The difference between rimfire and centerfire rifles would be the type of cartridge they use.
Rimfire cartridges are an older design. In a rimfire cartridge, the priming compound (impact-sensitive substance that produces the spark to ignite the gunpowder) is located inside the hollow rim of the cartridge case. The firing pin crushes the rim against the chamber mouth to fire the cartridge.
In a centerfire cartridge, the priming compound is located inside a small metal cup called a primer, which is made separate from the casing. The cup is inserted into a hole in the center of the base of the cartridge. The firing pin strikes the primer crushing it against an internal anvil to produce the spark.
Rimfire cases are made of soft brass so that the firing pin can crush the rim. However, this makes them unsuitable for higher chamber pressures. Centerfire cartridge brass is much harder, because only the primer cup needs to be soft.
With the switch from black powder to smokeless powder, higher chamber pressures became commonplace and rimfire cartridges became largely obsolete.
The most common rimfire cartridge in use today is .22LR, popular for target shooting and pest control. Due to low cost and low recoil it is probably the most popular cartridge in the world.
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