Sorption behavior of Co(II) on γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> in the presence of humic acid

The fate and transport of toxic metal ions and radionuclides in the environment is generally controlled by sorption reactions. The extent of sorption of divalent metal cations is controlled by a number of factors including cosorbing or complexing. In this work, the effects of pH, humic acid HA/Co(II) addition orders, ionic strength, concentration of HA, and foreign cations on the Co(II) sorption on γ-Al₂O₃ in the presence of HA were investigated. The sorption isotherms of Co(II) on γ-Al₂O₃ in the absence and presence HA were also studied and described by using S-type sorption model. The experimental results showed that the Co(II) sorption is strongly dependent on the pH values, concentration of HA, but independent of HA/Co(II) addition orders, ionic strength, and foreign cations in the presence of HA under our experimental conditions. The results also indicated that HA enhanced the Co(II) sorption at low pH, but reduced the Co(II) sorption at high pH. It was hypothesized that the significantly positive influence of HA at low pH on the Co(II) sorption on γ-Al₂O₃ was attributed to strong surface binding of HA on γ-Al₂O₃ and subsequently the formation of ternary surface complexes such as ≡S-OOC-R-(COO⁻) _x Co^2−x . Chemi-complexation may be the main mechanism of the Co(II) sorption on γ-Al₂O₃ in the presence of HA.     

Preconcentration and separation of copper(II), cadmium(II) and chromium(III) in a syringe filled with 3-aminopropyltriethoxysilane supported on silica gel

In this study, a syringe was filled with silica gel loaded with 3-aminopropyltriethoxysilane, for the separation and preconcentration of copper, cadmium and chromium prior to their determination by graphite furnace atomic absorption spectrometry (GFAAS) in seawater. For this purpose, a syringe was filled with 0.5 g of modified silica gel and the sample solution was drawn into the syringe and ejected back again. The analyte elements were quantitatively retained at pH 5. Then, the elements sorbed by the silica gel were eluted with 2.0 M of HCl and determined by GFAAS. At optimum conditions, the recovery of Cu, Cd and Cr were 96-98%. Detection limits (3delta) were 6.6, 7.5 and 6.0 micro g L(-1) for Cu, Cd and Cr, respectively. The elements could be concentrated by drawing and discharging several portions of sample successively but eluting only once. Cu, Cd and Cr added to a seawater sample were quantitatively recovered (>95%) in the range of the 95% confidence level. The method proposed in this paper was compared with a column technique. Optimum experimental conditions, reproducibility, precision and recoveries of both techniques are the same, but the syringe technique is much faster, easier and more practical than the column technique. It is a portable system and allows one to make the sorption process in the source of sample. In addition, the risk of contamination is less than in the column technique.     

Borate adsorption at Pt(111) in acidic medium

The adsorption/desorption process of borate was studied at Pt(111) in acidic solution by cyclic voltammetry. A so-called butterfly wave in the cyclic voltammogram of Pt(111) in HClO₄ shifted to negative direction upon the addition of boric acid with the disappearance of its sharp spikes. The shift in potential was found to be −57 mV with a tenfold increase of boric acid concentration. This illustrates that this anomalous wave is due to borate adsorption/desorption by a one-electron transfer process. The borate adsorption/desorption wave was observed to shift by −63 mV/pH. At pH>3, the anomalous wave splits forming two separate waves, depending on the pH and the scan rate. The appearance of two waves is assigned to the change in the adsorption mode of borate or the participation of OH in the adsorption process.     

Coordination of solvent molecules to VO(acac)<Subscript>2</Subscript> complexes in solution studied by hyperfine sublevel correlation spectroscopy and pulsed electron nuclear double resonance

Interactions and binding sites of the solvent molecules chloroform and ethanol to bis(acetylacetonate)oxovanadium(IV) (VO(acac)₂) complexes in (frozen) solutions have been investigated by pulsed electron nuclear double resonance, sum peak electron spin echo envelope modulation and hyperfine sublevel correlation spectroscopy. The experimental proton hyperfine coupling data of coordinating solvent molecules have been interpreted using quantum chemical calculations (density functional theory). Experimental and computed hyperfine couplings indicate that ethanol coordinates to vanadium in the equatorial plane of VO(acac)₂ and chloroform interacts via hydrogen bonding to oxygens of the acac ligands.     

Orientation control of perovskite thin films on glass substrates by the application of a seed layer prepared from oxide nanosheets

Orientation control of perovskite compounds was investigated by the application of a seed layer prepared from oxide nanosheets. An aqueous suspension of oxide nanosheets was prepared by the exfoliation of a layered compound of KCa₂Nb₃O₁₀ oxide grains. A seed layer composed of (TBA)Ca₂Nb₃O₁₀ nanosheets (TBA = tetrabutylammonium) was formed on a glass substrate by simply dip coating it in the suspension. Two kinds of perovskite compounds, LaNiO₃ (LNO) and Pb(Zr,Ti)O₃ (PZT) with a preferred orientation of (00l) were successfully grown on this seeded glass substrate. In this study, the relation between lattice mismatch and electrical properties is investigated. A large, oriented PZT film with a size of 5 ×4 cm shows an improved P-E hysteresis behavior by use of this orientation control.     

Safety Stock Determination with Serially Correlated Demand in a Periodic-Review Inventory System

We consider a periodic-review inventory replenishment model with an order-up-to-R operating doctrine for the case of deterministic lead times and a covariance-stationary stochastic demand process. A method is derived for setting the inventory safety stock to achieve an exact desired stockout probability when the autocovariance function for Gaussian demand is known. Because the method does not require that parametric time-series models be fit to the data, it is easily implemented in practice. Moreover, the method is shown to be asymptotically valid when the autocovariance function of demand is estimated from historical data. The effects on the stockout rate of various levels of autocorrelated demand are demonstrated for situations in which autocorrelation in demand goes undetected or is ignored by the inventory manager. Similarly, the changes to the required level of safety stock are demonstrated for varying levels of autocorrelation.     

Optimal Control of an <Emphasis Type="Italic">M/E</Emphasis><Subscript><Emphasis Type="Italic">k</Emphasis></Subscript>/1 Queueing System with a Removable Service Station

This paper studies the optimal operation of an M/E _k /1 queueing system with a removable service station under steady-state conditions. Analytic closed-form solutions of the controllable M/E _k /1 queueing system are derived. This is a generalization of the controllable M/M/1, the ordinary M/E _k /1, and the ordinary M/M/1 queueing systems in the literature. We prove that the probability that the service station is busy in the steady-state is equal to the traffic intensity. Following the construction of the expected cost function per unit time, we determine the optimal operating policy at minimum cost.     

An Algorithm for the Economic Design of <Emphasis Type="Italic">np</Emphasis> Charts for a Multiplicity of Assignable Causes

Chiu, in 1976, studied the economic design of np charts for processes subject to a multiplicity of assignable causes. Chiu developed a two-step minimization procedure to obtain the three control variables, namely, the sampling interval, the sample size and the acceptance number. Although Chiu's two-step minimization procedure is simple, applicable and down to earth, it is rather inefficient and has some drawbacks. This paper presents an algorithm to overcome these drawbacks. The results and the execution times of all numerical examples show that the accuracy and the efficiency of the algorithm is reasonably good.     

A Heuristic Decomposition Algorithm for Scheduling Problems on Mixed Graphs

We consider a scheduling problem where a set of n jobs has to be processed on a set of m machines and arbitrary precedence constraints between operations are given. Moreover, for any two operations i and j values a _ij >0 and a _ji >0 may be given where a _ij is the minimal difference between the starting times of operations i and j when operation i is processed first. Often, the objective is to minimize the makespan but we consider also arbitrary regular criteria. Even the special cases of the classical job shop problem J//C_max belong to the set of NP-hard problems. Therefore, approximation or heuristic algorithms are necessary to handle large-dimension problems. Based on the mixed graph model we give a heuristic decomposition algorithm for such a problem, i.e. the initial problem is partitioned into subproblems that can be solved exactly or approximately with a small error bound. These subproblems are obtained by a relaxation of a subset of the set of undirected edges of the mixed graph. The subproblems are successively solved and a proportion of the results obtained for one subproblem is kept for further subproblem definitions. Numerical results of the algorithm presented here are given.     

Availability Analysis of Repairable <Emphasis Type="Italic">N</Emphasis>-Server <Emphasis Type="Italic">n</Emphasis><Subscript><Emphasis Type="Italic">i</Emphasis></Subscript>-Replicated Systems

We develop an exact closed-form expression for the steady-state availability of a repairable, N-server system in which the ith server contains n _i identical, reconfigurable, breakdown-prone units. Our approach, which follows from the Markov chain balance equations and the recursive properties of Hessenberg matrix determinants, is simpler than previously proposed matrix geometric approaches, and can readily be adapted to the availability analysis of more complicated structures. We illustrate this by computing the steady-state availability of a mixed parallel-serial gracefully degrading replicated system.