液体非电解质水溶液粘度的预测

在Teju-Rice液体混合物粘度模型的基础上,对常用的液体混合物粘度关联式进行了分析和比较;导出了适用于二元和多元非电解质水溶液的粘度模型;结合实际数据导出的水溶液二元作用参数的估算式可进行水溶液粘度的预测。用该模型计算了7个体系398个不同温度和组成的二元水溶液和4个体系189个不同温度和组成的三元水溶液的粘度,结果表明,计算值对实验数据的总平均相对偏差分别为6.848%和5.043%,本文水溶液粘度估算式的计算准确性优于Teju-Rice法。     

有机物水溶液粘度的关联和预测

在Eyring的液体粘性流动模型的基础上,根据Sandler的水溶液过量自由焓溶质聚集模型,导出有机物水溶液的粘度模型。利用该模型方程参数与温度的关系,可预测低压下各种温度和不同组成的有机物水溶液的粘度。用该模型计算了7个体系442个不同温度和组成的二元水溶液和3个体系164个不同温度和组成的三元水溶液的粘度,计算值与实验值的总平均相对偏差分别为1.554%和2.588%,计算值与实验数据吻合很好。     

计算液体混合物导热系数的新型方程

依据Ｃｈａｐｍａｎ导热理论关于液体导热系数与粘度的关系，结合由Ｅｙｒｉｎｇ反应速率理论及ＮＲＴＬ方程导出的液体粘度关联式，得到一个计算液体混合物导热系数的新型方程。经对１８个二元体系和４个三元体系、１个四元体系共１６４６个数据点的检验，结果较为满意，与文献值或实测值相比总的平均误差仅为０．３９４％。     

低温甲醇洗汽液平衡计算的探讨

本文提出用于合成氨工艺中低温甲醇洗相平衡计算的新方法。以CH_3OH-CO_2为骨干体系,采用修正的PR方程,通过改进混合规则,引入δ_(ij)~1和δ_(ij)~2两个二元相互作用系数,可以比较精确地求得上述体系的二元相平衡数据。本文还对气体中的溶剂损失作了探讨,並给出了不同温度和压力下,上述体系中各组成的汽液平衡常数。最后,对国内应开展的试验提出了初步的看法。     

从液体混合物的粘度数据推算汽液平衡数据

<正>液体混合物的汽液平衡数据和粘度数据都是基本的物性数据,人们很早就开始了对它们的研究,并取得了不小的进展.对于汽液平衡的研究,人们提出了许多溶液理论和活度系数方程,例如Flory-Huggins方程,Van Laar方程,Margules方程,Wilson方程和其修正方程,NRTL方程以及UNIQUAC方程等;对于液体混合物的粘度,人们也提出了许多流体粘度理论,其中最著名的是Eyring反应速率理论.作者曾应用这一理论建立了一个新的液体混合物粘度方程,用于关联二元体系的粘度数据和推算多元体系的粘度数据,结果令人满意.     

2-甲基-1,3-丙二醇水溶液密度和粘度的测定及关联

常压下采用密度瓶测定了纯液体2-甲基-1,3-丙二醇(MPO)及不同浓度的MPO 水二元体系在298.15~367.15K范围的密度;用乌氏粘度计测定了纯液体MPO及该二元体系在相应温度下的粘度.结果表明:MPO及其水溶液的密度和粘度均随温度升高而减小,密度呈线性衰减,粘度呈指数衰减;一定温度下MPO 水二元体系的密度随浓度变化大约在70%处出现了一极大值. 同时分别由密度和粘度实验数据计算了不同温度及组成下该二元体系的超额摩尔体积V E和混合粘度变化△η,结果V E和△η均为负值, 说明产生了负偏差.并由实验数据拟合出Grunberg-Nissan模型中的MPO-水体系的二元交互参数△Gij,它与温度和组成均有关.     

液体非电解质水溶液粘度的关联

在Teju-Rice液体混合物模型的基础上,对常用的液体混合物粘度关联式进行了分析和比较,导出了适用于二元和多元水溶液的粘度模型。用该模型计算了6个体系388个不同温度和组成的三元水溶液的粘度,计算值对文献实验数据的总平均相对偏差分别为6.09%和5.54%,计算值准确性优于Teju-Rice模型。     

非电解质水溶液的粘度方程

在Eyring的液体粘性流动模型基础上,根据Rother等的假定和Shealy与Sand ler的水溶液过量自由焓溶质聚集模型,导出了一个双参数非电解质水溶液的粘度模型。利用该模型可由二元水溶液的2个模型参数预测多元水溶液的粘度。用该模型计算了6个体系391个不同温度和组成的二元水溶液和3个体系164个不同温度和组成的三元水溶液的粘度,计算值与实验值的总平均相对偏差分别为1.732%和2.977%,计算值与实验数据吻合很好。     

计算有机混合液体粘度的新型方程

在Ｅｙｒｉｎｇ的反应速率理论基础上，引用ＮＲＴＬ方程的　表达式，得到一个计算有机混合液体粘度的新型方程，该方程不但适用于非理想程度不大的体系，而且对极性的和缔合性的醇水、酸水体系均取得了较好的关联结果。经对１９个二元体系和２个三元体系，共１２１０个数据点的检验，与文献值相比总的平均误差仅为１．３１％。     

用改进的PR方程关联推算N_2-CH_4-CO_2体系的高压汽液平衡

改进的Peng-Robinson方程结合经典的二次型混合规则,在含N_2、CH_4、CO_2体系的高压汽液平衡(VLE)数据关联中获得了与温度无关的二元交互系数K_(ij)用于推算其三元VLE取得了简便有效的结果。压力平均百分偏差2.65％,汽相组成绝对平均偏差1.24％。     

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.     

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.     

液体混合物粘度与过量热力学性质的关联(Ⅰ)

基于Eyring的速率过程理论,并考虑了提供分子从一个平衡位置向另一位置迁移所需新位置的频率,得到了二元混台物粘度与过量吉布斯活化自由能间的关联式: K发现过量吉布斯活化自由能(?)对于相应的过量吉布斯自由能(?)有一通用比值,新位置的提供频率是组成和温度的函数.对10对二元系统(其中3对是水溶液系统)的粘度计算值与相应的55套数据进行比较,结果较为满意,均方根差为0.002一0.009.     

A new one parameter viscosity model for binary mixtures

The Grunberg & Nissian equation with one parameter is widely recommended in the viscosity calculation. However, it is demonstrated that this equation fails to generate satisfactory results for size‐asymmetric mixtures containing large and small molecules. In this work, a new one parameter viscosity model for binary mixtures has been developed on the basis of Eyring's absolute reaction rate theory and the Flory‐Huggins equation. The concept of molecular surface fraction is introduced for modeling liquid mixture viscosities. The viscosity calculations of the new equation are compared with the Grunberg & Nissian equation for a broad range of chemical mixtures including 527 binary systems (containing 63 binary ionic liquid cosolvent systems) and total 17,268 viscosity points. The new equation was found to have an improved performance over the frequently employed Grunberg & Nissian equation, especially for size‐asymmetric mixtures containing large and small molecules. © 2010 American Institute of Chemical Engineers AIChE J, 57: 517–524, 2011     

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。。     

Correlative and predictive models of viscosity study on Propiophenone with isomeric xylenes binary mixtures at <Emphasis Type="Italic">T</Emphasis>=(303.15 to 318.15) K

Densities and viscosities of binary mixtures of Propiophenone with o-xylene, m-xylene and p-xylene were measured over the entire composition range at T=(303.15 to 318.15) K and at 0.1Mpa atmospheric pressure. Experimental data used to calculate excess molar volume (V^E), deviation of viscosity (Δη), excess Gibb’s free energy (G^*E) activation of viscous flow for each binary system and the results were fitted to the Redlich-Kister polynomial equation to obtain the fitting coefficients and standard deviations. Viscosity values used to compute single adjustable interaction parameters from Grunberg and Nissan, Katti and Chaudhri, Hind et al., Tamara Kurata and Frenkel relations. Deviations in thermodynamic properties of the binary mixtures were discussed in terms of their molecular interactions between the components. Viscosity data correlated with the McAllister’s three body/four body models, Heric, Auslander, and Jouyban-Acree relations having two and three adjustable parameters for the studied binary mixtures. Viscosity relations like Kendall-Monroe, Bingham, Arrhenius, and Kendall were used to calculate and compare the standard deviation percentage, (σ %), between the experimental and calculated viscosity data. The studied systems showed specific intermolecular interactions and the percentage deviations were in good agreement with the experimental values. Obtained results are useful in various chemical and industrial processes.     

液体混合物粘度与过量热力学性质的关联(Ⅱ)

利用本文(I)报中提出的二元混合粘度与过量Gibbs活化自由能间的关联式,并以McAllister的多元体相互作用模型关联粘度数据,对九对二元系统(其中三对是含醇系统,一对是醇水系统)进行了从粘度数据推算汽液平衡数据.计算结果与相应的实验值比较,除一对系统的偏差较大外,其余八对的泡点均方根差为0.09—0.80℃,汽相组成均方根差为0.003—0.038.     

密度泛函方法在物理化学二元相图教学中的应用

用量子化学密度泛函方法研究了两个完全互溶的二元体系水一乙醇和三氯甲烷一丙酮中同种和异种分子之间的相互作用,并应用计算所得的结合能数据判断了分子间相互作用的强度,揭示了这两个体系对理想液态混和物产生偏差的原因。研究结果表明：在水-乙醇体系中,异种分子之间的结合能小于同种分子之间的结合能,说明当乙醇和水混和时,体系总的作用力降低,挥发性增强,导致该溶液蒸气压对理想液态混合物产生正偏差。在三氯甲烷一丙酮二元体系中,相互作用的情况正好与水一乙醇体系相反,致使该溶液蒸气压对理想液态混合物产生负偏差,这些结果均与实验事实一致。     

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.