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首页> 外文期刊>Environmental Science & Technology >Toward Rational Design of Amine Solutions for PCC Applications:The Kinetics of the Reaction of CO_2(aq) with Cyclic and Secondary Amines in Aqueous Solution
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Toward Rational Design of Amine Solutions for PCC Applications:The Kinetics of the Reaction of CO_2(aq) with Cyclic and Secondary Amines in Aqueous Solution

机译:面向PCC应用的胺溶液的合理设计:水溶液中CO_2(aq)与环胺和仲胺反应的动力学

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摘要

The kinetics of the fast reversible carbamate formation reaction of CO_2(aq) with a series of substituted cyclic secondary amines as well as the noncyclic secondary amine diethanolamine (DEA) has been investigated using the stopped-flow spectrophotometric technique at 25.0 ℃. The kinetics of the slow parallel reversible reaction between HCO_3~- and amine has also been determined for a number of the amines by 'H NMR spectroscopy at 25.0 ℃. The rate of the reversible reactions and the equilibrium constants for the formation of carbamic acid/carbamate from the reactions of CO_2 and HCO_3~- with the amines are reported. In terms of the forward reaction of CO_2(aq) with amine, the order with increasing rate constants is as follows: diethanolamine (DEA) < morpholine (MORP) ~ thiomorpholine (TMORP) < N- methylpiperazine (N-MPIPZ) < 4-piperidinemethanol (4-P1PDM) ~ piperidine (PIPD) < pyrrolidine (PYR). Both 2-piperidinemethanol (2-PIPDM) and 2- piperidineethanol (2-PIPDE) do not form carbamates. For the carbamate forming amines a Bronsted correlation relating the protonation constant of the amine to the carbamic acid formation rate and equilibrium constants at 25.0 ℃ has been established. The overall suitability of an amine for PCC in terms of kinetics and energy is discussed.
机译:在25.0℃下,采用停流分光光度法研究了CO_2(aq)与一系列取代的环状仲胺以及非环状仲胺二乙醇胺(DEA)的快速可逆氨基甲酸酯形成反应的动力学。还通过1 H NMR光谱在25.0℃下确定了许多胺在HCO_3和胺之间的缓慢平行可逆反应的动力学。报道了由CO_2和HCO_3〜-与胺反应生成氨基甲酸/氨基甲酸酯的可逆反应速率和平衡常数。就CO_2(aq)与胺的正向反应而言,速率常数递增的顺序如下:二乙醇胺(DEA)<吗啉(MORP)〜硫代吗啉(TMORP)

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  • 来源
    《Environmental Science & Technology》 |2012年第13期|p.7422-7429|共8页
  • 作者单位

    Department of Chemistry, The University of Newcastle, Callaghan, NSW 2308, Australia;

    Department of Chemistry, The University of Newcastle, Callaghan, NSW 2308, Australia,National Institute of Clean-and-low-carbon Energy, Beijing, 102209, China;

    Department of Chemistry, The University of Newcastle, Callaghan, NSW 2308, Australia;

    Department of Chemistry, The University of Newcastle, Callaghan, NSW 2308, Australia;

    Department of Chemistry, The University of Newcastle, Callaghan, NSW 2308, Australia;

    CSIRO Energy Technology, Newcastle, NSW 2300, Australia;

    Department of Chemistry, The University of Newcastle, Callaghan, NSW 2308, Australia;

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  • 正文语种 eng
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