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.
Open all abstracts, in this tab
P. Debye 1942 Trans. Electrochem. Soc. 82 265
Colin G. Fink and Frank L. Jones 1931 Trans. Electrochem. Soc. 59 461
A method has been developed for the electrodeposition of metallic tungsten from aqueous solutions. The tungsten deposit is smooth, hard and coherent, having a high luster. Like chromium, the electrodeposited tungsten needs no polishing if the plated article was previously polished. Tungsten has remarkable acid‐resisting properties, which make it desirable as a protective coating for other metals. Several types of solutions have been investigated in regard to their usefulness as tungsten plating baths. Solutions of tungsten salts in organic solvents were found unsuitable for this purpose. Aqueous solutions of an acid nature did not give satisfactory metal deposits. Alkaline solutions containing alkaline tungstates were preferably used as plating . baths. The temperature, cathode current density, and hydrogen ion concentration of the solution must be controlled. Alloys of tungsten and iron, and of tungsten and nickel, were electrodeposited from similar solutions containing very small concentrations of the ions of these second metals. The usefulness of highly alkaline solutions as plating baths for the electrodeposition of other metals is pointed out.
Colin G. Fink and V. S. de Marchi 1938 Trans. Electrochem. Soc. 74 271
With the aid of powder metallurgy, iron‐silver alloys at the iron‐rich end were prepared. Ohmic resistance measurements show that silver alloys with iron. The maximum amount of silver found alloyed with iron was between 0.5 and 1 per cent silver. Further evidence that silver does alloy with iron is shown by the fact that the ferrite grains of a 50 Fe—50 Ag alloy are stained. This is similar to the observation made in the case of the copper‐iron alloys. Corrosion studies of iron‐ silver alloys showed that small amounts of silver, up to about 1 per cent, improved the resistance of iron to the corrosive action of 10 per cent hydrochloric acid and 30 per cent acetic acid. Iron containing small percentages of silver behaves very similarly to iron containing small percentages of copper.
T. C. Manley 1943 Trans. Electrochem. Soc. 84 83
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.
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.
Louis E. Lovett 1938 Trans. Electrochem. Soc. 73 163
This paper deals with the general application of dialysis to the purification of caustic soda solutions containing hemicellulose in the viscose rayon industry, with special reference to the Cerini dialyzer. This commercial application of osmosis is of extraordinary value since, in the United States alone, the installed dialyzer capacity represents an annual recovery of 90,000,000 pounds (40,000,000 kg.) of actual NaOH.
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.
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.
Herbert Bandes 1945 Trans. Electrochem. Soc. 88 263
Copper can be electrodeposited from a very wide variety of solutions and in a variety of grain forms. The factors which appear to be most significant in affecting the physical nature of the deposit are: a. Type of solution, i.e., acid, cyanide, pyrophosphate, etc.; b. Current density; c. Temperature of solution; d. Degree of agitation of solution; e. Nature and concentration of addition agents. The recent literature of copper plating is reviewed and particular emphasis has been placed on the development of the ideas which have led to the modern high efficiency—high current density processes. Considerable attention has been given to the effects of various plating conditions upon the metallurgical nature of the electrodeposit.
W. Blum and G. W. Vinal 1934 Trans. Electrochem. Soc. 66 359
Taking the case of the electrolysis of water, with smooth platinum electrodes, as a typical example, the fundamental components of the cell or bath voltage are interpreted. Thereupon revised definitions are proposed and these are discussed at length. Finally the following recommendations are submitted: 1. The "equilibrium reaction potential" is preferably used to refer to the potential based on the free energy of the process. 2. The "decomposition potential" is the minimum potential required for continuous electrolysis. 3. The term "polarization" includes all departures of the potential from the equilibrium potential, and is a measure of irreversibility (excluding IR drop) regardless of whether the products are solid, liquid, or gaseous. 4. The term "overvoltage" preferably refers to the minimum polarization required for any electrode process to occur at an appreciable rate under given conditions.
Open all abstracts, in this tab
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.