Positronium interactions in organic solvents

In the present work, the chemistry of the positronium (Ps) species has been investigated in pure benzene, pyridine and their mixtures with pyridine concentrations at 4.12, 6.18 and 8.24 M, respectively, using the Doppler-broadened line-shape analysis technique. It is seen that the intensities of the para-(p-Ps) and ortho-Ps (o-Ps) in benzene and that of p-Ps in pyridine follow the Ore-model predictions while the intensity of o-Ps in pyridine is much lower than expected from this model. On the basis of these observations and of decrease in the o-Ps lifetime with increasing pyridine concentration in various organic solvents as reported in literature, it is concluded that pick-off is not the only quenching mechanism for Ps in organic solvents and pyridine is a quencher of Ps-species rather than an inhibitor. Calculations carried out considering a diffusion-controlled mechanism of Ps-quenching in pyridine via unstable (dissociative) complex/adduct formation and the bubble model show that the quenching rate is diffusion controlled and the pick-off rate is in accordance with the free-volume model. These conclusions were confirmed in the mixtures of benzene and pyridine.     

Extraction of cobalt(II) from aqueous thiocyanate solutions by tri-n-octylamine

The distribution of cobalt(II) between acidic thiocyanate solutions and tri-n-octylainine dissolved in various diluents has been measured for several cobalt(II) loadings and amine concentrations. Diluents investigated included n-hexane, cyclohexane, benzene, xylene, carbon tetrachloride, chloroform, chlorobenzene, o-dichlorobenzene and nitrobenzene. In all cases, the species extracted is bis(tri-n-octylammonium) tetrathiocyanatocobaltate(II). The ability of each diluent to extract cobalt(II) from acidic thiocyanate solutions is approximately correlated with the dielectric constant of the pure diluent, i.e., the smaller the dielectric constant, the larger the distribution ratio, with the exceptions of nitrobenzene and chloroform.     

Calorimetric study of the solvation of benzene and its chloro-, nitro-, and aminoderivatives by n-hexane, 1-butanol, and mixed solvent n-hexane-1-butanol

The heats of dissolution of benzene, chlorobenzene, ortho-dichlorobenzene, nitrobenzene, and aniline in n-hexane and 1-butanol and those of benzene, chlorobenzene, nitrobenzene, and aniline in a mixture of n-hexane and 1-butanol were measured by calorimetry at 25°C. The enthalpies of solvation of the compounds were calculated. The correlation between the enthalpies of solvation of the compounds and their molar refraction was studied. The enthalpies of solvation of the compounds and their functional groups by the mixture of n-hexane and 1-butanol were considered.     

Limiting activity coefficients of hydrocarbons in phenol

Temperature dependence of the limiting activity coefficients of saturated (n-hexane, n-heptane, n-octane, and cyclohexane) and aromatic (benzene, toluene, ethylbenzene, o-xylene) hydrocarbons in phenol was studied in the temperature range 308–348 K by the headspace analysis method.     

Interpretation of positron lifetime spectra arising from micellar solutions: Determination of the ortho-positronium diffusion coefficient in the solvent

Positron lifetime spectra arising from micellar solutions of sodium dodecylsulphate (SDS) are interpreted in terms of a classical positronium diffusion model published earlier. Unlike the generally accepted assumptions, this model results in a non-exponential ortho-positronium (o-Ps) lifetime density function. A new method is presented for the simultaneous fitting of this lifetime density function to independent lifetime spectra recorded under the same experimental conditions. Among the fit parameters D_p, the diffusion coefficient of o-Ps in the solvent (i.e. heavy water) phase is studied in detail; a detailed error analysis for D_p is also given. Provided that the mean aggregation number of SDS micelles is about 60, the published D_p values show that the diffusion coefficient of o-Ps in (heavy) water at room temperature is lower than that of small ions and molecules and the Arrhenius plot indicates a strong o-Ps localization in the solvent. The hydrodynamic radius of o-Ps is calculated from the o-Ps and micellar diffusion coefficients and from the micellar radius; it is greater than that of small ions and molecules and this can be considered as an independent indirect proof for the existence of o-Ps bubble in the (heavy) water.     

comments on the paper “contribution of quantum effects to the mechanism of positronium reactions”

Some results recently published on the o-Ps quenching reactions promoted by FeCl₂ and K₂Cr₂O₇ in glycerol aqueous solutions were interpreted by supposing that a significant fraction of o-Ps atoms diffuses by a quantum-mechanical effect or in quasi-free states even at room temperature. It is shown that the results can be interpreted in a different manner, so they cannot be invoked for supporting the hypotheses mentioned above about the mechanism of o-Ps diffusion at room temperature.     

The use of positron lifetime measurements in a study of electron scavenging by a range of radiosensitizer compounds

Positron lifetime measurements were made in aqueous solutions of a number of radiosensitizer compounds in order to measure the o-Ps inhibition and quenching constants. By making measurements in the presence and in the absence of perchloric acid, the inhibiting effects on the o-Ps yield due to epithermal and trapped electrons could be determined on the basis of the spur model. Inhibition constants relating to the scavenging by the sensitizer molecule of epithermal electrons. (K₁) and traped electrons, (K₂) were found for eight basic nitroimidazoles. The results are also discussed in terms of electron trap depth which is here taken to be equivalent to the one-electron redox potential, E¹₇. It is concluded that o-Ps lifetime measurements alone are not capable of determining the finer details of these spur reactions. Estimates of the respective yields of RS^- and OH^. species in oxygen and R—NO₂ compounds show that these are not able to explain the large differences in sensitizing efficiency.     

Diffusion and localization of o-Ps in D2O determined from positron annihilation in SDS micellar solutions

A microscopic diffusion model is presented for the determination of orthopositronium (o-Ps) lifetime in micellar solutions. Among other parameters, the lifetime density function depends on the o-Ps diffusion coefficient in the water phase. Orthopositronium diffusion coefficients are determined by fitting this lifetime density function to positron annihilation spectra obtained from 1 mol/dm³ solution of sodium dodecylsulphate (SDS) in D₂O at different temperatures. The activation energy of the o-Ps diffusion in D₂O obtained from an Arrhenius plot as E_a = 0.9₂₂ ± 0.1₀₃ eV indicates strong localization.     

Positronium formation in nonpolar solvents. A comparative study of the influence of chlorinated ethanes,ethenes and cyclohexanes on the yield of o-Ps

Inhibition of positronium formation caused by different chlorocyclohexanes, chloroethanes and chloroethenes used as additives in cyclohexane, 2,2,4-trimethylpentane, benzene and n-hexane has been investigated by means of positron lifetime measurements. Chlorocyclohexanes and chloroethanes cause increased inhibition with increasing chlorine substitution. Comparisons with earlier results of chlorobenzenes show that the behaviour of the actual additives is quite different from that of the chlorobenzenes. The results are discussed in terms of the “hot Ps-model” and the “spur-model”.     

On the o-Ps quenching reaction promoted by K2CrO4 in aqueous sucrose solutions

The o-Ps quenching reaction promoted by K₂CrO₄ was investigated in different sucrose aqueous solutions to confirm the influence of the dielectric constant of the reaction medium on the rate constant of the o-Ps diffusion-controlled reaction. The results obtained support the existence of such an effect. Its implications for the procedure usually applied for ascertaining if a reaction is diffusion controlled are briefly discussed.     

Effect of magnetic field on the radioluminescence of cyclohexane-benzene mixtures

The effect of magnetic fields on scintillation pulse shapes from p-terphenyl solutions in cyclohexane has been studied. Small additions of benzene increase the fluorescence enhancement at long times (50–200 ns); large amounts reduce the field effect. These results are discussed in terms offast hole transport in cyclohexane and a larger initial yield of triplet ion pairs in benzene.     

Positron annihilation in hypercrosslinked polystyrenes

Positron annihilation in hypercrosslinked polystyrene, called CPS(0.3)150E, has been studied as a function of temperature in the range from 35 to 370 K. The positron lifetime spectra were resolved into five components using the PATFIT and MELT programs. The annihilation rate constant of the longest-lived component was found to increase linearly with increasing temperature. Remarkably, the distribution of o-Ps lifetimes resolved by MELT was shown to broaden with decreasing temperature. Moreover, an effect of the oxygen pressure on the positronium characteristics was also investigated in another hypercrosslinked polystyrene, CPS(0.3)100E. The oxygen pressure varied from vacuum to 6 atm. The annihilation rate constants of the long-lived components were observed to increase linearly as a function of the oxygen pressure, which demonstrates a dependence of the kinetic of o-Ps quenching on the pore size.     

The yield of solvent excited states in the radiolysis of cyclohexane solutions

It is confirmed by pulse radiolysis that emitting solvent excited states are produced in the radiolysis of n-hexane, methylcyclohexane and cyclohexane. The emission is quenched by benzene and benzene emission appears. Applying stern - volmer kinetics to emissions from solvent, benzene and toluene in cyclohexane a very high energy transfer rate constant, viz., k = 2.8 × 10¹¹M⁻¹ sec⁻¹ is obtained. The yield of the excited state of cyclohexane is not greater than 0.3, and it is concluded that the major part of the excited states of other aromatics produced in cyclohexane solutions comes from ion neutralisation.     

Column packings for high-performance liquid chromatography and positron annihilation lifetime spectroscopy

Positron annihilation measurements as a function of temperature and the length of bonded alkyl groups have been carried out on silica gel samples. Silica gel samples were bare and bonded with alkyl group from C1 up to C18. The diameters of pores were deduced from the lifetime of trapped ortho-positronium (o-Ps), and it was found that o-Ps lifetime provides reasonable information on the pore sizes for both bare and alkyl bonded silica gels.     

On the Mechanism of Magnetic Quenching of Fluorescence in Gaseous State

The pressure dependence of fluorescence quenching of gaseous glyoxal has been measured in the presence of a magnetic field of 1–8 kG. Below 5 kG both the collision free lifetime and the collisional quenching constant were found to be dependent upon magnetic field strength. Above 5 kG the Collisional quenching constant turned out to be nearly equal to the value without magnetic field and the collision free lifetime took a constant value larger than that without magnetic field. The magnetic enhancement of the intramolecular radiationless transition of gaseous molecules has been studied theoretically. The phenomenon is shown to be explained by considering two mechanisms, mechanisms I and II. Mechanism I is due to the interaction of a primary state with secondary states through the Zeeman hamiltonian. Mechanism II is due to the shift and broadening of appropriate rovibronic levels by the Zeeman effect.     

p, T, x, y data of benzene + n-hexane and cyclohexane + n-heptane systems

The isothermal vapour—liquid equilibria of the benzene + n-hexane and cyclohexane + n-heptane systems have been studied using a dynamic method. The thermodynamic consistency of the data has been tested and the prediction from several empirical and semitheoretical models have been compared with the experimental values of different excess properties.     

Free volumes in solids under high pressure

A review of experimental work on ortho-positronium (o-Ps) lifetime in solids under the pressures up to 1 GPa is presented. Among the effects observed at high pressure one can mention: the disappearance of the energy level for Ps at the reduction of free volume size; pressure induced phase transitions; variation of Ps formation intensity with time; increase of o-Ps lifetime after intercalation of high pressure gas to the paraffin samples.     

Comments on the relation: positronium lifetime – free volume size parameters of the Tao–Eldrup model

The author is discussing the parameters appearing in the Tao–Eldrup (TE) model describing the ortho-positronium (o-Ps) lifetime dependence on the size of free volume in which Ps is trapped. Parameter values are not universal, applicable to all media. The Ps penetration to the bulk should depend on Ps work function; the o-Ps decay rate is strongly influenced by the contact density factor.     

Détermination des enthalpies de mélange de non-electrolytes á l'aide du microcalorimétre picker á écoulement continu

The performance of the Picker dynamic-flow microcalorimeter, which is able to scan and record (in 20 min) the enthalpy of mixing directly as a function of concentration, has been investigated at 298.15 K by measuring the three standard systems: cyclohexane + n-hexane, benzene + cyclohexane and carbon tetrachloride + benzene. Results agree to within better than 1%, in a large central range of concentration with the most reliable published data.     

Measurement of intracrystalline diffusion in NaX zeolite by capillary column gas chromatography

Chromatographic HETP (height equivalent to a theoretical plate) measurements are reported for a series of hydrocarbon sorbates (n-butane, n-hexane, cyclohexane, n-octane, benzene and decalin) in a capillary column (150 μm diameter) packed with 100-μm crystals of NaX zeolite. Such a column is superior to a conventional-packed column in terms of both heat transfer and external mass transfer characteristics. Dimensionless plots of reduced HETP versus reciprocal Peclet numbers show clearly that, for the more strongly adsorbed species, the HETP can be quantitatively accounted for by external mass transfer resistance and axial dispersion so that only lower limits for intracrystalline diffusivities can be obtained. The HETP data for butane, cyclohexane and decalin show clearly the intrusion of internal (micropore) diffusional resistance so, for these species, reasonably reliable intracrystalline diffusivities can be derived. The diffusivities so obtained (for butane and cyclohexane) are smaller than previously reported nuclear magnetic resonance (NMR) self-diffusivities but larger than the zero-length column (ZLC) values.