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32 bit OS
-A 32 bit OS can only address 4Gb of memory. Some of this is then allocated to hardware devices, usually dropping the available RAM to 3.25Gb or 3.5 Gb.
-The addressable space also applies to programs, giving a 2Gb limit of RAM to any one process. This means that 32 bit Photoshop can only ever access up to 2Gbs of RAM.
-Drivers are always a concern. Drivers for hardware usually have a 32 bit version, and there is usually not a problem with 32 bit drivers (finding or using).
-A 32 bit OS has a lower memory requirement to run. For Windows 7, the minimum RAM needed is 1Gb
64 bit OS
-A 64bit OS can address up too 8Tb of RAM (128 in 64 bit Vista, and 192Gb in Seven).
-The addressable space for a 64 bit process is 8Tb. However, a 32 bit process still has the 2Gb limit. So 64 bit Photoshop can access up to 8Tb of RAM, while 32 bit Photoshop (running on a 64 bit OS) will still only be able to access up to 2Gb.
-64 bit drivers can be somewhat more difficult to find than 32 bit drivers. They can also tend to be somewhat buggier. Personally, I have NEVER had trouble with driver incompatibility due to using a 64 bit system.
-64 bit OS needs more RAM to operate (minimum of 2Gb for Windows), and programs slightly more RAM. This is countered by being able to add WAY more RAM (I have never encountered a problem with 4Gb of RAM on my 64 bit system)
-There is no longer 16 bit compatibility
Misconceptions
-RAM limit is the only difference: This is obviously the most well-known difference, but is completely false. There are WAY more differences, some of which go way deep into computer architecture, and others that don't make a difference in performance.
-Non-compatibility: Some people believe that certain things will not work in 64 bit OS, etc. While 32 bit programs and 64 bit programs are NOT COMPATIBLE with the other system (64 bit and 32 bit respectively), Microsoft writes their Operating Systems with a Hybrid architecture (Windows In Windows, or WoW). This means that most 32 bit programs will work on 64 bit systems.
-No performance difference: This one is a quirky question. In general, there is not a large performance increase by switching to 64 bit. This is because most programs are still written with 32 bit architecture in mind, and do not need more than 2Gb of RAM. The difference starts to shine when running things like 64 bit Photoshop or CAD programs where LOTS of RAM is used.
Pros (of switching to a 64 bit OS)
-Certain programs written for 64 bit computers can make better use of CPU and RAM, giving a LARGE performance boost (such as 64 bit Photoshop)
-More RAM is available
-64 bit is becoming more and more common. As average RAM in a system increases, there will be no choice BUT a 64 bit system.
Cons (of switching to a 64 bit OS)
-Certain programs may not be compatible with the new OS (very rare)
-Needs a minimum of 2Gb of RAM to run
-Needs a 64 bit processor to run (most made since 2003 are 64 bit)
-System uses more RAM to run the OS and programs
-Drivers may be harder to find and use