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Would x86 assembly compile on an x64 machine and still work properly? If not, what is the difference between x86 assembly and x64 assembly?

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If by x64 you mean x86_64 (or amd64) and not IA-64 (Itanium), yes. It's intended to be backwards-compatible. However, you won't be able to take advantage of the additional instructions and hardware made available in 64-bit mode.

There are numerous additional features available in "long mode." 64-bit registers, additional general-purpose registers, SIMD features, larger address space, and so forth.

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