I upgraded from Xcode 4 to 5 and I can no longer validate archives created for Ad-Hoc distribution.
After creating an archive, I hit Validate, log into iTunes Connec
It looks like Apple disabled the ability to validate with just an ad hoc provisioning profile in XCode 5.
If you wish to validate an app that is intended only for Ad Hoc distribution, you must also have an App Store provisioning profile for the app too, against which to validate it.
Here you go, follow the screens below, it should help you..
And yes they have removed Profiles from Organizers, instead you can use iPhone Configuration Tool.
Hope it helps..
Cheers
Make sure that the bundle identifier in Xcode matches your App's bundle ID in iTunes connect.