1) A polynomial is separable if it has distinct roots. A field extension $E/F$ is separable if for each $\alpha \in E$, its minimal polynomial is separable. As DonAntonio says, for a field of characteristic zero, every irreducible polynomial $f$ is separable: if $f$ has degree $n$, then $f'$ has degree $n-1$ and since $f$ is irreducible this means that $f$ and $f'$ are relatively prime. (Recall that $f$ has a multiple root iff $\gcd(f,f') \neq 1$.) The reason this can fail in characteristic $p$ is because if $f(x) = x^p - a$ for some $a$, then $f'(x) = 0$. For more on separability, see here.
2) See Dummit and Foote, Theorem $8$, $\S 13.1$, p. $519$:
Theorem 8. Let $\varphi: F \overset{\sim}{\to} E$ be an isomorphism of fields. Let $p(x) \in F[x]$ be an irreducible polynomial and let $q(x) \in E[x]$ be the irreducible polynomial obtained by applying the map $\varphi$ to the coefficients of $p(x)$. Let $\alpha$ be a root of $p(x)$ (in some extension of $F$) and let $\beta$ be a root of $q(x)$ (in some extension of $E$). Then there is an isomorphism
\begin{align*}
\sigma: F(\alpha) &\overset{\sim}{\to} E(\beta)\\
\alpha &\mapsto \beta
\end{align*}
mapping $\alpha$ to $\beta$ and extending $\varphi$, i.e., such that $\sigma$ restricted to $F$ is the isomorphism $\varphi$.
In your example, to show the existence of $\sigma$ we can proceed as follows. Applying the theorem with $F = E = \mathbb{Q}(i)$, $\varphi$ the identity map $\operatorname{id}: \mathbb{Q}(i) \to \mathbb{Q}(i)$, $\alpha = \rho$ and $\beta = i \rho$, we get the desired isomorphism $\sigma: \mathbb{Q}(i)(\rho) \to \mathbb{Q}(i)(i \rho) = \mathbb{Q}(i)(\rho)$.
3) Every element of $\mathbb{Q}[\rho, i]$ is a polynomial in $\rho$ and $i$, i.e., given $\alpha \in E$ there exists a polynomial $g(x,y) \in \mathbb{Q}[x,y]$ such that $\alpha = g(\rho, i)$. An element $\sigma \in \operatorname{Gal}(E/\mathbb{Q}) =:G$ fixes $\mathbb{Q}$, so it is totally determined by its action on $\rho$ and $i$. In other words, given $\sigma, \tau \in G$, if $\sigma(\rho) = \tau(\rho)$ and $\sigma(i) = \tau(i)$, then $\sigma = \tau$. For instance, if $\alpha = 2 + 3i - 7 \rho^2$, then
$$
\sigma(\alpha) = \sigma(2 + 3i - 7 \rho^2) = \sigma(2) + \sigma(3)\sigma(i) - \sigma(7) \sigma(\rho^2) = 2 + 3 \sigma(i) - 7 \sigma(\rho)^2
$$
since $\sigma$ is a ring homomorphism. Thus we can compute $\sigma(\alpha)$ just by knowing $\sigma(\rho)$ and $\sigma(i)$.