基于磷酸三丁酯的超浓盐酸的研究  

On the Tributylphosphate-Based Super-Concentrated HCl System

作　　者：郭琳[1,2] 黄昆[3] 郭然[2] 贺安琪[2] 翁诗甫[2] 杨展澜[2] 赵莹[4] 夏锦明[5] 徐怡庄[2] 康廷国[1] 吴瑾光[2] 

机构地区：[1]辽宁中医药大学药学院,辽宁大连116600 [2]北京大学北京分子科学国家实验室稀土材料化学及应用国家重点实验室,北京100871 [3]中国科学院过程工程研究所中国科学院绿色过程与工程重点实验室,北京100190 [4]中国科学院化学研究所北京分子科学国家实验室工程塑料院重点实验室,北京100190 [5]沈阳度太生物制药研究中心,辽宁沈阳110031

出　　处：《光谱学与光谱分析》2015年第8期2241-2245,共5页Spectroscopy and Spectral Analysis

基　　金：国家自然科学基金项目(50973003);"863"重大项目(2010AA03A406);科技部平台项目(2005DKA32800)资助

摘　　要：利用磷酸三丁酯形成的反胶束在常温常压下制备出一种超浓盐酸,其酸水摩尔比（nHCl/nH2O）在0.50～1.50之间,高于常温常压下饱和浓盐酸的酸水摩尔比（0.28）。红外光谱的研究结果表明超浓盐酸中部分氯化氢未发生电离,而是以分子形式存在。同时HCl参与了体系内氢键网络的形成。超浓盐酸体系提供了一个特殊的物理化学环境,使得溶于其中的铜离子呈红棕色。采用FTIR及UV-Vis对含铜离子的超浓酸体系进行了表征。结果表明,超浓酸中,铜离子的d—d跃迁和电荷迁移跃迁谱带都发生了明显的变化。铜离子的加入对超浓盐酸体系中未电离的HCl分子的氢键体系产生明显影响。We reported a new super-concentrated hydrochloric acid system prepared by using tri-n-butyl phosphate（TBP）-constructed reversed micelles at ambient temperature and pressure.According to the titration result,the molar ratio of H＋to H2O（denoted as nH＋/nH2O）in the super-concentrated HCl range from 0.50 to 1.50 which are higher than that in saturated aqueous HCl bulk solution（0.28）.Significant a moment of hydrochloric acid is confined in W/O reversed micelles.Therefore,the behavior and status of HCl are different from those of conventional bluk solution.FTIR spectroscopic results demonstrate that a significant amount of HCl remains in the molecular form rather than being ionized into H＋ and Cl-.Thus,super-concentrated HCl provides an extraordinary chemical environment which may have significant influence on certain substances.We found that the color of the solution is reddish brown when copper ion is dissolved in super-concentrated HCl,while the color of the saturated HCl aqueous solution（37 Wt%）containing copper ion is green.That is to say,the copper ions exist in a special state under the unique chemical environment of super-concentrated HCl.UV-Vis-NIR spectra indicate that both d-d transition band and charge transfer transition band of copper ions in super-concentrated HCl solution underwent significant variations.In addition,copper ions also have obvious influence on the hydrogen bond network among HCl in the super-concentrated HCl solution.Remarkable variation is introduced in the H—Cl stretching band in FTIR spectra.

关 键 词：磷酸三丁酯 超浓盐酸 酸水摩尔比 铜离子 

分 类 号：TQ111.3[化学工程—无机化工]