Basic hydrolysis of glyceryl nitrate esters. III. Trinitroglycerin

Abstract

Kinetics of the basic hydrolysis of glyceryl trinitrate (TNG) were investigated in C0,-free aqueous calcium hydroxide solutions. The hydrolysis reactions were carried out in a temperature controlled reactor vessel with provision for continuous N, sparging of the reaction mixture. TNG hydrolyzed via second-order reaction at 25"C, 18"C, and 10°C. The activation energy of the hydrolysis reaction of TNG was calculated from the kinetic data and found to be equal to 27.53 kcal/mol. The major products of the hydrolysis of TNG in solution of calcium hydroxide were calcium nitrate and calcium nitrite, accounting for approximately 50% of the degradation products. The minor identified products such as calcium oxalate and nitrate esters amounted to approximatey 6% of the products. The remaining 30% of the isolated products was a mixture of calcium formate, a nitrate ester, and unidentified volatiles, polymerlike substances, and other organic residue.

Microwave-assisted hydrolysis of nitroglycerin (NG) under mild alkaline conditions: New insight into the degradation pathway

“…This is in line with the observation made earlier by Capellos et al (1984) on the absence of the partially denitrated DNGs and MNGs from NG hydrolysis (pH 12). Likewise we did not observe the fully denitrated NG product glycerol which is known to be the final product of NG reaction with Fe(0) (Oh et al, 2004) and frequently found during biodegradation of the nitrate ester (Wendt et al, 1978;Servent et al, 1991;Meng et al, 1995;Marshall and White, 2001).…”

“…In the present study the ratio of nitrite to nitrate calculated from Table 1 in the presence and absence of microwave heating was 2.5 and 2.8, respectively. Capellos et al (1984) and Wheals and Ellison (1989) found that the nitrite/ nitrate ratio ranged between 2 and 3. These findings suggested that b-hydrogen elimination reaction is the main route to nitrite formation in the NG hydrolysis in which the two primary Cs gave the two nitrite anion while the remaining secondary one gave the nitrate anion.…”

“…The use of excess amounts of reactants in these methods creates another disposal problem. Few other academic research articles have been reported on the hydrolysis of NG (Boschan et al, 1955;Capellos et al, 1984;Tsaplev, 2004), but little information is available on the eventual fate of the nitrate ester. To provide answers to these questions and to gain new insights into the degradation pathway of NG we studied the hydrolysis of the (Walter et al, 1997;Srogi, 2006) and to conduct organic synthesis (Gedye et al, 1991;Clarke et al, 2007).…”

“…Earlier literatures show that NG can be hydrolyzed under high alkaline conditions (pH P 12) to produce formate, oxalate, acetate often with a poor mass balance (Boschan et al, 1955;Capellos et al, 1984;Tsaplev, 2004). The use of mild alkaline conditions assisted with microwave irradiation were selected here because, (1) pH 9 is closer to natural environmental conditions found in contaminated soil and water, and (2) rapid hydrolysis by microwave can lead to the formation of intermediates in sufficient amounts that would allow detection thereby helping to gain more insights into the NG decomposition pathway(s).…”

Environmental Transport and Fate Process Descriptors for Propellant Compounds

“…Alkaline hydrolysis of nitroglycerine will proceed at temperatures between 10 and 25 ºC, and pH between 11.9 and 12.5. The predominant products of alkaline hydrolysis of NG by calcium hydroxide are calcium nitrate and calcium nitrite (Capellos et al 1984). Nitroglycerine disappeared within one week in sterile, anoxic solutions with mineral salts, presumably by an abiotic, aqueous reaction (Adrian 1996).…”