THE RADIOLYSIS OF DEUTERATED BIPHENYLS: MECHANISM OF HYDROGEN FORMATION
Certain general characteristics of the radiation chemistry of aromatic hydrocarhons are summarized. The values of G(hydrogen), G(H), G(D), and the H/ sub 2//HD//sub 2/ ratios observed in the radiolysis with Co/sup 60/ gamma rays of biphenyl, biphenyl-4,4'-d/sub 2/, biphenyl-2,2',6,6' -d/sub 4/, biphenyl- 3,3',5,5' d/sub 4/ biphenyl-2,2',4,4',6,6'-d/sub 6/, biphenyl-2,2',3,3',5,5',6,6'- d/sub 8/, and biphenyl-d/sub 10/ are reported. The formation of radiolytic hydrogen is insensitive to any difference between the ortho, meta, and para positions of biphenyl (although it is sensitive to the 1.3 kcal./mole difference between C--H and C-D (bonds) since the specific rates of H and D formation are insensitive to the location of deuterium on the hydrocarbon, and the total hydrogen yield is a linear function of the deuterium content of the biphenyl. The isotope effect in the formation of radiolytic hydrogen and deuterium (3.00) was observed to be different from that observed in the loss of one or two hydrogen atoms (or deuterium atoms) in the dissociation of the corresponding molecule-ion in the mass spectrometer (l.8). It is shown that this same isotope effect of 3.00 and simple statistical considerations can be used successfully to account for the H/sub 2/, HD, and D/sub 2/ ratios in the hydrogen from individual hydrocarhons. However, the H/sub 2/, HD, and D/sub 2/ content of the hydrogen from a mixture of biphenyl and biphenyl-d/sub 10/ cannot be so described; and was observed to be unequilibrated. It is suggested from this that at least two processes are involved in the formation of radiolytic hydrogen from biphenyl. (auth)
- Research Organization:
- Atomics International, Canoga Park, Calif.
- Sponsoring Organization:
- USDOE
- NSA Number:
- NSA-15-001437
- OSTI ID:
- 4134237
- Journal Information:
- Journal of Physical Chemistry (U.S.), Journal Name: Journal of Physical Chemistry (U.S.) Vol. Vol: 64; ISSN JPCHA
- Country of Publication:
- Country unknown/Code not available
- Language:
- English
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