Webster did a job on Nullification, but Nullification was a non-starter. Try Jefferson Davis's inaugural speech from February, 1861, as the president of the provisional Confederate government -- he was inaugurated again a few weeks later, so get the earlier one. He presents the arguments against Nullification, which revolved around the Supremacy Clause, and shows how secession was a separate issue entirely.
His farewell speech to the Senate can also be read profitably on these issues.