Smoluchowski's method of evaluating the fundamental frequency factor for the rate of a reaction like the coagulation of colloid suspension by employing a purely diffusional treatment is extended to include the electrostatic effects arising from the presence of net charges. The introduction of the concept of a diffuse ionic cloud and the potential calculated therefrom leads to the following results: (a) The wellestablished Bronsted‐Debye primary salt effect formula is derived. (b) The so‐called "solvent" term of the Christiansen‐Scatchard equation arising from the self potential of the ions is also derived but appears as the linear approximation of an exponential expression. The conspicuous absence of quantum theory in evaluating the absolute rate of a kinetic reaction merits attention. V. K. LaM
The Electrochemical Society was founded in 1902 to advance the theory and practice at the forefront of electrochemical and solid state science and technology, and allied subjects.
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P. Debye 1942 Trans. Electrochem. Soc. 82 265
Addison H. White and Lester H. Germer 1942 Trans. Electrochem. Soc. 81 305
Electron diffraction was used to measure the rate of the reaction between copper and pure dry oxygen at room temperature and 20 mm. pressure. The experimental technic is described in detail. The empirical rate of reaction is found to be inversely proportional to () for the time greater than two minutes; the constant is experimentally indistinguishable from zero but must be finite. It is estimated that the local thickness, , in Ångstrom units of the oxide film increases according to the equation: where is measured in minutes and is greater than 2 min. A limiting film thickness of about 50 Å is predicted by this equation.
E. G. Rochow 1946 Trans. Electrochem. Soc. 90 303
Many recent papers have been devoted to the synthesis of organosilicon intermediates and to the reactions by which these compounds are converted to the polymeric silicones. There remains some need, however, for a brief discussion of the composition and structure of the silicone polymers from the standpoint of the user, rather than from the standpoint of the research chemist. This paper seeks to present the chemistry of the silicones in the form of a consistent summary, on the assumption that a working knowledge of these new materials will aid in their intelligent use. Because the paper is general in its scope and content, no specific properties or uses of silicone materials are included.
M. M. Haring and B. B. Westfall 1934 Trans. Electrochem. Soc. 65 235
Cobalt is closely related to nickel and has possibilities for use instead of the latter in the electroplating and electro forming industries. Its potential has been studied by several investigators but the results are not in agreement and apparently do not have the reliability desired. The need for a more precise determination of this value is evident. The standard potential of cobalt was found to be −0.278 v. ± 0.002 v. at 25° C. The normal potential is, therefore, close to −0.300 v. The necessity of using pure metal free from strains prepared by high current density electrolysis and of maintaining oxygen free conditions is re‐emphasized.
E. Berl 1939 Trans. Electrochem. Soc. 76 359
A new commercial method for the cathodic production of hydrogen peroxide is described based on the use of cathodes made wholly or partly of activated carbon of good electric conductivity. The new process combines the production at the anode of oxygen (when alkali carbonates or hydroxides are used) or chlorine (when alkali chlorides are decomposed) or persulfates or perborates (when sulfates or borates are used). Diluted alkaline hydrogen peroxide solutions can be produced at current efficiencies better than 90 per cent. The hydrogen peroxide can be concentrated in the cell so that more than 250 g./L. of hydrogen peroxide are obtained. For the cathodic production of one pound of 30 per cent hydrogen peroxide in dilute solutions only 1/3 to 1/4 of the electrical energy required by the older anodic processes is necessary.
W. Kroll 1940 Trans. Electrochem. Soc. 78 35
Titanium is a very active metal and special precautions are necessary to prepare it free from oxygen and nitrogen. is reduced with pure magnesium in a molybdenum‐lined crucible, in the presence of pure argon, at a temperature of about 1,000° C. The metal is separated from magnesium salts by leaching and acid treatment. There is no alloying of titanium with magnesium. The powdered Ti metal is compressed into bars and melted in a special vacuum apparatus. The absence of all gases that might react with the metal is of special importance. After melting, the Ti is easily rolled hot. A strip less than 1 mm. thick can be bent cold without fracture.
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N. C. White 1947 Trans. Electrochem. Soc. 92 15
The chief factors influencing the efficiency and economy of electrolytic production of chlorates are discussed briefly. Usual methods of manufacture are outlined and a description of the process and equipment used by International Minerals & Chemical Corporation is given.
Milton Janes 1947 Trans. Electrochem. Soc. 92 23
A study of the rate of attack on graphite anodes in the electrolysis of chloride solutions to produce chlorate has been made. The effect of such factors as chloride concentration, temperature, and anode current density on graphite consumption has been investigated. Over a temperature interval of 25° to 66° C and a range of sodium chloride concentration of 75 to 250 g./L, a 22‐fold variation in rate of graphite attack has been found. With certain assumptions, the change in rate of graphite attack with anode current density has been utilized to determine the relative contributions of purely electrochemical and purely chemical oxidation of the graphite to the total attack.
Joseph C. Schumacher 1947 Trans. Electrochem. Soc. 92 45
The author reviews a theory of the mechanism of electrochemical formation of perchlorate, setting forth factors and variations thereof which influence current efficiency. Perchlorate cells employing platinum anodes of a new type are operated in a two‐stage electrolysis process. Details of cell design and operating technic for a large scale manufacturing plant are presented.
Clifford A. Hampel and P. W. Leppla 1947 Trans. Electrochem. Soc. 92 55
For several years an electrolytic process for the production of potassium perchlorate has been operated at Claremore, Oklahoma, by the Cardox Corporation of Chicago. This paper describes the process and the electrolytic cells. Sodium chloride is oxidized to sodium chlorate in one set of cells, and the sodium chlorate is oxidized to sodium perchlorate in a second set of cells. The sodium perchlorate is then reacted with potassium chloride to form potassium perchlorate and sodium chloride, and the latter salt is recycled to the chlorate cells. All operations are conducted batchwise. A graphite anode‐steel cathode cell is used for the conversion of chloride to chlorate, and a platinum‐clad anode‐steel cathode cell is used to change chlorate to perchlorate. Construction and operating data are presented for both cells.
M. E. Bretschger and E. S. Shanley 1947 Trans. Electrochem. Soc. 92 67
Some of the properties of concentrated hydrogen peroxide are summarized. Stability and stabilization of hydrogen peroxide solutions are discussed. Special attention is devoted to the compatibility and explosion hazard of concentrated hydrogen peroxide. Mention is made of the actual and potential uses of this newly available material.