In thermodynamics, superheating (sometimes referred to as boiling retardation, or boiling delay) is the phenomenon in which a liquid is heated to a temperature higher than its boiling point, without boiling. This is a so-called metastability state or metastate, where boiling might occur at any time, induced by external or internal effects.Debenedetti, P.G.Metastable Liquids: Concepts and Principles; Princeton University Press: Princeton, NJ, USA, 1996. Superheating is achieved by heating a homogeneous substance in a clean container, free of , while taking care not to disturb the liquid.
This may occur by microwaving water in a very smooth container. Disturbing the water may cause an unsafe eruption of hot water and result in .
Superheating is an exception to this simple rule; a liquid is sometimes observed not to boil even though its vapor pressure does exceed the ambient pressure. The cause is an additional force, the surface tension, which suppresses the growth of bubbles. Critical Droplets and Nucleation, Cornell Solid State Lab
Surface tension makes the bubble act like an elastic balloon. The pressure inside is raised slightly by the "skin" attempting to contract. For the bubble to expand, the temperature must be raised slightly above the boiling point to generate enough vapor pressure to overcome both surface tension and ambient pressure.
What makes superheating so explosive is that a larger bubble is easier to inflate than a small one; just as when blowing up a balloon, the hardest part is getting started. It turns out the excess pressure due to surface tension is inversely proportional to the diameter of the bubble. Atmosphere-ocean Interaction By Eric Bradshaw Kraus, Joost A. Businger Published by Oxford University Press US, 1994 , pg 60. That is, .
This can be derived by imagining a plane cutting a bubble into two halves. Each half is pulled towards the middle with a surface tension force , which must be balanced by the force from excess pressure . So we obtain , which simplifies to .
This means if the largest bubbles in a container are small, only a few micrometres in diameter, overcoming the surface tension may require a large , requiring exceeding the boiling point by several degrees Celsius. Once a bubble does begin to grow, the surface tension pressure decreases, so it expands explosively in a positive feedback loop. In practice, most containers have scratches or other imperfections which trap pockets of air that provide starting bubbles, and impure water containing small particles can also trap air pockets. Only a smooth container of purified liquid can reliably superheat.
Subsequent experimental studies have reported solids persisting above this limit under ultrafast heating. Thin gold films, for example, were observed to remain crystalline for more than two picoseconds when heated at rates up to ~1015 K s−1, corresponding to temperatures of nearly 14 times the melting point. This persistence has been attributed to the extreme heating rate and to the lattice's inability to expand on picosecond timescales.
|
|