Thermodynamics of Charge Regulation near Surface Neutrality

The interaction between two adjacent charged surfaces immersed in aqueous solution is known to be affected by charge regulation─the modulation of surface charge as two charged surfaces approach each other. This phenomenon is particularly important near surface neutrality where the stability of objects such as colloids or biomolecules is jeopardized. Focusing on this ubiquitous case, we elucidate the underlying thermodynamics and show that charge regulation is governed in this case by surface entropy. We derive explicit expressions for charge regulation and formulate a new universal limiting law for the free energy of ion adsorption to the surfaces. The latter turns out to be proportional to k_BT, and independent of the association energy of ions to surface groups. These new results are applied to the analysis of unipolar as well as amphoteric surfaces such as oxides near their point of zero charge or proteins near their isoelectric point.