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701.
Maria PC Massi L Box NS Gal JF Burk P Tammiku-Taul J Kutsar M 《Rapid communications in mass spectrometry : RCM》2006,20(13):2057-2062
In relation to the interaction between (137)Cs and soil organic matter, electrospray mass spectrometry experiments and density functional theory (DFT) calculations were carried out on the dissociation of positively charged adducts formed by cesium nitrate and cesium organic salts attached to a cesium cation [Cs(CsNO(3))(CsA)](+) (A = benzoate, salicylate, hydrogen phthalate, hydrogen maleate, hydrogen fumarate, hydrogen oxalate, and hydrogen malonate ion). These mixed clusters were generated by electrospray from methanol solutions containing cesium nitrate and an organic acid. Collision-induced dissociation of [Cs(CsNO(3))(CsA)](+) in a quadrupole ion trap gave [Cs(CsNO(3))](+) and [Cs(CsA)](+) as major product ions. Loss of HNO(3) was observed, and also CO(2) loss in the case of A = hydrogen malonate. Branching ratios for the dissociation into [Cs(CsNO(3))](+) and [Cs(CsA)](+) were treated by the Cooks' kinetic method to obtain a quantitative order of bonding energetics (enthalpies and Gibbs free energies) between Cs(+) and the molecular salt (ion pair) CsA, and were correlated with the corresponding values calculated using DFT. The kinetic method leads to relative scales of Cs(+) affinities and basicities that are consistent with the DFT-calculated values. This study brings new data on the strong interaction between the cesium cation and molecular salts CsA. 相似文献
702.
Dubois L Jacquamet L Pécaut J Latour JM 《Chemical communications (Cambridge, England)》2006,(43):4521-4523
Full reduction of the Mn(III)(mu-O)2Mn(IV) core to Mn(II)(mu-OH2)2Mn(II) is observed upon irradiation by an X-ray beam at ca. 20 K. 相似文献
703.
Falus P Porcar L Fratini E Chen WR Faraone A Hong K Baglioni P Liu Y 《J Phys Condens Matter》2012,24(6):064114
Recent combined experiments by small angle neutron scattering (SANS) and neutron spin echo (NSE) have demonstrated that dynamic clusters can form in concentrated lysozyme solutions when the right combination of a short-ranged attraction and a long-ranged electrostatic repulsion exists. In this paper, we investigate the temperature effect on the dynamic cluster formation and try to pinpoint the transition concentration from a monomeric protein phase to a cluster phase. Interestingly, even at a relatively high concentration (10% mass fraction), despite the significant change in the SANS patterns that are associated with the change of the short-ranged attraction among proteins, the normalized short-time self-diffusion coefficient is not affected between 5 and 40?°C. This is interpreted as a lack of cluster formation in this condition. However, at larger concentrations such as 17.5% and 22.5% mass fraction, we show that the average hydrodynamic radius increases significantly and causes a large decrease of the normalized self-diffusion coefficient as a result of cluster formation when the temperature is changed from 25 to 5?°C. 相似文献
704.
Robin G Vander Meulen F Wilkie-Chancellier N Martinez L Haumesser L Fortineau J Griesmar P Lethiecq M Feuillard G 《Ultrasonics》2012,52(5):622-627
In many industrial processes where online control is necessary such as in the food industry, the real time monitoring of visco-elastic properties is essential to ensure the quantity of production. Acoustic methods have shown that reliable properties could be obtained from measurements of velocity and attenuation. This paper proposes a simple, real time ultrasound method for monitoring linear medium properties (phase velocity and attenuation) that vary in time. The method is based on a pulse echo measurement and is self-calibrated. Results on a silica gel are reported and the importance of taking into account the changes of the mechanical loading on the front face of the transducer will be shown. This is done through a modification of the emission and reception transfer parameters. The simultaneous measurement of the input and output currents and voltages enables these parameters to be calculated during the reaction. The variations of the transfer parameters are in the order of 6% and predominate other effects. The evolution of the ultrasonic longitudinal wave phase velocity and attenuation as a function of time allows the characteristic times of the chemical reaction to be determined. The results are well correlated with the gelation time measured by rheological method at low frequency. 相似文献
705.
Supercritical multicomponent fluid thermodynamics are often built from equations of state. We investigate mathematically such a construction of a Gibbsian thermodynamics compatible at low density with that of ideal gas mixtures starting from a pressure law. We further study the structure of chemical production rates obtained from nonequilibrium statistical thermodynamics. As a typical application, we consider the Soave-Redlich-Kwong cubic equation of state and investigate mathematically the corresponding thermodynamics. This thermodynamics is then used to study the stability of H2-O2-N2 mixtures at high pressure and low temperature as well as to illustrate the role of nonidealities in a transcritical H2-O2-N2 flame. 相似文献
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