Popular Sovereignty allows residents to decide on slavery, Secession is the formal withdrawal from a political entity, while the Union represents the northern states opposing secession.
Popular Sovereignty refers to the idea that the residents of a territory should determine whether slavery would be legal there. Secession is the action of formally withdrawing from a political union or body, such as a state leaving the Union. The Union refers to the group of northern states during the Civil War that opposed the seceding Confederate states.
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