Surface acidity measurement recommendations

In the following section, we will critically review representative methods for measuring surface acidity of solid catalysts. Recommendations will then be made of the most appropriate methods from the standpoint of the needs of the investigator. The final section is devoted to updating research activities dealing with individual solid catalysts. Particular attention will be devoted to studies of acidities of unusually active catalysts such as crystalline zeolites, synthetic clays, and chlorinated aluminas. 

Fortunately, a great deal of work has been accomplished in a short time, and notably by aircraft manufacturers as well as adhesives suppliers. There are several important contributions in this area. First, in the area of FPL etch, the important consideration is what kind of bonding surface is provided by the preparation method. The chromic acid/sulfuric acid not only removes air oxide and leaves base metal it also has a chemical potential which produces a very thin anodic type oxide layer of the surface. This oxide layer is porous, due to the dissolving action of the strong acid mixture, and thus the surface produced may be characterized as a thin, porous anodic oxide. (A. W. Smith compared it to a 3V chromic acid anodize based on impedance measurements.) The optimum conditions for this etch as to time, temperature, and composition have been studied at Fokker and by Smith and generally a somewhat higher concentration of sodium dichromate or chromic acid was recommended than was commonly used. 

A9.5.2.4.1 For organic substances experimentally derived high-quality Kow values, or values which are evaluated in reviews and assigned as the recommended values , are preferred over other determinations of Kow. When no experimental data of high quality are available, validated Quantitative Structure Activity Relationships (QSARs) for log Kow may be used in the classification process. Such validated QSARs may be used without modification to the agreed criteria if they are restricted to chemicals for which their applicability is well characterized. For substances like strong acids and bases, substances which react with the eluent, or surface-active substances, a QSAR estimated value of Kow or an estimate based on individual -octanol and water solubilities should be provided instead of an analytical determination of Kow (EEC A.8., 1992 OECD 117, 1989). Measurements should be taken on ionizable substances in their non-ionized form (free acid or free base) only by using an appropriate buffer with pH below pK for free acid or above the pK for free base. 

The terms batch equilibration [653], pH drift method [654], addition method [552], solid addition method [655], powder addition method (cited in [656] after [654]), potentiometric titration [234] ( sic —in the present book, the term potentiometric titration is reserved for a different method, described in Section 2.5), and salt addition [573] ( sic —in the present book, the term salt addition is reserved for a different method, described later in this section) refer to the same method, which is now described. A series of solutions of different pHs is prepared and their pHs are recorded. Then, the powder is added and the final pH is recorded. The addition of a solid induces a shift in the pH in the direction of the PZC. The pH at which the addition of powder does not induce a pH shift is taken to be the PZC. Alternatively, the PZC is determined as the plateau in the pHfln, (pH ,.,., .j) curve. The method assumes that the powder is absolutely pure (free of acid, base, or any other surface-active substance), which is seldom the case. Even with very pure powders, the above method is not recommended for materials that have a PZC at a nearly neutral pH. Namely, the method requires accurate values of the initial pH, which is the pH of an unbuffered solution. The display of a pH meter in unbuffered solutions in the nearly neutral pH range is very unstable, and the readings are not particularly reliable. The problem with pH measurements of solutions is less significant at strongly acidic or strongly basic pHs (see Section 1.10.3). The above method (under different names) became quite popular, and the results are referred to as pH in the Method columns in the tables in Chapter 3. The experimental conditions in the above method (solid-to-liquid ratio, time of equilibration, and nature and concentration of electrolyte) can vary, but little attention has been paid to the possible effects of the experimental conditions on the apparent PZC. The plateau in the pH, , (pH, ,, ) curve for apatite shifted by 2 pH units as the solid-to-liquid ratio increased from 1 500 to 1 100 [653]. Thus, the apparent PZC is a function of the solid-to-liquid ratio. 

On the basis of this evidence, it is recommended that an experimental test program, consisting of both laboratory and field tests, be developed and Implemented to quantitatively measure the effects of acid deposition on both the as thetic and structural properties of PCC structures. It is, however, recommended that a preliminary series of controlled, accelerated laboratory tests be carried out before a full-scale field evaluation program is instituted. The objectives of the accelerated laboratory test program should be to identify the magnitude of the problem and to attempt to differentiate between the effects of wet deposition, dry deposition, and normal weathering. The preliminary test program should concentrate on surface chemistry effects and penetration rates of SO4, NOx, Cl as deposited from wet and dry deposition. The... 

Platinum electrodes may be coated with platimun black ( platinized ) to increase the surface area and sensitivity. This finely divided form of platimun is prepared by electrolysis in a chloroplatinic acid solution containing a small amount of lead acetate. Platinization of platinum cells is not recommended on cells for measurements below lOpScm", although a trace of platinum black is sometimes suggested in these regions. 

Iron sulfide is more protective than iron carbonate, and, if the acid gas contains sufficient H2S, a protective sulfide film can be formed. If contaminants which disrupt this iron sulfide film are not present, and if the mechanical design minimizes erosion-corrosion, wet acid corrosion of exposed carbon steel surfaces will be limited. On the other hand, if the gas is predominantly CO2, wet acid gas corrosion will occur and protective measures are required. As might be expected, there is disagreement on the exact CO2/H2S ratio above which protective measures are required. API Recommended Practice 943 suggests that wet CO2 corrosion occurs when the acid gas contains 93% or more CO2 (API, 1990). 

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