The extra wires in an 80-conductor cable don't connect to separate pins on the connector. There's still only 40 pins. They are ground wires used to help prevent crosstalk when the frequency is up in the ranges used for ATA66 and ATA100. So the connectors still fit and can be used with any drive (and may even provide a slight data reliability boost if you're using an ATA33 drive with a very long cable).
The fact that you've got an ATA33 hard drive makes it most likely that you have a 40-wire cable. If the cable came with the hard drive (or the computer system) it would only be as good as the drive it came with, and if you bought the cable separately, you'd have noticed whether it said it was an ATA66 cable. There's a significant visual difference between the types, so if your cable looks the same as other IDE cables you've seen, it's probably not 80-wire. Compare it to your CDROM cable, which is almost assuredly only a 40-wire since no optical drive is ATA66-capable.