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首页> 外文期刊>The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical >Temperature and Pressure Dependence of the Diffusion Coefficients and NMR Relaxation Times of Mixtures of Alkanes
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Temperature and Pressure Dependence of the Diffusion Coefficients and NMR Relaxation Times of Mixtures of Alkanes

机译:烷烃混合物的扩散系数和NMR弛豫时间的温度和压力依赖性

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摘要

Recently, it was shown(1,2) that the diffusion coefficient and nuclear magnetic resonance (NMR) relaxation times of a molecule in a mixture of alkanes follow scaling laws in the chain length of the molecule and the mean chain length of the mixture. These relations can be used to determine the chain length distribution of crude oils from diffusion and relaxation measurements. Oil reservoirs are Usually at elevated temperatures and pressures, so it is important to know how these scaling relations depend on temperature and pressure. In this paper, we obtain the relation between the molecular composition of mixtures of alkanes at elevated pressures and temperatures and their diffusion coefficients D-i and relaxation times T-1i and T-2i. Using proper-ties of free volume theory and the behavior of the density of alkanes, we show that, for a large range of pressures, the diffusion coefficients and relaxation times depend on pressure and mean chain length of the Mixture only through its density. We further show that the pressure effect can be taken into account in the power laws of refs 1 and 2 by a multiplicative prefactor that depends only on temperature and the free volumes of pure alkanes at the pressure of interest and a reference pressure. We also combine the scaling laws for D-i, T-1i, and T-2i and the Arrhenius dependence on temperature to obtain the temperature dependence of the diffusion coefficients and relaxation times. We obtain good fits between the scaling relations and literature data. These scaling relations can be used to determine the composition of a mixture of alkanes from measurements of diffusion coefficients or relaxation times at elevated pressures and temperatures.
机译:最近,有研究表明(1,2),烷烃混合物中分子的扩散系数和核磁共振(NMR)弛豫时间遵循分子链长和混合物平均链长的比例定律。这些关系可用于根据扩散和弛豫测量值确定原油的链长分布。油库通常处于升高的温度和压力下,因此了解这些比例关系如何取决于温度和压力非常重要。在本文中,我们获得了在高温和高压下烷烃混合物的分子组成与它们的扩散系数D-i和弛豫时间T-1i和T-2i之间的关系。利用自由体积理论的性质和烷烃密度的行为,我们表明,在很大的压力范围内,扩散系数和弛豫时间仅取决于混合物的密度,取决于压力和混合物的平均链长。我们进一步表明,在参考文献1和2的幂定律中,可以通过乘数系数来考虑压力效应,该系数仅取决于温度和目标压力和参考压力下纯烷烃的自由体积。我们还结合了D-i,T-1i和T-2i的缩放定律以及Arrhenius对温度的依赖性,以获得扩散系数和弛豫时间的温度依赖性。我们在比例关系和文献数据之间获得了很好的契合度。这些比例关系可用于根据在升高的压力和温度下的扩散系数或驰豫时间的测量值来确定烷烃混合物的组成。

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