated with the underrepresented ionic liquids or extreme temperatures. The best models were used for the virtual screening for potential azeotrope breakers of aniline + n-dodecane mixture. The subject of screening was a combinatorial library of ionic liquids, created based on the previously unused combinations of cations and anions from SelinfDB and the test set extractants. Both selectivity at infinite dilution and auxiliary models show good performance in the validation. Our models’ predictions were compared to the ones of the COSMO-RS, where applicable, displaying smaller prediction error. The best ionic liquid to extract aniline from n-dodecane was suggested.

Imidazolium Based Ionic Liquids: Unbiased Recovering of Vaporization Enthalpies from Infinite-Dilution Activity Coefficients

We propose and test an efficient approach for the assessment of the enthalpies of vaporization of ionic liquids at the reference temperature 298.15 K. The approach is based on activity coefficients at infinite dilution of volatile organic solutes in ionic liquids bearing the imidazolium cation of the general formula [Cnmim][Anion].