Non-statistical approach to solutions

Gutmann, V.; Resch, Gerhard

doi:10.1351/pac198153071447

Cited by 18 publications

(18 citation statements)

References 4 publications

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“…The 365, 404, and 434 nm irradiation mentary electrostatic theory, such as dipole moment, data do not align with the former ones. polarizability, and dielectric constant, are usually found to be As previously discussed (23), the 313 nm excitation popuunsuitable for the description of solvent effects (28). Double lates exclusively the Fe + CN-charge transfer state, namely reciprocal plots (I/@ vs. llq and I/@ vs. 11~) do not present 'CT.…”

Section: Physical Measurements and Proceduresmentioning

confidence: 93%

“…The quantum yield of strong tendency to form intermolecular hydrogen bonds (29,30), and keep the solvent structure from changing due to preferential solvation. Specific interactions, such as hydrogen bonding, have been recognized for a long time to be more important than dispersion forces, depending on polarizabilities, in accounting for solvent effects (28,30). The magnitude of the bulk solution properties for water-glycerol mixtures can be considered close to that for the coordination sphere.…”

Section: Physical Measurements and Proceduresmentioning

confidence: 99%

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Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)₅(tn)]³⁻ complex

Lima¹,

Iha²

1996

Can. J. Chem.

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Abstract:The solvent composition and wavelength effects on the quantum yield of the photoinduced ring closure process of the [~e (~~) , ( t n ) ]~-complex (tn = 1.3-diaminopropane) were investigated. The reactivity was shown to be controlled by the macroscopic properties of water-glycerol mixtures. A sharp decrease in quantum yields with increasing medium viscosity was observed for all the irradiation wavelengths employed (3 13,334,365,404, and 434 nm). The observed quantum yields ranged from 0.24 (Ai, = 313 nm, 66.48 wt.% of acetonitrile) to 0.010 (Ai, = 404 or 434 nm, 61.85 wt.% of glycerol). The overall efficiency is a complex function of the dynamics of radical recombination and dissociation pathways. The proposed cage model for the deactivation dynamics of the excited states illustrates that the decrease in medium viscosity favors a diffusional escapeof the cyanide from the solvent cage.Key words: photochemistry, pentacyanoferrate(I1) complexes, solvent effect, wavelength effect.Resume : L'effet de la composition du solvant et de la longueur d'onde de l'excitation dans le rendement quantique du processus photoinduit de fermeture d'anneau du complexe [~e ( c~) , ( t n ) ]~-(tn = 1.3-diaminepropane) a Ct C etudiC. La reactivitC semble &tre controlCe par les proprietCs macroscopiques des mClanges de solvant eau-glycerol. Une dtcroissance abrupte dans le rendement quantique est observCe avec la variation de la viscositC du milieu, pour tous les longueurs d'onde d'irradiation employCes (3 13, 334,365,404 et 434 nm). Le rendement quantique observC varie de 0,24 (Ai, = 313 nm; 66,48% poids acktonitrile) a 0,010 (Ai, = 404 ou 434 nm; 61,85% poids glycerol). L'efficacitC totale est une fonction complexe de la dynamique des ttapes de dissociation et de recombinasion radicale. Le modCle cage propost pour la dynamique de deactivation des Ctats excitCs montre que la dCcroissance dans la viscositC du milieu favorise la sortie de la cyanide de la cage du solvant.Mots elks : photochimie, complexes de pentacyanoferrate(II), effet du solvant, effet de la longueur d'onde de l'excitation,

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Section: Physical Measurements and Proceduresmentioning

confidence: 93%

Section: Physical Measurements and Proceduresmentioning

confidence: 99%

Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)₅(tn)]³⁻ complex

Lima¹,

Iha²

1996

Can. J. Chem.

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“…The quantitative balance of such interactions together with the solute-solute interactions determines the actual position of the chemical equilibrium [1][2][3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Complex Formation Equilibria between Ag(I) and Thioureas in Propan-2-ol

Marco

2013

ISRN Inorganic Chemistry

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(EnTu) in propan-2-ol as solvent medium have been investigated by potentiometry within the temperature range 10 ∘ C-40 ∘ C and self-determined ionic medium by (AgNO 3 ) concentration range 6.36 ⋅ 10 −6 -3.83 ⋅ 10 −5 m⋅dm −3 (no background electrolyte added). The experimental results can be interpreted with the stepwise formation of tris-coordinated complexes AgL ( = 1-3; hereafter charge is omitted). The stability constants log and the standard thermodynamic changes in enthalpy (Δ ∘ ) and entropy (Δ ∘ ) for overall complex formation reactions Ag(I) + L = AgL ( = 1-3) have been evaluated. The reactions are exothermic in nature and entropy disfavored for all the investigated ligands. The standard enthalpy and entropy changes for the stepwise reactionsThe stepwise enthalpy are mutually linearly related to the corresponding entropy changes with isoequilibrium temperatures iso = 285, 305, and 363 K for = 1, 2, or 3 respectively.

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“…9 The present situation has been characterized as follows: 10 'No theory on water structure has been proposed that is predictive, theoretically sound and suitable to account for the quality of the liquid. ' Because liquid water is actually a solution from which the last traces of both hydrophilic and hydrophobic solutes cannot be removed, 2,[11][12][13] we suggested extending the molecular concept and treating the liquid under consideration as a highly differentiated, well organized, flexible macromolecule. [11][12][13] In order to gain an understanding of the qualities, we started from the wealth of observations under complex conditions and took into consideration the unavoidable presence of both hydrophilic and hydrophobic solutes.…”

Section: Introductionmentioning

confidence: 99%

“…[11][12][13] In order to gain an understanding of the qualities, we started from the wealth of observations under complex conditions and took into consideration the unavoidable presence of both hydrophilic and hydrophobic solutes. [11][12][13] …”

Section: Introductionmentioning

confidence: 99%

Hydrophobic Interactions in Aqueous Solutions: Their Operation in Living Systems

Gutmann

Resch

1997

J. Phys. Org. Chem.

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Evidence is provided for the enormous role of hydrophobic interactions in aqueous solutions. It is concluded that complementary functions of hydrophilic and of hydrophobic species are in continuous operation and that these are a conditio sine qua non for the existence of the liquid. With regard to the supermolecular aggregations, hydrophobic interactions are operative on the highest hierarchic levels of the system organization, i.e. at the interface and at the holes around dissolved hydrophobic species. It is further emphasized that water is essential both for the unity and for the differentiation of each living organism. With regard to its role for the differentiation of the body, the hydrophobic interactions are of paramount importance, notably those provided by amphipathic solutes. The cell membrane is considered to be the result of interactions between the highest hierarchic levels of intracellular and extracellular water. The hydrophobic double layer provides the barriers for the separation of intracellular and extracellular water and at the same time the connections for recognition and for exchange of information between them. The DNA structures obtain conservative boundary conditions for their surrounding water systems which do not freeze at Ϫ 60°C. These water systems are dynamically superior to all other parts of the water system of the organism. It is suggested that more knowledge about the abilities of liquid water can be obtained by giving appropriate attention to its properties within the living body.

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Non-statistical approach to solutions

Abstract: Abstract

Cited by 18 publications

References 4 publications

Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)₅(tn)]³⁻ complex

Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)₅(tn)]³⁻ complex

Complex Formation Equilibria between Ag(I) and Thioureas in Propan-2-ol

Hydrophobic Interactions in Aqueous Solutions: Their Operation in Living Systems

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Non-statistical approach to solutions

Abstract: Abstract

Cited by 18 publications

References 4 publications

Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)5(tn)]3− complex

Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)5(tn)]3− complex

Complex Formation Equilibria between Ag(I) and Thioureas in Propan-2-ol

Hydrophobic Interactions in Aqueous Solutions: Their Operation in Living Systems

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Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)₅(tn)]³⁻ complex

Wavelength dependence and solvent effects on the ligand field photochemistry: the ring closure process in the excited [Fe(CN)₅(tn)]³⁻ complex