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Yes. Let $G$ be obtained from $K_{100}$ by adding two non-adjacent vertices $v$ and $w$ such that $|N_G(v)|=|N_G(w)|=50$ and $N_G(v) \cup N_G(w)=V(K_{100})$. Then collapsing $v$ and $w$ in $G$ yields $K_{101}$, which increases the chromatic number. On the other hand, it is easy to see that adding any edge to $G$ does not increase the chromatic number.