I suggest you visit the High Scalability blog, which discusses this topic almost on a daily basis and has many articles about projects that chose distributed hashes, etc. over RDMBS.
The quick (but very incomplete answer) is that not all data translates well to tables in efficient ways. For example, if your data is essentially one big dictionary, there are probably much faster alternatives that plain old RDBMS. Having said that, it mostly a matter of performance, and if performance isn't a huge concern in a project, and stability, consistency and reliability, for example, are, then I don't see much point in delving into these technologies when RDBMS is a much more mature and well developed scheme, with support in all languages and platforms and a huge set of solutions to choose from.
