THE ELECTROCHEMICAL MECHANISM OF SULFIDE SELF‐POTENTIALS

Geophysics ◽  
1960 ◽  
Vol 25 (1) ◽  
pp. 226-249 ◽  
Author(s):  
Motoaki Sato ◽  
Harold M. Mooney

Self‐potentials associated with a sulfide ore body result from the ohmic potential drop within the country rocks. The electric current is produced by separate but simultaneous reduction of oxidizing agents near the surface and oxidation of reducing agents at depth. The ore does not participate directly in either reaction, but serves as a conductor to transfer the electrons from the reducing agents to the oxidizing agents. The possibility for the above reactions to occur depends upon differences in oxidation potential of ground waters at different depths. In the zone of weathering, the oxidation potential is controlled by the reduction mechanism of oxygen, and ranges in value from 0.2 to 0.7 volt (on the hydrogen scale). If the ore tends to oxidize at some lower potential, then the latter is the available one. In the zone beneath the water table, the potential is probably controlled by the oxidation‐reduction equilibria of iron‐rich minerals, and ranges in value from 0 to −0.3 volt. The available potential is independent of ore type. The maximum potential difference available to produce natural currents is estimated at: graphite 0.8, pyrite 0.7, covellite 0.6, chalcocite 0.5, galena 0.3 volt. Self‐potentials will be large if the ore body (1) is composed of minerals difficult to oxidize, (2) has low electrical resistance (physical continuity together with low resistivity), (3) extends vertically across the water table, and (4) exists close to the surface.

1946 ◽  
Vol 29 (4) ◽  
pp. 219-247 ◽  
Author(s):  
David Grob

1. The literature on conditions affecting the activity of proteolytic enzymes has been reviewed. 2. Experimental data on the control of the activity of trypsin, leucoprotease, papain, serum antiprotease, leucopeptidase, and pancreatic peptidase have been presented. These data indicate that: (a) The polymorphonuclearleucocytes of the cat contain abundant proteinase and peptidase active at neutral pH; those of the rabbit lack proteinase active at neutral pH. (b) Reducing agents, including several biologically important thiol-sulfhydryl compounds and ascorbic acid, inhibit the activity of leucoprotease and trypsin. For each reductant the degree of inhibition is proportional to the reducing capacity of the medium. (c) p-Aminobenzoic acid, sulfonamides (especially sulfathiazole), and many diphenyl sulfones inhibit the activity of leucoprotease. (d) Serum, plasma, several heavy metals, ammonium salts, asparagine, thiourea, heparin, glutamic acid, tyrothricin, calcium chloride, and bile salts and bile acids also inhibit the activity of leucoprotease, and in most cases of trypsin too. (e) Preparations of tryptic digests of proteins, and egg white trypsin inhibitor, inhibit trypsin to a much greater degree than leucoprotease. (f) Mild oxidizing agents increase the activity of leucoprotease and trypsin. (g) Oxidizing agents and some inhibitors of sulfhydryl groups inhibit the antiproteolytic activity of the serum. It is suggested that serum antiprotease may consist (chiefly) of reducing agents, including thiol-sulfhydryl peptides which exert their antiproteolytic activity by virtue of the presence of sulfhydryl groups. (h) The antiproteolytic activity of the serum is progressively weakened by exposure to a hydrogen ion concentration below pH 6.5 or above pH 9.7. Because of this the pH optima of leucoprotease and trypsin are shifted in the presence of serum from pH of 7 and 8 to pH of 6 to 6.5, and the range of activity of these enzymes is slightly widened, in both acid and alkaline reactions. (i) Reducing agents increase the activity of leucopeptidase and pancreatic peptidase. Serum, sulfathiazole, and thiourea have little or no effect. 3. The significance of the oxidation-reduction system in the control of the activity of leucoprotease, trypsin, serum antiprotease, leucopeptidase, and pancreatic peptidase has been emphasized.


1996 ◽  
Vol 451 ◽  
Author(s):  
Gerald S. Frankel

ABSTRACTCorrosion of thin film structures commonly used in electronic and magnetic devices is discussed. Typical failure modes are presented, and galvanic corrosion is discussed in some detail since it is one common problem with such devices. A graphical explanation for the determination of the ohmic potential drop during galvanic corrosion is presented. The corrosion problem of thin film disks is shown to have changed during the past ten years owing to changes in disk structure. The corrosion susceptibility of two antiferromagnetic alloys used for exchange coupling to soft magnetic layers is discussed.


1999 ◽  
Vol 556 ◽  
Author(s):  
P. E. Raison ◽  
R. G. Haire ◽  
T. Sato ◽  
T. Ogawa

AbstractPolycrystalline pyrochlore oxides consisting of selected f elements (lanthanides and actinides) and Zr and Hf have been prepared and characterized. Characterization to date has been primarily by X-ray diffraction, both at room and at elevated temperatures. Initial studies concentrated on selected lanthanides and the Np, Pu and Am analogs (reported here) but have been extended to the other actinide elements through Cf. Data from these studies have been used to establish a systematic correlation regarding the fundamental materials science of these particular pyrochlores and structurally related fluorite-type dioxides. In addition to pursuing their materials science, we have addressed some potential technological applications for these materials. Some of the latter concern: (1) immobilization matrices; (2) materials for transmutation concepts; and (3) special nuclear fuel forms that can minimize the generation of nuclear wastes. For f elements that display both a III and IV oxidation state in oxide matrices, the synthetic path required for producing the desired pyrochlore oxide is dictated by their pseudo-oxidation potential the stability of the compound towards oxygen uptake. For the f elements that display an oxidationreduction cycle for pyrochlore-dioxide solid solution, X-ray diffraction can be used to identify the composition in the oxidation-reduction cycle, the oxygen stoichiometry and/or the composition. This paper concentrates on the Np, Pu and Am systems, and addresses the above aspects, the role of the crystal matrix in controlling the ceramic products as well as discussingsome custom-tailored materials.


2021 ◽  
Vol 23 (09) ◽  
pp. 656-687
Author(s):  
K.C. Mahesh ◽  
◽  
G.S. Suresh ◽  

The kinetics of electrochemical lithium ion intercalation into Li[Li0.2Co0.3Mn0.5]O2 electrode in 2 M Li2SO4 aqueous electrolyte has been studied using two electroanalytical methods, namely, potentiostatic intermittent titration technique (PITT) and galvanostatic intermittent titration technique (GITT). The results are compared with those from nonaqueous electrolytes. Layered, lithium-rich Li[Li0.2Co0.3Mn0.5]O2 cathode material was synthesized by reactions under autogenic pressure at elevated temperature (RAPET) method. The effects of ohmic potential drop and charge-transfer resistance have been considered while predicting the current transients obtained with aqueous electrolyte. For PITT and GITT, we have defined their characteristic time-invariant functions, It1/2 and dE/dt1/2, respectively to present the diffusion time constant τ. Application of different theoretical diffusion models for treating the results obtained by the above-mentioned techniques allowed us to calculate the diffusion coefficient of lithium ions (D) at different potentials (E). The intercalation process is explained by considering the possible attractive interactions of the intercalated species in terms of Frumkin intercalation isotherm. We have observed a strictcorrespondence between the peaks of the intercalation capacitance and the minima in the corresponding log D vs. E curve.


2018 ◽  
Vol 26 (5) ◽  
pp. 1693-1704 ◽  
Author(s):  
Li Chen ◽  
Wenke Wang ◽  
Zaiyong Zhang ◽  
Zhoufeng Wang ◽  
Qiangmin Wang ◽  
...  

2016 ◽  
Vol 83 (4) ◽  
pp. 479-486 ◽  
Author(s):  
Veronica Caldeo ◽  
John A Hannon ◽  
Dara-Kate Hickey ◽  
Dave Waldron ◽  
Martin G Wilkinson ◽  
...  

In cheese, a negative oxidation-reduction (redox) potential is required for the stability of aroma, especially that associated with volatile sulphur compounds. To control the redox potential during ripening, redox agents were added to the salted curd of Cheddar cheese before pressing. The control cheese contained only salt, while different oxidising or reducing agents were added with the NaCl to the experimental cheeses. KIO3 (at 0·05, 0·1 and 1%, w/w) was used as the oxidising agent while cysteine (at 2%, w/w) and Na2S2O4 (at 0·05 and 0·1%, w/w) were used as reducing agents. During ripening the redox potential of the cheeses made with the reducing agents did not differ significantly from the control cheese (Eh ≈ −120 mV) while the cheeses made with 0·1 and 0·05% KIO3 had a significantly higher and positive redox potential in the first month of ripening. Cheese made with 1% KIO3 had positive values of redox potential throughout ripening but no starter lactic acid bacteria survived in this cheese; however, numbers of starter organisms in all other cheeses were similar. Principal component analysis (PCA) of the volatile compounds clearly separated the cheeses made with the reducing agents from cheeses made with the oxidising agents at 2 month of ripening. Cheeses with reducing agents were characterized by the presence of sulphur compounds whereas cheeses made with KIO3 were characterized mainly by aldehydes. At 6 month of ripening, separation by PCA was less evident. These findings support the hypothesis that redox potential could be controlled during ripening and that this parameter has an influence on the development of cheese flavour.


2010 ◽  
Vol 181 (4) ◽  
pp. 327-335 ◽  
Author(s):  
Philippe Audra ◽  
Jean-Claude D’antoni-Nobecourt ◽  
Jean-Yves Bigot

Abstract Hypogenic caves develop by recharge from below, not directly influenced by seepage from the overlying land surface. Several processes of speleogenesis are combined, involving CO2 or H2S produced at depth. If the recharge from depth remains uniform, the growth of selected fissures is prevented, giving rise to maze cave systems with an upward development trend, which is defined as “transverse speleogenesis” [Klimchouk, 2003]. Hypogenic caves are much fewer than epigenic caves (i.e. developed downwards by meteoric water with aggressivity derived from soil). In France, as in the rest of the world, hypogenic caves were poorly recognized until recently because of their lower frequency, subsequent epigenic imprint often hiding the true origin, and the absence of a global conceptual model. However, about a hundred of hypogenic caves have been identified recently in France. The extreme diversity of hypogenic cave patterns and features is due to the variety of geological and topographic settings and types of flow. Thermal caves are a sub-set of hypogenic caves. Active thermal caves are few and small (Mas d’En Caraman, Vallon du Salut). Often, thermal influences only occur as point thermal infeeders into epigenic caves (Mescla, Estramar). In addition to the higher temperature, they may be characterized by CO2 (Madeleine) or H2S degassing, by warm water flowing in ceiling channels, or by manganese deposits. The Giant Phreatic Shafts locate along regional active faultlines. They combine all characteristics (thermal, CO2, H2S), due to the fast rising of deep water. The Salins Spring has been explored by scuba diving down to −70 m. Such a hyperkarstification is responsible for the development of the deepest phreatic shafts of the world: pozzo del Merro, Italy (−392 in). Inactive hypogenic caves may be recognized by their specific mineralization or by the presence of large calcite spar. Metallic deposits are due to the rising of deep waters that are warm, aggressive, and low in oxidation potential. Mixing with meteoric water generates Mississippi Valley Type (MVT) sulfidic ores. Iron deposits as massive bodies (Lagnes) or onto microbial media (Iboussières, Malacoste) making specific facies, such as “black tubes”, iron flakes, and iron pool fingers. Other frequent minerals are Mn oxides and Pb sulfur. In such low thermal conditions, calcite deposits occur as large spar in geodes or as passage linings. Other inactive hypogenic caves may also be recognized by characteristic patterns, such as mazes. The relatively constant recharge into confined karst aquifers suppresses fissure competition, so they enlarge at similar rates, producing a maze pattern. In horizontal beds, mazes extend centrifugally around the upwelling feeder. The juxtaposition of multiple discrete vertical feeders produces extended horizontal mazes. In gently tilted structures, 2D mazes extend below aquitards, or along bedding or more porous beds (Saint-Sébastien). In thick folded limestone the rising hypogenic flow alternatively follows joints and bedding planes, producing a 3D maze cave in a staircase pattern (Pigette). Isolated chambers are large cupola-like chambers fed by thermal slots. Thermal convection of air in a CO2-rich atmosphere causes condensation-corrosion that quickly produces voids above the water table (Champignons Cave). Sulfuric acid caves with replacement gypsum are produced by H2S degassing in the cave atmosphere. H2S oxidizes to H2SO4, which corrodes the carbonate rock and replaces it with gypsum. The strongest corrosion occurs above the water table, where sulfide degassing and thermal convection produce strong condensation-corrosion. Caves develop headward from springs and from thermo-sulfuric slots upward (Chevalley-Serpents System). The low-gradient main drains record base-level positions and even the slightest stages of water-table lowering (Chat Cave). Hypogenic speleogenesis provides better understanding of the distribution of karst voids responsible for subsidence hazards and the emplacement of minerals and hydrocarbons.


1927 ◽  
Vol 11 (2) ◽  
pp. 159-174 ◽  
Author(s):  
George H. Bishop

The active process in a short length of steel wire passivated by 65 per cent nitric acid has been observed under the influence of a polarizing current, and the form of the potential recorded by the cathode ray oscillograph. In the passive wire, 80 per cent of the total potential drop takes place at the anode, 20 per cent at the cathode. The change from active to passive states, as measured by the potential change, is very abrupt compared to the duration of activity and the potential curve at a point on the wire is probably almost rectangular. The duration of the refractory state is decreased at the anode and increased at the cathode, as in nerve. This fact is against the idea that reactivity after passivation results from a partial reduction of an oxide layer. Soft iron wire passivated by anodal polarization repassivates after activation in acid of a dilution that fails to passivate it initially. It soon becomes rhythmic with a very short refractory phase, and then reacts continuously. Such a wire exhibits a very sharp alternation between a dark brown oxide coat during activity, and a bright clean surface during passivation. A passive steel wire in nitric acid shows many of the characteristics of an inert electrode such as platinum, and it may be inferred that, superposed upon the primary passivation potential, there exists an electrode or oxidation-reduction potential equilibrium between the effects of the various constituents of the solution. It is suggested that the phenomena of nerve-like reactivity in this system may involve an alternation between two protective coatings of the steel wire. During activity, the surface becomes mechanically coated with a brown oxide. If this coating does not adhere, due to gas convection or to rapid solution of the oxide, passivation does not result. Under sufficiently intense oxidizing conditions, a second oxide coat may form in the interstices of the first, and cover the surface as the first coating dissolves off. This furnishes the electrochemical protection of passivation, which is followed by the gradual attainment of electrode equilibrium with the solution.


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