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.     

一种完全型形状因子对应态原理

In the two-parameter corresponding states principle(CSP), the critical compressibility factors of the fluid under study(called “α“ fluid) and the reference fluid(called “o“ fluid) must be identical. This is not generally observed in nature. To overcome this limitation, a perfect shape factor CSP is proposed in which the compressibility factors of “a“ and “o“ fluids are corresponded perfectly by introducing a new pressure shape factor 5. Using methane as the “o“ fluid, the shape factors of many fluids are calculated from PVT properties at saturation state and the second virial coefficients. Models are also formulated for the shape factors with the assumption of φ is a function of temperature and volume while θ and δ are temperature dependent only. The models described the shape factors satisfactorily in whole region including vapor, liquid and their co-existing phases. The perfect shape factor CSP could be applied for both polar and non-uolar fluids.     

用对应态基团贡献法估算有机物偏心因子

A new estimation method was proposed by combining the corresponding state principle with the group contribution method through introducing the concept of assumed-critical properties. Combining it with the Reidel equation, a new acentric factor correlation equation （CSGC-Reidel） was developed. Contribution values of 70 groups were obtained by correlating acentric factor data of 228 organic compounds of 14 type substances including saturated hydrocarbons, unsaturated hydrocarbons, cyclanes, aromatics, oxygen compounds, nitrogen compounds, halohydrocarbons, etc. The average error of acentric factor is 3.52% between the literature data and the predicated with the new estimation method.     

蒸气压关联和估算方法的评述

本文对纯物质的蒸气压关联和估算方法进行了评述,包括对应状态法,参考物质法,基团贡献法及对应态基团法等,重点介绍了几种基团贡献法,其中包括最新的对应态基团法（SCGC）,并指出了各种关联和估算方法的使用条件及优缺点。     

用对应状态基团贡献法估算纯物质的饱和蒸汽压

提出一种估算纯物质饱和蒸汽压的新对应状态基团贡献法———CSGC -PC方程 ,用 2 6 1种物质 1177个数据回归出了方程的参数 ,并得到了 94个基团对临界温度和临界压力的贡献值。回归的平均相对误差为 1.81%。该方程仅需物质的正常沸点Tb,对缺乏实验临界数据的热敏性物质和大分子物质尤其适用。     

Vapour pressures and saturated-liquid volumes for heavy fossil fuel fractions from a perturbed hard-chain equation of state

A semitheoretical equation of state has been used to correlate residual thermodynamic properties of heavy hydrocarbons. The correlation requires three characteristic molecular parameters obtained from liquid density and vapour pressure data. These parameters are presented for 61 hydrocarbons with molecular weights up to 560 and are correlated with molecular weight and structural features. The correlation is extended to narrow-boiling fractions. Molecular parameters for such fractions are obtained from experimental characterization data (molecular weight, aromaticity, naphthenicity and number of methyl groups per molecule). Calculated vapour pressures and liquid densities are in reasonable agreement with new experimental results obtained from Belridge crude oil.     

立方型状态方程用于蒸发热的计算

推导出立方型状态方程计算纯流体蒸发热的新公式,该计算式的特点是式中含有能量参数对温度的导数 da/dT,而与 a(T)无关。根据这一公式对立方型状态方程推算蒸发热进行了比较分析,提出a(T)与 da/dT 相互独立的计算方法,并用 Peng-Robinson 方程对70多种物质(包括烃、醇、卤代烃、酮、无机气体等)进行了关联计算,蒸汽压和蒸发热的平均相对误差分别为0.70%和1.33%。     

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。     

发展马丁-侯方程作为水的专用方程

发展了适用于极性物质水的MH方程。由线性最小二乘法拟合单相区和汽液共存区的PVT及相平衡数据 ,得到方程常数 ,并用统计方法检验了方程的有效性。计算结果表明 ,饱和蒸汽压和摩尔体积误差一般小于0 .6。单相区体积和压力平均误差分别为 0 .3 %和 2 .5 %。与Bender方程相比 ,新方程准确度更高     

Tao-Mason状态方程扩展用于重正烷烃(英文)

In our previous paper we extended the Tao and Mason equation of state (TM EOS) to refrigerant fluids, using the speed of sound data. This is a continuation for evaluating TM EOS in predicting PVT properties of heavy n-alkanes. Liquid density of long-chain n-alkane systems from C 9 to C 20 have been calculated using an analytical equation of state based on the statistical-mechanical perturbation theory. The second virial coefficients of these n-alkanes are scarce and there is no accurate potential energy function for their theoretical calculation. In this work the second virial coefficients are calculated using a corresponding state correlation based on surface tension and liquid density at the freezing point. The deviation of calculated densities of these alkanes is within 0.5% from experimental data. The densities of n-alkanes obtained from the TM EOS are compared with those calculated from Ihm-Song-Mason equation of state and the corresponding-states liquid densities (COSTALD). Our results are in favor of the preference of the TM EOS over other two equations of state.     

VAPOUR LIQUID EQUILIBRIA IN STRONG ELECTROLYTE SOLUTIONS BY THE CORGC EQUATION OF STATE

The capability of chain-of-rotalor group contribution equation of state (CORGC EOS) in prediction of vapour-liquid equilibria for electrolyte solutions is discussed. A new approach is considered in which salt is considered as a single component and therefore, there is no ion in the solution. The interaction parameters between water and 50 salts are determined and reported. The parameters are temperature dependent and thus, vapour-liquid equilibria calculations can be achieved at moderate temperature. The percent average absolute deviation for prediction of vapour pressure and osmotic coefficient for 50 aqueous solutions are equal to 0.89 and 16.7, respectively. Comparison between the calculated results and experimental data has been performed.     

由修正的SRK方程推算HF饱和蒸汽压

对ＳＲＫ方程吸力项温度依变参数作了修正，使之能精确的推算了ＨＦ体系的饱和蒸汽压。     

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     

SRK方程α的改进及其在汽-液相平衡预测中的应用

Based on results of saturated vapor pressures of pure substances calculated by SRK equation of state,the factor α in attractive pressure term was modified. Vapor-liquid equilibria of mixtures were calculated by original and modified SRK equation of state combined with MHV1 mixing rule and UNIFAC model, respectively. For 1447 saturated pressure points of 37 substance including alkanes; organics containing chlorine, fluorine, and oxygen; inorganic gases and water, the original SRK equation of state predicted pressure with an average deviation of 2.521% and modified one 1.673%. Binary vapor-liquid equilibria of alcohols containing mixtures and water containing mixtures also indicated that the SRK equation of state with the modified α had a better precision than that with the original one.     

A Modification of α in SRK Equation of State and Vapor-Liquid Equilibria Prediction

1 INTRODUCTION Equations of state (EOS), especially, cubic equa-tions of state are frequently used in modeling phase equi-librium for chemical process of designing. Among cubic equations of state, SRK[1] equation of state and PR[2] equation of state are the most commonly used. These two equations of state are similar in form. They are also similar in the correction factor of parameter a. When phase equilibria of mixtures were calculated, equations of state must be combining with mixing…     

应用PSRK状态方程预测高压汽液平衡

为预测高压汽液平衡,将过量吉布斯自由能混合规则和UNIFAC活度系数模型与SRK状态方程相结合,建立基团贡献状态方程PSRK。利用该状态方程对5个体系在不同压力和温度下的汽液平衡数据进行了关联实验测定的汽相压力和汽相组成与计算结果相比所得的相对平均偏差分别为2．16％和1．01％。结果表明,PSRK状态方程可以成功地预测高压下汽液平衡,其精度高于MHV1和MHV2模型。