Kinetic Characteristics of Amino Acid Salt Crystallization in Methanol‐Water System

Nucleation and growth mechanisms and kinetics of crystals of an amino acid salt were investigated in a methanol‐water system by measuring and evaluating the induction time as a function of the supersaturation ratio and temperature in batch salting out crystallization experiments. Discrimination between the possible crystallization mechanisms, and estimation of the kinetic parameters were carried out using nonlinear parameter identification. The results concerning the growth mechanism obtained were checked additionally by measuring the induction time as a function of number density of seed crystals.     

Kinetics of the pozzolanic reaction between lime and sugar cane straw ash by electrical conductivity measurement: A kinetic-diffusive model

The kinetics of the pozzolanic reaction between lime (calcium hydroxide) and sugar cane straw ash (SCSA) with 20% and 30% of clay burned at 800 and 1000 °C is studied. A simple experimental technique was used in which the conductivity is the experimental variable. For correlating the conductivity with the concentration of calcium hydroxide (CH), a calibration curve was established. We elaborated a mathematical model that allows us to describe the process in either kinetic or kinetic-diffusive regimes. The fitting of the model by computerized methods enables us determine the parameters that characterize the process: i.e. the diffusion coefficient and reaction rate constant. The pozzolanic activity is evaluated according to the obtained values of the reaction rate constant. The results show that SCSA has a good pozzolanic activity comparable to that of the rice husk ash (RHA).     

Kinetic of CO2 absorption and carbamate formation in aqueous solutions of diethanolamine

The absorption rates of CO₂ into aqueous solutions of Diethanolamine (DEA) with varying concentrations from 0.2 to 4M and temperature range from 293 to 323 K were measured by using a laboratory stirred reactor. The CO₂ partial pressure was varied in a range that the reaction would occur in pseudo first order regime. Experimental data were analyzed and the kinetic parameters associated with the reaction were determined. The activation energy for the deprotonation of the intermediate zwitterion was estimated at about 11.4 kcal/mol. The contribution of carbamate formation to the overall absorbed CO₂ was experimentally evaluated and found to be of the order of 100%.     

Characterization of colloidal polymer particles through stability ratio measurements

We propose a general methodology for the estimation of the doublet formation rate constant (proportional to the stability ratio of primary particles) in colloidal dispersions from measurements obtained by common optical techniques, such as dynamic light scattering, static light scattering (nephelometry) or turbidimetry. In contrast to previous approaches relying on the initial slopes of the measured quantities, such as the mean hydrodynamic radius, scattered light intensity or turbidity, we introduce a transformation of the measurables to properly scaled quantities, which grow linearly in time with a slope proportional to the doublet formation rate. Analysis of systematic and random errors allows one to control the error in the estimated value of the aggregation rate. Using this approach, we measured the aggregation rate constant of colloidal polymer particles prepared by surfactant-free emulsion copolymerization of styrene and 2-hydroxyethyl methacrylate (HEMA). It was found that the stability ratio at constant ionic strength decreases with increasing dilution of the original polymer latex. This can be explained by the presence of non-reacted stabilizing species (most likely oxidized HEMA) that desorb from the particle surface upon latex dilution and thus diminish the repulsive interactions between particles. In order to check if the stability of latex particles is influenced by reversibly adsorbed species it is always necessary to perform aggregation experiments at various dilutions.     

Host/guest complex of Me-β-CD/2,2-dimethoxy-2-phenyl acetophenone for initiation of aqueous photopolymerization: Kinetics and mechanism

Methylated-β-cyclodextrin (Me-β-CD) was used to complex the photoinitiator, 2,2-dimethoxy-2-phenyl acetophenone (DMPA), yielding a water-soluble host/guest complex. The comparative studies demonstrated that the Me-β-CD complexed DMPA exhibited a high photoreactivity identical to the uncomplexed DMPA, while the CD complex obviously influenced the products of primary photolysis of DMPA and the photopolymerization kinetics due to the steric effect of CD on the subsequent initiation reactions. The photopolymerization rate of acrylamide can be described by the equation: R_p=K[2a]^0.62[M]^1.37[I]^0.5[Me-β-CD]⁰. The mechanism of polymerization was also discussed.     

Optimized species growth in epoxy polymerization with real-coded NSGA-II

Satisfaction of twin objectives of maximization of M_n along with minimization of PDI do not necessarily guarantee the maximization of concentration of desired species in a semibatch epoxy polymerization process. As the final product consists of a number of polymer species, a need is felt to perform an advanced optimization study to come up with such process conditions for which the selective growth of a particular polymer species is maximized in minimum possible processing time and the population of other species should be at their lowest values. These above-mentioned conflicting objectives frame the platform for a multi-objective optimization problem, which is solved here using a real-coded non-dominated sorting genetic algorithm or NSGA II and Pareto optimal solutions are obtained. The decision variables are discrete addition rates of various ingredients, e.g. the amount of addition of bisphenol-A (a monomer), sodium hydroxide and epichlorohydrin at different time steps. All species balance equations, bounds on M_n, PDI and addition amounts are treated as constraints. Results are very promising in terms of optimized operations for selective enhancement of desired polymer species for the epoxy polymerization process. Total additions are kept very close to available experimental conditions to minimize probable extrapolation errors. It has been observed that preferential oligomer production is extremely difficult for epoxy polymerization. Lower chain polymers are the only choice for a good quality, stable polymer product.     

Multi-site phase transfer catalyst assisted radical polymerisation of glycidyl methacrylate using potassium peroxydisulphate as initiator – a kinetic study

In this work, the kinetics and mechanism of free-radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxydisulphate (PDS) as water soluble initiator in the presence of synthesized 1, 4-Bis (tributyl methyl ammonium) benzene dichloride (TBMABDC) as multi-site phase transfer catalyst (MPTC) was studied. The polymerisation reactions were carried out under inert and unstirred conditions at constant temperature of 60 ± 1°C in cyclohexane/water biphase media. The role of concentrations of monomer, initiator, catalyst and volume fraction of aqueous phase, solvent polarity and temperature on the rate of polymerisation (Rp) was ascertained. The order with respect to monomer and initiator was found to be unity. The order with respect to catalyst was found to be 0.51. The rate of polymerisation is independent of ionic strength and pH of the medium. However, an increase in the polarity of solvent has slightly increased the Rp value. Based on the results obtained, a suitable kinetic scheme has been proposed to account for the experimental observations and its significance discussed.     

Interfacial hybridization kinetics of oligonucleotides immobilized onto fused silica surfaces

Fused silica optical fibers have been used in an intrinsic mode optical configuration as biosensors for fluorescence based detection of hybridization of nucleic acids. In this work, the kinetics of hybridization of single-stranded oligonucleotides that were covalently immobilized were studied. The probe DNA was dT₂₀, and the target was Fluorescein-labeled non-complementary (dT₂₀) or complementary (dA₂₀) oligonucleotide. Chronofluorimetric monitoring of the adsorption and hybridization processes was used to investigate oligonucleotide films of different density, in different salt concentrations, at temperatures of 25 and 40 °C, with the concentration of the target DNA being 0.005–0.1 μM. Mathematical models based on first- and second-order Langmuir adsorption have been examined to describe both the adsorption and the hybridization processes. Experimental data were processed using the models, and the hybridization kinetics were calculated. Hybridization kinetics on these optical fiber DNA sensors was found to be up to three orders faster than results presented for a number of other experiments using different immobilization chemistries.