Processes and apparatus for quantitatively converting urea to ammonia on demand are disclosed. One process includes the steps of: receiving a demand rate signal for ammonia; feeding reactants including urea and water into a reactor to provide a reaction mixture; and controlling temperature and pressure in the reactor to produce a gaseous product stream including ammonia and carbon dioxide at substantially constant concentrations. Another process includes the steps of: feeding molten urea or solid urea to a reactor; feeding water (liquid or steam) to the reactor; and reacting the urea and water at elevated temperature and pressure to form a gaseous product stream including ammonia and carbon dioxide.