No matter how much Southerners hated the tariffs and no matter how unequal federal expenditures for infrastructure and corporate subsidies were, they were not unconstitutional. What was unconstitutional however was the North's refusal to enforce the Fugitive Slave Clause of the US constitution. On that point the Southern states could legitimately say the Northern states had violated the compact. So they seized it. When offered slavery forever by express constitutional amendment and massively strengthened fugitive slave laws, they refused. Obviously the protection of slavery was not their real concern.
Here they are. All of them mention slavery, although they surround it with arguments about "states rights" and the Constitution.
The readers can decide for themselves.