AN EMPIRICAL VIRIAL-LIKE CUBIC EQUATION OF STATE FOR PHASE EQUILIBRIUM CALCULATIONS

An empirical cubic equation of state(EOS) was obtained by truncating the virial expansion in reciprocal of molar volume after the third term. The constants of the EOS was generalized in terms of critical temperature, critical pressure and Pitzer's acentric factor.

In pure component applications the EOS exhibited a performance comparable to Peng-Robinson (1976) EOS in the reduced temperature range of 0.5 to 1. The present EOS tends to predict better saturation liquid volumes at reduced temperatures below 0.8, and better estimations for second virial coefficient at high reduced temperatures.

The EOS was successfully employed for vapor liquid equilibrium calculations for some mixtures of normal or slightly polar fluids with traditional one binary parameter mixing rule at moderately high pressures. At low reduced temperatures, where conventional one adjustable parameter applications of the cubic equations compare unfavorably with dual methods based on excess Gibbs energy functions for the liquid phase, a new two constant mixing rule introduced by Stryjek and Vera (1986) was employed for the present equation of state.     

方型状态方程在高压相平衡中的研究及应用

对近年来状态方程的研究及其在高压相平衡计算中的应用状况作了综述分析。以ＰＲＳＶ方程为基础，通过实际计算考察和评价不同混合规则在复杂体高压汽液平衡、超临界流体／固体体系相平衡计算中的性能     

PHASE EQUILIBRIUM OF COMPLEX MIXTURES WITH EQUATIONS OF STATE: AN UPDATE5

Here we review a new class of mixing rules that have extended range of mixtures and condi-tions that can now be described by equation of state models.One characteristic of these mixing rulesis that they simultaneously satisfy the boundary conditions of producing a second virial coefficientthat is quadratic in mole fraction,and a free energy of mixing like that of an activity coefficientmodel at high density,though the mixing rule is itself independent of density.We show that usingthis mixing rule,various asymmetric,highly nonideal mixtures can be accurately described.Oneserendipitous result is that the parameters in this mixing rule model are almost independent oftemperature,which allows accurate extrapolations of phase behavior to be made over large ranges oftemperature and pressure.     

关于立方型状态方程的若干评述和讨论

对在状态方程,尤其是立方型状态方程,研究与开发过程中的几个重要问题,从若干层面进行了评述和讨论。评价了统计力学在开发状态方程中的作用,并指出了其局限性。通过综述温度函数的发展状况,给出了温度函数仍然是纯经验性等看法。对混合规则的发展状况以及各种不同类型的混合规则进行了评述和比较。     

PREDICTION OF PHASE EQUILIBRIA IN BINARY MIXTURES USING AN IMPROVED EQUATION OF STATE AND A THEORETICALLY CONSISTENT MIXING RULE

Prediction of thermodynamic properties and phase equilibria in fluid mixtures using a simple cubic equation of state is still a challenging problem. In this paper, we have predicted vapor/ liquid phase equilibria of several binary fluid mixtures using our previously developed improved Peng-Robinson equation of state and a theoretically consistent mixing rule. Our mixing rule combines the mixing rule of Wong-Sandier with a physically based combination rule. Mixtures are composed of nonpolar, nonassociating polar and associating polar fluids. Comparisons of theoretical predictions with experimental data show a very good performance of our approach in describing vapor/liquid phase equilibria of several mixtures, namely, carbon dioxide/ propane, ethane/hexane, butane/methanol, benzene/methanol, acetone/methanol, methanol/ ethanol, methanol/1-butanol, methanol/water and ethanol/water.     

基于G~E模型的MH方程在二元流体相平衡中的应用

提出了ＭＨ方程基于Ｇ￣Ｅ模型的混合法则，并用于流体相平衡计算。研究结果表明：基于ＵＮＩＦＡＣ模型的ＭＨ方程能较好地预测汽液平衡，而基于ＮＲＴＬ模型的ＭＨ方程能满意地关联液液平衡数据。     

EXTENSION OF SOAVE EQUATION OF STATE TO LIQUID DENSITY

On the basis of vapor pressures, volumes of saturated vapor and liquid, both parameters "a" and "b" in Soave equation of state are treated as temperature dependent and an extended Soave equation is proposed in this work. The VLE for 38 pure components including polar substances have been calculated. The comparison of calculated results with experimental data shows the prediction of liquid density is improved over Soave equation without losing the accuracy of prediction in vapor pressure and vapor density.     

M-H-EOS的理论基础

根据virialEOS的推导方式 ,从具有分子体积的准理想气体模型出发 ,利用巨正则分布和势能函数 ,从理论上推导了M -H -EOS ,并探讨了M -H -EOS的理论基础。结果表明 ,M -H -EOS与virialEOS具有相同的理论基础 ,只是在考虑实际气体对理想气体在分子体积和分子间相互作用的偏差上做了不同的近似。M -H -EOS为了计算简便 ,在实验的基础上对分子间相互作用做了合理的近似 ,从而避免了高阶virial系数求解困难的问题 ,因此在实用中取得成功。了解M -H -EOS的理论基础 ,对进一步发展和改进M -H -EOS的应用领域和计算准确度具有一定的意义     

液态聚合物的内压与状态方程

由热力学关系建立了一个液态聚合物的状态方程.聚合物的热压力由对应状态原理得到,内压力由Lennard-Jones(6,12)势能函数导得.状态方程包含3个有明确物理意义的特性参数,能够满意地关联各种液态聚合物的pVT数据.对18个均聚物和4个共聚物的比体积关联结果表明,总的平均绝对偏差在0～50 MPa压力范围内为0.00042 cm³•g^-1,在全部实验压力范围内为0.00063 cm³•g^-1,优于Simha-Somcynsky方程算得的结果.     

立方型状态方程含过量自由焓模型的新混合规则

提出了在参考压力下将过量自由焓(g~E)模型引入状态方程的修正Huron-Vidal混合规则,由g~E模型确定状态方程中混合物的参数,以SRK方程和Wilson模型为例,取大气压为参考压力,计算了16个体系50组汽液平衡,结果表明本文建议的混合规则可直接使用现有文献报道的常压g~E模型参数由立方型状态方程预测常压汽液平衡,并对直接外推预测高压汽液平衡作了尝试.     

双流体配位状态方程在共聚物及共混物体系中的应用

采用双流体配位模型状态方程,对三个共聚物体系P(VAC/E)、P(S/MMA)及P(EP),两个共混物体系PVME/PS、PPO/PS进行了关联,精度较好.提出了共聚物的共混物假设的新设想.在关联中发现共聚物及共混物体系的二元模型参数具有一定的加和性,本文采用一个较为简单的混合规则,用均聚物的模型参数估算二元模型参数,进行了pVT数据预测,并与实验数据比较,具有良好的预测效果.     

用微扰理论状态方程预测电解质水溶液的密度

对微扰理论的电解质水溶液状态方程作了进一步简化．由水的分子参数和离子直径,计算了包含强酸在内的12个单一电解质水溶液、9个二元和1个四元电解质水溶液在不同温度下的密度．对单一电解质水溶液密度关联准确度在1％之内,对混合电解质水溶液密度预测的平均相对偏差在2％左右,若阳离子直径采用由单一电解质水溶液的回归值代替Pauling直径,则能进一步改善预测准确度．     

一个新的基团贡献型状态方程——GC-MCSPT方程

将超额Gibbs函数模型与修正的硬球三参数状态方程(MCSPT方程)相结合,导出由基团贡献模型定义的状态方程参数混合规则.直接利用低温下的基团贡献模型参数,如UNIFAC模型、修正的UNIFAC模型(简称MUNIFAC)的交互作用参数,分别预测了二元强极性物系的低压和高压相平衡以及三元强极性物系的汽液相平衡.结果表明,新模型具有广泛的预测能力和满意的预测精度.     

普遍化立方型状态方程中Wong-Sandler型混合规则的建立

<正>自70年代末期Huron和Vidal将过量Gibbs自由能模型引入状态方程的混合规则以来,状态方程新混合规则的研究引起了人们的高度重视并取得了重要成就,已成功地将状态方程推广到多种复杂体系的计算,其中近年来由Wong和Sandler等发展的Wong-San-dler（WS）混合规则模型受到了广泛的关注。他们工作的意义在于可以使用由低压汽液平衡数据得到的活度系数模型参数及二元交互作用参数直接推算高压汽液平衡。 但该模型的导出仅限于两参数的立方型状态方程,这样对于广泛应用WS型混合规则势必产生局限性,因此将此类型的混合规则推广到普遍化的立方型状态方程是十分必要的。本文报道了以五参数的Modified Kumar-Starling（MKS）立方型状态方程为工作方程,建立了将WS型混合规则推广到多参数立方型状态方程的途径。     

基于微扰理论的表面活性剂水溶液表面状态方程

应用微扰理论并借鉴二维气体理论的处理方法,建立了非离子表面活性剂水溶液的表面状态方程。将微扰理论与压力方程相结合,建立了离子表面活性剂水溶液的表面状态方程。运用提出的状态方程,分别对6种烷基聚氧乙烯醚、辛基酚聚氧乙烯醚、十二烷基硫酸钠等表面活性剂水溶液的表面压数据进行了关联,并利用关联所得的参数预测了其他种类的烷基聚氧乙烯醚及辛基酚聚氧乙烯醚和十二烷基硫酸钠水溶液在不同温度下的表面压。关联和预测的精度均较高,结果令人满意。     

基于化学缔合的链状YUKAWA流体的状态方程

从Yukawa流体出发,采用化学缔合的统计力学理论建立了链状Yukawa流体的分子热力学模型,其亥氏函数由作为参考流体的硬球Yukawa流体的贡献和链节成键的贡献两部分组成.采用链长为2的链状Yukawa流体压缩因子的Monte Carlo模拟结果关联得到成键贡献项中空穴相关函数,对势能函数参数λ=1.8和λ=3.0时链长为4和8的链状Yukawa流体的压缩因子的预测与Monte Carlo数据能很好地吻合,比Wang和Chiew的微扰理论结果更好.     

CO_2-C_4H_9OH-H_2O体系的立方型状态方程研究

利用 Ｐ Ｒ、 Ｓ Ｒ Ｋ、 Ｈ Ｋ、 Ｐ Ｔ 状态方程（ Ｅ Ｏ Ｓ）计算 Ｃ Ｏ２ 、 Ｃ４ Ｈ９ Ｏ Ｈ、 Ｈ２ Ｏ 纯组份的饱和性质及 Ｃ Ｏ２ 的压缩因子。结果表明, Ｐ Ｔ 方程对水、二氧化碳的蒸汽压及密度预测较佳。对丁醇的密度推算, Ｐ Ｔ 方程最佳, Ｐ Ｔ 方程对丁醇的饱和蒸汽压预测一般。考察了 Ｐ Ｔ 方程参数的影响,指出应根据相平衡的温度范围选取相应的 Ｐ Ｔ 方程参数。对 Ｃ Ｏ２  Ｃ４ Ｈ９ Ｏ Ｈ Ｈ２ Ｏ 体系相平衡的研究宜选用 Ｐ Ｔ 方程。     

应用遗传算法求解含化学反应体系的相平衡

基于Gibbs自由能最小原理 ,提出一种求解含化学反应体系相平衡的方法。采用反应进度和相分率消去等式约束 ,将含化学反应体系的相平衡计算转化为无约束的最优化问题 ,并应用遗传算法求解。采用本文提出的方法 ,能够避免计算中负数的组分摩尔数或摩尔分数的出现 ,确保得到组分的摩尔数或摩尔分数为非负的全局最优解。以聚甲醛反应体系的汽液平衡计算为例 ,表明本文所提出的方法是可行和有效的     

A MODIFIED LEE-KESLER EQUATION OF STATE FOR REFRIGERANTS

For calculation of the thermodynamic properties of refrigerants it is proposed that the extended corresponding states principle (ECSP) should be used using two specific reference fluids, CFC12 (CCI₂F₂) and HFC134a (CF₃CH₂F), in order to cover the field of interest for most refrigerants. The specific parameters of these refrigerants have been determined for the Lee-Kesler modification of the Benedict-Webb-Rubin equation of state. In the parameter estimation, it has been taken into accounl that all variables are subject to errors by using the so-called Error-in-Variables-Model (EVM). The parameters have been estimated from experimental pressure-volume-temperature data, vapour pressure and saturated liquid and vapour volume data for CFC12 and HFC134a.

The extended corresponding states principle proposed in this work with CFC12 and HFC134a as reference fluids has been used in calculations of the thermodynamic properties of a number of refrigerants. In comparison with the original Lee-Kesler equation this concept gives improved results in calculations of vapour pressure and liquid volume.