Department of Chemistry, University of North Bengal, Darjeeling 734 013, India.
J Phys Chem B. 2012 Sep 27;116(38):11687-94. doi: 10.1021/jp302465s. Epub 2012 Sep 14.
Precise measurements on electrical conductance (Λ) of solutions of an ionic liquid (IL) tetrabutylphosphonium tetrafluoroborate in acetonitrile (ACN), tetrahydrofuran (THF), and 1,3-dioxolane (1,3-DO) and their binary mixtures have been reported at 298.15 K. The conductance data have been analyzed by the Fuoss conductance equation (1978) in terms of the limiting molar conductance (Λ(o)), the association constant (K(A)), and the association diameter (R) for ion-pair formation. The Walden product is obtained and discussed. However, the deviation of the conductometric curves (Λ versus √c) from linearity for the electrolyte in THF and 1,3-DO and their binary mixtures indicated triple-ion formation and therefore the corresponding conductance data have been analyzed by the Fuoss–Kraus theory of triple ions. The limiting ionic conductances (λ(o)(±)) have been estimated from the appropriate division of the limiting molar conductivity value of tetrabutylammonium tetraphenylborate [Bu(4)NBPh(4)] as the “reference electrolyte” method along with a numerical evaluation of ion-pair and triple-ion formation constants (K(P) ≈ K(A) and K(T)). The results have been discussed in terms of solvent properties and configurational theory. Ionic association in the limiting molar conductances as well as the single-ion conductivity values have been determined for the electrolyte in the solvent media.
已经在 298.15 K 下报告了离子液体(IL)四丁基膦四氟硼酸盐在乙腈(ACN)、四氢呋喃(THF)和 1,3-二氧戊环(1,3-DO)及其二元混合物中的精确电导率(Λ)测量值。根据福斯电导方程(1978 年),用电导的极限摩尔电导(Λ(o))、缔合常数(K(A))和离子对形成的缔合直径(R)对电导数据进行了分析。得到了沃登产品并进行了讨论。然而,电解质在 THF 和 1,3-DO 及其二元混合物中的电导率曲线(Λ 与 √c)偏离线性表明形成了三离子,因此相应的电导数据已通过福斯-克劳斯三离子理论进行了分析。通过适当划分四丁基四苯硼酸盐 [Bu(4)NBPh(4)] 作为“参考电解质”的极限摩尔电导率值,用数值评估离子对和三离子形成常数(K(P) ≈ K(A)和 K(T))来估算极限离子电导率(λ(o)(±))。结果已根据溶剂性质和构形理论进行了讨论。已经确定了溶剂介质中电解质在极限摩尔电导率以及单离子电导率值中的离子缔合。