Reaction Progress Kinetic Analysis | Free Webinar
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Reaction Progress Kinetic Analysis

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A Powerful Methodology for Streamlining the Study of Complex Organic Reactions

Professor Donna Blackmond discusses how Reaction Progress Kinetic Analysis (RPKA) methodology simplifies kinetic studies of organic reactions.
Professor Donna Blackmond, Scripps Research Institute
32 Minutes

Reaction Progress Kinetic Analysis (RPKA) streamlines kinetic studies by exploiting the extensive data available from accurate in situ monitoring of global reaction progress under “synthetically relevant” conditions, where the concentrations of two or more reactants are changing simultaneously – in fact, in the same manner that they are expected to change during practical synthesis. This contrasts with the classical approach to kinetics, which uses concentration ratios that are highly distorted, typically ca. 10 equivalents, in order to examine the order in each substrate’s concentration while holding the other constant. We have shown that the concentration dependences of two different substrates may be determined from far fewer reaction progress experiments compared to a classical kinetic approach. RPKA methodology is made straightforward for interpretation via the graphical manipulation of a mathematically determined minimum set of carefully designed experiments. One advantage of the RPKA approach is that vital kinetic information may be rapidly obtained and extracted even in earliest studies of a new reaction and may thus help inform the direction of both further reaction optimization and fundamental mechanistic investigation by other methods. The method requires little mathematical prowess and no specialized kinetic modeling techniques.

At its most basic level, the RPKA methodology consists of two sets of experiments, called “same excess” and “different excess” experiments. The “different excess” protocol provides information similar to that obtained in classical kinetic studies, that is, it gives the order in various reactant concentrations. The principal advantage of RPKA in this case is that this information is obtained from far fewer experiments than required for traditional kinetic analysis. However, it is in the “same excess” protocol that the RPKA methodology is most innovative, because here it provides not simply the same information more rapidly and with higher accuracy, but it extracts information about a working catalytic cycle that is difficult to obtain by any other means: “same excess” experiments help to differentiate a catalyst cycle that is operating at steady-state from one which is subject to temporal effects unrelated to the intrinsic reaction kinetics, such as catalyst activation or deactivation.

Guest Presenter

Professor Donna Blackmond

Donna Blackmond received her Ph.D. in Chemical Engineering from Carnegie-Mellon University in 1984. She was a professor of Chemical Engineering at the University of Pittsburgh from 1984-1992. In 1992, she left academia for industrial research, becoming an Associate Director at Merck & Co., Inc., where she was responsible for setting up a new laboratory for research and development in the kinetics and catalysis of organic reactions. From 1996-99 Professor Blackmond was a Research Group Leader at the Max-Planck-Institut für Kohlenforschung in Mülheim an der Ruhr, Germany. She moved to the United Kingdom in 1999 to take up the position of Professor and Chair of Physical Chemistry at the University of Hull. She joined the faculty at Imperial College London in 2004, with joint professorial appointments in the Departments of Chemistry and Chemical Engineering & Chemical Technology as well as the Chair in Catalysis. In 2010, she moved to The Scripps Research Institute in La Jolla, California as Professor of Chemistry.

Professor Blackmond’s research focuses on blending the quantitative aspects of her chemical engineering background together with the synthesis of complex organic molecules by catalytic routes, particularly asymmetric catalysis with application in pharmaceutical processes. She has published over 150 papers in this field. She serves as a consultant to a number of major pharmaceutical companies, and she offers a short course on the kinetics of organic reactions in the pharmaceutical industry. Professor Blackmond received the 2009 Royal Society of Chemistry Award in Physical Organic Chemistry. She was awarded a Royal Society Wolfson Research Merit Award in 2007. She received an Arthur C. Cope Scholar Award from the Organic Chemistry Division of the American Chemical Society (2005). She was a Woodward Visiting Scholar at Harvard University (2002-2003) and a Miller Institute Research Fellow at University of California, Berkeley (2003). She received the Royal Society of Chemistry’s Award in Process Technology i(2003), the North American Catalysis Society’s Paul H. Emmett Award (2001), the Organic Reactions Catalysis Society’s Raul Rylander Award (2003), and the NSF Presidential Young Investigator Award (1986-91).


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