Conductometric and Dielectric Behaviour of Solutions of Tetrabutylammonium Perchlorate in Solvents of Low and Medium Permittivity.

Sigvartsen, T.; Gestblom, Bo; Noreland, E.; Songstad, Jon; Lönnberg, Harri; Colacio, Enrique; Mulichak, A. M.; Alminger, Tomas; Erickson, Magnus; Grundevik, Inger; Hagin, Inger; Hoffman, Kurt-Jürgen; Johansson, Svante; Larsson, Sam; Löfberg, Ingalil; Ohlson, Kristina; Persson, Björn; Skånberg, Inger; Tekenbergs-Hjelte, Lija

doi:10.3891/acta.chem.scand.43-0103

Cited by 59 publications

(48 citation statements)

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“…However, it is known that TBA+C104-(5) do not form quadrupoles or larger aggregates in solvents of medium polarity (22). Hence, it is more likely that in this case, the departure from the theoretical expression results from an increment of the dielectric constant of the medium with increasing concentration of the salt (22). We observed a similar behavior for the system Py/ DMA/TBA+C104 -(5).…”

Section: Methodssupporting

confidence: 70%

“…These authors proposed that the nonlinear behavior is produced by the formation of large salt aggregates that are much more efficient in inducing charge separation. However, it is known that TBA+C104-(5) do not form quadrupoles or larger aggregates in solvents of medium polarity (22). Hence, it is more likely that in this case, the departure from the theoretical expression results from an increment of the dielectric constant of the medium with increasing concentration of the salt (22).…”

Section: Methodsmentioning

confidence: 95%

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Salt‐induced Charge Separation in Photoinduced Electron Transfer Reactions. The Effect of Ion Size*

Grosso

Previtali

Chesta

1998

Photochem & Photobiology

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The effect of added salts on the efficiency for photoinduced charge separation in two typical electron acceptor (A)/electron donor (D) systems was studied by the technique of laser flash photolysis. We investigate the exciplex-forming pyrenelp-dicyanobeene (Fy/DCB) and pyrenelN,N-dimethylaniline (Py/DMA) systems in ethyl acetate. The salts selected for this study are tetrabutylammonium chloride, tetrahexylammonium chloride, lithium perchlorate, sodium perchlorate, tetrabutylammonium perchlorate, sodium tetraphenylborate and tetrabutylammonium tetraphenylborate. In most cases, the salts quench the emission of the exciplexes with rate constants near the ditTusional rate limit in ethyl acetate. An apparent red shift of the fluorescence maximum of the exciplexes with increasing salt concentration is also generally observed. Laser flash photolysis experiments showed that in the absence of the salts both A/ D systems yield exclusively the triplet excited state of the polyaromatic. However, in the presence of many of the electrolytes studied, induced free radical ion formation is observed. The experimental efficiencies for induced charge separation (q) depend on the A/D system and on the nature of the salt. The measured q values vary between 0 and 0.5. The most striking variation corresponds to the lithium and sodium perchlorates. These salts are almost totally inefficient in quenching the Py/DCB exciplex, while they quench and induce charge separation from the Py/DMA exciplex with a high yield. The effect of the different salts on both exciplexes may be rationalized by using the concept of the softhard character of the interacting ions.

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Section: Methodssupporting

confidence: 70%

Section: Methodsmentioning

confidence: 95%

Salt‐induced Charge Separation in Photoinduced Electron Transfer Reactions. The Effect of Ion Size*

Grosso

Previtali

Chesta

1998

Photochem & Photobiology

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“…As seen from Figure 4, at low salt concentrations up to about 60 wt % of Hex 4 N + I¯, the molar conductivity shows only a very slight increase, although one expects this to remain essentially constant. An increasing molar conductivity at low salt concentrations had been reported for several other electrolyte systems in this concentration range (Sigvartsen et al, 1989;Albinsson et al, 1993). A common explanation for this effect is the formation of triple ions in this concentration region as originally for data in the high salt concentration region.…”

Section: September 2013mentioning

confidence: 55%

Conductivity behaviour in novel quasi-solid-state electrolyte based on polyacrylonitrile and tetrahexylammonium iodide intended for dye sensitized solar cells

Bandara

Svensson

Dissanayake

et al. 2013

J. Natn. Sci. Foundation Sri Lanka

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The conduction of iodide ions in gel polymer electrolytes and the performance of dye sensitized solar cells containing such an electrolyte can be enhanced by incorporating a salt having a bulky cation. In this work, polyacrylonitrile (PAN) and Hex 4 N + I¯ based gel electrolytes with ethylene carbonate and propylene carbonate as plasticizers have been studied. The variation of conductivity and molar conductivity with salt concentration has been discussed in order to understand the mechanism of iodide ion conductivity in this system. Out of the various compositions studied, the electrolyte containing 120 % salt with respect to weight of PAN showed the highest conductivity, 2.0 × 10-3 Scm −1 at 25 °C and a glass transition at-102.3 °C. The electrolytes exhibit predominantly ionic behaviour and because of the bulky cation a negligible cationic transport is shown. A quasi-solid-state dye sensitized solar cell was fabricated employing the optimized gel electrolyte. This cell showed an energy conversion efficiency of 3.1 % and a short circuit current density of 8.1 mAcm-2 under irradiation of 1000 Wm-2 .

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“…Depending on the solvent's properties and the extent of ion association, dielectric constants for the mixed-solvent electrolyte solutions, ε r may increase or decrease with increasing electrolyte concentration (Wang and Anderko, 2001). Data for the dielectric constants of mixed-solvent electrolyte solutions are available in the literature (Akhadov, 1980;Barthel, 1996;Noertemann et al, 1997;Kaatze et al, 1980;La Manna et al, 1993;Lileev et al, 1992;Lileev et al, 1998;Sigvartsen et al, 1989;Sigvartsen et al, 1991;Wei and Sridhar, 1990;Winsor, 1982;Zasrtskii et al, 1994). The most common models for predicting ε r are those of Debye-Falkenhagen (Falkenhagen, 1934) for dilute solutions and the kinetic polarization deficiency model derived by Hubbard and Onsager (1977).…”

Section: Properties Of Mixed Solventsmentioning

confidence: 96%

Solution Properties of Inorganic Contamination in Mixed Solvents: Theory, Progress, and Limitations

Srour¹,

McDonald

2011

Critical Reviews in Environmental Science and Technology

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Most of what is known about the environmental fate and transport of contaminants comes from studies of dilute, aqueous solutions. Theoretical and practical aspects of hydrophobic organic contaminants in aqueous mixtures of organic solvents are well developed, but relatively little attention has been paid to those situations where inorganic contaminants such as metals, water, and organic solvents occur simultaneously. The authors discuss changes in solution properties accompanying the addition of organic solvents. They review more than 500 references to available data on ion solvation, solubility, activity, acidity, pairing, and pH in electrolyte and electrolyte-free solvent mixtures and tabulate selected experimental values. Whenever available, equations developed to estimate these properties are given and their applications and limitations described. The implications of the progress in mixed-solvents solution chemistry on contaminant behavior and transport are described. Major limitations to the study of inorganic contamination in mixed solvents include the absence of complete and comprehensive data (e.g., type of ionic species, activity coefficients, solubility constants) that characterize solute and solvent properties in these mixtures and the indefinite number of possible solute and solvent combinations. The generation of models predicting such data from easily measured benchmark solute and solvent properties is a major challenge. The availability of such database and models may open the field for environmental engineers and soil scientists to study the basic chemical processes and mechanisms of metal contamination in complex multicomponent systems.

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Conductometric and Dielectric Behaviour of Solutions of Tetrabutylammonium Perchlorate in Solvents of Low and Medium Permittivity.

Cited by 59 publications

References 0 publications

Salt‐induced Charge Separation in Photoinduced Electron Transfer Reactions. The Effect of Ion Size*

Salt‐induced Charge Separation in Photoinduced Electron Transfer Reactions. The Effect of Ion Size*

Conductivity behaviour in novel quasi-solid-state electrolyte based on polyacrylonitrile and tetrahexylammonium iodide intended for dye sensitized solar cells

Solution Properties of Inorganic Contamination in Mixed Solvents: Theory, Progress, and Limitations

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