Computation of equilibrium oxidation and reduction potentials for reversible and dissociative electron-transfer reactions in solution

Equilibrium free-energy cycles relating oxidation and reduction potentials in solution to ionization potentials and electron affinities in the gas phase are constructed and the utilities of various levels of theory for computing particular free-energy changes within these cycles are discussed within the context of several examples. Emphasis is placed on the use of quantum-mechanical continuum solvation models to compute free energies of solvation. Key systems discussed include quinones, substituted anilines, substituted phenols, and reductive dechlorination reactions.Dedicated to Prof. Jean-Louis Rivail, whose pioneering efforts in developing and exploiting continuum solvent models were critical in making quantum chemistry more applicable to solution phenomenaProceedings of the 11th International Congress of Quantum Chemistry satellite meeting in honor of Jean-Louis Rivail     

Interpreting the difference between conventional and bi-directional plate-height measurements in liquid chromatography

An experimental and theoretical study was conducted of the column characterization technique in which plate heights determined using the conventional pulse-response method are compared with those determined using a bi-directional method where an eluite sample is introduced into one end of a chromatographic column and elution occurs at the same end after the flow direction is reversed inside the column. Experiments are presented for a micropellicular HPLC column before and after its performance has been degraded by repeated sample injections, for a low-pressure column containing nonporous glass particles, and for an HPLC column containing particles with 300 Å pores. The results obtained are interpreted in terms of several different theories which apply in various Fourier number ranges. It was shown that the transcolumn contribution to convective dispersion in a chromatographic column is largely responsible for the difference observed between conventional and bi-directional plate-height measurements and that a collocation method can be employed to develop a useful analytical expression for this contribution.     

SCR催化剂碱(土)金属中毒的研究进展

在选择性催化还原(SCR)烟气脱硝系统中,催化剂碱(土)金属中毒和再生受到广泛关注。本文综述了SCR脱硝催化剂碱(土)金属中毒的失活机理及基于分子水平上碱金属中毒的研究新思路,并根据催化剂的各种失活机理,有针对性地综述了提高催化剂抗碱金属中毒的途径及中毒催化剂的再生方法。     

Combining linear polarization spectroscopy and the Representative Layer Theory to measure the Beer–Lambert law absorbance of highly scattering materials

Visible and Near Infrared (Vis–NIR) Spectroscopy is a powerful non destructive analytical method used to analyze major compounds in bulk materials and products and requiring no sample preparation. It is widely used in routine analysis and also in-line in industries, in-vivo with biomedical applications or in-field for agricultural and environmental applications. However, highly scattering samples subvert Beer–Lambert law's linear relationship between spectral absorbance and the concentrations. Instead of spectral pre-processing, which is commonly used by Vis–NIR spectroscopists to mitigate the scattering effect, we put forward an optical method, based on Polarized Light Spectroscopy to improve the absorbance signal measurement on highly scattering samples. This method selects part of the signal which is less impacted by scattering. The resulted signal is combined in the Absorption/Remission function defined in Dahm's Representative Layer Theory to compute an absorbance signal fulfilling Beer–Lambert's law, i.e. being linearly related to concentration of the chemicals composing the sample. The underpinning theories have been experimentally evaluated on scattering samples in liquid form and in powdered form. The method produced more accurate spectra and the Pearson's coefficient assessing the linearity between the absorbance spectra and the concentration of the added dye improved from 0.94 to 0.99 for liquid samples and 0.84–0.97 for powdered samples.     

SSZ-33分子筛的合成、表征及其对汽车尾气中碳氢化合物的捕集性能

采用碘化N,N,N-三甲基-8-氨基-三环[5.2.1.02.6]癸烷为结构导向剂, 通过过程控制方法, 经3-4 d成功合成了高性价比的B-SSZ-33分子筛. 以B-SSZ-33为母体, 经过Al(NO3)3溶液后处理制得了Al-SSZ-33分子筛. 采用X射线衍射(XRD), 傅里叶变换红外(FT-IR)光谱, 扫描电子显微镜(SEM), 热重(TG)分析, 电感耦合等离子体原子发射光谱(ICP-AES), N2吸附/脱附, 27Al核磁共振(27Al NMR)和NH3程序升温脱附(NH3-TPD)等手段对合成的B-SSZ-33、Al-SSZ-33样品进行了物理化学性能表征. 并以甲苯作为汽车尾气中碳氢化合物的探针分子, 通过甲苯程序升温脱附测试来考察样品的碳氢捕集性能. 结果表明: 后处理过程中Al同晶取代B, 从而制得了含骨架Al的Al-SSZ-33; 在甲苯的程序升温脱附测试中, 由于Al-SSZ-33相对于B-SSZ-33具有较强的酸性位, 且表面孔口由于骨架外硅铝物种的修饰, 限制了甲苯的扩散, 致使脱附速率最大时的温度(Tmax)和脱附最终的温度(Tend)均升高, 从而形成了新型汽车尾气捕集催化剂的雏形.     

Viscosity of liquid suspensions with fractal aggregates: Magnetic nanoparticles in petroleum colloidal structures

New physical model is presented resulting in a simple formula for the dependence of viscosity η of colloidal liquid solution on the shear rate G applicable to a wide variety of systems including complex natural liquids like petroleum. The principal point of the model is the fractal nature of colloid particle aggregates present in the liquid. Such aggregates are experimentally detected now in non-Newtonian liquids. The model is based on calculation of energy loss on colloidal particle aggregate of fractal structure localized in the flow of liquid with shear rate. We have performed the viscosity measurement experiments which confirmed successfully the developed physical model. Also, we demonstrate experimentally that petroleum colloidal particles and magnetic iron oxide nanoparticles can form composite fractal-like aggregates in natural petroleum materials. Our model can explain both the non-Newtonian properties of petroleum and sensitivity of petroleum viscosity to external magnetic fields.     

Real-time in situ monitoring of manufacturing process and CFRP quality by relative resistance change measurement

In situ monitoring of resin flow, impregnation of carbon fiber fabrics, and curing during composite manufacturing are very important for determining the quality of composite parts. In conventional methods, sensors, such as optical fibers and strain gages, are bonded to or embedded in the composites for measuring the changes in mechanical and chemical properties. Although they can detect resin curing behavior and impregnation of carbon fibers, they may adversely affect the manufacturing process or structural integrity of the composites. In this study, carbon fiber itself was used as a sensor that minimizes the degradation of mechanical properties and increases the efficiency of monitoring the manufacturing process. The change in the electrical resistance of carbon fiber fabrics was monitored during the various manufacturing processes when the resin flowed through the carbon fiber fabric and curing progressed. The effectiveness of this monitoring method was confirmed, and it is expected to be applicable in monitoring the quality of the finished composite parts.     

NIR analysis of pharmaceutical samples without reference data: improving the calibration

Using an appropriate set of samples to construct the calibration set is crucial with a view to ensuring accurate multivariate calibration of NIR spectroscopic data. In this work, we developed and optimized a new methodology for incorporating physical variability in pharmaceutical production based on the NIR spectrum for the process. Such a spectrum contains the spectral changes caused by each treatment applied to the component mixture during the production process. The proposed methodology involves adding a set of process spectra (viz. difference spectra between those for production tablets and a laboratory mixture of identical nominal composition) to the set of laboratory samples, which span the wanted concentration range, in order to construct a calibration set incorporating all physical changes undergone by the samples in each step of the production process. The best calibration model among those tested was selected by establishing the influence of spectral pretreatments used to obtain the process spectrum and construct the calibration models, and also by determining the multiplying factor m to be applied to the process spectra in order to ensure incorporation of all variability sources into the calibration model. The specific samples to be included in the calibration set were selected by principal component analysis (PCA). To this end, the new methodology for constructing calibration sets for determining the Active Principle Ingredients (API) and excipients was applied to Irbesartan tablets and validated by application to the API and excipients of paracetamol tablets. The proposed methodology provides simple, robust calibration models for determining the different components of a pharmaceutical formulation.     

Maintaining the predictive abilities of multivariate calibration models by spectral space transformation

In quantitative on-line/in-line monitoring of chemical and bio-chemical processes using spectroscopic instruments, multivariate calibration models are indispensable for the extraction of chemical information from complex spectroscopic measurements. The development of reliable multivariate calibration models is generally time-consuming and costly. Therefore, once a reliable multivariate calibration model is established, it is expected to be used for an extended period. However, any change in the instrumental response or variations in the measurement conditions can render a multivariate calibration model invalid. In this contribution, a new method, spectral space transformation (SST), has been developed to maintain the predictive abilities of multivariate calibration models when the spectrometer or measurement conditions are altered. SST tries to eliminate the spectral differences induced by the changes in instruments or measurement conditions through the transformation between two spectral spaces spanned by the corresponding spectra of a subset of standardization samples measured on two instruments or under two sets of experimental conditions. The performance of the method has been tested on two data sets comprising NIR and MIR spectra. The experimental results show that SST can achieve satisfactory analyte predictions from spectroscopic measurements subject to spectrometer/probe alteration, when only a few standardization samples are used. Compared with the existing popular methods designed for the same purpose, i.e. global PLS, univariate slope and bias correction (SBC) and piecewise direct standardization (PDS), SST has the advantages of implementation simplicity, wider applicability and better performance in terms of predictive accuracy.     

Teaching of process analytical chemistry

In the teaching of analytical chemistry for chemical engineering students it is essential today to teach the chemical analysis of dynamic systems, not only in the process control of the modern technological systems, where the control of composition or structure of different material streams is necessary, but also in all other instances where analysis, decision and intervention follow each other, forming a closed cycle. Teaching can be made effective if students already have a knowledge of the basic disciplines (including analytical chemistry). The schedule of the teaching programme should include the mathematical statistical treatment of process signals, quality of the signals, signal-improvement methods, characteristics of instruments, calibration and an introduction to sensors, analysers suitable for continuous or periodical measurements and local area networks. As practical exercizes an apparatus for investigation of the dynamic properties of a thermoanalytical detector system, a computer program for simulating process variables and the control loop including the measuring system are presented.