Ethanol loading in an inductively coupled plasma

Changes to the fundamental and analytical parameters of a plasma have been investigated when ethanol has been added to aqueous or organic solutions. Excitation temperature, electron number density, and intensity of the H(alpha) line increased when ethanol has been added to aqueous solutions, while an electron density decrease and signal reduction have been found when ethanol has been added to xylene. The sensitivity has been improved for all ethanol concentrations when water has been the solvent, but the reverse has been found for xylene solutions.     

Spectral properties and solution behavior of gold(III) coordination compounds with water-soluble porphyrins

Gold(III) coordination compounds with three water-soluble porphyrins―5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin (H₂TSPP^4–), 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin (H₂TMPyP⁴⁺), and 5,10,15,20-tetrakis(4-N,N,N-trimethylaminophenyl)porphyrin (H₂TTMAPP⁴⁺)―have been studied. Complex [Au(TTMAPP)]⁵⁺ has been prepared for the first time. The analysis of coordination-induced shifts of proton signals in NMR spectra and intensities of Q bands in absorption spectra indicates the high degree of bond covalence in the studied metal porphyrins and a partial transfer of electron density from porphyrin to gold ion. The cationic complexes [Au(TMPyP)]⁵⁺ and [Au(TTMAPP)]⁵⁺ in aqueous solutions has been found to exist in monomeric form, while anionic complex [Au(TSPP)]^3– undergoes dimerization upon growth of concentration and solution ionic strength. Equilibrium constant for dimerization has been calculated, the constant has been found to decrease when temperature rises. Thermodynamic parameters of dimerization process have been determined: ΔH° =–31.8 kJ/mol and ΔS° =–13.8 J/mol K.     

Ion-solvent interactions and ionic association in ethanol solutions

The electrical conductivities of potassium halides in ethanol have been measured at 25°C. The limiting molar conductances, ionic association constants and the closest approach parameter were calculated (Justice method) and compared with existing literature data. An inversion of the anion size dependence of ionic association constants for these solutions was observed. The results are explained by what has been called localized solvolysis, in which both the cation and the anion of the solvent separated ion pair are connected with different parts of the separating solvent molecule by donor-acceptor bonding. A correlation between K _A and protonic affinity of anions was found. Similar literature data for aqueous and non-aqueous solutions are also examined.     

Direct observation of hydrophobic interactions in aqueous solutions of organic compounds by supercooling and enthalpies of mixing

Supercooling temperatures and enthalpies of mixing with some solvents have been examined for two kinds of solutions subjected to different thermal treatments (solutions I and II) of tetrahydrofuran (THF), isopropyl alcohol (2-PrOH), and ethyleneglycol butylether (BE), and ethyleneglycol isobutylether (i-BE) in order to observe more directly the structural organization of water molecules around a nonpolar molecule in an aqueous solution. For THF and 2-PrOH solutions, supercooling temperatures of solution I were found to be 2–3 degrees higher than those of solution II, and differences H_I-H_II were found to be about 3 kJ mol^–1. It has been concluded that these results directly reflect the difference in the stability of hydrogen-bonded water networks in an aqueous solution.     

Dielectric properties of alcohol electrolyte solutions

Dielectric properties of ethanol and 1-hexanol solutions containing LiCl, CaCl₂·2H₂O and Ca(NO₃)₂·4H₂O, respectively, have been determined. It is found that LiCl reduces the static permittivity in ethanol, but CaCl₂·2H₂O and Ca(NO₃)₂·4H₂O both give an initial increase in _s. All the electrolytes studied increase the mean relaxation time of the ethanol solutions. In 1-hexanol the static permittivity is rather invariant for all studied electrolytes at low concentrations, while the same lengthening of the mean relaxation time is observed. When water is added in addition to the hydration water of the electrotyte, the static permittivity in hexanol is almost unaltered while the relaxation time is drastically shortened. The experimental result is discussed in terms of a formation of ion pairs, solvation sheaths, and kinetic depolarization, a partial release of hydration water and a structuring influence on the alcohol structure by the hydrated cation.     

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.     

Densities and apparent molal volumes of aqueous CaCl2 and MgCl2 solutions

The Pitzer ion interaction model has been used to evaluate literature data for the densities of aqueous CaCl₂ and MgCl₂ solutions between 0 and 100°C. The selected data can be adequately fitted by setting ^(1),v equal to zero. The variations of ^(0),v and C ^v with temperature have been found to be linearly correlated. The uncertainty in the calculated density is lower than 50 ppm below 1M but raises to 300 ppm at high concentrations. When plotted vs. the square root of the molality, the apparent molal volume of MgCl₂ shows a change at a concentration where a transition in the speed of sound has already been reported by Millero, et al.     

The radiation-induced degradation of a diazo dye in aqueous solution,II

The effect of -radiation on the color intensity of aerated, deaerated and oxygenated aqueous solutions of a diazo dye (Helion Red 8B) has been investigated. The decoloration yields of Helion Red 8B neutral aqueous solution, G(-Dye), for the nitrogen-, oxygen- and aerated-saturated solutions were found to be 0.77, 0.46 and 0.36 in the respective early stage. The rate constant for the reaction of the OH radical with the HR8B dye, obtained from competition kinetics using ethanol, was found to be 1.3·10¹⁰ M^–1·s^–1. In aerated solutions (pH 3), the G(-Dye) decreased markedly upon the addition of a very small amount of ethanol. Suggestions are made for possible use of the dye as a radiation dosimeter in the dose range of 0.1 to 2 kGy.     

Effect of inorganic electrolyte concentration on anionic-cationic adsorption films. Part 3: Dodecylpyridinium chloride + sodium octylsulfonate + sodium chloride

The effect of sodium chloride concentration on the simultaneous adsorption of dodecylpyridinium chloride (R₁₂PyCl) and sodium octylsulfonate (R₈SO₃Na) on the free surface of their aqueous solutions has been examined. The composition of mixed films adsorbed from equimolar solutions has been determined on the basis of the Gibbs adsorption equation as well as by using the regular solution model. It has been stated that this composition is dependent on the surface tension value (the degree of the surface coverage) as well as on the concentration of added inorganic electrolyte. The same factors influence the value of the interaction parameter , which negative values indicate a strong attraction between the components in the mixed monolayer.     

Hydrolysis of diphenylmethyltin(iv) chloride in different aqueous solutions of ethanol

The hydrolysis of [(Ph)₂MeSn(IV)]⁺ has been studied spectrophotometrically at 25ˆC and constant ionic strength of 0.1 mol dm⁻³ sodium perchlorate. Over a wide pH range, 1–11, the investigation has been performed in different aqueous solutions of ethanol. The species formed together with their formation constants have been determined using the computer program Squad. The hydrolysis constants at different media were analyzed in terms of Kamlet and Taft's parameters. A single‐parameter correlation of the formation constants, K_1‐1 and K_1‐2, versus α (hydrogen‐bond donor acidity), β (hydrogen‐bond acceptor basicity), and π^* (dipolarity/polarizability) for both cases are relatively poor in all solutions, but multiparameter correlation represents significant improvement with regard to the single‐parameter models. In this work, we have also used the normalized polarity parameter, E, alone and in combination with the Kamlet–Taft's parameters to find a better correlation of the formation constants in different aqueous solutions of ethanol. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:654–660, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20484     

Laser induced photoacoustic spectroscopy in liquid samples: temperature and solvent effects

Summary Laser induced photoacoustic spectroscopy (LIPAS) has been confirmed as an analytical tool, suitable for the determination of inorganic and organic species in aqueous and organic solvents, reaching detection limits two orders of magnitude lower than those obtained with conventional spectrophotometry.A significant influence of the solvent on the enhancement of the magnitude of the LIPAS response waveform of the piezoelectric detector has been found experimentally for inorganic species (neodymium ions) and organic compounds (e.g. -carotene and the cytochrome c), when water was replaced by organic solvents. This is particularly true, when a laser excitation wavelength above 500 nm was used, where the absorption coefficient for H₂O increases drastically.Furthermore, the temperature dependence of the magnitude of the LIPAS signal has been measured, in the range between 20–70°C in samples containing Nd³⁺,-carotene and the macromolecule cytochrome c in various aqueous and organic (polar and non-polar) solvents (H₂O, HClO₄, acetone, ethanol and petrol ether). A very strong enhancement of the LIPAS response was observed with increasing temperature (a factor of two in an interval between 20 and 40°C) for all inorganic and organic substances in aqueous solution. On the other hand, in polar and non-polar organic solvents only a slight decline of the signals of about 20% was found over the same temperature range.     

Voltammetry of Electroinactive Species Using Quinone/Hydroquinone Redox: A Known Redox System Viewed in a New Perspective

Electrochemical behavior of p‐benzoquinone (Q), hydroquinone (H₂Q) and quinhydrone complex (QH) have been investigated in aqueous unbuffered solutions. The results revealed that in unbuffered solution the half wave potential of hydroquinone has a significant difference with quinone's half wave potential. It shown that, added acid in an unbuffered solution of Q, give rise to a new reduction peak at a more positive potential than original reduction peak of Q. The half‐peak potential of this new peak is dependent on acidity of added acid (pK_a) and its height is proportional to the acid concentration. Also, added base in an unbuffered solution of H₂Q, give rise to a new oxidation peak at a more negative potential than original oxidation peak of H₂Q. The half‐peak potential of this new peak is dependent on basicity of added base (pK_b) and its height is proportional to the base concentration. This paper shows new perspectives for a known system in aqueous unbuffered solutions, by means of voltammetric responses that can be exploited for the electrochemical investigation of non electroactive species such as HPO , HCO or CH₃COOH.     

Partial Molar Volumes of Amino Acids and Peptides in Aqueous Salt Solutions at 25°C and a Correlation with Stability of Proteins in the Presence of Salts

Partial molar volumes for a homologous series of amino acids and peptides have been measured in aqueous 1M sodium acetate, sodium thiocyanate, and sodium sulfate at 25^°C. These data have been utilized in conjunction with the data in water to deduce partial molar volumes of transfer V _2,m ⁰(tr) from water to these aqueous salt solutions. The volumes of transfer for the amino acids and peptides are found to be positive. The interpretation is that this result arises from the dominant interaction of the sodium salts with the charged centers of amino acids and peptides. Thermal denaturation of the structurally homologous proteins lysozyme and -lactalbumin has been studied in the presence of these salts. Significant thermal stabilization of hen egg-white lysozyme has been observed in the presence of sodium acetate and sodium sulfate. However, the thermal stabilization observed for -lactalbumin is very small in the presence of these salts and sodium thiocyanate leads to a lowering of its thermal denaturation temperature. The rise in the surface tension of aqueous salt solutions with salt concentration has been correlated with the calorimetric and volumetric measurements. The results show that V _2,m ⁰(tr) depends less on the type of electrolyte than on the ionic strength of the solution. The V _2,m ⁰(tr) values correlate very well with the increase in the surface tension of aqueous salt solutions, indicating significant role of surface tension in interactions of amino acids, peptides, or protein with the salts.     

Determination of nonmetals using ICP-AES-techniques

The determination of iodine, bromine, sulphur and phosphorus using different modes of sampling in ICP-AES is described. Detection limits in the range of some 10 gL^–1 have been obtained using directly aqueous solutions with pneumatic nebulization. The influence of several anions and metals has been investigated. The addition of methanol and ethanol have improved sensitivities but decreased signal-to-background ratios and detection limits due to extended blank values and increased standard deviations. Using ultrasonic nebulization the sensitivities and the detection limits could be enhanced for these elements in aqueous solutions, but a significant decrease in sensitivity has been observed using additives as methanol or ethanol. By coupling of pneumatic nebulization and gas generation of iodine by addition of oxidizing agents, the detection limits of iodine could be improved to 6 ngL^–1 at the 178.28 nm line. Electrothermal vaporization has sucessfully been applied for microsampling of nonmetals and ICP-AES determination. Using aqueous solutions without any modifier the following absolute detection limits at the S (180.73 nm), P (178.27 nm), I (178.28 nm) and Br (163.34 nm) lines have been obtained: 0.25 ng of S, 0.44 ng of P, 0.36 ng of I and 43 ng of Br.Dedicated to Professor Dr. K. Doerffel on the occasion of his 70th birthday     

Influence of added water on pathways and efficiency of photocatalytic reactions in ethanol solutions of titanium tetrachloride

Electronic spectroscopy, ESR, and gas-liquid chromatography have been used in studying the action of light with =254 nm on ethanol-water solutions of titanium tetrachloride. It has been established that, in the course of irradiation, a photocatalytic process develops with the participation of coordination compounds of titanium(IV) and (III), resulting in oxidation and breakdown of the ethanol to form acetaldehyde, methane, ethane, ethyl chloride, and molecular hydrogen. In the presence of small amounts of added water (up to 0.5 M), the efficiency of CH₄ and C₂H₇ formation is much lower but the yield of H₂ is higher, in comparison with the yields of these products in absolute ethanol. With further increases in the water concentration, the rates of formation of methane, ethane, and acetaldehyde increase. The maximum quantum yields () are as follows: (CH₄)=1.8 · 10^–4 and (C₂H₆)=1 · 10^–3 in absolute ethanol; (CH₃CHO)= 1.6·10^–2 in ethanol with the addition of 6.0 M H₂O; (H₂)=6.7·10^–3 in solutions containing 0.5 M H₂O. The observed differences in the product yields are explained by a change in the composition and structure of the titanium compounds that act as the photocatalyst, a change that takes place when the water concentration is varied. A mechanism is proposed for these reactions.Translated from Teoreticheskaya i Éksperimentai'naya Khimiya, Vol. 22, No. 1, pp. 51–58, January–February, 1986.     

Volumetric Properties of Amino Acids and Hen-Egg White Lysozyme in Aqueous Triton X-100 at 298.15 K

The apparent molar volumes, V_,2, of glycine, alanine, -amino-n-butyric acid, valine, leucine, and lysine monohydrochloride have been determined in aqueous solutions of 0.05, 0.1, and 0.4 mol-kg^–1 Triton X-100 (TX-100), and the partial specific volume, v⁰, of hen-egg-white lysozyme in 0.4 mol-kg^–1 TX-100 by density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volumes, V_2,m⁰, for the amino acids in aqueous TX-100 solutions and the standard partial molar volumes of transfer, _tr V_2,m⁰, of the amino acids from water to the aqueous surfactant solutions. The linear correlation of V_2,m⁰ for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH₃⁺, COO^–), CH₂ group and other alkyl chains of the amino acids to V_2,m⁰. The results on _tr V_2,m⁰, of amino acids from water to aqueous TX-100 solutions have been interpreted in terms of ion–ion, ion–polar, hydrophilic–hydrophilic and hydrophobic–hydrophobic group interactions. For all the six amino acids studied, the values of _tr V_2,m⁰ from water to all the studied concentrations of aqueous TX-100 are small in spite of their different hydrophobic content, indicating an overall balance in interactions of zwitterionic/hydrophilic groups of amino acids with the hydrophilic groups of TX-100, and of hydrophobic and ionic/hydrophilic groups of the amino acids with hydrophobic groups of TX-100. Comparison of the interactions of the amino acids with nonionic, anionic and cationic surfactants has also been made and discussed. The partial specific volume of transfer of lysozyme from water to aqueous TX-100 solutions also indicates a balance of the hydrophobic and hydrophilic interactions in the protein–nonionic surfactant system.     

Effect of ascorbic acid and its derivatives on the radiation-chemical transformations of hydroxyl-containing organic compounds

The effect of ascorbic acid, 5,6-O-isopropylidyl-2,3-O-dimethylascorbic acid, and 2-O-glucopyranosylascorbic acid on the formation of main radiolysis products of ethanol and aqueous ethanol, ethylene glycol, α-methylglucopyranoside, and maltose solutions was studied by means of continuous radiolysis. The obtained results indicate that ascorbic acid effectively reacts with the carbon-centered hydroxyl-containing radicals derived from the substrates, thus decreasing the yield of their recombination and fragmentation products. It was found that the interaction of ascorbic acid and its derivatives with the carbon-centered radicals during the radiolysis of deaerated ethanol and its aqueous solutions may occur via both reducing and oxidizing mechanisms and that ascorbic acid in the aerated solutions acts as a hydrogen donor, reducing mainly the HO ₂ ^· radical to hydrogen peroxide.     

Aqueous solution of terbium as a scintillator for registration of actinoid alpha-radiation

A scintillator, based on the direct effect of a radiation upon a dissolved activator, has been suggested. Concentrated /2–2.5 mol/1/ solutions of Tb³⁺ in D₂O and H₂O, and aqueous solutions of HCl, HNO₃, and HClO₄ have been found to possess a high light output of scintillations affected by -particles of actionoids. The scintillation efficiency of terbium solution in D₂O is higher than that of some well-known organic scintillators. The terbium scintillator is quenched feebly by actinoid salts. Besides, it is of low sensitivity for the - and -radiation. The scintillations in terbium solutions represent groups of separate single-electron pulses with an exponentially decreasing frequency of their occurrence within groups.     

A double layer study of the (210) and (111) faces of gold in aqueous NaBF4 SOLUTIONS

Au(111) and Au(21O) faces of gold in aqueous NaBF₄ solutions have been investigated using cyclic voltammetry and admittance measurements. On Au(21O) no specific adsorption of $B{F}_4^{?}$ has been found. The results were first analysed accepting the Gouy-Chapman-Stern model for the double layer; like Ag(11O) and Ag(100) the inner layer capacity versus charge density curve has a broad maximum. For Au(111) it was not possible to draw clear conclusions and the variation of the inner layer capacity versus charge density seems to correspond to the accepted model only for the more negative densities of charge investigated.Models for the inner layer were discussed for the (210) face.     

A quantum chemical study of interchain hopping model of negatively charged solitons in polyacetylene

Phonon-assisted interchain hopping of negatively charged solitons in polyacetylene has been studied using a local chemical reaction model CH + CH₄ → CH₄ + CH. Quantum chemical characteristics of the electron transfer process have been analyzed in terms of the dynamic electron density and the mutual polarization moment. The CH stretching vibrational motion of CH₄, which is a local model of the sp³ defect, has been found to play a significant role for the electron transfer. The excitation of the corresponding vibrational mode of the sp³ defect would promote the interchain hopping of the charged soliton. The electron transfer process has also been studied in terms of the “regional” density functional theory. It has been shown that the driving force of the electron transfer is represented by the regional chemical potentials.