THE KINETIC ISOTOPE EFFECT IN DEUTERIUM- AND TRITIUM-EXCHANGE IN LIQUID AMMONIA (in Russian)
Fluorene labeled with D/sub 2/O or HTO (T = tritium) in the methylene group, and methyl- beta -naphthylketone labeled with the heavy isotope in the methyl group (0.1 to 0.2 g of material) were mixed with 11 to 13 g of purified liquid NH/sub 3/, and held for 1 to 2 hr under pressure at 25 deg C. The exchange reaction was interrupted by cooling to --78 deg C and the sample was burned in a current of oxygen. Deuterium was determined by the falling drop method with an accuracy of 1 to 2%, and the H/sup 3/ was determined by counting a mixture of hydrogen and tritiated butane at 1 to 4 mm pressure on a SBM-7 or SBC-5 counter with an accuracy of 2 to 3%. Calculation of the first-order reaction rate constants showed that the ratio of the constants for deuterium and H/sup 3/ (k/ sub D//k/sub t/) was equal to two for fluorene and methyl- beta -napthylketone. In both cases deuterium on the aliphatic group (C-H bonding) exchanged with the hydrogen of liquid NH/sub 3/ twice as fast as H/sup 3/. It is proposed that the rate of reaction is controlled by bond breakage of the C-H group of an intermediate activated complex. 35 references are given. (TTT)
- Research Organization:
- Karpov Inst. of Physics and Chemistry, USSR
- NSA Number:
- NSA-15-010808
- OSTI ID:
- 4083174
- Journal Information:
- Kinetika i Kataliz, Journal Name: Kinetika i Kataliz Vol. Vol: 1
- Country of Publication:
- Country unknown/Code not available
- Language:
- Russian
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