| 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. |
| Genre: | Article |
| ProdID: | 70024766 |
| Citation Author: | Ross, D. S.; Jayaweera, I. |
| Citation Contributing Office: | |
| Citation Datum: | |
| Citation Day: | |
| Citation Edition: | |
| Citation Editor: | |
| Citation End Page: | 162 |
| Citation Issue: | 1-2 |
| Citation Keywords: | |
| Citation Language: | English |
| Citation Larger Work Title: | Thermochimica Acta |
| Citation LatN: | |
| Citation LatS: | |
| Citation LonE: | |
| Citation LonW: | |
| Citation Month: | |
| Citation No Pagination: | |
| Citation Number Of Pages: | 8 |
| Citation Online Only Flag: | |
| Citation Phsyical Description: | |
| Citation Projection: | |
| Citation Public Comments: | |
| Citation Publisher: | |
| Citation Series: | |
| Citation Series Code: | |
| Citation Series Number: | |
| Citation Search Results Text: | The hydrothermolysis of the picrate anion: Kinetics and mechanism; 2002; Article; Journal; Thermochimica Acta; Ross, D. S.; Jayaweera, I. |
| Citation Start Page: | 155 |
| Citation Volume: | 384 |
| Citation Year: | 2002 |
| Type: | citation/reference |
| Text: | The hydrothermolysis of the picrate anion: Kinetics and mechanism; 2002; Article; Journal; Thermochimica Acta; Ross, D. S.; Jayaweera, I. |
| URL (THUMBNAIL): | http://pubs.er.usgs.gov/thumbnails/outside_thumb.jpg |
| URL (DIGITAL OBJECT IDENTIFIER): | http://dx.doi.org/10.1016/S0040-6031(01)00789-4 |
| Date Other: | Tue, 1 Jan 2002 00:00 -0600 |
| Publisher: | |
