The DMX data pair is pins 1/2 with pins 7/8 as the ground and pins 3/6 as the almost-never-used secondary pair. While I guess you could feed DC on the other pairs, it would be a non-standard application, and I would double-check that anything you plug in has those pins isolated. Also, some devices may not pass those pairs from the input to output connector.
RS485 is typically a 120-ohm bus; the difference between terminating at 100R and 120R is minor.
The 32-node limit isn't a hard one; it depends a lot on cable length and the types of driver and receiver chips used on the devices (some are good for 256 nodes). You can probably go a little over the limit without problems, A splitter, wireless RX, or the third connector on a LE all regenerate the signal, so the count starts fresh.
/mike