Monoprotic surface groups

Surface complexation models for the oxide-electrolyte interface are reviewed two models for surface hydrolysis reactions are considered (diprotic surface groups and monoprotic surface groups) and four models for the electric double layer (Helmholtz,... 

Gouy-Chapman, Stern, and triple layer). Methods which have been used for determining thermodynamic constants from experimental data for surface hydrolysis reactions are examined critically. One method of linear extrapolation of the logarithm of the activity quotient to zero surface charge is shown to bias the values which are obtained for the intrinsic acidity constants of the diprotic surface groups. The advantages of a simple model based on monoprotic surface groups and a Stern model of the electric double layer are discussed. The model is physically plausible, and mathematically consistent with adsorption and surface potential data. 

Following the presentation of the chemical model with monoprotic surface groups, four electrostatic models will be developed, from which the necessary relationship between i>Q and aq can be found. 

The monoprotic surface group model can be described in terms of the more familiar diprotic surface group model. In the diprotic model, the surface is thought of as an ensemble of Ng diprotic surface groups, which, under the condition of zero protonic charge, are occupied by Ns protons. 

Two models of surface hydrolysis reactions and four models of the electrical double layer have been discussed. In this section two examples will be discussed the diprotic surface group model with constant capacitance electric double layer model and the monoprotic surface group model with a Stern double layer model. More details on the derivation of equations used in this section are found elsewhere (3JL). ... 

If the constraint that is small is removed in interpretation of the data, one may consider the physical nature of the interface and other forms of experimental data in deciding what combinations of parameters are appropriate for describing the interface. In particular, the relationship of the diprotic surface group model to the monoprotic surface group model can be examined. 

Monoprotic Surface Groups. It has been stated that for some oxides the surface potential response to pH is close to the Nernstian value, and that relatively large values of in the model were necessary to be consistent with this observation. For -= 1,... 

The representation of the data for TiC in terms of the monoprotic surface group model of the oxide surface and the basic Stern model of the electric double layer is shown in Figure 5. It is seen that there is good agreement between the model and the adsorption data furthermore, the computed potential Vq (not shown in the figure) is almost Nernstian, as is observed experimentally. 

In order to maintain the complexity of the model at a level consistent with the resolution of the experimental data, the reactivity of these surface groups has been described by relatively simple models (i) as diprotic weak acids, and (ii) as monoprotic... 

It is important to establish the origin and magnitude of the acidity (and hence, the charge) of mineral surfaces, because the reactivity of the surface is directly related to its acidity. Several microscopic-mechanistic models have been proposed to describe the acidity of hydroxyl groups on oxide surfaces most describe the surface in terms of amphoteric weak acid groups (14-17), but recently a monoprotic weak acid model for the surface was proposed (U3). The models differ primarily in their description of the EDL and the assumptions used to describe interfacial structure. "Intrinsic" acidity constants that are derived from these models can have substantially different values because of the different assumptions employed in each model for the structure of the EDL (5). Westall (Chapter 4) reviews several different amphoteric models which describe the acidity of oxide surfaces and compares the applicability of these models with the monoprotic weak acid model. The assumptions employed by each of the models to estimate values of thermodynamic constants are critically examined. 

Typical values of pK[nt and pfor a humic acid are 2.67 and 4.46. The introduction of the electrostatic factor into the equilibrium constant is analogous to the coulombic term used in the definition of the intrinsic surface complexation constants. In addition another binding site (WAH) is recognised which is thought to behave as a weak acidic phenolic functional group. Although this site does not contribute to the titratable acidity and, therefore, no pK is needed for proton dissociation, it is involved in metal complexation reactions. The total number of the three monoprotic sites is estimated from titratable acidity and then paired to represent the humic substance as a discrete non-interacting mixture of three dipro-tic acids, which act as the metal complexation sites. The three sites are... 

Monoprotic groups are considered to be present at the surface. Equations 4.12 and 4.13 are repeated here ... 

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