Evaluation of the rate constants in chemical reactions

Abstract

This article is concerned with the application of a new method to recover the rate constants in chemical reactions. The method is based on treating the unknown parameters as time dependent. With appropriate experimental data the unknown rate constants are guided from an arbitrary initial condition to their true value at a final time. An explicit equation describing the time evolution of the parameters is obtained by minimizing the error along the trajectory. The method leads to an iterative algorithm which is described in detail. Numerical results with the method indicate that accurate estimates of the rate constants can be obtained directly from experimental data.

Solving Kinetic Inversion Problems via a Physically Bounded Gauss−Newton (PGN) Method

“…The KIP consisted of finding k 2 from measured [CF 3 NO] concentrations. In this study, the reported k 2 value was used to generate error-free observed data, the same as that observed in the previous study by Tadi and Yetter …”

“…The open literature reveals that there are several numerical methods, both local and global, devoted to studying reaction networks, but usually with <10 reactions. ,,, These small systems do not exhibit the complexity of most practical chemical reaction systems, where closed analytical expressions are often found embedded in a convolved legacy code. Without the ability to manipulate the complex reaction equations symbolically, it is difficult to apply advanced global methods such as the global terrain method of Lucia and Feng, , the interval method of Kearfott, and the α-BB algorithm of Esposito and Floudas .…”

An Ill‐posed inverse problem in enzymatic kinetics: Jack‐Bean urease denaturation by an anionic surfactant

“…In these approaches, one has to solve an ill‐posed inverse problem because noises in experimental data imply large errors in parameters to be estimated 11. Information concerning kinetic parameters are essential to optimization of several chemical processes and approaches such as rank annihilation factor analysis,12 curve resolution procedures,13 stochastic algorithms,14 control type techniques,15 and solution mapping programs16 have been used for this purpose. However, these techniques can fail in removing the ill‐posed feature of chemical kinetic inverse problems 17.…”

Retrieval of kinetic rates in reactions with semi batch liquid phase using ill-posed inverse problem theory

“…For example, calculation of kinetic parameters from experimental properties related to chemical concentrations is called inverse kinetic problem. Methods of parameters estimation such as rank annihilation factor analysis, 2 curve resolution methods, 3 Monte Carlo 4 or control type technique 5 have been extensively described in literature to estimate kinetic constants. A common difficulty in all these techniques is the sensitivity with respect to experimental random noises of the derivative operators, used to model the kinetic processes.…”