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# The "fourth phase" chemically reacting with surfaces
The "fourth phase" is seen in how metals rust when exposed to water (Chai, 2012). A metal like iron when submerged in water is hydrophilic, and water adsorbs to it to a 2-3 atom layer thick adsorbate where auto-ionization lets the more mobile hydrogen ion escape while the hydroxide ion is stuck, and the phase prefers to distribute itself so the hydrogen ions between the sheets are the ones lost, and the sheets are shifted half an oxygen relative to one another: Gerald Pollacks "fourth phase" of water, (H3O2-)n. Quantatively, this phase gives off hydrogen ions that will lower the pH up to 1 cm outwards to pH 5.5 (Chai, 2009). Iron will react with the hydrogen ions that are released from the adsorbate, and be oxidized, Fe --> Fe^2+ + 2e-, and the electrons combine with the hydrogen ions and O2 (this requires external O2) as 4 H+ + 4 e- + O2 --> 2 H2O. This consumes the hydrogen ions, and the electric field is between the iron and the hydrogen ions (i.e., inwards, thus opposite in direction to the electric field at surfaces that do not oxidize, where the field is instead between the low pH region and the adsorbate, which is outwards). Due to the H+ being consumed in the rusting process the bulk water beyond the adsosrbate (and "exclusion zone" above it) is also alkaline rather than acidic. The rust reaction is fastest on the parts of the metal surface that is not covered by adsorbate which is why rust process is "patchy" (Chai, 2012).
Conventional understanding of rust is the O2 directly oxidizes the metal, 2 Fe + O2 + 2 H2O --> 2 Fe^2+ + 4 OH-, and the rate limiting step is the diffusion of O2 in either scenario, so it is hard to use rust as proof of the "fourth phase".
In non-oxidizing surfaces like quartz, SiO2, the reactions with the fourth phase are harder to dismiss with other mechanisms. The silicon dioxide reacts with the hydroxide ions in and from the fourth phase as SiO2 + 2 OH- --> SiO3^2- + H2O. The SiO3^2 disolves into the bulk water, and there it is protonated in the low pH region and can separate into SiO2 and H2O again (and polymerise during this step when multiple H2SiO3 react). The acid-base separation at the adsorbate and bulk water interface provides the exact conditions needed to move silicon dioxide from the quartz and into the bulk water, where it clumps together. In the 1960s and 1970s, scientists experimenting with water in quartz containers found that the water acted in a very anomalous way, it was much thicked than normal water, denser (Fedyakin, 1962; Derjaguin, 1973). They believed they had found a form of water with distinct properties, "anomalous water" or "water 2" (later known as "polywater"). Eventually it was discovered this "polywater" was just contaminants dissolved out of the container used, and the interest died out. The contaminants in the early "anomalous water" experiments provide strong evidence that the 2-3 atomic layers thick adsorbed water is in Pollack's "fourth phase" - the adsorbate (or near surface) phase has to be very strongly ionized to form the quantities of contaminats observed, the quantities far exceed what dissolves passively.
# References
Chai, B., Mahtani, A. G., & Pollack, G. H. (2012). UNEXPECTED PRESENCE OF SOLUTE-FREE ZONES AT METAL-WATER INTERFACES. Contemporary Materials, 1(3). https://doi.org/10.7251/com1201001c
Chai, B., Yoo, H., & Pollack, G. H. (2009). Effect of Radiant Energy on Near-Surface Water. The Journal of Physical Chemistry B, 113(42), 13953 13958. https://doi.org/10.1021/jp908163w
Fedyakin, N. N. (1962). "Change in Water Structure on Condensation in Capillaries", Kolloidnyi Zhurnal, 24, pp. 497 501.
DERJAGUIN, B. V., & CHURAEV, N. V. (1973). Nature of Anomalous Water. Nature, 244(5416), 430 431. https://doi.org/10.1038/244430a0