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On the nature of the adsorbed phase of water
Liquids (or gases) that bind to surfaces will form a thin layer of adsorbate on the surface. For water this adsorbate can extend up to 300 micrometers outwards. It has been shown in diffraction photography the molecular structure is similar to normal ice but that each molecular layer is shifted one carbon in the hexagon. In the resulting crystal, only oxygen with a hydrogen atom in between them will face one another, whereas the other three oxygen will be in the center of the other hexagon. This adsorbate tends to auto-ionize with an auto ionization constant of around 8. The hydroxide ions are immobilized within the crystal structure whereas the hydrogen ions are free to move, causing the hydrogen ions to spread out by diffusion. The hydrogen ions can diffuse outwards up to 10 mm before an electrostatic equilibrium is formed (the diffusion current is then equal to the drift current), resulting in a pH of around 5.5 in that surrounding bulk water. A similar separation of charges has been shown in ethanol (Chai, 2010) and can be predicted to happen in adsorbates of all liquids where one charge carrier is more mobile within its adsorbate. Within the cell, the auto ionization constant of the adsorbate is much lower, closer to 2 (i.e., a pOH of 1 within the adsorbate) or lower. This is due to the released hydrogen ions being physically separated from the hydroxide ions and ability to recombine (thus shifting the auto-ionization equilibrium) by fully protonating the ATP + protein binding site complex (a complex that serves as a stronger base than ATP itself).
Fig 1. The molecular structure of adsorbed water is hexagonal lattice sheets layered on top of one another, and shifted one carbon such that there is always a hydrogen atom between each oxygen. Image reworked from Pollack, 2013.
Fig 2. Diffraction pattern obtained from water adsorbed onto protein shows hexagonal order. Image from Pollack, 2013.
Fig 3. The molecular structure overlain on top of the reflections in the diffraction pattern, showing a perfect match.
Fig 4. The pH of surrounding bulk water shows higher pH closer to the adsorbate. The image is taken early on after water has been added and adsorbate begins to form (roughly after 5 minutes). After about 60 minutes the pH is homogenous up to 10 mm outwards with a pH of around 5.5. Image from Chai, 2009.
The density of the adsorbate is higher than liquid water, known from that pressure increases the amount of adsorbate (Ypma, 2015). The molecular structure seen in the diffraction pattern fits perfectly with this higher density, as every oxygen that is above the hexagon center can be pushed down. The adsorbate is not a solid but a liquid-solid and there is wiggle room for the bond angles. The hydrogen atoms within the hexagon can also contribute an attractive force on the oxygen, pulling it down.
The pH of the surrounding bulk water is at pH 5.5 once equilibrium is reached after 60 minutes from adding water to container (prior to that, it is initially lower closer to the adsorbate but then gradually forms uniform distribution up to 10 mm outwards), see Chai, 2009. It is then known the adsorbate has ionized roughly 1 in 500000 water molecules. To calculate this, first note that pH 5.5 means 10^-5.5 = 0.000003 moles of H+ per liter. Water has concentration of 55.5 moles of H2O per liter, and adsorbate should be very close to that. The adsorbate extends outwards up to 0.3 mm and the bulk water with pH 5.5 extends 10 mm, thus that bulk water volume is 10/0.3 = 33 times larger than the adsorbate, thus adsorbate itself must release 33*10^-5.5 H+ per liter. Thus, out of the 55.5 moles of H2O per liter in the adsorbate, 33*10^-5.5 must be ionized, which means one in 55.5/(10^-5.5*33) which is roughly equal to 1 in 500000.
In the cell, K+ is adsorbed onto the negatively charged adsorbate while the H+ from the adsorbate is bound into the ATP-protein binding site complex (that complex acts as a base, and is protonated), specifically at the hydrogen bonds to the p-loop motif (the protonated hydroxyl groups act as the hydrogen bond donor, which accounts for electron-withdrawing effect of ATP on protein, see work of Gilbert Ling). ATP bound to protein is fully protonated. This further physical separation of OH- and H+ reduces recombination in the auto-ionization equilibrium. It can be inferred that ionization of the adsorbate in the cell has to provide H+ in same quantity as K+, roughly 150 mmol/L. This means that at a minimum, H+ equal to a pH of -log10(0.150) "H 1 has to be released. With this it can be inferred that the ionization ratio has to be below one in 55.5/0.150 "H 400 (if all cell water was adsorbate, ionization would be at 1 in 400). If for example 5% of all cell water is adsorbate, then the ionization in adsorbate has to be 20 times higher than the apparent ionization in the bulk water (i.e., it is diluted by 20 times). This means one in 55.5/0.150*20 "H 20 water would have to be ionized in that scenario.
References
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
Chai, B., & Pollack, G. H. (2010). Solute-free interfacial zones in polar liquids. The journal of physical chemistry. B, 114(16), 5371 5375. https://doi.org/10.1021/jp100200y
Ling, G. N. (1984). In Search of the Physical Basis of Life. New York: Plenum Press.
Pollack, G. (2013). The Fourth Phase Of Water. Seattle: Ebner and Sons.
Ypma, R. E., & Pollack, G. H. (2015). Effect of hyperbaric oxygen conditions on the ordering of interfacial water. Undersea & hyperbaric medicine : journal of the Undersea and Hyperbaric Medical Society, Inc, 42(3), 257 264.