The Third Axiom of Probability has been a well-accepted axiom yet there seems to be a nice proof of it. I couldn't trace an implicit assumption of this axiom anywhere in the proof. I'll write a sketch of the proof; please tell me if it could be replaced by it.
Thm : Let $\{E_1, E_2, \cdots\}$ be mutually exclusive events of some countable set $\Omega$ such that $P(\Omega) = 1$. Then $P(E) = \displaystyle\sum_{i=1}^{\infty} P(E_i)$.
Proof : The case when $E$ is finite can be proven easily (from definition) and hence is left out. (Edit : Added as comment #1) When $E$ is countable, choose some $\epsilon > 0$. Denote $\displaystyle\sum_{i=1}^{\infty} P(E_i)$ by $\text{P}$ and $F_n = \displaystyle\sum_{i=1}^{n} P(E_i)$.
Observe that we can get some $n$ in $\mathbb{N}$ such that $|P - F_n| \leq \epsilon$ (which basically follows from the monotone convergence thm and def. of convergence). Additionally, we can yield some (finite set) $E^{*}_i \subseteq E_i$ for each $1 \leq i \leq n$ so that $P(E_i) \leq P(E^{*}_i) + \epsilon$.
Obviously $\displaystyle\bigcup_{i=1}^{n} E_i^{*} \subseteq E$ and so by Boole's inequality implies $P\left(\displaystyle\bigcup_{i=1}^{n} E_i^{*}\right) \leq P(E)$. From all these above, it follows that : $$\text{P} \leq F_n + \epsilon \leq P\left(\displaystyle\bigcup_{i=1}^{n} E_i\right) + \epsilon \leq \displaystyle\bigcup_{i=1}^{n} P(E_i) + \epsilon \leq \bigcup_{i=1}^{n} P(E_i^*) + (n+1)\epsilon \leq P(E) + \epsilon'$$.
This shows that $\text{P} = \displaystyle\sum_{i=1}^{\infty} P(E_i) \leq P(E)$. We can also show the reverse to eventually conclude the equality of $\text{P}$ and $P(E)$. (I'm not attaching the proof, unless asked in comments to keep the size of the post decent)
Why is it an axiom and not a theorem then?
I would like to add that I have no background in measure theory and hence is not defined on a measure theoretic space in particular.
EDIT (as suggested by @Bungo in comments) : Please note that the $\Omega$ is assumed to be countable. I'm trying to see if setting $P(A \cup B) = P(A) + P(B)$ as the axiom ($A \cap B = \phi; A,B \subseteq \Omega$) proves both the finite and the infinite case.