Volumetric,ultrasonic and viscometric studies of binary liquid mixures of N-ethylaniline + chlorobenzene, + Bromobeneze, + 1, 2-dichlorobenzene + 1, 3-dichlorobenzene+1, 2, 4-trichlorobenzene at 303.15 and 308.15K

We measured densities (ρ), ultrasonic speeds (u) and viscosities (η) for binary binary mixtures of N-ethylaniline (N-EA) with chlorobenzene (CB), bromobenzene (BB), 1,2-dichlorobenzene (1,2-DCB), 1,3-dichlorobenzene (1,3-DCB), and 1,2,4-trichlorobenzene (1,2,4-TCB) and their pure liquids at 303.15 K and 308.15 K. These experimental data were used to calculate the excess volume (V ^E ), deviations in ultrasonic speeds (Δu), deviation in isentropic compressibility (Δ κ _s ), deviation in intermolecular free length (ΔL _f ), deviation in acoustic impedance (ΔZ), deviation in viscosity (Δη) and excess Gibbs free energy of activation of viscous flow (G* ^E ). The variations of these properties with composition of binary mixtures suggest loss of dipolar association, difference in size and shape of the component molecules, dipole-dipole interactions and hydrogen bonding between unlike molecules. The viscosity data were correlated with Grunberg and Nissan, Katti and Chaudhri, and Hind et al. equations and the results were compared with the experimental results. The excess parameters were fitted to the Redlich-Kister polynomial equation using multi parametric nonlinear regression analysis to derive the binary coefficients and to estimate the standard deviation.     

Solid-liquid phase equilibria,excess molar volume,and molar refraction deviation for the mixtures of ethanoic acid with propanoic,butanoic, and pentanoic acid

The paper reports the solid-liquid phase equilibria (SLE), excess molar volume (V^E), and molar refraction deviation (ΔR) for binary systems of ethanoic acid with the C₃ to C₅ carboxylic acids, propanoic, butanoic, and pentanoic acid, which are the main constituents of bio-butanol fermentation broth. The SLE was determined via a synthetic method using a custom-built glass tube at atmospheric pressure, whereas the thermodynamic mixture properties, V^E and ΔR were obtained from directly measured density and refractive index using a precision densitometer and refractometer, respectively. All of the SLE that were determined for binary mixtures of ethanoic acid+C₃-C₅ carboxylic acids showed a single eutectic point and regressed well with the NRTL activity model within 0.6 K of RMSD. The V^E values for the same binaries were positive for the entire composition ranges of all the systems, whereas the ΔR values were negative for all the systems. The V^E and ΔR were well regressed by polynomial equations, namely Redlich-Kister within 0.006 cm³·mol^?1 of the standard deviation for V^E and 0.02 cm³·mol^?1 for ΔR.     

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.     

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.     

STUDIES OF DYNAMIC VISCOSITY AND GIBBS ENERGY OF ACTIVATION OF BINARY AND TERNARY MIXTURES OF BENZYLCHLORIDE + NITROBENZENE + ISOBUTANOL FROM T = (288.15 TO 313.15) K

Densities and viscosities of ternary mixtures of benzylchloride + nitrobenzene + isobutanol and three corresponding binary mixtures (benzyl chloride + isobutanol, benzyl chloride + nitrobenzene, and nitrobenzene + isobutanol) have been determined over the whole concentration at a temperature range of 288.15 to 313.15 K under atmospheric pressure. Experimental data of resulting mixtures were used to calculate viscosity deviations, Δln η, and excess energies of activation of viscous flow, ΔG*^E, of the ternary system. The calculated data for binary mixtures have been fitted by the Redlich-Kister equation to determine the appropriate coefficients. In order to determine the coefficients of ternary data, Cibulka, Singh, and Nakata equations were used. The results have also provided a test for the Grunberg and Nissan equation for correlating the dynamic viscosities of binary and ternary mixtures with mole fractions.     

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.     

Ultrasonic study on binary liquid mixtures of propiophenone with anilines and alkyl substituted anilines at T=303.15 to 318.15 K

Densities ‘ρ’, ultrasonic speeds of sound ‘u’ of binary mixtures of propiophenone (PPH) with aniline, N-Methylaniline, N,N-dimethylaniline and N,N-diethylaniline were measured over the entire composition range from 303.15 K to 318.15 K and at atmospheric pressure 0.1 MPa. Experimental data of ultrasonic sound were compared and discussed with the computed values of ‘u’ from various velocity theories like Nomoto’s relation (U_NOM), impedance relation (U_IMP), Van Dael and Vangeel’s ideal mix relation (U_VDV), Rao’s specific velocity relation (U_RAO), Junjie’s theory (U_JUN) and Jouyban-Acree’s (U_JOE) relation for the above binary mixtures over the entire mole fraction range at the studied temperatures. The results are satisfactory and are in agreement between the theoretical and the experimental values. Further, the molecular interaction parameter (α), average percentage error and Chi-square test values were computed by using the values of experimental and theoretical ultrasonic velocities. The Δu values were correlated with Redlich-Kister polynomial equation to compute the coefficients and the standard deviations of the binary mixtures. The results were analyzed in terms of intermolecular interactions.     

Orientation effect on sign and magnitude of excess thermodynamic functions of non electrolyte solutions at different temperatures (303.15 K, 308.15 K,and 313.15K)

Experimental values of the density and viscosity have been measured for binary mixtures of N-ethylaniline with isomeric butanols (1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-propanol) at 303.15, 308.15 and 313.15 K over the entire mole fraction range. These data, the excess molar volumes, and deviation viscosity for the binary systems at the above-mentioned temperatures were calculated and fitted to Redlich-Kister equation to determine the fitting parameters and the root-mean-square deviations. The excess molar volumes, deviation viscosity and excess Gibbs energy of activation of viscous flow have been analyzed in terms of acid-base interactions, hydrogen bond, and dipole-dipole interaction between unlike molecules. The results obtained for dynamic viscosity of binary mixtures were used to test the semi-empirical relations of Grunberg-Nissan, Katti-Chaudhri, and Hind et al. equations.     

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.     

乙酸乙酯-1,2-丙二醇二元系的密度、折射率和黏度

常压下测定了乙酸乙酯和1,2-丙二醇二元系在298.15～323.15 K下的密度、折射率和黏度,建立了混合液密度、黏度随组成和温度变化关系的方程。计算了过量摩尔体积V^E,折射率偏差Δn_D,黏度偏差Δη和过量流动活化自由能ΔG^*E。结果表明,过量摩尔体积低温时在全浓度范围内为负值,但随温度升高,在富酯区变为正值;而折射率偏差高温时在富醇区为微小正值,其他情况都是负值;黏度偏差和过量流动活化自由能显示了相同的变化关系,均为负值,且都随温度降低而偏差增大。     

Volumetric,speed of sound data and viscosity at (303.15 and 308.15) K for the binary mixtures of N,N-dimethylaniline + aliphatic ketones (C3–C5), +4-methyl-2-pentanone, +acetophenone, +cyclicketones

Measurement of densities (ρ), ultrasonic sound speeds (u) and viscosities (η) has been carried out for binary mixtures of N,N-dimethylaniline (N,N-DMA) with acetone(AC), methylethylketone (MEK), methylpropylketone (MPK), diethylketone (DEK), methylisobutylketone (MIBK), acetophenone (AP), cyclopentanone (CP), cyclohexanone (CH) and 2-methylcyclohexanone (MeCH) and their pure liquids at (303.15 K and 308.15) K over the entire composition range. These experimental data have been used to calculate the excess molar volume (V^E), deviation in ultrasonic sound velocity (Δu), deviation in isentropic compressibility (Δκ_s) and deviation in viscosity (Δη) were evaluated. The variation of these properties with composition of the mixtures suggests dipole–dipole interactions and charge transfer complex formation between N,N-dimethylaniline and ketones. The magnitude of the property is found to depend on the chain length of the ketones molecule. These results have been fitted to the Redlich–Kister polynomial equation. The viscosity data have been correlated using three equations; Grunberg and Nissan, Katti and Chaudhri, Hind et al. for the system studied.     

Viscosities of binary mixtures of ethanenitrile with benzene and several substituted benzenes

Viscosities (η) and densities (?) of five binary mixtures of ethanenitrile with benzene and several substituted benzenes viz methylbenzene, 1,4-dimethylbenzene, chlorobenzene and 1,2-dichlorobenzene have been experimentally determined at 308.15 K. Viscosity deviations (Δη) from the linear blending rule have been evaluated for all the mixtures studied. These are small with a maximum negative deviation of about 6% for binary mixture with benzene and maximum positive deviation of about 3% for mixture with 1,4-dimethylbenzene. Δη Values are fitted into Redlich - Kister equation and standard deviations in Δη values, σ (Δη) have been evaluated. The correlating performance of several viscosity models such as Grunberg - Nissan, Katti and Chaudhari, Hind-McLaughlin - Ubbelohde and Sedgwick has been evaluated. Grunberg-Nissan viscosity model is suitable for viscosities of several binary systems studied. The results are discussed in terms of molecular interactions between the components of binary mixtures.     

Partition of <Emphasis Type="Italic">n</Emphasis>-Butanol Among Phases and Solubilization Ability of Winsor type III Microemulsions

The partition of n-butanol in Winsor type III (W-III) microemulsions was investigated in this work. Three kinds of anionic surfactants (sodium dodecyl sulfate (SDS), sodium dodecyl sulfonate (DSS), and sodium dodecyl benzene sulfonate (SDBS)) and two kinds of anionic/cationic surfactant mixtures (SDS/octadecyl trimethyl ammonium chloride (OTAC) mixtures and DSS/OTAC mixtures) were studied. Internal standard gas chromatography was employed in n-butanol content analysis. The results showed that no water exists in the excess oil (EO) phase and no oil exists in the excess water (EW) phase. For the W-III microemulsions obtained by salinity scanning, relatively constant n-butanol content in the EO (11–12 v%) and EW (1–4 v%) was found under different salinities. Accurate measurement of n-butanol content in each phase is important for those systems having low solubilization ability. For the W-III microemulsions prepared using SDS/OTAC surfactant mixture, the percentage of n-butanol distributed into the interfacial layer decreased while the fraction of n-butanol in the interfacial layer first increased sharply and then tended to be stable with the addition of n-butanol. For the different optimum W-III microemulsion systems tested, most of the surfactant-to-alcohol molar ratio data are near 1:3, but obvious deviation could be observed for some data. On the basis of the accurate measurement of n-butanol content in the EO and EW phases, the standard free energy, ΔG _o→in ^* (T = 298.15 K) of n-butanol transferring from the EO phase to the interfacial region was calculated. The results show negative ΔG _o→in ^* values. For microemulsions with the same components, n-butanol content is an important factor influencing the ΔG _o→in ^* value, and a high absolute value of ΔG _o→in ^* leads to high solubilization ability.     

Mixed Micellization of Polyoxyethylene (20) Oleyl Ether with Cetylpyridinium Chloride at the Air–Water Interface

Adsorption and micellization behaviour of binary surfactant mixtures containing a nonionic surfactant, polyoxyethylene (20) oleyl ether (C_18-1E₂₀), and a cationic surfactant, cetylpyridinium chloride (CPC), was studied at the air–water interface using the Wilhelmy plate method. A pseudo-phase separation model was used to analyse mixed micellization. A Margules equation with one constant (interaction parameter, β) was fitted to the nonideal behaviour of the mixed surfactant system. This system shows synergism (β = ?6.0) for micellization. The dynamic behaviour and foamability of binary mixtures at the same bulk concentration and at different mole fractions were also studied using drop volume and horizontal impinging jet methods, respectively. It was found that with an increase in the mole fraction of C_18-1E₂₀, the foamability of a mixture increases and t* value decreases.     

Synergism and Performance for Systems Containing Binary Mixtures of Anionic/Cationic Surfactants for Enhanced Oil Recovery

The surfactant structure–performance relationship and application properties in enhanced oil recovery (EOR) for binary mixtures of anionic and cationic surfactants are presented and discussed. A polyoxyethylene ether carboxylate anionic surfactant was blended with a quaternary ammonium chloride cationic surfactant and tested for a high-temperature, low-salinity, and high-hardness condition as found in an oil reservoir. These mixtures were tailored by phase behavior tests to form optimal microemulsions with normal octane (n-C8) and crude oil having an API gravity of 48.05°. The ethoxy number of the polyoxyethylene carboxylate anionic surfactant and the chain length of the cationic surfactant were tuned to find an optimal surfactant blend. Interfacial tensions with n-C8 and with crude oil were measured. Synergism between anionic and cationic surfactants was indicated by surface tension measurement, CMC determination, calculation of surface excess concentrations and area per molecule of individual surfactants and their mixtures. Molecular interactions of anionic and cationic surfactants in mixed monolayers and aggregates were calculated by using regular solution theory to find molecular interaction parameters β ^σ and β ^M . Morphologies of surfactant solutions were studied by cryogenic TEM. The use of binary mixtures of anionic/cationic surfactants significantly broadens the scope of application for conventional chemical EOR methods.     

二元混合物环丁酚和对二甲苯、乙苯在温度范围为303.15—353.15K下的密度、黏度及其相关性质

Densities and viscosities of the binary systems of sulfolane ＋ ethylbenzene, sulfolane ＋ p-xylene have been experimentally determined in temperature interval 303.15—353.15 K and at atmospheric pressure for the whole composition range. The excess molar volumes and viscosity deviations were computed. The computed quantities have been fitted to Redlich-Kister equation. Excess molar volumes and viscosity deviation show a systematic change with increasing temperature. Two mixtures exhibit negative excess volumes with a minimum which occurs approximately at χ = 0.5. The effect of the size, shape and interaction of components on excess molar volumes and viscosity deviations is discussed.     

二元混合物环丁酚和对二甲苯、乙苯在温度范围为303.15-353.15K下的密度、黏度及其相关性质

Densities and viscosities of the binary systems of sulfolane ethylbenzene, sulfolane p-xylene have been experimentally determined in temperature interval 303.15-353.15 K and at atmospheric pressure for the whole composition range. The excess molar volumes and viscosity deviations were computed. The computed quantities have been fitted to Redlich-Kister equation. Excess molar volumes and viscosity deviation show a systematic change with increasing temperature. Two mixtures exhibit negative excess volumes with a minimum which occurs approximately at x = 0.5. The effect of the size, shape and interaction of components on excess molar volumes and viscosity deviations is discussed.     

N,N-二甲基甲酰胺+醇二元混合物的黏度测定与关联

在288.15~313.15 K和常压下,利用乌氏黏度计测定了N,N-二甲基甲酰胺（DMF）分别与乙醇、丙醇、乙二醇和1,2-丙二醇组成的二元系全浓度范围内的黏度,计算了过量黏度△η和过量流动活化自由能△G^*E。用Redlich-Kister方程对过量黏度进行了关联;用黏度模型如Frenkel方程,Grunberg-Nissan方程,Katti-Chaudhari方程和McAllister方程对实验黏度数据进行了关联和预测,并利用Eyring理论方法计算了流动活化自由能、活化焓和活化熵等热力学函数。结果表明,4个二元系的过量黏度和过量流动活化自由能均为负值,且都随温度降低而偏差增大。过量黏度最低值均发生在DMF摩尔分数约为0.3处。McAllister模型对黏度数据的关联结果最好,预测值与实验值的平均相对偏差最小。比较并分析了DMF与一元醇和二元醇之间分子相互作用的差异。。     

Excess molar volumes at the 308.15 K for constituent binaries of n-decane,n-dodecane, 1-decanol and 1-dodecanol

Excess molar volumes (V_m ^E) of constituent binary mixtures of n-decane, n-dodecane, 1-decanol and 1-dodecanol which are the products of liquid phase oxidation of n-paraffins, have been measured experimentally as a function of composition x from density measurements at 308.15 K. The excess molar volumes of n-decane-n-dodecane system have negative deviation from the ideality while that of n-dodecane-1-decanol system have positive deviation. In the other systems, excess molar volume exhibits inversion in sign. Experimental data were successfully correlated with Redlich-Kister polynomial.     

离子液体[C4mim][PF6]与N, N-二甲基甲酰胺二元混合物在298.15 K～318.15 K的密度和粘度

Viscosities and densities for 1-butyl-3-methylimidazolium hexafluorophosphate （[C4mim][PF6]） and N, N-dimethylformamide （DMF） binary mixtures have been measured at the temperature range from 293.15 K to 318.15 K. It is shown that the viscosities and densities decrease monotonously with temperature and the content of DMF. Various correlation methods including Arrhenius-like equation, Sedclon et al.＇s equation, Redlich-Kister equation with four parameters, and other empirical equations were applied to evaluate these experimental data. A model based on an equation of state Ior estimating the viscosity of mixtures containing ionic liquids were proposed by coupling with the excess Gibbs free energy model of viscosity, which can synchronously calculate the viscosity and the molar volume. The results show that the model gives a deviation of 8.29% for the viscosity, and a deviation of 1.05% for the molar volume when only one temperature-independent adjustable parameter is adopted. The correlation accuracy is further improved when two parameters or one temperature-dependent parameter is used.