The point of zero charge is the pH for which the net surface charge of adsorbent is equal to zero. This concept has been introduced by an increase of interest in the pH of the solution during adsorption.^[1] The reason why pH has attracted much attention is that the adsorption of some substances is very dependent on pH. The pzc value is determined by the characteristics of an adsorbent. For example, the surface charge of adsorbent is described by the ion that lies on the surface of the particle (adsorbent) structure like image. At the lower pH, hydrogen ions (protons, H⁺) would be adsorbed more than other cations (adsorbate) so that the other cations would be less adsorbed in the case of the negatively charged particle. On the other hand, if the surface is positively charged and pH is increased, anions will be less adsorbed as hydroxide ions are increased. From the view of the adsorbent, if the pH is below the pzc value, the surface charge of adsorbent would be positive so that the anions can be adsorbed. Conversely, if the pH is above the pzc value, the surface charge would be negative so that the cations can be adsorbed.

For example, the charge on the surface of silver iodide crystals may be determined by the concentration of iodide ions in the solution above the crystals. Then, the pzc value of the AgI surface will be described by the concentration of I⁻ in the solution (or negative decimal logarithm of this concentration, pI⁻).

The pzc is the same as the isoelectric point (iep) if there is no adsorption of other ions than the potential determining H⁺/OH⁻ at the surface.^[8] This is often the case for pure ("pristine surface") oxides in water. In the presence of specific adsorption, pzc and isoelectric point generally have different values.

The pzc is typically obtained by acid-base titrations of colloidal dispersions while monitoring the electrophoretic mobility of the particles and the pH of the suspension. Several titrations are required to distinguish pzc from iep, using different electrolytes (including varying the electrolyte ionic strength). Once satisfactory graphs are obtained (acid/base amount—pH, and pH—zeta potential), the pzc is established as the common intersection point (cip) of the lines. Therefore, pzc is also sometimes referred to as cip.

Besides pzc, iep, and cip, there are also numerous other terms used in the literature, usually expressed as initialisms, with identical or (confusingly) near-identical meaning: zero point of charge (zpc), point of zero net charge (pznc), point of zero net proton charge (pznpc), pristine point of zero charge (ppzc), point of zero salt effect (pzse), zero point of titration (zpt) of colloidal dispersion, and isoelectric point of the solid (ieps)^[9] and point of zero surface tension (pzst^[10] or pzs^[11]).

In electrochemistry, the electrode-electrolyte interface is generally charged. If the electrode is polarizable, then its surface charge depends on the electrode potential.

IUPAC defines^[2] the potential at the point of zero charge as the potential of an electrode (against a defined reference electrode) at which one of the charges defined is zero.

The potential of zero charge is used for determination of the absolute electrode potential in a given electrolyte.

IUPAC also defines the potential difference with respect to the potential of zero charge as:

E_pzc = E − E_σ=0

where:

• E_pzc is the electrode potential difference with respect to the point of zero charge, E_σ=0
• E is the potential of the same electrode against a defined reference electrode in volts
• E_σ=0 is the potential of the same electrode when the surface charge is zero, in the absence of specific adsorption other than that of the solvent, against the reference electrode as used above, in volts

The structure of electrolyte at the electrode surface can also depend on the surface charge, with a change around the pzc potential. For example, on a platinum electrode, water molecules have been reported to be weakly hydrogen-bonded with "oxygen-up" orientation on negatively charged surfaces, and strongly hydrogen-bonded with nearly flat orientation at positively charged surfaces.^[12]

At pzc, the colloidal system exhibits zero zeta potential (that is, the particles remain stationary in an electric field), minimum stability (exhibits maximum coagulation or flocculation rate), maximum solubility of the solid phase, maximum viscosity of the dispersion, and other peculiarities.

In the field of environmental science, adsorption is involved in many parts of technologies that can eliminate pollutants and governs the concentration of chemicals in soils and/or atmosphere. When studying pollutant degradation or the geochemical process, the pzc value related to adsorption has been examined. For example, natural and organic substrates including wood ash, sawdust, etc. are to be used as an adsorbent by eliminating harmful heavy metals like arsenic, cobalt, mercury ion and so forth in contaminated neutral drainage (CND), which is a passive reactor that could possible metal adsorption with low-cost materials. Therefore, the pzc values of the organic substrates were evaluated to optimize the selection of materials in CND.^[3] Another example is that the emission of nitrous acid, which controls the atmosphere's oxidative capacity. Different soil pH leads to the different surface charges of minerals so the emission of nitrous acid would be varied, further impacting on the biological cycle involved in the nitrous acid species.^[4]

• Kosmulski M. (2009). Surface Charging and Points of Zero Charge. CRC Press; 1st edition (Hardcover). ISBN 978-1-4200-5188-9