### Abstract

Stoichiometrically, exact candidate pathways or mechanisms for deriving the rate law of a catalytic or complex reaction can be determined through the synthesis of networks of plausible elementary reactions constituting such pathways. A rigorous algorithmic method is proposed for executing this synthesis, which is exceedingly convoluted due to its combinatorial complexity. Such a method for synthesizing networks of reaction pathways follows the general framework of a highly exacting combinatorial method established by us for process-network synthesis. It is based on the unique graph-representation in terms of P-graphs, a set of axioms, and a group of combinatorial algorithms. In the method, the inclusion or exclusion of a step of each elementary reaction in the mechanism of concern hinges on the general combinatorial properties of feasible reaction networks. The decisions are facilitated by solving linear programming problems comprising a set of mass-balance constraints to determine the existence or absence of any feasible solution. The search is accelerated further by exploiting the inferences of preceding decisions, thereby eliminating redundancy. As a result, all feasible independent reaction networks, i.e. pathways, are generated only once; the pathways violating any first principle of either stoichiometry or thermodynamics are eliminated. The method is also capable of generating those combinations of independent pathways directly, which are not microscopically reversible. The efficiency and efficacy of the method are demonstrated with the identification of the feasible mechanisms of ammonia synthesis involving as many as 14 known elementary reactions.

Original language | English |
---|---|

Pages (from-to) | 265-292 |

Number of pages | 28 |

Journal | Computers and Chemistry |

Volume | 26 |

Issue number | 3 |

DOIs | |

Publication status | Published - 2002 |

### Fingerprint

### Keywords

- Algorithm
- Identification
- P-graph
- Reaction pathways
- Synthesis

### ASJC Scopus subject areas

- Applied Microbiology and Biotechnology
- Biotechnology
- Chemical Engineering(all)

### Cite this

**A graph-theoretic method to identify candidate mechanisms for deriving the rate law of a catalytic reaction.** / Fan, L. T.; Bertók, B.; Friedler, F.

Research output: Contribution to journal › Article

*Computers and Chemistry*, vol. 26, no. 3, pp. 265-292. https://doi.org/10.1016/S0097-8485(01)00119-X

}

TY - JOUR

T1 - A graph-theoretic method to identify candidate mechanisms for deriving the rate law of a catalytic reaction

AU - Fan, L. T.

AU - Bertók, B.

AU - Friedler, F.

PY - 2002

Y1 - 2002

N2 - Stoichiometrically, exact candidate pathways or mechanisms for deriving the rate law of a catalytic or complex reaction can be determined through the synthesis of networks of plausible elementary reactions constituting such pathways. A rigorous algorithmic method is proposed for executing this synthesis, which is exceedingly convoluted due to its combinatorial complexity. Such a method for synthesizing networks of reaction pathways follows the general framework of a highly exacting combinatorial method established by us for process-network synthesis. It is based on the unique graph-representation in terms of P-graphs, a set of axioms, and a group of combinatorial algorithms. In the method, the inclusion or exclusion of a step of each elementary reaction in the mechanism of concern hinges on the general combinatorial properties of feasible reaction networks. The decisions are facilitated by solving linear programming problems comprising a set of mass-balance constraints to determine the existence or absence of any feasible solution. The search is accelerated further by exploiting the inferences of preceding decisions, thereby eliminating redundancy. As a result, all feasible independent reaction networks, i.e. pathways, are generated only once; the pathways violating any first principle of either stoichiometry or thermodynamics are eliminated. The method is also capable of generating those combinations of independent pathways directly, which are not microscopically reversible. The efficiency and efficacy of the method are demonstrated with the identification of the feasible mechanisms of ammonia synthesis involving as many as 14 known elementary reactions.

AB - Stoichiometrically, exact candidate pathways or mechanisms for deriving the rate law of a catalytic or complex reaction can be determined through the synthesis of networks of plausible elementary reactions constituting such pathways. A rigorous algorithmic method is proposed for executing this synthesis, which is exceedingly convoluted due to its combinatorial complexity. Such a method for synthesizing networks of reaction pathways follows the general framework of a highly exacting combinatorial method established by us for process-network synthesis. It is based on the unique graph-representation in terms of P-graphs, a set of axioms, and a group of combinatorial algorithms. In the method, the inclusion or exclusion of a step of each elementary reaction in the mechanism of concern hinges on the general combinatorial properties of feasible reaction networks. The decisions are facilitated by solving linear programming problems comprising a set of mass-balance constraints to determine the existence or absence of any feasible solution. The search is accelerated further by exploiting the inferences of preceding decisions, thereby eliminating redundancy. As a result, all feasible independent reaction networks, i.e. pathways, are generated only once; the pathways violating any first principle of either stoichiometry or thermodynamics are eliminated. The method is also capable of generating those combinations of independent pathways directly, which are not microscopically reversible. The efficiency and efficacy of the method are demonstrated with the identification of the feasible mechanisms of ammonia synthesis involving as many as 14 known elementary reactions.

KW - Algorithm

KW - Identification

KW - P-graph

KW - Reaction pathways

KW - Synthesis

UR - http://www.scopus.com/inward/record.url?scp=0036007080&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0036007080&partnerID=8YFLogxK

U2 - 10.1016/S0097-8485(01)00119-X

DO - 10.1016/S0097-8485(01)00119-X

M3 - Article

C2 - 11868915

AN - SCOPUS:0036007080

VL - 26

SP - 265

EP - 292

JO - Computational Biology and Chemistry

JF - Computational Biology and Chemistry

SN - 1476-9271

IS - 3

ER -