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Cathode-Rays are streams of electrons. Having a charge of -1 and a small mass (about 1 /1836th of a proton), they interact easily. Since you don't want them to interact with the atoms in the tube (air, etc.), you evacuate the tube, leaving it in as near a vacuum state, or zero PSIA, as possible.

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Q: Why a tube used to examine photoelectric emission is evacuated?
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