bluuebunny/crossref_metadata_2025_split huggingface dataset:
A new approach to response surface development for detailed gas‐phase and surface reaction kinetic model optimization
Authors: Davis Scott G. , Mhadeshwar Ashish B. , Vlachos Dionisios G. , Wang Hai 
Published: December 2003

AbstractWe propose a new method for constructing kinetic response surfaces used in the development and optimization of gas‐phase and surface reaction kinetic models. The method, termed as the sensitivity analysis based (SAB) method, is based on a multivariate Taylor expansion of model response with respect to model parameters, neglecting terms higher than the second order. The expansion coefficients are obtained by a first‐order local sensitivity analysis. Tests are made for gas‐phase combustion reaction models. The results show that the response surface obtained with the SAB method is as accurate as the factorial design method traditionally used in reaction model optimization. The SAB method, however, presents significant computational savings compared to factorial design. The effect of including the partial and full third order terms was also examined and discussed. The SAB method is applied to optimization of a relatively complex surface reaction mechanism where large uncertainty in rate parameters exists. The example chosen is laser‐induced fluorescence signal of OH desorption from a platinum foil in the water/oxygen reaction at low pressures. We introduce an iterative solution mapping and optimization approach for improved accuracy. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 94–106, 2004
Characterizing complex reaction mechanisms using machine learning clustering techniques
Authors: Blurock Edward S. 
Published: December 2003

AbstractA machine learning conceptual clustering method applied to reaction mechanisms provides an automatic and, hence, unbiased means to differentiate between reactive phases within a total reactive process. Similar reactive phases were defined by means of local reaction sensitivity values. The method was applied to the Hochgreb and Dryer aldehyde combustion mechanism of 36 reactions. Three major time ranges were found and characterized: an initial phase of aldehyde reaction, an intermediate phase where only a small amount of aldehyde is left, and an end phase of reactions to final products. Further refinements of these phases into subtime intervals were found. All ranges found could be chemically justified. This method is meant as a supplement to existing methods of mechanism analysis and its main purpose is the automatic characterization of existing mechanisms and can potentially be used for mechanism reduction. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 107–118, 2004
Mechanistic disparity in the electron transfer reactions of thiosulfate with di‐μ‐oxo‐bis(1,4,8,11‐tetraazacyclotetradecane)‐dimanganese(III,IV) and di‐μ‐oxo‐bis(1,4,7,10‐tetraazacyclododecane)‐dimanganese(III,IV) complexes
Authors: Panja Anangamohan , Shaikh Nizamuddin , Banerjee Pradyot , Saha Basudeb 
Published: December 2003

AbstractA comparative kinetic study of the reactions of two mixed valence manganese(III,IV) complexes of macrocyclic ligands, [L1MnIV(O)2MnIIIL1], 1 (L1 = 1,4,8,11‐tetraazacyclotetradecane) and [L2MnIV(O)2MnIIIL2], 2 (L2 = 1,4,7,10‐tetraazacyclododecane) with thiosulfate has been carried out by spectrophotometry in aqueous buffer at 30°C. Reaction between complex 1 and thiosulfate follows a first‐order rate saturation kinetics. The pH dependency and kinetic evidences suggest the participation of two complex species of MnIII(μ‐O)2MnIV under the experimental conditions. Detailed kinetic study shows that reduction of 2 proceeds through an autocatalytic path where the intermediate (MnIII)2 species has been assumed to catalyze the reaction. The difference in the reaction mechanisms is ascribed to the difference in stability of the intermediate complex species, the evidence for which comes from the electrochemical behavior of the complexes and time dependent EPR spectroscopic measurements during the reduction of 2. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 119–128, 2004
A comparative kinetic study for the oxidation of 2‐mercaptoethanol by di‐μ‐oxo‐bis(1,4,7,10‐tetraazacyclododecane)‐dimanganese(III,IV) and di‐μ‐oxo‐bis(1,4,8,11‐tetraazacyclotetradecane)‐dimanganese(III,IV) complexes: Influence of copper(II)
Authors: Goswami Sanchita , Shaikh Nizamuddin , Panja Anangamohan , Banerjee Pradyot 
Published: December 2003

AbstractA comparative kinetic study of the reactions of two mixed valence manganese(III,IV) complexes with macrocyclic ligands, [L1MnIV(O)2MnIIIL1], 1 (L1 = 1,4,7,10‐tetraazacyclododecane) and [L2MnIV(O)2MnIIIL2], 2 (L2 = 1,4,8,11‐tetraazacyclotetradecane) with 2‐mercaptoethanol (RSH) has been carried out by spectrophotometry in aqueous buffer at (30 ± 0.1)°C. Rate of the reactions between the oxidants and the reductant was found to be negligibly slow with no systematic dependence on either redox partners. Externally added copper(II) (usually 5 × 10−7 mol dm−3), however, increases the rate of the reduction of 1 and 2 significantly. In the presence of catalytic amount of copper(II), the rate of the reaction is nearly proportional to [RSH] at lower concentration of the reductant but follows a saturation kinetics at higher concentration of the latter for the reaction between 1 and the thiol. Reaction rate was found to be strongly influenced by the variation of acidity of the medium and the observed kinetics suggests that the two reductant species ([Cu(RSH)]2+ and [Cu(RS)]+) are significant for the reaction between 1 and the thiol. The dependence of the rate on [RSH] for the reduction of 2 by the thiol was complex and rationalized considering two equilibria involving the catalyst (Cu2+) and the reductant. The pH rate profile suggests that both the μ‐O protonated [MnIII(O)(OH)MnIV] and the deprotonated [MnIII(O)2MnIV] forms of the oxidant 2 become important. The kinetic results presented in this study indicate the domination of outer‐sphere path. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 129–137, 2004
Parametric sensitivities for optimal control problems using automatic differentiation
Authors: Griesse Roland , Walther Andrea 
Published: December 2003

AbstractThis article presents a new area of application for Automatic Differentiation (AD): Computing parametric sensitivities for optimization problems. For an optimization problem containing parameters which are not among the optimization variables, the term parametric sensitivity refers to the derivative of an optimal solution with respect to the parameters. We treat non‐linear finite‐ and infinite‐dimensional optimization problems, in particular optimal control problems involving ordinary differential equations with control and state constraints, and compute their parametric sensitivities using AD. Particular attention is given to the generation of second‐order derivatives required in the process. Copyright © 2003 John Wiley & Sons, Ltd.
Four inventory models for deteriorating items with time varying demand and partial backlogging: A cost comparison
Authors: Skouri K. , Papachristos S. 
Published: December 2003

AbstractIn this paper we present four inventory control models under the following assumptions. Planning horizon is finite and demand is a general logconcave function of time. The models allow for deterioration of items over time and shortages partially backlogged at an exponential rate. For each of the models we establish the existence of a unique optimal policy. We then compute their optimal costs and rank them according to cost performance. This ranking indicates that model four gives the lowest cost. Numerical examples are given to support the theoretical findings and explain the application of procedures. Copyright © 2003 John Wiley & Sons, Ltd.
Application of LQ modelling and optimization in urban traffic control
Authors: Selekwa Majura F. , Mussa Renatus N. , Chiteshe Able 
Published: December 2003

AbstractThe increasing congestion on urban streets demands traffic control signal timing to be well co‐ordinated and optimized even during the transition between timing patterns used in different periods of time‐of‐day (TOD). The TOD timing plans, defined by fixed‐time co‐ordination parameters, need to change from one TOD period to another. The current methods used in transitioning are aimed at achieving quick transition rather than optimizing traffic flow during the transition period. As a result, they generally cause increased vehicle delays during the transition period particularly for vehicles on the minor street, which face lengthened red times.This paper proposes a quadratic optimization method that can be used to reduce disutility measures to motorists during the transition period. The transition is modeled as a linear dynamic process, and the disutility measures are modeled as the sum of squares of the deviations of the co‐ordination parameters—that is, cycle length, phase split, and offset—from the optimal values during the transition. A linear quadratic (LQ) optimization technique of optimal control is used to determine the step size and the number of steps necessary to complete the transition with minimum disutility. The proposed transition period optimization method has the advantage that the user need not specify minimum and maximum cycle length to achieve optimization, as is the case with current methods.Simulation results for three co‐ordinated intersections showed that the proposed method reduces total vehicle delay when compared to the ‘immediate’ transition method embedded in CORSIM traffic simulation software. This is due to the fact that vehicles on the minor street approaches get proportional green time without significantly affecting green times on the major street approach green phase. However, the method showed a slight increase in total delay for vehicles on the major street. Copyright © 2003 John Wiley & Sons, Ltd.
The discovery and progress of MgCl2‐supported TiCl4 catalysts
Authors: Kashiwa Norio 
Published: December 2003

AbstractPolyolefins represented by polyethylene (PE) and polypropylene (PP) are indispensable materials in our daily lives. TiCl3 catalysts, established by Ziegler and Natta in the 1950s, led to the births of the polyolefin industries. However, the activities and stereospecificities of the TiCl3 catalysts were so low that steps for removing catalyst residues and low stereoregular PP were needed in the production of PE and PP. Our discovery of MgCl2‐supported TiCl4 catalysts led to more than 100 times higher activities and extremely high stereospecificities, which enabled us to dispense with the steps for the removals, meaning the process innovation. Furthermore, they narrowed the molecular weight and composition distributions of PE and PP, enabling us to control the polymer structures precisely and create such new products as very low density PE or heat‐sealable film at low temperature. The typical example of the product innovations by the combination of the high stereospecificity and the narrowed composition distribution is high‐performance impact copolymer used for an automobile bumper that used to be made of metal. These process and product innovations established these polyolefin industries. The latest MgCl2‐supported TiCl4 catalyst is very close to perfect control of isotactic PP structure and is expected to bring about further innovations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1–8, 2004
Estimation of monomer reactivity ratios in free‐radical solution copolymerization of lauryl methacrylate–isobutyl methacrylate
Authors: Habibi A. , Vasheghani‐Farahani E. , Semsarzadeh M. A. , Sadaghiani K. 
Published: December 2003

AbstractCopolymers of isobutyl methacrylate (i‐BMA) and lauryl methacrylate (LMA) were prepared by free‐radical solution copolymerizations at 70 °C with azobisisobutyronitrile (AIBN) as an initiator. The synthesis of these copolymers was investigated over a wide composition range both at low and high conversion levels. Copolymer compositions were determined from the %C, %H, and %O contents of copolymer by elemental analysis. Monomer reactivity ratios were estimated by analyzing composition data with nonlinear least‐squares (NLLS) models based on Marquardt optimization and van Herk methods. The point estimates, 95% individual confidence intervals and 95% joint confidence intervals are obtained from differential and integral approaches. Even though no explicit integral form for penultimate unit model (PUM) is available, a numerical approach is developed for integral estimation of reactivity ratios from PUM. A simulator program was developed which upon coupling of experimental data, NLLS analysis, and D‐optimal criteria calculates the best optimized values of monomer reactivity ratios and monomer feed compositions in a sequential and iterative order for terminal and penultimate unit models. Moreover, the simulator has the capibilities to calculate all features of van Herk method, maximum compositional drift in each monomer feed composition, and data reconciliation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 112–129, 2004
Infrared and Raman spectroscopic investigation of crosslinked polystyrenes and radiation‐grafted films
Authors: Brack H.‐P. , Fischer D. , Peter G. , Slaski M. , Scherer G. G. 
Published: December 2003

AbstractThe crosslinking of functionalized polystyrene resins is often of critical importance in determining resin properties and performance in the application of these materials as membranes and supports. In this investigation model systems are developed for quantifying the infrared and Raman spectroscopic properties of copolymers based on poly(styrene‐co‐divinylbenzene). Analytical curves appropriate for the quantification of para‐ and metasubstituted species and pendant double bonds are reported, and corrections to previously reported spectroscopic assignments and analytical methods are made. The usefulness of these two analytical methods in characterizing radiation‐grafted films and commercial copolymers is compared, and typical characterization results are given. The relative concentrations of the species found in the grafted films are quite different from their concentrations in the grafting solution, and empirical relationships between the two are developed. In addition, the graft composition varies as a function of the base polymer film thickness and type and the penetration depth in the grafted film. Radiation‐grafted films are more highly crosslinked in their near surface regions, and thinner films are more extensively crosslinked. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 59–75, 2004
Atom transfer radical polymerization of methyl methacrylate via reversibly supported catalysts on silica gel via self‐assembly
Authors: Ding Shijie , Yang Jun , Radosz Maciej , Shen Youqing 
Published: December 2003

AbstractA reversible catalyst immobilization system via self‐assembly of hydrogen bonding between thymine anchored on silica gel support and 2,6‐diaminopyridine functionalized with a catalyst (copper bromide‐N,N,N′,N′‐tetraethyldiethylenetriamine (TEDETA) complex) was developed for the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). At elevated temperatures, the hydrogen bonding disassociated and released the catalyst as free small molecules for catalysis, which effectively mediated a living polymerization of MMA, producing PMMA with controlled molecular weight and narrow molecular weight distribution (<1.3). At room temperature, the catalyst assembled on the silica gel support by hydrogen bonding, and thus could be recovered and reused for a second run of ATRP. The recovered catalyst still mediated a living polymerization of MMA with reduced activity (54–64%), but had much improved control of the polymerization. The resulting PMMA had molecular weights very close to theoretical vales. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 22–30, 2004
Supramolecular poly(ether ketone)–polyisobutylene pseudo‐block copolymers
Authors: Binder Wolfgang H. , Kunz Michael J. , Ingolic Elisabeth 
Published: December 2003

AbstractThe association behavior of telechelic hydrogen‐bonded poly(ether ketone) (PEK) and polyisobutylene (PIB) polymers and the formation of a new class of pseudo‐block copolymers is reported. The attachment of complementing hydrogen bonds (thymine/2,6‐diaminotriazine and cytosine/2,6‐diaminotriazine) onto the respective PIB and PEK polymers leads to a dramatic increase in the miscibility between the normally immiscible PEK and PIB polymers. The structure formation in the liquid state was studied by dynamic NMR spectroscopy as well as in the solid state via solid‐state NMR‐spectroscopy, DSC, and TEM methods. The polymers form a nanophase structure with a periodicity of 70 nm with the microphase separation occurring specifically within the donor–acceptor pair with the higher binding constant (thymine/2,6‐diaminotriazine) and not within the weaker bonded cytosine/2,6‐diaminotriazine pair. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 162–172, 2004
Alumina as support for metallocene catalyst in ethylene polymerization
Authors: de Fátima V. Marques Maria , de Alcantara Moacir 
Published: December 2003

AbstractAluminas thermally and/or chemically treated were used as support for Cp2ZrCl2 and evaluated in ethylene polymerization at constant reaction conditions. Two different calcination temperatures were employed, and the metallocene was fixed either directly or after support pretreatment with MAO, TMA, or NaOH solutions. The obtained alumina‐supported catalysts showed activities comparable to the homogeneous precursor. It was noticed that the textural properties of the supports strongly influenced the catalyst performance. The direct fixation of the metallocene on alumina produced catalysts presenting lower activities in comparison to the ones obtained from the chemically treated supports. The chemical pretreatment of hydrated alumina with TMA originated catalysts whose activities were superior to those obtained by pretreatment with MAO. The pretreatment with NaOH produced the more active catalyst and generated branched polymer. The molecular weight of the PE produced by the supported catalysts was higher than the ones obtained with the homogeneous system. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 9–21, 2004
Controlled radical polymerization of 2‐hydroxyethyl methacrylate initiated by photofunctional 2‐(N,N‐diethyldithiocarbamyl)isobutyric acid
Authors: Ishizu Koji , Khan Ruhul A. , Ohta Yoshihiro , Furo Masahito 
Published: December 2003

AbstractWe demonstrated that density functional theory calculations provide a reliable and quantitative prediction of the trends in CS bond dissociation energies using several model compounds as photoinitiator. On the basis of this information, we designed a possible photofunctional initiator for the polymerization of hydrophilic vinyl monomers. Photopolymerization of 2‐hydroxyethyl methacrylate (HEMA) hydrophilic monomer was carried out in ethanol initiated by 2‐(N,N‐diethyldithiocarbamyl)isobutyric acid (DTCA) under UV irradiation. We performed the first‐order time‐conversion plots in this polymerization system, and the straight line in the semilogarithmic coordinates indicated first order in monomer. The molecular weight of the poly(2‐hydroxyethyl methacrylate) (PHEMA) increased with increasing conversion. The molecular weight distribution (Mw/Mn) of the PHEMA was about 1.5. Methyl methacrylate (MMA) could also be polymerized in a living fashion with such a PHEMA precursor as a macroinitiator because PHEMA exhibited a dithiocarbamate (DC) group at its terminal end. This system could be applied to the architecture of amphiphilic block copolymers. It was concluded that these polymerization systems proceeded with controlled radical mechanism. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 76–82, 2004
Two‐stage copolycondensation of preformed oligomers with bisphenols by tosyl chloride/dimethylformamide/pyridine from distributions of resulting oligomers determined by a combination of gel permeation chromatography and NMR
Authors: Higashi Fukuji , Sugishita Kanako 
Published: December 2003

AbstractA two‐stage co‐oligomerization of the oligomers initially formed from an equimolar mixture of isophthalic acid (IPA) and terephthalic acid (TPA) and 2,2‐bis(4‐hydroxyphenyl)propane (BPA, 50 mol %) with bisphenols (BPs, 20 mol %) was carried out using a tosyl chloride/dimethylformamide/pyridine condensing agent. The distributions of the resulting oligomers (nx‐mers), which were quenched with methanol, were determined by a combination of gel permeation chromatography (GPC) and NMR. These distributions (presented by molar percentage) were conveniently calculated with the equation nx (mol %) = nx (% mol by GPC) × n0 (mol % by NMR)/n0 (% mol by GPC), where nx (% mol) = nx (wt % by GPC)/its molecular weight. The results showed the distributions of the preformed IPA/TPA‐BPA oligomers to be in fairly good accord with those obtained directly from GPC and to be supported by the NMR results. The calculation was applied to the co‐oligomers prepared up to a reaction of 0.7, at which there was an increase in the number of higher oligomers indivisible by GPC and the distributions could no longer be determined by molar percentage. The calculated distributions are discussed in relation to the results of copolycondensation. The sequence distributions in the resulting co‐oligomers, which were also examined by NMR, are compared with those in the copolymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 44–51, 2004
Solid polymer electrolytes. VI. Microstructure of organic–inorganic hybrid networks composed of 3‐glycidoxypropyltrimethoxysilane and LiClO4 and affected by different synthetic routes
Authors: Liang Wuu‐Jyh , Kuo Ping‐Lin 
Published: December 2003

AbstractHybrid organic–inorganic materials derived from 3‐glycidoxypropyltrimethoxylsilane were prepared via two different synthetic routes: (1) the HCl‐catalyzed sol–gel approach of silane followed by the lithium perchlorate (LiClO4)/HCl‐catalyzed opening of epoxide and (2) the simultaneous gelation of tin/LiClO4‐catalyzed silane/epoxide groups. LiClO4 catalyzed the epoxide polymerization, and its effects on the structures of these hybrid materials were studied by NMR. The structure of the inorganic side was probed by solid‐state 29Si NMR spectroscopy, and the characterizations of the organic side and the chemical processes involved in the different synthetic routes were performed with solid‐state cross‐polarity/magic‐angle‐spinning 13C NMR. The different synthetic routes significantly affected the polymerization behaviors of the organic and inorganic sides in the presence of LiClO4. A larger amount of LiClO4 promoted the opening of epoxide and led to the formation of longer poly(ethylene oxide) chains via the HCl‐catalyzed sol–gel approach, whereas in the case of the tin‐catalyzed approach, the faster polymerization of the inorganic side hindered the growth of the organic network. The addition of LiClO4 was proven to be without crystalline salt present in the hybrid networks by wide‐angle X‐ray powder diffraction. Also, the interactions between the ions and hybrid host, examined with Fourier transform infrared and 7Li proton‐decoupled magic‐angle‐spinning NMR, further demonstrated that extensive ion aggregation existed in these hybrid materials. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 151–161, 2004