I know that there is a transfinite construction of the Borel sets, and, more generally, of the $\sigma$-algebra generated by a subset of $P(X)$ for any set $X$. This construction ends at the first uncountable ordinal, if I am not mistaken.
A mistake I have noticed in some of my peers is (perhaps through association with the much easier case for topological space generated by a subset) the assumption that one can make such a process terminating at the first countable ordinal. Of course, it is easy to shake and question this assumption, but I would like to have a practical example to show that it is irredeemably wrong.
To be more precise, it would be perhaps reasonable at first glance to assume the following:
Let $\mathcal{B}$ be the Borel $\sigma$-algebra on $\mathbb{R}$. Furthermore, define $B_0$ as the set of opens on $\mathbb{R}$, and define $B_{n+1}$ as $B_n$, plus the set of countable intersections of elements in $B_n$, plus the set of countable unions, plus the complementaries. It could be conjectured that $\mathcal{B} = \bigcup_{n=0}^\infty B_n$.
What I'm looking for is a proof that this conjecture is wrong, if possible by an example of a Borel set that isn't in any $B_n$.
Note: I think that there might be standardized notation to what I have called $B_n$, something to do with the Borel hierarchy, but I couldn't figure out what the correct notation would be, so I made up my own.
Asaf's answer exemplifies the point of departure from $\sigma$-algebras —and “universal” algebras with infinitary operations in general— from the customary realm of finitary operations: The union of an increasing sequence of infinitary algebras is not necessarily closed under the operations. And the fact that the first uncountable ordinal $\omega_1$ is regular (closed under limits of sequences, in this particular case) is what ensures that the union of an increasing transfinite sequence of $\sigma$-algebras with length $\omega_1$ is a $\sigma$-algebra. The same holds for any infinitary algebra with operations with countable arity.
A particular example of Borel subset not belonging to any of the $B_n$ would necessarily be contrived (all natural examples from analysis are in $B_5$ or so, and then jump into analytic sets). Such examples can be found in Kechris' Classical Descriptive Set Theory, Sect. 23.G.
For describing one of them, consider the Cantor ternary set $\mathcal{C}\subset\mathbb{R}$. There is a natural map (a homeomorphism, in fact) from $G :\{0,1\}^{\mathbb{N}}\to \mathcal{C}$ by using binary-to-ternary expansions. Now we can code total orders $R$ on $\mathbb{N}$ by functions $f_R:\mathbb{N}\to \{0,1\}$: $$ n \mathrel{R} m \iff f_R(2^n\cdot 3^m) = 1, $$ where $f_R(k) = 0$ for every $k$ such that $6\nmid k$. Finally, our set can be defined as $$ G\bigl(\{f_R\in 2^{\mathbb{N}} : R \text{ is a well-order of } \mathbb{N} \text{ in type}<\omega^\omega\}\bigr). $$