A desk-computer program for calculation of the parameters of acid-base titration curves and protonation or metal-complex stability constants from potentiometric data

The program MINIPOT is designed to run on a desk-computer with 16-kbyte of memory. It can calculate the optimum values of the parameters of a blank acid-base titration in any solvent, and the protonation/deprotonation or overall stability constants of a maximum of four species with compositions H(q)L(p) or M(q)L(p) from potential, titrant volume and analytical concentration data. The program, written in BASIC, is based on the least-squares principle and is capable of simultaneous refinement of a maximum of four parameters.     

水化介孔氧化硅表面酸碱平衡常数的测定

采用自动电位酸碱滴定技术研究了水化介孔氧化硅的表面脱质子反应.基于悬浮液的酸碱滴定数据,用Gran图法计算得到了介孔氧化硅表面氢离子键位点浓度.利用FITEQL4.0软件,采用双电层恒电容模型计算得到了相应的表面酸碱平衡常数.结果表明,与无定形氧化硅不同,介孔氧化硅表面存在对应于双齿表面硅羟基≡Si2OH和单齿表面硅羟基≡SiOH的两个脱质子常数,分别为pKa1=6.78±0.15,pKa2=10.25±0.22.根据测定得出的介孔氧化硅表面脱质子常数,构建了不同pH条件下,介孔氧化硅表面优势组分分布图,并讨论了表面电容预赋值对氧化硅表面组分分布的影响.     

螯合离子交换树脂的本征质子化常数

在25 ℃, 分别在水及乙醇-水混合溶剂中, 用电位滴定法研究了国产的含有胺亚二乙酸功能基的大孔螯合树脂D751的质子化反应. 在对树脂相中各组分的活度系数不作任何假定的前提下, 用外推法从表观质子化常数的对数值与滴定度间的关系, 求得了该树脂的三级本征质子化常数. 本文肯定了表观质子化常数对滴定度的依赖性, 合理地解释了在不同溶剂中树脂的酸碱性的变化.     

Temperature effects on the surface acidity properties of zirconium diphosphate

As part of the temperature effects study on the sorption of metallic cations onto zirconium diphosphate, we have first investigated the intrinsic surface properties of this synthetic compound for different temperatures (25, 50, 75 and 90 degrees C). A physico-chemical study (IR, XRD) assessed its purity, and the measured N(2)-BET specific area was 13.4+/-0.2 m(2)g(-1). Mass and potentiometric titrations showed that the experimental point of zero charge (pH(pzc)=2.6+/-0.2) and the surface site density remained constant between 25 and 90 degrees C. The potentiometric titration data were simulated with the constant capacitance model, considering two reactive surface sites, with a total surface site density equal to 7.2 sites nm(-2). The intrinsic protonation and deprotonation constants were found to increase with the temperature, as well as the calculated apparent constants. The simulation results showed that the capacitance increased with the temperature. The proportions of the neutral, protonated and deprotonated forms for each site type were quantified thermodynamically by application of the Van't Hoff relation.     

Acid-base properties of bentonite rocks with different origins

Five bentonite samples (35-47% montmorillonite) from a Sarmatian sediment series with bentonite sites around Sajóbábony (Hungary) is studied. Some of these samples were tuffogenic bentonite (sedimentary), the others were bentonitized tuff with volcano sedimentary origin. The acid-base properties of the edge sites were studied by potentiometric titrations and surface complexation modeling. It was found that the number and the ratio of silanol and aluminol sites as well as the intrinsic stability constants are different for the sedimentary bentonite and bentonitized tuff. The characteristic properties of the edges sites depend on the origins. The acid-base properties are compared to other commercial and standard bentonites.     

Effect of temperature on the acid-base properties of the alumina surface: microcalorimetry and acid-base titration experiments

Sorption reactions on natural or synthetic materials that can attenuate the migration of pollutants in the geosphere could be affected by temperature variations. Nevertheless, most of the theoretical models describing sorption reactions are at 25 degrees C. To check these models at different temperatures, experimental data such as the enthalpies of sorption are thus required. Highly sensitive microcalorimeters can now be used to determine the heat effects accompanying the sorption of radionuclides on oxide-water interfaces, but enthalpies of sorption cannot be extracted from microcalorimetric data without a clear knowledge of the thermodynamics of protonation and deprotonation of the oxide surface. However, the values reported in the literature show large discrepancies and one must conclude that, amazingly, this fundamental problem of proton binding is not yet resolved. We have thus undertaken to measure by titration microcalorimetry the heat effects accompanying proton exchange at the alumina-water interface at 25 degrees C. Based on (i) the surface sites speciation provided by a surface complexation model (built from acid-base titrations at 25 degrees C) and (ii) results of the microcalorimetric experiments, calculations have been made to extract the enthalpic variations associated respectively to first and second deprotonation of the alumina surface. Values obtained are deltaH1 = 80+/-10 kJ mol(-1) and deltaH2 = 5+/-3 kJ mol(-1). In a second step, these enthalpy values were used to calculate the alumina surface acidity constants at 50 degrees C via the van't Hoff equation. Then a theoretical titration curve at 50 degrees C was calculated and compared to the experimental alumina surface titration curve. Good agreement between the predicted acid-base titration curve and the experimental one was observed.     

Hydrous ferric oxide: evaluation of Cd-HFO surface complexation models combining Cd(K) EXAFS data,potentiometric titration results,and surface site structures identified from mineralogical knowledge

The surface properties of ferrihydrite were studied by combining wet chemical data, Cd(K) EXAFS data, and a surface structure and protonation model of the ferrihydrite surface. Acid-base titration experiments and Cd(II)-ferrihydrite sorption experiments were performed within 3<-log[H(+)]<10.5 and 0.5<[Cd(t)]<12 mM in 0.3 M NaClO(4) at 25 degrees C, where [Cd(t)] refers to total Cd concentration. Measurements at -5.5triple bond Fe-OH(-1/2),logk((int))=-8.29, assuming the existence of a unique intrinsic microscopic constant, logk((int)), and consequently the existence of a single significant type of acid-base reactive functional groups. The surface structure model indicates that these groups are terminal water groups. The Cd(II) data were modeled assuming the existence of a single reactive site. The model fits the data set at low Cd(II) concentration and up to 50% surface coverage. At high coverage more Cd(II) ions than predicted are adsorbed, which is indicative of the existence of a second type of site of lower affinity. This agrees with the surface structure and protonation model developed, which indicates comparable concentrations of high- and low-affinity sites. The model further shows that for each class of low- and high-affinity sites there exists a variety of corresponding Cd surface complex structure, depending on the model crystal faces on which the complexes develop. Generally, high-affinity surface structures have surface coordinations of 3 and 4, as compared to 1 and 2 for low-affinity surface structures.     

The protonation of polyacrylate in seawater. Analysis of concentration effects

The protonation of polyacrylate (PAA, MW 2 kDa) was studied potentiometrically at 25 degrees C, in mixed electrolyte aqueous solution simulating the composition of seawater, in the salinity range 30 < or = S < or = 40. The salt composition of different solutions was varied in order to study its effect on apparent protonation constants. Results were analysed using two fairly different approaches: by simple regression analysis on a combination of concentration parameters and salinity, and by canonical correlation analysis. Unexpectedly we found that variations on protonation constants, due to the different relative component concentrations, are fairly low, revealing a sort of buffering capacity of seawater respect to protonation properties of polyacrylate (and likely for other HMW and LMW polycarboxylates). The intrinsic protonation constant of polyacrylate 2 kDa at 25 degrees C and 35 salinity is log K(H*) = log K(int) = 4.399 +/- 0.004. The use of different pH scales and standard seawater compositions is also discussed.     

Ab initio study of sorption on pyrophyllite: structure and acidity of the edge sites

Pyrophyllite, Al2[Si4O10](OH)2, is the simplest structural prototype for 2:1 dioctahedral phyllosilicates. Since it does not possess permanent structural charge as other clay minerals do, it is used to investigate sorption properties of the clay surfaces not related to the permanent structural charge. The bulk structure and surface geometries of pyrophyllite have been modeled using an orthorhombic constrained supercell. The results of the calculations are in excellent agreement with available experimental data and earlier ab initio simulations. It is shown that the symmetry-constrained model is able to accurately reproduce the basic structural characteristic of pyrophyllite. The electrostatic potential near the (001) surface was used to analyze a possible scenario for the water sorption on the basal plane of pyrophyllite. The calculations predict a slightly hydrophobic behavior of the basal plane. The hydronium ion was found to form a strongly bonded conformation in the siloxane cavity. The relative stability and composition of lateral facets of pyrophyllite have been studied using the supercell approach. The crystals of pyrophyllite are predicted to have a prismatic habit dominated by (110) and (-110) edge facets and basal plane. On the basis of the Fukui functions and the relative protonation/deprotonation enthalpies, the relative acidity and density of the reactive surface sites have been predicted. The triple bond Al-O-Si triple bond sites have the highest proton affinity on the (100), (110), and (130) facets and three line sign Al-OH groups on the (010) edges. The deprotonation of the triple bond Al-OH2 sites is followed by triple bond Al-OH and triple bond Si-OH groups. The calculations suggest a new scale for acidities of edge sites in pyrophyllite that should facilitate the thermodynamic modeling of the sorption processes in compacted clays.     

The mechanism of the protonation of metal (hydr)oxides in aqueous solutions studied for various interfacial/surface ionization models and physicochemical parameters: a critical review and a novel approach

The mechanism of the protonation of solid metal (hydr)oxides in aqueous media was investigated using simulation and experimental work. It was found that the apparent acidity/basicity of each kind of surface sites of metal (hydr)oxides in aqueous suspensions is strongly influenced by the overall surface charge of the (hydr)oxide and thus by the electrical potential smeared out at the interfacial region. Depending on its sign this increases or decreases the hydrogen ion concentration on the surface, thus promoting or hindering protonation. This is manifested by the shifts of the protonation peaks of the various kinds of sites with respect to the -pK values of the corresponding intrinsic protonation constants and the appearance of an extra peak in the d[H+cons,surf]/dpH vs. pH curves. Potentiometric titrations experiments performed for four technologically important oxides showed that the proposed protonation mechanism describes indeed the protonation of polycrystalline (hydr)oxides in aqueous media.     

Surface stoichiometry of zinc sulfide and its effect on the adsorption behaviors of xanthate

ABSTRACT: In this paper, the surface stoichiometry, acid-base properties as well as the adsorption of xanthate at ZnS surfaces were studied by means of potentiometric titration, adsorption and solution speciation modeling. The surface proton binding site was determined by using Gran plot to evaluate the potentiometric titration data. Testing results implied that for stoichiometric surfaces of zinc sulfide, the proton and hydroxide determine the surface charge. For the nonstoichiometric surfaces, the surface charge is controlled by proton, hydroxide, zinc and sulfide ions depending on specific conditions. The xanthate adsorption decreases with increasing solution pH, which indicates an ion exchange reaction at the surfaces. Based on experimental results, the surface protonation, deprotonation, stoichiometry and xanthate adsorption mechanism were discussed.     

Comparative study of copper(II) interactions with monomeric ligands and synthetic or natural organic materials from potentiometric data

Potentiometric measurements were used to characterize the complexing properties of (a) a mixture of five monomeric ligands, (b) a synthetic humic-like substance and (c) fulvic acids extracted from soils, with copper (II). In order to compare the binding strengths involved, the same mathematical treatments of the data were used for all measurements. Calculations of the total ligand concentration with the Gran function give underestimated values for the multiligand mixture because of the known presence in the mixture of functional groups with pK^H ; 11 which > cannot be titrated and are revealed only by complexation phenomena. The acid-base properties of the humic substances are better described with a continuous model than with the descrete Henderson-Hasselbach model, because of the inability to distinguish properly between equivalent and independent types of functional groups. In the presence of copper (II), the formation functions show that a mixture of different kinds of complexes with different stability constants is probably formed. Extra protons released during the titration of the various copper (II) systems with alkali are attributed to untitrated functional groups with extremely low protonation constants in the case of the multiligand mixture, but ambiguity remains with the humic substances because their chemical structure is not known. Comparison of binding strengths can be made in terms of global conditional stability constants, by taking into account the three parameters, pH, concentrations of metal and of ligand. It is shown that the mechanisms of complexation are different for monomers and for polymers.     

Surface complexation modeling of uranium(VI) sorbed onto zirconium oxophosphate versus temperature: thermodynamic and structural approaches

This work presents an investigation of the interaction mechanisms between uranyl ions and a solid phosphate, the zirconium oxophosphate: Zr2O(PO4)2. Both thermodynamic and structural points of view are developed. Indeed, prior to any simulation of the retention data, it is necessary to precisely characterize the system under study in order to gain information at a molecular scale. First, the intrinsic surface properties of this synthetic compound have been investigated for different temperatures ranging from 25 to 90 degrees C. Mass and potentiometric titrations show that the surface site density remains constant between 25 and 90 degrees C, while the experimental point of zero charge slightly decreases from 4.8 to 4.5 with an increasing temperature. The potentiometric titration data are simulated, for each temperature, using the constant capacitance model and taking into account two surface sites ([TRIPLE BOND]ZrO and [TRIPLE BOND]PO) with a total surface site density equal to 7.0 sites nm(-2). For both reactive sites, the intrinsic protonation constants do not change with the temperature, while the deprotonation ones increase. These results led to the determination of the associated enthalpy and entropy changes according to the van't Hoff relation. Second, the speciation of U(VI) at the solid/solution interface has been studied using two complementary spectroscopic techniques probing the sorbed uranyl ions: time-resolved laser-induced fluorescence spectroscopy (TRLFS) and X-ray absorption spectroscopy (EXAFS). The substrate presents two different reactive surface sites against uranium retention, which are constituted by the oxygen atoms of the surface PO4 groups and the oxygen atoms linked to the zirconium atoms. Two inner-sphere complexes are thus present on the substrate, their relative proportion depending on the pH value of the suspension. The effects of the temperature (25-90 degrees C) on the surrounding uranium were checked using the TRLFS technique. The uranyl sorption constants onto the Zr2O(PO4)2 substrate were determined taking into account the structural investigation. The surface complexation modeling was performed using the constant capacitance model included in the FITEQLv4.0 code. The four adsorption edges obtained at 25, 50, 75, and 90 degrees C were simulated. The modeling of these experimental data was realized considering two surface complexes (([TRIPLE BOND]ZrOH)2UO(2+)2, ([TRIPLE BOND]PO)2UO2) according to the structural investigation. The constant value associated with the ZrO site does not change with the temperature, while the one corresponding to the PO site increases. Finally, the enthalpy and entropy changes associated with the uranyl sorption constants have been determined using the van't Hoff relation.     

Surface Complexation Modeling of K(+), NO(3)(-), SO(4)(2-), Ca(2+), F(-), Co(2+), and Cr(3+) Ion Adsorption on Silica Gel

Surface complex formation of K(+), NO(3)(-), SO(4)(2-), Ca(2+), F(-), Co(2+), and Cr(3+) ions was determined on the surface of silica gel. Experimental data obtained by acid-base titration of suspensions were interpreted in terms of the triple-layer model. The value of the deprotonation constant of surface OH could be determined precisely but the protonation constant was rather uncertain. The logarithms of ion pair formation constants for K(+), NO(3)(-), Ca(2+), and SO(4)(2-) adsorbed in the beta-plane are log K(ipM,X) approximately 0, therefore these species can be considered inert ions in the investigated pH range. F(-), Co(2+), and Cr(3+) ions were found to be strongly sorbed in the o-plane. In order to provide a good fit and to obtain parameters independent of their initial values, all possible equilibrium must be accounted for in the models. Copyright 2001 Academic Press.     

Surface acid-base properties and hydration/dehydration mechanisms of aluminum (hydr)oxides

In this paper, surface physiochemical properties of three typical aluminas, gamma-Al(OH)3, gamma-Al2O3, and alpha-Al2O3, were investigated by means of XRD, SEM, TEM, BET surface area, TG/DTA, and potentiometric titration techniques. Based on the titration data, surface protonation and deprotonation constants were determined using the constant capacitance model (CCM). The emphasis of this research was laid on the comparison of the crystal structure, surface hydration/dehydration and acid-base properties of these three typical alumina minerals. The calculation results revealed that the surface acidity of the aluminas is in the order of alpha-Al2O3>gamma-Al(OH)3>gamma-Al2O3 after being hydrated for 1 h. The correlation between the hydration/dehydration mechanisms of alumina and its acid/base properties is discussed.     

Enhanced protonation of cresol red in acidic aqueous solutions caused by freezing

The protonation degree of cresol red (CR) in frozen aqueous solutions at 253 or 77 K, containing various acids (HF, HCl, HNO3, H2SO4, and p-toluenesulfonic acid), sodium hydroxide, NaCl, or NH4Cl, was examined using UV/Vis absorption spectroscopy. CR, a weak organic diacid, has been selected as a model system to study the acid-base interactions at the grain boundaries of ice. The multivariate curve resolution alternating least-squares method was used to determine the number and abundances of chemical species responsible for the overlaying absorption visible spectra measured. The results showed that the extent of CR protonation, enhanced in the solid state by 2-4 orders of magnitude in contrast to the liquid solution, is principally connected to an increase in the local concentration of acids. It was found that this enhancement was not very sensitive to either the freezing rate or the type of acid used and that CR apparently established an acid-base equilibrium prior to solidification. In addition, the presence of inorganic salts, such as NaCl or NH4Cl, is reported to cause a more efficient deprotonation of CR in the former case and an enhanced protonation in the latter case, being well explained by the theory of Bronshteyn and Chernov. CR thus served as an acid-base indicator at the grain boundaries of ice samples. Structural changes in the CR molecule induced by lowering the temperature and a presence of the constraining ice environment were studied by the absorption and 1H NMR spectroscopies. Cryospheric and atmospheric implications concerning the influence of acids and bases on composition and reactivity of ice or snow contaminants were examined.     

Solvent Effects on Tautomeric and Microscopic Protonation Constants of Glycine in Different Aqueous Solutions of Methanol and Ethanol

The acid-base equilibria of glycine have been studied in different aqueous solutions of methanol and ethanol (0?C45?% v/v) using a potentiometric method. In this study, the macro and micro protonation constants of the amino acid and its tautomeric constant have been determined at 25?°C and constant ionic strength (0.1 mol?dm^?3 NaClO₄). The protonation and the tautomeric constants of glycine in different binary mixtures were analyzed in terms of the Kamlet, Abboud and Taft (KAT) parameters. Single-parameter correlations of the constants versus ?? (hydrogen-bond donor acidity), ?? (hydrogen-bond acceptor basicity) and ?? ^? (dipolarity/polarizability) are poor in all solutions. Multi-parameter correlations show better results, but dual-parameter correlations represent significant improvements with regard to the single- and multi-parameter models. Linear correlation is observed when the experimental protonation constant values are plotted versus the calculated ones when the KAT parameters are considered. Finally, the results are discussed in terms of the effect of the solvent on protonation and tautomeric constants.     

Acid-base and spectroelectrochemical properties of doubly N-confused porphyrins

The cis-doubly N-confused porphyrin, H2N2CP, containing two adjacent confused pyrrole rings has been investigated from the point of view of its acid-base and electrochemical behavior in dichloromethane. This novel porphyrin isomer can form two metal-carbon bonds in the central core, stabilizing metal ions in unusually high oxidation states. Furthermore, the two outside N-pyrrole atoms remain available for acid-base and specific solvent interactions. Protonation of the pyrrole N atoms proceeds according to two successive steps, while only a single deprotonation step has been observed in the presence of bases. Similarly, in the case of the silver and copper complexes the protonation and deprotonation of the outer pyrrole rings have been detected, confirming the structure of the metalated species as M(III)-HN2CP. The electrochemical reduction of the metal ions (III/II redox process) and oxidation of the macrocycle ring have been detected respectively at -0.9 and 1.4 V based on spectroelectrochemical measurements in conjunction with the acid/base equilibrium studies. Additional waves observed around -0.5 and 1.3 V have been assigned to redox processes involving water molecules associated with the doubly N-confused porphyrins.     

Influence of protonation on substrate and inhibitor interactions at the active site of human monoamine oxidase-A

Although substrate conversion mediated by human monoaminooxidase (hMAO) has been associated with the deprotonated state of their amine moiety, data regarding the influence of protonation on substrate binding at the active site are scarce. Thus, in order to assess protonation influence, steered molecular dynamics (SMD) runs were carried out. These simulations revealed that the protonated form of the substrate serotonin (5-HT) exhibited stronger interactions at the protein surface compared to the neutral form. The latter displayed stronger interactions in the active site cavity. These observations support the possible role of the deprotonated form in substrate conversion. Multigrid docking studies carried out to rationalize the role of 5-HT protonation in other sites besides the active site indicated two energetically favored docking sites for the protonated form of 5-HT on the enzyme surface. These sites seem to be interconnected with the substrate/inhibitor cavity, as revealed by the tunnels observed by means of CAVER program. pK(a) calculations in the surface loci pointed to Glu32?, Asp32?, His???, and Asp132 as candidates for a possible in situ deprotonation step. Docking analysis of a group of inhibitors (structurally related to substrates) showed further interactions with the same two docking access sites. Interestingly, the protonated/deprotonated amine moiety of almost all compounds attained different docking poses in the active site, none of them oriented to the flavin moiety, thus producing a more variable and less productive orientations to act as substrates. Our results highlight the role of deprotonation in facilitating substrate conversion and also might reflect the necessity of inhibitor molecules to adopt specific orientations to achieve enzyme inhibition.     

The thermodynamic model of inorganic arsenic species in aqueous solutions Potentiometric study of the hydrolitic equilibrium of arsenic acid

Protonation constants of arsenic acid were determined at different ionic strengths in NaClO(4) (0.1, 0.5, 1.0, 3.0 mol dm(-3)), NaCl (0.5 and 1.0 mol dm(-3)) and KCl (0.5, 1.0 and 3.0 mol dm(-3)) ionic media by means of a potentiometric study. The distribution of arsenate species was defined depending on two important variables in natural environments: pH and composition. All the experimentation was performed at 25 degrees C. The differences found in the protonation constants for different medium compositions, were explained by the different behaviour of the interaction parameters of the species considered in the different media and ionic strengths. These parameters were reported for all hydrolitic As(V) species and were calculated using the Modified Bromley's Methodology (MBM). The corresponding thermodynamic stepwise formation constants were also determined (log degrees K(1)=11.58+/-0.01, log degrees K(2)=7.06+/-0.01, log degrees K(3)=2.25+/-0.01). All the results obtained showed not only the importance of the ionic strength but also of the composition of the ionic medium on the distribution of the acid-base species of As(V) as a function of pH in natural waters.