Acta Phys. -Chim. Sin. ›› 2016, Vol. 32 ›› Issue (6): 1404-1415.doi: 10.3866/PKU.WHXB201603162

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Systematic Verification and Correction of the Group Contribution Method for Estimating Chemical Reaction Heats

Rui WANG1,Lin HAO1,*(),Xiao-Wu YANG2,Zi-Chao GUO1,Wen-Shuai BAI1,Shuai LI1,Hong-Yuan WEI1   

  1. 1 School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, P. R. China
    2 China Huanqiu Contracting & Engineering Corporation, Shanghai 200032, P. R. China
  • Received:2016-02-15 Published:2016-06-03
  • Contact: Lin HAO
  • Supported by:
    The project was supported by the National Natural Science Foundation of China(21576196)


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 (Qcalorimetry) and the GCM (QGCM) 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 QGCM to Qcalorimetry. Some recommended correction coefficients were proposed to correct QGCM to Qrecommended (Qr) 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 Qcalorimetry and QGCM 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


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