Transactions of the Electrochemical Society 

About: Transactions of the Electrochemical Society is an academic journal. The journal publishes majorly in the area(s): Corrosion & Copper. Over the lifetime, 741 publications have been published receiving 6891 citations.

Reaction Rates in Ionic Solutions

Abstract: Smoluchowski's method of evaluating the fundamental f requency 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 /3ronsted-Debye pr imary 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 customary way followed in order to answer the question how reaction rates are influenced by electric charges which may be carried by the reacting particles is that proposed by G. Scatchard a following a derivation of the Bronsted~-Bjerrum 3 activitv relationship given by J. A. Christiansen. 4 On the other hand, the method followed by Smoluchowski 5 for the calculation of the rate of coagulation of colloid suspensions (within the range of rapid coagulation) can certainly be considered as a calculation of reaction rates in a special case. The fundamental question answered by Smoluchowski's treatment is: How many times per second will one of a number, n, of particles per cc. suspended in a liquid be hit by one of the others as a result of their Brownian motion? Smoluchowski obtains the desired number of collisions v per sec. by stating that it can be calculated by solving a diffusion problem in which particles are supposed to diffuse steadily into a hole surrounding the particle in question. At the boundary of this hole the concentration is supposed to be kept 0 and at large dis* Manuscr ip t received July 20, I942. t Professor of Physical Chemistry, Cornell Univers i ty , I thaca, N . Y . a G. Scatchard, J . Am. Chem. Soc. $2, 52 (1930) ; Chem. Rev. 10, 229 (1931). 2 j . N. Bronsted, Z. physik. Chem. 102, 109 (1922); 115, 337 (1925). s N. Bje r rum, Z. physik. Chem. 108, 82 (1924). 4 j . A. Chris t iansen, Z. physik. Chem. 113, 35 (1924). 5 Smoluchowski, Physik. Z. 17, 557, 585 (1916); Z. physik. Chem. 92, I29 (1917).

The Electric Characteristics of the Ozonator Discharge

Abstract: Oscillographic studies of the ozonator discharge, together with power measurements, have shown that: (1) The ozonator discharge is intermittent; during each cycle of the alternating voltage there are two discharge periods alternating with two dark periods. (2) During the discharge periods, the potential drop across the air space has constant value of +e0 or −e0 depending on the direction of the current. The quenching of the discharge coincides with the maximum of the voltage wave. (3) During the succeeding dark period there appears to be no transport of charges across the air spaces, so that the charges accumulated on the inner surfaces of the dielectrics during one discharge period remain to influence the starting of the next discharge period. (4) An equation has been found which gives the power consumption of an ozonator in terms of the peak voltage, the capacity of the dielectrics, the frequency and the discharge potential, e0. (5) Methods have been found for measuring e0, which proves to be proportional to the spacing, d, and the air density : . at 0°C, 760 mm. This is considerably lower than the potential for spark breakdown at comparable spacing.

A Theory for the Mechanism of Chromium Plating; A Theory for the Physical Characteristics of Chromium Plate

Abstract: : The thought is developed that a considerable opportunity existed in application of the principles and tools of metallurgy to the study of electroplates. The initial aim, to develop a reason for the cracks in chromium plate, proved to be a fortunate choice, as all of the considerations later developed center around this cracking phenomenon.