We show that coverage fluctuations on catalyst particles can drastically alter their macroscopic catalytic behavior. Scrutinizing the occurrence of kinetic bistabilities, it is demonstrated by molecular beam experiments on model catalysts that macroscopically observable bistabilities vanish completely with decreasing particle size, as previously predicted by theory. The effect is attributed to ...

An algorithm is given in this paper for the computation of dynamically equivalent weakly reversible realizations with the maximal number of reactions, for chemical reaction networks (CRNs) with mass action kinetics. The original problem statement can be traced back at least 30 years ago. The algorithm uses standard linear and mixed integer linear programming, and it is based on elementary graph...

The present paper deals with the kinetics and mechanism of homogeneously Ir(III) chloride catalyzed oxidation of D-mannitol by chloramine-T [CAT] in perchloric acid medium in the temperature range of 30 to 45 0C. The reaction is carried out in the presence of mercuric acetate as a scavenger for chloride ion. The experimental results show first order kinetics with respect to the oxidant [CAT] an...

Reduction kinetics of the methylene green (MG) with ascorbic acid (AA) in acidic medium at max 660 nm was monitored through visible spectrophotomtry in absence and presence of sodium carbonate. CO2 release through reaction of sodium carbonate and oxalic acid, created deoxygenated atmosphere for reduction of dye which greatly boosted the reaction rate. Initially slow reaction in presence of atm...

The reaction-diffusion master equation is a stochastic model often utilized in the study of biochemical reaction networks in living cells. It is applied when the spatial distribution of molecules is important to the dynamics of the system. A viable approach to resolve the complex geometry of cells accurately is to discretize space with an unstructured mesh. Diffusion is modeled as discrete jump...

Here we develop an effective approach to simplify two-time-scale Markov chains with infinite state spaces by removal of states with fast leaving rates, which improves the simplification method of finite Markov chains. We introduce the concept of fast transition paths and show that the effective transitions of the reduced chain can be represented as the superposition of the direct transitions an...

A number of enzyme digestion assays show apparent first-order kinetics of reactant depletion. There are four possible explanations of this phenomenon: (i) the reaction is dominated by a first-order limiting step, (ii) the digestion follows a pseudo-first-order kinetics under the excess of a reactant species, (iii) the first-order kinetics is only applicable to the slow transient of the reaction...

In this paper we discuss the question of how to decide when a general chemical reaction system is incapable of admitting multiple equilibria, regardless of parameter values such as reaction rate constants, and regardless of the type of chemical kinetics, such as mass-action kinetics, Michaelis-Menten kinetics, etc. Our results relate previously described linear algebraic and graph-theoretic con...

The characterization of the notions of complex and detailed balancing for mass action kinetics chemical reaction networks is revisited from the perspective of algebraic graph theory, in particular Kirchhoff’s Matrix Tree theorem for directed weighted graphs. This yields an elucidation of previously obtained results, in particular with respect to the Wegscheider conditions, and a new necessary a...