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1.
J Phys Chem B ; 117(17): 5241-8, 2013 May 02.
Article in English | MEDLINE | ID: mdl-23534843

ABSTRACT

Systematic and precise measurements of electrical conductivities of aqueous solutions of cadmium chloride were performed in the 2 × 10(-5)-1 × 10(-2) mol·dm(-3) concentration range, from 278.15 to 313.15 K. Determined conductances were interpreted in terms of molecular model which includes a mixture of two 1:1 and 2:1 electrolytes. The molar limiting conductances of λ(0)(CdCl(+), T) and λ(0)(1/2Cd(2+), T), the equilibrium constants of CdCl(+) formation K(T) and the corresponding standard thermodynamic functions were evaluated using the Quint-Viallard conductivity equations, the Debye-Hückel equations for activity coefficients and the mass-action equation. An excellent agreement between calculated and experimental conductivities was reached.

2.
J Phys Chem B ; 117(2): 615-22, 2013 Jan 17.
Article in English | MEDLINE | ID: mdl-23241014

ABSTRACT

We study the conductance of dilute aqueous solutions for a series of guandinium salts at 298.15 K. The experimental molar conductivities were analyzed within the framework of the Quint-Viallard theory in combination with Debye-Hückel activity coefficients. From this analysis, we find no evidence for significant ion association in aqueous solutions of guanidinium chloride (GdmCl) and guanidinium thiocyanate (GdmSCN), and the molar conductivity of these electrolytes can be modeled assuming a complete dissociation. The limiting ionic conductivity of the guanidinium ion (Gdm(+)) is accurately determined to λ(Gdm(+)) = 51.45 ± 0.10 S cm(2) mol(-1). For the bivalent salts guanidinium sulfate (Gdm(2)SO(4)) and guanidinium carbonate (Gdm(2)CO(3)), the molar conductivities show small deviations from ideal (fully dissociated electrolyte) behavior, which are related to weak ion association in solution. Furthermore, for solutions of Gdm(2)CO(3), the hydrolysis of the carbonate anion leads to distinctively increased molar conductivities at high dilutions. The observed ion association is rather weak for all studied electrolytes and cannot explain the different protein denaturing activities of the studied guanidinium salts, as has been proposed previously.


Subject(s)
Carbonates/chemistry , Guanidine/chemistry , Guanidines/chemistry , Thiocyanates/chemistry , Water/chemistry , Electric Conductivity , Hydrolysis , Ions , Temperature
3.
J Phys Chem B ; 116(4): 1385-92, 2012 Feb 02.
Article in English | MEDLINE | ID: mdl-22220814

ABSTRACT

Precise measurements of electrical conductivities of methylparaben, ethylparaben, propylparaben, and butylparaben sodium salts in dilute aqueous solutions were performed from 278.15 to 313.15 K in 5 K intervals. Experimental conductivity data were analyzed applying the Quint-Viallard conductivity equations by taking into account the salt hydrolysis in aqueous solutions. These evaluations yield the limiting conductances of paraben anions and the dissociation constants of the investigated parabens in water. From temperature dependence of dissociation constants, the thermodynamic functions associated with the dissociation process were estimated. It was discovered that the contributions of enthalpy and entropy to the Gibbs free energy are quite similar. The Walden products of paraben anions in water are independent of temperature, indicating that the hydrodynamic radii are not significantly affected by temperature.


Subject(s)
Electric Conductivity , Parabens/chemistry , Water/chemistry , Ions/chemistry , Solutions , Temperature
4.
J Phys Chem B ; 112(23): 7032-44, 2008 Jun 12.
Article in English | MEDLINE | ID: mdl-18479161

ABSTRACT

The applicability of the Quint-Viallard conductivity equation to the representation of electrical conductivities in mixed solvents is examined. The concept of the modified Walden product is introduced, and the benefits compared with the ordinary Walden product are discussed. The universal curve of limiting conductances for all electrolytes (or for all ions) in a given pair of solvents is introduced and examined in a number of mixtures which include methanol, ethanol, 1-propanol, tert-butyl alcohol, 1,4-dioxane, N, N-dimethylformamide, sulfolane, tetrahydrofuran, and ethylene carbonate with water. Also examined are nonaqueous mixtures of acetone-ethanol, acetone-1-propanol, dimethyl sulfoxide-propylene carbonate, acetonitrile-methanol, acetonitrile-carbon tetrachloride, and acetonitrile-propylene carbonate. Many electrolytes were involved in the evaluation of the universal curves, but the majority are alkali-metal halides, tetraalkylammonium halides, tetraalkylammonium tetraphenylborides, and potassium xanthates (inorganic and organic acids are treated separately). If in a given mixed solvent system the limiting conductance of electrolyte is unknown, the universal curve permits estimating its value and gives an indication about the quality of performed conductivity measurements. The existence of universal curves of limiting conductances indicates that the properties of electrolytes in pure solvents are, to a great extent, preserved also in the mixture of solvents due to the simple dilution effect.

5.
J Phys Chem B ; 111(41): 11957-67, 2007 Oct 18.
Article in English | MEDLINE | ID: mdl-17887789

ABSTRACT

Systematic determinations of electrical conductivities of sodium penicillin G, potassium penicillin G, and potassium penicillin V in the 278.15-313.15 K temperature range are reported. These conductivities are examined by applying the Quint-Viallard conductivity equations and the Debye-Hückel equations for activity coefficients. Determined dissociation constants and the limiting conductances of penicillin anions are based on the assumption that in dilute aqueous solutions, penicillin salts behave as acidic salts of dibasic acids, which are the final products of degradation reactions in acidic media.


Subject(s)
Electric Conductivity , Penicillin G/chemistry , Penicillin V/chemistry , Potassium/chemistry , Sodium/chemistry , Temperature , Hydrolysis , Indicator Dilution Techniques , Solutions , Viscosity
6.
J Phys Chem B ; 110(17): 8893-906, 2006 May 04.
Article in English | MEDLINE | ID: mdl-16640450

ABSTRACT

A general approach is proposed to analyze electrical conductivities in aqueous solutions of polybasic organic acids. Experimental conductivities are examined in the context of dissociation and hydrolysis reactions by applying the Quint-Viallard conductivity equations and the Debye-Hückel equations for activity coefficients. The proposed numerical procedure is illustrated by the case of benzenehexacarboxylic (mellitic) acid and its neutral and acidic salts. From conductivity measurements of mellitic acid and its salts, performed in dilute aqueous solutions in the 278.15-308.15 K temperature range, the limiting conductances of mellitic anions, lambda(0)(1/jH(6-j)Mel(-j), T), j = 1, 2, 3, 4, 5, 6 are determined.


Subject(s)
Benzoates/chemistry , Electric Conductivity , Hydrogen-Ion Concentration , Hydrolysis , Salts/chemistry , Solutions/chemistry , Temperature , Water/chemistry
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