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101.
The title reaction has been used as an example to test the importance of using a hindered rotor treatment instead of a harmonic oscillator model for calculating vibrational partition functions corresponding to low-frequency internal rotation modes. First, a normal-mode analysis according to the Ayala and Schlegel's algorithm has been used to identify the internal rotation modes of methanethiol and the transition state structure. Then, after calculation of the energy barrier for each internal rotation, the corresponding hindered rotor partition functions have been calculated following the CW scheme of Chuang and Truhlar. The results show that the anharmonic treatment produces a rather modest improvement of the rate constants at room temperature or below. 相似文献
102.
Kinetics of chemiluminescence reactions of 2-methyl-6-phenylimidazo[1,2-a]pyrazin-3(7H)-one (1c, Cypridina luciferin analogue) and substituent effects of the 6-aryl group of derivatives 1 strongly suggest that the rate-determining step is a single electron transfer from an anion derived from 1 to a triplet molecular oxygen (O2) in the oxygenation process. 相似文献
103.
Summary {\rtf1\ansi\ansicpg1250\deff0\deflang1038\deflangfe1038\deftab708{\fonttbl{\f0\froman\fprq2\fcharset238{\*\fname Times New Roman;}Times New Roman CE;}}
\viewkind4\uc1\pard\f0\fs20 New explanations are given for two types of irregular thermogravimetric (TG) data. A TG relationship between mass and temperature is derived on the basis of migration behavior of bubbles generated in bulk of sample system, and superposed on that derived on the basis of kinetics of the 4\super th\nosupersub order event, which is superposed on the experimental TG data obtained from three reference papers. This suggests that these TG data are reflecting migration of bubbles. A dependence of TG behavior on heating rate, which is contrary to usual that, is shown and is explained in terms of event-rate determination by boiling.
\par } 相似文献
104.
The thermal decomposition characteristics of1,7-diazido-2,4,6-trinitrazaheptane (DATH) and multi-component systems containing
DATH were studied by using DSC, TG and DTG techniques. Three –NO2 groups in the DATH molecule break away first from the main chain when DATH is heated up to 200°C. Following this process,
the azido groups and the residual molecule decompose rapidly to release a great deal of heat within a short time. In the multi-component
systems, DATH undergoes a strong interaction with the binder of the double-base propellant and a weak interaction with RDX.
The burning rates of the two propellants were determined by using a Crawford bomb. The results showed that the burning rate
rises by about 19–66% when 23.5%DATH is substituted for RDX in a minimum smoke propellant. Meanwhile, the N2 level in the combustion gases is enhanced, which is valuable for a reduction of the signal level of the solid propellant.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
105.
催化裂化汽油脱硫添加剂USY/ZnO/Al2O3的性能评价 总被引:15,自引:0,他引:15
在固定流化床催化裂化装置上,以减压蜡油为原料,对制备的U\r\nSY/ZnO/Al2O3催化裂化汽油脱硫添加剂的性能进行了评价.结果表明\r\n,随着添加剂添加量和剂油比的增加,生成汽油的硫含量降低.在500\r\n℃和剂油比为5的条件下,在FCC平衡催化剂中添加30%的添加剂时,汽\r\n油的硫含量可由不加添加剂时的1230μg/g降低到770μg/g左右.添\r\n加剂的添加量(10%)较低时,对催化裂化产物的分布基本没有影响;\r\n添加30%的添加剂时,焦炭的产率有所增加,但汽油收率基本不变.X\r\nRD表征结果表明,USY/ZnO/Al2O3添加剂中的ZnO对USY的晶相结构有\r\n一定的破坏作用,但随着反应与再生次数的增多,ZnO与Al2O3之间形成\r\n较为稳定的锌铝尖晶石结构,使添加剂的性能趋于稳定. 相似文献
106.
E. P. Honig 《Rheologica Acta》1987,26(1):2-6
Equations are derived for the coaxial cylinder system in the combined oscillatory and steady-state shear mode. The limitations of the use of the various equations are presented. If the usual linear equations are used, the main limitation, in the case of oscillatory shear only, is that the frequency of measurement should be below 0.016 |
*|/(r
2
–r
1
)2. Here |
*| is the modulus of the complex viscosity, is the density of the liquid andr
1
andr
2
are the radii of the cylinders. Furthermore it is shown that there is a small error in the numerical factor of the usually applied equations. The calculations are set up in such a way that extension to higher harmonics follows in a natural way. An experimental example illustrates the use of the derived equations. 相似文献
107.
108.
Albert Brennauer 《Tetrahedron letters》2007,48(39):6996-6999
The decomposition of some NG-(ω-aminoalkanoyl)argininamides, which are key intermediates for the preparation of radiolabeled and fluorescent neuropeptide Y receptor ligands, prompted us to synthesize a small series of simple 1-(ω-aminoalkanoyl)guanidines, and to investigate these model compounds for stability in alkaline buffers. The degradation of acylguanidines was monitored by time resolved UV spectroscopy. The most labile compound, 1-(5-aminopentanoyl)guanidine, decomposed with a half life of 19 s to yield piperidin-2-one (pH 10.4 at 25 °C). In contrast the half life of 1-(6-aminohexanoyl)guanidine is 7.7 h, which is comparable to the hydrolysis of acetylguanidine (t1/2 = 9.6 h) in alkaline solution. 相似文献
109.
The influence of internal excitation on the reactions of O
2
+
+ CH4 and of CO
2
+
+ NO has been investigated using a slow flow drift tube. The rate coefficients for these reactions obtained as a function of relative kinetic energy in various buffer gases like He, Ne, Ar, and Kr showed higher values under conditions where the internal excitation of the reactant ions was enhanced. For both reactions the lowest reactivity at all kinetic energies was observed to occur in He, indicating that He is the least effective buffer for collisionally inducing internal excitation of molecular ions. 相似文献
110.
Radiation-chemical transformations of chloride solutions in the presence of iodide additives were studied by pulse radiolysis.
Radical anion Cl2
⋅− oxidize I− ion, while in the secondary reactions Cl2 reacts with I− to form a mixed trihalide ion ICl2
−. A reaction model that satisfactorily describes the experimental data was proposed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1336–1340, June, 2005. 相似文献