Ultrasonic relaxation kinetics on fast deuteron transfer reaction

Propylamine has been selected to investigate the isotope effect of a fast deuteron transfer reaction by ultrasonic relaxation method. Ultrasonic absorption coefficients of propylamine in heavy water (D2O) at 25 degrees C in the concentration range from 0.0107 to 0.6300 mol dm(-3) have been measured by pulse and resonance methods over the frequency range from 0.8 to 220 MHz. A Debye-type single relaxation absorption has been observed in the solution. From the dependence of the ultrasonic relaxation parameters on the concentration and solution pH, the source of the observed relaxation has been attributed to a perturbation of the chemical equilibrium associated with the deuteron transfer reaction. The rate and equilibrium constants have been determined by the measurement of the deuteroxyl ion concentration dependence of the relaxation frequency. Also the standard volume change of the reaction has been determined from the concentration dependence of the maximum absorption per wavelength and the adiabatic compressibility has been calculated from the density and the sound velocity in the solution. These results have then been compared with those obtained for propylamine in light water (H2O). The forward rate constant is greater and the reverse rate constant is smaller in DO than in H2O. The standard volume change for deuteron transfer is greater than that for proton transfer reaction, and the adiabatic compressibility shows a similar trend. These data support an argument that there exists a stronger hydrogen bond in D2O than in H2O. The difference of the stability in the intermediate states, R-ND3+... OD- and R-NH3+... OH-, has also been considered from the results of the isotope effects.

DETERMINATION OF PARAMETERS OF FAST CHEMICAL REACTION OF ALIZARIN RED S BY SPECTROELECTROCHEMICAL METHOD WITH LOPTLC

The rate constant of very fast chemical reaction generally can be measured by electrochemical methods, but can not by the thin layer electrochemical methods because of the influence of diffusion effect. Long optical path length thin layer cell (LOPTLC) with large ratio of electrode area to solution volume can be used to monitor the fist chemical reaction in situ with high sensitivity and accuracy. It enable the adsorption spectra to be measured without the influence of diffusion effect. In the present paper, a fast chemical reaction of Alizarin Red S (ARS) with its oxidative state has been studied. The reaction equilibrium constant (K) under different potentials can be determined by single step potential-absorption spectra in LOPTLC. An equilibrium constant of 7.94 x 10(5) l.mol(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)'). Rate constant (k) under different potentials can be measured by single step potential-chronoabsorptiometry. A rate constant of 426.6 l.mol(-1).s(-1) for the chemical reaction has been obtained from the plot of lgK vs. (E - E-1(0)') with (E - E-1(0)') = 0.

Fast microzooplankton grazing on fast-growing, low-biomass phytoplankton: a case study in spring in Chesapeake Bay, Delaware Inland Bays and Delaware Bay

Dilution experiments were performed to examine the growth and grazing mortality rates of picophytoplankton (< 2 mu m), nanophytoplankton (2-20 mu m), and microphytoplankton (> 20 mu m) at stations in the Chesapeake Bay (CB), the Delaware Inland Bays (DIB) and the Delaware Bay (DB), in early spring 2005. At station CB microphytoplankton, including chain-forming diatoms were dominant, and the microzooplankton assemblage was mainly composed of the tintinnid Tintinnopsis beroidea. At station DIB, the dominant species were microphytoplanktonic dinoflagellates, while the microzooplankton community was mainly composed of copepod nauplii and the oligotrich ciliate Strombidium sp. At station DB, nanophytoplankton were dominant components, and Strombidium and Tintinnopsis beroidea were the co-dominant microzooplankton. The growth rate and grazing mortality rate were 0.13-3.43 and 0.09-1.92 d(-1) for the different size fractionated phytoplankton. The microzooplankton ingested 73, 171, and 49% of standing stocks, and 95, 70, and 48% of potential primary productivity for total phytoplankton at station CB, DIB, and DB respectively. The carbon flux for total phytoplankton consumed by microzooplankton was 1224.11, 100.76, and 85.85 mu g C 1(-1) d(-1) at station CB, DIB, and DB, respectively. According to the grazing mortality rate, carbon consumption rate and carbon flux turn over rates, microzooplankton in study area mostly preferred to graze on picophytoplankton, which was faster growing but was lowest biomass component of the phytoplankton. The faster grazing on Fast-Growing-Low-Biomass (FGLB) phenomenon in coastal regions is explained as a resource partitioning strategy. This quite likely argues that although microzooplankton grazes strongly on phytoplankton in these regions, these microzooplankton grazers are passive.

Fast formation of NaA zeolite membrane in the microwave field

NaA zeolite membrane was successfully synthesized on the porous alpha-Al2O3 support by microwave heating. The synthesis of NaA zeolite membrane in the microwave field only needs 15 min and the synthesis time is 10 times shorter than that by conventional heating. SEM characterization indicates that the zeolite crystals in the NaA zeolite membrane synthesized by microwave heating are uniform in size; the membrane thickness is about 4 mu m and is thinner than that of the NaA zeolite membrane synthesized by conventional heating. Gas permeation studies indicate that the permeances of the NaA zeolite membrane synthesized by microwave heating are 3-4 times higher than those of the NaA zeolite membrane synthesized by conventional heating, while their permselectivities are comparable.

Fast analysis of capillary electrochromatography with non-porous ODS as the stationary phase

High-speed capillary electrochromatography was developed on both short and long packed columns with 2 mu m non-porous ODS as the stationary phase. Factors that affect the analysis time of samples, such as voltage, electrolyte concentration, pH and organic modifier concentration in the mobile phase, were studied systematically. Fast analysis of aromatic compounds within 13 seconds was realized with column efficiency of 573,000 plates/m and a R.S.D.% of the retention times of all components in 8 consecutive injections below 1.0%. which demonstrated the high efficiency and high reproducibility of such a technique. In addition, DNPH derived aldehydes and ketones in both standards and environmental samples were separated with high speed.

Photoelectron spectroscopy of ammonia via a fast predissociative state

We report a study on resonance enhanced multiphoton ionization photoelectron spectroscopy (REMPI-PES) involving the fast predissociative (A) over tilde state of ammonia, using nano- and femtosecond lasers. The multiphoton scheme involves (1 + 1), (2 + 2), (2 + 2) + 1 and (2 + 2) + 2 photon processes. We have found a progression of stretching vibrations nu(1) in the PE spectrum when pumping NH3 (A) over tilde upsilon(2) = 0, 1 and 3 as intermediate states. The stretching vibration intensity distributions in the photoelectron spectrum are calculated by using the Chebychev method of the wavepacket propagation. The femtosecond spectrum shows a similar feature to the nanosecond spectrum. However, high laser power also causes band broadening and shifting effect as well as above threshold multiphoton ionization.