Adding RAM is completely unrelated to the /3gb boot switch on 32-bit Windows. Many people incorrectly assume that the /3gb boot switch lets Windows use the installed RAM more efficiently.
If you’ve never had Pro/E crash because it tried to access more than 2GB memory, then you don’t need the /3gb boot switch. This switch controls how much virtual address space each process can address.
Virtual address space and RAM are not the same. A process’ virtual address space exists both in RAM and on the hard disk (page file). The Windows memory manager handles swapping memory pages to / from the disk so that any memory pages required by the CPU are loaded into RAM.
So you can see that using or not using the /3GB switch has no effect on how Windows uses the installed RAM.
Another good thing to know is how much memory ProE as an application is using. This TPI shows you how to use perfmon to determine exactly how much memory ProE is using.