CORRELATION OF TRITIUM AND DEUTERIUM ISOTOPE EFFECTS
The theory of relative tritium-hydrogen and deuteriumhydrogen isotope effects is developed for both rate and equilibrium processes. It is shown that the relative effects in equilibrium processes vary with the strength of the chemical bonding and the temperature. A lower limit of 1.33 and an upper limit of 1.55 is established for ln alpha /sub T-H// ln alpha /sub D-H/ Detailed calculations are given for a number of simple molecules. It is shown that the temperature independent frequency factor in rate processes increases the ratio ln(k/sub H//k/sub T/)/ln(k/sub H//k/sub D/) above the values found in equilibrium processes. Equations are given from which the increment can be calculated. It is shown that relative tritiumprotium versus deuterium-protium isotope effects may be of diagnostic use in characterizing secondary isotope effects and tunnelling in chemical reactions. Detailed calculations are given for processes involving water including equilibration with hydrogen, distillation, and electrolysis. In these processes, alpha /sub D-H/varies from 5 x 10/sup -2/ to 10, yet ln( alpha /sub T/ ./sub H/)/ ln( alpha /sub D-H/) is calculated to be in the range 1.33 to 1.40 for all three processes. (auth)
- Research Organization:
- Brookhaven National Lab., Upton, N.Y.
- DOE Contract Number:
- AT(30-2)-GEN-16
- NSA Number:
- NSA-15-019200
- OSTI ID:
- 4002934
- Report Number(s):
- BNL-5314
- Country of Publication:
- United States
- Language:
- English
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