Characterizing batch reactions with in situ spectroscopic measurements, calorimetry and dynamic modeling

• Published in: Journal of chemometrics 2003-08, Vol.17 (8-9), p.470-479
• Main Authors: Ma, Bei, Gemperline, Paul J., Cash, Eric, Bosserman, Mary, Comas, Enric
• Format: Article
• Language: English
• Subjects: Analytical chemistry; batch process analysis; calorimetry; Chemistry; Exact sciences and technology; General and physical chemistry; General. Nomenclature, chemical documentation, computer chemistry; kinetic fitting; Miscellaneous; multivariate curve resolution; multiway analysis; process analysis; self-modeling curve resolution; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; UV spectroscopy
• ISSN: 0886-9383; 1099-128X
• DOI: 10.1002/cem.793

A method for fully characterizing consecutive batch reactions using self‐modeling curve resolution of in situ spectroscopic measurements and reaction energy profiles is reported. Simultaneous measurement of reaction temperature, reactor jacket temperature, reactor heater power and UV/visible spectra was made with a laboratory (50 ml capacity) batch reactor equipped with a UV/visible spectrometer and a fiber optic attenuated total reflectance (ATR) probe. Composition profiles and pure component spectra of reactants and products were estimated without the aid of reference measurements or standards from the in situ UV/visible spectra using non‐negative alternating least squares (ALS), a type of self‐modeling curve resolution (SMCR). Multiway SMCR analysis of consecutive batches permitted standardless comparisons of consecutive batches to determine which batch produced more or less product and which batch proceeded faster or slower. Dynamic modeling of batch energy profiles permitted mathematical resolution of the reaction dose heat and reaction heat. Kinetic fitting of the in situ reaction spectra was used to determine reaction rate constants. These three complementary approaches permitted simple and rapid characterization of the reaction's rate of reaction, energy balance and mass balance. Copyright © 2003 John Wiley & Sons, Ltd.