Broadband Dielectric Spectroscopy: A Powerful Tool for the Determination of Charge Transfer Mechanisms in Ion Conductors

2012 ◽  
pp. 109-183 ◽  
Author(s):  
Vito Di Noto ◽  
Guinevere A. Giffin ◽  
Keti Vezzù ◽  
Matteo Piga ◽  
Sandra Lavina
2020 ◽  
Vol 16 ◽  
Author(s):  
Sheng-Yun Li ◽  
Fang Tian

: A spectrophotometry was investigated for the determination of epsilon aminocaproic acid (EACA) with p-nitrophenol (PNP). The method was based on a charge transfer (CT) complexation of this drug as n-electron donor with π-acceptor PNP. Experiment indicated that the CT complexation was carried out at room temperature for 10 minutes in dimethyl sulfoxide solvent. The spectrum obtained for EACA/PNP system showed the maximum absorption band at wavelength of 425 nm. The stoichiometry of the CT complex was found to be 1:1 ratio by Job’s method between the donor and the acceptor. Different variables affecting the complexation were carefully studied and optimized. At the optimum reaction conditions, Beer’s law was obeyed in a concentration limit of 1~6 µg mL-1. The relative standard deviation was less than 2.9%. The apparent molar absoptivity was determined to be 1.86×104 L mol-1cm-1 at 425 nm. The CT complexation was also confirmed by both FTIR and 1H NMR measurements. The thermodynamic properties and reaction mechanism of the CT complexation have been discussed. The developed method could be applied successfully for the determination of the studied compound in its pharmaceutical dosage forms with a good precision and accuracy compared to official method as revealed by t- and F-tests.


1991 ◽  
Vol 56 (1) ◽  
pp. 112-129 ◽  
Author(s):  
Takashi Kakiuchi ◽  
Mitsugi Senda

We have estimated the degree of polarizability of a polarized oil-water interface used as a working interface and that of the nonpolarizability of a nonpolarized interface used as a reference oil-water interface from the numerical calculation of dc and ac current vs potential behavior at both interfaces. Theoretical equations of dc and ac currents for simultaneous cation and anion transfer of supporting electrolytes have been derived for the planar stationary interface for reversible and quasi-reversible cases. In the derivation, the migration effect and the coupling of the cation and anion transfer have been incorporated. The transfer of ions constituting a supporting electrolyte contributes to the total admittance of the interface even in the region where the interface may be considered as polarized in dc sense, as pointed out first by Samec et al. (J. Electroanal. Chem. 126, 121 (1981)). Moreover, the reference oil-water interface is not ideally reversible, so that the contribution from this interface to the measured admittance cannot be negligible, unless the area of the reference oil-water interface is much larger than that of the working oil-water interface. The effect of non-ideality of the reference oil-water interface on the determination of double layer capacitances and kinetic parameters of charge transfer at the working oil-water interface has been estimated.


2020 ◽  
Vol 10 (1) ◽  
Author(s):  
Adrian Radoń ◽  
Dariusz Łukowiec ◽  
Patryk Włodarczyk

AbstractThe dielectric properties and electrical conduction mechanism of bismuth oxychloride (BiOCl) plates synthesized using chloramine-T as the chloride ion source were investigated. Thermally-activated structure rebuilding was monitored using broadband dielectric spectroscopy, which showed that the onset temperature of this process was 283 K. This rebuilding was related to the introduction of free chloride ions into [Bi2O2]2+ layers and their growth, which increased the intensity of the (101) diffraction peak. The electrical conductivity and dielectric permittivity were related to the movement of chloride ions between plates (in the low-frequency region), the interplanar motion of Cl− ions at higher frequencies, vibrations of these ions, and charge carrier hopping at frequencies above 10 kHz. The influence of the free chloride ion concentration on the electrical conductivity was also described. Structure rebuilding was associated with a lower concentration of free chloride ions, which significantly decreased the conductivity. According to the analysis, the BiOCl plate conductivity was related to the movement of Cl− ions, not electrons.


Molecules ◽  
2021 ◽  
Vol 26 (7) ◽  
pp. 2039
Author(s):  
Gamal A. E. Mostafa ◽  
Ahmed Bakheit ◽  
Najla AlMasoud ◽  
Haitham AlRabiah

The reactions of ketotifen fumarate (KT) with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) as π acceptors to form charge transfer (CT) complexes were evaluated in this study. Experimental and theoretical approaches, including density function theory (DFT), were used to obtain the comprehensive, reliable, and accurate structure elucidation of the developed CT complexes. The CT complexes (KT-DDQ and KT-TCNQ) were monitored at 485 and 843 nm, respectively, and the calibration curve ranged from 10 to 100 ppm for KT-DDQ and 2.5 to 40 ppm for KT-TCNQ. The spectrophotometric methods were validated for the determination of KT, and the stability of the CT complexes was assessed by studying the corresponding spectroscopic physical parameters. The molar ratio of KT:DDQ and KT:TCNQ was estimated at 1:1 using Job’s method, which was compatible with the results obtained using the Benesi–Hildebrand equation. Using these complexes, the quantitative determination of KT in its dosage form was successful.


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