Kinetics bimolecular reactions

The results presented below do indeed show that peroxynitrite is produced in high yields in 1 ps. The prompt formation and subsequent protonation of peroxynitrite offers a unique opportunity for studying bimolecular reactions under conditions where secondary reaction can safely be ruled out. In this work we measure the bimolecular reaction kinetics of ONOCT+ FT1" —y HONOO as a function of [it] and find it to be in excellent agreement with seminal theoretical work by Smoluchowsky. 

Experimentally it has proven very difficult to investigate bimolecular reaction kinetics. Although optical techniques have been developed with femtosecond time resolution, the bimolecular nature of the reactions precludes standard femtosecond pump-probe experiments, as a common starting time for the reaction is not readily established. Here we initiate the fast bimolecular acid-base reaction by converting a very weak base, NO3 to a weak base ONOO" and follow the reaction ONOO + H+ as a function of [ft]. 

As was demonstrated by Kikuchi and Brush [88], using the Ising model as an example, an increase of mo in the expansion in the form secures the monotonic approach of the calculated critical parameters to exact results, except for the critical exponents which cannot be reproduced by algebraic expressions. It is important to note here that the superposition approximation permits exact (or asymptotically exact) solutions to be obtained for models revealing the critical point but not the phase transition. This should be kept in mind when interpreting the results of the bimolecular reaction kinetics obtained using approximate methods. 

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