I'm purely guessing here, but...
I think the 25% size is just within the window size you have available. If you are opening multiple files at once, the program will stagger the window position. Photoshop calculates the displayed "zoom value" based on available screen space, and does take into account other windows that would overlay, e.g. the floating pallettes, so as the window position moves, the available space may not meet the requirements to display at 25% and it drops it to 16.7%
This is the most likely source of the behavior. In any case, it's nothing but a nuisance.
To confirm the hypothesis, try upping you screen resolution one notch if you can, then see if it goes away. I assume you are running 1024x768, unless you are running on an LCD screen, you should be able to increase it. Even on LCD, you may be able to increase it and let the desktop fall off the screen edge, you can still scroll over/down to the invisible areas by moving the mouse to the edge.
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