thermal gradient and concentration gradients in nonisothermal formation cells, its net effect is to increase the potential of the high-temperature electrode relative to that of the cooler electrode if the gradients of temperature and Ag2 § concentration are in the same direction and to decrease its relative potential if the gradients of temperature and X3-concentration are in the same direction. Although the possible existence of systematic errors, unrecognized and therefore uncorrected, precludes firm quantitative conclusions, the results suggest that the net effect in silver halide cells may be of the order of hundredths of a millivolt per degree and therefore capable of evaluation with increased accuracy of measurement of cell potentials and electrode temperatures. AcknowledgmentsThis work was supported by the U.S. Atomic Energy Commission. One of us (C. R. M.) is grateful for the award of a terminal year fellowship by the National Institute of General Medical Science and for the use of computing facilities at Purdue University during manuscript preparation.Manuscript submitted April 22, 1969; revised manuscript received Sept. 24, 1969. Any discussion of this paper will appear in a Discussion Section to be published in the December 1970 JOURNAL. REFERENCES 39, 544 (1947).6. H. Bloom, J. O'M. Bockris, N. E. Richards, and R. G. Taylor, J. Am. Chem. Soc., 80, 2044. 7. J.D. Corbett and S. Winbush, ibid., 77, 3964 (1955). 8. J. D. Van Norman, This Journal, 112, 1126. C. A. Bennett and N. L. Franklin~ "StatisticalAnalysis in Chemistry and the Chemical Industry," pp. 224-225, 245-255, 423-426, J. Wiley & Sons, Inc., New York (1954).10. W. J. Hamer, M. S. Malmberg, and B. Rubin, This Journal, 103, 8 (1956 Chem., 218, 250 (1961). 13. E. J. Salstrom, J. Am. Chem. Soc., 55, 2426(1933 62, 1325 (1958). 17. J. Leonardi and J. Brenet, Compt. Rend., 261, 113 (1965).18. B. F. Markov and E. B. Kuzyakin, Ukr. Khim. Zh., 32, 1180.19. R. Suchy, Z. Anorg. Allgem. Chem., 27, 152 (1901). 20. H. Reinhold, ibid., 171, 181 (1928 Conversion, 5, 205 (1965). 36. W. Fischer, Z. Naturforsch., 21a, 281 (1966). 37. J. J. Dupuy, Compt. Rend., Ser. C., 261, 957 (1965). 38. A. Kvist, A. Randsalu, and I. Svensson, Z. Naturforsch., 21a, 184 (1966). Advan. Energy Electrode Studies in Nonaqueous Electrolytes ABSTRACTThe electrochemical properties of the smooth lithium electrode in LiC104-propylene carbonate solutions were studied at temperatures up to 70~ by galvanostatic methods. For the range of current densities, temperatures, and LiC104 concentrations studied, the anodic and cathodic polarization data were symmetrical through zero current density. Values for the exchange current density, io, were calculated at each experimental condition; at 28~ and 1M LiC104, io was 0.95 • 0.05 mA/cm 2. The hH% value was 8.5 _ 0.3 kcal/mole, and a had a temperature independent value of about 0.67. The electrochemical reaction order was 1 for concentrations up to 1M in Li + ion.The extensive interest in organic electrolyte batteries (1-3) has...
The kinetics of the electrodeposition of tin were studied from simple acid solutions containing various nonionic organic additives. Many of these substances produced a large increase in the cathodic polarization. The similar behavior at solid polycrystalline tin and liquid tin-amalgam cathodes implies that the rate-determining step responsible for the polarization is substantially the same at each electrode in the presence of the adsorbed organic additive. Qualitative evidence is presented for the adsorption of nonionic organic molecules on the electrode surface. A probable rate-determining step is the transfer of cations through a barrier of adsorbed organic molecules to the electrode surface. The formation of this barrier is kinetically limited rather than diffusion-limited. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 169.230.243.252 Downloaded on 2015-03-14 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 169.230.243.252 Downloaded on 2015-03-14 to IP The principal impurities designated by the supplier, City Chemical Corporation, Brooklyn, New York, in the SnSO4 crystals from which the solutions were prepared were stannic content, 4.35%; iron, 0.0006%; antimony, 0.0003%; lead, 0.002%; and chloride, 0.008%. West Virginia Pulp and Paper Company. ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 169.230.243.252 Downloaded on 2015-03-14 to IP Vol. 110, No. 3 THE ELECTROCHEMISTRY OF TIN ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 169.230.243.252 Downloaded on 2015-03-14 to IP
Surface‐catalyzed anodes for the electrochemical oxidation of N2H4 were prepared by first codepositing a porous layer of Mond Ni powder with Ni on an electroformed Ni sheet substrate and then catalyzing by chemically precipitating nickel boride into the porous Ni layer. The parameters associated with the codeposition step were studied for their effect on (i) the structure and texture of the resultant deposit, and (ii) the electrochemical performance of the subsequently catalyzed electrode. Scanning electron micrographs were made after the Mond Ni was codeposited. The catalyzed electrodes were operated at 2 kA/m2 (200 mA/cm2) and the anode vs. reference potential was monitored. The most influential parameters was the total number of coulombs used during the codeposition process. When 1200 coulombs on 48 cm2 were exceeded, the rough texture of the Mond Ni was destroyed and the Ni2B catalyst was quickly shed during the electrochemical test.
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