A simple mathematical analysis on the effect of sand in Cr(VI) reduction using zero valent iron

A simple mathematical model was proposed to analyze the enhancement of Cr(VI) reduction when sand materials are added to the zero valent iron (ZVI). Natural decay of Cr(VI) in a control experiment was analyzed by using a zero-order decay reaction. Adsorption kinetics of Cr(VI) to sand was modeled as a first-order reversible process, and the reduction rate by ZVI was treated as a first-order reaction. Natural decay of Cr(VI) was also included in other experiments, i.e., the adsorption to sand, the reduction by ZVI, and both adsorption and reduction when sand and ZVI are present together. The model parameters were estimated by fitting the solution of each model to the corresponding experimental data. To observe the effect of sand addition to ZVI, both adsorption and reduction rate models were considered simultaneously including the natural decay. The solution of the combined model was fitted to the experimental data to determine the first-order adsorption and reduction rate constants when sand as well as ZVI is present. The first-order reduction rate constant in the presence of sand was about 35 times higher than that with ZVI only.     

十六烷基三甲基季铵阳离子改良二氧化硅对酸性染料的吸着

The sorption behavior of acid dyes onto cetyltrimethylammonium bromide (CTAB)-modified silica as a function of pH in the aqueous medium was studied. Single-and multi-solute sorption equilibria of orange Ⅱ（OR), phenol red (PR) and Eriochrome Black T (EBT) were studied at pH 3, unbuffered water pH and pH 11. Sorption behavior of EBT could not be conducted at pH3 due to its aggregation in acidic medium. All the reaction conditions, experimental protocols and techniques remained the same throughout the sorption process. Sorption isotherms for single-solute system were fitted by the Langmuir model, while Langmuir competitive model (LCM) and the ideal adsorbed solution theory (IAST) coupled with Langmuir model (IAST/Langmuir) were used for the prediction of multisolute competitive sorption. Sorption affinities influenced by the factors like physical interactive forces between the molecules of CTA on silica and sorbate, structural limitations of the dyes based on their geometrical arrangement were investigated. Sorption affinity of OR was found to be higher than that of EBT and PR at all the pH values investigated. Magnitude of the sorption capacities was observed to be higher in acidic medium but lower in alkaline medium. Trends of the sorption affinities in multisolute system were simlar to those in single-solute system but magnitude of the sorption capacities was significantly reduced due to the prevailing competition among the sorbates.     

Preparation and Thermoelectric Properties of p-Type Yb-Filled Skutterudites

p-Type Yb _z Fe_4?x Co _x Sb₁₂ skutterudites were prepared by encapsulated melting and hot pressing, and the filling and doping (charge compensation) effects on the transport and thermoelectric properties were examined. The electrical conductivity of all specimens decreased slightly with increasing temperature, indicating that they were in a degenerate state due to high carrier concentrations of 10²⁰ cm^?3 to 10²¹ cm^?3. The Hall and Seebeck coefficients exhibited positive signs, indicating that the majority carriers are holes (p-type). The Seebeck coefficient increased with increasing temperature to maximum values of 100 μV/K to 150 μV/K at 823 K. The electrical and thermal conductivities were reduced by substitution of Co for Fe, which was responsible for the decreased carrier concentration. Overall, the Yb-filled Fe-rich skutterudites showed better thermoelectric performance than the Yb-filled Co-rich skutterudites.     

Mode propagation in optical nanowaveguides with dielectric cores and surrounding metal layers

The mode spectrum in an optical nanowaveguide consisting of a dielectric-core layer surrounded by two identical metal layers is investigated. A simple model based on mode matching to predict the properties of mode propagation in such optical nanowaveguides is proposed. It is shown that quasi-TM00 and quasi-TM10 modes supported by an optical microstrip line do not have a cutoff frequency, regardless of the size of the metal strips, the thickness of the dielectric slab, and the cross-sectional shape. The transverse size of the TM00 mode supported by a nanosized microstrip line was found to be approximately equal to the transverse dimension of the microstrip line. In closed rectangular and elliptical nanowaveguides, i.e., in which all dielectric surfaces are covered with metal films, the cross-sectional shape of the waveguide should be stretched along one side to produce propagation conditions for the fundamental mode.     

Three-parameter empirical isotherm model: its application to sorption onto organoclays

A new three-parameter empirical isotherm model (the Song isotherm model, hereinafter) is proposed. This model satisfies the Henry's law and the Freundlich isotherm model in the low and high concentration ranges, respectively. We applied this model to the single-solute sorption of 2-chloro-, 3-cyano-, and 4-nitrophenol from water to montmorillonites organically modified with either hexadecyltrimethylammonium (HDTMA) cation or both HDTMA and tetramethylammonium (TMA) dual cations. Sorption to organoclays (i.e., organically modified clays) modified with the long-hydrocarbon chain organic cations or the short- and long-hydrocarbon chain dual organic cations usually occurs by a partition mechanism. Sorption of polar organic compounds to organoclays, however, becomes nonlinear when the solution-phase concentration covered is more than 3 orders of magnitude. The three parameters contained in the presently proposed model could be estimated from the plot, log(q/c) versus log c. The partition coefficient in the Henry's law region (K) can be estimated from the ordinate value of the asymptote in the low concentration region, the Freundlich index (n) can be estimated from the slope of the asymptote in the high concentration region, and the parameter (beta) corresponding to the crossover point can be estimated from the intersection point of the two asymptotes. By performing nonlinear curve fitting to the raw data, q versus c, using the initial guesses estimated from the manipulated data, log-(q/c) versus log c, the optimum set of parameters could be determined without worrying much over the annoying local minima. The Song model was compared with other existing two- and three-parameter isotherm models. The Song model fitted our experimental data better than the Langmuir and Freundlich models and showed nearly the same goodness-of-fit as the Redlich-Peterson and dual-mode models. The obvious merit of the Song model is that it provides us with the partition coefficient in the Henry's law region. The organic carbon-normalized partition coefficients in the Henry's law region were found to be about 1 order of magnitude higher than the corresponding octanol-water partition coefficients, at least for the phenolic compounds covered in this study.     

Precision measurements of reaction wheel disturbances with frequency compensation process

The reaction wheel, an actuator for satellite attitude control, produces disturbance torque and force as well as axial control torque. The disturbances are so crucial to the pointing stability of this high precision satellite that a measurement of disturbances is necessary for such a satellite. The measurement table that is equipped with several load cells is one of the favorite types of measurement devices. The disturbance force and torque caused by the wheel's rotation, however, stimulate the elasticity of the loadcells from the measurement table and induce the vibration of the table. This then causes the measurement error, which is especially large near the resonance frequencies of the table. In order to reduce this type of error, a calibration process with frequency compensation is suggested in this paper. The “filtered” disturbance spectrum is obtained from the raw data and the degradation of data accuracy caused by the table vibration is alleviated. Since the exact measurement is made possible by this compensation process even in the resonance area, the measurement range can be expanded up to the frequency area including the resonance frequencies. The compensation method has been adopted for the HAU measurement table where three uni-directional loadcells are used. The validity of the use of uni-directional loadcells is also tested theoretically.     

The second vs. the third moment matching between diffusion models for dynamic adsorber

Four diffusion models for the dynamic adsorber, i.e. LDF model, single diffusivity diffusion model, two diffusivity diffusion model for beds packed with bidisperse and/or zeolite-type particles, were considered. The third moments for the four diffusion models were obtained. Relations between the system parameters involved in each model were derived by matching mean, vanance or the third moment between diffusion models. The two relations from either variance or the third moment matching were examined to investigate which one is superior when model simplification is required, by comparing the time domain elution curves for the single and the two diffusivity diffusion models. For the symmetric elution curves, relation from the variance matching is much better as expected, than the relation matching the third moment which measures skewness about mean. As the elution curves become highly asymmetric, eluting shortly after injection and exhibiting long tailing due to both the small intraparticle diffusivities and small space time in the adsorber, either relation failed to satisfactorily simplify the two diffusivity diffusion model. Contrary to the expectation that the third moment matching would work better in the asymmetric curves due to the nature of the third moment, variance matching still gives slightly better results. Relation from the variance, instead of the third moment, matching is strongly recommended for model simplification due to its simplicity in formula.     

Oxidation of 17alpha-ethinylestradiol with Mn(III) and product identification

With increasing concern about the contamination of aquatic environments by estrogenic pollutants, removal of synthetic estrogens such as 17alpha-ethinylestradiol (EE2) has been widely studied, especially with respect to the treatment methods. However, the degradation products have rarely been identified. The purpose of this study was to identify structurally the oxidation products of EE2. Mn(III) was used as an oxidizing agent. To obtain sufficient oxidation products for HPLC, LC-MS and NMR spectroscopy, a highly concentrated solution of EE2 (1mM) was prepared in a mixture of water and a water-miscible organic solvent. From HPLC of the reaction products, a single compound (I) was found to be predominant. From LC-MS, its molecular mass was found to be 294, and two hydrogens were believed to have been removed from EE2 (M.W. 296) to form a C=C . The structure of compound I (position of the double bond) was determined using 1H NMR, 13C NMR, H-H COSY, HSQC and HMBC. As minor products, isomeric dimers (M.W. 590) of EE2, as well as the products (M.W. 588) in which EE2 was coupled to compound I were also formed during the Mn(III)-mediated oxidation of EE2.     

Grain-Size Effects on the High-Temperature Oxidation of Modified 304 Austenitic Stainless Steel

The high-temperature oxidation behavior of modified 304 austenitic stainless steels in a water vapor atmosphere was investigated. Samples were prepared by various thermo mechanical treatments to result in different grain sizes in the range 8–30 μm. Similar Σ3 grain boundary fraction was achieved to eliminate any grain-boundary characteristics effect. Samples were oxidized in an air furnace at 700 °C with 20 % water vapor atmosphere. On the fine-grained sample, a uniform Cr₂O₃ layer was formed, which increased the overall oxidation resistance. Whereas on the coarse-grained sample, an additional Fe₂O₃ layer formed on the Cr-rich oxide layer, which resulted in a relatively high oxidation rate. In the fine-grained sample, grain boundaries act as rapid diffusion paths for Cr and provided enough Cr to form Cr₂O₃ oxide on the entire sample surface.     

Sorption and desorption kinetics of PAHs in coastal sediment

Sorption and desorption kinetics of PAHs (naphthalene, phenanthrene and pyrene) in coastal sediment were investigated. Several kinetic models were used to analyze the kinetics: one-site mass transfer model (OSMTM), pseudo-first-order kinetic model (PFOKM), pseudo-second-order kinetic model (PSOKM), two compartment firstorder kinetic model (TCFOKM) and modified two compartment first-order kinetic model (MTCFOKM). Among the models, the MTCFOKM was the best in fitting both sorption and desorption kinetic data, and therefore could predict the most accurately. In MTCFOKM, the fast sorption fraction (f′_{1, s} ) increased with the hydrophobicity (K _ow ) of the PAHs, whereas the fast desorption fraction (f′_{1, d} ) decreased. The fast sorption rate constant (k′_{1, s} ) was much greater than the slow sorption rate constant (k′_{2, s} ). Effect of aging on the desorption kinetics was also analyzed. The f′_{1, d} in MTCFOKM decreased but the slow desorption fraction (f′_{2, d} ) increased with aging, indicating that slow desorption is directly related to aging.