Uptake of phenol on aerosol particles

We present a study of the interaction between a phenol molecule and an aerosol particle. The aerosol particle is represented by a cluster of 128 water molecules. Using a classical approach, we present interaction energy surfaces for different relative distances and for three orientations of phenol relative to the particle. From the energy surfaces we find the reaction pathways with the largest interaction between the molecule and the particle. We use a quantum mechanics/molecular mechanics (QM/MM) method to calculate a potential energy curve for each reaction path. Coupled cluster methods are used for the part of the system described by quantum mechanics, while the part described by molecular mechanics is represented by a polarizable force field. We compare results obtained from the classical approach with the QM/MM results. Furthermore, we use the QM/MM results to calculate mass accommodation coefficients using a quantum-statistical (QM-ST) model and show how the mass accommodation coefficient depends on the relative orientation of phenol with respect to the aerosol particle.     

Protonation of different goethite surfaces--Unified models for NaNO3 and NaCl media

Acid-base titration data for two goethites samples in sodium nitrate and sodium chloride media are discussed. The data are modeled based on various surface complexation models in the framework of the multi site complexation (MUSIC) model. Various assumptions with respect to the goethite morphology are considered in determining the site density of the surface functional groups. The results from the various model applications are not statistically significant in terms of goodness of fit. More importantly, various published assumptions with respect to the goethite morphology (i.e., the contributions of different crystal planes and their repercussions on the "overall" site densities of the various surface functional groups) do not significantly affect the final model parameters within simple 1-pK approximations. The simultaneous fit of the chloride and nitrate data results in electrolyte binding constants, which are applicable over a wide range of electrolyte concentrations including mixtures of chloride and nitrate. Model parameters for the goethite sample with 90 m2/g specific surface area are in excellent agreement with parameters that were independently obtained by another group on different goethite titration data sets.     

The electrochemical behavior of Al2S3 in molten MgCl2 + NaCl + KCl eutectic

The electrochemical behavior of Al₂S₃ in MgCl₂ + NaCl + KCl eutectic has been studied at graphite electrodes at 1023 K using the technique of linear sweep voltammetry. The electrolytic decomposition of Al₂S₃ in the eutectic involves the cathodic reduction of aluminum ions (or aluminum-ion-containing species) and the anodic oxidation of sulfide ions (or sulfide-ion-containing species). The reduction has been found to proceed by a reversible, three-eletron transfer that forms an insoluble product. The average apparent diffusion coefficient for aluminum ions during deposition is 1.03 × 10⁻⁵ cm² s⁻¹. The oxidation involves the two-electron discharge of sulfide ions (S²⁻ ⇌ S + 2e), followed by the dimerization of sulfur atoms to S₂ (S + S ⇌ S₂), which is very fast and very much displaced towards S₂. The average apparent diffusion coefficient for sulfide ions is calculated to be 2.73 × 10⁻⁵ cm² s⁻¹.     

Thermodynamics of saturated electrolyte mixtures of NaCl with Na2SO4 and with MgCl2

The ion=interaction equation is used to calculate the mean activity coefficients for the saturated aqueous mixtures, NaCl+Na₂SO₄ and NaCl+MgCl₂. A comparison between these values with those obtained from solubility shows a good agreement over a wide temperature range as well as at high ionic strengths for both mixed systems.     

Effects of concentration and temperature on molar volumes of L-serine, L-isoleucine, and L-glutamine in aqueous NaCl and NaNO3 solutions

Densities of L-serine, L-isoleucine, L-glutamine in 1.5 mol kg^?1 aqueous NaCl, and NaNO₃ solutions have been measured for several molal concentrations of amino acids at temperatures from 298.15 to 323.15 K. The partial molar volumes (? _v ⁰ ) of L-serine, L-isoleucine, and L-glutamine in 1.5 mol kg^?1 aqueous NaCl/NaNO₃ solutions have been computed using density data. The transfer partial molar volumes (Δ_tr? _v ⁰ ) of L-serine, L-isoleucine, and L-glutamine from water to 1.5 mol kg^?1 aqueous NaCl/1.5 mol kg^?1 aqueous NaNO₃ solutions have been determined at 298.15 K. The trends of variation of ? _v ⁰ and Δ_tr? _v ⁰ with change in temperature have been discussed in terms of ion-ion, ion-hydrophilic, and ion-hydrophobic interactions operative in solutions.     

The conductivity of concentrated aqueous mixtures of NaCl and MgCl2 at 25°C

As part of a cooperative study of the thermodynamic and transport properties of aqueous mixtures of NaCl and MgCl₂ at 25°C, we report values of the molar conductivities of the mixed electrolyte in the concentration range 0.5 to 3.6 molar. It was found that the conductivities in the mixtures differ from those calculated assuming additivity of the conductivities of the component binary solutions by 4.65 S-cm²-mol^–1 at constant total molarity and 0.50 S-cm²-mol^–1 at total ionic strength.     

Activity coefficient of hydrochloric acid in HCl/MgCl2 mixtures and HCl/NaCl/MgCl2 mixtures from 5 to 45°C

Magnesium, the dominant bivalent cation in natural seawater, exerts a substantial influence on the patterns of ion interactions in this saline medium. Mean activity coefficients of hydrochloric acid in mixtures of this acid with magnesium chloride at four ionic strengths, namelyI=0.1, 0.3809, 0.6729, and 0.8720 mole-kg^–1, were obtained from emf measurements of cells without liquid junction at nine temperatures from 5 to 45°C. The three highest ionic strengths correspond to seawater of salinities 20, 35, and 45, respectively. In addition, mixtures of HCl, NaCl, and MgCl₂ were studied atI=0.6729, the molal ratio of NaCl to MgCl₂ being maintained at 7.202 as in natural seawater. The Harned coefficients _{1 2} were found to decrease slowly with increase in temperature. The trace activity coefficient of HCl in solutions of MgCl₂ as well as in NaCl MgCl₂ mixtures was found to be nearly identical with that measured earlier in synthetic seawater of the same ionic strength but containing NaCl, MgCl₂, KCl, and CaCl₂.     

Ion sites in deuterated dimethylsulfoxide solutions of NaNO3 and cryptand complexed NaNO3 by digital infrared spectroscopy

Infrared spectra in digitized form were measured for NaNO₃ and [Na·C221]⁺NO ₃ ^– solutions in DMSO-d₆ between 1150 and 1500 cm^–1 using a technique and instrumentation that obtains each point of the average absorbance spectrum at the same (reduced) noise level. Similar spectra were also obtained for the solvent and the Na⁺ complexed cryptand C221 and used to remove the contribution of these entities from the above spectra. By taking appropriate differences of spectra, it was possible to reveal both bands of the contact ion pair in the NaNO₃/DMSO-d₆ solution-removing one from under the strong band of the D_3h site—and to show the presence of three ion sites in this solution. The third site is tentatively identified as a close ion pair. Two ion sites are also identified in the [Na·C221]⁺NO ₃ ^– /DMSO-d₆ solution.Paper X in the series, Studies of Solution Character, by Molecular Spectroscopy.     

Kinetics of heterogeneous reactions of HO2 radical at ambient concentration levels with (NH4)2SO4 and NaCl aerosol particles

The HO2 uptake coefficient (gamma) for inorganic submicrometer wet and dry aerosol particles ((NH4)2SO4 and NaCl) under ambient conditions (760 Torr and 296 +/- 2 K) was measured using an aerosol flow tube (AFT) coupled with a chemical conversion/laser-induced fluorescence (CC/LIF) technique. The CC/LIF technique enabled experiments to be performed at almost the same HO2 radical concentration as that in the atmosphere. HO2 radicals were injected into the AFT through a vertically movable Pyrex tube. Injector position-dependent profiles of LIF intensity were measured as a function of aerosol concentration. Measured gamma values for dry aerosols of (NH4)2SO4 were 0.04 +/- 0.02 and 0.05 +/- 0.02 at 20% and 45% relative humidity (RH), respectively, while those of NaCl were <0.01 and 0.02 +/- 0.01 at 20% and 53% RH, respectively. For wet (NH4)2SO4 aerosols, measured gamma values were 0.11 +/- 0.03, 0.15 +/- 0.03, 0.17 +/- 0.04, and 0.19 +/- 0.04, at 45%, 55%, 65%, and 75% RH, respectively, whereas for wet NaCl aerosols the values were 0.11 +/- 0.03, 0.09 +/- 0.02, and 0.10 +/- 0.02 for 53%, 63%, and 75% RH, respectively. Wet (NH4)2SO4 and NaCl aerosols doped with CuSO4 showed gamma values of 0.53 +/- 0.12 and 0.65 +/- 0.17, respectively. These results suggest that compositions, RH, and phase for aerosol particles are significant to HO2 uptake. Potential HO2 loss processes and their atmospheric contributions are discussed.     

Protonation and complex formation of 5-sulfosalicylate in NaCl,CaCl2 and MgCl2 aqueous media. Speciation in synthetic seawater

The binding capacity of 5-sulfosalicylic acid (ssa) towards cationic macro-components of natural waters has been investigated in different ionic media (NaCl, MgCl2 and CaCl2 aqueous solutions) and in the ionic strength range 0 < or = I < or = 1 mol dm-3. In order to contribute to the speciation of this multi-sites ligand, measurements have been carried out also in a synthetic seawater (SSWE) containing the major components of seawater (Na+, K+, Ca2+, Mg2+, Cl- and SO4(2-)). Measurements have been performed by potentiometry ([H+]-glass electrode), at t = 25 degrees C. A critical analysis on the experimental and literature data is also given.     

Activity coefficients of sodium,potassium, and nitrate ions in aqueous solutions of NaNO3, KNO3, and NaNO3+KNO3 at 25°C

Ion selective electrodes have been used to measure the activity coefficients at 25°C of individual ions in aqueous solutions of NaNO₃ up to 3.5 molal, KNO₃ up to 3.5 molal and mixtures of NaNO₃ and KNO₃ up to 2.4 molal total nitrate ion concentration. The experimental results confirm that the activity coefficient of anion and cation in aqueous single electrolyte solutions of NaNO₃ and KNO₃ were different from each other over the whole range of concentrations studied. These effects are attributed to the ion-ion and ion-solvent interactions. The results also show that the activity coefficients of nitrate ions in the presence of sodium and potassium counterions do not depend significantly on the nature of the counterions present in the solution. The experimental data obtained in this study were correlated by a model proposed previously.     

Investigation of aerosol particles by atomic force microscopy

AFM has been applied for studying morphology and size distribution of nanometer-sized particles adsorbed on flat surfaces. In order to optimize imaging of these ultrafine particles different substrates were evaluated with respect to their roughness and stability under the influence of the sensing tip. Moreover, a method for calculating particle volumes from the three-dimensional AFM data is described. This greatly enhances the information content of AFM images, because a large number of particles in the raw data can be evaluated automatically in order to derive information on size distribution or surface coverage. This evaluation method has also been applied successfully to quantitatively describe changes on particles induced by different humidity of the surrounding atmosphere. Received: 15 July 1996 / Revised: 18 December 1996 / Accepted: 3 January 1997     

A comparison of electrochemical and electrokinetic parameters determined for cellophane membranes in contact with NaCl and NaNO3 solutions

Electrochemical and electrokinetic characterizations of cellophane membrane samples have been carried out by measuring membrane potential, salt diffusion, and tangential streaming potential, which allow the determination of different characteristic membrane parameters. Experiments were made with the membrane samples in contact with NaCl and NaNO(3) solutions at different concentrations and under different external conditions (concentration gradients), in order to obtain differences in transport and membrane characteristic parameters, depending on the electrolyte considered. Salt permeability across the membrane, which was obtained from diffusion measurements, is about twice as high for NaCl solutions as for NaNO(3) solutions, which is attributed to the different sizes of the electrolytes. Membrane potential measurements keeping the concentration ratio constant (C(1)/C(2)=2) were used to determine both the effective fixed charge concentration in the membrane, X(f), and the average value of transport numbers, t(i); taking into account these values, concentration dependence of membrane potential under a different external condition (C(1)=cte=0.01 M, 5 x 10(-3)< or =C(M)< or =5 x 10(-2)) was predicted. Results show that cellophane membrane behaves as a weak cation-exchange membrane and its permselectivity to cations is practically independent of the electrolyte considered. From electrokinetic results, assuming a Langmuir-type adsorption of anions on the cellophane surface, the number of accessible sites per surface unit was obtained, which is higher for Cl(-) than for NO(3)(-), in agreement with the small radii of chlorine ions; however, no significant differences in the specific adsorption free energy were found (DeltaG(Nacl)=-22.0 x 10(3) J/mol) and (DeltaG(NaNO(3))=-23.2 x 10(3) J/mol).     

Sampling and analysis of individual particles by aerosol mass spectrometry

Over the past decade, aerosol mass spectrometry has developed into a powerful method for characterizing individual particles in air. Recent advances in the design of inlets and mass spectrometers have extended the size range of particles that can be analyzed. In this tutorial, fundamental aspects of particle motion in sampling inlets are introduced. Basic experimental configurations for achieving a high analysis rate and the ability of laser ablation to provide chemical composition information are reviewed. An example of the use of this technology to study atmospheric phenomena is also presented. Significant opportunity exists for designing new experiments at the interface of aerosol mass spectrometry and conventional molecular mass spectrometry.     

Regioselective Nitration of Phenols by NaNO3 in Microemulsion

Highly regiospecific mononitration of phenols and substituted phenols was carried out in TX100-based microemulsion. The use of inexpensive and relatively nontoxic acidic reagent is an advantage of this method. The effect of various parameters such as concentration of NaNO₃, temperature, and agitation speed on reaction system have been investigated. Exclusive ortho-selectivity was observed for all the phenols subjected to this protocol.     

Interactions in L-phenylalanine/L-leucine/L-glutamic Acid/L-proline + 2 M aqueous NaCl/2 M NaNO3 systems at different temperatures

Density (ρ) and speed of sound (u) in 2 M aqueous NaCl and 2 M NaNO₃ solutions of amino acids: L-phenylalanine, L-leucine, L-glutamic acid, and L-proline have been measured for several molal concentrations of amino acids at different temperatures. The ρ and u data have been used to calculate the values of isothermal compressibility and internal pressure at different temperatures. The trends of variations of κ _T and P _i with an increase in molal concentration of amino acid and temperature have been discussed in terms of solute-solvent and solute-solute interactions in the systems.     

Reduction of nitrate during release of stored energy from γ-irradiated NaCl crystals in aqueous NaNO3 solution

Reduction of nitrate to nitrite takes place when the stored energy in the form of colour centres is released during dissolution of -irradiated NaCl crystals in aqueous sodium nitrate solution. Various parameters like dose, amount, storage time and particle size of irradiated NaCl salt which control the yield of nitrite have been studied. Similarly, the effect of concentration of NaNO₃ and the role of precipitation on the yields of nitrite in aqueous TlNO₃ and AgNO₃ have been investigated. The energy transfer parameter has been determined as the ratio of G/NO ₂ ^– / obtained by the addition of irradiated NaCl to that of direct -radiolysis. The data permit the evaluation of the concentration of colour centres in the irradiated NaCl crystals on the basis of the mechanism of reduction of nitrate.