Surface charge of detonation nanodiamond particles in aqueous solutions of simple 1 : 1 Electrolytes

Adsorption isotherms of potential-determining H⁺ and OH⁻ ions and the pH dependences of the specific surface charge of detonation nanodiamond (DND) particles are obtained in a pH range of 3–10 by the acid-base titration of their hydrosols containing 0.001–1 M LiCl, NaCl, KCl, NaNO₃, KNO₃, and NaClO₄ as background electrolytes. The data obtained attest to the chemical nonuniformity (heterogeneity) of a DND surface and different degrees of binding of background electrolyte cations and anions with ionized groups. It is revealed that the adsorption of OH-anions diminishes in the lyotropic series of cations Na⁺ > K⁺ > Li⁺ and increases with a decrease in the adsorbability of anions in the following series: NO₃⁻ ≊ ClO₄⁻ > Cl⁻. The adsorption of potential-determining H⁺ and OH⁻ ions on a DND surface containing two types of functional groups, i.e., acidic carboxyl and amphoteric hydroxyl groups, is simulated by the Protofit software package. The optimal surface densities and ionization constants that correspond to minimal deviations of model adsorption isotherms from the experimental curves are found for these groups.     

Electrochemical properties and stability of emulsifier-free polystyrene latexes in 1: 1 electrolyte solutions

The electrokinetic and adsorption characteristics of monodisperse emulsifier-free latexes of polystyrene (particle sizes of 0.25–0.40 μm) with surface carboxyl and sulfo groups are comprehensively studied depending on pH and the concentration of background NaCl solutions. The constants of surface carboxyl group dissociation and surface complexation, as well as the adsorption potentials of OH^? and Na⁺ ions, are calculated. The stability of latex suspensions is investigated and the coagulating concentrations of NaCl and HCl solutions are determined. An analysis of the curves plotted for the pair interaction between latex particles at different concentrations of NaCl solutions suggests that the system possesses an additional stability factor, which is probably associated with polymer chains that protrude over the particle surface into a solution.     

Investigation of ion adsorption on silver sulfide,iodide and bromide precipitates by the radioactive tracer technique

The radioactive tracer method was used to investigate the adsorption of iodide and europium ions from aqueous solution on dried isoelectric precipitates of silver sulfide, silver iodide and silver bromide. The relationship between the amount of iodide ions adsorbed on Ag₂S and the iodide ion and HNO₃ concentrations in the solution was determined. It was shown that the iodide ions adsorbed on Ag₂S could be desorbed with sulfide ions. Using Ag₂S, AgI and AgBr precipitates, a relationship between the europium ion adsorption and Eu(NO₃)₃, H₂S, NaI, NaBr and NaCl concentration in solution was established. The adsorption of europium ions was also assessed in respect to the presence of lanthanum and barium ions. For adsorption measurement iodide and europium ions were labeled with their radioactive isotopes and the amounts adsorbed were determined from the measured radioactivities of the precipitates after reaching the equilibrium between the solid phase and the solution.     

The electrosurface characteristics of dispersions of silicon and titanium aeroxides in solutions containing indifferent and specifically sorbed ions

The electrokinetic potentials of silicon and titanium aeroxides and the adsorption of potential-determining ions on them are measured as functions of pH in 10^?3-1 M NaCl solutions. The positions of the points of zero charge and the isoelectric points are determined. The adsorption of a cationic dye, oxazine 1, from aqueous solutions free of background electrolytes and in the presence of 10^?2 M NaCl is measured for both the oxides. The effect of the adsorption of the specifically sorbed cation on the electrokinetic behavior of the tested aeroxides is analyzed.     

Tin– and Titanium–Oxygen Nanostructures on the Various Hydr(oxides) Surfaces

Tin– and titanium–oxygen nanostructures were synthesized by molecular layer-by-layer deposition from the gaseous phase onto various substrates (SnO₂, SiO₂, AlOOH) using (in the course of synthesis) hydroxyl and methoxy surface groups. The electrokinetic (electrokinetic potential, isoelectric point) and adsorption (adsorption of potential-determining ions, the point of zero charge) properties of prepared composites were studied as a function of pH of NaCl background solutions. Synthesis conditions that make it possible to obtain (on the boehmite substrate) nanostructures with electrosurface characteristics similar to the properties of corresponding bulk oxides were determined.     

十二烷基硫酸钠水溶液的动态表面吸附性质

利用MPTC型气泡压力张仪研究了十二烷基硫酸钠(SDS)溶液在不同NaCl 浓度下的动态表面吸附性质, 分析了离子型表面活性剂在表面吸附层和胶束中形成双电层结构产生表面电荷对动态表面扩散过程和胶束性质的影响. 结果表明, SDS在表面吸附过程中, 表面电荷的存在会产生5.5 kJ·mol^-1的吸附势垒(E_a), 显著降低十二烷基硫酸根离子(DS^-)的有效扩散系数(D_eff). 十二烷基硫酸根离子的有效扩散系数与自扩散系数(D)的比值(D_eff/D)仅为0.013, 这表明SDS与非离子型表面活性剂不同, 在吸附初期为混合动力控制吸附机制. 加入NaCl可以降低吸附势垒. 当加入不小于80 mmol·L^-1 NaCl后, E_a小于0.3 kJ·mol^-1, D_eff/D在0.8-1.2之间, 表现出与非离子型表面活性剂相同的扩散控制吸附机制. 同时, 通过分析SDS胶束溶液的动态表面张力获得了表征胶束解体速度的常数(k₂). 发现随着NaCl 浓度的增大, k₂减小, 表明SDS胶束表面电荷的存在会增加十二烷基硫酸根离子间的排斥力, 促进胶束解体.     

Effect of background electrolytes and pH on the adsorption of Cu(II)/EDTA onto TiO2

Cu(II)/EDTA adsorption onto TiO2 has been studied with a variation of pH, ionic strength, and type of background electrolytes. Cu(II) adsorption onto TiO2 increased as ionic strength increased when NaClO4 was used as a background electrolyte. This can be explained by the increase of exp(-FPsi/RT) as a part of the electrostatic correction within a surface complexation model. Model predictions described experimental adsorption trends. Types of background anions (ClO4, Cl, NO2, NO3, SO3, and PO4) did not affect adsorption trends and adsorption amounts of Cu(II) onto TiO2. However, different trends were observed with various types of background ions used as ionic strength in EDTA and Cu(II)-EDTA adsorption. EDTA adsorption was decreased by using Na2SO3 and Na3PO4 as background ions, while NaClO4, NaCl, NaNO2, and NaNO3 showed negligible interference on the EDTA adsorption, which matched well with model predictions. The presence Na2SO3 and Na3PO4 also interfered with Cu(II)-EDTA adsorption, to a somewhat greater extent compared to EDTA adsorption, especially at lower pH. This interference was also noted in Cu(II)-EDTA adsorption with a variation of Cu(II)-EDTA concentration at constant ionic strength (3 x 10(-3) M) by using Na2SO3 and Na3PO4, especially at lower ratios of Cu(II)-EDTA to Na2SO3 and Na3PO4. These results suggest that the ratio of Cu(II)-EDTA to Na2SO3 and Na3PO4 is an important factor for the controlling of competition between these background ions and Cu(II)-EDTA onto TiO2. Model prediction generally matched well with experimental adsorption using NaClO4, NaCl, NaNO2, and NaNO3 as backgrounds ions, while a severe deviation was observed in the presence of Na2SO3 and Na3PO4. These results suggest that the mobility of copper ions as Cu(II)-EDTA can be increased from polluted area in the presence of multivalent background ions, especially as the ratio of adsorbates/background ions decreased.     

Adsorption and desorption of binary mixtures of copper and mercury ions on natural and crosslinked chitosan membranes

Copper and mercury ion adsorption on chitosan membranes was investigated in batch systems (with both single and binary solutions). The Langmuir model and its extensions (extended Langmuir, Jain-Snoeyink, and Langmuir-Freundlich models) were tested for the modeling of experimental data. Chitosan membranes presented more affinity for Hg ions than for Cu ions. The decrease of the amount of metal adsorbed on natural chitosan in binary systems (compared to single-metal solutions) showed the competition effects between the two metal ions. For glutaraldehyde-crosslinked chitosan and epichlorohydrin-crosslinked chitosan, the mixture effect was present, producing unexpected result such as higher adsorption capacities, when compared to the monocomponent solution of each metal. The desorption of the metals was also investigated, and copper and mercury ions could be selectively recovered using a combined process by using NaCl and H₂SO₄ as eluant.     

Adsorption of citrate ions on hydroxyapatite synthetized by various methods

The specific adsorption of citric acid ions at hydroxyapatite interface was investigated by the means of radioisotope method (¹⁴C) as a function of citric acid ions concentration, NaCl concentration and pH. Application of the hydroxyapatite has become wide in the biomaterial field as the Ca₁₀(OH)₂(PO₄)₆ possess biocompatibility with human hard tissue. Hydroxyapatite was synthesized using three different methods. The physical properties of the resulting powder were characterized by DTA/TG, XRD, AFM and SEM microscopy. Physicochemical qualities characterizing the electrical double layer of the hydroxyapatite/NaCl solution interface were determined. The zeta potential and the adsorption of citric acid molecule were studied as a function of pH. The point of zero charge and the isoelectric point of samples were determined. Electrical double layer parameters of hydroxyapatite/NaCl interface are influenced by a synthesis method. The points pH_pzc and pH_IEP for sample 1 are pH_pzc 7.5 and pH_IEP 3; for sample 2 pH_pzc 7.05 and pH_IEP 3, for smaple 3 pH_pzc 6.7 and pH_IEP 3. Temperature has weak influence both on pure substance and with citric acid adsorbed, as derivatographic analysis has shown, and characterization of hydroxyapatite structure may be carried out by this thermal analysis. Two phenomena are responsible for citric acid adsorption: phosphate group’s replacement at hydroxyapatite surface by citric ions parallel to intraspherical complexes formation.     

Competitive adsorption in the system: carboxymethylcellulose/surfactant/electrolyte/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The adsorption of carboxymethylcellulose (CMC) in the presence or absence of the surfactants: anionic SDS, nonionic Triton X-100 and their mixture SDS/TX-100 from the electrolyte solutions (NaCl, CaCl₂) on the alumina surface (Al₂O₃) was studied. In each measured system the increase of CMC adsorption in the presence of surfactants was observed. This increase was the smallest in the presence of SDS, a bit larger in the presence of Triton X-100 and the largest when the mixture of SDS/Triton X-100 was used. These results are a consequence of formation of complexes between the CMC and the surfactant particles. Moreover, the dependence between the amount of surfactants’ adsorption and the CMC initial concentration was measured. It comes out that the surfactants’ adsorption amount is not dependent on the CMC initial concentration and moreover, it is unchanged in the whole measured concentration range. The influence of kind of electrolyte, its ionic strength as well as pH of a solution on the amount of the CMC adsorption at alumina surface was also measured. The amount of CMC adsorption is larger in the presence of NaCl than in the presence of CaCl₂ as the background electrolyte. It is a result of the complexation reaction between Ca²⁺ ions and the functional groups of CMC belonging to the same macromolecule. As far as the electrolyte ionic strength is concerned the increase of CMC adsorption amount accompanying the increase of electrolyte ionic strength is observed. The reason for that is the ability of electrolyte cations to screen every electrostatic repulsion in the adsorption system. Another observation is that the increase of pH caused the decrease of CMC adsorption. The explanation of this phenomenon is connected with the influence of pH on both dissociation degree of polyelectrolyte and kind and concentration of surface active groups of the adsorbent.     

Electokinetic and adsorption properties of different titanium dioxides at the solid/solution interface

Six samples of titanium dioxide of different phase compositions and specific surface areas have been characterized by XRD, Raman-and FTIR spectroscopy, adsorption of nitrogen, electrophoresis. Adsorption of Zn(II) ions at the TiO₂/NaCl aqueous solution interface as well as the effect of adsorption on the structure of electrical double layer have been studied. The influence of ionic strength, pH and presence of ions on the adsorption of Zn(II) ions at the TiO₂/NaCl solution interface have also been investigated. The zeta potential, surface charge density, parameters of adsorption edge pH_50% and ΔpH_10–90% for different concentrations of basic electrolyte have been determined. Studied unpurified samples showed lower values of isoelectric point pH_iep compared with literature data due to the presence of anion impurities. The antibate dependence between pH_iep values and particle size has been established. Adsorption of Zn(II) ions using monophase samples is completed at a lower pH than for the biphase TiO₂. Appearance of the point CR3 is associated with the charge turnover from positive to negative at high values of pH and formation of Zn(OH)₂.      

Influences of salt concentration,loading and pH on strontium adsorption

The adsorption of Sr on clay which contains zeolites and montmorillonite mixtures was investigated in solutions of NaCl by means of a batch technique. Sr retention was reduced with increasing NaCl concentration from 5·10^–4 to 5·10^–1M. Distribution coefficients (K _d ) linearly increased with pH in the acidic region but they were almost independent of pH in neutral and alkaline solutions. By fitting the data of the Dubinin-Radushkevich (D-R) isotherm, the mean energies of adsorption and adsorption capacities of Sr at different pH values were calculated. The results showed that the mode of adsorption below pH 4.5 is ion exchange, while above that value a multilayer adsorption occurs. Adsorption data were fitted to the Freundlich isotherm and from empirical Freundlich parameters a site distribution function was calculated.     

Effects of Salts Containing Mono-, Di-, and Trivalent Ions on Electrical and Rheological Properties of Oil-Water Interface in Presence of Cationic Surfactant: Importance in the Stability of Oil-in-Water Emulsions

Many industrial applications of oil-in-water emulsions involve salts containing ions of different valence. The properties of the oil-water interface (e.g., interfacial tension, zeta potential and interfacial shear viscosity) are strongly influenced by the presence of these salts. This work investigates the role of NaCl, CaCl₂ and AlCl₃ on these properties of the hexane-water interface in presence of a cationic surfactant, viz., hexadecyltrimethylammonium bromide. Addition of salt enhanced the adsorption of surfactant molecules at the hexane-water interface, which increased the interfacial charge density, and consequently, the zeta potential. Interfacial shear viscosity significantly decreased in the presence of salt. The effectiveness of salt at a given concentration was in the sequence: AlCl₃ > CaCl₂ > NaCl. The hexane-in-water emulsions coarsened with time due to the coalescence of hexane droplets. The increase in droplet size with time was analyzed by a model based on the frequency of rupture of the thin aqueous film. The rate constants for coalescence were determined. The rate of coalescence increased in presence of salt.      

Role of titania incorporated on activated carbon cloth for capacitive deionization of NaCl solution

Adsorption isotherms of NaCl on activated carbon cloth (ACC) and titania-incorporated activated carbon cloth (Ti-ACC) under an electric field were investigated to deduce the role of titania in capacitive deionization (CDI) of NaCl. Electrosorption of NaCl on the ACC was significantly increased by titania incorporation, whereas its physical adsorption was considerably decreased, resulting in an improved performance of the Ti-ACC as a CDI electrode. Langmuir isotherms based on a localized and fixed amount of adsorption were suitable for the simulation of electrosorption and physical adsorption of ions on the ACC electrodes. The variances of q(m) and b of Langmuir isotherms with electric potential indicate increases in the number of ions per adsorption site and in electrosorption strength of ions by titania incorporation. A cyclic voltammetric study for ion adsorption on ACC electrodes confirms the reversibility between electrosorption and desorption of ions, regardless of titania incorporation.     

Adsorption of copper(II) ions from aqueous solutions on alumina industrial wastes

Equilibrium adsorption of copper(II) ions on red mud (alumina industrial wastes) modified by various methods was studied. The effect exerted by the nature the modifier (NaHSO₄, NaCl + HCl, and H₂SO₄) on the sorption activity of red mud was determined.     

Adsorption of sodium dodecyl sulfate onto clathrate hydrates in the presence of salt

This work presents the effect of NaCl on the adsorption of sodium dodecyl sulfate (SDS) at the cyclopentane (CP) hydrate-water interface. The adsorption isotherms and the SDS solubility in NaCl solutions are obtained using liquid-liquid titrations. The solubility data are determined at typical hydrate forming temperatures (274-287K) to ensure that the adsorption isotherms are obtained within SDS solubility limits in NaCl solutions. The isotherms show L-S (Langmuir-Step) type behaviors with 1mM and 10mM NaCl solutions while L type isotherm is determined for 25mM NaCl solutions due to the low SDS solubility in this salt concentration. Zeta potentials of CP hydrate particles in the aqueous solutions support the shape of the adsorption isotherm with the 1mM NaCl solution. The 1mM NaCl case shows the highest SDS adsorption amount among the cases with 0mM, 10mM, and 25mM NaCl solutions. In this case, the competition for adsorption between Cl(-) and DS(-) is not as strong compared to the 10 and 25mM NaCl cases and the presence of Na(+) ions may reduce the repulsion between DS(-) ions, which results in a higher adsorption of DS(-) ions and enhanced enclathration.     

Zn2+ and Sr2+ adsorption at the TiO2 (110)-electrolyte interface: influence of ionic strength, coverage, and anions

The X-ray standing wave technique was used to probe the sensitivity of Zn2+ and Sr2+ ion adsorption to changes in both the adsorbed ion coverage and the background electrolyte species and concentrations at the rutile (alpha-TiO2) (110)-aqueous interface. Measurements were made with various background electrolytes (NaCl, NaTr, RbCl, NaBr) at concentrations as high as 1 m. The results demonstrate that Zn2+ and Sr2+ reside primarily in the condensed layer and that the ion heights above the Ti-O surface plane are insensitive to ionic strength and the choice of background electrolyte (with <0.1 A changes over the full compositional range). The lack of any specific anion coadsorption upon probing with Br-, coupled with the insensitivity of Zn2+ and Sr2+ cation heights to changes in the background electrolyte, implies that anions do not play a significant role in the adsorption of these divalent metal ions to the rutile (110) surface. Absolute ion coverage measurements for Zn2+ and Sr2+ show a maximum Stern-layer coverage of approximately 0.5 monolayer, with no significant variation in height as a function of Stern-layer coverage. These observations are discussed in the context of Gouy-Chapman-Stern models of the electrical double layer developed from macroscopic sorption and pH-titration studies of rutile powder suspensions. Direct comparison between these experimental observations and the MUltiSIte Complexation (MUSIC) model predictions of cation surface coverage as a function of ionic strength revealed good agreement between measured and predicted surface coverages with no adjustable parameters.     

Naphthalene sulfonate functionalized dendrimers at the solid-liquid interface: influence of core type, ionic strength, and competitive ionic adsorbates

The adsorption of naphthalene disulfonic acid surface-functionalized dendrimers (generation 4) on to colloidal alumina particles is reported, considering the role of dendrimer core type (ammonia vs benzylhydrylamine-polylysine) and electrolyte addition on the adsorption affinity and interfacial packing and competitive adsorption. Irrespective of the dendrimer core type, the maximum adsorbed amount increased with increasing ionic strength. The adsorption affinity of a benzylhydrylamine-cored SPL-7013 increased with increasing ionic strength, whereas a decrease was observed for the ammonia-cored SPL-2923. At high ionic strengths (>or=10(-1) M NaCl) dendrimers close pack at the interface as an array of equivalent hard spheres, whereas at lower ionic strengths both dendrimers occupy a lower area than theoretically predicted for either cubic or hexagonal close packing, based on double layer repulsion. The additional attraction between dendrimers is attributed to the intercalation of the neighboring dendrons. Adsorption of SPL-2923 is enhanced by the presence of Ca2+ ions and depressed by the presence of HCO3- and HPO4(2-) ions, whereas SPL-7013 adsorption is only depressed by the presence of HPO4(2-) ions, suggesting a dendrimer-specific competitive adsorption process. This work clearly demonstrates the role of dendrimer architecture on adsorption at an interface, a process of fundamental importance to a wide range of dendrimer applications.     

Ice/Water Interface: Zeta Potential, Point of Zero Charge, and Hydrophobicity

The ice/water interface is a common and important part of many biological, environmental, and technological systems. In contrast to its importance, the system has not been extensively studied and is not well understood. Therefore, in this paper the properties of the H₂O ice/water and D₂O ice/water interfaces were investigated. Although the zeta potential vs pH data points were significantly scattered, it was determined that the isoelectric point (iep) of D₂O ice particles in water at 3.5°C containing 10⁻³ M NaCl occurs at about pH 3.0. The negative values of the zeta potential, calculated from the electrophoretic mobility, seem to decrease with decreasing content of NaCl, while the iep shifts to a higher pH. The point of zero charge (pzc) of D₂O ice and H₂O ice, determined by changes in pH of 10⁻⁴ M NaCl aqueous solution at 0.5°C after the ice particle addition, was found to be very different from the iep and equal to pH 7.0 ± 0.5. The shift of the iep with NaCl concentration and the difference in the positions of the iep and pzc on the pH scale point to complex specific adsorption of ions at the interface. Interestingly, similar values of iep and pzc were found for very different systems, such as hydrophilic ice and highly hydrophobic hexadecane droplets in water. A comparison of the zeta potential vs pH curves for hydrophilic ice and hydrophobic materials that do not possess dissociative functional groups at the interface (diamond, air bubbles, bacteria, and hexadecane) indicated that all of them have an iep near pH 3.5. These results indicate that the zeta potential and surface charge data alone cannot be used to delineate the electrochemical properties of a given water/moiety interface because similar electrical properties do not necessary mean a similar structure of the interfacial region. A good example is the aliphatic hydrocarbon/water interface in comparison to the ice/water interface. Although the experiments were carried out with care, both the zeta potential, measured with a precise ZetaPlus meter, and ΔpH values (a measure of surface charge) vs pH were significantly scattered, and the origin of dissemination of the data points was not established. Differently charged ice particles and not fully equilibrium conditions at the ice/water interface may have been responsible for the dissemination of the data.     

Synthesis of phosphorus-modified poly(styrene-co-divinylbenzene) chelating resin and its adsorption properties of uranium(VI)

A new phosphorus-modified poly(styrene-co-divinylbenzene) chelating resin (PS–N–P) was synthesized by P,P-dichlorophenylphosphine oxide modified commercially available ammoniated polystyrene beads, and characterized by Fourier transform infrared spectroscopy and elemental analysis. The adsorption properties of PS–N–P toward U(VI) from aqueous solution were evaluated using batch adsorption method. The effects of the contact time, temperature, pH and initial uranium concentration on uranium(VI) uptake were investigated. The results show that the maximum adsorption capacity (97.60 mg/g) and the maximum adsorption rate (99.72 %) were observed at the pH 5.0 and 318 K with initial U(VI) concentration 100 mg/L and adsorbent dose 1 g/L. Adsorption equilibrium was achieved in approximately 4 h. Adsorption kinetics studied by pseudo second-order model stated that the adsorption was the rate-limiting step (chemisorption). U(VI) adsorption was found to barely decrease with the increase in ionic strength. Equilibrium data were best modeled by the Langmuir isotherm. The thermodynamic parameters such as ?G ₀, ?H ₀ and ?S ₀ were derived to predict the nature of adsorption. Adsorbed U(VI) ions on PS–N–P resin were desorbed effectively (about 99.39 %) by 5 % NaOH–10 % NaCl. The synthesized resin was suitable for repeated use.