Thermogalvanic Potentials

Carr, Dodd S.; Bonilla, C.F.

doi:10.1149/1.2779639

Cited by 10 publications

(3 citation statements)

References 2 publications

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“…In the present work, this potential has been evaluated for both sulfate and chloride solutions on the basis of the following equation: E : --0.470--(1.0.10 -~) (t--25) + (0.9915) (104) T log a+ [1] where a+ is the activity of the nickelous ion and t and T are the temperature on the Centigrade and absolute scales, respectively. This equation is based on the data of Carr and Bonilla (22) for the thermogalvanic potentials of nickel in 0.1 and 1.0M nickel sulfate solutions. In using the above equation for chloride as well as sulfate solutions, the assumption has been made that the liquid junction potentials and the temperature coefficients are the same for the chloride solutions as for the sulfate solutions.…”

Section: Resultsmentioning

confidence: 99%

The Electrochemistry of Nickel

Yeager¹,

Cels²,

Yeager³

et al. 1959

J. Electrochem. Soc.

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The simultaneous electrodeposition of nickel and hydrogen has been studied in chloride and sulfate solutions and the individual polarization curves determined from efficiency measurements. Nickel polarization has a Tafel slope of 0.10 and is independent of pH and type of anion at constant nickel ion activity. The nickel polarization data can be explained readily in terms of the transfer of a nickel ion from the solution across an unsymmetrical potential energy barrier to the metal phase. The hydrogen overvoltage evaluated during codeposition at constant pH is substantially the same for both chloride and sulfate solutions with a Tafel slope of 0.12. Hydrogen and nickel deposition appear to occur without any appreciable interdependence over the range of conditions involved in the present work.

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Section: Resultsmentioning

confidence: 99%

The Electrochemistry of Nickel

Yeager¹,

Cels²,

Yeager³

et al. 1959

J. Electrochem. Soc.

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“…The electromotive force of a thermal cell (in its initial state) is the resultant of three effects: (a) the metallic thermocouple effect, (b) the electrode temperature effect, and (c) the thermal liquid junction potential. Effect (a) can be eliminated by keeping all metal-metal junctions isothermal, as in cell [2], a technique used by Richards (13), or it can be corrected for, as in the work of Carr and Bonilla (31). Effect (a) has a magnitude of the order of 1% of the sum of (b) and (c) and will be considered eliminated in what follows.…”

Section: Thermal Temperature Coefficientsmentioning

confidence: 99%

The Temperature Coefficients of Electrode Potentials

deBethune

Licht

Swendeman

1959

J. Electrochem. Soc.

284

154

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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

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“…Many values for the Co/Co2potential have been reported and what value is the best is not at all clear. Review' of the literature suggests that the work of Haring and Westfall (6) leading to a potential of 0.278c is preferable to the value, 0.259c, obtained by adding 0.027c to the Ni/Ni2 potential due to Carr and Bonilla (3). Using the potential 0.278c for Co/Co2-(a difference of 0.046c between Co/Co2and Ni/Ni2-) leads to -25.7 cal.…”

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confidence: 99%