When a cation of higher valence is added to an ionic solid as an impurity to it, the cation of higher valence replaces more than one cation of lower valence so as to keep the crystal electrically neutral. As a result, some sites become vacant. For example, when Sr2+ is added to NaCl, each Sr2+ ion replaces two Na+ ions. However, one Sr2+ ion occupies the site of one Na+ ion and the other site remains vacant. Hence, vacancies are introduced.
