Study on improving the turbidity measurement of the absolute coagulation rate constant

The existing theories dealing with the evaluation of the absolute coagulation rate constant by turbidity measurement were experimentally tested for different particle-sized (radius = a) suspensions at incident wavelengths (lambda) ranging from near-infrared to ultraviolet light. When the size parameter alpha = 2 pi a/lambda > 3, the rate constant data from previous theories for fixed-sized particles show significant inconsistencies at different light wavelengths. We attribute this problem to the imperfection of these theories in describing the light scattering from doublets through their evaluation of the extinction cross section. The evaluations of the rate constants by all previous theories become untenable as the size parameter increases and therefore hampers the applicable range of the turbidity measurement. By using the T-matrix method, we present a robust solution for evaluating the extinction cross section of doublets formed in the aggregation. Our experiments show that this new approach is effective in extending the applicability range of the turbidity methodology and increasing measurement accuracy.

A nonmonotonic dependence of standard rate constant on reorganization energy for heterogeneous electron transfer processes on electrode surface

In the present work a nonmonotonic dependence of standard rate constant (k(0)) on reorganization energy (lambda) was discovered qualitatively from electron transfer (Marcus-Hush-Levich) theory for heterogeneous electron transfer processes on electrode surface. It was found that the nonmonotonic dependence of k(0) on lambda is another result, besides the disappearance of the famous Marcus inverted region, coming from the continuum of electronic states in electrode: with the increase of lambda, the states for both Process I and Process II ET processes all vary from nonadiabatic to adiabatic state continuously, and the lambda dependence of k(0) for Process I is monotonic thoroughly, while for Process II on electrode surface the lambda dependence of k(0) could show a nonmonotonicity.

Determination of the standard heterogeneous rate constant in polyelectrolyte using steady state microdisk voltammograms

The steady state voltammogram at a microdisk electrode is used to measure the diffusion coefficient and standard heterogeneous rate constant (k(s)) of ferrocene in polyelectrolyte PEG + LiClO4. The k(s) obtained is smaller in polyelectrolyte than in liquid medium. It is proposed that the polymer solvent electron transfer dynamics are affected by the relaxation rates of the ether dipole sites on the polymer chains, which are in turn constrained by the rates of polymer chain segment, or local structure, relaxations. The dependence of k(s) on temperature is observed. The k(s) increases with increasing temperature.

STUDY ON ELECTROCATALYTIC OXIDATION OF NADH BY FERROCENE DERIVATIVES AND DETERMINATION OF CATALYTIC RATE-CONSTANT AT MICRODISK ELECTRODE

The electrocatalytic oxidation of NADH by ferrocene derivatives and the influence of complexation with beta-cyclodextrin (beta-CD) were investigated at a microdisk electrode in a buffer solution. The cyclic voltammetric behavior of the ferrocene derivatives on the microdisk electrode was used to determine the electron-transfer rate constant from NADH to the ferricinium species. The heterogeneous rate constants and the diffusion coefficient of ferrocene derivatives were determined with the microdisk electrode. The effect of temperature and pH on the electrocatalytic oxidation of NADH were assessed.

APPLICATIONS OF RAPID SCAN SPECTROELECTROCHEMISTRY - DETERMINATION OF HETEROGENEOUS ELECTRON-TRANSFER RATE-CONSTANT OF BILIVERDIN OXIDATION

The rapid scan spectrometer was used to determine the heterogeneous electron transfer rate parameters for the oxidation of Biliverdin in DMF by single potential step thin layer spectroelectrochemical techniques and yielded an average formal heterogeneous electron transfer rate constant K(s, h)0' = 2.45 (+/-0.12) x 10(-4) cm s-1, electrochemical transfer coefficient alpha = 0.694+/-0.008. The oxidation process of Biliverdin was also studied and the formal potential E0 = 0.637 V (vs. Ag/AgCl) was obtained.

DETERMINATION OF THE RATE-CONSTANT OF A CATALYTIC REACTION USING A PARALLEL INCIDENT SPECTROELECTROCHEMICAL CELL

The possibility of determining the rate constant of a catalytic reaction using a parallel incident spectroelectrochemical cell was investigated in this work. Various spectroelectrochemical techniques were examined, including single-potential-step chronoabsorptometry, single-potential-step open-circuit relaxation chronoabsorptometry and double-potential-step chronoabsorptometry. The values determined for the kinetics of the ferrocyanide-ascorbic acid system are in agreement with the reported values. The parallel incident method is much more sensitive than the normal transmission method and can be applied to systems which have smaller molar absorptivities, larger rate constants or lower concentrations.

Temperature Dependence of Rb(2) Molecule Formation Rate Constant in a Magneto-Optical Trap

In this paper, we report the measurement of Rb(2) molecule formation rate constant due to a two body process in a magneto-optical trap as a function of the sample temperature. The ground state molecules are detected by two-photon ionization, through the intermediate a(3)Sigma(+)(u) -> 2(3)Pi(g) molecular band. Our results show that the Rb(2) molecules formed in the MOT could be due to a wave shape resonance, which enhances the molecule formation rate. This effect may be used to enhance the molecule production; and therefore it maybe important to future experiments involving production and trapping of cold ground state molecules.

Effect of organic exudates of Phaeodactylum tricornutum on the Fe(II) oxidation rate constant

[EN] Fe(II) oxidation kinetics were studied in seawater and in seawater enriched with exudates excreted by Phaeodactylum tricornutum as an organic ligand model. The exudates produced after 2, 4, and 8 days of culture at 6.21 .. 107, 2.29 .. 108, and 4.98 .. 108 cell L?1 were selected. The effects of pH (7.2?8.2), temperature (5?35 ºC), and salinity (10?36.72) on the Fe(II) oxidation rate were studied. All the data were compared with the results for seawater without exudates (control). The Fe(II) rate constant decreased as a function of culture time and cell concentration in the culture at different pH, temperature, and salinity. All the experimental data obtained in this study were fitted to a polynomial function in order to quantify the fractional contribution of the organic exudates from the diatoms to the Fe(II) oxidation rate in natural seawater. Experimental results showed that the organic exudates excreted by P. tricornutum affect Fe(II) oxidation, increasing the lifetime of Fe(II) in seawater. A kinetic model approach was carried out to account for the speciation of each Fe(II) type together with its contribution to the overall rate.

The rate constant of photoinhibition, measured in lincomycin-treated leaves, is directly proportional to light intensity.

Pumpkin leaves grown under high light (500-700 micromol of photons m-2.s-1) were illuminated under photon flux densities ranging from 6.5 to 1500 micromol.m-2.s-1 in the presence of lincomycin, an inhibitor of chloroplast protein synthesis. The illumination at all light intensities caused photoinhibition, measured as a decrease in the ratio of variable to maximum fluorescence. Loss of photosystem II (PSII) electron transfer activity correlated with the decrease in the fluorescence ratio. The rate constant of photoinhibition, determined from first-order fits, was directly proportional to photon flux density at all light intensities studied. The fluorescence ratio did not decrease if the leaves were illuminated in low light in the absence of lincomycin or incubated in darkness in the presence of lincomycin. The constancy of the quantum yield of photoinhibition under different photon flux densities strongly suggests that photoinhibition in vivo occurs by one dominant mechanism under all light intensities. This mechanism probably is not the acceptor side mechanism characterized in the anaerobic case in vitro. Furthermore, there was an excellent correlation between the loss of PSII activity and the loss of the D1 protein from thylakoid membranes under low light. At low light, photoinhibition occurs so slowly that inactive PSII centers with the D1 protein waiting to be degraded do not accumulate. The kinetic agreement between D1 protein degradation and the inactivation of PSII indicates that the turnover of the D1 protein depends on photoinhibition under both low and high light.

Vibrational relaxation effects in dissociation rate-constant measurements.

"Contract no. NASr-119."

A priori prediction of aggregation efficiency and rate constant for fluidized bed melt granulation

This paper presents a predictive aggregation rate model for spray fluidized bed melt granulation. The aggregation rate constant was derived from probability analysis of particle–droplet contact combined with time scale analysis of droplet solidification and granule–granule collision rates. The latter was obtained using the principles of kinetic theory of granular flow (KTGF). The predicted aggregation rate constants were validated by comparison with reported experimental data for a range of binder spray rate, binder droplet size and operating granulator temperature. The developed model is particularly useful for predicting particle size distributions and growth using population balance equations (PBEs).

Thiothionyl bromide (S=SBr2): The elusive isomer of dibromodisulfane (BrSSBr)

CCSD(T) with a series of correlation consistent basis up to quadruple-zeta is used to investigate the structures, vibrational spectra, relative stability, heats of formation, and barrier to isomerization of S=SBr2 and BrSSBr. It represents the most accurate and detailed characterization of these molecules to date. We show that the frequency mode at 302 cm(-1), detected in various studies and assigned to impurities by some authors, and to the anti-symmetric SBr stretch in BrSSBr by others, thus in fact corresponds to the anti-symmetric SBr stretch in the elusive S=SBr2 species; it thus corroborates and complements an earlier partial IR spectra study attributable to S=SBr2. Including corrections for relativistic and core-valence correlation effects, we also predict 26.33 (12.74) kcal/mol for Delta H-f (298.15 K) of S=SBr2 (BrSSBr). For the S=SBr2 -> BrSSBr reaction, our best estimates for the Gibbs free energy and the enthalpy of the reaction at 298.15 K are -13.71 and -13.44 kcal/mol, respectively. For a value of Delta G(#) equal to 23.52 kcal/mol, we estimate a TST rate constant, at 298.15 K, of 3.57 x 10(-5) s(-1). (c) 2007 Elsevier B.V. All rights reserved.