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Leon, XP can only address 3.2Gb of ram, the rest is unavailable to the XP OS. If your PC is not too old it would be worth a new load, live on the edge and install W8.
I'm probably one of Win8's harshest critics, but if you load the free Classic start menu it's friendly enough and certainly boots heaps faster than the older OS'.
FWIW we had the same problem on an XP machine at work, tried everrything but never managed to find the problem. One thing I did find was that shortcuts on the desktop to anything out in the web can cause real issues, as can links to unavailable network resources.
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