 Solution

The oxygen-pressure exponents can be explained by a change in the dominant charge state of metal vacancies, with holes carrying the p-type current. For a divalent metal oxide, a doubly negative metal vacancy is $V_{\mathrm{M}}^{\prime \prime }$ in Kröger–Vink notation. A conventional oxygen-incorporation reaction isTreating regular oxygen-site activity as constant, the law of mass action gives $K_2=[V_{\mathrm{M}}^{\prime \prime }]p_h^2/p_{{\mathrm{O}}_2}^{1/2}$. If these are the compensating defects, charge neutrality gives $p_h=2[V_{\mathrm{M}}^{\prime \prime }]$, hence $p_h^3\propto p_{{\mathrm{O}}_2}^{1/2}$ and $\sigma \propto p_{{\mathrm{O}}_2}^{1/6}$, assuming nearly constant hole mobility.

For singly negative vacancies, useNow $p_h=[V_{\mathrm{M}}^{\prime }]$ and $p_h^2\propto p_{{\mathrm{O}}_2}^{1/2}$, so $\sigma \propto p_{{\mathrm{O}}_2}^{1/4}$. The charge-state equilibrium $V_{\mathrm{M}}^{\prime }\rightleftharpoons V_{\mathrm{M}}^{\prime \prime }+h^{\bullet }$ gives $[V_{\mathrm{M}}^{\prime \prime }]/[V_{\mathrm{M}}^{\prime }]=K_{\mathrm{ion}}/p_h$: the singly charged fraction can therefore dominate as oxygen pressure and hole concentration increase. This is a consistent dilute-defect model, not a unique experimental identification of every defect. Changes in mobility, defect association or other compensating defects require independent tests.