Applications of the Eastman Thermocell Equation.<sup>1</sup> I. Certain Absolute Ionic Entropies and Entropies of Transfer of Alkali Metal and Tetraalkylammonium Bromides and Hydroxides

Goodrich, Justin C.; Goyan, Frank M.; Morse, E. E.; Preston, Roger G.; Young, M. B.

doi:10.1021/ja01166a020

Cited by 34 publications

(14 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The two transport entropies S%, and S~ for an ion s do not coincide with its ordinary ionic entropy (based on the standard S ~ (H § : 0 at all temperatures) and neither do they coincide with one another. S~E, is the entropy transported by an 3 S*E~ has been referred to (18,29,41) as the "absolute ionic entropy," and S*M~ as the "entropy of transfer," Agar and Breck (33) have referred to S*B~ + S*~ as the "transported entropy" and to S*~ as the "molar entropy of transport." See Temkin and Khoroshin (33).…”

Section: Thermodynamics Of Thermal Ce~lsmentioning

confidence: 99%

“…With the assumption that the tljp of saturated potassium chloride is zero, Fales and Mudge's (14) measurements lead to a value of the entropy of electrochemical transport S% of the hydrogen ion, as Equation [131 has been referred to as the Eastman thermocell equation (29) and applies to a thermal cell in its initial state, before the onset of thermal diffusion. Wherever the Soret effect is allowed to develop, it can be shown, by introducing solute diffusion into the set of Onsager fiuxes [6][7], that the cell reaches a final steady .…”

Section: Thermodynamics Of Thermal Ce~lsmentioning

confidence: 99%

See 1 more Smart Citation

The Temperature Coefficients of Electrode Potentials

deBethune

Licht

Swendeman

1959

J. Electrochem. Soc.

284

154

View full text Add to dashboard Cite

The temperature coefficient of the potential of an electrode can be defined experimentally by reference to (a) the potential of the SHE at the same temperature, (b) the potential of the same electrode at some fixed temperature. These two definitions give rise to the "isothermal" and "thermal" temperature coefficients of electrode potentials. The isothermal coefficient is AS/nF where ~S is the reaction entropy of the "SHE//Electrode" cell. The thermal coefficient is S*/nF where S* is the entropy transported from the hot to the cold heat reservoir by the passage of n faradays of positive electricity through the cell from the cold to the hot electrode (before the onset of thermal diffusion). The entropy S* is divided into an entropy S*E of electrochemical transport which determines the electrode temperature effect, and an entropy S*. of migration transport which determines the thermal liquid junction potential.By assuming that S*~ is negligible in a saturated potassium chloride bridge, we have deduced that the thermal temperature coefficient of the SHE is +0.871 mv/~ [hot electrode (+) terminal] at 25~ The standard ionic entropy S* ~ of electrochemical transport of hydrogen ion is --4.48 cal/deg. Thermal temperature coefficients are computed for calomel, silver chloride, and copper sulfate electrodes and are compared with experiment. Thermal and isothermal temperature coefficients are computed and tabulated for nearly 300 standard electrode potentials.) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 132.174.255.116 Downloaded on 2015-03-10 to IP Vol. 106, No. 7 COEFFICIENTS OF ELECTRODE POTENTIALS ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 132.174.255.116 Downloaded on 2015-03-10 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 132.174.255.116 Downloaded on 2015-03-10 to IP

show abstract

Section: Thermodynamics Of Thermal Ce~lsmentioning

confidence: 99%

Section: Thermodynamics Of Thermal Ce~lsmentioning

confidence: 99%

The Temperature Coefficients of Electrode Potentials

deBethune

Licht

Swendeman

1959

J. Electrochem. Soc.

284

154

View full text Add to dashboard Cite

show abstract

“…The large values obtained for the conventional entropy of migration S~ of the tetraalkylammonium ions (Table III) appear surprising at first, since Eastman's students (44) had speculatively expected values close to zero, and had even used this hypothesis as a basis for evaluating a set of S~ values, which proved inconsistent with known values of S% from the Soret effect (Table I). The large values actually obtained point to another mechanism than just the electrostatic one discussed above.…”

Section: Ionic Transport Entropiesmentioning

confidence: 96%

“…The large values actually obtained point to another mechanism than just the electrostatic one discussed above. The hydrocarbon chains must exert some ordering influence on the neighboring water structure, perhaps by the formation of "icebergs" (44). The removal of the alkyl chains by migration of the ions then allows a disordering of the water structure left behind, i.e., a "melting of the icebergs" (44), with a consequent absorption of heat and a positive entropy of migration.…”

Section: Ionic Transport Entropiesmentioning

confidence: 99%

Irreversible Thermodynamics in Electrochemistry

deBethune

1960

J. Electrochem. Soc.

View full text Add to dashboard Cite

The Onsager thermodynamics of irreversible processes provides a unified approach to the study of electrolytic systems out of equilibrium, such as concentration cells with transference, the initial and final emf's of thermal cells, and thermal diffusion (Soret effect) of ions. For concentration cells, the method justifies the classical results obtained by Nernst from equilibrium considerations. For nonisothermal systems, the product S*dT is the thermodynamic driving force of a process, where S* is the entropy transported reversibly from the "hot" to the "cold" heat reservoir (in the limiting case of equal temperatures) by the occurrence of a reversible process in the system. The emf of a concentration cell, the initial emf of a thermal cell, and the Soret coefficient, all properties of systems out of equilibrium, are determined, according to the Onsager relations, by the ratios of the reversible fluxes of matter to electricity, of entropy to electricity, and of entropy to matter, respectively, as they occur in systems completely at equilibrium.

show abstract

“…The reason for this is that the bulk solutions are electrically neutral, meaning that a transferred cation must be accompanied by a neutralizing anion and vice verse. [47][48][49][50] There are significant controversy regarding the correct solvation entropy for the proton in this method. [40][41][42] In this regard, there are four assumptions which can be used.…”

Section: Introductionmentioning

confidence: 99%

A Simple Method for Estimating the Absolute Solvation Free Energy of Monovalent Ions in Different Solvents

Farrokhpour

Manassir

2014

J. Phys. Chem. A

View full text Add to dashboard Cite

The solvation Gibbs free energies (SGFE) of 39 ions were estimated in protic and aprotic solvents including methanol, ethanol, N,N-dimethylformamide (DMF) and acetonitrile (ACN) using a proposed approach. In this method, the error of the applied computational method, used for estimating the SGFE of a specific ion in water and dimethyl sulfoxide (DMSO) solvents, was used as a reference value to correct the calculated SGFE of the ion in other protic and aprotic solvents, respectively. The estimated values of SGFE of ions, obtained in this work, show good agreement with those obtained using the other methods reported in literature. New correlation equations were also proposed for correlating the estimated values of SGFE of ions in a specific solvent to the corresponding values in water and DMSO for protic and aprotic solvent. By using the proposed method in this work, it is possible to estimate the values of SGFE of ions in the solvents that there are no experimental and theoretical reports on them in literature provided that the appropriate and correct reference solvent is selected. Typically, this method was applied on two most popular solvents in organic chemistry including acetone and 1-propanol to estimate the SGFE of the considered ions in them for the first time.

show abstract

Applications of the Eastman Thermocell Equation.¹ I. Certain Absolute Ionic Entropies and Entropies of Transfer of Alkali Metal and Tetraalkylammonium Bromides and Hydroxides

Cited by 34 publications

References 1 publication

The Temperature Coefficients of Electrode Potentials

The Temperature Coefficients of Electrode Potentials

Irreversible Thermodynamics in Electrochemistry

A Simple Method for Estimating the Absolute Solvation Free Energy of Monovalent Ions in Different Solvents

Contact Info

Product

Resources

About

Applications of the Eastman Thermocell Equation.1 I. Certain Absolute Ionic Entropies and Entropies of Transfer of Alkali Metal and Tetraalkylammonium Bromides and Hydroxides

Cited by 34 publications

References 1 publication

The Temperature Coefficients of Electrode Potentials

The Temperature Coefficients of Electrode Potentials

Irreversible Thermodynamics in Electrochemistry

A Simple Method for Estimating the Absolute Solvation Free Energy of Monovalent Ions in Different Solvents

Contact Info

Product

Resources

About

Applications of the Eastman Thermocell Equation.¹ I. Certain Absolute Ionic Entropies and Entropies of Transfer of Alkali Metal and Tetraalkylammonium Bromides and Hydroxides