Re-evaluation of Activity Coefficients in Dilute Aqueous Hydrobromic and Hydriodic Acid Solutions at Temperatures from 0 to 60 °C

Simple two-parameter Hückel equations can be used for the calculation of the activity coefficients in aqueous hydrobromic and hydriodic acid solutions at temperatures from 0 to 60 °C and from 0 to 50 °C, respectively, at least up to a molality of 0.5 mol·kg^?1. The data measured by Macaskill and Bates (J. Solution Chem. 12:607–619, 1983) at 25 °C and those measured by Hetzer et al. (J. Phys. Chem. 68:1929–1933, 1964) at various temperatures on galvanic cells without a liquid junction were used in the parameter estimations for the hydrogen bromide (HBr) and hydrogen iodide (HI) solutions, respectively. The latter data consist of sets from 0 to 50 °C at intervals of 5 °C. The parameter values for HBr solutions were also tested using the numerous galvanic cell points from the other three data sets existing in the literature for hydrobromic acid solutions and covering wide range of temperatures from 0 to 60 °C. It was observed in the parameter estimations and tests that all of the estimated parameters are independent of the temperature. The recommended parameter values were additionally tested using the isopiestic data of Macaskill and Bates (see the citation above) and those of Harned and Robinson (Trans. Faraday Soc. 37:302–307, 1941) for dilute HBr and HI solutions at 25 °C, respectively. In more concentrated solutions up to a HBr molality of 4.5 mol·kg^?1 and up to a HI molality of 3.0 mol·kg^?1, an extended Hückel equation was used, which contains an additional quadratic term with respect to the molality. The parameters for the extended Hückel equations were determined from these isopiestic data and tested using these data and the existing galvanic cell data. The activity and osmotic coefficients calculated from the resulting equations are recommended in the present study for the more concentrated solutions. The recommended values are compared to the activity values reported in several previous tabulations.     

Raman Spectroscopic Study of Aluminum Silicate Complexes at 20°C in Basic Solutions

Raman spectroscopic measurements were performed at ambient temperature onaqueous silica-bearing solutions (0.005 < m _Si < 0.02; 0 < pH < 14). The spectraare consistent with the formation of monomeric Si(OH)^o ₄, SiO(OH)^– ₃ andSiO₂(OH)^2– ₂ species at acid to neutral, basic, and strongly basic pH, respectively.Raman spectra of aqueous Al-bearing solutions at basic pH confirm thepredominance of the Al(OH)^– ₄ species in a wide concentration range (0.01 < m _Al < 0.1).Raman spectra of basic solutions (12.4 < pH < 14.3), containing both Al andSi, exhibit a strong decrease in intensities of SiO(OH)^– ₃, SiO₂(OH)^2– ₂, andAl(OH)^– ₄ bands in comparison with Al-free Si-bearing and Si-free Al-bearingsolutions of the same metal concentration and pH, suggesting the formation ofsoluble Al—Si complexes. The amounts of complexed Al and Si derived fromthe measurements of the Al and Si band intensities in strongly basic solutions(pH 14) are consistent with the formation, between Al(OH)^– ₄ andSiO₂(OH)^2– ₂, of the single Al—Si dimer SiAlO₃(OH)^3– ₄ according to the reactionSiO₂(OH)^2– ₂ + Al(OH)^– ₄ SiAlO₃(OH)^3– ₄ + H₂OAt lower pH ( 12.5) the changes in band intensities are consistent with theformation of several, likely more polymerized, Al—Si complexes.     

Conductivity Studies of Dilute Aqueous Solutions of Oxalic Acid and Neutral Oxalates of Sodium, Potassium, Cesium, and Ammonium from 5 to 35°C

Conductivity measurements of oxalic acid and neutral oxalates (disodium oxalate, dipotassium oxalate, dicesium, and diammonium oxalate) were performed on dilute aqueous solutions, c < 3 × 10^–3 mol-dm^–3, from 5 to 35°C. These data and those available from the literature were analyzed in terms of dissociation steps of oxalic acid, the Onsager conductivity equation for neutral oxalates, the Quint–Viallard conductivity equation for the acid, and the Debye–Hückel equation for activity coefficients, to give the limiting equivalent conductances of bioxalate anion ;(HC₂O₄ ^–) and oxalate anion (1/2C₂O₄ ^2–) and the corresponding dissociation constants K ₁ and K ₂.     

Photostability Study of Nanoporous TiO2 Film Electrodes in Basic Solutions

The nanoporous TiO2 film electrodes have been prepared by a sol-gel deposition process The photostability of the electrodes in basic solutions has been studied. The results show that the photostability of the electrodes decreases rapidly in strong basic solutions with or without methanol. The reaction of holes to O^2- produces active O^2- atoms and the products O^2- atomsoxidize Ti^3 to Ti^4 on TiO2 film surface and subsurface. This results in the TiO2 film electrodes unstable in basic solutions both without methanol and with too low concentration.     

Electrical conductivity of titanium pyrophosphate between 100 and 400 °C: effect of sintering temperature and phosphorus content

The synthesis of titanium pyrophosphate is carried out, and the material is sintered at different temperatures between 370 and 970 °C. Yttrium is added during the synthesis to act as acceptor dopant, but it is mainly present in the material in secondary phases. The conductivity is studied systematically as a function of sintering temperature, pH₂O, pO₂, and temperature (100–400 °C). Loss of phosphorus upon sintering above 580–600 °C is confirmed by energy dispersive spectroscopy and combined thermogravimetry and mass spectrometry. The conductivity decreases with increasing sintering temperature and decreasing phosphorus content. The highest conductivity is 5.3?×?10^?4 S cm^?1 at 140 °C in wet air (pH₂O?=?0.22 atm) after sintering at 370 °C. The conductivity is higher in wet atmospheres than in dry atmospheres. The proton conduction mechanism is discussed, and the conductivity is attributed to an amorphous secondary phase at the grain boundaries, associated with the presence of excess phosphorus in the samples. A contribution to the conductivity by point defects in the bulk may explain the conductivity trend in dry air and the difference in conductivity between oxidizing and reducing atmospheres at 300–390 °C. Slow loss of phosphorus by evaporation over time and changes in the distribution of the amorphous phase during testing are suggested as causes of conductivity degradation above 220 °C.     

Solubilities, Densities and Refractive Indices of Rubidium Chloride or Cesium Chloride in Ethanol Aqueous Solutions at Different Temperatures

The data of solubilities, densities and refractive indices of rubidium chloride or cesium chloride in the system CEHsOH-H2O were measured by using a simple accurate analytical method at different temperatures, with mass fractions of ethanol in the range of 0 to 1.0. In all cases, the presence of ethanol significantly reduced the solubility of rubidium chloride and cesium chloride in aqueous solution. The solubilities of the saturated solutions were fitted via polynomial equations as a function of the mass fraction of ethanol. The CsC1-C2H5OH-H2O ternary system appeared in two liquid phases： alcoholic phase and water phase, when the mass fractions of ethanol were in the range of 10.37% to 49.59% at 35 ℃. Density and refractive index were also determined for the same ternary systems with varied unsaturated salt concentrations. Values for both experiment and theory were correlated with the salt concentrations and proportions of alcohol in the solutions. The equations proposed could also account for the saturated solutions.     

The Activity Coefficients of HCl in HCl–Na2SO4 Solutions from 0 to 50°C and Ionic Strengths Up to 6 Molal

The electromotive force of HCl−Na₂SO₄ solutions has been determined from 5 to 50°C and ionic strengths from 0.5 to 6m with a Harned type cell The results have been used to determine the activity coefficient of HCl in the mixtures. The activity coefficiencts have been analyzed with the Pitzer equations to account for the ionic interactions. The measurements were used to determine interaction coefficients (β⁰, β¹) for NaHSO₄ solutions from 5 to 50°C. The model represents the mean activity coefficients HCl in the mixtures to ±0.005 over the entire temperature and concentration range of the measurements. The results have been combined with literature data to provide parameters that are valid from 0 to 250°C for NaHSO₄ solutions.     

Ionic Interactions of Calcium Sulfate Dihydrate in Aqueous Calcium Chloride Solutions: Solubilities, Densities, Viscosities, and Electrical Conductivities at 30°C

Different physicochemical properties such as solubilities, densities, viscosities, and electrical conductivities of calcium sulfate dihydrate in aqueous calcium chloride solutions have been measured at 30°C to examine the ionic interactions in the system. Density values have been used to calculate the mean apparent molar volumes of ternary mixtures. Viscosity values have been analyzed using different empirical equations and the experimental values of viscosity were combined with conductivity values to get the Walden product. The experimental data have been fitted by a polynomial equation for least-squares analysis to obtain the coefficients and the standard errors. Results have been examined in the light of the structure making or structure breaking effect of the various ions present in the solution.     

Isotope Effects and Hydrogen Exchange Mechanism in Compounds Having Labile Aliphatic CÄH Bonds in Basic Liquid Ammonia Solutions

Specific features of the stepwise hydrogen exchange mechanism and transition state structure in the systems acetophenone-liquid ammonia in the absence of foreign compounds and in the presence of bases and toluene-liquid ammonia in the presence of potassium amide were studied in terms of an approach based primary and secondary kinetic isotope effects of the substrate and the solvent. The mechanisms of reactions involving acetophenone and toluene were compared. In the first case, an elementary act of CH-acid ionization is contributed to a small extent by diffusion-controlled separation of the carbanion and ammonia molecule. hydrogen exchange in toluene is characterized by complete absence of the internal ion pair return effect. The ratio k _D NH ₃/k _T NH ₃ for hydrogen exchange in acetophenone tends to decrease on addition of bases (with simultaneous increase in its rate), which may be explained by formation of an adduct via interaction between the unshared electron pair on the heteroatom in the base molecule and the carbonyl carbon atom. The anomalous temperature dependence of k _D NH ₃/k _T NH ₃ for hydrogen exchange in toluene is interpreted as a result of contribution of side metalation of the CÄH bond by potassium amide. The change in the solvent protophilicity due to replacement of the "light" solvent by deuterated one differently affects the kinetics and mechanism of hydrogen exchange in acetophenone and toluene. Measurements of the -deuterium effect gave information on the mode of angular deformation of CÄD bonds in the methyl group of toluene in the hydrogen exchange transition state.     

Synthesis and Properties of Solid Solutions in The FeVMoO7–CrVMoO7 System

X-ray phase analysis (XRD), differential thermal analysis (DTA) and IR spectroscopy have shown that continuous substitution solid solutionsin are formed in the FeVMoO₇–CrVMoO₇ system. With increasing the degree of Cr³⁺ ion incorporation into the FeVMoO₇ structure, a crystal lattice contraction of the Fe_1–xCrxVMoO₇ solid solution arise. Elevation of temperature of its incongruent melting and gradual shifting of the corresponding IR absorption bands towards higher wavenumbers have been noticed, as well. The solid product of incongruent melting for x≤0.5 is the Fe_4–yCr_yV₂ Mo₃ O₂₀ solid solutions phase, whereas for x>0.5 Fe_2–zCr_z(MoO₄)₃ and Fe_2–u Cr_u O₃ solid solutions. This revised version was published online in July 2006 with corrections to the Cover Date.     

UV-Visible Absorption Characteristics of TEOS-Derived and Cr-Doped Silica Sonogels Aged in Different pH Solutions and Heat Treated up to 600°C

Cr-doped xerogels were obtained by sol-gel process from the acid-catalyzed and ultrasound-stimulated hydrolysis of tetraethoxysilane (TEOS) with addition of CrCl₃6H₂O in water solution during the liquid step of the process. The gels were aged immersed in different pH solutions for about 30 days, after that they were allowed to dry. The samples were annealed at temperatures ranging from 40 to 600°C and analyzed by UV-visible absorption spectroscopy. Cr³⁺ is the preferable oxidation state of the chromium ion in the gels annealed up to 250–300°C, in the case of aging in solutions of pH = 5 and 11. A high UV absorption below 320 nm, due to the host gel, and different absorption bands, depending on the temperature, due to the chromium ion were observed in the xerogels at temperatures below 250°C, in the case of aging in solutions of pH = 1 and 2. These absorption bands have not been assigned. Above 300°C up to 600°C, Cr⁵⁺, and possibly Cr⁶⁺, are the preferable oxidation states of the chromium ion independent of the pH of the aging solution, so the xerogels turn to a yellowish appearance in all cases.     

General Solutions to Some Types of Solitons in the Atmosphere

In terms of the Bargmann potential technique the problem of solutions to atmospheric solitary waves is investigated with the derivation of the solutions and their dispersion relations of such solitary waves as of inertial, internal gravity and Rossby modes, and some further appreciation and significant outcome have been achieved.     

Conversion of Heterocycles of The Dihydrothiazine–Thiazoline Series in Aqueous Solutions

When heterocycles of the dihydrothiazine–thiazoline series are treated with an aqueous solution of base, they undergo ring opening, leading to formation of ureidoalkanethiols. Study of solvolysis of the heterocycles when treated with ammonia permitted us to observe a novel heterocyclic ring opening reaction, occurring with formation of 2(3)-guanidinoalkanethiols. We have developed a novel preparative method for obtaining 2(3)-guanidinoalkanethiols.     

Fractal analysis of pit morphology of Inconel alloy 600 in sulphate,nitrate and bicarbonate ion-containing sodium chloride solution at temperatures of 25–100 °C

Pit morphology of Inconel alloy 600 in sulphate (SO₄ ^2-), nitrate (NO₃ ^-) and bicarbonate (HCO₃ ^-) ion-containing 0.5 M sodium chloride (NaCl) solution was analysed in terms of fractal geometry as functions of solution temperature and anion concentration using the potentiostatic current transient technique, scanning electron microscopy, image analysis and ac-impedance spectroscopy. Potentiostatic current transients revealed that the pitting corrosion is facilitated by the increase in solution temperature, irrespective of anion additives, and that it is hindered by the increase in NO₃ ^- and HCO₃ ^- ion concentration, regardless of solution temperature. Above 60 °C, it was also found that the addition of SO₄ ^2- ions impedes pit initiation, but enhances pit growth. The value of fractal dimension D _f of the pits increased with increasing solution temperature and with decreasing NO₃ ^- and HCO₃ ^- ion concentration. Moreover, the value of D _f increased above 60 °C with increasing SO₄ ^2- ion concentration. This is caused by the increase in the ratio of pit perimeter to pit area, implying the formation of pits with micro-branched shape due to the acceleration of the local attack in the pits. From the decrease of the depression parameter with increasing solution temperature, it is inferred that the roughness of the pits increased with increasing solution temperature. In addition, the depression parameter was found to increase with increasing NO₃ ^- and HCO₃ ^- ion concentration. But, above 60 °C, in the case of SO₄ ^2- ion addition, the depression parameter decreased with increasing SO₄ ^2- ion concentration. From the experimental findings, the three-dimensional pit morphology is discussed in terms of the values of D _f of the pits and the depression parameter, with respect to anion concentration and solution temperature.     

A New Method to Remove Neutral Template in the Synthesis of HMS

The synthesis of mesoporous molecular sieves is believed to be one of the most exciting discoveries in the field of material science1. The formation of mesoporous structure relies on the template effect of the surfactant micelles2-4. Generally three kinds of interactions are involved in this process, i.e. electrostatic charge matching, hydrogen bonding and coordinative interaction5. After template-directed synthesis procedure, the after-treatment process is needed to remove the surfactant temp…     

Retention Behaviors of Uronic Acid-containing Polysaccharides and Neutral Polysaccharides in HPGPC

The determination of molecular weights (Mw) of polysaccharides has served as an important process since the physical properties of the polysaccharides are closely related to their Mw and/or molecular weights distribution (MWD). For Mw and MWD determinations, high performance gel permeation chromatography (HPGPC) has gained wide acceptance as a preferred method due to its high sensitivity, speed and reproducibility. In chromatography, it is well known that the molecular weights are determ…     

Raman Spectroscopic Study of Aluminum Silicate Complextion in Acidic Solutions from 25 to 150°C

Raman spectroscopic measurements were performed on aqueous acid to neutral silica-bearing solutions (0.005 ≤ m _Si ≤ 0.02, 0 ≤ pH ≤ 8) and Al–silica solutions at temperature from 20 to 150°C. At 20°C, the spectrum of silica-bearing solutions exhibits only the bands of water and a completely polarized band at 785 cm^?1. This band is attributed to the ν₁ band of the tetrahedral Si(OH)₄ molecule. In ${\text{Si(OH)}}_{\text{4}} {\kern 1pt} {\kern 1pt} - {\kern 1pt} {\text{AlCl}}_3 {\kern 1pt} - {\kern 1pt} {\text{HCl}}$ solutions, the intensity of this band decreases with increasing Al concentration, temperature, and pH. This decrease can be explained by the formation of an inner sphere complex between Al³⁺ and Si(OH)₄ according to the reaction: ${\text{Al}}^{{\text{3 + }}} {\text{ + H}}_{\text{4}} {\text{SiO}}_{\text{4}}^{\text{0}} ({\text{aq}}){\text{ }} \Leftrightarrow {\text{ AlH}}_{\text{3}} {\text{SiO}}_{\text{4}}^{{\text{2 + }}} {\text{ + H}}^{\text{ + }} $ The fraction of complexed silica deduced from raman spectroscopic measurements is in good agreement with that calculated for the similar solution compositions and temperatures using the complexation constant generated by Pokrovski et al. ⁽²³⁾ from potentiometric measurements. At ambient temperature, the formation of aluminum silicate complex is weak and does not account for more than ca. 5 % of the total Al in most natural waters. As temperature increases, this complex becomes more significant and can dominate Al speciation in acid (pH ≤ 2) hydrothermal solutions.