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141.
The geometries,heats of formation and electronic structures of 15 azido-derivatives of 1,2,3-TNB (Ⅰ),1,2,4-TNB (Ⅱ) and 1,3,5-TNB (Ⅲ) have been studied using quantum chemical AMI method at HF level.The effect of azido substitution on the structures and properties of TNBs has been discussed and the relative stability of the title compounds has been established.The processes of the decomposition of the title compounds by breaking C-NO2,C-N3 and CN-N2 bonds are investigated at UHF-AM1 level.It is shown that the decomposition of the title compounds may be initiated by the cleavage of both C-NO2 and N-N2 bonds. 相似文献
142.
Laurence E. Strong Christopher L. Brummel Robert Ryther John R. Radford Alan D. Pethybridge 《Journal of solution chemistry》1988,17(12):1145-1167
Precision molar conductances of benzoic, o-toluic, 2,6-dimethylbenzoic, 2,3,6-trimethylbenzoic, and, o-fluorobenzoic acids have been determined in aqueous solution as a function of temperature and of concentration up to near saturation (<0.035 M). At the higher concentrations molar conductances are found to be less than anticipated for the simple dissociation of a 1-1 electrolyte. Although the deviations are only 1% or less they have been interpreted to show that these acids are dimerized in solution. The interpretation includes an assumption that the dimer ionizes to produce a triple ion. Increasing numbers of methyl groups lead to increasing dimerization. For those acids with two ortho groups the dimerization increases with increasing temperature while the other three show decreasing dimerization with increasing temperature. Temperature functions have been determined for the dimerization constants and from these functions standard changes in enthalpy, entropy, and heat capacity have been determined. Comparisons are made with dimerization studies in non-aqueous solvents. From these as well as the behavior of benzene in water it is concluded that a major factor driving the dimerization is hydrophobic interaction. To provide a limiting conductance of the triple ion needed in the dimerization calculations a conductance study was also made for o-Phenylbenzoic acid on the assumption that its anion provides an approximate model of the triple ion. 相似文献
143.
An ordinary plating solution for indium hexacyanoferrate (InHCF) thin film deposition, mainly composed of equal concentrations
of In3+ and [Fe(CN)6]3–, usually forms precipitates rapidly when either concentration is higher than few millimolar. This contributes to the plating
solution's instability. Moreover, electrodeposited capacities are limited accordingly. In this work, the plating solution's
stability and the electrodeposition of InHCF were greatly enhanced by adding a large amount of K+ and/or H+. It was found that a 10-mM plating solution added with 1 M HCl and 1 M KCl could be stored as fresh over a one-week period,
whereas an unmodified plating solution became useless within a couple of minutes. Also, such cationic additions, especially
adding H+, increased the electrodeposited capacity ca. 18 times at least, as compared with that obtained from the unmodified plating
solution. Furthermore, related enhancing mechanisms were proposed and verified. To sum up, this study offers a means for better
InHCF electrodeposition and should promote the applications of InHCF films.
Electronic Publication 相似文献
144.
A
DSC investigation has been performed on a Mg–RE–Y–Zr (RE=rare earth) technical alloy WE43. Hardness trend
during isothermal treatments has been correlated to the calorimetric traces
evolution and to the forming β phases with its precursors. Oversaturation
of solute elements occurs at temperatures higher than 150±C, on cooling
at room temperature after the anneals. Activation energies, found under non-isothermal
conditions on artificially aged samples, suggest a slow transformation velocity,
while the hardness response is relatively fast. 相似文献
145.
Apparent molal heat capacities
of some piperidine, morpholine, and piperazine derivatives in aqueous solution have been determined by adiabatic calorimetry
in the temperature range 20–55°C and in the molality range 0.2–1m. Comparison of experimental
values with those calculated through group contributions, found for monofunctional compounds, indicates strong interactions
between the hydrophilic centers. An interpretation is given of the possible mechanism of this interaction. Also, values of
ΔC
p
for the addition reaction of proton to nitrogen centers of mono- and bifunctional organic compounds are examined. 相似文献
146.
利用精密自动绝热热量计直接测定了配合物Zn(Phe)(NO3)2·H2O(s) (Phe:苯丙氨酸)在78-370 K温区的摩尔热容. 通过热容曲线的解析得到该配合物的起始脱水温度为, T0=(324.27±0.37) K. 将该温区的摩尔热容实验值用最小二乘法拟合得到摩尔热容(Cp, m)对温度(T)的多项式方程, 并且在此基础上计算出了它的舒平热容值和各种热力学函数值. 依据Hess定律, 通过设计热化学循环, 选择体积为100 mL浓度为2 mol·L-1 的盐酸作为量热溶剂, 利用等温环境溶解-反应热量计分别测定混合物{ZnSO4·7H2O(s)+2NaNO3(s)+L-Phe(s)}和{Zn(Phe)(NO3)2·H2O(s)+Na2SO4(s)}的溶解焓为, ⊿dH0m,1 =(69.42±0.05) kJ·mol-1, ⊿dH0 m,2 =(48.14±0.04) kJ·mol-1, 进而计算出该配合物的标准摩尔生成焓为, ⊿fH0m =-(1363.10±3.52) kJ·mol-1. 另外, 利用紫外-可见(UV-Vis)光谱和折光指数(refractiveindex)的测量结果检验了所设计的热化学循环的可靠性. 相似文献
147.
本文论述了WO_3薄膜氢离子敏器件的结构、原理、制备技术和测试分析。利用WO_3薄膜在H+溶液中由绝缘转化为导电特性,成功地研制成氢离子敏器件。这是一种简易而经济的微型pH敏器件技术。 相似文献
148.
A. Y. Lee 《Journal of Optimization Theory and Applications》1987,52(1):151-162
Bounded terminal conditions of nonlinear optimization problems are converted to equality terminal conditions via the Valentine's device. In so doing, additional unknown parameters are introduced into the problem. The transformed problems can still be easily solved using the sequential gradient-restoration algorithm (SGRA) via a simple augmentation of the unknown parameter vector . Three example problems with bounded terminal conditions are solved to verify this technique.This research was supported in part by the National Aeronautics and Space Administration under NASA Grant No. NCC 2-106. 相似文献
149.
We use a driving field, of the type first suggested by Evans, to generate a steady heat current in the simplest possible system, a two-dimensional periodic fluid of three hard disks. Hard-disk motion equations can be conveniently derived from repulsive constant-force or linear-force potentials by considering the infinitely repulsive limit of these potentials. We show that the isoenergetic and isokinetic forms of the nonequilibrium equations of motion generate steady-state heat conductivities differing by terms of order 1/N, whereN is the number of particles. The resulting conductivities appear to vary as the logarithm of the driving field strength. Even at low fields, the three-body periodic-system results lie well below Enskog's infinite-system prediction. 相似文献
150.
T'-214相化合物R2-xCexCuO4(R为稀土离子)成为超导体决定于R3+的离子半径大小、Ce4+的取代量和化合物的热处理时的稳定性.从Raman光谱实验结果提出热处理过程中发生电荷转移.Ce4+的取代引起TN(Cu)下降,当TN(Cu)降到0时,超导性出现。不同的稀土离子TN(Cu)不同,稀土离子的反铁磁性(AFM)与超导性(SC)共存。热电势的测量结果可以用双通道模型解释,n型超导体中电子与空穴共存. 相似文献