混合工质临界性质的推算研究

采用五种不同的方法计算了四种不同二元混合工质的临界温度和临界压力,研究对比不同方法在推算二元混合临界性质时的精度。其中Peng-Robinson（PR）方程和Soave-Redlich-Kwong（SRK）方程,两种状态方程结合Heidemann等提出的临界点判据计算得到的临界参数与实验结果吻合较好。两种经验公式,改进的Chueh-Prausnitz（MCP）方法和Redlich-Kister方法,以及径向基函数神经网络（RBFNN）在计算混合工质的临界性质时也都有着较高的计算精度。对于临界温度的计算,PR方程、SRK方程、MCP方程、Redlich-Kister方程以及径向基函数神经网络计算结果的绝对平均偏差的最大值分别为1.82%、1.73%、0.95%、0.17%和0.20%。对于临界压力的计算,通过PR方程、SRK方程、MCP方程、Redlich-Kister方程以及径向基函数神经网络计算的绝对平均偏差的最大值分别为6.07%、5.04%、3.49%、1.90%以及0.67%。     

水与乙醇饱和蒸气压的静态法测定

利用静态法分别测定了纯水及无水乙醇在40～60℃和25～45℃的饱和蒸气压。通过lnp对1/T作图和线性回归,求得了相应温度区间的平均摩尔蒸发焓,对比了实验值与理论值,相对误差分别15.59%与0.49%。表明乙醇更接近真实值,误差较小。而Antoine方程计算对蒸气压数据进行了对比分析,结果表明,纯水的计算值与实验值的平均偏差为12,96%,最大偏差为17.75%。纯乙醇的计算值与实验值的平均偏差为1.1%,最大偏差为3.36%。表明Antoine方程对纯乙醇测量误差更小,更精确。综合可知,乙醇可替代水作为静态法测定液体饱和蒸气压的理想介质。     

新型制冷工质HFO-1234ze(E)蒸气压方程

为了更完善地认识新型制冷剂HFO-1234ze(E)的热物性,在公开发表的HFO-1234ze(E)饱和蒸气压实验数据的基础上,通过仔细分析各个实验数据的精确程度,筛选出一套由118组数据点组成的综合数据,经过拟合得到一系列蒸气压方程,对比各个方程对拟合数据的绝对偏差和相对偏差,得到一个适用范围较宽(232.990—380.002 K)且精度良好的四项Wanger型HFO-1234ze(E)蒸气压专用方程。该方程对拟合数据的平均相对偏差为-0.02%。同时,通过新方程计算得到HFO-1234ze(E)的正常沸点以及偏心因子,可以供物性计算和工程运用,具有较高的实际应用价值。     

甲基叔丁基醚的状态方程

利用公开发表的实验数据开发了甲基叔丁基醚（MTBE）的状态方程,方程以Helmholtz自由能为显式、以温度和密度为自变量。方程计算饱和蒸气压的不确定度430 K以下为1.0%,随着温度的升高,由于缺少实验数据不确定度增大为2.0%。方程计算密度的不确定度由液相区的0.2% 变到临界区和气相区的1.0%。方程计算能量相关物性（如比热容和音速）的不确定度为0.5%。临界区,除了饱和蒸气压,方程计算所有其它热力学性质的不确定度都较高。正如文中分析,本文方程不但能准确的复现实验数据,而且方程的外推性也是合理的。文中对方程进行了详细的分析。     

Equation of State for Methyl tert-butyl ether (MTBE)

利用公开发表的实验数据开发了甲基叔丁基醚（MTBE）的状态方程,方程以Helmholtz自由能为显式、以温度和密度为自变量。方程计算饱和蒸气压的不确定度430 K以下为1.0%,随着温度的升高,由于缺少实验数据不确定度增大为2.0%。方程计算密度的不确定度由液相区的0.2% 变到临界区和气相区的1.0%。方程计算能量相关物性（如比热容和音速）的不确定度为0.5%。临界区,除了饱和蒸气压,方程计算所有其它热力学性质的不确定度都较高。正如文中分析,本文方程不但能准确的复现实验数据,而且方程的外推性也是合理的。文中对方程进行了详细的分析。     

FK蒸气压方程与系数回归

本文评价了 Frost-kalkwarf 蒸气压方程,并讨论了方程系数的三种回归方法,即 Har 法,改良 Har 法和线性回归法.建立了回归方程系数的数学模型,编制了回归系数的计算机程序,搜集了文献发表的蒸气压数据.回归出355种化合物的方程系数.适用范围是 1mmHg～临界点,与文献数据十分吻合,平均误差都小于1%,总平均误差为0.314%,能在科研和化工设计计算中使用.     

标准氢的黏度方程

在广泛搜集标准氢（25%仲氢）黏度实验数据的基础上,运用单纯形算法拟合了标准氢的黏度计算方程,方程计算值与实验数据的偏差一般在2.0%以内。方程的适用范围为温度100～500 K,压力不超过200 MPa的区域。方程的不确定度为2.0%。方程具有一定的外推性,可以用于标准氢三相点温度到100 K以及500～1000 K,压力不超过500 MPa的区域;100 K以下,除临界区和气相区,方程的不确定度为3.0%,500 K相似文献   

2,4-二氯苯酚在水中溶解度的测定及关联

在pH值为6.2或9.3条件下,采用综合法测定了2,4-二氯苯酚在水中的固液平衡数据,分别用经验方程、W ilson方程、固液平衡λH方程对实验数据进行了拟合处理。结果说明,在pH值为9.3条件下,2,4-二氯苯酚的水溶解度增大;W ilson方程、λH方程模型均能很好地关联2,4-二氯苯酚的水溶解度数据,pH=9.3时平均相对误差分别为3.00%,1.17%,其中λH方程拟合效果更好。     

基团对应状态法(CSGC)用于纯物质饱和蒸气压的估算

将对应态原理与基团贡献法相结合,引入拟临界性质的概念,提出基团对应状态法(Correspounding State with Group Contribution,简称CSGC)。并将其与Riedel方程相结合用于饱和蒸气压的估算,提出新的蒸气压估算方程(CSGC-PR方程)。88种基团的参数由包括饱和烃、不饱和烃、环烃、芳烃、含氧化合物、含硫化合物、含氮化合物、含卤化合物等350种物质5255个饱和蒸气压实验数据关联获得。新模型的估算精度优于现有的对应状态法,不仅对于高碳数分子有良好的估算精度,并对非极性物质能较好地外推高压下的饱和蒸气压。     

R1234ze(Z)蒸气压方程

为了对第4代新型制冷剂R1234ze(Z)的热物性有更多认识,文中在公开发表的文献中,搜集了关于R1234ze(Z)的饱和蒸气压实验数据。对每组数据精度进行分析后,筛选得到140组实验数据。经过非线性拟合,获得了R1234ze(Z)的4项Wagner型蒸气压专用方程。该方程适用温度区间为283—413 K,压力区间为12—2 950 kPa。将拟合数据与该方程进行对比,其压力绝对偏差大部分在±2 kPa,相对偏差分布于±1%范围,平均绝对偏差为0.193%。对比文献数据与该方程,其压力相对偏差范围为-1%—2%,最大相对偏差为1.827%,平均绝对偏差为0.282%。因此,新方程对各组实验数据点都有很好的拟合度。根据此方程,计算得到R1234ze(Z)的标准沸点为284.751 K,偏心因子为0.325,可供物理性质的计算和工程实践的应用。     

高精度全氟甲烷R14饱和蒸汽压测定及关联

在141.76—225.71 K温度条件下,运用高精度(温度精度为±0.01 K,压力精度为±0.01%)可视化汽液相平衡装置测量了30组全氟甲烷(R14)的饱和蒸汽压实验数据,并分别运用Wagner方程,朱明善提出的改进Wagner方程及项-谭提出的方程对实验数据进行拟合。对计算值和实验数据进行对比分析,前2个方程计算结果较为接近,朱明善改进型方程略优,项-谭提出的方程误差最大。通过拟合得到上述温度范围内的较高精度的饱和蒸汽压方程。     

Estimation of vapor pressure of liquid oxygen between the triple and critical points

The existing vapor pressure measurements available in the literature for the liquid oxygen between the triple and critical points have been utilized to establish the constants and exponent of the modified Frost-Kalkwarf vapor pressure equation in the reduced form as follows: $$\ln P_r = 6.372408 - \frac{{6.637925}}{{T_r }} - 1.975760 \ln T_r + 0.265517T_r^5 $$ In order to calculate the vapor pressure, only the normal boiling point (T_b=90.180 K) and the critical pressure (P_c=5037.17 kPa) and critical temperature (T_c=154.33 K )are necessary to obtain an overall average deviation of 0.36 % for 540 experimental vapor pressure data.     

A new vapor pressure equation for pure substances

A new simple equation for prediction of vapor pressure of pure substances is proposed. The equation which has the Clausius-Clapeyron (C-C) equation form consists of three parameters: critical temperature, critical pressure and normal boiling point. Experimental data for organic and inorganic substances have been used to calculate equation parameters in the boiling point ranges from 169.45 to 457.55 K and critical temperature ranges from 282.75 to 699.15 K. Comparison of proposed equation estimation results with experimental data shows that the new equation has minor average error. The new equation is also 68 percent more accurate than the C-C equation     

A REDUCED VAPOR PRESSURE EQUATION BASED ON THE THEOREM OF CORRESPONDING STATES

A reduced vapor pressure equation based on the theorem of corresponding states is proposed in this work by the use of the third parameter to and the fourth parameter X. This equation yields an overall average absolute deviation of 1.09% for 111 normal fluids involving a total of 6968 vapor pressure data points, and 0.67% for 20 polar fluids involving a total of 1516 data points, respectively. A relationship of estimating acentric factors is obtained by applying the reduced vapor pressure equation at the normal boiling point. This relationship is very accurate for the prediction of the values of the acentric factor     

The new simple extended corresponding-states principle: vapor pressure and second virial coefficient

A new simple extended corresponding-states principle has been developed to represent and predict the thermophysical properties of fluids. The extended corresponding-states principle only requires the substance-dependent critical parameters and acentric factor which enhances the corresponding-states principle of Pitzer et al. to include the behavior of substances whose force fields deviate strongly from spherical symmetry. The additional corresponding-states parameter defined in terms of the deviation of the critical compression factor of a real molecule from that of spherical molecules is independent of experimental data for any specific property. The new simple extended corresponding-states principle presented here remarkably improves the representation of the vapor pressure from the triple point to the critical point and the second virial coefficient from the triple point to the highest temperatures over which experimental data exist. Accurate results for these two well-understood properties are given for simple, normal, polar, hydro-bonding and associating compounds. The results also show that the new simple extended corresponding-states principle is more reliable and accurately predicts the vapor pressure and second virial coefficient of a strongly nonspherical fluid than any other existing methods.     

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%。     

Thermodynamic properties of carbon up to the critical point

Thermodynamic data on solid, liquid, and gaseous carbon have been carefully selected from the literature or estimated, and vapor pressure have been calculated up to the critical point. Using certain assumptions about the properties of liquid carbon and nonideal gas corrections for carbon vapor, our calculations show the triple point and critical point to be 4765 and 6810°K, respectively, with critical density 0·64 g/cm³, and critical pressure 2200 atm. The dominant vapor species above ～ 2000°K is C₃, while C₇ is also of importance from 4500 to 6810°K. Coexistence curves which summarize the densities and enthalpies of solid, liquid, and vapor carbon are plotted. The density of liquid carbon is assumed to be 20% less than that of graphite at the triple point. The enthalpy of fusion is given as 30 kcal/g-atom C. Sublimation enthalpies are found to be 50–66 kcal/g-atom C at 3000–4765°K, and vaporization enthalpies about 20 kcal/g-atom C at 4765–6000°K.     

A fundamental equation of state for the calculation of thermodynamic properties of chlorine

A fundamental equation of state is presented for the calculation of thermodynamic properties of chlorine. It is expressed in terms of the Helmholtz energy with the independent variables temperature and density. Based on the available experimental data from the literature, the equation is valid from the triple point temperature 172.17–440 K with a maximum pressure of 20 MPa. The quality of the equation is evaluated by comparisons with experimental measurements. Since the equation was developed in part for use in mixture models relevant for carbon capture and storage applications, special focus was also given to correct extrapolation behavior.     

A generalized vapor pressure equation for hydrocarbons

A reduced vapor pressure relationship of the following form has been developed: The optimum value of n was established to be 8.00 from vapor pressure data for n-heptane. A method was developed for the determination of the constants A, B, C and D from one reliable vapor pressure point. By this procedure vapor pressures were calculated for 33 hydrocarbons, including saturated and unsaturated paraffins, naphthenes, and aromatics, and were compared with corresponding experimental values. For these substances the overall average deviation between calculated and actual vapor pressure was 0.38% (1879 points). This relationship was also applied to seven additional hydrocarbons not included in its development, and for these substances the resulting average deviation was 0.36% (99 points).     

A GENERALIZED EQUATION OF STATE FOR POLAR AND NON-POLAR FLUIDS BASED ON FOUR-PARAMETER CORRESPONDING STATES THEOREM

A new generalized equation of state for polar and non-polar fluids based on the corresponding states theorem is developed, f n addition to two critical parameters, four parameters are required; two for the calculation of volumetric properties and two for the calculation of pressure and departure functions. Parameteres for more than 100 polar and non-polar fluids are given. Comparison with the existing generalized state equations showed that the new method, in general, shows a better agreement with the experimental data. The absolute average deviation is 0.48% for the vapor pressure and 0.32% for the saturated liquid volume.