Search results for "chemical kinetics"
showing 10 items of 60 documents
Convective mass transfer to partially recessed and porous electrodes
2003
Abstract The diffusional problem of a rotating porous electrode has been analysed based on the mass transfer equations for a partially blocked electrode. It is shown that the porous geometry leads to a dependence of the current on rotation rate identical to that corresponding to a coupled diffusion-activated electron transfer mechanism. The apparent rate constant, however, is related only to the geometry of the porous surface. It is shown that the characteristic diffusional length corresponds to the pore dimension modified by a term including the transition from linear to spherical diffusional geometry at the pore entrance. The theory is compared with experimental results for the reduction …
Scalable heterogeneous synthesis of metallic nanoparticles and aggregates with polyvinyl alcohol
2009
Here we report on a new route to synthesize colloidal silver and gold nanoparticles, potentially scalable for massive nanoparticle-production. This method is based on the microwave-assisted heterogeneous reduction of the metal salts with polyvinylalcohol. The reaction is carried out in alcohols, which are non-solvents for polyvinylalcohol. Nanoparticles can be very easily separated by filtration. The reaction kinetics are extremely fast. Size-controlled formation of nanoparticle agglomerates is accomplished with a seed-mediated synthesis of nanoparticles upon MW exposure.
Quantum dynamics of 16O + 36O2 and 18O + 32O2 exchange reactions
2015
We present quantum dynamical investigations of (16)O + (36)O2 and (18)O + (32)O2 exchange reactions using a time-independent quantum mechanical method and an accurate global potential energy surface of ozone [Dawes et al., J. Chem. Phys. 135, 081102 (2011)]. Initial state-selected integral cross sections, rate constants, and Boltzmann averaged thermal rate constants are obtained and compared with earlier experimental and theoretical results. The computed thermal rate constants for the oxygen exchange reactions exhibit a negative temperature dependence, as found experimentally. They are in better agreement with the experiments than the previous studies on the same reactions.
Spatiotemporal reaction kinetics of an ultrafast photoreaction pathway visualized by time-resolved liquid x-ray diffraction.
2006
We have studied the reaction dynamics for HgI 2 in methanol by using time-resolved x-ray diffraction (TRXD). Although numerous time-resolved spectroscopic studies have provided ample information about the early dynamics of HgI 2 , a comprehensive reaction mechanism in the solution phase spanning from picoseconds up to microseconds has been lacking. Here we show that TRXD can provide this information directly and quantitatively. Picosecond optical pulses triggered the dissociation of HgI 2 , and 100-ps-long x-ray pulses from a synchrotron probed the evolving structures over a wide temporal range. To theoretically explain the diffracted intensities, the structural signal from the solute, the…
Die kinetik der allendimerisation, ein beitrag zum mechanismus
1971
Zusammenfassung The reaction kinetics of the dimerization of some polyhalogenated allenes with the general formula Cl2CCCCIX (X = Cl, Br, C6H5, COOEt) and of tetrabromoallene was studied by an IR spectrophotometric method. The reaction was found to be of strictly second order kinetics. The activation parameters were determined and the experimental data and the influence of the substituents were discussed in terms of the accepted general theory of allene cycloaddition. All data are in agreement with a non-concerted two-step electrocyclic addition mechanism. Within the experimental limits no paramagnetic species like a diradical could be detected by the ESR-method during the dimerization re…
The impact of TiO2 modifications on the effectiveness of photocatalytic processes [review]
2018
This paper outlines the recent studies on the application of photocatalysis using semiconductors, with modified titanium dioxide (TiO2) in the process of reducing chemical contamination of surface and ground waters. During the last forty years, an increasing interest in catalysts of this type is noticeable. Hence, a wide range of methods of TiO2 modifications have been proposed so far by using its various polymorphs, composites with metals and non-metals and polymer-coatings or impregnating it with dyes that effectively absorb sunlight.
Studies of polyamines transport through liquid membranes with D2EHPA as a carrier.
2008
The transport of polyamines through the liquid membranes with di‐2‐ethylhexyl phosphoric acid (D2EHPA) was investigated. The study was performed in three main steps: liquid–liquid extraction (LLE), bulk liquid membrane (BLM) extraction, and supported liquid membrane (SLM) extraction. Equilibrium distribution experiments allowed determining the extraction constants and stoichiometric coefficients for each polyamine. It turned out that one amino group binds two molecules of carrier (one D2EHPA dimer) and the extractability of polyamine rises with the increase in number of function groups in the molecule. The BLM and SLM experiments showed that despite considerable differences in distribution …
Polymer dynamics in thin p-type conducting films investigated by ac-electrogravimetry. Kinetics aspects on anion exclusion, free solvent transfer, an…
2015
A new transfer model is proposed to explain ac-electrogravimetry response of p-doped films. This model takes into account the exclusion effect occurring as a result of the anion transfer. The insertion/expulsion of anions inside a film involves simultaneously the expulsion/insertion of free solvent molecules. The number of solvent molecules excluded depends on the volume of anion transferred. Solvent transfer stimulated by the conformational changes of films constitutes the remaining electrogravimetric response when the exclusion process cannot explain by itself this response. Consequently, the kinetics of this free solvent transfer can be directly related to the kinetics of conformational …
Flow chemistry: Imidazole-based ionic liquid syntheses in micro-scale
2010
The quarternization of an N-atom in the 1-methyl-imidazole with different alkylating agents was investigated to form so-called Ionic Liquids. (3-Chloropropyl)-trimethoxysilane, 1-chlorobutane, diethyl sulfate and methyl trifluoromethanesulfonate were used as alkylating agents. Reaction kinetics range from very slow to instantaneous and the reaction heat from endothermal to extremely exothermal respectively. The reactions were performed under flow conditions using different types of microstructured reactors as well as pre-structurized reactants in the micro-scale. Unusual heat management with integrated heat pipes allow safer performing of highly exothermal reactions with comparably high thr…
Co-occurrence of resonant activation and noise-enhanced stability in a model of cancer growth in the presence of immune response.
2006
We investigate a stochastic version of a simple enzymatic reaction which follows the generic Michaelis-Menten kinetics. At sufficiently high concentrations of reacting species, the molecular fluctuations can be approximated as a realization of a Brownian dynamics for which the model reaction kinetics takes on the form of a stochastic differential equation. After eliminating a fast kinetics, the model can be rephrased into a form of a one-dimensional overdamped Langevin equation. We discuss physical aspects of environmental noises acting in such a reduced system, pointing out the possibility of coexistence of dynamical regimes where noise-enhanced stability and resonant activation phenomena …