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61.
对甲醛单分子热反应模拟给出了分子渠道Eckart垒,计算了该渠道在不同温度下的隧道校正因子,研究了分子渠道与游离基渠道间的相互作用,计算了存在反应渠道间相互作用时各渠道的K_(uni)(i)、Ea(i),分子渠道考虑隧道效应,而游离基渠道无隧道效应,计算结果与实验结果一致。 相似文献
62.
Kharitonov SV 《Analytical and bioanalytical chemistry》2005,382(7):1642-1651
The construction and electroanalytical response characteristics of poly(vinyl chloride) matrix ion-selective sensors (ISSs) for drotaverine hydrochloride are described. The membranes incorporate ion-association complexes of drotaverine with tetraphenylborate, picrate, tetraiodomercurate, tetraiodobismuthate, Reinecke salt, and heteropolycompounds of Keggin structure—molybdophosphoric acid, tungstophosphoric acid, molybdosiliconic acid and tungstosiliconic acid as electroactive materials for ionometric sensor controls. These ISSs have a linear response to drotaverine hydrochloride over the range 8×10–6 to 5×10–2 mol L–1 with cationic slopes from 51 to 58 mV per concentration decade. These ISSs have a fast response time (up to 1 min), a low determination limit (down to 4.3×10–6 mol L–1), good stability (3–5 weeks), and reasonable selectivity. Permeabilities and ion fluxes through a membrane were calculated for major and interfering ions. Dependences of the transport properties of the membranes on the concentrations of the ion exchanger and near-membrane solution and their electrochemical characteristics are presented. The ISSs were used for direct potentiometry and potentiometric titration (sodium tetraphenylborate) of drotaverine hydrochloride. Results with mean accuracy of 99.1±1.0% of nominal were obtained which corresponded well to data obtained by use of high-performance liquid chromatography. 相似文献
63.
This work describes a hybrid procedure for eliminating major interference sources in aqueous near-infrared (NIR) spectra, that include aqueous influence, noise, and systemic variations irrelevant to concentration. The scheme consists of two parts: extension of wavelet prism (WPe) and orthogonal signal correction (OSC). First, WPe is employed to remove variations due to aqueous absorbance and noise; then OSC is applied to remove systemic spectral variations irrelevant to concentration. Although water possesses strong absorption bands that overshadow and overlap the absorption bands of analytes, along with noise and systematic interference, successful calibration models can be generated by employing the method proposed here. We show that the elimination of major interference sources from the aqueous NIR spectra results in a substantial improvement in the precision of prediction, and reduces the required number of PLS components in the model. In addition, the strategy proposed here can be applied to various analytical data for quantitative purposes as well. 相似文献
64.
Jian-binSong Min-qiaoRen Qing-yongChen Shu-yunWang Qing-xiangZhao Hong-fangZhang 莫志深 《高分子科学》2004,(5):491-496
Based on the X-ray scattering intensity theory and using the approximate expression for the atomic scattering factor, the correction factors for three crystalline peaks and an amorphous peak of Nylon 1212 were calculated and the formula of degree of crystallinity of Nylon 1212 was derived by a graphic multipeak resolution method. The degree of crystallinity calculated from the WAXD method is compatible with those obtained by density and calorimetry methods. 相似文献
65.
Correlated intermolecular interaction components from asymptotically corrected Kohn-Sham orbitals 总被引:1,自引:0,他引:1
SONG Huajie XIAO Heming & DONG Haishan . Department of Chemistry Nanjing University of Science Technology Nanjing China . Institute of Chemical Materials China Academy of Engineering Physics Mianyang China 《中国科学B辑(英文版)》2004,47(6):466-479
In these years there was considerable interest inunderstanding of intermolecular forces in energetic(explosive) systems[1—3]. The supermolecular approach(SM) is widely adopted for calculating ab initio in-termolecular interactions. Nevertheless, it is unable toprovide physically meaningful interaction contribu-tions such as electrostatic, induction, repulsion anddispersion energies. In contrast, the symmetry-adaptedperturbation theory (SAPT)[4—8] has the ability to de-rive these correlated… 相似文献
66.
本文提出在原子吸收光谱测定中,采用Smith-Hieftje法校正背景时,空心阴极灯供电条件(即最佳宽窄脉冲电流)的选择依据和选择方法;并给出24个常见元素的宽窄脉冲电流的选定结果。 相似文献
67.
M. Asmann A. Wank H. Kim J. Heberlein E. Pfender 《Plasma Chemistry and Plasma Processing》2001,21(1):37-63
Enthalpy probe measurements were taken of the converging plasma plume in a triple torch plasma reactor and related to substrate heat flux measurements. Results show excellent entrainment of process gases injected into the converging plasma plume by way of the central injection probe. At lower pressures (40 kPa), the plasma volume is equivalent to at least a 3 cm diameter, 4 cm long cylinder, with relatively uniform temperature, velocity, and substrate heat flux profiles when compared to a typical dc arc jet. Converging plasma plume size, substrate heat flux, and enthalpy profiles are also shown to be a strong function of applied system power. Substrate heat flux measurements show smaller radial gradients than enthalpy probe measurements, because of the high radial velocity component of gases above the substrate boundary layer. Enthalpy probe measurements were also conducted for diamond deposition conditions and approximate temperature and velocity profiles obtained. Problems with the uniform gas mixture assumption prohibited more accurate measurements. Reproducibility of enthalpy measurement results was shown with an average standard deviation of 11.8% for the velocity and 7.6% for the temperature measurements. 相似文献
68.
小波变换用于高效液相色谱的基线校正 总被引:26,自引:9,他引:26
本文根据小波变换将信号分频的性质,用Daubechies小波成功地解决了高效液相色谱中基线校正问题,用于定量分析乳酸-稀土络合物体系中的十六个稀土元素,所得结果与仪器给出了结果进行比较,准确度提高,重现性良好。 相似文献
69.
70.
在pH4.3的B-R缓冲体系中,用微相吸附-光谱修正技术[1]研究了茜素红(ARS)与牛血清白蛋白(BSA)、人血清白蛋白(HSA)的结合反应。其吸附结合常数分别为:KBSA-ARS=3.950×104,KHSA-ARS=4.377×104。染料与蛋白的最大结合数分别为NARS∶NBSA=9∶1,NARS∶NHSA=7∶1。经光谱修正技术计算结合产物的实际摩尔吸光系数分别为εBSA-ARS(537nm)=2.517×104L.mol-1.cm-1,εHSA-ARS(519nm)=2.051×104L.mol-1.cm-1,检出限BSA为19mg/L,HSA为23mg/L。经探讨该结合反应机理符合Langmuir吸附聚集反应方程。 相似文献