TAILIEUCHUNG - Corrosion P2

Pure Acid-Base Reactions. The previous computations showed that there are possible equilibria between the metal and its ions (such as Ni2+/Ni) and between the metal and its oxide (NiO/Ni). In the case of cobalt it is possible, as shown in Fig. 16, to determine the equilibria for Co2+/Co and for CoO/Co. | The equilibrium potential is then given by NOJ E log----t pH NH4 K MH- It can be represented in an E-pH diagram for equal activity in v and by a decreasing line in Fig. 15. Fig. 15 Partial E-pH diagram for the 8H 6e 2H2O reaction Above the line there is a region in which is predominantly stable but in equilibrium with smaller activities of . Below the line v 11 is predominantly stable with smaller quantities of . Pure Acid-Base Reactions. The previous computations showed that there are possible equilibria between the metal and its ions such as Ni2 Ni and between the metal and its oxide NiO Ni . In the case of cobalt it is possible as shown in Fig. 16 to determine the equilibria for Co2 Co and for CoO Co. The two equilibrium potential lines meet at some point P and above them are two domains of stability for Co2 and CoO. These two species are submitted to an acid-base chemical reaction Co2 H2O CoO 2H Eq 18 which does not involve electrons. It does not depend then on the potential and it will be represented by a vertical line. Point P in Fig. 16 is one point on that line located at a pH for an activity of 1 in Co2 ions. Fig. 16 Partial E -pH diagram for Co2 Co and CoO Co The pH value of that line can also be computed from the chemical equilibrium with the general equation AG -RT In K or . M-R FP log K - -------- ------------- RT Eq 19 where K is a constant vR is the stoichiometric coefficient of the reactants vP is the stoichiometric coefficient of the product p R is the standard chemical potential of the reactant and p p is the standard chemical potential of the product. In this case the equilibrium as given in Eq 18 can be written CoOXH z Fho - Fcoo log .------- ------------------ 23 RT By assuming that CoO and H2O both have activities of 1 and by replacing the standard chemical potentials by their values given in the Atlas of Electrochemical Equilibria Ref 13 it is possible to write H r 12 800 56 690 52 3101 log - Co21 23 x x 298 Eq

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