Maximal bimolecular rates

The maximal bimolecular rate constant turns out to be diffusion controlled and can be approximated according to [3]... 

Beyond Interval II, the second maximal polymerization rate can be attributed to the gel effect. The bimolecular termination reaction becomes diffusion-controlled in the latex particles and the average number of free radicals per particle increases signihcantly in the latter stage of polymerization, thereby leading to an acceleration of the free radical polymerization. The rate of polymerization then decreases continuously toward the end of polymerization due to the depletion of monomer and/or the diffusion-controlled propagation reaction in the reaction loci. 

Electron transport rates within an MFC film become maximized when the concentration of MFC becomes equal to that of MFC + due to the bimolecularity of the reaction. The notion of a bimolecular mechanism for ET is found in experiments of network polymer films with fixed charge gradient redox sites and mixed-valent osmium bipyridine clusters. Later, it was shown that MFCs with a specific charge state in the solution retain that same charge when dried, allowing selection of specific relative proportions of donors and acceptors within a dry film. Rate constants of ET in mixed-valent Au MFC films can therefore be expressed as ... 

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