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Molar heat capacity and molar excess enthalpy measurements of various aqueous tertiary and diamine solutions.

机译：各种叔和二胺水溶液的摩尔热容和摩尔过量焓的测量。

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摘要

Experimental measurements of molar heat capacity and molar excess enthalpy for aqueous solutions of 1-Dimethylamino-2-propanol (1DMAP), 3-Dimethylamino-1-propanol (3DMAP), Diethlyethanolamine (DEEA), Diethylenetriamine (DETA), and Ethylenediamine (EDA) were conducted using a C80 Calorimeter, for a range of temperatures between 303.15 and 353.15 K and over the entire range of mole fractions. Uncertainties with regard to the measured values of molar heat capacity and molar excess enthalpy were found to be +/- 1% and +/- 2%, respectively.;Molar excess enthalpy values were modeled using the following solution theory models: Non-Random Two Liquid (NRTL), UNIversal QUAsi Chemical (UNIQUAC) and the modified UNIversal Functional group Activity Coefficients -- Dortmund (UNIFAC). The modified UNIFAC was found to be the most accurate model with regard to representation and prediction of molar excess enthalpy values. The negative values of the excess molar enthalpies were in the following order: DETA > DEEA > EDA > 1DMAP > 3DMAP. The influence of the --OH group and the --NH group in molar excess enthalpies of aqueous binary mixtures is opposite in nature. An increase in the number of --CH3 radicals increased the values of the negative molar excess enthalpies when all amines were compared. Whereas, an addition of --OH groups decreased the negative excess enthalpy. The degree of amine hydrophobicity and their rate of reaction with CO2 can be attributed to the large negative values of the molar excess enthalpies.;Molar heat capacities were measured for five amines using a continuous three-step method. The values were found to be in the following order: DETA > DEEA > 1DMAP > 3DMAP > EDA. The solvents increased in molar heat capacity with temperature and mole fraction. Positive molar excess heat capacity ( CEp ) values were obtained for aqueous 1DMAP, 3DMAP, DEEA, DETA, and EDA at all temperatures and mole fractions. The Redlich-Kister equation was employed to correlate the excess molar heat capacities, and molar enthalpies at infinite dilution were derived. Group additivity and molecular connectivity analyses were conducted with the five amines in order to study the behavior of C p with respect to structural changes in amines. The percentage AAD for group additivity analysis was less than 4.5%, and for molecular connectivity it was found to be less than 6%. The contributions of each group are listed in the following order for all temperatures: CH > OH > NH2 > CH 3 > NH > CH2 > C > N.
机译：1-二甲基氨基-2-丙醇（1DMAP），3-二甲基氨基-1-丙醇（3DMAP），二乙撑乙醇胺（DEEA），二亚乙基三胺（DETA）和乙二胺（EDA）水溶液的摩尔热容和摩尔过量焓的实验测量）是使用C80量热计在303.15和353.15 K之间的温度范围内以及整个摩尔分数范围内进行的。摩尔热容量和摩尔过剩焓的测量值的不确定度分别为+/- 1％和+/- 2％.;摩尔过剩焓值使用以下溶液理论模型建模：非随机两个液体（NRTL），通用化学试剂（UNIQUAC）和改进的通用官能团活性系数-多特蒙德（UNIFAC）。在表示和预测摩尔过剩焓值方面，修改后的UNIFAC被认为是最准确的模型。过量摩尔焓的负值按以下顺序排列：DETA> DEEA> EDA> 1DMAP> 3DMAP。在水性二元混合物的摩尔过量焓中，-OH基团和-NH基团的影响在本质上是相反的。当比较所有胺时，-CH3自由基数量的增加会增加负摩尔过量焓的值。而-OH基团的添加降低了负的过量焓。胺的疏水性程度及其与CO2的反应速率可归因​​于摩尔过量焓的大负值。使用连续三步法测量了五种胺的摩尔热容。发现这些值按以下顺序：DETA> DEEA> 1DMAP> 3DMAP> EDA。溶剂的摩尔热容随温度和摩尔分数而增加。在所有温度和摩尔分数下，水性1DMAP，3DMAP，DEEA，DETA和EDA的正摩尔过量热容量（CEp）值均获得。使用Redlich-Kister方程关联过量的摩尔热容，并推导出无限稀释时的摩尔焓。为了研究C p与胺的结构变化有关的行为，对这5种胺进行了基团加和和分子连通性分析。用于基团加和分析的AAD百分比小于4.5％，而对于分子连通性，其百分比小于6％。在所有温度下，每个组的贡献按以下顺序列出：CH> OH> NH2> CH 3> NH> CH2> C>N。

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  • 作者

    Narayanaswamy, Kamal.;

  • 作者单位

    The University of Regina (Canada).;

  • 授予单位 The University of Regina (Canada).;
  • 学科 Engineering Chemical.;Engineering Industrial.;Engineering Environmental.
  • 学位 M.A.Sc.
  • 年度 2011
  • 页码 143 p.
  • 总页数 143
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类
  • 关键词

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