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It means breaking away from the Union, to form part of an embryonic new naton. The viability of a new nation depends on overseas recognition. This nearly happened in 1862, but Lincoln managed to head it off by issuing the Emancipation Proclamation. So the Confederacy was never officially a nation.
As in Hawaii Five-0, Hawaii is the 50th state admitted to the union.
Union
The first frontier state to enter the Union was Vermont in 1791.