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

ZHANG Guohui; WANG Xiaoguang; William Conway; Marcel Maeder; SUN Qi; YU Hai

doi:10.3969/j.issn.0438-1157.2013.08.026

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

更新时间：2025-12-10

- Kinetics of CO₂(aq),HCO₃^- with primary and secondary amines in aqueous solution
- CIESC Journal Issue 8, Pages: 2883-2890(2013)
- 作者机构：
  
  1. 神华研究院,北京,102209
  2. 澳大利亚纽卡斯尔大学化学系, 新南威尔士州,纽卡斯尔,2308
  3. 北京低碳清洁能源研究所,北京,102209
  4. 澳大利亚联邦科学与工业研究组织, 新南威尔士州,纽卡斯尔,2304
- 作者简介：
- 基金信息：
- DOI：10.3969/j.issn.0438-1157.2013.08.026
  CLC： Q013.2
- Online First：05 August 2013，
  
  Published：05 August 2013
- 稿件说明：
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ZHANG Guohui, WANG Xiaoguang, William Conway, et al. Kinetics of CO₂(aq),HCO₃^- with primary and secondary amines in aqueous solution[J]. CIESC Journal, 2013, (8): 2883-2890. DOI: 10.3969/j.issn.0438-1157.2013.08.026.
DOI：

ZHANG Guohui, WANG Xiaoguang, William Conway, et al. Kinetics of CO₂(aq),HCO₃^- with primary and secondary amines in aqueous solution[J]. CIESC Journal, 2013, (8): 2883-2890. DOI: 10.3969/j.issn.0438-1157.2013.08.026. DOI：

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。

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.

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