I tend to read books as a whole and don't consider the individual chapters, although maybe this is my sign to start looking at the chapter as its own thing.

I don't know about best of all time, but I remember being really moved in Rabbit, Run by John Updike, when we finally see his wife's perspective. Throughout the whole book, we kind of hear from every character, but we only see Jan through Rabbit's eyes (and it's not flattering). Then when we see her on her own and the terrible climax of the book happens, I felt like I understood exactly how she had ended up in that spot, and felt empathy for her.