Heller Andreas, Koller Thomas M, Rausch Michael H, Fleys Matthieu S H, Bos A N René, van der Laan Gerard P, Makrodimitri Zoi A, Economou Ioannis G, Fröba Andreas P
Erlangen Graduate School in Advanced Optical Technologies (SAOT), University of Erlangen-Nuremberg , Paul-Gordan-Straße 6, D-91052 Erlangen, Bavaria, Germany.
J Phys Chem B. 2014 Apr 10;118(14):3981-90. doi: 10.1021/jp500300y. Epub 2014 Apr 2.
It is demonstrated that thermal and mutual diffusivities of binary mixtures of n-octacosane (n-C28H58) with carbon monoxide (CO), hydrogen (H2), and water (H2O) are simultaneously accessible by dynamic light scattering (DLS). As the light-scattering signals originating from thermal and concentration fluctuations appear in similar time scales, different data evaluation strategies were tested to achieve minimum uncertainties in the resulting transport properties. To test the agreement of the respective theoretical model with the DLS signals in the regression, an improved multifit procedure is introduced. With the selected data evaluation strategy, uncertainties of 4 to 15% and 4 to 30% in the thermal and mutual diffusivities, respectively, could be obtained for the binary mixtures. The mutual diffusivities for the mixtures measured at temperatures ranging from 398 to 523 K and pressures of 5 to 30 bar at saturation conditions are in good agreement with molecular dynamics simulations and data from the literature.
结果表明,通过动态光散射(DLS)可同时获取正二十八烷(n-C₂₈H₅₈)与一氧化碳(CO)、氢气(H₂)和水(H₂O)的二元混合物的热扩散率和互扩散率。由于源自热涨落和浓度涨落的光散射信号出现在相似的时间尺度内,因此测试了不同的数据评估策略,以在所得的输运性质中实现最小不确定性。为了在回归中测试各自的理论模型与DLS信号的一致性,引入了一种改进的多重拟合程序。采用选定的数据评估策略,二元混合物的热扩散率和互扩散率的不确定性分别可达4%至15%和4%至30%。在398至523 K的温度范围和5至30 bar的饱和压力下测量的混合物的互扩散率与分子动力学模拟以及文献数据吻合良好。