Department of Chemistry, Middle East Technical University , Ankara 06800, Turkey.
J Phys Chem A. 2014 May 1;118(17):3081-9. doi: 10.1021/jp500760t. Epub 2014 Apr 16.
Investigation of frequency dependent permittivity of mixture solutions provides information on the role of intermolecular interactions on relaxation processes of solvent and solute molecules. In this study the dielectric properties of ethanol/gasoline mixtures in the terahertz spectral region are investigated. Frequency dependent absorption coefficients, refractive indices, and complex permittivities of pure ethanol and gasoline, and their mixtures at varying ethanol volume percentages (v/v %) are reported. As the mixing ratio changes, meaningful shifts are observed in the frequency dependent refractive index and absorption coefficients associated with the dominant component, ethanol. The relaxation dynamics of the pure gasoline and ethanol are successfully modeled with the Debye model using the ultrafast nature of the terahertz transients, and those of mixture solutions are investigated by an additive model with an assumption of minimum interaction due to the significant differences in their molecular natures; polar and nonpolar. Successful modeling of the mixtures confirms the weak interaction assumption and enables us to accurately determine the ethanol content. Among five ethanol/gasoline blends, except for one mixture, the estimated percent ethanol in gasoline is predicted with an accuracy of ca. 1% with respect to the actual ethanol percentage. In addition, the results show that free OH contribution to the macroscopic polarization is significantly higher at low concentrations (5-20%) and lower at 50% compared to the case of pure ethanol. The measurements and analysis presented here show that time domain terahertz studies can offer invaluable insight into development of new models for polar/nonpolar complex mixture solutions.
研究混合溶液的频率相关介电常数可以提供关于分子间相互作用对溶剂和溶质分子弛豫过程影响的信息。本研究在太赫兹光谱区域内研究了乙醇/汽油混合物的介电特性。报道了纯乙醇和汽油以及不同乙醇体积百分比(v/v%)混合物在太赫兹瞬变的超快特性下,其频率相关吸收系数、折射率和复介电常数。随着混合比的变化,与主要成分乙醇相关的频率相关折射率和吸收系数发生了有意义的偏移。利用德拜模型成功地对纯汽油和乙醇的弛豫动力学进行了建模,假设由于它们的分子性质(极性和非极性)存在显著差异,相互作用最小,通过一个加性模型对混合物溶液的弛豫动力学进行了研究。混合物的成功建模证实了弱相互作用的假设,并使我们能够准确地确定乙醇的含量。在所研究的五种乙醇/汽油混合物中,除了一种混合物之外,对于其余四种混合物,预测的汽油中乙醇的估计百分比与实际乙醇百分比的误差约为 1%。此外,结果表明,与纯乙醇相比,在低浓度(5-20%)下,宏观极化中游离 OH 对的贡献明显更高,而在 50%时则更低。这里呈现的测量和分析结果表明,时域太赫兹研究可以为开发新的极性/非极性复杂混合物溶液模型提供宝贵的见解。