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Mechanism of the Water Clusters Formation in the Organic Phase in the Presence of Hydrated Ions
Holub, Karel ; Samec, Zdeněk ; Mareček, Vladimír
A two-electrode cell comprising a liquid/liquid interface is used to study the water clusters formation in the organic solvent phase following the extraction of tetraalkylammonium chloride (TAACl) from the aqueous phase. The change in the concentration of the common TAA+ ion on the aqueous side of the interface is monitored by the open circuit potential measurements. It is shown that the amount of TAACl extracted into the organic phase exceeds considerably the limit determined by the concentration of Cl- in the organic phase at a given interfacial potential difference and the electroneutrality condition. A mechanism is proposed including an accumulation of the excess TAACl in the water clusters formed from the hydration shell of the Cl- ions, water already dissolved in the organic phase, and additional water extracted from the aqueous phase. At higher concentration of TAACl in the aqueous phase this process leads to the formation of emulsion in the organic phase.
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Application and interpretation of seismic surface waves in broad frequency range
Gaždová, Renata ; Vilhelm, Jan (advisor) ; Novotný, Oldřich (referee) ; Holub, Karel (referee)
Submitted Ph.D. thesis is concerning the application and interpretation of seismic surface waves in a broad range of frequencies and scales. Using surface waves as a supplement to the methods dealing with body waves seems to be worth the effort. Surface wave interpretation can be used to obtain new information about the studied medium and simultaneously it can overcome, in some cases, the limitations of other seismic techniques. Moreover, surface waves are usually present on measured records and hence for its usage it is not necessary to modify the standard measuring procedures. One of the results of this thesis is an original algorithm for dispersive waveform calculation. The program works in an arbitrary range of frequencies and scales. The input parameter for the calculation is the dispersion curve. In this point the algorithm differs from all other approaches used so far. Algorithm is based on a summation of frequency components with shifts corresponding to the velocity dispersion and distance. The resulting waveform only contains an individual dispersive wave of the selected mode, thus being particularly suitable for testing of methodologies for dispersive wave analysis. The algorithm was implemented into the program DISECA. Furthermore, a new procedure was designed to calculate the dispersion...
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Noise Analysis of Ion Transfer Kinetics at the Micro Liquid/Liquid Interface
Josypčuk, Oksana ; Holub, Karel ; Mareček, Vladimír
Fluctuation analysis was utilized to determine the TEA ion transfer kinetics across the water/1,2-dichloroethane interface. The average value ks = 0.34 cm s-1 is comparable with the previously reported value ks = 0.2 cm s-1, derived from electrochemical impedance spectroscopy experiments. The experimental approach utilizing a thick wall glass microcapillary to fix the interface exhibits a very small stray capacitance value, proving this system to be suitable for determining the kinetics of the fast ion transfer across a liquid/ liquid interface. Application of a method employing a small perturbation signal prevents polarization of the inner capillary surface by current flowing through the cell. The induced polarization of the capillary can affect ion concentration at the interface due to electroosmosis and thus make the kinetics data evaluation difficult or erroneous.
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Proton transfer across a liquid/liquid interface facilitated by phospholipid interfacial films
Holub, Karel ; Jänchenová, Hana ; Štulík, Karel ; Mareček, Vladimír
The five-step mechanism proposed earlier for the formation of phospholipid films at aqueous/organic interfaces and for their behavior involving transfer of protons from the aqueous to the organic phase was further studied by cyclic voltammetry. A theoretical model was created for this mechanism and compared with the experimental results. Both the experimental and theoretical results support the proposed mechanism and evaluate the importance of the individual steps. It seems that the decisive step is the regenration of the zwitterionic form of the phospholipid at the interface, ensuring stability of the film in time and its continuous functioning.
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