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I'm not a professional (don't even own a 64-bit system, no need for one) but as far as I know, 64-bit system isn't compatible with 32-bit apps. Just like you can't usually run old 16-bit programs on your Windows XP which is 32-bit system. There are some exceptions, for example I've (force-)installed Wine (which doesn't have, or didn't have then, 64-bit version) on a 64-bit Ubuntu and it did work somehow (not perfectly well, but it's Wine). I guess it's per-program-thing; I'm not aware of a general all-powerful method, if such even exists.
I'm sorry if you've already considered this option, but in case you didn't know, it is possible to run 32-bit applications without installing a chroot system. If you are going to run a lot and complex programs chroot is probably the way to go, but for the occasional program just install ia32-libs and linux32 packages (and perhaps ia32-libs-openoffice.org). I run Opera, Skype and Openoffice transparently in my 64-bit system.
...but as far as I know, 64-bit system isn't compatible with 32-bit apps....
FYI, this is true of older 64-bit architectures like the Alpha, but both Intel and AMD's new chips have been built with backward compatibility in mind and can also run 32-bit code. That's doubtlessly the reason wine runs for you, not because of it's Windows-related nature.
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