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61.
多电解质溶液中带电胶体粒子的电势分布由球形Poisson-Boltzmann方程(PBE)描述.PBE是一个非线性的微分方程,且难以求得其解析解.本文采用非线性P-B积分方程,计算电势分布的数值解.首先,根据静电场和热力学系统中的物理定理,导出描述电势分布的P-B积分方程(PBIE);其次,用迭代方法求PBIE的数值解.最后,计算了在3-1型电解液中无量纲半径κa分别为0.12和0.22,无量纲表面电势ξ分别为1,2,4,6时球形胶体粒子外部的电势值.为了检验数值解的精度,计算了表面电荷密度,并与Loeb(1961)和Oshima(1995)等人的结果比较,本文结果的相对误差小于1%,优于Oshima的结果. 相似文献
62.
无机层状复合氢氧化物中顺铂-DNA模型分子的选择性插入 总被引:5,自引:0,他引:5
药物分子的选择性包裹和控制释放是药物研究领域中具有挑战性的研究方向。本文研究表明:顺铂-DNA模型分子cis-[Pt(NH3)2(5′-GMP)2](5′-GMP 5′-单磷酸鸟苷)可插入无机层状复合氢氧化物[Zn0.68Al0.32(OH)2](NO3)0.32·mH2O。但另一种层状复合氢氧化物[LiAl2(OH)6]Cl·H2O由于其阳离子层中正电荷密度较高、阳离子层与层间阴离子之间静电作用较强,因而顺铂-DNA模型分子不能通过离子交换方式插入其层间。光谱数据证实插入层间的顺铂-DNA模型分子结构不变。这可能为铂-DNA分子的传递提供新的方法。 相似文献
63.
The effect of Ni substitution for Mn on magnetic and transport properties has been investigated for layered manganese oxides LaSr2Mn2-xNixO7. Nickel doping hampered the canted antiferromagnetic (AFM) exchange at low temperature and their Neel temperature (TN) decreased from 138 K (x=0) to 102 K (x=0.3). Meanwhile, spin glass, charge ordering and metal-insulator transition are suppressed by Ni addition. The resistivity increases obviously with increasing x due to double exchange interaction channel broken by Ni2+ addition. The resistivity of all samples in low temperature range fits to the Mott′s variable rang hopping (VRH) model, while it fits to nearest neighbor hopping of small polarons model in high temperature range. 相似文献
64.
Chromium and yttrium-doped magnesium aluminum oxides prepared from layered double hydroxides 总被引:1,自引:0,他引:1
J.M. García-García M.E. Prez-Bernal R.J. Ruano-Casero V. Rives 《Solid State Sciences》2007,9(12):1115-1125
Layered double hydroxides with the hydrotalcite-like structures, containing Mg2+ and Al3+, doped with Cr3+ and Y3+, have been prepared by precipitation at constant pH. The weight percentages of Cr3+ and Y3+ were 1, 2, or 3%, and 0.5 or 1%, respectively. Single phases were obtained in all cases, whose crystallinity decreased as the content in Cr and Y was increased. The solids have been characterised by element chemical analysis, powder X-ray diffraction, thermal analyses (differential, thermogravimetric and programmed reduction), FT-IR and UV–vis spectroscopies; the specific surface areas have been determined from nitrogen adsorption isotherms at −196 °C. Upon calcination at 1200 °C for 5 h in air all solids display a mixed structure (spinel and rock salt for MgO); these solids have also been characterised by these techniques and their chromatic coordinates (CIE – L*a*b*) have been determined. Their pink colour makes these solids suitable for being used as ceramic pigments. 相似文献
65.
FT-IR and Raman spectroscopic study of hydrated rubidium (cesium) borates and alkali double borates 总被引:1,自引:0,他引:1
Zhu Lixia Yue Tao Wang Jiang Gao Shiyang 《Russian Journal of Inorganic Chemistry》2007,52(11):1786-1792
FT-IR and Raman spectra of five hydrated alkali borates and five hydrated alkali double borates have been recorded at room
temperature in the range 400 to 4000 cm−1, and analyzed. Fundamental vibrational modes have been identified and assignments tentatively made in comparison with the
work of Janda and Heller, and Li Jun.
The text was submitted by the authors in English. 相似文献
66.
通过流动相中电解质浓度对毛细管电色谱柱效能的流动相平均线速度的影响,研究了CEC中双电层叠加现象。提出选择合适电解质组成的浓度及在制备色谱柱过程中避免细小和破碎的固定相颗粒进入柱中,以有效地减小双电层叠加作用。 相似文献
67.
Òscar Rubio-Pons Boris Minaev Oleksandr Loboda Hans Ågren 《Theoretical chemistry accounts》2005,113(1):15-27
The phosphorescence spectrum of p-dichlorobenzene has been calculated using multiconfiguration self-consistent-field wave functions and the quadratic response technique. Attention has been paid to the intensity distribution of the singlet–triplet (3B1u1Ag) transition through a number of vibronic subbands. The second order spin–orbit coupling (SOC) contribution to the spin splitting of the 3B1u (3*) state is found to be almost negligible, and the calculations therefore provide a good estimate for the zero-field splitting (ZFS) parameters based only on the electron spin–spin coupling expectation values. Nuclear quadrupole resonance constants for the different Cl isotopes are also calculated to accomplish the ZFS assignment. The electric dipole activity of the spin sublevels in the triplet–singlet transitions to the ground-state vibrational levels is estimated by calculations of derivatives using distorted geometries which are shifted from the equilibrium position along different vibrational modes. A vibrational analysis of the phosphorescence spectrum, based on the SOC-induced mixing of the singlet and triplet states calculated along different vibrational modes, provides reasonable agreement with experimental data.Acknowledgment O. R.-P. would like to thank the European MOLPROP network for support. The authors thank Alexander Baev for fruitful discussions. This work was supported by the Swedish Royal Academy of Science (KVA). 相似文献
68.
The total energy of all π-electrons in a conjugated hydrocarbon (within the framework of HMO approximation) is the sum of the absolute value of all
the eigenvalues of its corresponding graph. In this paper, we consider “double hexagonal chains” as benzenoids constructed
by successive fusions of successive naphthalenes along a zig–zag sequence of triples of edges as appear on opposite sides
of each naphthalene unit. It is shown that if the fusions are such as to give a polyaceacene then the total π-electron energy
is the minimum from among all the double hexagonal chains with the same number of naphthalene units.
相似文献
69.
Cr(VI)在Mg-Al型类水滑石上的吸附-脱附性研究I.吸附性 总被引:1,自引:0,他引:1
研究了Cr(VI)在带结构正电荷的Mg-Al型类水滑石(HTlc)上的吸附性能,考察了pH、无机电解质添加剂NaCl,NaNO3,Na2SO4和Na3PO4及有机添加剂EDTA和柠檬酸等因素的影响,并结合红外光谱和XRD实验结果探讨了吸附机理.研究表明,Mg-Al型HTlc对Cr(VI)有很强的吸附能力,其吸附动力学和吸附等温线分别符合准二级速率方程和Langmuir方程,饱和吸附量达105mg/g,有望成为一种优良的含Cr(VI)污水处理剂和Cr(VI)污染土壤修复剂.初始pH增大,吸附量降低.无机电解质和有机添加剂均能明显抑制Cr(VI)在HTlc上的吸附,其抑制吸附作用的强弱顺序分别为Na3PO4≥Na2SO4≥NaCl>>NaNO3和柠檬酸>EDTA.Cr(VI)在HTlc上的吸附可分为层间的离子交换吸附和外表面的吸附,其中外表面的吸附层在微观上又可分为因化学键合作用而形成的内络合层和因静电作用而形成的外络合层. 相似文献
70.
E. T. Denisov 《Russian Chemical Bulletin》2004,53(8):1602-1608
The transition state of addition of free radicals and atoms to multiple bonds is considered as a result of intersecting of two parabolic potential curves. One of them characterizes the stretching vibration of the attacked multiple bond, and another curve characterizes the stretching vibration of the bond formed in the transition state. The force constant of the latter is calculated by an empirical equation that correlates the force constant with the bond dissociation energy. In the framework of this model, the thermally neutral activation energy (E
e0) and the elongation of the attacked and formed bonds (r
e) in the transition state were calculated from the experimental data (activation energy (E
e) and enthalpy of reaction (H
e)) for the addition of an H atom and methyl, alkoxyl, aminyl, triethylsilyl, and peroxyl radicals to the C=C bond and the addition of H and CH3 to the C=O and CC bonds. Analysis of the data obtained showed that E
e0 depends linearly on the |H
e| + Ee sum, i.e., Ee0/kJ mol–1 = 14.2 + 0.61 · (Ee – H
e), and the bond elongation in the transition state for addition of the most part of radicals to ethylene and acetylene vary within (0.65–0.87)·10–10 m. The factors affecting the activation energy of the radical addition reactions are discussed.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1542–August, 2004. 相似文献