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Nitric/nitrous acid equilibria in supercritical water

Journal Article · · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
DOI:https://doi.org/10.1021/jp983745o· OSTI ID:351499

Reactions involving No, NO{sub 2}, H{sub 2}O, HNO{sub 3}, HNO{sub 2}, and O{sub 2} in the gas phase play a crucial role in nitric acid production, combustion, and waste incineration. UV-vis spectroscopy was utilized to measure the decomposition of aqueous HNO{sub 3} solutions above 300 C, in some cases with added NaOH, H{sub 2}O{sub 2}, and/or NaNO{sub 2}, to form NO{sub 2}, HNO{sub 2}, NO, N{sub 2}O, and oxygen. Individual bands corresponding to HNO{sub 2} and NO{sub 2} were deconvoluted from the spectra up to 400 C. With constrained nonlinear optimization, areas of these bands were used to determine extinction coefficients of NO{sub 2} and HNO{sub 2} and equilibrium constants for the reactions: HNO{sub 3} {r_equilibrium} H{sup +} + NO{sub 3}{sup {minus}}; 2HNO{sub 3} {r_equilibrium} H{sub 2}O + 2NO{sub 2} + (1/2)O{sub 2}; 2NO{sub 2} + H{sub 2}O {r_equilibrium} HNO{sub 3} + HNO{sub 2}; 2HNO{sub 2} {r_equilibrium} H{sub 2}O + 2NO + (1/2)O{sub 2}; 2NO {r_equilibrium} N{sub 2}O + (1/2)O{sub 2}; (Na{sup +})(NO{sub 3}{sup {minus}}) {r_equilibrium} Na{sup +} + NO{sub 3}{sup {minus}}.

Sponsoring Organization:
USDOE, Washington, DC (United States); Department of the Army, Washington, DC (United States); Welch (Robert A.) Foundation, Houston, TX (United States); Texas Univ., Austin, TX (United States)
OSTI ID:
351499
Journal Information:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Journal Name: Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory Journal Issue: 11 Vol. 103; ISSN 1089-5639; ISSN JPCAFH
Country of Publication:
United States
Language:
English

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