Pressure-dependent muonium kinetics in aqueous solution

Muonium decay rates have been measured as a function of pressure for the first time in condensed matter. The reactions of muonium with NO^-₃ and MnO^-₄ were found to have activation volumes of -7.1 ± 1.5 cm³ mol^-1 and + 3.1 ± 1.6 cm³ mol^-1, respectively. These volumes are compared with -5 cm³ mol^-1 and +2cm³ mol^-1 for activated and diffusion-controlled reactions of hydrogen atoms. The results support the concept of local order of the water molecules around each H or Mu atom in solution.     

Quantum diffusion of hydrogen and muonium atoms in liquid water and hexagonal ice

We have used the ring polymer molecular dynamics method to study the diffusion of muonium, hydrogen, and deuterium atoms in liquid water and hexagonal ice over a wide temperature range (8-361 K). Quantum effects are found to dramatically reduce the diffusion of muonium in water relative to that predicted by classical simulation. This leads to a simple explanation for the lack of any significant isotope effect in the observed diffusion coefficients of these species in the room temperature liquid. Our results indicate that the mechanism of the diffusion in liquid water is similar to the intercavity hopping mechanism observed in ice, supplemented by the diffusion of the cavities in the liquid. Within the same model, we have also been able to simulate the observed crossover in the c-axis diffusion coefficients of hydrogen and deuterium in hexagonal ice. Finally, we have been able to obtain good agreement with experimental data on the diffusion of muonium in hexagonal ice at 8 K, where the process is entirely quantum mechanical.     

Reactivity of hydrogen atoms with liquid water

The reactivity of hydrogen atoms with liquid water was investigated by determination of the final products obtained by the photolysis (λ = 184.9 nm) of two systems in the range pH 10 – 13: (a) OH⁻/N₂O/H₂O and (b) OH⁻/H₂O (air free). Based on the product yields of the two systems, non-linear fitting computations were performed including all possible reactions; a value of k(H + H₂O) = 10 ± 2 dm³ mol⁻¹ s⁻¹ was determined. The share of each individual reaction leading to the formation of H₂ was also deduced.     

Energy of the surface segregation of Ag atoms in Ag–Au alloys in an aqueous solution

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Reactivity of vibrationally excited methane molecules in reactions with chlorine atoms

At 148–298 K, the rate constant for the reaction of methane molecules excited into bending vibration with atomic chlorine does not exceed by more than 30 times the corresponding constant for methane in thermal equilibrium. Consequently, at low temperatures and thermal equilibrium the reaction of methane with atomic chlorine proceeds through the vibrational ground state of methane.

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, 148–298°K , , 30 , . , .

     

Reactivity of H atoms and hydrated electrons with chlorobenzoic acids

H radicals react with chlorobenzoic acids and chlorobenzene (k(H+substrates)=(0.7–1.5)×10⁹ dm³ mol⁻¹ s⁻¹) by addition to the benzene ring forming H adducts with characteristic absorption bands in the range of 310–360 nm. The rate constants for their second-order decay are 2k=(3.5–6)×10⁸ dm³ mol⁻¹ s⁻¹. By reduction with e_aq⁻ fragmentation and chloride release was established for 2- and 4-chlorobenzoic acid, for 3-chlorobenzoic acid the addition of electrons to the carboxylate group was observed by pulse radiolysis. By gamma radiolysis could be proved that these radical anions undergo intramolecular electron transfer and quantitave dechlorination. The efficiency in degradation was 4-chlorobenzoic acid>3-chlorobenzoic acid>2-chlorobenzoic acid. Benzoic acid was found as final product for all substrates.     

Copper and zinc removal from aqueous solution by mixed mineral systems I. Reactivity and removal kinetics

This study investigates the reactivity and removal kinetics of Cu and Zn onto mixed mineral systems from aqueous solution related to acid mine drainage impacted areas. The sorbents used were kaolinite, Al-montmorillonite, goethite, and their mixtures. The effects of surface charge, proton coefficient, and sorption kinetics were studied at room temperature (23+/-2 degrees C). Using an empirical model, mineral mixing reduced the exchange of protons for sorbing ions and the acidity of the reactive sites, thus impeding Cu and Zn removal by proton exchange. Based on the amount of Cu and Zn sorbed on the mixed mineral suspensions at ionic strength 0.01 to 0.1 M and pH 4, it is suggested that Cu and Zn removal from aqueous solution was by both inner and outer sphere complexation. Mineral mixing reduced the transfer rate of Cu relative to the single mineral suspensions in both slow and fast reaction phases. The behavior of the mixed suspensions in Cu and Zn sorption suggest that different reactive sites were involved at the onset of sorption, becoming similar to those of the single mineral components over time.     

Poloxamer association in aqueous solution

Aqueous solutions of the surface active poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) block copolymers (poloxamers) were studied using photon correlation spectroscopy (quasi-elastic light scattering) and viscosity measurements. Poloxamers 184 and 237 showed detectable aggregates at 25° only at concentrations above about 6% with size increasing with concentration and with significant polydispersity, probably indicating a multiple association process. At 35°, however, essentially invariant values for the hydrodynamic radius were found over a wide concentration range and the systems were essentially monodisperse: these systems are more likely to be represented by a closed association model. The more hydrophilic poloxamer 188, however, retained its concentration dependence of aggregate size up to 55°. The variation with temperature of both the hydrodynamic radius of aggregates and the intrinsic viscosity of several poloxamers was rationalized by relating the temperature-dependency curves to the cloud point of the poloxamer. In some cases only certain sections of the curve are observable when the cloud point is high, e.g., >100°, or low, e.g., <40°.     

Social self-sorting in aqueous solution

Self-sorting-the ability to efficiently distinguish between self and nonself-is common in nature but is still relatively rare in synthetic supramolecular systems. We report a 12-component mixture comprising 1-11 and KCl that undergoes thermodynamically controlled self-sorting in aqueous solution based on metal-ligand, ion-dipole, electrostatic, charge-transfer interactions, as well as the hydrophobic effect. We refer to this molecular ensemble-characterized by high-fidelity host-guest interactions between components-as a social self-sorting system to distinguish it from narcissistic self-sorting systems based on self-association processes. The influence of several key variables-temperature, pH, concentration, and host/guest stoichiometry-was explored by a combination of simulation and experiment. Variable temperature NMR experiments, for example, revealed a kinetically controlled irreversible process upon cycling from 298 to 338 K, which is an emergent property of this molecular ensemble. Variable pH and concentration experiments, in contrast, did not reveal any emergent properties of the molecular ensemble. Simulations of a four-component mixture establish that by proper control of the relative magnitude of the various equilibrium constants, it is possible to prepare socially self-sorted mixtures that are responsive (irresponsive) to host/guest stoichiometry over narrow (broad) ranges. The 12-component mixture is relatively irresponsive to host/guest stoichiometry. Such social self-sorting systems, like their natural counterparts, have potential applications as chemical sensors, as artificial regulatory elements, and in the preparation of biomimetic systems.     

N Reactivity vs. O reactivity in aqueous chlorination

Nitrogenated compounds react with hypochlorous acid yielding N-chloro compounds. In principle, α-amino acids chlorination may take place on the oxygen of the carboxylic group or on the nitrogen of the amino group. In this framework, we discuss the different reactivities of nitrogen and oxygen towards chlorine, and come to the conclusion that the nitrogen is the preferred reaction site in α-amino acids chlorination. © 1994 John Wiley & Sons, Inc.     

Chitosan structure in aqueous solution

Chitosans having three different degrees of acetylation (DA) were studied in acid solution using the uranyl staining technique and electron microscopy. Strings of approximately spherical aggregates were seen. The aggregates were interpreted as micelle-like agglomerates formed by almost fully acetylated polysaccharide, interconnected by blocks of almost fully deacetylated polysaccharide stretched by electrostatic repulsion. These agglomerates include NH₃⁺ groups which produce electrostatic swelling of the agglomerates, giving a radius proportional to the degree of deacetylation. The length of the strings are also proportional to the deacetylation degree. These strings are extended because of the electrostatic repulsion between charged ammonium groups.     

Microdetermination of acetone in aqueous solution

Diazotized anthranilic acid has been found to be a possible reagent for the spectrophotometric microdetermination of acetone in aqueous solution. The determination range is 10–130 μg/ml. The coefficient of variation does not usually exceed 12% for 60–130 μg of acetone but increases to 2.8% at the 10-μg level. The average relative error for five determinations ranges from ?1.5 to 2%. The molar absorptivity is 9.28 × 10³ liter · mol^?1 · cm^?1 in the presence of starch as a surfactant. Possible reaction path mechanism has been suggested for the colored body formation.     

Ozonolysis of phenols in aqueous solution

In the ozonolysis of phenol in aqueous solution at pH 3, 7 and 10 the following products were quantified: catechol, hydroquinone, 1,4-benzoquinone, cis,cis-muconic acid, H2O2, 2,4-dihydroxybiphenyl and 4,4-dihydroxybiphenyl. At pH 10, material balance (products vs. phenol consumption) is obtained. Singlet dioxygen, O2(1 delta g), and .OH are formed as short-lived intermediates. The precursor of the latter, O3.-, and a phenoxyl radical is suggested to arise from electron transfer from phenol/phenolate to ozone. Addition of .OH to phenol gives rise to dihydroxycyclohexadienyl radicals which add dioxygen and eliminate HO2. thereby forming catechol/hydroquinone. In competition and catalysed by H+ and OH-, the dihydroxycyclohexadienyl radical eliminates water yielding a phenoxyl radical. At pH 10, they readily oxidize catechol and hydroquinone. This reforms phenol (accounting for the low phenol consumption) and yields higher-oxidised products, eventually 1,4-benzoquinone. cis,cis-Muconic acid can be accounted for by the Criegee mechanism, while O2(1 delta g) is released on the way to (some of the) catechol and hydroquinone. Similar reactions proceed with hydroquinone (products: 1,4-benzoquinone, 2-hydroxy-1,4-benzoquinone and H2O2, with high yields of O2(1 delta g) and .OH) and with catechol (products: 2-hydroxy-1,4-benzoquinone, cis,cis-muconic acid, H2O2 with high yields of O2(1 delta g) and .OH). Material balance is not obtained for these two systems. Pentachlorophenolate, pentabromophenolate and 2,4,6-triiodophenolate ions give rise to halide ions, O2(1 delta g) (58%/48%/10%) and .OH (27%/2%/0%). It is suggested that together with O2(1 delta g) the corresponding ortho- and para-quinones plus a halide ion are formed. Further halide ion is released upon the hydrolysis of these and other products. For pentachlorophenolate the material balance with respect to the short-lived intermediates is 85%. With the bromo- and iodophenolates the O2(1 delta g) yields are substantially lowered, most likely due to release of triplet (ground state) dioxygen induced by the heavy atom effect.     

Diffusion of polyols in aqueous solution

The diffusion coefficients of aqueous solutions of the polyols CH₂OH-(CHOH)₄-CH₂OH (dulcitol, sorbitol, and myo-inositol) have been determinated using the Gouy interferometric method. Viscosity and density measurements have been carried out at the same temperature and concentration range for these and for mannitol. The concentration dependence of the diffusion coefficients are discussed in terms of solute-solute interactions with the help of thermodynamic literature data. Among the studied polyols, only dulcitol and myo-inositol exhibit a strong evidence for solute-solute interaction, whereas the other shows a preferential interaction with the solvent.     

Reactivity and electronic property of decaphenylmetallocenes of Mo and W atoms

The perphenylmetallocene complexes (η⁵-C₅Ph₅)₂W (1), [(η⁵-C₅Ph₅)₂W]⁺I₃⁻ (1⁺I₃), (η⁵-C₅Ph₅)₂Mo (2) and [(η⁵-C₅Ph₅)₂Mo]⁺I₃⁻ (2⁺I₃) have been prepared. Hydrogenation of 1 in THF produces (η⁵-C₅Ph₅)₂WH₂ (4), while (η⁵-C₅Ph₅)₂WHCl (3) is afforded in 1,2-dichloroethane solvent. Carbonylation of 1 produces (η⁵-C₅Ph₅)₂W(CO) (5). Treatment of 1 with the strong acid CF₃SO₃H leads to the dicationic species [(η⁵-C₅Ph₅)₂W]⁺²[CF₃SO₃]⁻₂ (1⁺²Tf₂) after crystallization. The structures of 2⁺I₃ and 1⁺²Tf₂ have been determined by an X-ray diffraction study. The magnetic susceptibility study indicates a ³E_2g ground-state for 1 and 2, and a ⁴A_2g ground-state for 1⁺ and 2⁺.     

Autoxidation of NO in aqueous solution

The reaction of NO with O₂ has been investigated in aqueous solution. As demonstrated by ion chromatography, the sole product is NO₂^?. Kinetic studies of the reaction by stopped-flow methods with absorbance and conductivity detection are in agreement that the rate law is -d[O₂]/dt=k[NO]²[O₂] with k = 2.1 × 10⁶ M^?2 s^?1 at 25°C. This rate law is unaffected by pH over the range from pH 1 to 13, and it holds with either NO or O₂ in excess. By studying the reaction over the temperature range from 10 to 40°C, the following activation parameters were obtained: ΔH^≠ = 4.6 ± 2.1 kJ mol^?1 and ΔS^≠=?96 plusmn; 4 J K^?1 mol^?1. © 1993 John Wiley & Sons, Inc.     

Reactivity of polymer substituents. II. Aminolysis of p-nitrophenyl acrylate copolymers with acrylamide or N,N-dimethylacrylamide in aqueous solution

Rates of the benzylaminolysis of acrylamide and dimethylacrylamide copolymers with a small amount of p-nitrophenyl acrylate in water solution were compared with the analogous reaction of p-nitrophenyl isobutyrate. Rates of the dimethylacrylamide copolymer and analog were also measured in methanol. The copolymer reactions were much slower than those of the analog, in contrast with results obtained in dioxane. It was found that the reaction of the analog is much more sensitive to the medium than the reaction of the polymer, because the “effective solvent medium” in the polymer domain is largely determined by properties of the polymer chain backbone.