Kinetics of two-step anionic polymerization

This article deals with the kinetics of two-step anionic polymerization by way of a non-steady state method. Several molecular parameters can be evaluated using the formulae developed. A bimodal molecular weight distribution function for the resulting polymer is derived from the set of kinetic differential equations, which is in agreement with the experimental data reported.     

Ring‐opening polymerization of D,L‐lactide by rare earth 2,6‐dimethylaryloxide

Ring‐opening polymerization of D,L ‐lactide (LA) has been successfully carried out by using rare earth 2,6‐dimethylaryloxide (Ln(ODMP)₃) as single component catalyst or initiator for the first time. The effects of different rare earth elements, solvents, monomers and catalyst concentration as well as polymerization temperature and time on the polymerization were investigated. The results show that La(ODMP)₃ exhibits higher activity to prepare poly(D,L ‐lactide) (PLA) with a viscosity molecular weight of 4.5 × 10⁴ g mol^?1 and the conversion of 97 % at 100 °C in 45 min. The catalytic activity of Ln(ODMP)₃ has following sequence: La > Nd > Sm > Gd > Er > Y. A kinetic study has indicated that the polymerization is first order with respect to both monomer and catalyst concentration. The apparent activation energy of the polymerization of LA with La(ODMP)₃ is 69.6 kJ mol^?1. The analyses of polymer ends indicate that the LA polymerization proceeds according to ‘coordination–insertion’ mechanism with selective cleavage of the acyl–oxygen bond of the monomer. Copyright © 2004 Society of Chemical Industry     

重馏分油加氢脱氮反应动力学模型的研究

简要地介绍了一些典型的模型氮化物的ＨＤＮ反应规律。根据胜利ＶＧＯ在３７２２Ｂ催化剂上的大量ＨＤＮ实验数据，提出了如下的ＨＤＮ基本反应动力学方程：ｄＣＮｄｔ＝－ｋ１＋Ｋ＊ＣＮＣＮＰＨ２为了扩大上式的应用范围，详细分析了各种因素（如原料油种类和馏程及Ｈ２Ｓ等）对ＨＤＮ的影响，并开发了相应的经验关联式，从而得到了一个较完整的馏分油ＨＤＮ反应动力学模型。验证实验表明，该模型是成功的。     

Kinetic model for water/oil absorption of mesquite gum (Prosopis juliflora) and gum arabic (Acacia senegal)

The water and oil uptake of mesquite and arabic gums in powdered form was studied at temperatures of 23, 35 and 45°C. A previously proposed equation to predict osmotic equilibrium was tested using the experimental data with both gums and a good statistical fit was obtained. Mesquite gum showed the highest water and oil absorption at all temperatures studied. Temperature dependence of the reciprocal of the S₁ and WL_∞ were determined using an Arrhenius equation. The activation energy for water and oil absorption for gum arabic was 21.98 and 39.57 kJ mol⁻¹, compared to that of mesquite gum having values of 15.79 and 46.16 kJ mol⁻¹, respectively. A second order kinetic model was obtained for water and oil absorption for both gums.     

Development and simulation studies of an unsteady state biofilter model for the treatment of cyclic air emissions of an α‐pinene gas stream

This paper describes the development and simulation of an unsteady state biofilter model used to predict dynamic behaviour of cyclically‐operated biofilters and compares it with experimental results obtained from three, parallel, bench‐scale biofilters treating both periodically fluctuating concentrations and constant concentrations of an α‐pinene‐laden gas stream. The dynamic model, using kinetic parameters estimated from the constant concentration biofilter, was able to predict the performance of cyclic biofilters operating at short cycle periods (ie, in the order of minutes and hours). Steady state kinetic data from a constant concentration biofilter can be used to predict unsteady state biofilter operation. At a 24 h cycle period, the dynamic model compared well with experimental results. For long cycle periods (ie, hours and days), removal efficiency decreased after periods of non‐loading: the longer the period of non‐loading, the poorer the biofilter's performance at the re‐commencement of pollutant loading. At longer time scales the model did not effectively predict transient behaviour, as adsorption and changes in kinetic parameters were not accounted for. Modelling results showed that similar biofiltration performance for the cyclic and constant concentration biofiltration of α‐pinene is expected for biofilters operating solely in the first order kinetics regime. Poorer performance for cyclic biofilters following Monod kinetics spanning the entire kinetics range is expected as the cycle amplitude increases. The most important parameters affecting the performance of a cyclically‐operated biofilter with short cycle periods are: amplitude of cyclic fluctuations, C_{g, max}/C_g, relative value of the half‐saturation constant in the Monod expression, K_s, and effective diffusivity of α‐pinene in the biofilm, D_e. Copyright © 2005 Society of Chemical Industry     

Mass transfer kinetics of neodymium(III) extraction by calix[4]arene carboxylic acid using a constant interfacial area cell with laminar flow

BACKGROUND: Thermodynamics and kinetics data are both important to explain the extraction property. In order to develop a novel separation technology superior to current extraction systems, many promising extractants have been developed including calixarene carboxylic acids. The extraction thermodynamics behavior of calix[4]arene carboxylic acids has been reported extensively. In this study, the mass transfer kinetics of neodymium(III) and the interfacial behavior of calix[4]arene carboxylic acid were investigated. RESULTS: The rate constant (K_ao) becomes constant when the stirring speed was controlled between 250 rpm and 400 rpm. The activation energy (E_a) was calculated to be 21·41 kJ mol^?1 or 88·17 kJ mol^?1 (dependent on temperature) from the slope of log K_ao against 1000/T. The linear relationship between the specific area and the extraction rate is the characteristic of an interfacial reaction control. The minimum bulk concentration of the extractant necessary to saturate the interface (C_min) is lower than 4·19 × 10^?4 mol L^?1. CONCLUSION: The effect of stirring speed, temperature, and species concentration on the extraction rate demonstrates that the extraction regime depends on the extraction conditions. The chemical reaction control governs the extraction regime at temperatures below 303 K and a mixed control regime occurs when the temperature is between 303 K and 318 K. The probable locale for the chemical reaction is at the liquid–liquid interface and the rate equation is deduced to be: ? d[Nd³⁺]_(a)/dt = k_f[Nd³⁺]_(a)[H₄A]_(o)^0·727[H⁺]_(a)^?0·978. The rate‐controlling step was suggested by the analysis of the experimental results. Copyright © 2008 Society of Chemical Industry     

Identification and modelling of aerobic hydrolysis – application of optimal experimental design

Hydrolysis mechanism plays a dominant role in the delicate balance of electron donor/electron acceptor ratios in BNR and EBPR systems as an important carbon source. In this study, the surface‐saturation‐type hydrolysis kinetics was investigated based on respirometric measurements, within the context of the theoretical and the practical identifiability of mathematical models. The identifiable parameters of a selected model were derived from respirograms. In addition, the information from the experiments was evaluated on the basis of Optimal Experimental Design (OED) methodology for different initial conditions of the batch respirometric experiment. © 2003 Society of Chemical Industry     

Non-steady-state model for kinetics of free radical polymerization, 4. Direct thermal initiation

This paper deals with the non-steady-state kinetics of direct thermal initiated polymerization. The initiation is assumed to be a bimolecular reaction of the monomer. The relationship between the radical concentration and the monomer conversion is rigorously derived. In further treatment a few very close approximations are introduced based on the fact that the number of monomer molecules reacting in the initiation step is much less than that consumed in the propagation step for a process producing high polymer, and the value of the rate constant for propagation or chain transfer is much lower than that for chain termination. Expressions for various molecular parameters, such as molecular weight distribution, number-average and weight-average degrees of polymerization, and dispersity, are given. Several numerical examples are provided.     

Significance of fluid regime in biological filtration

A dispersed flow model previously developed to study substrate utilization in unsaturated media was experimentally verified and its practical application was considered. For this purpose, measurements were made using tap water and a synthetic feed solution. The importance of the change in fluid regime as regards to the simultaneous transport and reaction within biological filters were demonstrated. The effect of drop formation and the breakage of liquid jets inside the filters on substrate utilization was also shown.