Journal of Chemical Thermodynamics最新文献

{"title":"Exploring molecular interactions between methyl Myristate and 2-alcohols: Free volume theory perspective","authors":"Sanaz Gharehzadeh Shirazi,&nbsp;Samaneh Heydarian,&nbsp;Hassan Moghanian,&nbsp;Mohamad Naseh","doi":"10.1016/j.jct.2025.107485","DOIUrl":"10.1016/j.jct.2025.107485","url":null,"abstract":"<div><div>This study investigates the thermophysical properties of binary mixtures consisting of methyl myristate (MM) and a homologous series of 2-alkanols (ranging from 2-propanol to 2-hexanol) over a temperature range of 293.15 to 323.15 K. Experimental measurements of liquid densities and viscosities reveal significant deviations from ideal behavior, characterized by positive excess molar volumes and negative viscosity deviations across all examined mixtures. The observed positive deviations in excess molar volume suggest weak intermolecular interactions between MM and the 2-alkanols. Furthermore, both an increase in the alkyl chain length of the 2-alkanols and temperature rise were found to reduce these molecular interactions, leading to more pronounced excess volumes. To better understand the viscosity behavior of both pure components and their mixtures, we applied free volume theory. This theoretical approach demonstrated excellent agreement with experimental data, with a maximum deviation of only 2.41 % observed in the MM/2-propanol system.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107485"},"PeriodicalIF":2.2,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143747200","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The 2,2,4-trimethylpentane + ethyl propanoate binary system: density, Bancroft point and vapor–liquid equilibrium at 30, 60 and 101.3 kPa","authors":"Stéphane Vitu ,&nbsp;Kaoutar Berkalou ,&nbsp;Jean-Louis Havet ,&nbsp;Vincent Caqueret","doi":"10.1016/j.jct.2025.107486","DOIUrl":"10.1016/j.jct.2025.107486","url":null,"abstract":"<div><div>The 2,2,4-trimethylpentane (isooctane) – ethyl ethanoate binary system was experimentally investigated. The density of the mixture was measured using a vibrating-tube apparatus and is reported at temperatures <em>T</em> = (288.15, 298.15, 308.15 and 318.15) K. The mixture exhibits positive excess molar volumes. Isobaric vapor-liquid equilibrium (VLE) of the system were obtained at three pressures <em>P</em> = (30, 60 and 101.3) kPa. Pure components vapor pressures were also acquired over a range of <em>P</em> = (20 to 160) kPa. Equilibrium data were measured using a recirculation ebulliometer (Gillespie-type VLE cell).</div><div>The 2,2,4-trimethylpentane – ethyl ethanoate presents a Bancroft point within the investigated pressure range and, consequently, an azeotropic behavior at each studied pressure. The azeotropic coordinates, derived from the measured VLE data, are reported. A notable dependence of the azeotropic composition on pressure was observed.</div><div>The NRTL and Wilson activity coefficient models were used to correlate the VLE data. Temperature-dependent interaction parameters were determined, enabling precise correlation of the reported VLE data. The predictive UNIFAC (Dortmund) model was also tested. While it produced accurate results at 30 kPa, significant deviations were noted at higher pressures.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107486"},"PeriodicalIF":2.2,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143739693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Measurement and correlation solubility of 7-amino-6-nitrobenzodifuroxan in fifteen pure solvents from 288.15 to 333.15 K","authors":"Hai-Fang Wang","doi":"10.1016/j.jct.2025.107487","DOIUrl":"10.1016/j.jct.2025.107487","url":null,"abstract":"<div><div>7-Amino-6-nitrobenzodifuroxan (ANBDF) solubility was determined using a laser dynamic technique from 288.15 K to 333.15 K under 0.1 MPa in fifteen pure solvents, including methanol, ethanol, acetone, cyclohexanone, ethyl acetate, acetonitrile, dichloromethane, 1,2-dichloroethane, ethanoic acid, propanoic acid, toluene, o-xylene, N-Methylpyrrolidone (NMP), <em>N</em>,<em>N</em>-Dimethylformamide (DMF), Dimethyl sulfoxide (DMSO). ANBDF might become more soluble in fifteen pure solvents as the temperature rose. At 298.15 K, the following substances dissolve ANBDF in the following order: DMSO &gt; NMP &gt; DMF &gt; cyclohexanone &gt; acetone &gt; acetonitrile &gt; ethyl acetate &gt; ethanoic acid &gt;1,2-dichloroethane &gt; o-xylene &gt; propanoic acid &gt; methanol &gt; dichloromethane &gt; toluene &gt; ethanol. The KAT-LSER model was used to study the influence of the solvent, and it revealed that the acidity of the solvents' hydrogen bonds has a stronger impact on the solubility of ANBDF. The solubility of ANBDF was correlated using van't Hoff equation, modified Apelblat equation, Yaws equation and polynomial empirical equation. In addition, thermodynamic parameters such as the standard dissolution enthalpy, standard dissolution entropy, and standard Gibbs free energy were calculated based on the experimental solubility values. The dissolution process of ANBDF could be an enthalpy-driven, non-spontaneous and endothermic process in fifteen pure solvents. The measurement and fitting solubility of ANBDF have important guiding significance for the purification and crystallization of its preparation process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107487"},"PeriodicalIF":2.2,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143747199","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comments on “solubility determination, correlation, solvent effect and thermodynamic properties of tolnaftate in ten mono-solvents and binary solvent systems from 283.15 K to 328.15 K\"","authors":"Allison Kabin,&nbsp;Dhishithaa Kumarandurai,&nbsp;Bradley Lin,&nbsp;William E. Acree","doi":"10.1016/j.jct.2025.107484","DOIUrl":"10.1016/j.jct.2025.107484","url":null,"abstract":"<div><div>A polemic is given regarding the solution models used by Wang and coworkers to correlate the solubility behavior of tolnaftate in ten organic mono-solvents and in binary acetic acid + ethylene glycol solvent mixtures. For several of the mixtures studied authors' calculated curve-fit parameters yielded mole fraction solubilities that exceeded unity.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"207 ","pages":"Article 107484"},"PeriodicalIF":2.2,"publicationDate":"2025-03-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143704238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Liquid−liquid equilibrium for ternary systems of 1-Octene +2-Hexanone + ionic liquid: Phase equilibrium measurement and correlation","authors":"Xianming Zhang ,&nbsp;Yanping Li ,&nbsp;Yongli Wu ,&nbsp;Yunfei Wang ,&nbsp;Panpan Yan ,&nbsp;Zhilei Zheng ,&nbsp;Hongyu Peng ,&nbsp;Yuexin Chu","doi":"10.1016/j.jct.2025.107483","DOIUrl":"10.1016/j.jct.2025.107483","url":null,"abstract":"<div><div>Liquid–liquid equilibrium (LLE) for the binary systems of 1-octene +1-ethyl-3-methylimidazolium acetate ([EMIM][Ac]), 1-octene +1-butyl-3-methylimidazolium acetate ([BMIM][Ac]), 1-octene +1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF₄]), 2-hexanone + [EMIM][Ac], and 2-hexanone + [BMIM][Ac], and the ternary systems of 1-octene +2-hexanone + [EMIM][Ac], 1-octene +2-hexanone + [BMIM][Ac], and 1-octene +2-hexanone + [BMIM][BF₄] were measured at 298.15 K, 303.15 K and 313.15 K under 101.3 kPa. The solute distribution coefficient (<em>D</em>) and selectivity (<em>S</em>) were calculated to investigate the efficiencies of [EMIM][Ac], [BMIM][Ac], and [BMIM][BF₄] as solvents. Moreover, the temperature dependencies of <em>D</em> and <em>S</em> were investigated in this study. NRTL and UNIQUAC models were applied to correlate the experimental LLE data.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107483"},"PeriodicalIF":2.2,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143621166","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solubility determination, model evaluation, molecular simulation and thermodynamic analysis of sulfentrazone (Form I) in single and binary solvents","authors":"Haifang Mao ,&nbsp;Jiangmei Chen ,&nbsp;Qiyu Wang ,&nbsp;Mengjie Luo ,&nbsp;Zhiqing Li ,&nbsp;Changtao Zhou ,&nbsp;Bing Wei ,&nbsp;Jibo Liu ,&nbsp;Miaomiao Jin","doi":"10.1016/j.jct.2025.107475","DOIUrl":"10.1016/j.jct.2025.107475","url":null,"abstract":"<div><div>The molar fraction solubility of sulfentrazone (Form I) in ethanol, n-propanol, i-propanol, n-butanol, and binary solvents (ethanol + water) was measured by a laser dynamic method at temperatures from 278.15 <em>K</em> to 313.15 <em>K</em> under 101.6 <em>kPa</em> (standard uncertainty is <span><math><mi>u</mi><mfenced><mi>p</mi></mfenced></math></span> = 1.2 <em>kPa</em>). The solid-liquid phase equilibrium data were verified using five thermodynamic models: van't Hoff equation, modified Apelblat equation, <em>λh</em> equation, Wilson model, and modified Jouyban-Acree model. The modified Apelblat equation showed the best fitting results for the solubility correlation of sulfentrazone (Form I). In addition, the molecular interaction was analyzed using the Hirshfeld surface analysis, molecular electrostatic potential surface analysis, and Hansen solubility parameters to understand the dissolution mechanism of sulfentrazone (Form I). Molecular dynamics simulation was used to analyze the radial distribution function to explore intermolecular interactions of sulfentrazone (Form I) in ethanol + water binary solvents. Finally, the thermodynamic properties of sulfentrazone (Form I) in the studied solvents were also discussed using the van't Hoff equation, and the results implied that the dissolution of sulfentrazone (Form I) was an endothermic and entropy-driven process. The solubility data and the relevant thermodynamic analysis of sulfentrazone (Form I) provide fundamental guidance for the crystallization and purification of sulfentrazone (Form I).</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107475"},"PeriodicalIF":2.2,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548559","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Density, isothermal compressibility, isobaric thermal expansion, and related excess properties of mixtures of 2-(2-ethoxyethoxy)ethanol + 2-propanol at temperatures from 293.15 K to 353.15 K and pressures up to 70 MPa: Measurements, correlation, and PC-SAFT modeling","authors":"Mohamed Lifi ,&nbsp;Jean-Patrick Bazile ,&nbsp;Jean-Luc Daridon ,&nbsp;Eduardo A. Montero ,&nbsp;Fernando Aguilar ,&nbsp;Natalia Muñoz-Rujas","doi":"10.1016/j.jct.2025.107476","DOIUrl":"10.1016/j.jct.2025.107476","url":null,"abstract":"<div><div>High-temperature and high-pressure density data for the binary mixtures <em>x</em> 2-(2-ethoxyethoxy)ethanol + (1-<em>x</em>) 2-propanol are presented in this work, covering temperatures from 293.15 to 353.15 K and at pressures from 0.1 to 70 MPa. The experimental density data were generated using a vibrating tube densimeter with an uncertainty of 0.5 kg/m³. Experimental density data was fitted by using the Tait-like equation, yielding low standard deviations. Derivative properties such as excess molar volumes, isothermal compressibilities, excess isothermal compressibilities, and isobaric thermal expansions were calculated from the obtained density data. Additionally, the experimental measurements were modeled using PC-SAFT equation of state. The intermolecular interactions, as reflected in the derivative properties for each binary mixture, are thoroughly discussed.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107476"},"PeriodicalIF":2.2,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143548558","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Research on solubility, solvent effect and thermodynamics analysis of Lisinopril dissolution and molecular dynamics simulation","authors":"Yang Yu,&nbsp;Yue Wang,&nbsp;Cunbin Du","doi":"10.1016/j.jct.2025.107474","DOIUrl":"10.1016/j.jct.2025.107474","url":null,"abstract":"<div><div>The knowledge of solubility is indispensable in the pharmaceuticals development, crystal forms design, manufacturing and application. The high-quality solubility facilitates the selection of appropriate solvents for the formulation and purification of pharmaceutical products. In this study, the phase equilibrium of Lisinopril was established in ethanol, 1-propanol, 2-propanol, 1-butanol, acetone, acetonitrile, ethyl acetate, dimethyl sulfoxide (DMSO), <em>N,N</em>-dimethylformamide (DMF), <em>N</em>-methylpyrrolidone (NMP), as well as mixtures of DMSO + ethanol and DMSO +2-propanol. The solubility, solvent effect discussion, molecular dynamics (MD) simulations, molecular interaction analysis, model correlation and thermodynamics evaluation were all conducted. The outcomes of Lisinopril solubility in molarity show a direct correlation with temperature, and the rank was as listed: DMSO (1.013 × 10⁻³, 318.15 K) &gt; ethanol (3.887 × 10⁻⁴, 318.15 K) &gt; 1-propanol (3.277 × 10⁻⁴, 318.15 K) &gt; NMP (2.292 × 10⁻⁴, 318.15 K) &gt; 1-butanol (1.642 × 10⁻⁴, 318.15 K) &gt; DMF (1.217 × 10⁻⁴, 318.15 K) &gt; 2-propanol (8.504 × 10⁻⁵, 318.15 K) &gt; acetone (5.212 × 10⁻⁵, 318.15 K) &gt; acetonitrile (3.201 × 10⁻⁵, 318.15 K) &gt; ethyl acetate (1.851 × 10⁻⁵, 318.15 K). The solubility of Lisinopril in DMSO +2-propanol increased with the increasing content of DMSO, however, co-solvency phenomenon exhibited at <em>w</em> = 0.80 in mixture of DMSO + ethanol, and the maximum solubility is 1.271 × 10⁻³ (3.21-fold increase). The molecular interaction was discussed by preferential solvation in depth. Solvent effect was evaluated by KAT-LSER model which concluded that solute-solvent interactions significantly affect solubility more than solvent-solvent interactions. The contributions of solute-solvent interactions and solvent-solvent interactions 71.01 % and 28.99 %. Furthermore, MD simulation at the molecular level showed that hydrogen bonds can form more readily between molecules and play a crucial role in enhancing dissolution of Lisinopril. Additionally, the Apelblat, Wilson, Jouyban-Acree and Apelblat-Jouyban-Acree models were applied to correlate the Lisinopril solubility data. The greatest values of relative average deviation (<em>RAD</em>) and root-mean-square deviation (<em>RMSD</em>) values were 1.75 % and 1.68 × 10⁻⁵, respectively. Finally, the values of thermodynamic properties were all positive which indicated that the dissolution of Lisinopril was an endothermic and entropy increment process.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107474"},"PeriodicalIF":2.2,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143592414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Gas mixture analysis by temperature-independent, multi-wavelength refractive mixing rules","authors":"J.B.S. Santos ,&nbsp;H.A. Helfstein ,&nbsp;M.T. Saita ,&nbsp;F.T. Degasperi ,&nbsp;R.B. Torres ,&nbsp;E.A. Barbosa","doi":"10.1016/j.jct.2025.107473","DOIUrl":"10.1016/j.jct.2025.107473","url":null,"abstract":"<div><div>The characterization of gaseous mixtures is an increasingly important issue in the fields of fuel analysis and aerosol research. Analyses by refractometry combined with refractive mixing rules are also powerful tools in this area. In this work a setup comprised by a six-laser interferometer and a vacuum system was projected and constructed in order to measure the refractivity of pure inert gases like N₂, CO₂, Ar and O₂ and to study the validity of the refractive mixing rules with binary mixtures of N₂ and Ar for different wavelengths. The light sources used in the experiments were a He<img>ne laser (632.8 nm), a frequency-doubled diode-pumped Nd:YAG laser (532 nm) and four diode lasers emitting at 406.4 nm, 453 nm, 655.3 nm and 825 nm. The experimental refractivity data of the binary mixtures were compared with the theoretical ones obtained from a modified, temperature invariant, Gladstone-dale based refractive mixing rule, by introducing the parameter thermal refractivity (TR). The results obtained by the modified refractive mixing rule proposed by us for dry air were also compared with the refractive measurements of atmospheric air for the six wavelengths. In general the experimental results have shown good agreement with the theoretical predictions, and the dispersive character of the thermal refractivities point out to promising applications in evaluating gas mixtures.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107473"},"PeriodicalIF":2.2,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143512352","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Solid-liquid equilibrium of abscisic acid in twelve pure solvents: Experiments, modeling, and molecular simulation","authors":"Ting Qin ,&nbsp;Jiawei Zhao ,&nbsp;Xiongtao Ji ,&nbsp;Jinyue Yang ,&nbsp;Na Wang ,&nbsp;Baohong Hou ,&nbsp;Ting Wang ,&nbsp;Hongxun Hao","doi":"10.1016/j.jct.2025.107472","DOIUrl":"10.1016/j.jct.2025.107472","url":null,"abstract":"<div><div>Abscisic acid (ABA) is one of the five natural growth regulators for plants and crystallization technology is used in the manufacturing of it. The thermodynamic behavior of it plays an important role in the development and design of crystallization processes. In this study, the solubility of ABA in twelve pure solvents was gravimetrically investigated over the temperature range of 278.15 K to 313.15 K. It was found that the solubility of ABA increased steadily with the rise of temperature. Four thermodynamic models (the modified Apelblat equation, <em>van't Hoff</em> equation, <em>λh</em> model and NRTL model) were applied to correlate the experimental solubility data, and the modified Apelblat equation model showed better fitting performance. The mixed thermodynamic properties of ABA in various pure solvents were also calculated, indicating that the mixed process is spontaneous and entropy-driven. Furthermore, to further explore the solid–liquid equilibrium behavior, Hirshfeld surface of ABA crystal was calculated and molecular dynamics simulations of different systems were performed. Based on equilibrium configurations of different systems, solute–solvent interaction energy was calculated, providing a reasonable explanation for the solubility of ABA. Meanwhile, the radial distribution function (RDF) plots were also employed to analyze the hydrogen bonding interactions between ABA molecules and solvent molecules.</div></div>","PeriodicalId":54867,"journal":{"name":"Journal of Chemical Thermodynamics","volume":"206 ","pages":"Article 107472"},"PeriodicalIF":2.2,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143509486","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}