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especially Facebook has some "sub categories", such as Mail, Apps, Chat, etc (at least in 184.108.40.206). Generally the application controll is a different approach of blocking access to complete websites or website features. If you want to work with Youtube for example you would need to take multiple things into consideration, such as the URL (youtube.com, probably other TLDs), content servers associated to Youtube, categories associated to Youtube. Instead of doing so you can use the application control list to identify every request that belongs to Youtube. The list is updated and maintained by McAfee, so if new Youtube related URLs are in place, this will automatically be updated and there is no need for you to update your rules.
I think this is the major advantage of using application control rather than URL.* properties or working with categories.
You are especially looking for features of applications. This is something we are making progress with every release, for example Facebook now contains several sub-categories, so does LinkedIn for example. More should be available with future versions.
I hope this gives you some ideas where the application control feature could be useful.