Structure and Population of Complex Ionic Species in FeCl2 Aqueous Solution by X-ray Absorption Spectroscopy

Technologies for mass production require cheap and abundant materials such as ferrous chloride (FeCl₂). The literature survey shows the lack of experimental studies to validate theoretical conclusions related to the population of ionic Fe-species in the aqueous FeCl₂ solution. Here, we present an in situ X-ray absorption study of the structure of the ionic species in the FeCl₂ aqueous solution at different concentrations (1–4 molL⁻¹) and temperatures (25–80 °C). We found that at low temperature and low FeCl₂ concentration, the octahedral first coordination sphere around Fe is occupied by one Cl ion at a distance of 2.33 (±0.02) Å and five water molecules at a distance of 2.095 (±0.005) Å. The structure of the ionic complex gradually changes with an increase in temperature and/or concentration. The apical water molecule is substituted by a chlorine ion to yield a neutral Fe[Cl₂(H₂O)₄]⁰. The observed substitutional mechanism is facilitated by the presence of the intramolecular hydrogen bonds as well as entropic reasons. The transition from the single charged Fe[Cl(H₂O)₅]⁺ to the neutral Fe[Cl₂(H₂O)₄]⁰ causes a significant drop in the solution conductivity, which well correlates with the existing conductivity models.     

The influence of temperature on rheological properties of blood mixtures with different volume expanders—implications in numerical arterial hemodynamics simulations

During the complicated cardiac surgery on a non-beating heart with cardiopulmonary bypass, protection of the heart is accomplished by injecting cold cardioplegic solutions. In most forms of circulatory shock, it is necessary to immediately restore the circulating volume. Intravenous solutions of volume expanders, such as hydroxyethyl starch and dextrans, are used to increase the volume of fluid in the circulating blood. In this work, blood samples of six donors were obtained and used to prepare mixtures with different volume expanders in concentrations ranging from 10 to 50 vol./vol.%. The flow curves of all mixtures in the temperature range from 4°C to 37°C were constructed and fitted to the Herschel–Bulkley model, in order to extract the shear thinning and yield stress parameters. To assess the influence of the observed changes in the rheological properties of blood on the hemodynamics in arterial vasculature, a realistic three-dimensional rigid-wall computational model was constructed from MRI images of the right carotid bifurcation obtained in vivo from a healthy male volunteer. The time-varying flow field was numerically computed using the Newtonian model as well as the Herschel–Bulkley model with the Papanastasiou regularization. The numerical simulations indicate only moderate changes in the time-averaged flow field that become accentuated when the instantaneous flow field is considered. We also found that although the influence of temperature, hematocrit, and volume expanders on hemodynamics is significant, this can primarily be attributed to the changes in the nominal viscosity of the flow medium.     

Raman tensor elements for multiferroic BiFeO3 with rhombohedral R3c symmetry

A quantitative assessment of the Raman spectrum emitted from a coarse‐grained polycrystal of multiferroic BiFeO₃ has been carried out by means of a polarized Raman microprobe. The dependence of the intensity of Raman phonon modes has been first theoretically modeled as a function of crystal rotation. Then, the Raman tensor elements have been experimentally determined from the analysis of the A_g and E_g vibrational modes. Copyright © 2009 John Wiley & Sons, Ltd.     

Electrolysis energy efficiency of highly concentrated FeCl2 solutions for power-to-solid energy storage technology

An electrochemical cycle for the grid energy storage in the redox potential of Fe involves the electrolysis of a highly concentrated aqueous FeCl₂ solution yielding solid iron deposits. For the high overall energy efficiency of the cycle, it is crucial to maximize the energy efficiency of the electrolysis process. Here we present a study of the influence of electrolysis parameters on the energy efficiency of such electrolysis, performed in an industrial-type electrolyzer. We studied the conductivity of the FeCl₂ solution as a function of concentration and temperature and correlated it with the electrolysis energy efficiency. The deviation from the correlation indicated an important contribution from the conductivity of the ion-exchange membrane. Another important studied parameter was the applied current density. We quantitatively showed how the contribution of the resistance polarization increases with the current density, causing a decrease in overall energy efficiency. The highest energy efficiency of 89 ± 3% was achieved using 2.5 mol L⁻¹ FeCl₂ solution at 70 °C and a current density of 0.1 kA m⁻². In terms of the energy input per Fe mass, this means 1.88 Wh g⁻¹. The limiting energy input per mass of the Fe deposit was found to be 1.76 Wh g⁻¹_.

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Optical–feedback cavity–enhanced absorption: a compact spectrometer for real–time measurement of atmospheric methane

We report on the application of the new technique of optical–feedback cavity–enhanced absorption spectroscopy to the real–time quantitative measurement of tropospheric methane traces from an airplane using a compact, low cost instrument based on a telecommunication–type diode laser operating close to room temperature. Methane concentration is obtained by fitting the absorption line centered at 1658.96 nm (6026.23 cm^-1) which belongs to the first overtone transition of the CH stretch vibration. The measurement rate is about 30 Hz, but the response time is limited to about 0.3 s by the gas flow in the measurement cell. The instrument provides the absolute ambient methane concentration accurate to ±1% (±20 ppb) without need for a periodic calibration. This is demonstrated by a hands–off comparison with a self–calibrating chromatographic setup during 10 days. The observed measurement stability can be extrapolated to much longer time periods. With respect to the short–term performance (minutes) fast concentration changes at the level of 1 ppb can be detected, and we believe this performance can be extended to the long term. Finally, a laboratory comparison with a lead–salt mid–infrared diode laser multipass spectrometer (operating close to 3028 cm^-1 at liquid nitrogen temperature) demonstrates a similar performance. PACS 07.88.+y; 42.55.Px; 42.62.Fi     

Calibration methods and avoidance of errors in measurement of intracellular pH (pHcyt) using the indicator bis(carboxyethyl)-5(6)-carboxyfluorescein (BCECF) in human platelets

Determinations of pH_cyt in suspensions of human platelets using BCECF [bis(carboxyethyl)-5(6)-carboxyfluorescein] can be seriously biased by leakage of the fluorescent indicator. Two methods (pH jump and Mn²⁺) are presented for determining the fraction of external indicator (B _ext) and eliminating this error. Both methods rely on rapid perturbations (pH jump or Mn²⁺ addition), which affect the fluorescence of the external dye immediately and the intracellular dye more slowly. Identical values ofB _ext are reported. Failure to correct for dye leakage can result in overestimation of pH_cyt by as much as 0.4 unit at physiological external pH (pH_ext). Two methods of calibration of the cytoplasmic signal were compared after correcting forB _ext: the digitonin lysis method and the nigericin calibration method. In the digitonin method the dye is released at the end of the experiment and the dependence of its fluorescence is determined as a function of pH. The method assumes that the fluorescence and titration characteristics of the dye in the cytoplasm are not different from those in solution. It gives pH_cyt=6.75±0.07 for pH_ext=7.3. In the nigericin method, 150 mM external K⁺ and 10 M nigericin are used for the purpose of setting pH_cyt=pH_ext to accomplish anin situ calibration. The method was complicated by extra leakage induced by nigericin. Assuming that the ionophore could equilibrate pH in the alkaline range, the fluorescence of the anionic form of BCECF in the cytoplasm would be 15% lower than in solution and pH_cyt would be 0.3 unit higher than presented above. A number of observations favor the digitonin lysis method of calibration. The fluorescence polarization of BCECF in platelets is small and indistinguishable from that in solution (0.000±0.022). The spectrofluorimetric characteristics of the intracellular dye are identical to those in solution (150 mM NaCl or KCl). There was no evidence for self-quenching or binding to cellular elements for cytoplasmic BCECF concentrations up to 1.8 mM. The following agents are capable of introducing error: (1) the Na⁺ substituteN-methyl-d-glucamine doubles theK _d and decreases by 13% the F _max of BCECF; (2) the Na⁺/H⁺ exchange inhibitor amiloride quenches BCECF fluorescence and is intrinsically fluorescent; and (3) bovine serum albumin (used to remove nigericin) quenches external BCECF with kinetics mimicking acidification of the cytoplasm.