Improved Method for Kinetic Studies in Microreactors Using Flow Manipulation and Noninvasive Raman Spectrometry

• Published in: Journal of the American Chemical Society Vol. 133; no. 10; pp. 3601 - 3608
• Main Authors: Mozharov, Sergey, Nordon, Alison, Littlejohn, David, Wiles, Charlotte, Watts, Paul, Dallin, Paul, Girkin, John M
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 16.03.2011
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja1102234

A novel method has been devised to derive kinetic information about reactions in microfluidic systems. Advantages have been demonstrated over conventional procedures for a Knoevenagel condensation reaction in terms of the time required to obtain the data (fivefold reduction) and the efficient use of reagents (tenfold reduction). The procedure is based on a step change from a low (e.g., 0.6 μL min−1) to a high (e.g., 14 μL min−1) flow rate and real-time noninvasive Raman measurements at the end of the flow line, which allows location-specific information to be obtained without the need to move the measurement probe along the microreactor channel. To validate the method, values of the effective reaction order n were obtained employing two different experimental methodologies. Using these values of n, rate constants k were calculated and compared. The values of k derived from the proposed method at 10 and 40 °C were 0.0356 ± 0.0008 mol−0.3 dm0.9 s−1 (n = 1.3) and 0.24 ± 0.018 mol−0.1 dm0.3 s−1 (n = 1.1), respectively, whereas the values obtained using a more laborious conventional methodology were 0.0335 ± 0.0032 mol−0.4 dm1.2 s−1 (n = 1.4) at 10 °C and 0.244 ± 0.032 mol−0.3 dm0.9 s−1 (n = 1.3) at 40 °C. The new approach is not limited to analysis by Raman spectrometry and can be used with different techniques that can be incorporated into the end of the flow path to provide rapid measurements.