[1]郭登峰,柳娜,罗士平,等.碳酸二甲酯和碳酸二乙酯合成碳酸甲乙酯的热力学分析[J].南京理工大学学报(自然科学版),2009,(06):829-832.
 GUO Deng-feng,LIU Na,LUO Shi-ping,et al.Thermodynamic Analysis for Synthesis of Ethyl Methyl Carbonate from Dimethyl Carbonate and Diethyl Carbonate[J].Journal of Nanjing University of Science and Technology,2009,(06):829-832.
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碳酸二甲酯和碳酸二乙酯合成碳酸甲乙酯的热力学分析
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《南京理工大学学报》(自然科学版)[ISSN:1005-9830/CN:32-1397/N]

卷:
期数:
2009年06期
页码:
829-832
栏目:
出版日期:
2009-12-30

文章信息/Info

Title:
Thermodynamic Analysis for Synthesis of Ethyl Methyl Carbonate from Dimethyl Carbonate and Diethyl Carbonate
作者:
郭登峰;柳娜;罗士平;薛冰;
江苏工业学院化学化工学院, 江苏常州213164
Author(s):
GUO Deng-fengLIU NaLUO Shi-pingXUE Bing
School of Chemistry and Chemical Engineering,Jiangsu Polytechnic University,Changzhou 213164,China
关键词:
碳酸甲乙酯 基团贡献 热力学分析 平衡常数
Keywords:
ethyl methyl carbonate group contributions thermodynamic analysis equilibrium constant
分类号:
TQ225.52
摘要:
为了得到碳酸二甲酯(DMC)和碳酸二乙酯(DEC)酯交换合成碳酸甲乙酯(EMC)反应的热力学数据,用Benson基团贡献法计算了相关物质的标准摩尔生成焓、吉布斯自由能和摩尔定压热容。计算了300~1 000 K温度范围内,该反应的焓变、自由能变、平衡常数和平衡转化率。结果表明:由DMC和DEC酯交换合成EMC的反应的自由能变在300~1 000 K范围内均为负值,因此是热力学上可自发进行的反应。随着温度的升高,反应的自由能变逐渐减小,因此高温有利于反应的进行。但即使在1 000 K时,反应的平衡常数也仅为33.20,这说明该反应自发进行的程度不高。
Abstract:
In order to obtain the thermodynamic data of the synthesis of ethyl methyl carbonate(EMC) from dimethyl carbonate(DMC) and diethyl carbonate(DEC),the standard molar enthalpies of formation,Gibbs free energy and molar heat capacity under constant pressure are calculated by the method of Benson group contributions.The enthalpy change,free energy change,equilibrium constant and equilibrium conversion rate of the reaction are calculated and discussed according to the principles of chemical thermodynamics under 300~1 000 K.The results show that the free energy change in the synthesis of EMC by transesterification of DMC with DEC is negative and the reaction is thermodynamically feasible.The free energy change decreases with the increase in the temperature,and higher temperature is in favor of the reaction.The equilibrium constant of the reaction is only 33.20 even at 1 000 K and the spontaneous degree of the reaction is low.

参考文献/References:

[ 1] ShenZ, JiangX, ZhaoW. Anewcatalytic transester-i fication for the synthesisofethylmethylcarbonate[ J]. Catal letters, 2003, 91( 1/2): 63-67.
[ 2] 朱绪飞, 李东栋,孟大伟, 等. 多孔阳极氧化铝形成过程的研究[ J]. 南京理工大学学报(自然科学版), 2006, 30( 5): 644-648.
[ 3] 李琳, 朱大建,熊辉, 等. 酯交换法合成碳酸甲乙酯 [ J]. 合成化学, 2004, 12(2): 197- 200.
[ 4] PalaniA, GokulakrishnanN, PalanichamyM, et a.l Transesterification of dimethyl carbonate with diethyl carbonate overA-lZn-MCM-41andA-lMCM-41molec-ular sieves[ J]. ApplCatalA: Gen, 2006, 304( 1): 152-158.
[ 5] ZhouY, Song J, LiangS, et a.l Meta-lorganic frame-works as an acid catalyst for the synthesis of ethyl methyl carbonate via transesterification[ J]. J Mol CatalA: Chem, 2009, 308( 1/2): 68-72.
[ 6] 鲁亚琳, 宋伟红. 催化羰基化合成丙二酸二乙酯 [ J]. 南京理工大学学报(自然科学版), 2004, 28 (6): 658- 662.
[ 7] BensonSW, CrickshankF R, GoldenDM, et a.l Additivity rules for the estimation of thermochemical properties[ J]. ChemRev, 1969, 69( 3): 279-323.
[ 8] RobertCR, JohnMP, Bruce EP. The properties of gasesand liquids[M]. 4thEd. USA: McGraw-Hil,l Inc, 1987. 173- 191.
[ 9] 赵国良, 靳长德. 有机物热力学数据的估算[M]. 北京: 高等教育出版社, 1983. 64.
[ 10] Sidney WB. Thermochemical kinetics: Methods for the estimationof thermochemical data andrate param-eters[M]. 2ndEd. NewYork, USA: JohnWiley and Sons, Inc, 1976. 271-275.
[ 11] 郑卓群, 吴廷华,茆福林, 等. 甲醇和氨基甲酸甲酯制碳酸二甲酯的热力学分析[ J]. 石油与天然气化工, 2005, 34( 2): 87-88.
[ 12] 张立庆, 史辰,王静峰. 乙醇羰基化法合成碳酸二乙酯的热力学计算与分析[ J]. 石油与天然气化工, 2004, 33(3): 152- 154.
[ 13] 陈英, 韩金玉,刘艳平. 固体碱催化剂上碳酸甲乙酯的洁净合成[ J]. 天津大学学报, 2007, 40( 3): 285-288.

备注/Memo

备注/Memo:
基金项目: 国家自然科学基金( 20671045)
作者简介: 郭登峰( 1964- ), 男,副教授, 主要研究方向:精细化工及工业分析, E-mail: gdf166@163. com。
更新日期/Last Update: 2012-11-19