Excess molar enthalpies of ternary and constituent binary systems {1,2-dichloropropane+2-propanol+2-butanol} at T=298.15 K

Ternary excess molar enthalpies at T=298.15 K and P=101.3 kPa for the system of {1,2-dichloropropane+2-propanol+2-butanol} and their constituent binary systems {1,2-DCP+2-propanol}, {1,2-DCP+2-butanol}, and {2-propanol+2-butanol} have been measured over the whole composition range using an isothermal micro-calorimeter with flow-mixing cell. All of the binary and ternary systems, including three pseudobinary systems, show endothermic behavior except for the binary mixture {2-propanol+2-butanol}, which shows small exothermicity. The Redlich-Kister equation was used to correlate the binary H _{m, ij} ^E data, and the Morris equation to correlate the ternary H _{m, 123} ^E data. Comparisons between the Morris and Radojkovi equations for the prediction of H _m,123 ^E have been also made. The experimental results have been qualitatively discussed in terms of self-association, isomeric effect and chain length among molecules.     

Excess molar volumes for titanium butoxide contained binary and ternary systems at 298.15 K

The reported mixture properties of metal alkoxide are almost none in spite of their increasing usages. In this work, the excess molar volumes (V^E) were determined from measured densities for six binary systems of titanium butoxide (1) + ethanol (2), titanium butoxide (1) + 1-propanol (2), titanium butoxide (1) + 1-butanol (2), ethanol (1) + 1-propanol (2), 1-propanol (1) + 1-butanol (2) and ethanol (1) + 1-butanol (2) at 298.15 K. The experimental V^E were correlated with the Redlich–Kister polynomial. The partial excess molar volumes at infinite dilution were calculated with fitted binary parameters. Additionally the ternary V^E data at 298.15 K were also predicted for three systems of titanium butoxide (1) + ethanol (2) + 1-propanol (3), titanium butoxide (1) + ethanol (2) + 1-butanol (3) and titanium butoxide (1) + 1-propanol (2) + 1-butanol (3) by using the binary contribution model of Radojkovič with the binary Redlich–Kister parameters.     

Experimental data and modeling for excess enthalpies of 2-Pentanol with n-alkanes(C7–C9) at T =(293.15, 298.15 and 303.15) K

Excess molar enthalpies, H~E, for the binary mixtures of 2-pentanol with n-alkanes(n-heptane, n-octane, and nnonane) have been determined at three different temperatures T =(293.15, 298.15 and 303.15) K and normal atmospheric pressure over the entire composition range using a Calvet microcalorimeter. All mixtures show endothermic mixing with the maximum values of the excess enthalpies occurring in the n-alkane-rich region. The H~Edata are smoothed using Redlich–Kister equation. The applicability of the Treszczanowicz–Benson, ERAS,Renon–Prausnitz and Chen–Bagley models to correlate H~Eof studied mixtures is tested, and the agreement between experimental and theoretical results is satisfactory. Each model includes a self-association equilibrium constant that represents hydrogen bonding and an adjustable parameter that reflects physical interactions.     

Excess molar enthalpies for the binary and ternary mixtures of ether compounds (di-isopropyl ether, di-butyl ether, propyl vinyl ether) with ethanol and isooctane at 298.15 K

Excess molar enthalpy (H ^E ) data at 298.15 K are reported for the binary systems di-isopropyl ether (1)+ethanol (2), di-isopropyl ether (1)+isooctane (2), ethanol (1)+isooctane (2), di-butyl ether (1)+ethanol (2), di-butyl ether (1)+isooctane (2), propyl vinyl ether (1)+ethanol (2) and propyl vinyl ether (1)+isooctane (2). These data were obtained by using an isothermal flow calorimeter. The experimental binary H ^E data were well correlated with the Redlich-Kister model, and infinitely dilute partial excess molar enthalpies for each binary were calculated with the fitted Redlich-Kister parameters. Additionally, the isoclines of H ^E for ternary systems di-isopropyl ether (1)+ethanol (2)+isooctane (3), di-butyl ether (1)+ethanol (2)+isooctane (3) and propyl vinyl ether (1)+ethanol (2)+isooctane (3) at 298.15 K were calculated by using the Radojkovič equation. H ^E for all the measured systems in this work shows that mixing is endothermic.     

1-丁基-3-甲基咪唑磷酸二丁酯+甲醇/乙醇+水三元工质溶液混合焓的测量及预测

采用绝热量热法测量了由离子液体1-丁基-3-甲基咪唑磷酸二丁酯([bmim][DBP])分别与CH₃OH、C₂H₅OH和H₂O所组成的3个二元工质溶液体系[bmim][DBP](1)+ CH₃OH(2)/C₂H₅OH(2)/H₂O(2),以及2个三元工质溶液体系[bmim][DBP](1)+ CH₃OH(2)/C₂H₅OH(2)+ H₂O(3)在298.15 K和常压下的摩尔混合焓H_m^E。利用Gibbs-Helmholtz方程和NRTL活度系数模型,对每个二元溶液体系摩尔混合焓的实验数据进行关联,获得模型方程中的组分作用参数。摩尔混合焓的模型拟合值与实验值的平均相对偏差分别为1.81%、1.44%和0.72%。在此基础上预测了2个三元工质溶液体系的摩尔混合焓。结果表明:三元工质溶液体系的摩尔混合焓在实验浓度范围内均为负值,混合为放热过程。表明三元工质溶液具有成为吸收制冷循环新工质溶液的基本特征;采用NRTL模型预测2个三元溶液体系摩尔混合焓的计算值与实验值的平均相对误差分别为2.31%、2.49%。     

四元体系NaCl+NaBO2+Na2CO3+H2O 298.15 K 相平衡研究

柴达木盐湖中具有丰富的盐湖离子,对其中的一个四元体系水盐相图开展研究,采用等温溶解平衡法开展了298.15 K时四元体系NaCl+NaBO₂+Na₂CO₃+H₂O相平衡研究,测定了体系平衡液相组成及密度和折光率,绘制了四元体系NaCl+NaBO₂+Na₂CO₃+H₂O 298.15 K的相图及相应的物化性质图。研究发现NaCl+NaBO₂+Na₂CO₃+H₂O四元体系298.15 K 时包含2个共饱点（E₁、E₂）、5条溶解度曲线（AE₁、BE₁、CE₂、DE₂、E₁E₂）、4个结晶区（NaCl、NaBO₂·4H₂O、Na₂CO₃·7H₂O、NaCl·NaBO₂·2H₂O）。其中三元体系NaCl+NaBO₂+H₂O在298.15 K下产生了复盐NaCl·NaBO₂·2H₂O,通过研究发现该四元体系NaCl+NaBO₂+Na₂CO₃+H₂O在298.15 K下也具有NaCl·NaBO₂·2H₂O复盐区。     

Excess volume and excess enthalpy of binary mixtures composed of 1,2-dichloropropane and 1-alkanol (C5-C8)

The excess molar volumes and excess molar enthalpies at T=298.15 K and atmospheric pressure for the binary systems {CH₃CHClCH₂Cl (1)+CH₃(CH₂) _n?1OH (2)} (n=5 to 8) have been determined over the whole range of composition from the density and heat flux measurements using a digital vibrating-tube densimeter and an isothermal calorimeter, respectively. The measured excess molar volumes of all binary mixtures showed positive symmetrical trend with values increasing with chain length of 1-alkanol. Similarly, excess enthalpy values of all binary mixtures showed skewed endothermic behavior with values increasing with chain length of 1-alkanol. The maxima of excess molar enthalpy values were observed around x₁=0.65 with excess enthalpy value ranging from 1,356.8 J/mol (1-pentanol) to 1,543.4 J/mol (1-octanol). The experimental results of both H _m ^E and V _m ^E are fitted to a modified version of Redlich-Kister equation using the Padé approximant to correlate the composition dependence. The experimental H _m ^E data were also fitted to three local-composition models (Wilson, NRTL, and UNIQUAC). The correlation of excess enthalpy data in these binary systems using UNIQUAC model provides the most appropriate results.     

298.15K时甘露醇-山梨醇-葡萄糖-水四元系及其二元系的密度和黏度

To check the applicabilities of the simple density equation and viscosity equation in the semi-ideal solution theory to nonelectrolyte solutions, the densities and viscosities were measured for the quaternary system mannitol-sorbitol-D-glucose-H2O and its ternary subsystems mannitol-D-glucose-H2O and sorbitol-D-glucose-H2O at 298.15K. The results were used to test the applicability of the simple equations for the density and viscosity of the multicomponent nonelectrolyte solution. The agreements between the predicted and measured results are good.     

Experimental and predicted enthalpies of mixing of mixtures formed from alcohols and sunflower oil at 298.15 K

The enthalpies of mixing of systems formed from alcohols (methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol) and sunflower oil at 298.15 K are presented. Enthalpies were measured in the composition range in which the compounds were miscible. From the experimental measurements, we calculated the heat capacities of the mixtures. Several group contribution models were applied to estimate the enthalpies of mixing of these mixtures. The average deviations varied from 10 to 60%, depending on the model and compound. The best prediction in all cases was the Nitta model, with average deviations from 10 to 30%. The novelty of the work is that models of this type have not been applied previously to predict enthalpies of such large molecules, and the results of the estimates are of the same order as other types of compounds (pure compounds of small size).     

Excess molar volumes and deviations of refractive indices at 298.15 K for binary and ternary mixtures with pyridine or aniline or quinoline

Excess molar volume (V^E) at 298.15 K are reported for the binary systems of heterocyclic nitric compounds: {ethanol + pyridine}, {ethanol + aniline}, {ethanol + quinoline}, {pyridine + aniline}, {pyridine + quinoline}, {aniline + quinoline}, {N-methylformamide (NMF) + pyridine}, {NMF + aniline}, {NMF + quinoline}, {N,N-dimethylformamide (DMF) + pyridine}, {DMF + aniline} and {DMF + quinoline}. The deviations in molar refractivity (ΔR) at 298.15 K are also reported for binary systems: {ethanol + pyridine}, {ethanol + aniline}, {NMF + pyridine}, {NMF + aniline}, {DMF + pyridine}, {DMF + aniline} and {pyridine + aniline}. The determined V^E and ΔR were correlated with the Redlich–Kister equation. In addition, the ternary V^E data at 298.15 K were predicted with correlated binary parameters for the systems: {ethanol + pyridine + aniline}, {ethanol + pyridine + quinoline}, {ethanol + aniline + quinoline}, {NMF + pyridine + aniline}, {NMF + pyridine + quinoline}, {NMF + aniline + quinoline}, {DMF + pyridine + aniline}, {DMF + pyridine + quinoline} and {DMF + aniline + quinoline}. The ternary ΔR data at 298.15 K are also predicted for the systems: {ethanol + pyridine + aniline}, {NMF+ pyridine + aniline} and {DMF + pyridine + aniline}.     

Measurement and correlation of excess enthalpies for water+ethanol+1-buthyl 3-methylimidaozolium tetrafluoroborate system

It is difficult to find physical properties data for systems containing ionic liquids, excess molar enthalpies, binary interaction parameter, etc. In this study, the excess molar enthalpies were measured for water+ethanol+ionic liquid system using a isothermal microcalorimeter at 298.15 K. The ionic liquid used was 1-butyl 3-methyl imidazolium tetrafluoroborate, [BMIM] [BF₄]. The isothermal microcalorimeter (IMC) is a flow-type calorimeter that measures the heat of mixing directly, using specific mixing cell. By employing NRTL, electrolyte-NRTL and UNIQUAC models, binary interaction parameters were determined and investigated for the correlation with vapor liquid equilibrium (VLE). The e-NRTL model with the partial dissociation was employed to correlate the ionic liquid system. The binary data of VLE system were used from literatures. Specifically, UNIQUAC volume and surface area parameters were determined using Bondi radius.     

Excess properties and spectroscopic studies for binary system polyethylene glycol 600 + dimethyl sulfoxide at T =(298.15, 303.15,308.15, 313.15, and 318.15) K

The work presents density (ρ) and viscosity (η) data of binary system polyethylene glycol 600 (PEG) + dimethyl sulfoxide (DMSO) over the entire concentration range at T =(298.15,303.15,308.15,313.15 and 318.15) K and atmospheric pressure.On the basis of density and viscosity values,the excess properties of PEG (1) + DMSO (2) mixtures,including excess molar volume (VEm),viscosity deviation (△η),excess free energies of activation (△G*E),and isobaric thermal expansion coefficient (αp),were calculated.At the same time,in order to conjecture the density viscosity under different conditions,the density and viscosity data were fitted with the corresponding formula.The calculated results of VEm,△η,and △G*E were fitted with the Redlich-Kister equation to derive coefficients and estimate the standard deviations (σ) between the experimental and calculated values.Moreover,the intermolecular interaction of PEG with DMSO was discussed on the basis of FTIR and UV-Vis spectral results of PEG (1) + DMSO (2) mixtures.The results indicated that there were the hydrogen bonding and interactions of hvdroxvl hydrogen atoms in PEG with oxygen atoms in DMSO.     

Viscometric and FTIR studies of molecular interactions in 2-propanol+hydrocarbons mixtures at 298.15 and 308.15 K

The deviation in viscosity was coupled with respective excess molar volume data to study the molecular interaction in binary mixtures with one associated component. This approach was applied to the experimentally measured viscosity and excess molar volume data of the 2-propanol+hydrocarbons at 298.15 K and 308.15 K. It was suggested that depolymerization power of aromatic hydrocarbon toward 2-propanol as well as strength of intermolecular interactions (electron-donor-acceptor type) between monomer of 2-propanol and aromatics depend on π-electron density of the aromatic hydrocarbon. These interactions were further confirmed by FTIR spectroscopy. The viscosity of these binary mixtures was best predicted by Gruenberg-Nissan correlation among the four correlations applied.     

离子液体N-乙基吡啶四氟硼酸盐与碳酸钠在298.15K下相行为的测定与关联

实验测定了离子液体([EPy]BF4)-碳酸钠(Na2CO3)-H2O双水相体系在298.15 K时液液相平衡数据。采用Merchuk方程关联双节线数据,相关系数达到0.995 9;采用Cashmere-Tobias和Bancroft方程关联系线数据,其相关系数分别为0.926 9和0.923 2。实验测定了系统、完整、准确的双水相体系相图数据,并用有效排除体积(EEV)评估了碳酸钠的盐析能力,为设计双水相萃取提供了数据基础。     

Measurement and correlation of liquid-liquid equilibrium for the ternary system (water + 1,2-dichloroethane + sulfolane) at 288.15, 298.15, and 308.15 K

Sulfolane is an important aprotic polar solvent. Liquid-liquid equilibrium(LLE) data for the ternary systems of water + 1,2-dichloroethane + sulfolane were measured at temperatures of 288.15, 298.15 and 308.15 K under the atmospheric pressure. The distribution coefficient and selectivity were determined from the measured LLE data, which showed that 1,2-dichloroethane is a suitable extractant for the recovery of sulfolane from its aqueous solution. The nonrandom two-liquid(NRTL) model and the uni...     

Densities,ultrasonic speeds,refractive indices,and COSMO analysis for binary mixtures of dichloromethane with acetone and dimethylsulfoxide at T = (298.15, 303.15, and 308.15) K

Experimental densities (ρ), ultrasonic speeds (u), and refractive indices (n_D) of binary mixtures of dichloromethane (DCM) with acetone (ACT) and dimethylsulfoxide (DMSO) were measured over the whole composition range at T?=?298.15, 303.15, and 308.15?K. From the experimental data, excess molar volume (V^E), deviations in isentropic compressibility (Δk_s), deviations in intermolecular free length (ΔL_f), deviations in refractive index (Δn_D), and deviations in ultrasonic speed (Δu) were calculated. Moreover, the Benson–Kiyohara theory was applied to the binary mixtures to obtain the theoretical Δk_s values. The COSMO calculations depending on density functional theory were utilized to estimate the σ-profiles for the DCM, ACT, and DMSO. The interpreted σ-profile trends were found supportive with the experimental findings. Applicability of different empirical and semi-empirical relations of refractive index data were tested against the measured results, and good agreement has been obtained. The possible results of intermolecular molecular interactions among mixture components were interpreted.     

五元体系HCl-NaCl-CaCl2-H3BO3-H2O在298.15K的Pitzer模型及其应用研究

采用等温溶解法测定了三元体系CaCl₂-H₃BO₃-H₂O在298.15 K的溶解度和液相的折射率,该三元体系为简单共饱型,有1个共饱点,2条溶解度曲线和2个单盐结晶区,分别为CaCl₂·6H₂O和H₃BO₃。结合本文测定和文献中的溶解度数据,拟合了五元体系HCl-NaCl-CaCl₂-H₃BO₃-H₂O中含H₃BO₃的Pitzer参数,结合固相的溶解平衡常数,构建了该五元体系的Pitzer模型,并计算了该五元体系及其子体系的溶解度。根据Pitzer模型和计算相图,对氯化钠、氯化钙共存卤水中硼酸的分离进行了计算,获得了分离过程中的析盐顺序和卤水组成的变化规律。计算结果表明酸性条件下更容易实现H₃BO₃的分离。     

Viscosities of binary liquid mixtures of cyclohexanone with alkanes,benzene, toluene and tetrachloromethane at 298.15 K

Viscosities for the binary liquid mixtures of cyclohexanone with n-hexane, n-heptane, 2, 2, 4-trimethylpentane, benzene, toluene and tetrachloromethane have been determined at 298.15 K. The deviation in viscosity from the ideal law is negative in all the systems except in the system, cyclohexanone with tetrachloromethane. In this system excess viscosity exhibits a positive deviation over the entire range of mole fraction. The results have been interpreted in terms of molecular interactions, and of difference in size and shape of components. The theoretical excess viscosities have been calculated from absolute reaction rate theory and free volume theory of flow by making use of the Bloomfield and Dewan relations. Theoretical excess viscosities are in qualitative agreement with experimental results for four out of the six systems examined.     

Density, ultrasonic velocity, viscosity and their excess parameters of the binary mixtures of N,N-dimethylaniline+1-alkanols (C3-C5), +2-alkanols (C3-C4), +2-methyl-1-propanol, +2-methyl-2-propanol at 303.15K

The density, ultrasonic velocity of sound and viscosity of binary mixtures of N,N-dimethyl aniline (N,NDMA) with 1-propanol, +2-propanol, +1-butanol, +2-butanol, +1-pentanol, +2-methyl-1-propanol, +2-methyl-2-propanol were measured at 303.15 K. These experimental data have been used to calculate excess volume V ^E , excess ultrasonic speeds u ^E , excess intermolecular free length L _f ^E , excess acoustic impedance Z ^E , excess isentropic compressibility κ _s ^E , deviation in viscosity Δη and excess Gibbs free energy of activation of viscous flow (G* ^E ). The values of L _f ^E and κ _s ^E are negative over the wide range of composition for all the binary mixtures, while the values of Z ^E are positive. These results have been used to discuss the nature of interaction between unlike molecules in terms of hydrogen bonding, dipole-dipole interaction, proton-acceptor interaction and dispersive forces. The viscosity data have been correlated using three equations: Grunberg and Nissan, Katti & Chaudhri and Hind et al. The excess/deviations were fitted by a Redlich-Kister equation and the results were analyzed in terms of specific interactions present in these mixtures.