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Order Kinetics (order + kinetics)
Kinds of Order Kinetics Selected AbstractsComparison of biodegradation kinetic parameters for naphthalene in batch and sand column systems by pseudomonas putidaENVIRONMENTAL PROGRESS & SUSTAINABLE ENERGY, Issue 2 2001Jeong-Hun Park Kinetic parameters for the degradation of naphthalene by Pseudomonas putida ( ATCC 17484) were estimated in both batch and column assays, in order to evaluate the role of flow and cell attachment on biodegradation rates. Suspended cells and cells attached to Ottawa sand were used under a variety of biomass levels, column flow-rates, and substrate concentrations. In batch systems, degradation followed zero order kinetics across the entire concentration range, while the columns exhibited decreased rates at concentrations less than 100 (,g/L), describable by Michaelis-Menten kinetics. This is reflected in elevated values of the half-saturation constant, Ks, in columns. We offer the explanation that this may have resulted from reactive heterogeneity within the porous media, imposing a distribution of length-scales for transfer of substrate to the cell surfaces. Well-mixed batch systems are expected to have both shorter and more uniform transfer distances. When kinetic parameters obtained in batch system are used for prediction of degradation in columns, at least two factors,exposed reduction of exposed cell surface are a and heterogeneity of cell distribution,will likely reduce overall column degradation rates. [source] The effects of physiologically important nonmetallic ligands in the reactivity of metallothionein towards 5,5,-dithiobis(2-nitrobenzoic acid)FEBS JOURNAL, Issue 18 2001A new method for the determination of ligand interactions with metallothionein The reaction of Cd5Zn2 -metallothionein (MT) with 5,5,-dithiobis(2-nitrobenzoic acid) (Nbs2) has been studied at different reagent stoichiometries, pH and temperature conditions and in the presence of several ligands. At stoichiometries of Nbs2 to MT from 0.5 to 5, the reaction followed first order kinetics. The first order rate constants obtained were independent from the concentration of Nbs2 but were linearly dependent on the concentration of MT. At higher Nbs2/MT stoichiometries, the reaction deviates from first order kinetics and the observed rate constant increases. The reactivity of MT towards Nbs2 has been probed at 4 µm concentration of both reagents where the reaction is monophasic and is characterized by a linear Arrhenius plot (Ea = 45.8 ± 2.7 kJ·mol,1). It has been demonstrated that metal release at low pH or subtraction from MT by EDTA substantially increases the reactivity of MT towards Nbs2. At the same time, a number of nonmetallic ligands moderately accelerate the reaction of MT with Nbs2 and hyperbolic dose,response curves were obtained. The data have been interpreted with the binding of ligands to MT and following MT. Ligand binding constants were calculated as follows: ATP, K = 0.31 ± 0.06 mm; ADP, K = 0.26 ± 0.07 mm. Several compounds such as AMP, S -methylglutathione, and phosphate had no effect on the reaction, but Zn2+ ions showed an inhibitory effect at micromolar concentrations. [source] A closed-loop proposal for hydrogen generation using steel waste and a prototype solar concentratorINTERNATIONAL JOURNAL OF ENERGY RESEARCH, Issue 5 2009Abdul-Majeed Azad Abstract An economically viable and environmental-friendly method of generating PEM grade hydrogen has been proposed and is by the reaction of certain metals with steam, appropriately called ,metal,steam reforming',MSR. The drawbacks of conventional processes (hydrogen and carbothermic reduction schemes) are overcome by resorting to solution-based reduction schemes and are made economically feasible using iron oxides from steel industry's mill-scale waste. A novel aqueous-based room temperature technique using sodium borohydride (NaBH4) as the reducing agent has been developed that produces highly active nanoscale iron particles (,40,nm). By using hydrazine as an inexpensive and, compared with NaBH4, more stable reductant, body centered cubic iron particles with ,5,nm edges were obtained via solvothermal process under mild conditions from acid digested mill-scale waste. The nanoscale zerovalent iron (nZVI) powder showed improved kinetics and greater propensity for hydrogen generation than the coarser microscale iron. The rate constants for the MSR were obtained for all the reduction schemes employed in this work and are given by khydrogen=0.0158,min,1kcarbon=0.0248,min,1ksodiumborohydride=0.0521,min,1 and khydrazine=0.1454,min,1, assuming first order kinetics. Another innovative effort converted the magnetite waste directly into nZVI under solvothermal conditions, thus obviating the sluggish and time-consuming acid dissolution step. This particular aspect has significant ramification in terms of time and cost of making the iron precursor. To initiate and sustain the somewhat endothermic MSR process, a solar concentrator consisting of a convex polyacrylic bowl with reflective aluminum coating was fabricated and evaluated. This unique combination of mill-scale waste as iron source, hydrazine as reductant, mild process conditions and solar energy as the MSR actuator obviates several drawbacks plaguing the grand scheme of producing and delivering pure and humidified H2 to a PEMFC stack. Copyright © 2008 John Wiley & Sons, Ltd. [source] Advanced oxidation processes for destruction of cyanide from thermoelectric power station waste watersJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 2 2004José M Monteagudo Abstract Several advanced oxidation processes for the destruction of cyanide contained in waste waters from thermoelectric power stations of combined-cycle were studied. Thus, oxidation processes involving ozonation at basic pH, ozone/hydrogen peroxide, ozone/ultraviolet radiation and ozone/hydrogen peroxide/ultraviolet radiation have been carried out in a semi-batch reactor. All these methods showed that total cyanide can be successfully degraded but with different reaction rates, and the decrease in the total cyanide concentration can be described by pseudo-first order kinetics. The influence of pH and initial concentration of hydrogen peroxide was studied to find the optimal conditions of the oxidation process. Experimental results of the single ozone treatment indicated that total cyanide is destroyed more rapidly at higher pH (12), while ozonation combined with H2O2 and/or UV is faster at pH 9.5. The optimum concentration of H2O2 was 20.58 × 10,2M because an excess of peroxide decreases the reaction rate, acting as a radical scavenger. The total cyanide degradation rate in the O3/H2O2(20.58 × 10,2M) treatment was the highest among all the combinations studied. However, COD reduction, in the processes using UV radiation such as O3/UV or O3/H2O2/UV was about 75%, while in the processes with H2O2 and/or O3/H2O2 was lower than 57% and was insignificant, when using ozone alone. Copyright © 2003 Society of Chemical Industry [source] Influence of protein binding on acrolein turnover in vitro by oxazaphosphorines and liver microsomesJOURNAL OF CLINICAL LABORATORY ANALYSIS, Issue 3 2005Frank Baumann Abstract For a correct determination of acrolein amounts generated in in vitro turnover experiments with oxazaphosphorines, it is necessary to characterize the interaction of acrolein with liver microsomal proteins. Acrolein, a highly reactive metabolite of oxazaphosphorines, readily forms covalent adducts with proteins by electrophilic attack on nucleophiles, such as the sulfhydryl group of cysteine, imidazole group of histidine, and amino group of lysine. The current investigations were mainly directed toward determination of the degree of acrolein-protein binding under conditions of in vitro experiments with liver microsome preparations. The acrolein concentration in protein dilution was determined by a fluorescence method. Moreover, the influence of sucrose and glycerine on the extent of acrolein-protein binding commonly used for the stabilization of microsomal preparations during storage was investigated. The current investigations show evidence that the chemical reaction of acrolein with liver microsomal proteins strictly follows first order kinetics. The main part of the formed acrolein in the in vitro attempts is available as bound part. Results of these investigations indicate that the calibration should be carried out with mixtures from liver microsome preparations and known amounts of acrolein under the same conditions as the in vitro experiments to record the entirely formed acrolein part (free and bound) in oxazaphosphorine turnover experiments. Glycerine is recommended as a preservative to store liver microsomes instead of sucrose because the latter reacts with acrolein. J. Clin. Lab. Anal. 19:103,109, 2005. © 2005 Wiley-Liss, Inc. [source] Inactivation of Shigella boydii 18 IDPH and Listeria monocytogenes Scott A with Power Ultrasound at Different Acoustic Energy Densities and TemperaturesJOURNAL OF FOOD SCIENCE, Issue 4 2007Edgar Ugarte-Romero ABSTRACT:, The effect of acoustic energy density (AED) on inactivation of Shigella boydii 18 IDPH and Listeria monocytogenes Scott A in a cell suspension was studied at sublethal temperatures and at AEDs of 0.49, 0.85, and 1.43 W/mL. The effect of temperature on ultrasonic inactivation of L. monocytogenes Scott A at 35, 50, and 65 °C was examined at an AED of 1.43 W/mL. Increasing AED increased the rate of inactivation for both S. boydii and L. monocytogenes. The destruction of S. boydii and L. monocytogenes followed 1st order kinetics in a 20-min treatment, except for S. boydii inactivation at 1.43 W/mL where a tailing effect was observed after 15 min. At sublethal temperatures, the D-values of S. boydii were 8.8, 4.3, and 2.5 min for AEDs of 0.49, 0.85, and 1.43 W/mL, whereas those for L. monocytogenes at the 3 AED levels were 31.5, 13.5, and 7.3 min, respectively. Ultrasonic treatment of L. monocytogenes at 35 and 50 °C enhanced inactivation. However, at 65 °C, application of ultrasound did not result in additional inactivation compared to thermal treatment alone at the same temperature. With the experimental conditions and the ultrasound system used in this study, an upper temperature limit for thermosonication was evident above which no added killing due to ultrasound was observed. [source] Texture Changes During the Ripening of Port Salut Argentino Cheese in 2 Sampling ZonesJOURNAL OF FOOD SCIENCE, Issue 5 2002R.A. Verdini ABSTRACT: Texture changes during ripening of Port Salut Argentino cheese for different sampling zones were studied. Compression relaxation tests were performed and results were analyzed using both Maxwellian and Peleg's models. Elastic equilibrium modulus obtained from the Maxwellian model decreased from 1.22 to 0.11 104Pa during ripening. The constants derived from Peleg's model, k1 and k2, diminished with ripening time from 1.18 to 0.71 min and from 1.27 to 1.12, respectively. Asymptotic equilibrium modulus from Peleg's model decreased from 0.95 to 0.07 104Pa during ripening. Rate parameters derived from a 1st order kinetics applied to both equilibrium moduli showed that the decrease was faster in the external zone (0.0846 d,1) than in the central zone (0.0368 d,1). The correlation between equilibrium moduli, salt concentration, moisture content, and maturation indexes was obtained with a determination coefficient of 0.76. [source] Impact of deposit ageing on thermal fouling: Lumped parameter modelAICHE JOURNAL, Issue 2 2010Edward. Abstract The thermal and hydraulic performance of heat exchangers can be seriously impaired by the formation of fouling deposits on the heat transfer surfaces. The thermal effect of fouling can be complicated when the deposit is subject to ageing, represented here as a change in deposit thermal conductivity (but not thickness) over time. In this article, we revisit the ageing concept for crude oil fouling proposed by Nelson (Refiner Nat Gas Manufacturer. 1934;13:271,276, 292,298), using a numerical model incorporating first order kinetics to generate quantitative comparisons of different ageing rates. Results are reported for lumped parameter systems (which also simulate point measurement methods commonly used in laboratory testing) that demonstrate that ageing can have a substantial influence on the rate of heat transfer and hence on the surface temperature and rate of fouling. Rapid ageing (compared with the rate of deposition) does not pose problems, but slow ageing, or the use of constant heat fluxes in experiments, can lead to modified thermal fouling behavior. It is concluded that deposit ageing dynamics should be considered alongside deposition rate dynamics when interpreting experimental fouling data and when modeling fouling behavior in support of heat exchanger design or operation. © 2009 American Institute of Chemical Engineers AIChE J, 2010 [source] Core-shell particles with glycopolymer shell and polynucleoside core via RAFT: From micelles to rodsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 6 2009Samuel Pearson Abstract Amphiphilic block copolymers were synthesized via the reversible addition fragmentation chain transfer (RAFT) copolymerisation of 2-methacrylamido glucopyranose (MAG) and 5,- O -methacryloyl uridine (MAU). Homopolymerisations of both monomers using (4-cyanopentanoic acid)-4-dithiobenzoate (CPADB) proceeded with pseudo first order kinetics in a living fashion, displaying linear evolution of molecular weight with conversion and low PDIs. A bimodal molecular weight distribution was observed for PMAU at low conversions courtesy of hybrid behavior between living and conventional free radical polymerization. This effect was more pronounced when a PMAG macroRAFT agent was chain extended with MAU, however, in both cases, good control was attained once the main RAFT equilibrium was established. A stability study on PMAU found that its hydrolysis is diffusion controlled, and is accelerated at physiological pH compared with neutral conditions. Self-assembly of four block copolymers with increasing hydrophobic (PMAU) block lengths produced micelles, which demonstrated an increased tendency to form rods as the PMAU block length increased. Interestingly, none of the block copolymers were surface-active. An initial assessment of PMAU's ability to bind the nucleoside adenosine through base pairing was highly promising, with DSC measurements indicating that adenosine is fully miscible in the PMAU matrix. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1706,1723, 2009 [source] Use of a spouted bed to improve the storage stability of wheat germ followed in paper and polyethlyene packagesJOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 8 2005Füsun Yöndem-Makasc Abstract Stabilization of wheat germ by heating in a spouted bed for 180,540 s with air at 140,200 °C was studied. The lipase activity decreased by 6,65%. Wheat germ processed at 200 °C for 360 s was ranked highest in sensory evaluation, described as having ,a golden color' and ,nutty flavor', and its lipoxygenase activity had decreased by 91.2%. This product and raw wheat germ were stored in paper, polyethylene and vacuum-packed polyethylene pouches at 5 °C, room temperature (18,26 °C) and 40 °C, and the moisture contents, water activities, free fatty acid contents and peroxide values were followed for 20 weeks. The increases were faster in paper pouches than in the polyethylene ones; vacuum packaging in polyethylene did not bring about significant improvement. The peroxide values of raw samples exceeded 10 meq O2 kg,1 oil after 3,23 days while those of the processed samples stored at room temperature or 5 °C were still less than 10 after 20 weeks. The free fatty acid content and peroxide value changes were expressed by zero order kinetics, resulting in similar activation energies for the raw and processed samples. Copyright © 2005 Society of Chemical Industry [source] Evaluation of heat and oxidative damage during storage of processed tomato products.JOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE, Issue 9 2003Abstract Tomato products (pulp, puree and paste) submitted to accelerated aging (30, 40 and 50 °C for 3 months) were studied to evaluate variations in the kinetics of the degradation of antioxidants and antioxidant activity. The carotenoids lycopene and ,-carotene, ascorbic acid, rutin and total phenolics were analysed. The antioxidant activity was measured using (a) the xanthine oxidase (XOD)/xanthine system, which generates superoxide radicals and hydrogen peroxide, and (b) the linoleic acid/CuSO4 system, which promotes lipid peroxidation. The ascorbic acid content decreased even at 30 °C, following pseudo-first-order kinetics, with an activation energy of 105 200 J mol,1 for tomato pulp and 23 600 J mol,1 for tomato paste. The lower the initial ascorbic acid content, the higher was the degradation rate. Variations in phenolic compounds occurred at 40 °C and higher, following pseudo-zero order kinetics. The antioxidant activity of the hydrophilic fraction of the tomato products depended on both antioxidant degradation and the Maillard reaction and could not be described by a kinetic model. The ,-carotene content decreased even at 30 °C, whereas the lycopene content was stable in all samples. The antioxidant activity of the lipophilic fraction of the tomato products decreased following pseudo-first order kinetics, with an activation energy of 22 200 J mol,1 for tomato pulp and 20 200 J mol,1 for tomato paste. It is concluded that significant ,oxidative damage' can occur in tomato products during their commercial shelf-life. Copyright © 2003 Society of Chemical Industry [source] Novel Triaromatic Ester Mesogenic Liquid Crystalline Epoxy Resin Containing Both Methyl Substituent and Ethoxy Flexible Spacer: Synthesis and CuringMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 11 2008Guo-dong Liu Abstract A novel triaromatic ester liquid crystalline epoxy resin (LCER) that contains both a methyl substituent and an ethoxy flexible spacer, p -methylphenylene di{4-[(2,3-epoxypropoxy)ethoxy]benzoate} (MPEPEB), has been synthesized. The mesotropic property has been investigated by differential scanning calorimetry (DSC) and polarized light optical microscopy (POM). MPEPEB shows a lower melting temperature at 78.7,°C and a broad nematic mesophase temperature range of about 55,°C. Meanwhile MPEPEB shows a mesophase to ,50,°C upon cooling. The curing behavior of MPEPEB with 2,6-diamino-3,5-diethyltoluene (DAE) has been investigated by means of DSC and POM during isothermal and dynamic processes. Although there is little difference between the activation energies obtained from the kinetic data, a marked difference is found between the isothermal and dynamic investigation. The curing reaction in the isothermal investigation roughly obeys n- th order kinetics, while two exothermal peaks appear in the dynamic DSC curves of MPEPEB/DAE. A comparison of the isothermal and dynamic data shows that the curing rate is not a unique function of temperature and curing degree. The cured networks have lower glass temperatures and show a mesophase at room temperature which disappears at about 86,88,°C. [source] Absorbance kinetics of dye-doped systems with photochemical first order kineticsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 6 2007Romano A. Rupp Abstract Often it is assumed that absorbance decays in photochromic materials with the time dependence of the photochemical kinetics, i.e. exponentially for first order kinetics. Although this may hold in the limiting case of vanishing absorbance, deviations are to be expected for realistic samples, because the local photochemical kinetics slows down with increasing initial absorption and penetration depth of the radiation. We discuss the theory of the kinetics of initially homogeneous photochromic samples and derive analytical solutions. In extension of Tomlinson's theory we find an analytical solution that holds with good approximation even for samples that exhibit a small residual absorption in the saturation limit. The theoretical time dependence of the absorbance originating from photochemical first order kinetics of dye-doped systems is compared with experimental data published by Lafond et al. for fulgides doped in different polymer matrices. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Thermal stability of some self-assembling hydrogen-bonded polymers and related model complexes,POLYMER INTERNATIONAL, Issue 11 2002Gordon Armstrong Abstract The thermal stability of polymers is of fundamental importance both in processing and in many applications, eg, injection moulding, hot melts. As part of an investigation to determine the suitability of supramolecular polymers for novel applications in materials science, the thermal behaviour of two model compounds representing the principal classes of supramolecular polymer has been studied in some detail. p -Methoxybenzoic acid was complexed with 1,2-di(4-pyridyl)ethylene in 2:1 ratio as a model compound representing liquid,crystal association chain supramolecular polymers. It is proposed that the model compound degrades as a single species obeying first-order kinetics; the activation energy (Eact) of the degradation process was calculated to be 127,kJ,mol,1. A model ureidopyrimidinone dimer degraded in two steps, also following first order kinetics, with Eact,=,71.5,kJ,mol,1. The dimer was unaffected by annealing, suggesting that related polymers may be used at elevated temperatures. Polymer analogues of both model compounds were synthesized and their thermal behaviour was found to parallel that of the models. In light of these results, the implications for processing both supramolecular polymers are also considered. © 2002 Society of Chemical Industry [source] Studies of cure kinetics of polyisoimide by differential scanning calorimetry in the solid statePOLYMER INTERNATIONAL, Issue 5 2002Young Jun Kim Abstract Detailed kinetic studies of the thermal imidization of polyisoimide based upon 4,4,-oxydianiline and 4,4,-oxydiphthalic anhydride by differential scanning calorimetry are described. Both isothermal and dynamic methods have been used to obtain kinetic parameters and a phenomenological rate equation for estimating the degree of imidization as a function of time. The thermal imidization of polyisoimides in the solid state showed a maximum degree of imidization that can be achieved at a given isothermal temperature, probably due to the diffusion controlled characteristics of reactions near vitrification. That the reaction stopped near to the point of vitrification was considered when developing a phenomenological rate equation for thermal imidization of polyisoimide in the solid state. The thermal imidization is well described by modified first order kinetics with an activation energy of 170,181,kJ,mol,1 and a pre-exponential factor of 4.1,×,1013,s,1. © 2002 Society of Chemical Industry [source] In situ magnetic separation for extracellular protein productionBIOTECHNOLOGY & BIOENGINEERING, Issue 2 2009Tobias Käppler Abstract A new approach for in situ product removal from bioreactors is presented in which high-gradient magnetic separation is used. This separation process was used for the adsorptive removal of proteases secreted by Bacillus licheniformis. Small, non-porous bacitracin linked magnetic adsorbents were employed directly in the broth during the fermentation, followed by in situ magnetic separation. Proof of the concept was first demonstrated in shake flask culture, then scaled up and applied during a fed batch cultivation in a 3.7 L bioreactor. It could be demonstrated that growth of B. licheniformis was not influenced by the in situ product removal step. Protease production also remained the same after the separation step. Furthermore, degradation of the protease, which followed first order kinetics, was reduced by using the method. Using a theoretical modeling approach, we could show that protease yield in total was enhanced by using in situ magnetic separation. The process described here is a promising technique to improve overall yield in bio production processes which are often limited due to weak downstream operations. Potential limitations encountered during a bioprocess can be overcome such as product inhibition or degradation. We also discuss the key points where research is needed to implement in situ magnetic separation in industrial production. Biotechnol. Bioeng. 2009;102: 535,545. © 2008 Wiley Periodicals, Inc. [source] Sorption Removal of Pb(II) from Solution by Uncalcined and Calcined MgAl-Layered Double HydroxidesCHINESE JOURNAL OF CHEMISTRY, Issue 10 2007Shu-Qin ZHANG Abstract Layered double hydroxide (LDH) with a Mg/Al molar ratio of 1:1 was synthesized by using a co-precipitation method and its calcined product (CLDH) was obtained by calcination of the MgAl-LDH at 500 °C. The sorption removal of Pb2+ from solution was investigated, finding that both LDH and CLDH show good sorption ability and they could be used as a new type of environmental sorbent for the removal of Pb2+ from water. The sorption kinetics and the sorption isotherms of Pb2+ on both LDH and CLDH can be described by the pseudo-second order kinetics and Freundlich isotherm, respectively, under the studied conditions. The sorption amounts of Pb2+ on LDH and CLDH are independent of pH in a pH range of about 3,10. The presence of NaNO3 may inhibit the sorption ofPb2+ on LDH while hardly affect that on CLDH. The sorption mechanism of Pb2+ on LDH and CLDH may be attributed to the surface precipitation and the surface complex adsorption. The surface complex adsorption may be further distinguished to the chemical binding adsorption forming the inner-sphere surface complexes and the electrostatic binding adsorption forming the outer-sphere surface complexes. The sorption mechanism of Pb2+ on LDH may be attributed to the surface precipitation and the electrostatic binding adsorption, while that on CLDH may be attributed to the surface precipitation and the chemical binding adsorption. [source] | ||||||||||||||||||||||||||||