It was the Constitution, specifically Article VI and the supremacy clause, that denied them this right and not the federal government.
When nullification would not work and states felt that they were no longer respected, they moved towards secession.
Twenty years later, when a perceived threat to their institution of slavery appeared.
The first union of the original 13 colonies was effected by the Articles of Confederation, adopted in 1781. The articles established a confederation of sovereign states in a permanent union. The “permanence” lasted only until 1788, when 11 states withdrew from the confederation and ratified the new Constitution, which became effective on March 4, 1789. The founding fathers recognized the defects in the Articles of Confederation, learned from these defects, and scrapped the articles in favor of the “more perfect union” found in the Constitution.
Nowhere in the Constitution is there any mention of the union of the states being permanent. This was not an oversight by any means. Indeed, when New York, Rhode Island, and Virginia ratified the Constitution, they specifically stated that they reserved the right to resume the governmental powers granted to the United States. Their claim to the right of secession was understood and agreed to by the other ratifiers, including George Washington, who presided over the Constitutional Convention and was also a delegate from Virginia. In his book Life of Webster Sen. Henry Cabot Lodge writes, “It is safe to say that there was not a man in the country, from Washington and Hamilton to Clinton and Mason, who did not regard the new system as an experiment from which each and every State had a right to peaceably withdraw.” A textbook used at West Point before the Civil War, A View of the Constitution, written by Judge William Rawle, states, “The secession of a State depends on the will of the people of such a State.”
Some important facts should be pointed out.
First, the ratifications of the Constitution by New York, Virginia, and Rhode Island were not given conditionally upon those states being granted the right to secede by the other states. Had that been the case, the ratifications would have been invalid. Ratifications of the Constitution had to be unconditional. Those who voted to ratify the Constitution in New York, Virginia, and Rhode Island simply put into writing a right they thought naturally belonged to their respective states. The states were voluntarily joining the Union, and most people believed the same principles toward self-governance that gave states the right to join the Union also gave states the right to withdraw from the Union.
Second, the ratifications of Virginia, New York, and Rhode Island were unanimously accepted as valid. Those states’ claims to the right of secession was understood and agreed to by the other ratifiers, including George Washington who presided over the Constitutional Convention and served as a delegate from Virginia.
Third, many lawyers believe that the acceptance of these three ratifications (New York, Virginia, and Rhode Island) as valid guarantees all states the right to secede. This conclusion is based on the principle that whatever rights are held by some states must be held by all states. [Exceptional rights have been granted to some states in order to encourage them to join the Union. But those special rights were understood by all states already in the union at the time the states granted special rights were accepted.]
Well into the 19th century, the United States was still viewed by many as an experimental confederation from which states could secede just as they had earlier acceded to it.
It took a bloody war to prove them wrong. LEGALITY did not win out, FORCE did, at the cost of over 620,000 lives.