Search results for " rate constant"
showing 10 items of 220 documents
Versuche zur Bestimmung des wahren K-Efflux im Rattenzwerchfell
1960
In an isolated muscle loaded with 42K the potassium efflux through the muscle fibre membrane can be calculated from the rate constant of the loss of 42K into an inactive bathing solution. The calculation can only be valid if the amount of 42K leaving all the individual fibres is equivalent to the amount of 42K entering the bathing solution from the surface of the whole muscle. It seems possible that 42K ions which have already left a muscle cell can be taken up again into a muscle fibre before diffusing into the bathing solution. Thus the calculated potassium efflux might be smaller than the real efflux.
Electrochemical reactions with adsorption of the reactants and electrosorption. Simple analytical solutions for a Henry isotherm
1998
Abstract A theoretical treatment of an electrochemical reaction O + ne− R with adsorption of the reactants is presented when the adsorption, at equilibrium, obeys a Henry isotherm. A simple analytical solution, valid for any degree of adsorption of O and or R, is established for a polarographic wave. In LSV, for slow sweep rates and weak adsorption, both the cathodic and anodic peaks have a ‘diffusional’ character; for high sweep rates and strong adsorption, they are both of a ‘surface’ nature. In the intermediate case, one peak has a ‘diffusional’ character (deposition process), while the other is of a ‘surface’ nature (redissolution process). Expressions of the peak potentials are given i…
Racemic S ‐(ethylsulfonyl)‐ dl ‐cysteine N ‐Carboxyanhydrides Improve Chain Lengths and Monomer Conversion for β‐Sheet‐Controlled Ring‐Opening Polyme…
2020
The secondary structure formation of polypeptides not only governs folding and solution self-assembly but also affects the nucleophilic ring-opening polymerization of alpha-amino acid-N-carboxyanhydrides (NCAs). Whereby helical structures are known to enhance polymerization rates, beta-sheet-like assemblies reduce the propagation rate or may even terminate chain growth by precipitation or gelation. To overcome these unfavorable properties, racemic mixtures of NCAs can be applied. In this work, racemicS-(ethylsulfonyl)-dl-cysteine NCA is investigated for the synthesis of polypeptides, diblock and triblock copolypept(o)ides. In contrast to the polymerization of stereoregularS-(ethylsulfonyl)-…
Kinetic parameters of a cyanate ester resin catalyzed with different proportions of nonylphenol and cobalt acetylacetonate catalyst
2005
The isothermal cure of a dicyanate ester monomer has been investigated by differential scanning calorimetry (DSC) in the presence of different quantities of a catalyst system formed by nonylphenol (NP) and cobalt (II) acetylacetonate (Co(AcAc)2). Two sets of experiences were studied. Firstly, the NP composition was varied from 0 to 10 per hundred resin (phr) and secondly, the Co(AcAc)2 loadings were changed at 2 phr of NP. It has been observed that the cyanate conversion increases significantly after the first addition of the metal catalyst and, also, at the same time the thermal stability improves. Moreover, the kinetic data have been fitted with a second-order equation respect to the cyan…
Peculiar mechanism of solubilization of a sparingly water soluble drug into polymeric micelles. Kinetic and equilibrium studies.
2012
Complementary kinetic and equilibrium studies on the solubilization process of the sparingly water soluble tamoxifen (TAM) drug in polymeric aqueous solutions have been performed by using the spectrophotometric method. In particular, the amphiphilic copolymers obtained by derivatization of polymeric chain of poly(N-2-hydroxyethyl)-dl-aspartamide, PHEA, with poly(ethylene glycol)s, PEG (2000 or 5000 Da), and/or hexadecylamine chain, C16, namely PHEA-PEG2000-C16, PHEA-PEG5000-C16, PHEA-C16, have been employed. Preliminary to the kinetic and equilibrium data quantitative treatment, the molar absorption coefficient of TAM in polymeric micelle aqueous solution has been determined. By these studi…
Unraveling the kinetics and molecular mechanism of gas phase pyrolysis of cubane to [8]annulene
2020
The kinetic and electron density flows are studied theoretically for the gas phase pyrolysis of cubane via its cage opening to reach bicyclooctatriene and then thermal rearrangement of bicyclooctatriene to produce [8]annulene which is the experimentally observed major product. The observed kinetic data at the MN15-L/maug-cc-pVTZ level of theory were in good agreement with the experimental results as compared to the CBS-QB3 method. The cage opening and the thermal rearrangement steps at the experimentally employed temperature of 520 K were exergonic and exothermic. The atmospheric rate constants calculated by means of the RRKM theory show that the cage opening is the rate-determining step. T…
Glow Rate Technique for Spectroscopy of Complex Thermostimulated Relaxation Processes
1996
The glow rate technique (GRT) developed for the analysis of complex trap spectra, is the extension of the known heating rate method to the full glow curve. It is shown that using two glow curves measured at different heating rate constants, a special mean activation energy of simultaneously emptied traps can be obtained as a function of temperature or emitted light sum to a good approximation. Expressions have been derived for the calculation of the mean activation energy function from data measured using a linear, logarithmic or a hyperbolic heating mode. Theoretical expressions for the mean activation energy function have been obtained and discussed for arbitrary trap distribution functio…
Accumulation and discharge behavior of Cs-137 by zebra fish (Brachydanio rerio) in different aquatic environments
1990
The uptake and release kinetics of137Cs from water by the tropical fishBrachydanio rerio has been studied under controlled laboratory condition. The accumulation of this radionuclide from food was avoided by feeding the fishes separately in an inactive environment. A steep inverse dependence of bioconcentration factor (BCF) with potassium concentration has been observed. This can formally be described by the equation BCF=5.2 · [K+]−0.44. The elimination rate constant K in fresh water conditions has been found to have a magnitude of 0.014±0.03 d−1 which corresponds to a biological half-life of 51±10 days. The uptake and release kinetics ofBrachydanio rerio has been compared with earlier stud…
State-to-State Quantum Dynamics Calculations of the C plus OH Reaction on the Second Excited Potential Energy Surface
2011
Accurate three-dimensional quantum-mechanical scattering calculations using a time-indepedent hyperspherical method have been performed for the C((3)P) + OH(X(2)Π) → CO(a(3)Π) + H((2)S) reaction on the second excited potential energy surface of 1(4)A″ symmetry. State-to-state reaction probabilities at a total angular momentum J = 0 have been computed in a wide range of collision energies. Many pronounced resonances have been found, espcially at low energy. The product vibrational distributions are noninverted. The present results therefore suggest that the title reaction proceeds via a long-lived intermediate complex. An approximate quantum-mechanical rate constant has also been calculated,…
Second-order tensorial calibration for kinetic spectrophotometric determination
1996
Abstract Kinetic-diode array spectrophotometric detection, as well as other multichannel techniques when used in non-equilibrium conditions, constitute second-order instrumentation. The second-order response provided will be bilinear, under certain conditions even trilinear, thus allowing the use of the generalized rank annihilation method (GRAM) and the trilinear decomposition method (TLD). Both numerically simulated and experimental data were used to evaluate the performance of these calibration techniques. The conditions in which the ‘second-order advantage’ (the possibility of quantifying the analytes in the presence of unknown reactions or interferences) is preserved were investigated.…