Thermodynamics Works! Enthalpy and Heat Capacity Changes on Solution from Gas Solubility Data

Battino, Rubin

doi:10.1021/je800315f

“…The thermodynamic relationships connecting many phenomena of solubility were described in ref . The paper discusses how calorimetric information, including enthalpy and heat capacity changes in solution, can be derived from the solubility data of gases in liquids as a function of temperature.…”

Section: Introductionmentioning

confidence: 99%

Influence of Solvent Nature on the Solubility of Halogenated Alkanes

Prezhdo

¹

,

Zubkova

²

,

Prezhdo

³

2012

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The solubility of 19 halogenated alkanes was measured in polar and nonpolar organic solvents using a dynamic method that produces more precise measurements than static methods. The solutions were analyzed with gas chromatography. A discrete-continuum solvation model was applied to investigate the influence of the solvent nature on the solubility of the compounds studied. It was shown that universal interactions between the solvent and the solute molecules, including the dispersive, inductive, and dipole–dipole interactions, dominate the solvation process. The dependences ln x 298 ∼ φα and ln x 298 ∼ φμ were obtained between the solubility logarithms at 298 K (ln x 298) and the parameters that determine the solute–solvent interactions for nonpolar (φα) and polar (φμ) solvents, respectively. The role of the cavity formation energy in the solvation process was demonstrated. Finally, the correlation ln x 298 = f(V 2) was suggested, where V 2 is the volume of a solute molecule in the solution.

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“…Solubilization of oxygen in water is characterized by negative entropy and enthalpy effects and large heat capacity increase . The heat capacity of solubilization of oxygen gas in water at 25 °C is 200 J mol –1 K –1 corresponding to 24 R . , This value is close to those observed for gases with similar molecular size, such as argon or methane. , Based on the above, molecules of oxygen dispersed in water can be considered as hydrophobic solutes promoting the formation of clathrate-like “cages” of water molecules surrounding them ,− or other structures expelling of “fast” molecules of water. , …”

Section: Introductionmentioning

confidence: 63%

State of Oxygen Molecules in Aqueous Supersaturated Solutions

Li

¹

,

Buckin

²

2019

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The state of oxygen in aqueous supersaturated solutions prepared by different methods was studied using highresolution ultrasonic spectroscopy in combination with other techniques. This allowed for nondestructive evaluation of the properties of oxygen solute particles, composed of oxygen molecules and surrounding (coordinating) molecules of water, at equilibrium, supersaturated conditions, and different temperatures and concentrations of O 2 . The results were compared with the behaviors of other types of solutes in water, including H 2 O 2 , which has similar molecular size and mass to O 2 but is characterized by a significantly different type of interaction with water molecules. Additionally, theoretical modeling was performed to assess the ultrasonic characteristics of dispersions of oxygen nanobubbles stabilized by a surface electrical charge. The obtained data indicate a clathrate-like organization of water in the coordination shells of single molecules of O 2 . We did not find any signs of formation of clusters of oxygen molecules in supersaturated solutions. No quantifiable presence of oxygen nanobubbles in the solutions was detected. The state of O 2 molecules was not affected by supersaturation within the analyzed concentration range of oxygen. The results also demonstrated the potential of the ultrasonic technique in precision real-time nondestructive monitoring of oxygen solubilization and outgassing processes.

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“…321) with directly obtained high-precision calorimetric results constitutes a particularly severe test of solubility data. Recently, Wilhelm [169], Wilhelm and Battino [240,241], and Battino [284] presented essentially comprehensive compilations of van 't Hoff-based partial molar enthalpy changes on solution ΔH ∞ 2 and partial molar heat capacity changes on solution ΔC ∞ P,2 for gases dissolved in liquid water at T = 298.15 K and P σ,1 H 2 O; 298.15 K = 3.1691 kPa, and compared them with calorimetrically determined results for Δ sol H and Δ sol C P at high dilution and ambient pressure. Note that high-precision solubility data for nitrogen and carbon monoxide dissolved in water [285,286] are available, but somewhat surprisingly no calorimetric results have been reported so far.…”

Section: And By Analogous Argumentsmentioning

confidence: 99%

Solutions, in Particular Dilute Solutions of Nonelectrolytes: A Review

Wilhelm¹

2021

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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.

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Thermodynamics Works! Enthalpy and Heat Capacity Changes on Solution from Gas Solubility Data

Cited by 5 publications

References 38 publications

Influence of Solvent Nature on the Solubility of Halogenated Alkanes

Influence of Solvent Nature on the Solubility of Halogenated Alkanes

State of Oxygen Molecules in Aqueous Supersaturated Solutions

Solutions, in Particular Dilute Solutions of Nonelectrolytes: A Review

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