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511.
512.
We report quantum mechanics calculations (B3LYP flavor of density functional theory) to determine the chemical reaction mechanism underlying the hypergolic reaction of pure HNO(3) with N,N,N',N'-tetramethylethylenediamine (TMEDA) and N,N,N',N'-tetramethylmethylenediamine (TMMDA). TMEDA and TMMDA are dimethyl amines linked by two CH(2) groups or one CH(2) group, respectively, but ignite very differently with HNO(3). We explain this dramatic difference in terms of the role that N lone-pair electrons play in activating adjacent chemical bonds. We identify two key atomistic level factors that affect the ignition delay: (1) The exothermicity for formation of the dinitrate salt from TMEDA or TMMDA. With only a single CH(2) group between basic amines, the diprotonation of TMMDA results in much stronger electrostatic repulsion, reducing the heat of dinitrate salt formation by 6.3 kcal/mol. (2) The reaction of NO(2) with TMEDA or TMMDA, which is the step that releases the heat and reactive species required to propagate the reaction. Two factors of TMEDA promote the kinetics by providing routes with low barriers to oxidize the C: (a) formation of a stable intermediate with a C-C double bond and (b) the lower bond energy for breaking the C-C single bond (by 18 kcal/mol comparing to alkane) between two amines. Both factors would decrease the ignition delay for TMEDA versus TMMDA. The same factors also explain the shorter ignition delay of 1,4-dimethylpiperazine (DMPipZ) versus 1,3,5-trimethylhexahydro-1,3,5-triazine (TMTZ). These results indicate that TMEDA and DMPipZ are excellent green replacements for hydrazines as the fuel in bipropellants. 相似文献
513.
514.
The physical properties of three laterally fluorinated liquid crystalline compounds with negative dielectric anisotropy have been studied from static dielectric permittivity, optical birefringence, bend elastic constant, relaxation time and rotational viscosity measurements. Such negative dielectric anisotropy materials find use as components of mixtures for application in vertically aligned mode liquid crystal displays. Moreover, the physical properties of one phenyl cyclohexane compound with positive dielectric anisotropy have also been studied. A five-component mixture comprising these four mesogens and a non-mesogenic component has been formulated and its physical properties have been thoroughly investigated. An attempt has been made to strike a balance between the optical birefringence of the mixture to adjust the cell gap and the dielectric anisotropy and threshold voltage (Vth ) to ensure low driving voltages. The pretilt angle effect on the threshold voltage and the relaxation time has also been studied. At T?=?20°C, the response time decreases to 22% and 41% for the mixture for 2° and 5° pretilt as compared to zero pretilt. On the other hand, at the same temperature the Vth values are decreased by 5% and 9%, respectively. 相似文献
515.
Mark A. W. Lawrence Sonia E. Thomas Paul T. Maragh Tara P. Dasgupta 《Transition Metal Chemistry》2011,36(5):553-563
The kinetics of the intra-molecular electron transfer of an adduct of l-ascorbic acid and the [Fe3IIIO(CH3COO)6(H2O)3]+ cation in aqueous acetate buffer was studied spectrophotometrically, over the ranges 2.55 ≤ pH ≤ 3.74, 20.0 ≤ θ ≤ 35.0 °C,
at an ionic strength of 0.50 and 1.0 mol dm−3 (NaClO4). The reaction of l-ascorbic acid and the complex cation involves the rapid formation of an adduct species followed by a slower reduction in
the iron centres through consecutive one-electron transfer processes. The final product of the reaction is aqueous iron(II)
in acetate buffer. The proposed mechanism involves the triaqua and diaqua-hydroxo species of the complex cation, both of which
form adducts with l-ascorbic acid. At 25 °C, the equilibrium constant for the adduct formation was found to be 86 ± 15 and 5.8 ± 0.2 dm3 mol−1 for the triaqua and diaqua-hydroxo species, respectively. The kinetic parameters derived from the rate expression have been
found to be: k
0 = (1.12 ± 0.02) × 10−2 s−1 for the combined spontaneous decomposition and k
1 = (4.47 ± 0.06) × 10−2 s−1 (ΔH
1‡ = 51.0 ± 2.3 kJ mol−1, ΔS
1‡ = −100 ± 8 J K−1 mol−1), k
2 = (4.79 ± 0.38) × 10−1 s−1 (ΔH
2‡ = 76.5 ± 0.8 kJ mol−1, ΔS
2‡ = 6 ± 3 J K−1 mol−1) for the triaqua and diaqua-hydoxo species, respectively. 相似文献
516.
Ion exchange membranes (IEMs) are used in a variety of analytical devices, including suppressors, eluent generators and other components used in ion chromatography. Such membranes are flexible and undergo substantial dimensional changes on hydration. Presently the push to miniaturization continues; a resurgent interest in open tubular ion chromatography requires microscale adaptation of these components. Incorporating IEMs in microscale devices is difficult. Although both macroporous and microporous ion exchange materials have been made for use as chromatographic packing, ion exchange material used as membranes are porous only on a molecular scale. Because such pores have vicinal ion exchange sites, ions of the same charge sign as those of the fixed sites are excluded from the IEMs. Monolithic polymers, including ion exchangers derived therefrom, are presently extensively used. When used in a separation column, such a monolithic structure contains an extensively connected porous network. We show here that by controlling the amount of porogen added during the synthesis of monolithic polymers derived from ethylene dimethacrylate – glycidyl methacrylate, which are converted to an anion exchanger by treatment with trimethylamine, it is possible to obtain rigid ion exchange polymers that behave like IEMs and allow only one charge type of ions to pass through, i.e., are permselective. We demonstrate successful open tubular cation chromatography suppressor performance. 相似文献
517.
We report the low-threshold operation of a nanosecond β-BaB2O4 optical parametric oscillator (OPO) pumped by the third harmonic of a Q-switched Nd:YAG laser. Using cylindrical focusing of the pump beam, a threshold pulse energy of 0.5 mJ is obtained at the signal wavelength of 560 nm, which is about sixteen times lower than that of a spherical focusing configuration. The importance of diffraction loss in the design of tightly focused OPOs is discussed in terms of a simple extension of the conventional OPO model. 相似文献
518.
Collective neutrino flavor transformations deep inside a supernova are sensitive to the neutrino mass hierarchy even at extremely small values of theta_(13). Exploiting this effect, we show that comparison of the antineutrino signals from a galactic supernova in two megaton class water Cherenkov detectors, one of which is shadowed by Earth, will enable us to distinguish between the hierarchies if sin(2)theta_(13) < or approximately 10(-5), where long baseline neutrino experiments would be ineffectual. 相似文献
519.
Hinde DJ Thomas RG du Rietz R Diaz-Torres A Dasgupta M Brown ML Evers M Gasques LR Rafiei R Rodriguez MD 《Physical review letters》2008,100(20):202701
Forming the same heavy compound nucleus with different isotopes of the projectile and target elements allows nuclear structure effects in the entrance channel (resulting in static deformation) and in the dinuclear system to be disentangled. Using three isotopes of Ti and W, forming 232Cm, with measurement spanning the capture barrier energies, alignment of the heavy prolate deformed nucleus is shown to be the main reason for the broadening of the mass distribution of the quasifission fragments as the beam energy is reduced. The complex, consistently evolving mass-angle correlations that are observed carry more information than the integrated mass or angular distributions, and should severely test models of quasifission. 相似文献
520.
Narrow-band laser performance of alcohol solutions of pyrromethene 567 (PM567) and rhodamine 6G (RH6G) dye was investigated
using a home-made GIG-configured dye laser, excited by the second-harmonic radiation (at 532 nm) of a pulsed Nd:YAG laser.
Higher laser efficiency was observed with PM567 dye (∼23% peak) in comparison to the commonly used RH6G dye (16.5%), in spite
of much lower fluorescence quantum efficiency of the PM567 (0.83) vis-à-vis RH6G (0.98) dye solutions in ethanol. First principle-based electronic structure calculations were performed on PM567 dye
in the ground (S
0) and excited states (S
1) using density functional theory to elucidate the structure and photophysical properties of the dye. 相似文献