What is the principle behind the high heat transfer coefficient of liquefaction latent heat?

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After liquefaction, the temperature of the condensed water remains unchanged, yet it releases five times as much heat as boiling water instantly – what force is driving this? The kinetic theory of molecules is also vague; it merely states that the attractive forces between molecules do work, resulting in an increase in their kinetic energy. Based on this, it can be inferred that microscopic, localized ultra-high temperatures (in terms of molecular kinetic energy) are generated at the contact surface, from where heat is transferred away. This explanation seems reasonable for the concept of heat transfer coefficient as well. But on the other hand, why hasn’t such an extremely high temperature vaporized it back again? Since it is an ultra-high temperature, why is the heat transfer coefficient of superheated gas lower than that of latent heat release? I still have many questions regarding the theory of molecular motion. For example, why do molecules get trapped and vibrate within a very small range when the temperature (speed) drops slightly? And why did all those billions of collisions between gas molecules earlier cause no problem at all?