I'm not an expert but my understanding is that all updated versions of XP/Vista/7 can handle multiple core processors. Specifically, 32bit versions can handle up to 32 cores and 64bit versions can handle up to 256 cores.
The biggest limitations are:
1) 32bit versions of windows (more specifically 32bit processors) cannot utilize any more than 4gb of ram. Whereas 64bit supports some ridiculous number.
2) Although 64bit is slowly becoming the standard, most applications (including SC2) are still designed for a 32bit environment. Meaning if you have a high end system it still won't be utilizing what you have.
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