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The hydrothermolysis of the picrate anion: Kinetics and mechanism

Thermochimica Acta

By:
and
DOI: 10.1016/S0040-6031(01)00789-4

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Abstract

The hydrothermolysis of the picrate anion in aqueous solution has been studied at 260-325??C in liquid water. At starting pH values above 12, the disappearance of picrate begins immediately and is first order in OH-. At lower pH, there is an induction period preceding the disappearance, and over the pH range 6.7-11.9 there is no pH dependence in the developed reaction phase. Added borate and silicate salts promote the reaction, suggesting their acting as nucleophiles at hydrothermal conditions. Nitrite is an initial product, while acetate is a final product and reflective of a vigorous oxidative sequence consuming the intermediate products. A reaction sequence consistent with the results at the lower pH includes initiation of a chain process by displacement of nitrite by water, followed by nucleophilic displacement of nitrite by nitrite such that a nitro group is replaced by an O-N=O group. The ester then rapidly hydrolyzes, and the net reaction is the production of an additional nitrite with each cycle. A simple modeling of this system satisfactorily fits the experimental findings. ?? 2002 Elsevier Science B.V. All rights reserved.

Additional Publication Details

Publication type:
Article
Publication Subtype:
Journal Article
Title:
The hydrothermolysis of the picrate anion: Kinetics and mechanism
Series title:
Thermochimica Acta
DOI:
10.1016/S0040-6031(01)00789-4
Volume
384
Issue:
1-2
Year Published:
2002
Language:
English
Larger Work Type:
Article
Larger Work Subtype:
Journal Article
Larger Work Title:
Thermochimica Acta
First page:
155
Last page:
162