Prace Naukowe Instytutu Gérnictwa Nr9s Politechniki Wroctawskiej 7 Nr 95 Konferencje Nr 31 2001 Marek KOSMULSKI* EVALUATION OF POINTS OF ZERO CHARGE OF ALUMINUM OXIDE REPORTED IN THE LITERATURE In 1965 Parks compiled PZC of metal oxides and hydroxides and his paper is still the most frequently cited source of PZC of these materials. The recent compilation (Kosmulski 2001) covers not only oxides and hydroxides, but also mixed oxides, sparingly soluble salts and other materials whose surface charging is pH dependent. One set of data from this compilation (155 PZC of Al Published in 150 papers between 1969 and 2001) was selected to show the effect of crystalline structure on the one hand and of the choice of the experimental method on the other on the PZC. There is no significant difference between the a form (32 entries, average 8.2, median 8.55) and the y form (58 entries, average 8.2, median 8.4) and the other forms, mixtures of different forms and materials of unknown structure (65 entries, average 8.3, median 8.7). On the other hand, the choice of the method substantially affects the PZC. The isoclectric point IEP from electroacoustic measurements (II entries, average 9.3, median 9,5) is significantly above the IEP from classical electrokinetic measurements (78 entries, average 8.2, median 8.7) and potentiometic titration at one ionic strength (29 entries, average and median 8). The results obtained by means of two latter methods are much more scattered than in other methods. The lowest standard deviation was observed in the set of PZC obtained by means of combination of titration (the common intersection point of titration curves for three or more ionic strengths is identified with the PZC) and electrokinetic ‘measurements (7 entries, average and median 8.6), and this value is the “recommended” PZC for alumina, Key words: point of ero charge, adsorption, isoelectric point, aluminum oxide {TRODUCTION The sign of the surface potential defines the ability to adsorb anions and cations. Therefore one can hardly imagine a serious study of adsorption from solution without knowledge of the PZC of the adsorbent. Two opposite approaches to the PZC of materials can be distinguished (Kosmulski 1997): + All materials representing the same chemical formula have identical PZC. + Each sample of material has its own PZC. * Department of Electrochemistry, Technical University of Lublin, Potand.6 M. Kosmulski The discrepancies in the PZC of materials having the same chemical formula reported in different sources may support the later approach, but these discrepancies can very well be due to insufficient purity of materials and/or incorrect experimental procedures. Many compilations of “recommended” PZC of important materials (for references cf. (Kosmulski 1997)) and correlations found between the PZC and ionic radii, electronegativities, and other quantities favor the former approach. Parks (1965) compiled PZC of metal oxides and hydroxides and his paper is still the most frequently cited source of PZC of these materials. The recent compilation (Kosmulski 2001) covers not only oxides and hydroxides, but also mixed oxides, sparingly soluble salts and other materials whose surface charging is pH dependent. LITERATURE SURVEY The present literature survey of PZC of alumina (this compound was selected as an example) is based on 155 entries from 150 publications. The detailed referencing can be found elsewhere (Kosmulski 2001, pp. 90-101, 732, 739). Sometimes the results reported in two or more papers clearly represented the same set of experimental results. In such instance all these papers are treated as one entry in the present analysis. A few publications report PZC for two or more different samples, and each sample is represented as different entry in the present analysis. These two effects partially cance! out so the number of entries is approximately equal to the number of publications. When PZC of the same sample was dependent on the nature and/or concentration of inert electrolyte only one value is used. In such a case the results obtained in the presence of sodium and potassium salts were favored over the results obtained in the presence of lithium, rubidium or cesium salts, the results obtained in the presence of nitrates V and chlorates VII were favored over the results obtained in the presence of halides, and the results obtained at low ionic strength were favored over those obtained at high ionic strength, Namely, there is some evidence of specific adsorption of ions at high ionic strengths from electrolytes which act as inert electrolytes at low ionic strengths. In view of the temperature effect on the PZC of alumina only the results obtained at 15-40 °C were taken into account, and the PZC at the temperature closest to 25°C were chosen from publications reporting the PZC at different temperatures. ‘Two dozens of other papers reporting PZC of alumina were found (for referencing cf. (Kosmulski 2001, pp. 90-101, 258)) but deliberately neglected in the present analysis. This was when: + The experimental method was different from the methods listed in Table 2 or not specified. For example some publications report PZC taken from other sources (reports, theses, etc.) which are not readily available + The experiment failed (e.g. the titration curves failed to crossover in one point). + There was serious doubt about the purity of materials and/or correctness of the experimental procedure.Evaluation of points of zero charge of aluminum oxide reported in the literature 1 MATERIALS Most materials were reagent grade or commercial aluminas which underwent different cleaning procedures aimed at removal of surface active substances from the surface. Indeed, even very pure chemicals (in terms of concentration of the impurities related to the bulk) often have relatively dirty surfaces and this is demonstrated in unusual IEP. Some synthetic samples were also studies. Details about the source of commercial materials and preparation of synthetic samples can be found elsewhere (Kosmulski 2001 pp. 90-101, 732, 739). The materials were sorted into three groups: c, ¥ oF 8, and other forms, mixtures of different forms or structure unknown solely on basis of the information reported in the original publications, i.e., no attempt was made to identify the crystallographic structure from information published on similar samples in other papers. Therefore many materials reported under the category “other forms, mixtures of different forms or structure unknown” can actually represent pure a, yor 8 forms. EXPERIMENTAL METHODS Lyklema (1995) recommends the combination of potentiometric titration and electrokinetic method to determine the pristine PZC of materials. Namely, the PZC and IEP shift in two opposite directions in the presence of specific adsorption of cations or anions. Thus, matching CIP (crossover point of titration curves obtained at at least three ionic strengths) and IEP is very likely the pristine PZC of the adsorbent. On the other hand, lack of coincidence indicates specific adsorption. Unfortunately, publications reporting CIP and IEP of the same sample are scarce. Publications reporting CIP only are more numerous, but existence of CIP does not prove purity of the sample, namely, CIP occurs also in the presence of specific adsorption (Lyklema 1995), Instead of titrations at different ionic strengths some publications report salt titration (at PZC addition of inert electrolyte does not induce a change in the pH of the dispersion), and such results are basically ‘equivalent to the CIP and they are listed under the same category. Classical electrokinetic methods (electrophoresis, clectroosmosis) make it possible to readily determine the IEP. User friendly equipment is available nowadays, but it takes some effort and experience to avoid different pitfalls, e.g. related to sample preparation. Very recently electroacoustic equipment became commercially available (Kosmulski 2001, p. 80). Basically the results obtained by means of this method represent the IEP, but unlike in electrophoresis the experiments are carried out at relatively high solid to liquid ratio. The theory of electroacoustic phenomena and the equipment are not yet fully developed, and this may justify concerns about the significance of the results. Mass titration became recently popular as a method to determine the PZC (Kosmulski 2001, p.82, 83). In this method the natural pH of concentrated dispersion is identified with the PZC. In this respect the mass titration is not very much different from8 ‘M, Kosmulski potentiometric titration at one ionic strength (in which the PZC is also the natural pH of the dispersion) and results obtained using these two methods are combined into one group. Many less common methods to determine the PZC were proposed (e.g., from inflection point of titration curves), but the results obtained by means of these methods are not analyzed here. RESULTS AND DISCUSSION The results are presented in Tables | and 2 and Figures 1-8. Table 1. The PZC of alumina as the function of the crystalline structure | ” | @ | voré | Other forms, mixtures of different forms | Total aL I L orswueture unknown | entries 2 I nc 133 median [855_[ 84 87 [78s average 21] 8.18 $29 [823 standard deviation 110] _ 115 139 13 Table 2. The PZC of alumina as the function of the experimental method [cip-ep ] cp [TEP (elas | TEP (electro- | Titration (one ionie | Total , | sical) acoustic) strength) | [entries 7 30 78 u 29 155 median 86 | 835 87 95 8 85 [average [se | sis | 820 9.25 795 823 standard deviation] 0.34 | 0.79 13 0061 14 123 | Table 1 and Figures 1-3 clearly indicate that the crystalline structure of alumina has rather insignificant effect on the PZC. Thus allegations that can be found in older literature that the form has higher PZC than the y form are unsupported In this respect alumina is similar to titania (no substantial difference between rutile and anatase), but very different from iron oxide, namely, hematite has substantially higher PZC than maghemite (Kosmulski 2001, p. 160, 161). The choice of the experimental method substantially affects the results as indicated in Table 2 and Figures 4-8. The results from different sources obtained as matching CIP and IEP are very consistent and they most likely represent the “true” PZC of alumina (pH 8.640.3). Such a result is more reliable than “recommended” PZC published in different sources (Kosmulski 1997) which are based on subjective assessment, and only limited number of references was taken into account. In comparison with these results the PZC obtained from CIP alone (pH 8.1+0.8) are somewhat underestimated.Evaluation of points of zero charge of aluminum oxide reported in the literature PLC of aAlOy Fig. 2. The distribution of PZC of y- and B-alumina (black bars) and all results (white bars)10 M, Kosmulski PZC oA AO, (ther ana.) frequency Fig. 3. The distribution of PZC of alumina, other forms, mixtures of different forms or structure unknown (black bars) and all results (white bars) PZO of ALO ratching CIP and 1=P frequency Fig. 4. The distribution of PZC of alumina obtained as matching IEP and CIP (black bars) and all results, (white bars)Evaluation of points of zero charge of aluminum oxide reported in the literature u " 10 frequency etn enaarae Fig, 5. The distribution of PC of alumina obtained as CIP (black bars) and all results (white bars) IEP fr AO, lossical electrokinetic metnods frequency Fig. 6. The distribution of IEP of alumina obtained by means of classical electrokinetic methods {black bars) and all resuits (white bars)2 M. Kosmulski TEP for AljOs electroacoustic meted Fig. 7. The distribution of IEP of alumina obtained by means of electroacoustic method (black bars) and all results (white bars) PZC of ALO, uncorsected tiation ‘ang mase trates frequency enn veaaree Fig. 8. The distribution of PZC of alumina obtained from potentiometric titration at one ionic strength or mass titration (black bars) and all results (white bars)Evaluation of points of zero charge of aluminum oxide reported in the literature 13 The low average IEP obtained by means of classical electrokinetic methods is due toa few outstanding data points representing IEP at very low pH (Fig.6). The later are very likely caused by adsorption of silicates (leached out from glassware). This effect has been systematically studied, and it is specially important in microelectrophoresis, when the solid to liquid ratio is much lower than in other methods. The shift in IEP due to sorption of silicates can be easily avoided namely it only occurs when the dispersion is stored for many hours in glassware at neutral or basic pH. In other methods including the electroacoustic method (high solid to liquid ratio) the fraction of the surface occupied by adsorbed silicate is too low to induce such a dramatic shift in the PZC or IEP even when no special precautions against silicate adsorption are exercised, The low PZC obtained by potentiometric titration at one ionic strength or mass titration can be also rationally explained, Namely, dry alumina usually contains some acid associated with the surface which is not taken into account in the bookkeeping of acid and base in potentiometric titration when the experiments are carried out at one ionic strength. This acid origins from a thin film of solution that cannot be completely removed when alumina is separated from solution in the process of preparation. When titrations are carried out at three or more different ionic strengths this problem disappears because the crossover point of potentiometric curves is identified with the PZC. Surprisingly the IEP from electroacoustic methods seems to be substantially overestimated. There is no clear explanation for this effect. Hysteresis (different course of acid and base titrations) reported by some authors may suggest insufficient equilibration time as a potential pitfall. SUMMARY The present paper is not meant as sensu stricto statistical analysis. Results reported in different publications have different “weight” related to significance of different methods and to the number of data points used to estimate the PZC. Matching CIP and IEP indicate absence of specific adsorption. Thus, the PZC of alumina at pH 8.6 obtained as matching CIP and IEP is more reliable than the results obtained using single method. For example very low IEP reported in some publications is due to insufficient purity of materials or other experimental errors. REFERENCES KOSMULSKI M, (1997), Attempt to determine pristine points of zero charge of NbOs, TasOs and H/O3, Langmuir, Vol.13, 6315-6320. KOSMULSKI M, (2001), Chemical properties of material surfaces, Marcel Dekker, New York. LYKLEMA J, (1995), Fundamentals of Interface and Colloid Science. Vol. II. Academic Press, London, pp. 3.103-3.109, PARKS G.A. (1965), The isoelectric points of solid oxides, solid hydroxides, and aqueous hydroxo complex systems, Chem Rev., Vol. 65, 177-198.4 M. Kosmulski Received March , 2001; reviewed and accepted May 15, 2001 Kosmulski M., Ocena literaturowych wartosci punktu zerowego tadunku tlenku glinu, Prace Naukowe Instytutu Gérnictwa Politechniki Wroctawskiej 95, Konfetencje 31, 2001, 5-14, (w jez. ang.) Parks opublikowal w 1965 roku przeglad PZC tlenkéw i wodorotlenk6w metali, kt6ry do chwili obecne} jest najczescie} eytowanym Zrédlem informacji. Najnowszy preeglad PZC (Kosmulski 2001) ‘obejmuje nie tylko tlenki } wodorotlenki metali, ecz t6wnie2 tlenki mieszane, trudno rozpuszczatne sole i inne materialy, ktérych ladunek powierzchniowy zalezy od pH. Na podstawie przykladowego zestawut danych z tego przegladu (155 wartosci PZC dla Al,0, opublikowanych w 150 pracach w latach 1969- 2001) badano wplyw struktury krystalograficane| probki i doborumetod doswiadczalnych na otrzymang ‘wartosé PZC. Stwierdzono brak istotne} ré¢nicy pomigdzy odmianami o. (32 wartosci, srednia 8.2, mediana 8.55) i (58 wartosci, srednia 8.2, mediana 84) oraz innymi odmianami, mieszaninami réznych odmian i materialami o nieznanej strukturze (65 wartosc, srednia 8.3, mediana 8.7), Natomizst wartosei PZC wyraénie zaleza od zastosowane} metody. Metoda elektroakustyczna (11 wartosei, Srednia 9.3, mediana 9.5) daje zdecydowanie wy2szy punkt izoelektryczny IEP niz klasyezne metody elektrokinetycane (78 wartosci, srednia 8.2, mediana 8,7) i miareczkowanie potencjometryczne pray jedne} sile jonowej (29 wartosci, Srednia i mediana 8). W dwéch ostatnich metodach odchylenie standardowe jest wigksze niz w pozostalych metodach. Najmniejsze odchylenie standardowe wystepuje w zbiorze danych otrzymanych przy jednoczesnym zastosowaniy misreczkowania potencjometrycanego {jako PZC preyjmuje sig punkt przecigcia kraywych miareezkowania przy co najmniej trzech roanych silach jonowych) i pomiaréw elektrokinetycznych (7 wartosci, srednia i mediana 8.6) i tg wartosé mozna uzna¢ za najbardziej wiarygodna,