Windows XP is 32bit. Windows 64 will be 64 bit for the new 64bit processors.
There are some compatability problems with XP and older programs (mainly pre win95) but you can try running these older programs in compatability mode.
You can do this by finding the EXE of the program you want to run and right clicking on it.
Go to the Propertites option on the menu, then click on the compatability tab in the window that appears. Then you can tick the box which will run the program in compability mode and you can select which OS you want to use.
This will help in some situations, but it will not cover all eventualities.
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