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.

A band at 745 cm.-1 for zirconium oxide has been reported (74). A band found at 1035 cm.-1 for divinylzinc has been attributed to a carbon-oxygen-zinc vibration from the oxidation of divinylzinc (77). 9) is in agreement with the assignment of the C--0 stretch vibration to the very strong, band in this region. Thus the 1020-to 990-cm.-1 band is apparently shifted by the influence of the specific metal on the C-O vibration. Recent work on dialkyltin dialkoxides (There is no definite correlation of the mass of the metal atom and the degree of shift observed. The lowest frequency band at 996 cm.-1 was for the isopropoxide of the heaviest metal, 157 (1956). ( 22) Sheppard, N., Trans. Faraday Soc. 46, 527 (1950).

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The thermoanalytical techniques of differential thermal analysis and thermogravimetry have been used to elucidate the thermal phenomena occurring as the binary oxidant system potassium perchlorate-barium nitrate is heated to elevated temperatures. The fusion, at 465°, of a eutectic mixture immediately precedes the barium nitrate catalyzed decomposition of potassium perchlorate. The thermal instability of the eutectic mixture precludes its study by conventional cooling curve techniques. Therefore, the eutectic composition, nominally 2 to 1 potassium perchlorate-barium nitrate, was obtained from the integrated areas of the fusion endotherms on the DTA curves for a series of mixtures. It is noted that the presence of potassium ion, in addition to that of barium ion, provides increased thermal stability for the nitrate ion.

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