Blanco Sofía T, Gil Laura, García-Giménez Pilar, Artal Manuela, Otín Santos, Velasco Inmaculada
Departamento de Química Orgánica y Química Física, Facultad de Ciencias, Universidad de Zaragoza, 50009-Zaragoza, Spain.
J Phys Chem B. 2009 May 21;113(20):7243-56. doi: 10.1021/jp9005873.
Critical properties and volumetric behavior for the {CO2(1)+C3H8(2)} system have been studied. The critical locus was measured with a flow apparatus and detected by critical opalescence. For the mixtures, repeatabilities in critical temperature and pressure are rTc<or=0.15 K and rPc<or=0.013 MPa, respectively, and the confidence intervals calculated are c.i.(Tc)<0.32 K and c.i.(Pc)<0.034 MPa. The value for the Krichevskii parameter, AKr=-4.12 MPa, was obtained from the experimental critical data in this work. Additionally, the density measurements of 15 {CO2(1)+C3H8(2)} binary mixtures at 308.15 K and pressures up to 20 MPa were carried out using an Anton Paar DMA 512-P vibrating-tube densimeter calibrated with the forced path mechanical calibration model. The mean relative standard deviation of density, srhor, was estimated to be better than 0.1%, and the uncertainties in temperature and pressure are +/-0.01 K and +/-0.001 MPa, respectively. In the experimental setup, an uncertainty in the mole fraction, u(xj)=+/-0.0015, has been achieved. Other properties related to P-rho-T-x data such as saturated densities, rhoL and rhoV, compressibility factor, Z, excess molar volumes,VmE, and partial molar volumes, Vi, have been calculated. Structural properties such as direct and total correlation function integrals and cluster size were calculated using the Krichevskii function concept. Both the critical and volumetric behavior have been compared with literature data and with those obtained from the PC-SAFT and Patel-Teja equations of state.
已对{CO₂(1)+C₃H₈(2)}体系的临界性质和体积行为进行了研究。使用流动装置测量临界轨迹,并通过临界乳光现象进行检测。对于混合物,临界温度和压力的重复性分别为rTc≤0.15 K和rPc≤0.013 MPa,计算得到的置信区间为c.i.(Tc)<0.32 K和c.i.(Pc)<0.034 MPa。在本工作中,根据实验临界数据得到的克里切夫斯基参数值AKr = -4.12 MPa。此外,使用通过强制路径机械校准模型校准的安东帕DMA 512-P振动管密度计,对15种{CO₂(1)+C₃H₈(2)}二元混合物在308.15 K和高达20 MPa的压力下进行了密度测量。密度的平均相对标准偏差srhor估计优于0.1%,温度和压力的不确定度分别为±0.01 K和±0.001 MPa。在实验装置中,摩尔分数的不确定度u(xj)=±0.0015已实现。还计算了与P-ρ-T-x数据相关的其他性质,如饱和密度ρL和ρV、压缩因子Z、过量摩尔体积VmE和偏摩尔体积Vi。使用克里切夫斯基函数概念计算了诸如直接和总相关函数积分以及团簇大小等结构性质。已将临界和体积行为与文献数据以及从PC-SAFT和Patel-Teja状态方程获得的数据进行了比较。