Activity Coefficients and Gibbs Energies of Transfer of Tetraalkylammonium Dianilinetetraisothiocyanatochromates(III)

1994 ◽  
Vol 59 (8) ◽  
pp. 1738-1744
Author(s):  
Vladislav Holba
Keyword(s):  
Activity Coefficients ◽  
Transfer Functions ◽  
Butyl Alcohol ◽  
Methyl Ethyl ◽  
Tetraalkylammonium Ions ◽  
Ionic Transfer ◽  
Gibbs Energies ◽  
Gibbs Energies Of Transfer ◽  
Acetonitrile Solutions ◽  
Mixed Systems

The solubilities of tetraalkylammonium dianilinetetraisothiocyanatochromates(III) (alkyl = methyl, ethyl, 1-propyl, and 1-butyl) in water, water - methanol, water - tert-butyl alcohol and water - acetonitrile solutions were measured at 25 °C. The results were used to evaluate the activity coefficients and Gibbs energies of transfer of the saturating salts from water to the mixed systems. The Gibbs energies of transfer of the [Cr(C6H5NH2)2(NCS)4]- ion were obtained by means of known ionic transfer functions for the tetraalkylammonium ions based on the TATB assumption.

Solubility of Tris(ethylenediamine)chromium(III) and Hexaureachromium(III) Hexacyanoferrates(III) in Water and Mixed Water-Organic Solvents

1995 ◽  
Vol 60 (4) ◽  
pp. 537-544 ◽  
Author(s):  
Vladislav Holba ◽  
Marcela Hanková
Keyword(s):  
Experimental Data ◽  
Aqueous Solutions ◽  
Binary Mixtures ◽  
Organic Solvents ◽  
Activity Coefficients ◽  
Butyl Alcohol ◽  
Gibbs Energies ◽  
Gibbs Energies Of Transfer ◽  
Mixed Water

The solubilities of tris(ethylenediamine)chromium(III) and hexa(urea)chromium(III) hexacyanoferrates(III) in aqueous solutions of different supporting electrolytes as well as in binary mixtures of water with methanol, tert-butyl alcohol and acetonitrile were measured at 25 °C. The experimental data have been used to evaluate the activity coefficients of the saturating salts in water and their Gibbs energies of transfer from water into the binary mixtures investigated.

Solubility and Thermodynamic Transfer Functions of Cesium Dianilinetetraisothiocyanatochromate(III)

1998 ◽  
Vol 63 (3) ◽  
pp. 293-298
Author(s):  
Vladislav Holba
Keyword(s):  
Experimental Data ◽  
Isopropyl Alcohol ◽  
Transfer Functions ◽  
Butyl Alcohol ◽  
Aqueous Methanol ◽  
Gibbs Energies ◽  
Gibbs Energy Of Transfer ◽  
Energy Of Transfer ◽  
The Given ◽  
Reference Electrolyte

The solubilities of cesium dianilinetetraisothiocyanatochromate(III) in water as well as in aqueous methanol, isopropyl alcohol, tert-butyl alcohol and acetonitrile were measured as a function of temperature and solvent composition. The Gibbs energies, enthalpies and entropies of transfer of the salt from water to the given solvents have been evaluated from experimental data. The contribution of [Cr(C6H5NH2)2(NCS)4]- ion to the Gibbs energy of transfer of the investigated salt has been calculated using the tetraphenylarsonium tetraphenylborate (TATB) reference electrolyte assumption.

Activity Coefficients of Tris(ethylenediamine)cobalt(III) Hexacyanoferrate(III) in Water and Mixed Water-Alcohol Solvents

1993 ◽  
Vol 58 (8) ◽  
pp. 1791-1797 ◽  
Author(s):  
Vladislav Holba
Keyword(s):  
Aqueous Solution ◽  
Activity Coefficients ◽  
Transfer Functions ◽  
Butyl Alcohol ◽  
Alcohol Solvents ◽  
Mixed Water ◽  
Mean Activity Coefficients ◽  
Water Alcohol

The solubility of tris(ethylenediamine)cobalt(III) hexacyanoferrate(III) were measured in aqueous solution of NaClO4, NaCl, KCl, KBr, K2SO4, Mg2SO4, (CH3)4NBr, (C2H5)4NBr, (1-C3H7)4NBr, and (1-C4H9)4NBr, as well as in the solution of NaClO4 in mixtures of water with methanol and tert-butyl alcohol. The experimental mean activity coefficients are compared with theoretical ones evaluated with the aid of extended Debye-Huckel relation. From the solubilities in water and in water-alcoholic solvents the thermodynamic transfer functions of the saturating salt were calculated.

Alkaline hydrolysis of methyl hydrogen malonate in water-organic solvents

1986 ◽  
Vol 51 (6) ◽  
pp. 1187-1194 ◽  
Author(s):  
Oľga Grančičová ◽  
Vladislav Holba ◽  
Ľudmila Beluská
Keyword(s):  
Experimental Data ◽  
Ethylene Glycol ◽  
Alkaline Hydrolysis ◽  
Transfer Functions ◽  
Butyl Alcohol ◽  
Gibbs Energies ◽  
Tert Butyl Alcohol ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Activated Complex

Kinetics of alkaline hydrolysis of methyl hydrogen malonate in water-methanol, water-dioxane, water-tert-butyl alcohol and water-ethylene glycol mixtures was examined. The valuse of the transfer functions of the activated complex δmμ≠ from water to the first two mixed media were calculated from the measured solubilities of tetrabutylammonium hydrogen malonate, the activation Gibbs energies and the known values of transfer functions for tetrabutylammonium and hydroxide ions. Some conclusions concerning the effect of a nonaqueous component of the solvent on solvation of the reactants and the activated complex have been drawn from the experimental data obtained.

Temperature dependence of activity coefficients and Gibbs energies of transfer of LiBr in acetonitrile, dimethyl sulfoxide, and N,N-dimethylacetamide from EMF measurements

1997 ◽  
Vol 75 (11) ◽  
pp. 1500-1507 ◽  
Author(s):  
J. Barthel ◽  
R. Neueder ◽  
A. Schröder
Keyword(s):  
Dimethyl Sulfoxide ◽  
Activity Coefficients ◽  
Redox Reaction ◽  
Electromotive Force ◽  
Association Constants ◽  
Aprotic Solvents ◽  
Temperature Dependent ◽  
Emf Measurements ◽  
Gibbs Energies ◽  
Gibbs Energies Of Transfer

Electromotive force (EMF) measurements based on the redox reaction[Formula: see text]are reported for solutions of LiBr at concentrations 0.005 < cLiBr/(mol dm−3) < 0.1 in acetonitrile (AN), dimethyl sulfoxide (DMSO), and N.N-dimethylacetamide (DMA) in the temperature range 278.15 < T/K < 308.15. Gibbs energies of transfer and activity coefficients are estimated. The association constants of LiBr in AN, DMSO, and DMA from EMF measurements and the enthalpy of transfer AN → DMSO are compared to those from other methods of determination. Keywords: temperature-dependent EMF measurements, aprotic solvents, LiBr, TlBr(s) | TlxHg(l) electrode, activity coefficients, transfer quantities.

Transfer of 1,1'-dialkyl-4,4'-bipyridinium dication (viologen) across the water-dichloroethane and water-nitrobenzene interfaces

1987 ◽  
Vol 52 (4) ◽  
pp. 830-837 ◽  
Author(s):  
Josef Hanzlík ◽  
Zdeněk Samec
Keyword(s):  
Cyclic Voltammetry ◽  
Charge Transfer ◽  
Ion Association ◽  
Association Constants ◽  
Methyl Ethyl ◽  
Considerable Influence ◽  
Conductivity Measurements ◽  
Gibbs Energies ◽  
Gibbs Energies Of Transfer ◽  
Voltammetric Measurements

Transfer of viologen dications R2V2+ (R = methyl, ethyl, propyl, butyl, pentyl, heptyl or benzyl) across the water-1,2-dichloroethane and water-nitrobenzene interfaces has been studied by cyclic voltammetry. Effects of the changes in the viologen structure and in the composition of solutions of both phases on the voltammetric behaviour have been inspected. Ion association, in particular that occuring in the organic phase, has a considerable influence on the viologen dication transfer and plays the key role in the proposed charge transfer mechanism. From the conductivity measurements the association constants for viologen tetraphenylborates in nitrobenzene have been evaluated. From the voltammetric measurements the Gibbs energies of transfer of viologen dications across the water-nitrobenzene interface have been determined.

Thermodynamic and Kinetic Investigation of the Solvent Effect on the Oxidation of [Co(en)2SCH2COO]+ with S2O82- In Water-Methanol and Water-tert-Butyl Alcohol Mixtures

1993 ◽  
Vol 58 (5) ◽  
pp. 1001-1006 ◽  
Author(s):  
Oľga Vollárová ◽  
Ján Benko
Keyword(s):  
Transfer Functions ◽  
Activation Parameters ◽  
Butyl Alcohol ◽  
Oxidation Of Co ◽  
Kinetics Of Oxidation ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Alcohol Mixtures ◽  
Kinetics Of

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.

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