Afraid not. PSU has to be installed into chassis and then that has to be connected to the socket on the wall. Switch off of course.
A case sitting on the worktop isn't grounded to anything. A mistake everyone makes, including my old college lecturer!
But why would this be a problem? All you're doing is putting yourself at the same potential as the case. As long as you're just working on the case, it wouldn't be a issue?
I remember on a TV program how engineers needed to work on live power cables so they were in a helicopter and connected themselves to the wire. This put them at the same potential (40,000v if I remember correctly) but they had no connection to ground (Due to the heli, which was also at 40,000v).
Voltage is just the difference of potential between two points.
Please correct me if I'm wrong, I'm studying Electronics after all

