基团贡献法在估算反应热过程中的系统性验证及校正

doi:10.3866/PKU.WHXB201603162

摘要/Abstract

摘要：

在进行化工过程危险评估和安全设计时，反应热是一项非常重要的热力学参数。通常情况有两种方法获得反应热：量热法与估算法。相比来说，量热法的结果更精确，但所需时间和费用较多，也经常由于实验条件的限制无法进行；而估算法相比来说更便捷，但结果却不够准确。基团贡献法(GCM)就是一种常见的估算法。为了系统地研究估算法的准确度，从而使其能够在工业生产中对反应热进行初筛，本文分别通过量热实验法和GCM估算得到了包括11种常见反应类型在内的33个反应的反应热，并对结果进行了详细对比；按照反应类型对量热结果(Q_calorimetry)和估算结果(Q_GCM)之间的误差进行了总结；根据相对误差范围，反应类型被分为不同的组从而能够将Q_GCM校正为Q_calorimetry；并且针对不同的反应类型，提出了一些校正系数将QGCM校正为Q_recommended (Q_r)，使得GCM在工业应用中，量热方法不方便的时候可以服务生产。最后，本文对误差来源进行了详细的分析，并且为如何能够估算得更准确提出了一些建议。

关键词: 反应热, 量热, 基团贡献法, 误差分析, 校正系数

Abstract:

Reaction heat (Q) is an important parameter in chemical thermodynamics that is widely used in the hazard evaluation and safety design of chemical processes. Reaction heats can be obtained by either calorimetry or estimation. Calorimetry is generally more accurate, but is time-consuming, and sometimes precluded by the experimental conditions. By comparison, estimation techniques are quick and convenient, but are necessarily less accurate. The group contribution method (GCM) is one of the most commonly used estimation techniques. To investigate the accuracy of the estimations and make a primary screening of reaction heats for the industrial application of the GCM, calorimetric measurements of 33 reactions of 11 reaction types, including hydrogenation, reduction, nitration, oxidation, amidation, amination, ester hydrolysis, nitrogen substitution, ring-opening, and esterification, were conducted. The 33 reaction heats were also estimated by the GCM, and were compared with the calorimetric results. The relative errors between calorimetry (Q_calorimetry) and the GCM (Q_GCM) were also summarized for the different types of reactions. According to the range of relative errors, the reaction types were divided into different groups for calibrating Q_GCM to Q_calorimetry. Some recommended correction coefficients were proposed to correct Q_GCM to Q_recommended (Q_r) for the different types of reactions, which could be employed in industrial settings where experimental results are difficult to acquire. Finally, the sources of error between Q_calorimetry and Q_GCM were analyzed, and advice for making accurate estimations was proposed for future work.

Key words: Reaction heat, Calorimetry, Group contribution method, Error analysis, Correction coefficient

MSC2000:

O642

王睿,郝琳,杨晓武,郭子超,白文帅,李帅,卫宏远. 基团贡献法在估算反应热过程中的系统性验证及校正[J]. 物理化学学报, 2016, 32(6): 1404-1415.

Rui WANG,Lin HAO,Xiao-Wu YANG,Zi-Chao GUO,Wen-Shuai BAI,Shuai LI,Hong-Yuan WEI. Systematic Verification and Correction of the Group Contribution Method for Estimating Chemical Reaction Heats[J]. Acta Phys. -Chim. Sin., 2016, 32(6): 1404-1415.

参考文献

1	Weisenburger G. A. ; Barnhart R. W. ; Clark J. D. Org. Process Res. Dev 2007, 11 (6), 1112.
2	Frurip D. J. Determination of Chemical Process Heats by Experimentation and Prediction. In International Symposium on Runaway Reactions and Pressure Relief Design; Melhem, G. A., Fisher, H. G. Eds. American Institute of Chemical Engineers: New York, 1995; p 95.
3	Marrero J. ; Gani R. Fluid Phase Equilib 2001, 183, 183.
4	Saraf S. R. ; Rogers W. J. ; Mannan M. S.
5	Curtiss L. A., Redfern P. C. Frurip D. J. Theoretical Methods for Computing Enthalpies of Formation of Gaseous Compounds. In Reviews in Computational Chemistry; Lipkowitz, K. B., Boyd, D. B. Eds., Wiley-VHC: New York, 2000; Vol. 15, p 147.
6	Barkert U., Allinger N. L. Molecular Mechanics; American Chemical Society: Washington D.C, 1982; pp 174-175.
7	Saraf S. R. ; Rogers W. J. ; Ford D. M. Fluid Phase Equilib 2004, 222, 205.
8	Joback K. G. ; Reid R. C. Chem. Eng. Commun. 1987, 57 (1), 233.
9	Lydersen A. L. Estimation of Critical Properties of Organic Compounds; College Engineering University Wisconsin, Engineering Experimental Station Report 3: Madison, WI, April 1955.
10	Ambrose D. Correlation and Estimation of Vapor-Liquid Critical Properties. I. Critical Temperatures of Organic Compounds; National Physical Laboratory: Teddington, UK, NPL Report Chem., 92, September 1978.
11	Klincewicz K. M. ; Reid R. C. AIChE J. 1984, 30 (1), 137.
12	Lyman W. J. ; Reehl W. F. ; Rosenblatt D. H. Handbook of Chemical Property Estimation Methods; American Chemical Society: Washington, DC 1990.
13	Horvath A. L. Molecular Design; Elsevier: Amsterdam, 1992; p 637.
14	Wang X. L. ; Dong H. ; Zeng Z. H. ; Wu C. J. Solution Chem. 2015, 44, 67.
15	Zeng Z. X. ; Li X. N. ; Xue W. L. ; Zhang C. S. ; Bian S. C. Ind. Eng. Chem. Res 2010, 49, 5543.
16	Basa?ová P. ; Svoboda V. Fluid Phase Equilib 1995, 105 (1), 27.
17	Benkouider A. M. ; Kessas R. ; Guella S. J. Mol. Liq. 2014, 194, 48.
18	Conilio L. ; Daridon J. L. Fluid Phase Equilib 1997, 139, 15.
19	Huo Y. ; Xia S. ; Zhang Y. Ind. Eng. Chem. Res. 2009, 48 (4), 2212.
20	Gharagheizi F. ; Ilani-Kashkouli P. ; Sattari M. J. Mol. Liq. 2014, 190, 223.
21	Gharagheizi F. ; Salehi G. R. Thermochim. Acta 2011, 521 (1), 37.
22	Zhang X. ; Kobayashi N. ; He M. Energy Procedia 2014, 61, 492.
23	Carreo?n-Caldero?n B. ; Uribe-Vargas V. ; Ramírez-de-Santiago M. Ind. Eng. Chem. Res. 2014, 53 (13), 5598.
24	Cunico L. P. ; Ceriani R. ; Guirardello R. Chem. Eng. Trans. 2013, 32, 535.
25	Albert J. ; Mu?ller K. Ind. Eng. Chem. Res. 2014, 53 (44), 17522.
26	Lazzús J. A. ; Pulgar-Villarroel G. J. Mol. Liq. 2015, 209, 161.
27	Lazzús J. A. Thermochim. Acta 2012, 528, 38.
28	Lazzús J. A. J. Mol. Liq. 2012, 168, 87.
29	Sattari M. ; Gharagheizi F. ; Ilani-Kashkouli P. J. Therm. Anal. Calorim 2014, 115 (2), 1863.
30	Valderrama J. O. ; Forero L. A. ; Rojas R. E. Ind. Eng. Chem. Res. 2015, 54 (13), 3480.
31	Nancarrow P. ; Lewis M. ; AbouChacra L. Chem. Eng. Technol. 2015, 38 (4), 632.
32	Argoub K. ; Benkouider A. M. ; Yahiaoui A. Fluid Phase Equilib 2014, 380, 121.
33	Regenass W. J. Therm. Anal. Calorim. 1997, 49 (3), 1661.
34	Zogg A. ; Stoessel F. ; Fischer U. Thermochim. Acta 2004, 419 (1), 1.
35	Benson S. W. ; Cruickshank F. R. ; Golden D. M. Chem. Rev. 1969, 69 (3), 279.
36	Benson S. W. Thermochemical Kinetics 2nd edJohn Wiley:New York, 1976.
37	Cohen N. ; Benson S. Chem. Rev 1993, 93 (7), 2419.
38	Poling B. E. ; Prausnitz J. M ; O′Connell J. P The Properties of Gases and Liquids 5th edMcGraw-Hill:New York, 1976, 314.
39	Domalski E.S. ; Hearing E. D. J. Phys. Chem. Ref. Data 1993, 22 (4), 805.
40	Chemical Thermodynamic and Energy Release Evaluation (CHETAH), Version 8.0; available through the ASTM website: http://www.astm.org/cgi-bin/SoftCart.exe/BOOKSTORE/PUBS/1026.htm?L + mystore + vkkc4412.
41	Frurip D. ; Britton L. ; Fenlon W. Process Saf. Prog. 2004, 23 (4), 266.
42	Irikura K. K. ; Frurip D. J. Computational Thermochemistry; ACS Symposium Series 677, American Chemical Society: Washington, DC 1998.
43	Gasteiger J. Comput. Chem 1978, 2, 85.
44	Margrave J. L. J. Chem. Educ 1955, 32. 52.
45	Cox J. D ; Pilcher G Thermochemistry of Organic and Organometallic CompoundsAcademic Press:London, 1970, 523.
46	Pedley J. B. Thermochemical Data and Structures of Organic CompoundsThermodynamics Research Center:Texas, 1994, 1
47	Wagman D. D. J. Phys. Chem. Ref. Data,1982, 11:Supplemental No 2.
48	http://webbook.nist.gov/chemistry/.

[1]	谢文,周莲娇,徐娟,郭清莲,蒋风雷,刘义. 生物热化学和热动力学研究进展[J]. 物理化学学报, 2020, 36(6): 1905051 -0 .
[2]	胡之楠,左剑涛,夏美晨,房大维,臧树良. Pitzer方程应用于离子液体[C_nmim][H₂PO₄](n= 3, 4, 5, 6)溶解焓研究[J]. 物理化学学报, 2018, 34(8): 933 -937 .
[3]	袁莲,刘玉娇,何欢,蒋风雷,李会荣,刘义. 不同条件下离体大鼠肝脏线粒体能量代谢微量热分析[J]. 物理化学学报, 2018, 34(1): 73 -80 .
[4]	李旭,李强国,蒋建宏,谷惠文,李传华,肖圣雄,李霞. 一种精密恒温环境微量燃烧-溶解-反应多用量热计的设计及应用[J]. 物理化学学报, 2017, 33(6): 1114 -1122 .
[5]	白光月,刘君玲,王九霞,王玉洁,李艳娜,赵扬,姚美焕. 阳离子双子表面活性剂诱导的α-CT超活性和构象变化[J]. 物理化学学报, 2017, 33(5): 976 -983 .
[6]	肖明,黄在银,汤焕丰,陆桑婷,刘超. Ag₃PO₄表面热力学性质及光催化原位过程热动力学的晶面效应[J]. 物理化学学报, 2017, 33(2): 399 -406 .
[7]	赵顺省,李兰兰,刘向荣,丁作成,杨再文. 三种2-羟基-1-萘醛酰腙的晶体结构、热分解及其与CT-DNA的相互作用[J]. 物理化学学报, 2017, 33(2): 356 -363 .
[8]	王娇,杨利军,朱甜甜,汪慎之,陈忠秀. 大分子拥挤环境中脂肪酸影响磷脂囊泡相变的差示扫描量热研究[J]. 物理化学学报, 2016, 32(8): 2027 -2038 .
[9]	汤焕丰,黄在银,肖明,梁敏,陈栎莹. 立方体纳米氧化亚铜反应动力学的理论及实验研究[J]. 物理化学学报, 2016, 32(12): 2891 -2897 .
[10]	谢湖均,刘程程,孙强,顾青,雷群芳,方文军. 季铵盐型阳离子表面活性剂与牛血清白蛋白的相互作用[J]. 物理化学学报, 2016, 32(12): 2951 -2960 .
[11]	武克忠, 孙晓龙, 陈磊, 阮北. 相变贮热材料四氯合钴酸铵共析物的制备和热性能[J]. 物理化学学报, 2015, 31(7): 1260 -1264 .
[12]	杨庭, 陈利平, 陈网桦, 张彩星, 高海素, 路贵斌, 周奕杉. 分解反应自催化性质快速鉴别的实验方法[J]. 物理化学学报, 2014, 30(7): 1215 -1222 .
[13]	彭敏君, 路贵斌, 陈网桦, 陈利平, 吕家育. 苯胺溶剂中偶氮二异丁腈热分解特性及动力学[J]. 物理化学学报, 2013, 29(10): 2095 -2100 .
[14]	李娜, 赵凤起, 高红旭, 胡荣祖, 肖立柏, 姚二岗, 黄新萍, 常佩. 3-硝基-1,3,4-三唑-5-酮金属(Li, Na, Pb, Cu)盐的制备反应热动力学[J]. 物理化学学报, 2013, 29(10): 2101 -2106 .
[15]	高肖汉, 徐培, 段文超, 吕雪川, 谭志诚, 鲁强. Ho(NO₃)₃(C₂H₅O₂N)₄·H₂O的低温热容和热力学函数[J]. 物理化学学报, 2013, 29(10): 2123 -2128 .