Harifi-Mood Ali Reza, Habibi-Yangjeh Aziz, Gholami Mohammed Reza
Department of Chemistry, Sharif University of Technology, P.O. Box 11365-9516, Tehran, Iran.
J Phys Chem B. 2006 Apr 6;110(13):7073-8. doi: 10.1021/jp0602373.
The solvatochromic parameters (ET(N), normalized polarity parameter; pi*, dipolarity/polarizability; beta, hydrogen-bond acceptor basicity; alpha, hydrogen-bond donor acidity) were determined for binary solvent mixtures of 1-(1-butyl)-3-methylimidazolium tetrafluoroborate ([bmim]BF4) with water, methanol, and ethanol at 25 degrees C over the whole range of mole fractions. In nonaqueous solutions, the value of the mixture increases with mole the fraction of [bmim]BF4 and then decreases gradually to the value of pure [bmim]BF4. Positive deviation from ideal behavior was observed for the solvent parameters ET(N), pi*, and alpha, whereas the deviation of the beta parameter is negative. The applicability of the combined nearly ideal binary solvent/Redlich-Kister equation for the correlation of various solvatochromic parameters with solvent composition was proved too for the first time. This equation provides a simple computational model to correlate and/or predict various solvatochromic parameters for many binary solvent systems. The correlation between the calculated and the experimental values of various parameters was in accordance with this model. Solute-solvent and solvent-solvent interactions have been applied for interpretation of the results.
在25℃下,测定了1-(1-丁基)-3-甲基咪唑四氟硼酸盐([bmim]BF4)与水、甲醇和乙醇的二元溶剂混合物在整个摩尔分数范围内的溶剂化显色参数(ET(N),归一化极性参数;π*,偶极/极化率;β,氢键受体碱度;α,氢键给体酸度)。在非水溶液中,混合物的值随着[bmim]BF4摩尔分数的增加而增大,然后逐渐减小至纯[bmim]BF4的值。对于溶剂参数ET(N)、π*和α,观察到偏离理想行为的正偏差,而β参数的偏差为负偏差。首次证明了组合的近理想二元溶剂/Redlich-Kister方程对于各种溶剂化显色参数与溶剂组成之间相关性的适用性。该方程提供了一个简单的计算模型,用于关联和/或预测许多二元溶剂体系的各种溶剂化显色参数。各种参数的计算值与实验值之间的相关性符合该模型。溶质-溶剂和溶剂-溶剂相互作用已被用于解释结果。