The BBs help spread the prep evenly -- as mentioned above, they are a pain to clean them out and make sure that you get them all.
The evaporation rate definitely changes how the prep is absorbed into the rubber. Consider that many preps use acrysol, or some type of mineral spirits or other solvent to help drive the prep into the rubber. Unfortunately, these solvents all evaporate at a much higher rate than many of the ingredients that actually "prep" the tire (ie silicone base or other oils.) Generally, the solvents evaporate first, leaving the base prep chemicals just sitting on the surface of the rubber. Some even stay wet or slimy even through several heat cycles. I think the big key to prepping is consistency. If you prep (whatever brand you use) the same way every time, then your results become more consistent. If you are forced to prep a tire unmounted, and your norm is to prep them mounted, don't expect the results to be the same for both methods. I've always got some extra wheels lying around the shop here if I've got a customer that wants me to prep just tires for them. Sure, it's a pain to mount and dismount, but with the proper tools, it's not so much of a pain as it is a time inconvenience. I try to sell the customer wheels if they need, or they are always welcome to ship their wheels here, but occasionally, we still get requests for unmounted prepped tires.
Someone mentioned 15 cc (that's only 1/2 ounce) -- if you're prepping that little internally, you might do well to just wipe the inside of the tread and that way you won't get ANY on the sidewalls. 1/2 ounce is about two wipes. Pretty simple to do that with unmounted tires.
It's true that the prep wicks into the sidewall/shoulder of the tires. I try to limit internal prepping to 2 ounces per roll. Ie, if I need a 4 ounce tire, I roll 2 ounces 24 hours, then roll another 2 ounces the next day. This definitely helps on keeping prep off the sidewall and your spring rates up when internal prepping with anything that softens a tire. This is especially important on thick rubber tires and ELs.
Thanks,
Brian