40 conductor cables has 40 conductors and guess what 80 conductor cables has 80 conductors
They are easy to distinguish. Simply count the number of conductors. The two types are almost functionally equivalent, however, in 80 conductor cables the PDIAG- signal is not connected to the BLUE connector (the one that goes to the mobo). This makes it possible for the mobo/bios to detect whether a 40 or 80 conductor cable is used. Some systems may use this to automatically set the transfer mode. The other main difference is the addition of 40 extra ground wires interleved with the existing 40 conductors. This reduces crosstalk between wires at high frequencies.
80 conductor cables should be used for UDMA66 and above. Below you can safely use 40 conductor cables.