The ion product of H2O,dissociation constants of H2CO3 and pitzer parameters in the system Na+/H+/OH−/HCO 3 − /CO 3 2- /ClO 4 − /H2O at 25°C

The ion product of water and the dissociation constants of carbonic acid have been determined in 0.1, 1.0, 3.0, and 5.0M NaClO₄ at 25°C. The ion product of water K _w ^' has been evaluated by emf measurements with a combined glass electrode in NaClO₄ solutions containing 0.001–0.1M HCLO₄ or NaOH. The product K _H ^' K _l ^' K ₂ ^' of the Henry constant for CO₂ and the dissociation constants for H₂CO₃ have been determined by titration of carbonate solutions equilibrated with pCO₂ =10^–3.52 atm, and K ₂ ^' has been evaluated by potentiometric titration and by measuring the H⁺ concentration at fixed HCO ₃ ^– and CO ₃ ^2- concentrations. The ion interaction (Pitzer) equations are applied to describe the constants K _w ^' , K ₂ ^' and K _H ^' H ₁ ^' K ₂ ^' as a function of the NaClO₄ concentration. The experimental data are used to evaluate the mixing parameters _{i/ClO 4} and _{i/ClO 4} ^-/Na⁺ fori = OH ^-,HCO ₃ ^- andCO ₃ ^2-     

烟酰胺辅酶模型对N－芳基芴亚胺的酸催化还原反应的研究

报道了５种Ｎ－芳基芴亚胺在酸性条件下被烟酰胺辅酶模型（Ｈａｎｔｚｓｃｈ酯，ＢＮＡＨ）还原的反应。结果表明：亚胺的结构、酸的强度以及溶剂的不同均会影响亚胺的还原效率，本文结合反应的结构效应、溶剂效应和同位素效应，对其可能的酸催化氢负离子转移机理进行了讨论。     

Polymer characterization and gas permeability of poly(1-trimethylsilyl-1-propyne) [PTMSP], poly(1-phenyl-1-propyne) [PPP], and PTMSP/PPP blends

Pure gas and hydrocarbon vapor transport properties of blends of two glassy, polyacetylene-based polymers, poly(1-trimethylsilyl-1-propyne) [PTMSP] and poly(1-phenyl-1-propyne) [PPP], have been determined. Solid-state CP/MAS NMR proton rotating frame relaxation times were determined in the pure polymers and the blends. NMR studies show that PTMSP and PPP form strongly phase-separated blends. The permeabilities of the pure polymers and each blend were determined with hydrogen, nitrogen, oxygen, carbon dioxide, and n-butane. PTMSP exhibits unusual gas and vapor transport properties which result from its extremely high free volume. PTMSP is more permeable to large organic vapors, such as n-butane, than to small, permanent gases, such as hydrogen. PPP exhibits gas permeation characteristics of conventional low free volume glassy polymers; PPP is more permeable to hydrogen than to n-butane. In PTMSP/PPP blends, both n-butane permeability and n-butane/hydrogen selectivity increase as the PTMSP content of the blends increases. © 1996 John Wiley & Sons, Inc.     

化学计量学定量分析模型的评价及应用

本文介绍了评价化学计量学校正技术所建立的定量分析模型定量分析效果的一种实用方法，根据定量分析模型对样品待测组分的计算值ｘ与样品待测组分的标准值ｙ建立简单回归模型：ｙ＝ａ＋ｂｘ通过检验回归参数ａ＝０，ｂ＝１的假设能否在一定概率水平上被接受，评价定量分析模型对样品待测组分的预测效果。     

关于PW－1480 X44软件中的数学通式问题

本文讨论ＰＷ－１４８０Ｘ４４软件中的数学通式问题。作者指出，软件中所提供的数学通式不妥，应该改正，软件应作适当修改。     

Experimental study on high-pressure adsorption of hydrogen on activated carbon

A systematic measurement of H2 adsorption on activated carbon over a wide scope of conditions was completed for the first time using a novel cryostat developed by the present authors. The equilibrium temperatures covered 77-298 K with the space of about 20 K, and the equilibrium pressures increased from 0 to about 7MPa. A set of adsorption/desorption isotherms was obtained by a standard volumetric method. This set of experimental data was fitted to all the well-known models of type-I isotherms, and Dubinin-Astakhov (D-A) equation was found to be the best-fit one On the basis of D-A model one can predict adsorption with relative error of ±4%. A 3-dimensional adsorption surface was also constructed, and the isosteric heat of adsorption was analytically determined. Except in the low pressure area, the calculated values agreed well with the experimental ones. Finally, the troubles encountered in applying D-A equation to supercritical adsorption is discussed.     

配体交换反应速差动力学法同时测定稀土混合物的数学模型

提出了用可逆模型进行曲线拟合处理数据,并以稀土偶氮肿Ⅲ络合物与CyDTA交换反应为例作验证,结果理论曲线与实验曲线能很好地吻合,提高了用动力学法测定混合稀土的准确度。     

反相液相色谱二元流动相组成的计算机统计试验全局最佳化

本文用一类非线性规划形式表述的分离模型作为最优化标准,用统计试验全局最佳化方法寻求二元流动相的最佳组成。实验证明:至多5个试验和10分钟左右的计算时间即可找到全局最佳点。     

A refined physico-chemical model of solute retention in reversed-phase high-performance liquid chromatography with ternary mobile phases

Summary In our previous publication we have introduced a new model of solute retention in RP-HPLC systems with ternary mobile phases of the B+AB₁+AB₂ type (B: acetonitrile or tetrahydrofuran; AB₁: methanol; AB₂: water). That model proposed no stoichiometric differentiation between acetonitrile and tetrahydrofuran, alternatively present in the solvent system; moreover, it made some very rough assumptions only as to the intermolecular interactions among the mobile phase constituents.This paper introduces a significant refinement to the already established retention model, which is based on the simple quantitative relationships between acetonitrile and tetrahydrofuran, and the remaining components of the ternary liquid system. The refined model is tested with same experimental data.