Kinetics of CO2(aq),HCO3- with primary and secondary amines in aqueous solution

doi:10.3969/j.issn.0438-1157.2013.08.026

Abstract

Abstract: The reaction kinetics of of CO₂(aq),HCO₃^- with monoethanol amine(MEA),2-amino-1-propanol(2-AP),1-amino-2-propanol,iso-butyl amine(IBA),3-amino-1-propanol(3-AP),diethanol amine(DEA),morpholine(MORP),piperidine(PIPD),and 4-piperidine methanol(4-PIPDM)in aqueous solution at 25℃ was investigated by stopped-flow and ¹H NMR spectrometric technologies.One plausible and universal mechanism was proposed.The rate constants for reactions of CO₂(aq),HCO₃^- with the selected amines,the protonation constant of carbamate,and the stability constant of carbamates were obtained by the fitting results.The plot of lgk₇ versus lgK₉ was linear for the primary and secondary amines,respectively.The above relationships indicated that the stability constant of carbamate represented the overall contribution of its electronic,steric and solvation effects.This discovery may provide a theoretical guidance for the design of novel poly-amines in improving CO₂ capture efficiency.

Key words: reaction kinetics, CO₂, amine, bicarbonate, carbamate

摘要： 采用停留光谱法和核磁共振(氢谱)法系统地研究了二氧化碳(aq)、碳酸氢盐与一乙醇胺(MEA)、L-氨基丙醇(2-AP)、1-氨基-2-丙醇(1-AP)、N-甲基正丙胺(IBA)、3-氨基丙醇(3-AP)、二乙醇胺(DEA)、吗啉(MORP)、哌啶(PIPD)和4-哌啶甲醇(4-PIPDM)在水溶液中25℃下的反应动力学,阐明其反应机理,给出二氧化碳、碳酸氢盐与有机胺的反应速率常数、氨基甲酸盐质子化常数和氨基甲酸盐的稳定常数。研究发现:二氧化碳与伯胺和仲胺的反应速率常数与其氨基甲酸盐的稳定常数具有线性关系。发现氨基甲酸盐稳定常数代表液态有机胺(氨)分子的空间位阻效应、溶剂化效应和电子效应的协同作用,它对于设计新型液态有机胺分子具有重要理论指导作用。

关键词: 反应动力学, 二氧化碳, 有机胺, 碳酸氢盐, 氨基甲酸盐

CLC Number:

TQ013.2

ZHANG Guohui, WANG Xiaoguang, William Conway, Marcel Maeder, SUN Qi, YU Hai. Kinetics of CO₂(aq),HCO₃^- with primary and secondary amines in aqueous solution[J]. CIESC Journal, 2013, 64(8): 2883-2890.

张国辉, 王晓光, William Conway, Marcel Maeder, 孙琦, 于海. 二氧化碳、碳酸氢盐与有机伯胺和仲胺反应机理[J]. 化工学报, 2013, 64(8): 2883-2890.

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Kinetics of CO₂(aq),HCO₃^- with primary and secondary amines in aqueous solution

二氧化碳、碳酸氢盐与有机伯胺和仲胺反应机理

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