This pin is usually connected to the frame of one of the devices, either the DCE or the DTE, which is properly grounded. The sole purpose of this connection is to protect against accidental electric shock and usually this pin should not be tied to Signal Ground .
Ground loops are low impedance closed electric loops composed from ground conductors.
Since the loops impedance is low, this current can be quite high and easily burn out electric components. Electrical storms could also cause a burst of destructive current across such a loop. Therefore, connection of the Protective Ground pin is potentially hazardous. Furthermore, not all signal grounds are necessarily isolated from the chassis ground, and using a RS-232 interface, especially across a long distance, is unreliable and could be hazardous. 30 meters is considered the maximum distance at which the grounding signals can be connected safely.