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Deuterium and Shift Calculation (Paperback, Softcover reprint of the original 1st ed. 1991)
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Deuterium and Shift Calculation (Paperback, Softcover reprint of the original 1st ed. 1991)
Series: NMR Basic Principles and Progress, 23
Expected to ship within 10 - 15 working days
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In 1931 Vrey, Brickwedde, and Murphy discovered the hydrogen
isotope deuterium. The isotopic enrichment was found to arise from
the fact that the electrolysis oflight water is faster than of
heavy water [1,2]. This success showed that although different
isotopes of an element behave identically from a chemical
standpoint the different isotopic masses nevertheless lead to both
isotope effects on equilibrium as well as on rate constants of
chemical reactions. Soon, ratios of equilibrium constants of
isotopic reactions were called "equilibrium isotope effects" (EIE),
ratios of isotopic rate constants "kinetic isotope effects" (KIE).
Isotope effects have been found to be especially large for those
elements which are directly involved in bond breaking and bond
formation during the reaction studied [3]. Such effects are,
therefore, referred to as "primary". Isotopic substitution in
atomic sites which maintain all chemical bonds with their neighbors
during the reaction of interest leads then only to smaller
"secondary" isotope effects. Because of the unique mass relation
between the different hydrogen isotopes hydrogen/deuterium isotope
effects are particularly large and have attracted most attention.
The largest contributions to these effects arise from changes in
the vibrational frequencies of the reactants. The theory of
equilibrium isotope effects has been founded by Vrey [4] and
Bigeleisen [5,6] and has widely been accepted [3].
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