If $M$ is an oriented $2n$-dimensional manifold with boundary $\partial M$, then the natural map $H_n(M)\to H_n(M,\partial M)$ can be identified (via Lefschetz duality) with a map $H_n(M)\to H^n(M)$. If, moreover, $H_{n-1}(M)$ is torsion-free or we take coefficients in a field, we can further identify this with a map $H_n(M)\to \operatorname{Hom}(H_n(M),\Bbb Z)$. Now, according to Madsen & Milgram (page 165), this last map can be taken as the intersection form on $H_n(M)$ (i.e., $\sigma\mapsto \sigma\cap -$). This seems plausible to me, but I cannot see why it is actually true. To summarize:
Why can we take the map $H_n(M)\to H_n(M,\partial M)$, appearing in the long exact sequence of $(M,\partial M)$, to be the map given by the intersection form $H_n(M)\otimes H_n(M)\to \Bbb Z$ (under the identification $H_n(M,\partial M)\cong H^n(M)\cong\operatorname{Hom}(H_n(M),\Bbb Z)$)?
This sort of geometric reasoning has never come easily to me, so I'm hoping people could bring their own perspectives here.
Background:
This occurs during construction of an exotic $7$-sphere ($\partial M$). The intersection pairing on $H_n(M)$ is easily determined, and the idea is to use this to determine the homology of $\partial M$. In particular, $M^{2n}$ is homotopy equivalent to a wedge of $n$-spheres and the claim is that, if the Gram matrix of the intersection form on $H_n(M)$ is unimodular, then the exact sequence $$0\to H_n(\partial M)\to H_n(M)\xrightarrow{*} H_n(M,\partial M)\to H_{n-1}(\partial M)\to 0$$ forces $H_n(\partial M)=H_{n-1}(\partial M)=0$ (where $*$ is given by the matrix of the intersection form). After this, it follows easily that $\partial M$ is a homotopy sphere and thus (via the h-cobordism theorem) a topological sphere.
The book by Madsen & Milgram I referenced is "The Classifying Spaces for Surgery and Cobordism of Manifolds" (1979).