Gateway analysis for complex reaction mechanisms: Kinetic Informative Detachable (KID) sub-mechanisms

•A mechanism decomposition procedure for first-order mechanisms in CSTR is proposed.•A complex mechanism is decomposed into detachable and feeding sub-mechanisms.•Intersections of concentration dependences in the detachable mechanism are studied.•The space times at these intersections are not affect...

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Bibliographic Details
Published in:Chemical engineering science 2018-03, Vol.178, p.183-193
Main Authors: Branco, P. Daniel, Yablonsky, Gregory S., Marin, Guy B., Constales, Denis
Format: Article
Language:English
Subjects:
CSTR
Detachable mechanism
Feeding mechanism
Intersections
Kinetic coefficients determination
Mechanism decomposition
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Summary:•A mechanism decomposition procedure for first-order mechanisms in CSTR is proposed.•A complex mechanism is decomposed into detachable and feeding sub-mechanisms.•Intersections of concentration dependences in the detachable mechanism are studied.•The space times at these intersections are not affected by the feeding mechanism.•Space times are used to determine kinetic coefficients of the detachable mechanism. In solving the kinetic model reduction problem for CSTR studies, a new procedure of decomposing the full mechanism was developed. In this procedure, the full mechanism was decomposed in two sub-mechanisms, Kinetic Informative Detachable (KID) mechanism and Feeding Mechanism (FEM) linked by a special bridging reaction via a single gateway substance which belongs to FEM. Requirements for such decomposition were formulated. This procedure allows to produce relationships which depend only on the kinetic coefficients of the KID mechanism and the gateway substance reaction. In a typical case, say for the mechanism A→k1B⇄k2-k2+C, the reciprocal space time value τ at the intersection of the B and C kinetic dependences is characterized by a simple relation 1τ=k2+-k2-. In general, this or similar dependences can be used for extracting the kinetic coefficients. Mathematically, the procedure is grounded on a generalized eigenvalue problem. Decomposition of a given mechanism into sub-mechanisms can be done in multiple ways with different corresponding gateways, and, consequently, different kinetic coefficients can be extracted. Theoretical concepts are illustrated by many examples of mechanisms.
ISSN:0009-2509
1873-4405
DOI:10.1016/j.ces.2017.12.018