The influence of chloride ions on the kinetics of iron dissolution

The anodic dissolution of pure iron was studied in oxygen-free solutions at high concentrations of chloride and hydrogen ions at 25°C under potentiostatic steady-state conditions. In the range c_H⁺ ? 1 M the following kinetic data were obtained: Tafel slope b₊ ? +100 mV, electrochemical reaction order related to C_H⁺, n_+.H⁺ = +1·1, and electrochemical reaction order related to the chloride ion concentration, n_+,Cl^? = +0·6. These values cannot be correlated to the currently proposed mechanisms of iron dissolution, another mechanism is suggested for the described conditions. The correlations to known mechanisms are discussed.     

Ortho-experiment study on formation of potassium sulfate from the system of K+, Ca2+, NH4+ ‖ Cl−, SO42− in H2O

An ortho-experiment design and the analysis method of mathematical statistics are adopted to study the conversion of gypsum and potassium chloride to potassium sulfate in the system of K⁺, Ca²⁺, NH₄⁺ ‖ Cl^?, SO₄^2? in H₂O. Optimal reaction parameters and engineering mean are acquired to attain a conversion yield of potassium chloride of 94.52%.     

Study of ClO2 generation reaction via experimental data of aqueous mixed electrolyte solutions: HClO4–NaCLO3–H2O and HCLO4–NaCl–H2O

A new model for mixtures (two and more solutes) of aqueous electrolyte solutions was found to be as accurate as other models, or more accurate, in prediction of new experimental results of the ternary systems HClO₄–NaClO₃–H₂O and HClO₄–NaCl–H₂O. The water activity values are then used to study the mechanism of the chloride–chlorate reaction, generating chlorine dioxide: 2H⁺ + ClO^?₃ + Cl^? → ClO₂ + 1/2Cl₂ + H₂O Spectrophotometric measurements of the production rate of ClO₂ have confirmed that the intermediary species in the proposed equilibrium H⁺(mH₂O) → H⁺(m-n)H₂O + nH₂O Is actually H(H₂0)⁺_m-n. The final kinetic expression for the reaction rate of chlorine dioxide generation, used in pulp bleaching, is then derived to explain the high order with respect to acid concentration.     

Scavenging Ratios in an Urban Area in the Spanish Basque Country

For a period of six years (1995–2000) the scavenging ratio, which is the ratio of a pollutant's concentration in water to its concentration in air, collected at an urban site in the Spanish Basque Country was studied. The aerosol is characterized by SO₄ ^2? and NO₃? with 1.79 and 1.61 μg m^?3, respectively. Greater fractions of SO₄ ^2?, NO₃?, and NH₄+ ions were present in the fine particle range, while greater fractions of other ions appeared in the coarse range. The most important species found in the precipitation is SO₄ ^2? with 3.0 mg l^?1. NO₃?, Ca²⁺, and Cl^? are the second most important ions. The volume-weighted mean concentration of H⁺ is 4.6 μg l^?1 (pH = 5.3). The concentration of all analyzed ions (except H⁺) decreases throughout the rain event, showing the washout phenomenon of the rainwater. The scavenging ratio for the anthropogenic ions NO₃?, SO₄ ^2?, NH₄+, and K⁺ is lower than the scavenging ratio for the marine-terrigenous ions, Cl^?, Na⁺, and Ca²⁺.     

Kinetics of armco iron dissolution in an anhydrous methanol and hydrochloric acid solution

The polarization behaviour of Armco iron in anhydrous solutions of CH₃OH+HCl and CH₃OH+HCl+LiCl was studied by the potentiostatic method. The following reaction orders were found for the anodic process: Z_a(Cl^?) = 1.7 –1.82 and Z_a(H⁺) = 0. The following mechanism of dissolution is proposed: Fe+Cl^? ? FeCl^?_ads, FeCl^?_ads+Cl^? → FeCl₂+2e (rate-determining step), FeCl₂?FeP²⁺ + 2Cl^?.     

A Novel Oxidation of Valine by N-Bromophthalimide in the Presence of Ruthenium(III) Chloride as a Homogeneous Catalyst

Kinetics of Ruthenium(III) [Ru(III)] chloride catalyzed oxidation of valine (Val) has been studied by N-bromophthalimide (NBP) in the acidic medium at 35 °C. The reaction rate follows first-order and zero-order dependence with respect to [NBP] and [Val]. First-order kinetics was observed for Ru(III) chloride at low range of concentrations and tending towards zero-order at higher concentrations. A negative effect was observed for [H⁺] and [phthalimide], while a positive effect was observed for [Cl^?] on the reaction rate. Hg(OAc)₂, ionic strength (I), and dielectric constant (D) of the medium did not change significantly the reaction rate. The rate constants as a function of temperature (298–318 K) were used to calculate activation parameters of the oxidation of Val by NBP. A plausible mechanism was proposed to explain the results of kinetic studies, reaction stoichiometry and product analysis.     

The role of Cl− in a Li+-ZnO-Cl− catalyst on the oxidative coupling of methane and the oxidative dehydrogenation of ethane

The effect of Cl^? ion addition to a Li⁺-ZnO catalyst has been studied with respect to the oxidative coupling of CH₄ and the oxidative dehydrogenation (OXD) of C₂H₆. Increasing the Cl/Li ratio from 0.65 to 0.90 had relatively little effect on the CH₄ conversion, whereas the C₂H₄/C₂H₆ ratio was enhanced significantly as a result of an increase in the OXD reaction rate. Conversely, loss of Cl^? from the catalyst during the reaction had a much more deleterious effect on ethane OXD activity than on methane coupling activity. Addition of Cl^? ions at a Cl/Li ratio of 0.9 caused a decrease both in the number of basic sites and in the basic strength of these sites, as determined by temperature-programmed desorption of CO₂. The similarities between the results obtained over Li⁺-ZnO-Cl^? catalysts and those previously reported for Li⁺-MgO-Cl^? catalysts confirm that basicity of the host oxide plays only a minor role in determining the properties of these chlorided catalysts.     

Simultaneous Monitoring of pH and Chloride (Cl−) in Brain Slices of Transgenic Mice

Optosensorics is the direction of research possessing the possibility of non-invasive monitoring of the concentration of intracellular ions or activity of intracellular components using specific biosensors. In recent years, genetically encoded proteins have been used as effective optosensory means. These probes possess fluorophore groups capable of changing fluorescence when interacting with certain ions or molecules. For monitoring of intracellular concentrations of chloride ([Cl⁻]_i) and hydrogen ([H⁺] _i) the construct, called ClopHensor, which consists of a H⁺- and Cl⁻-sensitive variant of the enhanced green fluorescent protein (E²GFP) fused with a monomeric red fluorescent protein (mDsRed) has been proposed. We recently developed a line of transgenic mice expressing ClopHensor in neurons and obtained the map of its expression in different areas of the brain. The purpose of this study was to examine the effectiveness of transgenic mice expressing ClopHensor for estimation of [H⁺]_i and [Cl⁻]_i concentrations in neurons of brain slices. We performed simultaneous monitoring of [H⁺]_i and [Cl⁻]_i under different experimental conditions including changing of external concentrations of ions (Ca²⁺, Cl⁻, K⁺, Na⁺) and synaptic stimulation of Shaffer’s collaterals of hippocampal slices. The results obtained illuminate different pathways of regulation of Cl⁻ and pH equilibrium in neurons and demonstrate that transgenic mice expressing ClopHensor represent a reliable tool for non-invasive simultaneous monitoring of intracellular Cl⁻ and pH.     

Kinetics of absorption of oxygen in aqueous solutions: (1) acidic chromous chloride, (2) acidic titanous chloride and (3) ammoniacal cuprous chloride

The kinetics of absorption of oxygen in aqueous solutions of acidic chromous chloride and ammoniacal cuprous chloride were studied in a stirred cell. Both these reactions were found to be very fast and the theory of gas absorption accompanied by fast pseudo-m^th order reaction was used to analyse the results. The kinetics of absorption of oxygen in aqueous acidic solutions of titanous chloride were investigated in a bubble column where the reaction was found to be free from diffusional resistance.The reaction between oxygen and chromous chloride was found to be first order with respect to oxygen and second order with respect to chromous ion. The value of the third order rate constant for 2·0 M HCl solution was found to be 2·7 × 10¹² (cm³/g mole)² sec^?1 at 30°C.The oxidation of titanous chloride was observed to be zero order with respect to titanous ion and first order with respect to oxygen. The value of the first order rate constant was found to be 8·6 × 10^?3 sec^?1. It has been suggested that in this case hydrolysis precedes the oxidation and it is likely that the reaction of oxygen with the hydrolysed product is the rate controlling step.The absorption of oxygen in aqueous ammoniacal cuprous chloride was found to be third order; first order with respect to each species, namely Cu⁺, oxygen and free ammonia. The value of the third order rate constant was found to be 7·5 × 10¹⁰ (cm³/g mole)² sec^?1. The higher value of the rate constant compared to that for oxidation of acidic solutions of curpous chloride indicates that the presence of a complexing agent such as ammonia increases the rate of absorption of oxygen substantially.     

A diamino based resin modified silica composite for the selective recovery of tungsten from wastewater

A new adsorbent was developed by synthesizing 1,8‐diaminonaphthalene formaldehyde resin (DANFR) and coating it over the surface of silica gels. The silica composite was then treated with HCl for the activation of binding sites (?NH₃⁺Cl^?) on its surface. The structure of DANFR and its coating over the silanols were thoroughly characterized. Further, the adsorbent was applied to remove tungsten (W) from printed circuit board recycling unit wastewater that contained various co‐metal ions such as Na⁺, K⁺, Ca²⁺, Mg²⁺, Pb²⁺, NH₄⁺, Zn²⁺, Cu²⁺ and Mn²⁺. The selective removal was achieved due to the anion exchange mechanism of Cl^? with W(VI) while other cations get repelled from the surface (?NH₃⁺) of the DANFR‐silica composite. X‐ray photoelectron spectroscopy studies, Raman spectra and overlay chromatograms of ion chromatography demonstrated selective separation of WO₄^2? species from the wastewater. A removal capacity of 55.32 mg g^?1 for W(VI) was achieved from the wastewater within 45 min of reaction (pH ca 6.0). Simultaneous treatment with neat aqueous solution of W brings out 63.27 mg g^?1 of W(VI) removal. Finally, recovery of WO₄^2? ions and regeneration of the adsorbent were carried out by using alkaline solution which demonstrated successful desorption, as investigated by using ion chromatography. © 2016 Society of Chemical Industry     

Influence of H+ and Cl− ions on inhibitive performance of poly(aniline) for iron corrosion in acid

The inhibition effect of poly(aniline) on pure iron corrosion in 1M HCl and with various H⁺ ions and Cl^? ions concentrations was investigated by the polarization and electrochemical impedance spectroscopy methods. The results showed that poly(aniline) suppressed both cathodic and anodic processes of iron dissolution in 1M HCl by its adsorption on the iron surface according to Langmuir's adsorption isotherm. The inhibition efficiency of poly(aniline) was found to increase with the inhibitor concentrations. Further, it was observed that, there was no significant variation in corrosion potential (E_corr) values in the presence of inhibitors suggesting that, this polymer behaved as mixed type inhibitor. Similar studies for the inhibitor at 500 ppm in various concentrations of H⁺ and Cl^? ions, have shown that the inhibition efficiency decreases with decrease in concentrations of H⁺ ions and Cl^? ions in aqueous solution. It reveals that, the adsorption of inhibitor on iron surface is by more cationic form of inhibitor and higher efficiency at higher H⁺ and Cl^? ions is due to enhanced adsorption of cat ionic form of inhibitor molecules. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Characterization of acidic pumice and determination of its electrokinetic properties in water

In this study some characterization tests of acidic pumice were performed using various techniques such as Mercury Intrusion Porosimetry (MIP), Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Thermal Analysis (DTA–TG), FTIR and its electrokinetic properties in water such as zeta potential (ZP), isoelectrical point (IEP), indifferent, specifically adsorbing and potential determining ions were determined. The results showed that (i) pore dimensions of the irregular or oval and fibrous cavities of the pumice varied between 0.05 μm and 2 mm depending on its particle size and these cavities usually did not intersect each other; (ii) as the pumice particle size decreases, both total pore volume and total pore surface area significantly decrease as well; (iii) pumice maintained its thermal stability approximately up to 900 °C; (iv) pumice had a negative surface charge between pH 1.8 and 11.4; and (v) Cl^?, Br^? SO₄^2?, Na⁺, Al(OH)₂⁺ and Ca²⁺ ions were indifferent, C₁₆H₃₃(CH₃)₃N⁺, Al³⁺ and Al(OH)²⁺ cations were specifically adsorbing and, H⁺ and OH^? ions were potential determining ions for acidic pumice.     

Electrokinetic Properties of Vermiculite and Expanded Vermiculite: Effects of pH,Clay Concentration and Mono- and Multivalent Electrolytes

Abstract

In this study, the zeta potential values of vermiculite and expanded vermiculite were measured to determine the effect of pH, clay concentration, and various mono- and multivalent electrolytes including NaCl, KCl, NH₄Cl, NaNO₃, NaClO₄, Na₂SO₄, Na₂CO₃, Na₃PO₄·12H₂O, MgCl₂·6H₂O, CaCl₂·2H₂O, BaCl₂, SrCl₂·6H₂O, CuCl₂·2H₂O, CoCl₂·6H₂O, NiCl₂, AlCl₃, and CrCl₃·6H₂O on the electrokinetic properties of vermiculite samples. It was found that generally the measured zeta potential values of expanded vermiculite for the studied systems were slightly more negative than that of vermiculite. The pH profiles of vermiculite and expanded vermiculite at acidic, natural, and basic pH values were obtained to determine the effect of time on the pH values of clay suspensions. The zeta potential measurements showed that the surface charge of clay particles was negative in water. The isoelectric point of vermiculite and expanded vermiculite were determined as pH 2.30 and 2.57, respectively. Divalent cations (Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺), heavy metal ions (Cu²⁺, Ni²⁺, and Co²⁺) and trivalent cations (Al³⁺ and Cr³⁺) were potential determining ions for vermiculite and expanded vermiculite particles. Moreover, divalent and trivalent cations caused the change of surface charge from negative to positive. On the other hand, monovalent cations (Na⁺, K⁺ and NH₄ ⁺), monovalent anions (Cl^?, NO₃ ^?, and ClO₄ ^?) and multivalent anions (SO₄ ^2?, CO₃ ^2?, and PO₄ ^3?) acted as indifferent ions for these clay particles.     

The Role of Cations in Some Inorganic Hydrolysis Reactions

Cations which shift certain equilibria from left to right by forming a compound with one of the reaction products were investigated with respect to their kinetic role in the process. Silver ions have no influence on the rate of the hydrolysis of cyanogen iodide. Similarly, cations which form sparingly soluble carbonates do not influence the rate of hydration of carbon dioxide. On the other hand, the hydrolysis of chlorine is accelerated by Ag⁺ and, to a lesser extent, by Cd²⁺ and Fe(III). It is shown that the effect is not due simply to a bimolecular reaction between chlorine and the cation. In the case of Ag⁺, heterogeneous catalysis may play some role, in analogy with the solvolysis of organic halides. In the case of Cd²⁺, there is spectrophotometric evidence for compounds between Cl₂ and HOCl on the one hand, and the cation on the other. It is suggested that these compounds interconvert more rapidly than do the parent substances. A similar mechanism may be operative in the case of Fe(III), and, possibly, also in the case of Ag⁺.     

Solvatation des ions par le nitromethane

The direct potentiometric determination of the normal potentials of Cu/Cu⁺, Cu⁺/Cu²⁺, Ag/Ag⁺, Hg/Hg²⁺₂ couples in nitromethane and the comparison of these values with the normal potentials in aqueous solution makes possible the calculation of solvation coefficients γ_(t)(Mⁿ⁺) of the corresponding cations; the Strehlow hypothesis (γ(Fc) = γ(Fc⁺)) has been used. An indirect method using the determination of the solubility constants of alkaline chlorides and alkaline earth chlorides leads to the normal potentials of alkaline and Mg²⁺ cations and thus to the γ_(t) values of these ions.The measures of the AgX^-₂ stability constants and of the AgX solubility constants lead to the γ_(t) values of X^? and AgX^?₂ anions (X^? = Cl^?, Br^?, I^?, Scn^?, CH₃CO^?₂, CN^?, BrO^?₃, (C₆H₅)₄B^?). A comparison of γ_(t)(H⁺) and γ_(t)(Ag⁺) for 20 solvents is given.     

UV-LEDs assisted peroxymonosulfate/Fe<Superscript>2+</Superscript> for oxidative removal of carmoisine: The effect of chloride ion

The performance of UVA-LEDs assisted peroxymonosulfate (PMS)/Fe²⁺ system was evaluated on carmoisine (E122) decolorization. Complete color removal was obtained under the conditions of pH=3.0, PMS=1.5 mM, Fe²⁺=1 mM and 25 min reaction time. UVA-LEDs were preferable compared to conventional UVA lamp in terms of decolorization. The functions of Co²⁺, Cu²⁺, Mn²⁺ and Fe²⁺ were compared and their results showed that Co²⁺ and Fe²⁺ had the highest efficiencies. Moreover, the presence of chloride ion showed a double role in different concentrations in which promotional effect was observed in 100 mM Cl^?<, while inhibitory effect occurred in 1–10 mM Cl^?. However, the high concentration of chloride had no influence on mineralization of E122. The scavenging results demonstrated that the UV irradiation increased the contribution of HO^?. In addition, in the presence of chloride ion, HOCl along with sulfate and hydroxyl radicals were the major oxidative agents.     

Uranyl Halide Species Sorbed on Ion Exchangers

Uranyl ions were sorbed on a cation and anion exchanger from fluoride, chloride, and bromide solutions. The visible and IR spectra of the sorbed species were recorded. The species identified were UO₂F^?₃, UO₂Cl⁺, UO₂Cl^?₃ and UO₂Cl^2?₄, UO₂Br⁺ and UO₂Br^2?₄. Analysis of the spectra obtained made possible the determination of the coordination number and the symmetry of the species, i.e., the cationic species have the coordination number six, while the anionic species have the coordination number four.     

Aluminium alloys in sulphuric acid Part I: Electrochemical behaviour of rotating and stationary disc electrodes

Anodic oxidation of various aluminium alloys was investigated by means of rotating disc electrodes in 3 M H₂SO₄ as a function of Cl^–, F^–, Zn²⁺ and In³⁺ concentration. Al-In, Al-Zn/In and Al-Zn/Sn alloys yielded current-potential curves at the lowest overpotentials and faradaic efficiencies for anodic oxidation of up to 98% at currents 50 mA cm^–2. While these alloys were electrochemically active in the presence of chloride as the only additive in sulphuric acid, binary aluminium alloys with Ce, Ga, La, Nd, Sn, Ta, Te, Ti or Tl were only active when Cl^–, Zn²⁺ and In³⁺ species were added to the electrolyte. With the exception of Al-Ga, binary alloys displayed high faradaic efficiencies of up to 95%. Fluoride additives resulted in current-potential curves at even more negative potentials than those with chlorides. In contrast to Cl^–, fluoride ions are consumed during the aluminium oxidation process due to complexation with Al(III).     

The effect of some soluble inorganic admixtures on the early hydration of portland cement

The effects of the soluble chlorides, bromides, nitrates, sulphates and acetates of Ca²⁺, Mg²⁺, Li⁺, Na⁺ and Zn²⁺ as well as the corresponding mineral acids on the early hydration of neat Portland cement pastes have been studied. Both the cations and anions are ranked according to their general effectiveness as accelerators of the hydration of the Ca₃SiO₅ phase: Ca²⁺>Mg²⁺>Li⁺>Na⁺>H₂O>Zn²⁺ and OH^? >Cl^?>Br^? >NO₃^?SO₄²～H₂O > CH₃CO₂^?.     

Electrode reactions of nickel(II) at mercury electrodes in aqueous solutions of pyridine at high ionic strengths

At high ionic strength the ion pair (NiPy²⁺₄, nX^?) or complex (NiPy₄X₂), n = 0, 1, 2; X^? = Cl^?, Br^?, SCN^?, N^?₃, F^?, NO^?₃, ClO^?₄; is adsorbed at the surface of mercury electrode. Under specified conditions in chloride, bromide, and thiocyanates solutions the electroreduction is preceded by a crystallization of a complex on the electrode surface. The inductive role of specifically coadsorbed Cl^? ions is discussed.