{"title":"胆碱盐的二元水溶液:液体密度(298.15 或 313.15 K)和蒸汽压渗透压(313.15 K)的测定与建模","authors":"Pedro Velho , Eduardo Sousa , Eugénia A. Macedo","doi":"10.1016/j.fluid.2024.114197","DOIUrl":null,"url":null,"abstract":"<div><p>Salts composed of the cholinium cation (such as choline hydroxide and choline chloride) have become one of the main reactants for the synthesis of greener ionic liquids, but, for a proper description of the aqueous solutions of these strong electrolytes by thermodynamic modelling, reliable data on liquid density <span><math><mrow><mo>(</mo><mi>ρ</mi><mo>)</mo></mrow></math></span> and vapour pressure <span><math><mrow><mo>(</mo><mi>p</mi><mo>)</mo></mrow></math></span> are needed, which are often unavailable. So, in this work, the liquid density <span><math><mrow><mo>(</mo><mi>ρ</mi><mo>)</mo></mrow></math></span> of binary aqueous solutions of choline bicarbonate ([Ch][Bic]), choline (2R,3R)-bitartrate ([Ch][Bit]), choline chloride ([Ch]Cl), choline dihydrogen citrate ([Ch][H<sub>2</sub>Cit]) and choline hydroxide ([Ch]OH) were measured at 298.15 or 313.15 K and 0.1 MPa and correlated using second-degree polynomials with salt molality <span><math><mrow><mo>(</mo><mi>m</mi><mo>)</mo></mrow></math></span>, obtaining determination coefficients <span><math><mrow><mo>(</mo><msup><mrow><mi>R</mi></mrow><mn>2</mn></msup><mo>)</mo></mrow></math></span> higher than 0.9974. Furthermore, the osmotic coefficients <span><math><mrow><mo>(</mo><mi>ϕ</mi><mo>)</mo></mrow></math></span> of these binaries were determined using vapour pressure osmometry (VPO), at 313.15 K and 0.1 MPa, being satisfactorily described by the Extended Pitzer Model of Archer, which yielded low values of standard deviation <span><math><mrow><mo>(</mo><mn>3.58</mn><mo><</mo><mspace></mspace><msub><mi>σ</mi><mi>ϕ</mi></msub><mo>·</mo><msup><mrow><mn>10</mn></mrow><mn>3</mn></msup><mo><</mo><mn>12.86</mn><mo>)</mo></mrow></math></span>. Then, the mean molal activity coefficients <span><math><mrow><mo>(</mo><msub><mi>γ</mi><mo>±</mo></msub><mo>)</mo></mrow></math></span> and excess Gibbs free energies <span><math><mrow><mo>(</mo><mrow><msup><mrow><mi>G</mi></mrow><mi>E</mi></msup><mo>/</mo><mi>R</mi><mi>T</mi></mrow><mo>)</mo></mrow></math></span> were calculated, following the order [Ch][H<sub>2</sub>Cit] > [Ch][Bit] > [Ch][Bic] > [Ch]OH > [Ch]Cl, which corresponds to the decreasing polarity of the choline salts and agrees with the empirical law of matching water affinities (LMWA).</p></div>","PeriodicalId":12170,"journal":{"name":"Fluid Phase Equilibria","volume":"587 ","pages":"Article 114197"},"PeriodicalIF":2.8000,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0378381224001730/pdfft?md5=65d168bf91c9bb8476dced56941c57d8&pid=1-s2.0-S0378381224001730-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Binary aqueous solutions of choline salts: Determination and modelling of liquid density (298.15 or 313.15 K) and Vapour Pressure Osmometry (313.15 K)\",\"authors\":\"Pedro Velho , Eduardo Sousa , Eugénia A. Macedo\",\"doi\":\"10.1016/j.fluid.2024.114197\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>Salts composed of the cholinium cation (such as choline hydroxide and choline chloride) have become one of the main reactants for the synthesis of greener ionic liquids, but, for a proper description of the aqueous solutions of these strong electrolytes by thermodynamic modelling, reliable data on liquid density <span><math><mrow><mo>(</mo><mi>ρ</mi><mo>)</mo></mrow></math></span> and vapour pressure <span><math><mrow><mo>(</mo><mi>p</mi><mo>)</mo></mrow></math></span> are needed, which are often unavailable. So, in this work, the liquid density <span><math><mrow><mo>(</mo><mi>ρ</mi><mo>)</mo></mrow></math></span> of binary aqueous solutions of choline bicarbonate ([Ch][Bic]), choline (2R,3R)-bitartrate ([Ch][Bit]), choline chloride ([Ch]Cl), choline dihydrogen citrate ([Ch][H<sub>2</sub>Cit]) and choline hydroxide ([Ch]OH) were measured at 298.15 or 313.15 K and 0.1 MPa and correlated using second-degree polynomials with salt molality <span><math><mrow><mo>(</mo><mi>m</mi><mo>)</mo></mrow></math></span>, obtaining determination coefficients <span><math><mrow><mo>(</mo><msup><mrow><mi>R</mi></mrow><mn>2</mn></msup><mo>)</mo></mrow></math></span> higher than 0.9974. Furthermore, the osmotic coefficients <span><math><mrow><mo>(</mo><mi>ϕ</mi><mo>)</mo></mrow></math></span> of these binaries were determined using vapour pressure osmometry (VPO), at 313.15 K and 0.1 MPa, being satisfactorily described by the Extended Pitzer Model of Archer, which yielded low values of standard deviation <span><math><mrow><mo>(</mo><mn>3.58</mn><mo><</mo><mspace></mspace><msub><mi>σ</mi><mi>ϕ</mi></msub><mo>·</mo><msup><mrow><mn>10</mn></mrow><mn>3</mn></msup><mo><</mo><mn>12.86</mn><mo>)</mo></mrow></math></span>. Then, the mean molal activity coefficients <span><math><mrow><mo>(</mo><msub><mi>γ</mi><mo>±</mo></msub><mo>)</mo></mrow></math></span> and excess Gibbs free energies <span><math><mrow><mo>(</mo><mrow><msup><mrow><mi>G</mi></mrow><mi>E</mi></msup><mo>/</mo><mi>R</mi><mi>T</mi></mrow><mo>)</mo></mrow></math></span> were calculated, following the order [Ch][H<sub>2</sub>Cit] > [Ch][Bit] > [Ch][Bic] > [Ch]OH > [Ch]Cl, which corresponds to the decreasing polarity of the choline salts and agrees with the empirical law of matching water affinities (LMWA).</p></div>\",\"PeriodicalId\":12170,\"journal\":{\"name\":\"Fluid Phase Equilibria\",\"volume\":\"587 \",\"pages\":\"Article 114197\"},\"PeriodicalIF\":2.8000,\"publicationDate\":\"2024-08-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S0378381224001730/pdfft?md5=65d168bf91c9bb8476dced56941c57d8&pid=1-s2.0-S0378381224001730-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Fluid Phase Equilibria\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0378381224001730\",\"RegionNum\":3,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Fluid Phase Equilibria","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0378381224001730","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Binary aqueous solutions of choline salts: Determination and modelling of liquid density (298.15 or 313.15 K) and Vapour Pressure Osmometry (313.15 K)
Salts composed of the cholinium cation (such as choline hydroxide and choline chloride) have become one of the main reactants for the synthesis of greener ionic liquids, but, for a proper description of the aqueous solutions of these strong electrolytes by thermodynamic modelling, reliable data on liquid density and vapour pressure are needed, which are often unavailable. So, in this work, the liquid density of binary aqueous solutions of choline bicarbonate ([Ch][Bic]), choline (2R,3R)-bitartrate ([Ch][Bit]), choline chloride ([Ch]Cl), choline dihydrogen citrate ([Ch][H2Cit]) and choline hydroxide ([Ch]OH) were measured at 298.15 or 313.15 K and 0.1 MPa and correlated using second-degree polynomials with salt molality , obtaining determination coefficients higher than 0.9974. Furthermore, the osmotic coefficients of these binaries were determined using vapour pressure osmometry (VPO), at 313.15 K and 0.1 MPa, being satisfactorily described by the Extended Pitzer Model of Archer, which yielded low values of standard deviation . Then, the mean molal activity coefficients and excess Gibbs free energies were calculated, following the order [Ch][H2Cit] > [Ch][Bit] > [Ch][Bic] > [Ch]OH > [Ch]Cl, which corresponds to the decreasing polarity of the choline salts and agrees with the empirical law of matching water affinities (LMWA).
期刊介绍:
Fluid Phase Equilibria publishes high-quality papers dealing with experimental, theoretical, and applied research related to equilibrium and transport properties of fluids, solids, and interfaces. Subjects of interest include physical/phase and chemical equilibria; equilibrium and nonequilibrium thermophysical properties; fundamental thermodynamic relations; and stability. The systems central to the journal include pure substances and mixtures of organic and inorganic materials, including polymers, biochemicals, and surfactants with sufficient characterization of composition and purity for the results to be reproduced. Alloys are of interest only when thermodynamic studies are included, purely material studies will not be considered. In all cases, authors are expected to provide physical or chemical interpretations of the results.
Experimental research can include measurements under all conditions of temperature, pressure, and composition, including critical and supercritical. Measurements are to be associated with systems and conditions of fundamental or applied interest, and may not be only a collection of routine data, such as physical property or solubility measurements at limited pressures and temperatures close to ambient, or surfactant studies focussed strictly on micellisation or micelle structure. Papers reporting common data must be accompanied by new physical insights and/or contemporary or new theory or techniques.