Uncertainty Analysis in the Use of Chemical Thermometry: A Case Study with Cyclohexene

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• 作者：Joshua S. Heyne ; Frederick L. Dryer
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：July 3, 2013
• 年：2013
• 卷：117
• 期：26
• 页码：5401-5406
• 全文大小：258K
• 年卷期：v.117,no.26(July 3, 2013)
• ISSN：1520-5215

文摘

A general method to evaluate the absolute uncertainties in temperatures derived using chemical thermometry is developed and applied to the retro Diels鈥揂lder reaction of cyclohexene. Experiments from previous studies of this reaction are reanalyzed to establish the minimum absolute uncertainty limit. Chemical thermometry results are compared with thermocouple measurements in experiments performed in a flow reactor at 6.1 atm pressure and at temperatures from 957 to 978 K . Using conservative uncertainty estimates, our analysis yields absolute (1蟽) uncertainties of temperature through chemical thermometry using this reaction greater than 卤20 at 1000 K. Neither more refined experimental techniques nor computational theory is likely to refine rate correlation parameters sufficiently to reach the absolute temperature uncertainties often reported in the literature for chemical thermometry using the retro Diels鈥揂lder reaction of cyclohexene. Published chemical thermometry uncertainty estimates typically have not quantitatively considered the absolute uncertainties of the original data from which the reference rate correlations were based.