How to prove exactness of the hom-sequence:
We have to do two things:
- Show $\operatorname{img} (0) = \ker (g\#)$, i.e. $g\#$ is injective, as you said.
Show $\operatorname{img} (g\#) = \ker (f\#)$, which can be split up to showing:
(a) $\operatorname{img} (g\#) \subseteq \ker (f\#)$, and
(b) $\operatorname{img} (g\#) \supseteq \ker (f\#)$.
Proving $g\#$ has trivial kernel, take an $γ ∈ \ker (g\#)$, wich is a linear map $V'' → W$.
Now, $g\#(γ) = 0$, this means $γ∘g = 0$.
Use the surjectivity of $g$.
Proving $\operatorname{img} (g\#) \subseteq \ker (f\#)$, take $β ∈ \operatorname{img} (g\#)$.
It can be written as $β = g\# (γ) = γ∘g$ with $γ ∈ \operatorname{Hom} (V',W)$. What happens if you $f\#$ this $β$ now?
Proving $\ker (f\#) \subseteq \operatorname{img} (g\#)$ is the trickiest bit.
Take $β ∈ \ker (f\#)$, meaning $β∘f = 0$.
So you know $\ker (g) = \operatorname{img} (f) \subseteq \ker (β)$.
This should give you a hint that it’s possible to find a $γ \colon V'' → W$ such that $β = γ∘g$. Try to construct such, using the surjectivity of $g$.