Home About us Contact
|
Home About us Contact | ||
|
|
||
Rate Process (rate + process)
Selected AbstractsA Determination of Hydration Mechanisms for Tricalcium Silicate Using a Kinetic Cellular Automaton ModelJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 7 2008Jeffrey W. Bullard Reaction mechanisms for the early stages of hydration of tricalcium silicate (Ca3SiO5) have not been agreed upon, although theories have appeared in the literature. In this paper, a mechanistic description is proposed that is consistent with a wide range of reported experimental observations, and which is supported quantitatively by simulations using HydratiCA, a new three-dimensional microstructure model of chemical kinetics. Rate processes are quantitatively modeled using probabilistic cellular automaton algorithms that are based on the principles of transition state theory. The model can test alternate assumptions about the reaction paths and rate-controlling steps, making it a kind of experimental tool for investigating kinetics and interpreting experimental observations. It is used here to show that hydration of Ca3SiO5 is most likely controlled by nucleation and growth of a compositionally variable calcium silicate hydrate solid, mediated at very early times by a transient, thermodynamically metastable solid that rapidly covers and sharply reduces the dissolution rate of Ca3SiO5. This proposed mechanism involves important elements of two leading theories of Ca3SiO5 hydration, neither of which alone has been able to capture the full range of experimental data when tested by the model. [source] Analytical Model for Removal of a Uniformly Distributed Single-Component NAPL Under Nonequilibrium ConditionsGROUND WATER MONITORING & REMEDIATION, Issue 3 2001H.J.H. Brouwers In this paper a simple analytical model is presented for the one-dimensional transport equation describing the removal of a uniformly distributed, single-component NAPL under nonequilibrium conditions. Both advective and dispersive transport are included in the model. The model describes two distinct stages: a solution for the time the amount of NAPL declines but the length of the NAPL-containing region remains constant, and a solution from the moment the front, behind which all NAPL is depleted, starts to move. The model is valid for both dissolution (i.e., by water) or volatilization (i.e., by air). Dissolution (or volatilization) is considered a firstorder rate process with a constant mass-transfer rate coefficient. As expected, the model approaches the solution for equilibrium conditions if the mass-transfer coefficient tends to infinity. Even though the model is based on some rigorous assumptions, the simplicity of the model makes it useful for obtaining an initial mass-transfer rate coefficient from experimental data, which can be used to estimate the time required to dissolve all NAPL, as shown for two data sets taken from the literature. [source] Mechanism of interaction of DNA bases with dichloro-[1-alkyl-2-(naphthylazo)imidazole]palladium(II) complexes: A cytosine caseINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2009Pradip Kumar Ghosh Interaction of cytosine (C) with dichloro-[1-alkyl-2-(,-naphthylazo)imidazole]-palladium(II) [Pd(,-NaiR)Cl2, 1] and dichloro-[1-alkyl-2-(,-naphthylazo)imidazole]-palladium(II) [Pd(,-NaiR)Cl2, 2] complexes {where alkyl R = Me (a), Et (b) or Bz (c)} in acetonitrile (MeCN)-water (50% v/v) medium to yield [{1-alkyl-2-(,-naphthylazo)-imidazole}bis(cytosine)]palladium(II)dichloride (3a, 3b, 3c) and [{1-alkyl-2-(,-naphthylazo)-imidazole}bis(cytosine)]palladium(II)dichloride (4a, 4b, 4c) was studied. The products were characterized by microanalytical data and spectroscopic techniques (FT-IR, UV,vis, and NMR). The reaction kinetics show first-order dependence of the rate on each of the concentration of Pd(II) complex and C. External addition of Cl, ion (LiCl) did not influence this nucleophilic substitution rate process and has proved the cleavage of first PdCl bond is the rate-determining step. Thermodynamic parameters standard enthalpy of activation (,,Ho) and standard entropy of activation (,,So) were determined from variable temperature kinetic studies. The negative values of ,,So indicate that the reaction proceeds through an associative inner sphere mechanism. The magnitude of the second-order rate constant k2 increases in the following order: Pd(NaiEt)Cl2 (b) < Pd(NaiMe)Cl2 (a) < Pd(NaiBz)Cl2 (c) as well as Pd(,-NaiR)Cl2 (1) < Pd(,-NaiR)Cl2 (2), which corroborates with the experimental ,,Ho values. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 463,472, 2009 [source] International real interest rate differentials, purchasing power parity and the behaviour of real exchange rates: the resolution of a conundrumINTERNATIONAL JOURNAL OF FINANCE & ECONOMICS, Issue 1 2004Mark P. Taylor Abstract According to one strand of the international finance literature, market efficiency implies that the real exchange rate follows a martingale process, in direct conflict with the long-run absolute purchasing power parity hypothesis, which requires a stationary real exchange rate process. This conflict between market efficiency and long-run PPP appears as something of a conundrum. We resolve this conundrum by relaxing the assumption of a constant real interest rate differential and analysing the vector equilibrium correction system linking prices and the exchange rate, and draw out the economic intuition of our result. Copyright © 2004 John Wiley & Sons, Ltd. [source] Substituent effects in solvolysis of 1,1-diphenylethyl p -nitrobenzoates.JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 8 2002Symmetrically disubstituted, monosubstituted systems Abstract The rates of solvolysis of 1,1-diarylethyl p -nitrobenzoates and chlorides were determined conductimetrically at 25,°C in 80% (v/v) aqueous acetone. Applying the Yukawa,Tsuno (Y,T) equation, the symmetrical (X,=,Y) subseries gave a precise additivity relationship for the whole substituent range with a ,sym value of ,3.78 and an rsym value of 0.77. While any Y subsets gave statistically less reliable Y,T correlations, the apparent , value changed significantly depending on the fixed Y substituents; the , value decreases with the more electron-donating fixed substituents Y, which is compatible with the Hammond shift of the transition state coordinate. Nevertheless, the concave correlations of the More O'Ferrall non-linearity relationship for any Y subsets are not in line with what is expected from the reactivity,selectivity relationship suggesting an anti-Hammond shift of transition state. However, we found a precise extended Brønsted relationship between the pK values of 1,1-diarylethylenes and solvolysis rate process with a constant slope of ,,=,1.03,±,0.03. This is direct evidence indicating that there is no significant shift of the transition-state coordinate over the whole range of substituent change. Copyright © 2002 John Wiley & Sons, Ltd. [source] PORTFOLIO OPTIMIZATION WITH DOWNSIDE CONSTRAINTSMATHEMATICAL FINANCE, Issue 2 2006Peter Lakner We consider the portfolio optimization problem for an investor whose consumption rate process and terminal wealth are subject to downside constraints. In the standard financial market model that consists of d risky assets and one riskless asset, we assume that the riskless asset earns a constant instantaneous rate of interest, r > 0, and that the risky assets are geometric Brownian motions. The optimal portfolio policy for a wide scale of utility functions is derived explicitly. The gradient operator and the Clark,Ocone formula in Malliavin calculus are used in the derivation of this policy. We show how Malliavin calculus approach can help us get around certain difficulties that arise in using the classical "delta hedging" approach. [source] On the Existence of Finite-Dimensional Realizations for Nonlinear Forward Rate ModelsMATHEMATICAL FINANCE, Issue 2 2001Tomas Björk We consider interest rate models of the Heath,Jarrow,Morton type, where the forward rates are driven by a multidimensional Wiener process, and where the volatility is allowed to be an arbitrary smooth functional of the present forward rate curve. Using ideas from differential geometry as well as from systems and control theory, we investigate when the forward rate process can be realized by a finite-dimensional Markovian state space model, and we give general necessary and sufficient conditions, in terms of the volatility structure, for the existence of a finite-dimensional realization. A number of concrete applications are given, and all previously known realization results (as far as existence is concerned) for Wiener driven models are included and extended. As a special case we give a general and easily applicable necessary and sufficient condition for when the induced short rate is a Markov process. In particular we give a short proof of a result by Jeffrey showing that the only forward rate models with short rate dependent volatility structures which generically possess a short rate realization are the affine ones. These models are thus the only generic short rate models from a forward rate point of view. [source] A two-mean reverting-factor model of the term structure of interest ratesTHE JOURNAL OF FUTURES MARKETS, Issue 11 2003Manuel Moreno This article presents a two-factor model of the term structure of interest rates. It is assumed that default-free discount bond prices are determined by the time to maturity and two factors, the long-term interest rate, and the spread (i.e., the difference) between the short-term (instantaneous) risk-free rate of interest and the long-term rate. Assuming that both factors follow a joint Ornstein-Uhlenbeck process, a general bond pricing equation is derived. Closed-form expressions for prices of bonds and interest rate derivatives are obtained. The analytical formula for derivatives is applied to price European options on discount bonds and more complex types of options. Finally, empirical evidence of the model's performance in comparison with an alternative two-factor (Vasicek-CIR) model is presented. The findings show that both models exhibit a similar behavior for the shortest maturities. However, importantly, the results demonstrate that modeling the volatility in the long-term rate process can help to fit the observed data, and can improve the prediction of the future movements in medium- and long-term interest rates. So it is not so clear which is the best model to be used. © 2003 Wiley Periodicals, Inc. Jrl Fut Mark 23: 1075,1105, 2003 [source] Mechanism of oxidation of alanine by chloroaurate(III) complexes in acid medium: Kinetics of the rate processesINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2009Pratik K. Sen The kinetics of the oxidation of alanine by chloroaurate(III) complexes in acetate buffer medium has been investigated. The major oxidation product of alanine has been identified as acetaldehyde by 1H NMR spectroscopy. Under the experimental conditions, AuCl and AuCl3(OH), are the effective oxidizing species of gold(III). The reaction is first order with respect to Au(III) as well as alanine. The effects of H+ and Cl, on the second-order rate constant k2, have been analyzed, and accordingly the rate law has been deduced: k2, = (k1[H+][Cl,] + k3K4K5)/(K4K5 + [H+][Cl,]). Increasing dielectric constant of the medium has an accelerating effect on the reaction rate. Activation parameters associated with the overall reaction have been calculated. A mechanism involving the two effective oxidizing species of gold(III) and zwitterionic species of alanine, consistent with the rate law, has been proposed. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 41: 473,482, 2009 [source] Tracer studies of high-shear granulation: II.AICHE JOURNAL, Issue 9 2001Population balance modeling A population balance framework developed describes the tracer studies in Part I. A two internal coordinate population balance equation (PBE) links the evolution with time of granule-size and tracer-mass distributions to underlying rate processes. A new analytical PBE was developed for the tracer distribution and novel numerical techniques, including a new discretized population balance equation for breakage or grinding. Also developed is a general differential technique for extracting rate constants from measurements of particle-size distributions. Granulation in a high-shear mixer proceeds after nucleation, not studied here, with very high initial breakage rates but a relatively unchanging aggregation rate constant. The breakage function is bimodal on a mass basis and the selection rate decays exponentially over about 20 s. A heterogeneous strength hypothesis was used to account for this time dependence. Aggregation rates are the highest for interactions between small and large granules and may be quantitatively given by the Equipartition of kinetic energy kernel developed from the theory of collisions between gas molecules. The model can describe granule-size and tracer-mass distributions simultaneously with great accuracy. The need to replace time as a driving force variable in the kinetics for these systems is identified. [source] How to design perforated polymeric films for modified atmosphere packs (MAP)PACKAGING TECHNOLOGY AND SCIENCE, Issue 6 2001Luciano ZanderighiArticle first published online: 12 APR 200 Abstract Increasing proportions of fresh produce are being sold in modified atmosphere packs (MAP) with the aim of preserving product quality longer and reducing freight costs. A rigorous theoretical analysis was made of the transport phenomena across packaging film (composite, perforated, etc.) in order to find out whether polymeric film will permit a stationary modified atmosphere (MA) inside the pack, and if so when, and to investigate the effect of the size and shape of the holes in the perforated film. The continuity equations of the pack, for all diffusing species, were written and solved for stationary conditions, with the boundary conditions that species not involved in metabolic processes do not diffuse across polymeric film. After a detailed analysis of the transport phenomena across both continuous and perforated film, and of the metabolic rate processes, it transpires that no stationary conditions compatible with any MA can be found for continuous film, owing to the permeation characteristics of the film and the rate of the metabolic processes. With perforated film it is possible to find, at least for certain metabolic process rates, a stationary state where a constant MA is maintained inside the pack. A proposal is given, provided the rate of the metabolic process is known, for the design of a pack in terms of polymeric materials and of the pinhole size. Two case studies, strawberry and cabbage, are presented and discussed, along with the optimization of the polymeric film and the size and length of the pinholes of the packs. Another point raised deals with the advantages of using perforated film and/or of making holes or openings along the edges where the polymeric film is welded. Copyright © 2001 John Wiley & Sons, Ltd. [source] Fingerprints of Damped Quantum Rotation Observed in Solid-State Proton NMR SpectraCHEMPHYSCHEM, Issue 4 2006Peter Gutsche Dr. Abstract 1H NMR spectra of the methyl group in an oriented crystal sample of methylmalonic acid with all three non-methyl protons replaced by deuterons are interpreted in terms of the damped quantum rotation (DQR) theory of NMR line shapes. The DQR approach offers a perfect theoretical reproduction of the observed spectra while the conventional Alexander-Binsch line-shape model shows evident defects in the present case. The temperature trends of the quantities characterizing the coherent and incoherent dynamics of the methyl group in the DQR approach (the effective tunnelling frequency and two coherence-damping rates) derived from the spectra are fairly reproduced using a model reported previously. The present findings provide further evidence of limitations to the validity of the common belief that molecular rate processes in condensed phases are necessarily classical. [source] | ||||||||||||||||