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The county was named for John Montgomery, an early settler who founded the city of Clarksville, the county seat. The county was initially organized as Tennessee County, but its name was changed in 1796, the year that Tennessee was admitted as a state, to reduce confusion. Montgomery County is located 30 minutes northwest of Nashville at the Tennessee-Kentucky state line. It is home to the fifth largest city in the state.
Montgomery County was the site of several saltpeter mines. Saltpeter is the main ingredient of gunpowder and was obtained by leaching the earth from several local caves. Bellamy Cave contains the remains of two dozen saltpeter leaching vats and was apparently a large operation. Cooper Creek Cave also shows evidence of extensive mining and contains the remains of "many saltpeter hoppers" Dunbar Cave is also reported to have been mined for saltpeter during the Mexican War, but commercial development has erased any evidence of this mining. Dunbar Cave is the centerpiece of Dunbar Cave State Park, which encompasses approximately 110 acres and is one of the most visited units in the Tennessee State Park System.