Until recently the answer was unknown, but a short time ago it was discovered that the reaction is in fact a Coulombic explosion. The rapid exchange of electrons between the sodium and the water causes the surface of the sodium droplet to become positively charged, and the ions repel each other. This behaves very like a negative surface tension, and the surface of the droplet increases in area rapidly forming a spiny, porcupine like shape as fingers of the molten metal are shot into the liquid at astonishing speed. The larger the surface area gets the faster the reaction occurs, leading to a runaway effect. The study was published in Nature chemNature Chem. (Ref.1).
http://www.nature.com/nchem/journal/vaop/ncurrent/full/nchem.2161.htmlReferences:
- Philip E. Mason, Frank Uhlig, Václav Vaněk, Tillmann Buttersack, Sigurd Bauerecker, Pavel Jungwirth, "Coulomb explosion during the early stages of the reaction of alkali metals with water," Nature Chemistry 2015, 7, 250–254 (https://doi.org/10.1038/nchem.2161).