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Characterization of autocatalytic decomposition reactions is important
for the safe handling and storage of energetic materials. Isothermal differential
scanning calorimetry (DSC) has been widely used to detect autocatalytic decomposition
of energetic materials. However, isothermal DSC tests are time consuming and
the choice of experimental temperature is crucial. This paper shows that an
automatic pressure tracking calorimeter (APTAC) can be a reliable and efficient
screening tool for the identification of autocatalytic decomposition behavior
of energetic materials.
Hydroxylamine nitrate (HAN) is an important
member of the hydroxylamine family. High concentrations of HAN are used as
liquid propellants, and low concentrations of HAN are used primarily in the
nuclear industry for decontamination of equipment. Because of its instability
and autocatalytic decomposition behavior, HAN has been involved in several
incidents. 相似文献
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Several magnetic and optical processes contribute to the magneto-optical response of nickel thin films after excitation by a femtosecond laser pulse. We achieved a first complete identification by explicitly measuring the time-resolved Kerr ellipticity and rotation, as well as its temperature and magnetic field dependence in epitaxially grown (111) and (001) oriented Cu/Ni/Cu wedges. The first hundreds of femtoseconds the response is dominated by state filling effects. The true demagnetization takes approximately 0.5-1 ps. At the longer (sub-ns) time scales the spins are found to precess in their anisotropy field. Simple and transparent models are introduced to substantiate our interpretation. 相似文献
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Tenn WJ Murphy JL Bim-Merle JK Brown JA Junia AJ Price MA Nagorski RW 《The Journal of organic chemistry》2007,72(16):6075-6083
The kinetic study of the aqueous reaction, between pH 10 and 14, of eight N-(hydroxymethyl)benzamide derivatives in water at 25 degrees C, I = 1.0 M (KCl), has been performed. In all cases, the reaction proceeds via a specific-base-catalyzed deprotonation of the hydroxyl group followed by rate-limiting breakdown of the alkoxide to form aldehyde and amidate (E1cB-like). Such a mechanism was supported by the lack of general buffer catalysis and the first-order dependence of the rate of reaction at low hydroxide concentrations and the transition to zero-order dependence on hydroxide at high concentration. A rho-value of 0.67 was found for the Hammett correlation between the maximum rate for the hydroxide independent breakdown of the deprotonated carbinolamide (k1) and the substituent on the aromatic ring of the title compounds. Conversely, the substituents on the aromatic ring of the amide portion of the carbinolamide had only a small effect on the Ka of the hydroxyl group indicating that the amide group does not strongly transmit the electronic information of the substituents. These observations led to the conclusion that the major effect of electronic changes on the amide of carbinolamides is reflected in the nucleofugality of the amidate once the alkoxide is formed and not in the pKa of the hydroxyl group of the carbinolamide. 相似文献
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Tenn WJ Young KJ Bhalla G Oxgaard J Goddard WA Periana RA 《Journal of the American Chemical Society》2005,127(41):14172-14173
A thermally and air stable O-donor, iridium-methoxo complex is reported that undergoes stoichiometric, intermolecular C-H activation of benzene with co-generation of methanol and the iridium-phenyl complex. 相似文献