Microwave dielectric properties of aqueous solutions of potassium and cesium fluorides

The microwave dielectric properties of aqueous solutions of potassium and cesium fluorides are studied over a wide concentration range at frequencies of 13 to 25 GHz and temperatures of 288, 298, and 308 K. The static dielectric constant ?_s and the time τ and enthalpy of activation ΔH _? ⁺⁺ of dielectric relaxation for the solutions are calculated. It is demonstrated that, for fluorides, the disruptive effect of ions on the hydrogen bond network of water is weaker than that for the other halogenides.     

Dielectric properties of aqueous solutions of the ammonium heptamolybdate-poly(vinyl alcohol)-water system

The microwave dielectric properties of aqueous solutions of the ammonium heptamolybdate (AHM)-poly(vinyl alcohol)-water ((NH₄)₆Mo₇O₂₄-PVA-water) system are studied along sections with constant concentrations of the components in the frequency region in which the dispersion peak of the dielectric constant of water falls (13–25 GHz) at 298 and 313 K. The static dielectric constant ε_s and the dielectric relaxation time τ of the solutions are found. The dielectric characteristics along the sections vary additively as a function of concentration with respect to the relationships observed in the AHM-water and PVA-water binary systems. The rotational mobility of water molecules is mainly controlled by polymer additives. We suggest that two (water and polymer-ion) subsystems exist in the solution in this case; these subsystems only weakly affect each other.     

Hydration and dielectric properties of aqueous solutions of protonated diallylmethylammonium polymer: transition from monomer to polymer

Abstract

The high-frequency dielectric relaxation of aqueous solutions of protonated diallylammonium polyelectrolyte, namely poly(diallylmethylammonium trifluoroacetate) has been studied at the maximum water dispersion frequencies, 7.5–25?GHz, and temperatures of 288, 298, and 308?K. Dielectric relaxation parameters have been calculated and compared with similar characteristics of aqueous solutions of monomer, diallylmethylammonium trifluoroacetate, and pyrrolidinium trifluoroacetate salt simulated structure of pyrrolidinium polymer link. It has been concluded that although the monomer features hydrophobic hydration, its polymer exhibits hydrophilic hydration properties. This change is related to conformation of hydrophilic-hydrophobic polycations in aqueous solutions and the change in the structure of polymer links.     

Microwave dielectric permittivity and relaxation of aqueous potassium trimethylacetate solutions

The MW dielectric properties of aqueous potassium trimethylacetate (pivalate) solutions have been measured at six frequencies (10–25 GHz) at 288, 298, and 308 K. The static dielectric constants and dielectric relaxation times and activation parameters have been calculated. Trimethylacetate ion leads to the decrease in the mobility of water molecules and strengthening of their hydrogen bonds. These changes of water are similar to those in solutions of other carboxylates with a large number of nonpolar groups. The hydrophobic hydration of the trimethylacetate ion is maximal in this series.     

Complex dielectric constant and relaxation parameters of aqueous solutions of barium nitrate

Microwave dielectric properties of aqueous solutions of barium nitrate are studied as a function of concentration at frequencies from 3.4 to 23.5 GHz and temperatures from 283 to 313 K. The following dielectric parameters of the solutions are determined: static dielectric constant ε_s, dielectric relaxation time τ, and enthalpy of activation of dielectric relaxation ΔH _ε ⁺⁺ . In transfer from water to the solutions, the static dielectric constant decreases for all test solutions. Decreases in τ and ΔH _ε ⁺⁺ are induced by the increasing mobility of water molecules in ion hydration shells. The ionic effect disappears as temperature increases.     

Ion mobilities in DMF-water mixtures at 25°C

Densities and viscosities of mixtures of N,N-dimethylformamide (DMF) with water at 25°C have been determined. Limiting equivalent conductances of cesium chloride, potassium chloride, potassium bromide and potassium thiocyanate in these solvent mixtures at 25°C are presented together with corresponding values of ion association constants and distance of closest approach parameters. The transference number of the potassium ion has been determined in solvent mixtures ranging from 0 to 0.75 mol fraction in DMF in water at 25°C. The conductimetric Hittorf method has been used for both potassium bromide and potassium chloride in solutions of up to 0.496 mole fraction of DMF. For solutions of potassium thiocyanate in 0.5 and 0.75 mole fraction in DMF the cationic transference number has been determined using the moving boundary method. Stokes radii have been evaluated. Transport properties are examined in relation to-solvent properties such as composition, dielectric constant, excess volume of mixing and free volume.To whom correspondence should be addressed.     

Microwave dielectric properties of potassium hydroxide aqueous solutions

Microwave dielectric properties of potassium hydroxide aqueous solutions were studied at frequencies of 13 to 25 GHz over a wide range of concentrations and temperatures of 288 to 308 K. Experimental electrical conductivity data were used to determine ionic losses at high frequencies. The static dielectric permittivity σ_s, dielectric relaxation time τ, and thermodynamic activation parameters of dielectric relaxation (ΔH _ɛ⁺⁺, ΔG _ɛ⁺⁺, and ΔS _ɛ⁺⁺) were calculated. These quantities decrease in transfer from water to solutions. Thereby we demonstrate that potassium hydroxide has a disturbing effect on the initial hydrogen-bond network of water.     

GC–MS analysis of phenolic compounds in fuels after conversion to trifluoroacetate esters

The GC–MS characteristics of trifluoroacetate esters of phenolic compounds are discussed. Linear temperature programmed retention indices and total ion current MS response factors of over 120 phenolic esters are reported. The main GC advantages from analysis of trifluoroacetate esters as compared to plain phenols are enhanced volatility and improved resolution. For example, the elution temperature of a given phenol is typically 50 °C greater than that of the corresponding trifluoroacetate ester. Also, while retention of compounds with two trifluoroacetate groups is only moderately greater than mono esters, underivatized dihydroxy compounds are very difficult to elute from any GC column. Complete resolution of isomeric C₀-, C₁- and C₂-alkylphenol esters is readily achieved on conventional fused silica GC columns; resolution of the corresponding underivatized compounds requires specialized GC columns with low temperature limits. In general, mass spectra of trifluoroacetate esters are more characteristic of a given structure than those of the corresponding phenols and may be more rigorously interpreted towards structural elucidation. A table in the report summarizes some of the more important spectral features used in compound identification. Example applications in analysis of coal-, shale- and petroleum-derived materials are presented. Selected ion monitoring is used to determine individual phenolic components in whole distillates; reconstructed ion chromatograms are used to illustrate distributions of selected species as a function of fuel storage and thermal stress.     

Solution Properties of NaHSO4 and Na2SO4: A New Sight from the Water–Ion and Water–Dipole Cooperative Interactions Using Dielectric Relaxation Spectroscopy

The aqueous NaHSO₄ and Na₂SO₄ solutions at concentrations of 0.1–1.0 mol/l in a limited frequency range 0.2–20 GHz are studied by dielectric relaxation spectroscopy with a newly developed fractal concept spectral function. The fractal analysis with α(lnτ) diagrams from dielectric relaxation spectroscopy as functions proposed a new strategy to shed light on the dual nature of ion–water and dipole–water cooperative interactions. A distinct cooperative interaction of ion–water and dipole–water is observed and water molecules perturbed by ions contributing to dielectric constant beyond the first hydration shell is obtained.     

Studies on reactivity of benzoyl and benzoylperoxy radicals produced by laser flash photolysis of dibenzoyldiazene in aerated solutions

Photolysis of dibenzoyldiazene gives benzoyl radicals. In aerated solutions, the benzoyl radicals react with oxygen to yield benzoylperoxy radicals. Spin trapping studies indicate that 5,5′dimethyl-1-pyrroline N-oxide reacts with the benzoylperoxy radicals to produce the adduct which exhibits ESR parameters, A_N = 13.8 G and A_Hβ = 10.1 G. Laser photolysis studies reveal that the rate constants for the reaction between the benzoyl radical and oxygen are ca. 4 × 10⁹ M^-1 s^-1 in toluene, acetone, and ethyl acetate. The benzoylperoxy radicals undergo one-electron oxidation of tetramethyl-p-phenylenediamine, TMPD, to give an ion pair. The ion pair has an absorption spectrum similar to that of the TMPD cation radical. The formation of the ion pair is detected by monitoring the absorbance change at 600 nm after laser pulsing. From the kinetic studies for the formation of the ion pair in the presence of olefins, the bimolecular rate constants for reactions between several olefins and the benzoylperoxy radical are determined. The electrophilic addition of the benzoylperoxy radicals to olefins is discussed in comparison with the addition reactions of thiyl radicals to olefins. The detection and determination of the dipole moments of both the benzoylperoxy radicals and the ion pair are carried out with the use of the time-resolved microwave dielectric absorption technique. The distance between the positive and negative ions in the ion pair is estimated as 0.20 nm.     

Temperature changes of dielectric permittivity and relaxation in aqueous lithium iodide solutions

The complex permittivity of aqueous LiI solutions is studied over a wide range of concentrations at temperatures of 288–323 K in the water permittivity dispersion region at seven frequencies in the range of 7.5–25 GHz. One relaxation region describable by the Debye or Cole-Cole equation is observed in these solutions. Dielectric relaxation time τ and static permittivity ?_s are studied as dependent on temperature and concentration. The time and enthalpy of activation of dielectric relaxation decrease in going from water to solutions, which corresponds to the distortion of the initial water structure and the increasing mobility of water molecules in hydration shells of ions. In the initial concentration range, the water activity is a linear function of 1/?_s. The negative temperature dependence of ?_s disappears in going to concentrated solutions. At high concentrations, the static dielectric constant increases in response to increasing temperature. The new trends in ?_s and τ at elevated temperatures of 313–323 K are due to the formation of ion pairs and other ion-water groups having high dipole moments.     

A study of the differential capacitance of zinc in aqueous solution with potassium silicate additions

The differential capacitance of the polycrystalline zinc electrode has been studied in aqueous solutions of KCl, KNO₃ and KOH both with and without the addition of potassium silicate. Double layer capacitance measurements can be made in KCl and KNO₃ without the interaction of OH^? at low pH values < 3.0. The reduction of the nitrate ion takes place at the zinc electrode in aqueous potassium nitrate.The silicate ion is adsorbed on the zinc electrode in aqueous KOH solutions at a potential close to the dissolution potential. This results in inhibition of metal dissolution, due to limited interaction of OH^? with the metal surface. The electrode resistance is increased by this adsorbed layer of silicate ion. In alkaline solution the h.e.r. is stimulated by the addition of potassium silicate.     

The Possible Presence of Triple Ions in Electrolyte Solutions of Low Dielectric Permittivity

The cause of the appearance of a minimum in the molar electrical conductivity in many electrolyte solutions with increasing electrolyte concentration, in solvents of low dielectric permittivity, is reviewed. Tentative explanations include the formation of triple ions or, alternatively, changes in the electrical polarization of the solutions due to the presence of electrolyte ion pairs. Theoretical models for linear triple ions and apolar dimers are examined. Experimental evidence favors the polarization hypothesis over triple ions; the presence of a maximum in the dielectric permittivity with increasing electrolyte concentration is consistent with the presence of an equilibrium between ion pairs, AB, and their dimers, A₂B₂, at higher concentrations.     

Selective hydrothermal microwave synthesis of various manganese dioxide polymorphs

Hydrothermal microwave treatment of mixed solutions of potassium permanganate and hexamethylenetetramine within the pH range 0.5–6.9, resulted in various polymorphs of nanocrystalline manganese dioxide: α-MnO₂ (cryptomelane), γ-MnO₂ (nsutite), β-MnO₂ (pyrolusite), and δ-MnO₂ (birnessite). The pH values of the medium at which single-phase samples form were determined.     

Hydration and dielectrical properties of aqueous pyrrolidinium trifluoroacetate solutions

Results from microwave measurements of the dielectrical properties of aqueous pyrrolidinium trifluoroacetate solutions at maximum water dispersion frequencies (13–25 GHz) and temperatures of 288, 298, and 308 K are given. The static dielectrical constants, times, and activation parameters of the dielectrical relaxation of solutions are calculated. The enthalpy and time of dielectrical relaxation activation are increased by deceleration of the motion of water molecules in the hydrate shells of ions. The changes in dielectrical parameters are in this case minimal in a series of aqueous solutions of diallylammonium salts with cations of different structures and degrees of substitution. It is shown that pyrrolidinium ions are characterized by weak hydrophobic hydration.     

Reaction between silver trifluoroacetate and quercetin in low-polarity organic media

CF₃COOAg-Qr-P systems, where Qr is quercetin and P is an organic solvent, have been studied by spectroscopic methods. The reaction between silver trifluoroacetate and quercetin has been shown to produce colloid solutions, whose destruction terminates with the precipitation of a silver phase. The kinetic characteristics of the reaction between silver trifluoroacetate and quercetin in ethyl acetate have been determined.     

Conductance of potassium lodide in mixed solvents

The conductance of potassium iodide has been measured in the solvents ethylene carbonate, water, methyl ethyl ketone, and pairwise mixtures of these solvents at 40°C; and ethylene carbonate-water, tetramethylene sulfone-water, dimethyl sulfoxide-water, tetrahydrofuran-water, ethylene carbonate-tetramethylene sulfone-water, ethylene carbonate-tetramethylene sulfone, and tetrahydrofuran-dimethyl sulfoxide at 25°C. For dielectric constants greater than about 60, the pairing constants K_A are in the range 0.3–2.0; no correlation between K_A and solvent properties could be established. For lower dielectric constants, K_A increases exponentially with decreasing dielectric constant. Addition of a proton, acceptor to water initially decreases K_A regardless of whether the dielectric constant of the mixture is higher or lower than that of water, suggesting that ion pairs in water may be stabilized by cage structures. The Walden product A_o is also decreased by the addition of proton acceptors.     

Effects of concentration on the microwave dielectric spectra of aqueous urea solutions

Several models of relaxation for the dielectric spectra of aqueous urea solutions in the microwave region are compared. The spectra are shown to contain two main Debye components arising from the rotational motions of urea and water molecules. Two essentially different concentration regions in urea solutions are identified. The first is characterized by a small increase in the mobility of water molecules (τ₁ = 7.8 ps) and the existence of hydrated urea molecules (τ₂ = 19 ps). Due to the aggregation of urea molecules, the relaxation times for the latter process grow considerably in highly concentrated solutions. At the same time, faster molecular motions (τ₃ = 6 ps) are observed for water molecules.     

Internal rotation of para-substituted phenols. A low temperature dielectric relaxation study

The dielectric relaxation rates of 18 phenols and 3 thiophenols have been determined in paraffin solutions at 4.2 or 77 K and used to obtain relative values of the tunnel splitting of the ground torsional state. Where comparison is possible the results are compatible with vapour phase microwave spectroscopic data. The barriers to hydroxyl rotation are calculated and are fairly consistent with barriers derived from far infrared data. Para-substituents F, CH₃, Cl, C(CH₃)₃, Br and I in order of decreasing effectiveness, lower the barrier. COOH and CHO raise it by 350–400 cm^?1.