两种量热模式下物质热分解的动力学补偿效应

引用本文: 尹瑞丽, 陈利平, 陈网桦, 吴珂, 张彩星, 李焓, 于诚. 两种量热模式下物质热分解的动力学补偿效应[J]. 物理化学学报, 2016, 32(2): 391-398. doi: 10.3866/PKU.WHXB201511023 shu

Citation: YIN Rui-Li, CHEN Li-Ping, CHEN Wang-Hua, WU Ke, ZHANG Cai-Xing, LI Han, YU Cheng. Kinetic Compensation Effect under Two Different Calorimetric Modes for Thermal Decomposition[J]. Acta Physico-Chimica Sinica, 2016, 32(2): 391-398. doi: 10.3866/PKU.WHXB201511023 shu

两种量热模式下物质热分解的动力学补偿效应

尹瑞丽 ^1, ,
陈利平 ^{1,
,} ,
陈网桦 ^1, ,
吴珂 ^2, ,
张彩星 ^1, ,
李焓 ^1, ,
于诚 ^1,

1.
1 南京理工大学化工学院安全工程系, 南京 210094;
2.
2 常州出入境检验检疫局, 江苏常州 213003

通讯作者: 陈利平

基金项目:
国家自然科学基金(51204099) (51204099)

江苏出入境检验检疫局科技计划(2014KJ59)资助项目 (2014KJ59)

摘要: 热分析量热仪主要包括动态、等温、恒温及绝热四种操作模式。很多学者基于动态及等温模式的测试结果,采用Arrhenius 速率常数进行动力学计算,进而发现了所谓的“动力学补偿效应”。为了解绝热模式下是否也存在动力学补偿效应,分别采用绝热加速量热法(ARC)及动态差示扫描量热法(DSC)研究了过氧化二异丙苯(DCP)、40%(质量分数,下同)DCP溶液、葡萄糖、45%葡萄糖溶液的热分解特性,在此基础上基于Arrhenius 公式计算了对应的表观活化能E和指前因子A,并对计算结果进行了分析。结果表明:绝热模式下,不同质量的同种样品及其溶液的最佳动力学参数,或者同一组数据采用不同的反应级数获得的lnA和E之间均存在明显的线性关系。此外,尽管由动态DSC数据计算获得的E和lnA普遍小于绝热模式的结果,但两种模式下获得的lnA和E之间仍然存在动力学补偿效应。由此可以推断,具有相同或类似反应机理的反应,虽然实验模式不同,但其E和lnA之间存在明显的动力学补偿效应。

关键词:

English

Kinetic Compensation Effect under Two Different Calorimetric Modes for Thermal Decomposition

1.
1 Department of Safety Engineering, School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, P. R. China;
2.
2 Changzhou Entry-Exit Inspection and Quarantine Bureau, Changzhou 213003, Jiangsu Province, P. R. China

Corresponding author: 陈利平

Received Date: 06 October 2015
Fund Project:
国家自然科学基金(51204099)

江苏出入境检验检疫局科技计划(2014KJ59)资助项目

Abstract: Thermal analysis calorimeters can be used with different temperature control modes. Dynamic, isothermal, isoperibolic, and adiabatic modes are commonly used. A kinetic compensation effect was discovered when the kinetic parameters were calculated using the Arrhenius equation, based on dynamic and isothermal data. To determine whether the kinetic compensation effect existed in adiabatic mode, accelerating rate calorimetry (ARC) and differential scanning calorimetry (DSC) were used to obtain thermal decomposition curves of dicumyl peroxide (DCP), 40%(w) DCP in ethylbenzene, glucose, and 45% (w) glucose in water. The apparent activation energies (E) and pre-exponential factors (A) were calculated based on the Arrhenius rate constant. An obvious kinetic compensation effect was observed in a plot of lnA vs E for a given sample at different concentrations or for the same set of ARC data analyzed with different reaction orders n. Although the calculated lnA and E values using the dynamic differential scanning calorimetry data were usually lower than those using the adiabatic ARC data, a significant kinetic compensation effect existed between the two sets of results. This result suggested that the kinetic compensation effect existed between the activation energy and pre-exponential factor in reactions with the same or similar reaction mechanisms, regardless of the temperature control mode.

Key words:

1. [1]
  (1) Chen, J. H.; Li, C. R. Thermal Analysis and Its Application, 1th ed.; Science Press: Beijing, 1985; pp 6-118. [陈镜泓, 李传儒. 热分析及其作用. 第一版. 北京: 科学出版社, 1985: 6-118](1) Chen, J. H.; Li, C. R. Thermal Analysis and Its Application, 1th ed.; Science Press: Beijing, 1985; pp 6-118. [陈镜泓, 李传儒. 热分析及其作用. 第一版. 北京: 科学出版社, 1985: 6-118]
2. [2]
  (2) Hu, R. Z.; Gao, S. L.; Zhao, F. Q.; Shi, Q. Z.; Zhang, T. L.; Zhang, J. J. Thermal Analysis Kinetics, 2nd ed.; Science Press: Beijing, 2008; pp 151-155. [胡荣祖, 高胜利, 赵凤起, 史启祯, 张同来, 张建军. 热分析动力学. 第二版. 北京: 科学出版社, 2008: 151-155.](2) Hu, R. Z.; Gao, S. L.; Zhao, F. Q.; Shi, Q. Z.; Zhang, T. L.; Zhang, J. J. Thermal Analysis Kinetics, 2nd ed.; Science Press: Beijing, 2008; pp 151-155. [胡荣祖, 高胜利, 赵凤起, 史启祯, 张同来, 张建军. 热分析动力学. 第二版. 北京: 科学出版社, 2008: 151-155.]
3. [3]
  (3) Tang, H.; Yan, Y. D.; Zhang, M. L.; Xue, Y.; Zhang, Z. J.; Du, W. C.; He, H. Acta Phys. -Chim. Sin. 2013, 29 (8), 1698. [唐浩, 颜永得, 张密林, 薛云, 张志俭, 杜卫超, 何辉. 物理化学学报, 2013, 29 (8), 1698.] doi: 10.3866/PKU.WHXB201305102(3) Tang, H.; Yan, Y. D.; Zhang, M. L.; Xue, Y.; Zhang, Z. J.; Du, W. C.; He, H. Acta Phys. -Chim. Sin. 2013, 29 (8), 1698. [唐浩, 颜永得, 张密林, 薛云, 张志俭, 杜卫超, 何辉. 物理化学学报, 2013, 29 (8), 1698.] doi: 10.3866/PKU.WHXB201305102
4. [4]
  (4) Su, H. Z.; Yin, J. M.; Liu, Q. S.; Li, C. P. Acta Phys. -Chim. Sin. 2015, 31 (8), 1468. [宿洪祯, 尹静梅, 刘青山, 李长平. 物理化学学报, 2015, 31 (8), 1468.] doi: 10.3866/PKU.WHXB201506111(4) Su, H. Z.; Yin, J. M.; Liu, Q. S.; Li, C. P. Acta Phys. -Chim. Sin. 2015, 31 (8), 1468. [宿洪祯, 尹静梅, 刘青山, 李长平. 物理化学学报, 2015, 31 (8), 1468.] doi: 10.3866/PKU.WHXB201506111
5. [5]
  (5) Gallagher, P. K.; Johnson, D.W. Thermochim. Acta 1976, 14 (3), 255. doi: 10.1016/0040-6031(76)85002-2(5) Gallagher, P. K.; Johnson, D.W. Thermochim. Acta 1976, 14 (3), 255. doi: 10.1016/0040-6031(76)85002-2
6. [6]
  (6) Zhang, D. M.; Zheng, C. M.; Heng, S. Y.; Liu, Z. R.; Pan, Q.; Lu, H. L. Chinese Journal of Explosives & Propellants 2014, 37 (3), 82. [张冬梅, 郑朝民, 衡淑云, 刘子如, 潘清, 陆洪林. 火炸药学报, 2014, 37 (3), 82.](6) Zhang, D. M.; Zheng, C. M.; Heng, S. Y.; Liu, Z. R.; Pan, Q.; Lu, H. L. Chinese Journal of Explosives & Propellants 2014, 37 (3), 82. [张冬梅, 郑朝民, 衡淑云, 刘子如, 潘清, 陆洪林. 火炸药学报, 2014, 37 (3), 82.]
7. [7]
  (7) Qin, Z.; Balasubramanian, S. K.; Wolkers, W. F.; Pearce, J. A.; Bischof, J. C. Annals of Biomedical Engineering 2014, 42 (12), 2392. doi: 10.1007/s10439-014-1100-y(7) Qin, Z.; Balasubramanian, S. K.; Wolkers, W. F.; Pearce, J. A.; Bischof, J. C. Annals of Biomedical Engineering 2014, 42 (12), 2392. doi: 10.1007/s10439-014-1100-y
8. [8]
  (8) Pouretedal, H. R.; Ravanbod, M. J. Therm. Anal. Calorim. 2015, 119 (3), 2281. doi: 10.1007/s10973-014-4330-1(8) Pouretedal, H. R.; Ravanbod, M. J. Therm. Anal. Calorim. 2015, 119 (3), 2281. doi: 10.1007/s10973-014-4330-1
9. [9]
  (9) Chen, H.W.; Chen, J. T.; Wei, R. G.; Chen, L. Journal of Central South University: JCR-SC 2013, 44 (4), 1695. [陈鸿伟, 陈江涛, 危日光, 陈龙. 中南大学学报: 自然科学版, 2013, 44 (4), 1695.](9) Chen, H.W.; Chen, J. T.; Wei, R. G.; Chen, L. Journal of Central South University: JCR-SC 2013, 44 (4), 1695. [陈鸿伟, 陈江涛, 危日光, 陈龙. 中南大学学报: 自然科学版, 2013, 44 (4), 1695.]
10. [10]
  (10) Barrie, P. J. Phys. Chem. Chem. Phys. 2012, 14 (1), 318. doi: 10.1039/C1CP22666E(10) Barrie, P. J. Phys. Chem. Chem. Phys. 2012, 14 (1), 318. doi: 10.1039/C1CP22666E
11. [11]
  (11) Yelon, A.; Sacher, E.; Linert, W. Phys. Chem. Chem. Phys. 2012, 14 (22), 8232. doi: 10.1039/c2cp40618g(11) Yelon, A.; Sacher, E.; Linert, W. Phys. Chem. Chem. Phys. 2012, 14 (22), 8232. doi: 10.1039/c2cp40618g
12. [12]
  (12) Zuniga-Hansen, N.; Silbert, L. E.; Calbi, M. M. Breakdown of Kinetic Compensation Effect in Physical Desorption. http://arxiv.org/abs/1503.06362 (accessed Mar 21, 2015).(12) Zuniga-Hansen, N.; Silbert, L. E.; Calbi, M. M. Breakdown of Kinetic Compensation Effect in Physical Desorption. http://arxiv.org/abs/1503.06362 (accessed Mar 21, 2015).
13. [13]
  (13) Garn, P. D. Therm. Anal. 1976, 10 (1), 99. doi: 10.1007/BF02179195(13) Garn, P. D. Therm. Anal. 1976, 10 (1), 99. doi: 10.1007/BF02179195
14. [14]
  (14) Brill, T. B.; Gongwer, P. E.; Williams, G. K. J. Chem. Phys. 1994, 98 (47), 12242.(14) Brill, T. B.; Gongwer, P. E.; Williams, G. K. J. Chem. Phys. 1994, 98 (47), 12242.
15. [15]
  (15) Liu, T. T.; Ran, Y. Y.; Wang, B. C.; Dong, W. B.; Wu, S. G.; Gong, J. B. Front. Chem. Sci. Eng. 2014, 8 (1), 55.(15) Liu, T. T.; Ran, Y. Y.; Wang, B. C.; Dong, W. B.; Wu, S. G.; Gong, J. B. Front. Chem. Sci. Eng. 2014, 8 (1), 55.
16. [16]
  (16) Koga, N.; Šesták, J. Thermochim. Acta 1991, 182 (2), 201. doi: 10.1016/0040-6031(91)80005-4(16) Koga, N.; Šesták, J. Thermochim. Acta 1991, 182 (2), 201. doi: 10.1016/0040-6031(91)80005-4
17. [17]
  (17) Townsend, D. I.; Tou, J. C. Thermochim. Acta 1980, 37 (1), 1. doi: 10.1016/0040-6031(80)85001-5(17) Townsend, D. I.; Tou, J. C. Thermochim. Acta 1980, 37 (1), 1. doi: 10.1016/0040-6031(80)85001-5
18. [18]
  (18) Stoessel, F. Thermal Safety of Chemical Process: Risk Assessment and Process Design; Science Press: Beijing, 2009; pp 73-74; translated by Chen, W. H., Peng, J. H., Chen, L. P. [Stoessel, F. 化工工艺热安全: 风险评估与工艺设计. 陈网桦, 彭金华, 陈利平, 译. 北京: 科学出版社, 2009: 73-74.](18) Stoessel, F. Thermal Safety of Chemical Process: Risk Assessment and Process Design; Science Press: Beijing, 2009; pp 73-74; translated by Chen, W. H., Peng, J. H., Chen, L. P. [Stoessel, F. 化工工艺热安全: 风险评估与工艺设计. 陈网桦, 彭金华, 陈利平, 译. 北京: 科学出版社, 2009: 73-74.]
19. [19]
  (19) Lu, K. The Influence of the Typical Additives of Emulsion Explosives on the Thermal Decomposition of Emulsion Explosives. M. S. Dissertation, Nanjing University of Science and Technology, Nanjing, 2009. [鲁凯. 乳化炸药中典型组分对其热分解行为影响的研究[D]. 南京: 南京理工大学, 2009.](19) Lu, K. The Influence of the Typical Additives of Emulsion Explosives on the Thermal Decomposition of Emulsion Explosives. M. S. Dissertation, Nanjing University of Science and Technology, Nanjing, 2009. [鲁凯. 乳化炸药中典型组分对其热分解行为影响的研究[D]. 南京: 南京理工大学, 2009.]
20. [20]
  (20) Fisher, H. G.; Forrest, H. S.; Grossel, S. S.; Huff, J. E.; Muller, A. R.; Noronha, J. A.; Shaw, D. A.; Tilley, B. J. Emergency Relief System Design Using DIERS Technology: The Design Institute for Emergency Relief Systems (DIERS) Project Manual; JohnWiley & Sons: New York, 2010: pp 385-395.(20) Fisher, H. G.; Forrest, H. S.; Grossel, S. S.; Huff, J. E.; Muller, A. R.; Noronha, J. A.; Shaw, D. A.; Tilley, B. J. Emergency Relief System Design Using DIERS Technology: The Design Institute for Emergency Relief Systems (DIERS) Project Manual; JohnWiley & Sons: New York, 2010: pp 385-395.
21. [21]
  (21) Liu, R. H.; Chen, W. H.; Hu, Y. T. Safety Principle and Dangerous Chemicals Assessment Technology, 1st ed.; Chemical Industry Press: Beijing, 2004; pp 158-163. [刘荣海, 陈网桦, 胡毅亭. 安全原理与危险化学品测评技术. 第一版. 北京: 化学工业出版社, 2004: 158-163.](21) Liu, R. H.; Chen, W. H.; Hu, Y. T. Safety Principle and Dangerous Chemicals Assessment Technology, 1st ed.; Chemical Industry Press: Beijing, 2004; pp 158-163. [刘荣海, 陈网桦, 胡毅亭. 安全原理与危险化学品测评技术. 第一版. 北京: 化学工业出版社, 2004: 158-163.]
22. [22]
  (22) Chen, L. P. Experimental and Theoretical Studies on Thermal Hazards of Toluene Nitrations. Ph. D. Dissertation, Nanjing University of Science and Technology, Nanjing, 2009. [陈利平. 甲苯硝化反应热危险性的实验与理论研究[D]. 南京: 南京理工大学, 2009.](22) Chen, L. P. Experimental and Theoretical Studies on Thermal Hazards of Toluene Nitrations. Ph. D. Dissertation, Nanjing University of Science and Technology, Nanjing, 2009. [陈利平. 甲苯硝化反应热危险性的实验与理论研究[D]. 南京: 南京理工大学, 2009.]
23. [23]
  (23) Zhou, Y. S.; Chen, L. P.; Chen, W. H.; Yang, T.; Zhang, C. X.; Yin, R. L. CIESC Journal 2014, 65 (11), 4383. [周奕杉, 陈利平, 陈网桦, 杨庭, 张彩星, 尹瑞丽. 化工学报, 2014, 65 (11), 4383.](23) Zhou, Y. S.; Chen, L. P.; Chen, W. H.; Yang, T.; Zhang, C. X.; Yin, R. L. CIESC Journal 2014, 65 (11), 4383. [周奕杉, 陈利平, 陈网桦, 杨庭, 张彩星, 尹瑞丽. 化工学报, 2014, 65 (11), 4383.]
24. [24]
  (24) Kissinger, H. E. Anal. Chem. 1957, 29 (11), 1702. doi: 10.1021/ac60131a045(24) Kissinger, H. E. Anal. Chem. 1957, 29 (11), 1702. doi: 10.1021/ac60131a045
25. [25]
  (25) Peng, M. J.; Lu, G. B.; Chen, W. H.; Chen, L. P.; Lü , J. Y. Acta Phys. -Chim. Sin. 2013, 29 (10), 2095. [彭敏君, 路贵斌, 陈网桦, 陈利平, 吕家育. 物理化学学报, 2013, 29 (10), 2095.] doi: 10.3866/PKU.WHXB201307122(25) Peng, M. J.; Lu, G. B.; Chen, W. H.; Chen, L. P.; Lü , J. Y. Acta Phys. -Chim. Sin. 2013, 29 (10), 2095. [彭敏君, 路贵斌, 陈网桦, 陈利平, 吕家育. 物理化学学报, 2013, 29 (10), 2095.] doi: 10.3866/PKU.WHXB201307122

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 468
HTML全文浏览量: 31

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

两种量热模式下物质热分解的动力学补偿效应

通讯作者: 陈利平

English

Kinetic Compensation Effect under Two Different Calorimetric Modes for Thermal Decomposition

Corresponding author: 陈利平

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

两种量热模式下物质热分解的动力学补偿效应

通讯作者: 陈利平

English

Kinetic Compensation Effect under Two Different Calorimetric Modes for Thermal Decomposition

Corresponding author: 陈利平

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs