[guided]The equivalence (i) $\Leftrightarrow$ (iii) is the fundamental characterisation of separable extensions in terms of embeddings. Let us verify it carefully.
For a simple extension $k(\alpha)/k$: the $k$-embeddings $\sigma: k(\alpha) \hookrightarrow \overline{k}$ correspond bijectively to the roots of $\operatorname{min}(\alpha, k)$ in $\overline{k}$, via $\sigma \mapsto \sigma(\alpha)$. This is because $\sigma$ is determined by $\sigma(\alpha)$ (by the [Structure of Simple Algebraic Extensions](/theorems/1251), every element of $k(\alpha)$ is a polynomial in $\alpha$), and $\sigma(\alpha)$ must be a root of $\operatorname{min}(\alpha, k)$ (applying $\sigma$ to $\operatorname{min}(\alpha, k)(\alpha) = 0$ gives $\operatorname{min}(\alpha, k)(\sigma(\alpha)) = 0$ since $\sigma|_k = \operatorname{id}$). Conversely, every root $\beta$ of $\operatorname{min}(\alpha, k)$ defines an embedding via the isomorphism $k(\alpha) \cong k[x]/(\operatorname{min}(\alpha, k))$ and the evaluation $x \mapsto \beta$.
So $[k(\alpha) : k]_s$ = number of distinct roots of $\operatorname{min}(\alpha, k)$, and $[k(\alpha) : k] = \deg \operatorname{min}(\alpha, k)$. These are equal iff $\operatorname{min}(\alpha, k)$ has no repeated roots, i.e., $\alpha$ is separable.
For a general finite extension $K/k$: write $K = k(\alpha_1, \ldots, \alpha_r)$ and build the tower $k \subset k(\alpha_1) \subset k(\alpha_1, \alpha_2) \subset \cdots \subset K$. By the [Multiplicativity of Separable Degree](/theorems/3331), $[K : k]_s = \prod [k(\alpha_1, \ldots, \alpha_i) : k(\alpha_1, \ldots, \alpha_{i-1})]_s$ and similarly for degrees. Each factor satisfies $[\cdot]_s \leq [\cdot]$, with equality iff the added element is separable. So the product equals $[K : k]$ iff each $\alpha_i$ is separable over $k(\alpha_1, \ldots, \alpha_{i-1})$, which by the [Multiplicativity of Separable Degree](/theorems/3331) is equivalent to $K/k$ being separable.[/guided]