ISOTOPE EFFECTS IN Hg(6$sup 3$$P$$sub 1$)-PHOTOSENSITIZED REACTIONS: H$sub 2$ + N$sub 2$O AND H$sub 2$ + NO

Journal Article · Tue Nov 01 04:00:00 EST 1960 · Journal of Physical Chemistry (U.S.)

DOI:https://doi.org/10.1021/j100840a038· OSTI ID:4113971

Hoffman, M Z; Bernstein, R B

The N/sup 14//N/sup 15/ and O/sup 16//O/sup 18/ isotope effects in the Hg(6/sup 3/P/sub 1/)photosensitized (MPS) reaction of hydrogen with nitrous oxide and with nitric oxide were measured. In the MPS reaction of N/sub 2/O + H/sub 2/ , the N/sup 14//N/sup 15/ isotope effect was independent of the ratio (H/sub 2/)/ (N/sub 2/O) over the range 1.0 to 12, with an average value of S/sup 0/ = 1.018 0.001 compared with S/sup 0/ = 1.017 0.001 for the MPS decomposition of N/ sub 2/O. The O/sup 16// O/sup 18/ isotope effect was 1.017 0.002 compared with 1.019 0.001 for the decomposition. These observations imply that the rate of hydrogen-atom attack on N/sub 2/O is a small fraction of the rate of the N/sub 2/O decomposition. In the MPS reaction of NO + H/sub 2/, the N/sup 14//N/sup 15/ isotope effect was found to be "inverted," the first fraction of N/sub 2/ produced was enriched in N/sup 15/ relative to the original NO. At a ratio (H/ sub 2/)/(NO) = 1.0, the fractionation factor was 1.008, diminishing to the null value of 1.000 at a ratio of 29. The N/sup 15/ enrichment is interpreted on the basis of a postulated isotope exchange equilibrium between NO and HNO. (auth)

• Research Organization: Univ. of Michigan, Ann Arbor
• Sponsoring Organization: USDOE
• NSA Number: NSA-15-004018
• OSTI ID: 4113971
• 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

Related Subjects

CHEMISTRY
DECOMPOSITION
ENRICHMENT
HYDROGEN
ISOTOPE EFFECTS
ISOTOPIC EXCHANGE
MEASURED VALUES
NITROGEN 15
NITROGEN OXIDES
OXYGEN 18