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Indeed, 2.5 GB of free RAM is very much, and Vista is a quite resource hog. If you want more performance I suggest you to upgrade to Windows 7 since it's quite faster and use less resource. Or you might consider to upgrade your whole system (CPU + MB + Graphic Card).
Anyway, 4 GB of DDR2 is quite adequate for today. I'm also have 2 x 2 GB DDR2 800 MHz here, and with a good graphic card (HD 4850), I can play any game at their high settings quite smoothly. I think you will need a good reason to upgrade to more than 4 GB (or 6 GB for triple channel) or it'd be quite a waste.
And ReadyBoost is a feature introduced in Windows Vista so it doesn't available on XP.
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