No, a 64-bit process can only load 64-bit DLLs and a 32-bit process can only load 32-bit DLLs. What you're probably thinking of is that a 64-bit operating system can run 32-bit processes .
You can run x86 apps on a 64 bit OS using WOW32 emulation. Some pitfalls that I have encountered - you can't mix and match 32/64 in the same process. So if you intend to run IIS as 64 all the assemblies need to be 64 otherwise you'll have to run In 32 bit mode.
64 bit helps some apps more than others. Running SQL sever's 64 bit version provides several advantages over the 32 bit version, biggest advantage being that yo can install more than 4 GB of memory on the target server and that SQL will be able to use more than 4 GB of memory. It does not benefit IIS as much because IIS typically can't use more than 3 gb of memory.
My advice would be to make sure your SQL server/os/version are 64 if possible. It's not going to make a. Huge dfference if the other servers are 64 but typically it's easier to work with and find 32 bit versions.
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