Measurement of the association constants through micro-Raman spectra of supersaturated lithium perchlorate droplets  

作　　者：GUO Xin Tan SeeHua PANG ShuFeng ZHANG YunHong 

机构地区：[1]College of Sciences,Central South University of Forestry and Technology [2]The Institute of Chemical Physics,School of Chemistry,Beijing Institute of Technology

出　　处：《Science China Chemistry》2013年第11期1633-1640,共8页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of (41175119; 20933001 and 20873006);the National Key Program for Basic Research of China (2009CB220100); the 111 Project B07012;the Trans-Century Training Program Foundation for the Talents;also supported by a grant-in-aid for Youth Innovation Fund from Central South University of Forestry and Technology (104︱0261)

摘　　要：High quality micro-Raman spectra of the LiClO4 droplet with mass of nanogram scale were obtained at various concentrations from dilute to supersaturated state. From component band analysis of the v1-ClO4^- band, four peaks at 933.3, 936.8, 942.1 and 950.7 cm^-1 were identified and assigned to free solvated perchlorate anion, solvent-shared ion pair, contact ion pair and com- plex ion aggregates, respectively. As expected, the signature of free solvated CIO4 ion was observed to decrease in intensity with the increase in concentration. The intensity of the signature from solvent-shared ion pair was observed to rise with in- crease in concentration from 1.8 mol/kg to 5.0 mol/kg before decreasing as the concentration was further increased to 5.6 mol/kg. Signatures of contact ion pair and of complex ion aggregates were shown to increase as the concentration was enhanced. Based upon the Eigen mechanism, we show that three association equilibria can be used to describe the transfor- mations between free solvated perchlorate anion, solvent-shared ion pair, contact ion pair and complex ion aggregates. The overall association constant, K, and the stepwise association constants Ki （i = 1 to 3） in the Eigen mechanism were determined separately with values of 0.025 ± 0.003, 0.023 ± 0.002, 0.068 ± 0.033 and 0.686 ± 0.174. Based on these constants, the electronic performance can be reasonably predicted by the optimum choice of electrolyte concentrations.High quality micro-Raman spectra of the LiClO4droplet with mass of nanogram scale were obtained at various concentrations from dilute to supersaturated state.From component band analysis of the v1-ClO4band,four peaks at 933.3,936.8,942.1 and950.7 cm 1were identified and assigned to free solvated perchlorate anion,solvent-shared ion pair,contact ion pair and complex ion aggregates,respectively.As expected,the signature of free solvated ClO4ion was observed to decrease in intensity with the increase in concentration.The intensity of the signature from solvent-shared ion pair was observed to rise with increase in concentration from 1.8 mol/kg to 5.0 mol/kg before decreasing as the concentration was further increased to 5.6mol/kg.Signatures of contact ion pair and of complex ion aggregates were shown to increase as the concentration was enhanced.Based upon the Eigen mechanism,we show that three association equilibria can be used to describe the transformations between free solvated perchlorate anion,solvent-shared ion pair,contact ion pair and complex ion aggregates.The overall association constant,K,and the stepwise association constants Ki(i=1 to 3)in the Eigen mechanism were determined separately with values of 0.025±0.003,0.023±0.002,0.068±0.033 and 0.686±0.174.Based on these constants,the electronic performance can be reasonably predicted by the optimum choice of electrolyte concentrations.

关 键 词：lithium perchlorate association constant ion pair Raman spectra 

分 类 号：O657.37[理学—分析化学]