排序方式: 共有46条查询结果,搜索用时 31 毫秒
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用氯化石腊和邻硝基苯辛醚为混合溶剂制备中性载体ETH5214的镁离子选择性微电极,相对于钾离子的电位选择性系数较单独以邻硝基苯辛醚为溶剂的ETH5214镁微电极改善0.9个数量级。在纯MgCl~2和在含细胞内典型离子背景的MgCl~2溶液中,响应斜率为Nernst响应,检测下限分别为4×10^-^7mol.dm^-^3和2×10^-^5mol.dm^-^3。在pH3.5-9.5范围内,氢离子对电极的电位响应无影响。测量的重现性良好。电极的实用响应时间(t~9~5)≤3s,有效寿命长于5天。 相似文献
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Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty. 相似文献
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《Composite Interfaces》2013,20(5):377-385
Metal–metal composites are prepared by dispersing copper particulates in an aluminium matrix using stir-cast technique. Behaviour of the same is compared with the alloy having similar composition. Wear behaviour of the alloy in the cast condition is superior to the homogenized condition, though cast structure exhibit low hardness compared to the other. This is attributed to the easy crack propagation along the CuAl2 precipitates in the homogenized condition, compared to the grain boundary in the as-cast structure. Wear properties of the resultant composite are superior to the alloy. Effect of particulate composition is studied by varying the copper concentration between 5 and 15 wt%. Composites with high copper content exhibit better wear resistance than the dilute ones, which is attributed to the increased hardness due to large population of intermetallics. 相似文献
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A. Di Prisco N. Falcón L. Herrera M. Esculpi N. O. Santos 《General Relativity and Gravitation》1997,29(11):1391-1405
The influence of processes occurring before the system relaxes into diffusion, on the evolution of a radiating sphere, is exhibited in a specific example. The luminosity profiles, and consequently the general evolution of the object, are shown to be quite sensitive to the value of relaxation time. 相似文献
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硝酸铬与组氨酸配合行为的相化学与热化学研究 总被引:3,自引:0,他引:3
用相平衡方法研究了硝酸铬-组氨酸-水体系在298.15K时的溶度,绘制了体系的相图,发现并制备了文献未报道的一致溶解配合物:Cr(His)(NO3)3·3H2O(A),Cr(His)2(NO3)3·3H2O(B)和Cr(His)3(NO3)3·3H2O(C),经分析确定了其组成。用微热量计热测定了硝酸铬和组氨酸在水中的反应焓,计算了这些反应的热动力学参数(活化焓、活化熵及活化自由能)、速率常数和动力学能数(活化能、指前因子及反应级数)。 相似文献
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多氰基立方烷生成热的DFT-B3LYP和半经验MO研究 总被引:5,自引:1,他引:4
运用密度泛函理论(DFT)B3LYP方法和半经验MO(MINDO/3,MNDO,AM1和PM3)方法系统计算了全部21种多氰基立方烷的生成热,首先,在DFT-B3LYP/6-31G^*水平下通过不破裂立方烷笼状骨架(亦即选择立方烷为参考物)的等键反应设计,精确计算了9种多氰基立方烷的生成热;发现B3LYP/6-31G^*结果分别地均与上述四种半经验MO方法求得的生成热之间存在良好的线性关系(相关系数均在0.9994以上),且以AM1生成热与B3LYP/6-31G^*计算值最为接近,其次,其它12种多氰基立方烷的精确生成热借助上述线性关系通过校正对应的AM1结果而获得,多氰基立方烷的生成热很高,且随-CN基数目的增加而线性地增大,表明它们属于极具潜力的“新一低高能炸药”而具开发价值。 相似文献