The concept of a critical potential below which pitting of 18–8 and other passive alloys does not occur in aqueous Cl− media is affirmed. Increasing Cl− concentration shifts the critical potential to more active values. The potential is shifted to more noble values by presence of other anions, e.g.,
ClO4−
,
SO4−−
,
NO3−
,
OH−
, sufficient concentrations of which act as pitting inhibitors. Lowering of temperature similarly enobles the critical potential. The shift at 0°C exceeds the oxidation‐reduction potential for
Fe++→Fe++++e
accounting for resistance of 18–8 to pitting in
FeCl3
solutions at ice temperature but not at room temperature. The critical potential is not affected appreciably in the acid pH range; it moves markedly in the noble direction in the alkaline range corresponding to observed resistance to pitting in alkaline Cl− media. These results are interpreted in terms of competitive adsorption of Cl− and other anions for sites on the alloy surface. Only at a sufficiently high surface concentration of Cl− is oxygen, making up the passive film, displaced locally, and passivity thereby destroyed resulting in a pit. The special behavior of
NO3−
inhibition and factors affecting reproducibility of measurements are discussed.
Critical pitting potentials for the binary Cr‐Fe and Cr‐Ni alloys in
0.1N normalNaCl
become more noble (correspondingly more resistant to pitting) with increasing
normalCr
content, particularly in the region 25–40%
normalCr
and 10–20% Cr, respectively. The potentials for 57.8% Cr‐Fe and pure Cr fall within the transpassive region. Ni containing 3.2% Mo, to the contrary, shows a lower (more active) critical potential; higher per cent Mo‐Ni alloys appear to fall within the transpassive region corroding anodically as
MoO4−−
plus Ni++ without pitting. Ni alloyed with 15% Cr‐Fe shifts the potential in the noble direction; Mo alloyed with 15% Cr, 13% Ni stainless steel has a similar but even greater effect. At 0°C, 15% Cr, 13% Ni stainless steel exhibits a potential 0.5v more noble than at 25°C, corresponding to greatly increased resistance to pitting. This shift is less pronounced for the stainless steels containing Mo; in fact, at or above 1.5% Mo, the critical potentials at 0°C are below those at 25° C. In
0.1N normalNaBr
, alloyed Mo shifts the potentials slightly in the active direction, contrary to a marked noble shift in
0.1N normalNaCl
. At 0°C the potentials are still more active. These trends correlate with observed pitting for 15% Cr, 13% Ni stainless steel and the similar alloy containing 2.4% Mo in 10%
FeBr3
both at 0° and 25°C. Absence of pitting is observed in 10%
FeCl3
at 0°C for 15% Cr, 13% Ni stainless steel, but not for the similar alloy containing 2.4% Mo, which pits. The over‐all results are explained on the basis of competitive adsorption at the metal surface and an effect of temperature on the structure of the double layer.
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