Fast reactions, study

DR. EYRING If it is, I am not aware of it. One of the attractive features about the early fast reaction studies of proton transfer systems is that they were comparatively simple. Some of the problems which have been mentioned today, such as perchlorate ions causing complications, are not present in extra pure water to which Dr. Ken Kustin has added just a trace of HF. If you take a membrane or some other kind of a surface, the proton transfer is certainly a great deal more complex. 

Velocity Constants from Initial Bate Measurements and Fast Reaction Studies... 

G. Khemmis Methods of fast reactions studying, Mir, Moscow (1977) (in Russian). 

Pure Solvents Miscellaneous.—Solvent Exchange. Recent examples of kinetic studies of solvent exchange at metal cations, formally the simplest substitution reaction in solution, include exchange of DMF at chromium(iii) and of DMSO at aluminium(m). The latter investigation used an ingeniously modified stopped-flow device integrated with a pulse Fourier-transform n.m.r. spectrometer, an apparatus of considerable potential value in fast-reaction studies. ... 

The introduction of pressure as a variable in fast reaction studies goes back to Brower who designed a pressure-jump technique for work under pressure. The temperature-jump technique has been adapted by a few research groups. The field has been reviewed recently (4). 

Dorfman LM (1963) Pulse radiolysis fast reaction studies in radiation chemistry. Science 141 493 98... 

The development of fast-reaction studies may be dated from investigations begun in the 1920 s on bimolecular reactions using flow techniques. Reaction was initiated by rapidly... 

The remarkable advances in both these aspects of fast-reaction studies contribute to our understanding of chemical reaction mechanisms, but in different ways. Marcus theory is concerned with the calculation of rate constants, relating them to potential-energy diagrams these are expressed in macroscopic units. Studies of ultrafast processes, on the other hand, are concerned with the microscopic world of nuclear and electronic motions they describe what actually happens when individual molecules undergo reaction. Both types of theory are important for a full understanding of chemical reactivity. 

However, at the present time the Mo(VI)/Mo(IV) scheme is no more than a hypcthesis for these two enzymes. Further work, particularly stoichiometric titrations and more fast-reaction studies, as well as oxygen tracer work, is called for to help to clarify matters. 

---