Potentiometric Acid-base Titrations Research Articles

Striking analogies and dissimilarities between graphene oxides and humic acids: pH-dependent charging and colloidal stability

This study provides a comparative framework on the elucidation of analogies and differences in the interfacial protolytic processes and the associated colloidal behaviour of a typical humic acid (HA) and a set of single-layer graphene oxide (SLGO) and (multi-layered) graphite oxide samples in aqueous electrolyte media. The pH dependence of the surface charge densities of HA and SLGO was explored at three different salt concentrations by potentiometric acid-base titration, along with simultaneous determination of zeta potential and hydrodynamic sizes. Charging curves obtained in the pH range of 3 to 10 by cyclic titrations reveal the presence of a small hysteresis, proving the chemical stability of SLGO and graphite oxides in weakly acidic and alkaline solutions. HA and SLGO display a parallel shift of the pH-dependencies of their negative charge densities with increasing ionic strength, demonstrating a unique combination of particle and polyelectrolyte-like behaviour, which is absent for multi-layered graphite oxide exhibiting charging curves that resemble to “classical” colloidal particles. An accurate purification of SLGO results in inherent change in its surface properties; however, the salt tolerance of aqueous HA solutions is still superior to that of SLGO dispersions.

Surface charge properties of variable charge soils influenced by environmental factors

The variable charge soils that have been developed in tropical and subtropical zones are unique soils compared with the constant charge soils that have been developed in Europe and North America, especially the sensitivity of the particle surface charges to environmental factors in the variable charge soils. In this study, to avoid the interference of side reactions, experiments were performed using a fast potentiometric acid-base titration under non-equilibrium condition, and simulation by the surface complexation model to investigate the effects of environmental factors, including the impact of CO2 (in nitrogen/in air), the impact of different ionic strengths, the impact of dry-wet rotation (different soil-to-liquid (S/L) ratios), and the impact of seasonal temperature variation (different reaction temperatures), on the surface acidity constants and on the protonation/deprotonation processes in a typical variable charge soil collected in southern China. The titration results demonstrate that the observed measured apparent pH when surface charge equal to zero (pHQ=0) were significantly negative shifted in air, and negative correlations were proven between the S/L ratios, the reaction temperatures and the observed pHQ=0 values. The simulation results from the fast titration prove that changing the S/L ratios modifies the surface species concentration (≡SOH, ≡SOH2+, and ≡SO−), further influencing the modification of the surface charge properties of the soil. Meanwhile, an increase in temperature not only increases the amount of the surface species concentration but also causes an enlargement of the protonation/deprotonation processing range, which may increase the acid-base buffer capacity of soils. Taken together, these results can help us to further understand the natural soil acidification processes occurring in variable charge soils, especially in the southern areas of China.

Synthesis of a Novel Sensor Electrode Based on Bromothymol Blue as an Indicator Electrode in Potentiometric Acid-Base Titration in Aqueous Solution

Synthesis of a Novel Sensor Electrode Based on Bromothymol Blue as an Indicator Electrode in Potentiometric Acid-Base Titration in Aqueous Solution

Synthesis of a Novel Sensor Electrode Based on Bromothymol Blue as an Indicator Electrode in Potentiometric Acid-Base Titration in Aqueous Solution

Synthesis of a Novel Sensor Electrode Based on Bromothymol Blue as an Indicator Electrode in Potentiometric Acid-Base Titration in Aqueous Solution

OBTAINING AN ACID-BASE NATURAL INDICATOR FROM THE FRUIT Punica Granatum L. (POMEGRANATE): A CONTRIBUTION FOR THE SUBSTITUTION OF SYNTHETIC INDICATORS

The research proposes to obtain a natural acid-base indicator from the extract of the arils of the Punica granatum L.(pomegranate) fruit as an option to replace the synthetic indicators (phenolphthalein). The indicative actions of the fruit extract Punica granatum L. is due to the presence of phytochemicals (anthocyanins). The identification of some of the anthocyanins present was carried out by an analysis in the UHPLC-ESI-Q-Orbitrap-MS / MS equipment, of Reverse Phase C-18. The preliminary tests for the anthocyanin test were to measure the color change of the extract against HCl and NaOH, likewise a pH scale curve was performed and its stability was measured in different periods of time (5, 10 and 15 min), which were analyzed in the UV-Vis Spectrophotometer, the potentiometric acid-base titrations, determined the values ​​of the first and second derivatives, obtaining the pKInd interval of the fruit extract Punica granatum L. Finally, it was confirmed that the pH variation is one of the factors that significantly affected the color of the extract of the Punica granatum L. fruit, while the effect of light at different time periods oxidized the extract (discoloration).

Adsorption of strontium on manganese oxide (δ-MnO2) at elevated temperatures: experiment and modeling

Strontium adsorption has been studied by the method of acid-base potentiometric titrations at three different temperatures: 25, 50, 75C. The effect of pH, ionic strength, sorbate/sorbent ratio, and temperature on adsorption was investigated. Experimental data were simulated using two various surface complexation models, with two different electrostatic descriptions of the interface: the constant capacitance model (CCM) and the triple-layer model (TLM). Although the both models used are able to account for the acid-base reactions and surface complexation of strontium on birnessite, we consider that the TLM is more applicable for a description of heterophaseous system H+ MnOH Sr2+. Under conditions of low ionic strength and negatively charged surface, Sr2+ ions compete with the electrolyte ions and form outer-sphere complexes along with inner-sphere complexes. Consequently, using the CCM for description of strontium adsorption data could be mathematically satisfactory, but physically senseless. The equilibrium model proposed here consists of the complexes of inner (MnOHSr2+, MnOSr+, MnOSrOH0) and outer types ([MnO Sr2+]+). The corresponding intrinsic equilibrium constants of the formation of these surface complexes were calculated for 25,50, and 75C.

Strontium Adsorption on Manganese Oxide (δ-MnO2) at Elevated Temperatures: Experiment and Modeling

Strontium adsorption was studied by acid–base potentiometric titration at various pH, ionic strength, the sorbate/sorbent ratio, and temperatures (at 25, 50, and 75°C). The experimental data were interpreted using two models of surface complexation with two different electrostatic models of the interface: the constant capacitance (CCM) and triple-layer (TLM) models. Although both models are able to take into account acid–base reactions and surface complexation of Sr on birnessite, we believe that TLM is more suitable for the description of the H+–>MnOH–Sr2+ heterogeneous system. At a low ionic strength and negatively charged surface, Sr2+ ions compete with electrolyte ions and form both inner- and outer-sphere complexes. Although the application of CCM in describing Sr adsorption may be mathematically satisfactory, it has little physical sense. We suggest a model that involves both inner-sphere (>MnOHSr2+, >MnOSr+, >MnOSrOH0) and outer-sphere ([>MnO–Sr2+]+) surface complexes. The corresponding constants of formation of these surface complexes were calculated at 25, 50, and 75°C.

Bamboo charcoal modified with Cu2+ and 3‐aminopropyl trimethoxy silane for the adsorption of acid fuchsin dye: Optimization by response surface methodology and the adsorption mechanism

ABSTRACTThe bamboo charcoal modified with Cu2+ and 3‐aminopropyl trimethoxy silane (BC‐Cu/Si‐NH2) was synthesized and characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, and surface acid–base potentiometric titration. The adsorption for acid fuchsin (AF) dyes onto BC‐Cu/Si‐NH2 was investigated. Moreover, response surface methodology was performed to optimize the process parameters including pH, initial dye concentration, adsorbent dosage, and temperature. The results presented that the adsorption process was mainly influenced by initial AF concentration and adsorbent dosage. Isotherm studies revealed that the adsorption data fitted well with the Sips model and Dubinin–Radushkevich (D–R) model, which indicated the monolayer, homogeneous, and physical nature of the adsorption process. The maximum adsorption capacity calculated from D–R model could approach approximately to 14.91 mg g−1 at 40 °C, and the maximum adsorption capacity of Sips reached to 10.77 mg g−1 at 40 °C. The kinetic experimental data matched well with Spahn and Schlunder model as well as pseudo‐second‐order model. In addition, intraparticle diffusion was not the only rate‐controlling step of adsorption process. Thermodynamic parameters revealed the feasibility, spontaneity, and endothermic nature of adsorption. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47728.

PEGylation of Superparamagnetic Iron Oxide Nanoparticles with Self-Organizing Polyacrylate-PEG Brushes for Contrast Enhancement in MRI Diagnosis.

For biomedical applications, superparamagnetic nanoparticles (MNPs) have to be coated with a stealth layer that provides colloidal stability in biological media, long enough persistence and circulation times for reaching the expected medical aims, and anchor sites for further attachment of bioactive agents. One of such stealth molecules designed and synthesized by us, poly(polyethylene glycol methacrylate-co-acrylic acid) referred to as P(PEGMA-AA), was demonstrated to make MNPs reasonably resistant to cell internalization, and be an excellent candidate for magnetic hyperthermia treatments in addition to possessing the necessary colloidal stability under physiological conditions (Illés et al. J. Magn. Magn. Mater. 2018, 451, 710–720). In the present work, we elaborated on the molecular background of the formation of the P(PEGMA-AA)-coated MNPs, and of their remarkable colloidal stability and salt tolerance by using potentiometric acid–base titration, adsorption isotherm determination, infrared spectroscopy (FT-IR ATR), dynamic light scattering, and electrokinetic potential determination methods. The P(PEGMA-AA)@MNPs have excellent blood compatibility as demonstrated in blood sedimentation, smears, and white blood cell viability experiments. In addition, blood serum proteins formed a protein corona, protecting the particles against aggregation (found in dynamic light scattering and electrokinetic potential measurements). Our novel particles also proved to be promising candidates for MRI diagnosis, exhibiting one of the highest values of r2 relaxivity (451 mM−1s−1) found in literature.

Removal of cationic and anionic dyes using purified and surfactant-modified Tunisian clays: Kinetic, isotherm, thermodynamic and adsorption-mechanism studies

ABSTRACTPurified and surfactant-modified Tunisian clays were investigated for their capacity to remove cationic and anionic dyes (crystal violet, CV and methyl orange, MO) from aqueous solution. The samples were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and potentiometric acid-base titration. Batch-sorption experiments were carried out to evaluate the influence of pH, contact time, initial dye concentration and temperature on the adsorption of dyes. Pseudo-first order, pseudo-second order, intra-particle diffusion and Elovich kinetic models were considered to evaluate the kinetic parameters. To understand the interaction of the dye with the adsorbent, Langmuir, Freundlich, Temkin and Dubinin-Radushkevish isotherms were applied. Thermodynamics studies were conducted to calculate the changes in free energy (Δ°G), enthalpy (Δ°H) and entropy (Δ°S). A difference in the maximum adsorption capacity was observed, suggesting that the retention of dyes was influenced by structure, functional groups of dyes and surface properties of the adsorbents. Moreover, different mechanisms may control the removal of dyes. The purified Tunisian clays are excellent adsorbents for removal of the cationic dye CV and its modified form is suitable for removal of the anionic dye, MO, from aqueous solution.

DEVELOPMENT OF SULFENTRAZONE EXTRACTION PROCEDURE FROM COMMERCIAL HERBICIDE FORMULATION AND DETERMINATION OF ITS IONIZATION CONSTANT (pKa) BY POTENTIOMETRIC TITRATION

The herbicide sulfentrazone (SFZ) is widely used in soybean and sugarcane crops, although it is classified as very dangerous to the environment. To minimize barriers to the development of research with this herbicide due to the high cost of acquisition of its analytical standard and the availability of few distributors to acquire the standard in the country, a procedure of extraction and purification of SFZ was developed from a commercial herbicide formulation available in Brazil. Using the most suitable experimental conditions established for the extraction procedure, the SFZ content in the resulting solid after extraction and drying was 97.5% (m/m), which value was determined by acid-base potentiometric titrations. To characterize the solid obtained in this procedure, the material was studied by thermal analysis (thermogravimetry and differential scanning calorimetry) and Fourier transform infrared photoacoustic spectroscopy (FTIR-PAS) to confirm the presence of functional groups present in the SFZ molecule. Thermal analysis of the solid resulting from the extraction indicated processes of melting, thermal degradation and volatilization of the SFZ during its heating. By potentiometric titrations of the purified solid dissolved in water/acetonitrile (ACN) binary mixtures, it was possible to determine the ionization constant (pKa) of SFZ in water at 25.0ºC. By this study, extrapolated value of pKa in water is 6.45 obtained from the linear correlation of pKa versus molar ACN fraction plot. The value obtained at 25.0 °C by potentiometry in this study is quite close to the literature value of 6.56 determined at 20 °C by the spectrophotometric technique. However, the pKa value determined by potentiometric titrations of dilute solutions of the SFZ commercial formulations was much higher than that of 6.56, indicating that the degree of ionization of SFZ under herbicide application conditions can be quite distinct in the presence of possible adjuvants present in the commercial formulation of the herbicide.

Charging and Aggregation Behavior of Cellulose Nanofibers in Aqueous Solution.

To understand the charging and aggregation of cellulose nanofibers (CNFs), we performed the following experimental and theoretical studies. The charging behavior of CNFs was characterized by potentiometric acid-base titration measuring the density of deprotonated carboxyl groups at different KCl concentrations. The charging behavior from the titration was quantitatively described by the 1-pK Poisson-Boltzmann (PB) model for a cylinder. The electrophoretic mobility of CNFs was measured as a function of pH by electrophoretic light scattering. The mobility was analyzed with the equation for an infinitely long cylinder considering the relaxation of the electric double layer. Good agreement between experimental mobilities and theoretical calculation was obtained by assuming a reasonable distance from the surface to the slipping plane. The result demonstrated that the negative charge of CNFs originates from the deprotonation of β(1-4)-d-glucuronan on the surface. The aggregation behavior of CNFs was studied by measuring the hydrodynamic diameter of CNFs at different pH and KCl concentrations. Also, we calculated the capture efficiencies of aggregation, using interaction energies of perpendicularly and parallelly oriented cylinders. The interaction energies between cylinders in both orientations were obtained by the Derjaguin, Landau, Verwey, and Overbeek theory, where the electrostatic repulsion was calculated from the surface potential obtained by the 1-pK PB model. From comparison of the theoretical capture efficiency with the measured hydrodynamic diameter, we suggest that CNFs can be aggregated in perpendicular orientation at low pH and low salt concentration, and the fast aggregation regime of CNFs is realized by the reduction of electric repulsion for both perpendicularly and parallelly interacting CNFs. Meanwhile, the application of Smoluchowski's equation to the mobility of CNFs results in the underestimation of the zeta potential.

Room-Temperature Synthesis of UiO-66 and Thermal Modulation of Densities of Defect Sites

UiO-66 is an archetypal zirconium-based metal–organic framework (MOF) that is constructed from hexanuclear zirconium oxide clusters as secondary building units (SBUs) and 1,4-benzenedicarboxylate (bdc) linkers. For the first time, a room-temperature solution-based synthesis is reported for UiO-66 and several of its derivatives, UiO-66-X (X = NH2, OH, or NO2), resulting in materials that are as porous and crystalline as those made at elevated temperatures. In addition, via modulation of the temperature at which UiO-66 is synthesized, the number of defect sites can be varied. It was found through N2 sorption isotherm analysis and potentiometric acid–base titrations that increasing the synthesis temperature from 25 to 130 °C results in a systematic decrease in the number of defect sites in UiO-66. The results suggest that, with respect to this synthetic procedure, a maximal number of defect sites is achieved [∼1.3 missing linkers per Zr6O4(OH)4(bdc)6] at a temperature of 45 °C.

Adsorption of hexavalent chromium onto Bamboo Charcoal grafted by Cu2+-N-aminopropylsilane complexes: Optimization, kinetic, and isotherm studies

Abstract The adsorption mechanism of Cr(VI) uptake onto Bamboo Charcoal grafted by Cu2+-N-aminopropylsilane complexes (BC/Cu-N) was investigated. The properties of BC/Cu-N were characterized using XRD, FTIR, SEM, EDS, potentiometric acid–base titration and electrochemical analysis. Results indicated that the framework integrity of BC was kept after modification and the quantity of functional groups on BC/Cu-N surface has changed. There existed functional groups on the BC/Cu-N which could consume OH− and the pHpzc was found to be 6.20. Moreover, electrochemical analysis showed that new electron transfer pathway was imported. Parameters such as pH, initial Cr(VI) concentration, adsorbent dosage and temperature were optimized using RSM. Analysis of variance of the quadratic model for Cr(VI) was suitable to predict the adsorption of Cr(VI) (F value = 134.23 and P value

Determination of pKa values of alendronate sodium in aqueous solution by piecewise linear regression based on acid-base potentiometric titration

As a mono-sodium salt form of alendronic acid, alendronate sodium presents multi-level ionization for the dissociation of its four hydroxyl groups. The dissociation constants of alendronate sodium were determined in this work by studying the piecewise linear relationship between volume of titrant and pH value based on acid-base potentiometric titration reaction. The distribution curves of alendronate sodium were drawn according to the determined pKa values. There were 4 dissociation constants (pKa1=2.43, pKa2=7.55, pKa3=10.80, pKa4=11.99, respectively) of alendronate sodium, and 12 existing forms, of which 4 could be ignored, existing in different pH environments.

Calculation of parameters of an electrical double layer at the magnetite/solution interface from potentiometric titration data on magnetite suspension

A three-layer model of an electrical double layer at magnetite/aqueous 0.001–1 mol/L KCl solution interfaces has been considered in a pH range of 3.5–9.5. A procedure has been proposed for determining the constants of equilibrium reactions and the parameters of electrical double layers from the acid–base potentiometric titration data of magnetite suspensions in the solutions taking into account the generation of a surface charge. The determination of these constants and the parameters of the electrical double layer is based on the use of the point of zero charge. Software has been developed and used for calculating the main parameters of the electrical double layer within the framework of the three-layer model and the Graham–Parsons concepts.

Ozonated graphene oxides as high efficient sorbents for Sr(II) and U(VI) removal from aqueous solutions

Ozone was used to oxidize graphene oxides (GO) to generate ozonated graphene oxides (OGO) with higher oxygen-containing functional groups. The as-prepared OGO was characterized by Fourier transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Based on the results of potentiometric acid-base titrations, the total carboxylic acid concentration on OGO surface was calculated to be 3.92 mmol/g, which was much higher than that on GO surface. The results of adsorption experiments indicated that the adsorption capacities of OGO for Sr(II) and U(VI) removal were improved significantly after ozonization.

Electrosurface properties of single-crystalline detonation nanodiamond particles obtained by air annealing of their agglomerates

A complex study of electrosurface properties has been performed for single-crystalline detonation nanodiamond particles with sizes of 4–5 nm obtained by air annealing of their agglomerates. FTIR spectroscopy and X-ray photoelectron spectroscopy data indicate that the investigated properties result from the presence of two types of ionogenic functional groups on the particle surface, i.e., acidic carboxyl and amphoteric hydroxyl groups. Acid-base potentiometric titration, laser Doppler electrophoresis, and conductometry have been employed to measure the Γ H + (pH) and Γ OH - (pH) adsorption isotherms of potential-determining ions, as well as the pH dependences (in a pH range of 3.5–10.5) of the surface charge density, electrophoretic mobility, and specific surface conductivity of detonation nanodiamond particles in aqueous 0.0001–0.01 M KCl solutions.

Comparison of the surface ion density of silica gel evaluated via spectral induced polarization versus acid–base titration

Surface complexation models are widely used with batch adsorption experiments to characterize and predict surface geochemical processes in porous media. In contrast, the spectral induced polarization (SIP) method has recently been used to non-invasively monitor in situ subsurface chemical reactions in porous media, such as ion adsorption processes on mineral surfaces. Here we compare these tools for investigating surface site density changes during pH-dependent sodium adsorption on a silica gel. Continuous SIP measurements were conducted using a lab scale column packed with silica gel. A constant inflow of 0.05M NaCl solution was introduced to the column while the influent pH was changed from 7.0 to 10.0 over the course of the experiment. The SIP measurements indicate that the pH change caused a 38.49±0.30μScm−1 increase in the imaginary conductivity of the silica gel. This increase is thought to result from deprotonation of silanol groups on the silica gel surface caused by the rise in pH, followed by sorption of Na+ cations. Fitting the SIP data using the mechanistic model of Leroy et al. (Leroyet al., 2008), which is based on the triple layer model of a mineral surface, we estimated an increase in the silica gel surface site density of 26.9×1016sitesm−2. We independently used a potentiometric acid–base titration data for the silica gel to calibrate the triple layer model using the software FITEQL and observed a total increase in the surface site density for sodium sorption of 11.2×1016sitesm−2, which is approximately 2.4 times smaller than the value estimated using the SIP model. By simulating the SIP response based on the calibrated surface complexation model, we found a moderate association between the measured and estimated imaginary conductivity (R2=0.65). These results suggest that the surface complexation model used here does not capture all mechanisms contributing to polarization of the silica gel captured by the SIP data.

Determination of acid sites in porous aluminosilicate solid catalysts for aqueous phase reactions using potentiometric titration method

A potentiometric acid–base titration method was developed to characterize the acid–base properties of H-Beta-25, H-Beta-300, H-Ferrierite-20 and Si-MCM-48 zeolites in aqueous solutions. The method is based on linearization of the titration curve. The zeolite powders were dispersed in a sodium nitrate solution which was then titrated with a standard solution of sodium hydroxide. Various acid sites were found in the studied zeolites, and both the protonation constants and the concentrations of these acid sites were determined. The chemical composition (aluminum and silicon), distribution of the aluminum sites, crystallinity as well as the acidic properties of the titrated zeolites were compared with those of the pristine zeolites by using Inductively Coupled Plasma Optical Emission Spectrometer (ICP-OES), X-ray Diffraction (XRD), 27Al NMR spectroscopy and the commonly used gas phase Fourier Transform Infrared spectroscopy (FTIR) of pyridine adsorption method.