Observations passive

De Gromoboy and Shreir(43) argued in their experimental study of nickel in sulfuric acid that higher oxides may form directly from the metal and at the metal surface the observed "passivation potentials" (determined from anodic charging curves) were found to correspond closely with the potentials calculated for Ni - NiO, Ni Ni O, Ni - Ni.,0, and... 

Crevice corrosion initiated immediately upon application of +0.4 V (SCE), as expected for JR -controlled crevice corrosion. An example of the attack observed afterwards is shown in Fig. 19 for a gap of 93 pm. Three regions of attack were observed passive dissolution was observed from the mouth to some distance inside the crevice (termed Xcnt), a region of accelerated attack was then observed at intermediate distances, and finally a region of variable attack was observed at the greatest distances from the mouth. 

In recent years the theory of coherent chemistry has shifted towards attempts to actively control molecular dynamics rather than just to observe passively these ultrafast phenomena. These studies have created huge interest and much activity in the optical and chemical communities [426-428]. The first promising experiments have confirmed the fascinating theoretical predictions (see in [428]). 

When we say cycloheptatriene is not aromatic but cycloheptatrienyl cation is we are not comparing the stability of the two to each other Cycloheptatriene is a stable hydrocarbon but does not possess the special stability required to be called aromatic Cycloheptatrienyl cation although aromatic is still a carbocation and reasonably reac tive toward nucleophiles Its special stability does not imply a rock like passivity but rather a much greater ease of formation than expected on the basis of the Lewis struc ture drawn for it A number of observations indicate that cycloheptatrienyl cation is far more stable than most other carbocations To emphasize its aromatic nature chemists often write the structure of cycloheptatrienyl cation m the Robinson circle m a ring style... 

Nuclear Reactors. Nuclear power faciUties account for about 20% of the power generated in the United States. Although no new plants are plaimed in the United States, many other countries, particularly those that would otherwise rely heavily on imported fuel, continue to increase their nuclear plant generation capacity. Many industry observers predict that nuclear power may become more attractive in future years as the price of fossil fuels continues to rise and environmental regulations become more stringent. In addition, advanced passive-safety reactor designs may help allay concerns over potential safety issues. 

Titanium is susceptible to pitting and crevice corrosion in aqueous chloride environments. The area of susceptibiUty for several alloys is shown in Figure 7 as a function of temperature and pH. The susceptibiUty depends on pH. The susceptibiUty temperature increases paraboHcaHy from 65°C as pH is increased from 2ero. After the incorporation of noble-metal additions such as in ASTM Grades 7 or 12, crevice corrosion attack is not observed above pH 2 until ca 270°C. Noble alloying elements shift the equiUbrium potential into the passive region where a protective film is formed and maintained. 

Griess has observed crevice corrosion of titanium in hot concentrated solutions of Cl , SOj I ions, and considers that the formation of acid within the crevice is the major factor in the mechanism. He points out that at room temperature Ti(OH)3 precipitates at pH 3, and Ti(OH)4 at pH 0-7, and that at elevated temperatures and at the high concentrations of Cl ions that prevail within a crevice the activity of hydrogen ions could be even greater than that indicated by the equilibrium pH values at ambient temperatures. Alloys that remain passive in acid solutions of the same pH as that developed within a crevice should be more immune to crevice attack than pure titanium, and this appears to be the case with alloys containing 0-2% Pd, 2% Mo or 2[Pg.169]

This area will be passivated by the increase in pH due to the cathodically produced OH ions, and partially cathodically protected by the electrons liberated by the anodic processes within the pit. The tubercle thus results in an occluded cell with the consequent acidification of the anodic sites. Wranglen considers that in view of the fact that crystals of FeClj -4H20 are sometimes observed at the bottom of a pit the solution within the pit is a saturated solution of that salt, and that this will correspond with an equilibrium pH of about 3-5. 

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