Mass transport control, anodic dissolution corrosion

Just as in the limiting case of ohmic control, the depth of the corrosion pit increases with the square root of the time. However, the proportionality constant here differs, it includes the saturation concentration rather than the potential and the diffusion coefficient rather than the electrolyte conductivity. Figure 7.64 shows experimental results for potentiostatic anodic dissolution of nickel in chloride solution. The geometry of the electrochemical cell corresponds to the one-dimensional pit model represented in Figure 7.62. The results show that, after a certain time, the current density decreases according to the square root of the polarization time, independent of potential. Mass-transport controlled growth of corrosion pits is favored by a highly electrolyte conductivity and weakly soluble dissolution products. 

In acidic solutions, the corrosion rate is relatively high. Studies on cadmium monocrystals and polycrystals in acidic chloride solutions revealed anodic dissolution independent of the crystallographic orientation the dissolution rate was controlled by the mass transport of CdCl" ions [331]. The inhibitive influence of adsorbed organic substances, for example, alcohols [332], phenotiazine [333], and some polymers (e.g. poly (vinyl alcohol), poly(acrylic acid), sodium polyacrylate. 

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