German physicist who was corecipient, with R.G.W. Norrish and George
Porter, of the 1967 Nobel Prize for Chemistry for work on extremely
rapid chemical reactions. By perturbing a system at equilibrium, then
following its return to equilibrium via a "relaxation" process,
Eigen was able to avoid the time required to mix reagents, and thus
study the kinetics of very fast reactions. He found, for example, that
the reaction H+ + OH- > H2O occurs at every encounter between the
solvated ions. Using similar methods, Eigen measured rates of proton
transfer in organic acids and bases, and extended the method to complex
sequences of biological reactions.
Eigen was able to study many extremely fast chemical reactions by a
variety of methods that he introduced and which are called relaxation
techniques. These involve the application of bursts of energy to a solution
that briefly destroy its equilibrium before a new equilibrium is reached.
Eigen studied what happened to the solution in the extremely brief interval
between the two equilibria by means of absorption spectroscopy. Among
specific topics thus investigated were the rate of hydrogen ion formation
through dissociation in water, diffusion-controlled protolytic reactions,
and the kinetics of keto-enol tautomerism.
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