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Isotopic Fractionation of Nitrogen in the Nitrogen Oxide-Nitrate Exchange System

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.1732607· OSTI ID:4807014

The single-stage fractionation factors for nitrogen exchange between nitric oxide and nitrate salt solutions were found to range from 1.073 at 25 deg to l,056 at 70 deg . The experimental values are about 0.007 less than the values calculated from spectroscopic data, a result not unexpected, since the statistical mechanical calculations do not take interactions in a condensed phase into account. Within the estimated experimental error of plus or minus 0.004, the isotope effect appears to be independent of the nature and degree of complexing of the nitrate ion in solution. Measurements were also made of the fractionation factors between nitric oxide and nitric acid solutions (l- l2 M) over the temperature range 25- 70 deg . The formation of additional oxy-nitrogen species in both phases introduces addttional exchange reactions which lower the over-all isotope effect significantly. Due to the changes in the chemical composltions of the phases, the observed factors go through a maximum in the viclnity of 6 M nitric acid. The experimental effective fractionation factors are in general agreement with the values calculated from the chemical compositions of the systems and the partition function ratios for the chemical species involved. (auth)

Research Organization:
Rutgers Univ., Newark, N.J.
Sponsoring Organization:
USDOE
NSA Number:
NSA-16-012007
OSTI ID:
4807014
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 3 Vol. 36; ISSN JCPSA6; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
Country unknown/Code not available
Language:
English