Some motherboards will support upto 64Gb of ram. Presently ram is limited to 16Gb per stick at best, so you'd need to fill all 4 slots with 16Gb sticks (1 kit) to get the maximum the board can handle. Most ppl have no need for more than 8Gb of ram, any programs they may use don't use the whole 8Gb, so having 12 or 16 or 32Gb is just a waste of money. Most gamers or power pc users benefit from having 16Gb or better. Most kits come in specific sizes, 8Gb kit can be 1x8Gb stick, or 2x4Gb or even 4x2Gb sticks.
The memory controller works like a convoy, it'll run at the speed and timings of the slowest ram, so if you have 8Gb of 1333MHz ram, even if you added 16Gb of 2400MHz, all 4 sticks will run at 1333MHz at best, possibly due to incompatibility running lower speeds. So for best compatibility chances, getting near identical ram is usually better. Not always, but usually. The higher the ram speeds, the more temperamental the ram seems to be.
As far as right slots, that's a channel issue. Your mobo is generally set with 2 ram channels, A+B. So slot 1-2 is A, slot 3-4 is B. For best performance you'll want to run your ram in dual channel, it's about roughly 20% better than ram in single channel. So using 2x sticks, if you use slots 1-3 or 2-4 you use channels A+B, dual channel, if you have sticks in just 1-2 or 3-4 you are A+A or B+B, single channel. Using 4x sticks, if 1 kit, you automatically use A+B and A+B which is both sets of 2x sticks in dual channel. If using mixed kits you could use either 2x dual channels or end up with 2x running single channel. They'll still work, just not as good.
This, of course, is IF the new ram works with the old at all. Best bet is 1 kit of 2x8Gb ram, in slots 2-4 to maximize all 16Gb being not only compatible (it's factory tested) but running dual channel and not taxing the memory controller by using 4x slots (keeps cpu temps lower, makes for easier OC if any)