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NMR temperature-jump method for measuring reaction rates: reaction of dimethylanthracene with H2@C60
Michael Frunzi1, Hai Xu, R James Cross
1Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Abstract:
We show a simple variant on Eigen's familiar temperature-jump method to measure rate constants. The sample is prepared in a sealed NMR tube, which is heated and then abruptly cooled. The NMR spectrum is then taken repeatedly until equilibrium is reestablished at the new temperature. The sample can be used over and over again. We demonstrate the technique on the reversible addition of 9,10-dimethylantracene to C(60). The C(60) contains H(2), and this provides an NMR signal upfield from TMS, well away from the rest of the spectrum. We show that the equilibrium constant for H(2)@C(60) is the same as that for (3)He@C(60).
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Atoms, molecules, or ions must collide before they can react with each other. Atoms must be close together to form chemical bonds. This premise is the basis for a theory that explains many observations regarding chemical kinetics, including factors affecting reaction rates.
The collision theory is based on the postulates that (i) the reaction rate is proportional to the rate of reactant collisions, (ii) the reacting species collide in an orientation allowing contact between...