Spin conversion of positronium in paramagnetic solutions studied by age-momentum-correlation method

Correlated measurement of the lifetime and of the lineshape of the 511 keV annihilation radiation of positrons (age-momentum correlation, AMOC) has become a powerful tool for investigating reactions of positron or positronium in condensed matter as a function of time. The beam-based ⁺ AMOC method installed at the Stuttgart relativistic positron beam facility (E _kin ^e+ 4MeV) offers substantial advantages over the conventional E coincidence technique resulting in a fast data taking due to the unity detection efficiency of the ⁺ scintillator which provides the start signal for the lifetime measurement. In this paper the application of AMOC to positronium chemistry is illustrated by the study of spin conversion of positronium in the system methanol/HTEMPO as a function of HTEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, a paramagnetic solute) concentration. The same technique can be applied to other systems and other reactions in positronium chemistry, e. g., oxidation or complex formation.     

Critical evaluation and experimental determination of the nuclear activation and decay parameters for the reactions:6 4Zn(n, γ)6 5Zn,1 1 2Sn(n, γ)1 1 3 (m)Sn (E. C.)1 1 3mIn,1 7 4Yb(n, γ)1 7 5(m)Yb

A best choice from literature was made of the isotopic abundance values for⁶⁴zn,¹¹²Sn and¹⁷⁴Yb, and of the absolute gamma-intensities for⁶⁵Zn,^113mIn and¹⁷⁵Yb. From these data and from activation method experiments, the following 2200 m·s^–1 cross sections were determined:⁶⁵Zn(n, )⁶⁵Zn; ₀=(0.726±0.0007) barn [cf. literature 0.76–0.78 barn];¹¹²Sn(n,)¹¹³(m)Sn; ₀(0.91 m⁺g)=(0.539±0.011) barn [cf. literature 1 barn];¹⁷⁴Yb(n,)¹⁷⁵(m)Yb; ₀(m⁺g)=(130+4) barn [cf. literature 65 barn].     

Viscoelastic behavior of linear polyethylene and of paraffin mixtures

Summary The complex shear modulus of a linear polyethylene (Marlex 50), of which samples were either crystallized from the melt at various temperatures or precipitated from a dilute xylene solution, has been measured as a function of temperature at fixed frequencies between 10⁵ and 10^–1 c/s. The three relaxation regions, , can be distinguished, and activation energies are determined from the relaxation map. The-process shows a frequency-temperature characteristic which has been divided into three parts _I, _II, _III. Further experimental evidence for the kink model, proposed in an earlier paper (reference 4) is taken from the investigation of suitable paraffin mixtures. Measurements on six n-alkane systems, each consisting of an even n-paraffin mixed with a few percent of a paraffin with a chain longer by two C-atoms, are reported.

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Zusammenfassung Es wurde die TemperaturabhÄngigkeit des komplexen Schubmoduls eines linearen PolyÄthylens (Marlex 50) bei festen Frequenzen zwischen 10^–1 und 10⁵ Hz untersucht, wozu die Proben entweder aus der Schmelze bei verschiedenen Temperaturen kristallisiert oder aus verdünnter Xylollösung bei 80 C gefÄllt, in Methanol ausgewaschen und gepre\t worden waren. Drei Dispersionsgebiete, , können unterschieden werden. Die/max-1/T- Charakteristik des -Relaxations-prozesses wird in drei Bereiche _I, _II, _III unterteilt. Aktivierungsenergien werden aus geradlinigen Kurvenstücken dieser Charakteristiken bestimmt.Eine erneute experimentelle Stütze für das in einer früheren Arbeit (4) vorgeschlagene Kinkenmodell stellen Messungen an 6 weiteren n-Paraffin-Mischungssystemen dar, wobei die KettenlÄngen der Mischungspartner sich jeweils um zwei CH₂-Gruppen unterscheiden.

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Parts of this paper were read at the 4th International Congress on Rheology, Providence R. I., 1963.     

Synthesis of Δα,β-butenolides by oxidative dehydrocarboxylation of paraconic acids

Conclusions A new method is proposed for the synthesis of -alkyl-,-butenolides by oxidative dehydrocarboxylation of -alkylparaconic acids by the S₂O₈ ^2–-AgNO₃-CuSO₄ system.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No.1, pp.117–120, January, 1976.     

Equilibrium Particle Distribution in the Disperse System with Coagulation and Aggregate Disintegration

Kinetic equations were formulated, which describe coagulation–fragmentation process in a low concentrated suspension flow at a low shear rate. In such a system dispersed phase divided into fine and coarse fractions as the system is brought to equilibrium. Kinetic equations of two-fraction model were formulated. An approximate solution and, in one particular case, the exact solution of these equations were obtained for the equilibrium state. Detailed analysis of equilibrium particle distribution over the mass m was performed for an exponential coagulation kernel = ₀ m and an degenerated disintegration kernel = ₁₂, in which the disintegration frequency is an exponential function of aggregate mass ₁ = ₀ m ⁺ , and the probability of the fragment detachment from an aggregate is independent ofm and decreases exponentially with an increase in mass of a fragment: ₂ = ₀ ^–1exp(–/₀). The equilibrium distribution was shown to exist only at > 0, and in particular, it is described at = = 1 by the f() = ₀₀ ^–1exp(–/₀) and F(m) = Cx ^–1(x + 1)^{2 – 1} e ^–x functions for the particles of fine and coarse fractions (x = m/m ₀, = m ₀/₀, m ₀ and ₀ are the characteristic masses of coarse and fine fractions, respectively). The particle distribution for the fine fraction at 1 is well approximated by the Gaussian distribution exp[–(m – m ₀)²/(4^–1 m ₀₀)].     

A new improved expression for gamma-ray detection efficiency of Ge(Li) detectors

In the present paper, a new improved expression for -ray detection efficiency of Ge(Li) detectors, ⁰ , is given. It is represented as a continuous function of x (viz. E ^–1) with a maximum and decreases very rapidly to a small positive value as -ray energy, E, drops to 40 keV or lower, but slowly as E rises to 1.7 MeV or higher. Since it can well represent the whole physical process of the -ray detection, this expression may be one of the simplest and most precise representations, for ⁰ at the present time.     

Role of multiple bonds of tetracoordinated phosphorus atom in the magnetic shielding of its nucleus

On the basis of a previously proposed approach to investigation of the nature of the chemical shift ³¹P, it has been shown that the dependence of shielding of the ³¹P nucleus on the multiplicity of one of the bonds (PM) of the phosphorus atom in the molecule is not monotonic over the entire interval of variation of the corresponding parameter _PM. When _PM is smaller than a certain value ₀, which is determined by the difference between interactions of the P atom with the atom in question (M) and other substituents, the dependence of ³¹P nuclear shielding on _PM should be antibatic, and when _PM > ₀ symbatic.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 4, pp. 439–446, July– August, 1989.     

Selective Thermolysis of Azide Groups in 2,4,6-Triazidopyridines

When refluxed in 1,4-dichlorobenzene, the compound 2,4,6-triazido-3,5-dichloropyridine and its 3,5-dicyano derivative undergo selective thermolysis of the -azide groups, forming the corresponding 4-amino-2,6-diazidopyridines in high yields. According to quantum-chemical calculations, the selectivity of thermolysis of the -azide groups in triazides is due to the weaker bonding interactions between the N₍₎ and N₍₎ atoms in these azide groups.     

Fast non-destructive determination of silicon in coal by means of /n,n′ γ/ and /n, γ/ processes

The possibilities were evaluated of nondestructive determination of silicon content in large-scale samples of coal /about 20–50 kg/, based on the spectrometry of prompt -radiation from processes /n, n /, E=1779 keV and /n, /, E=3539 keV and 4935 keV. The neutron sources were either²⁴¹Am–Be or²⁵²Cf located additionally in D₂O moderator. A Ge/Li/ detector was used for -radiation detection. In exposure times of up to 2 h, the detection limits of 1.3% and 0.9% and accuracies of silicon determination of 0.66% and 0.40% have been achieved in case of /n, / and /n, n / processes, respectively.     

Environmental importance of the107Ag(n,γ)108Agm reaction in nuclear power reactors,and new 327-1327-1327-1and Iγ measurements

127-year¹⁰⁸Ag^m is an (n,) activation product of¹⁰⁷Ag and is produced in nuclear power reactors. Due to the wide range of reported values for the o ⁰ cross section of the¹⁰⁷Ag(n,)¹⁰⁸Ag^m reaction new measurements were made—resulting in a o ⁰ value of 0.477±0.033 barn, and an I value of 0.80±0.15 barn. The environmental importance of the¹¹⁰Ag^m and¹⁰⁸Ag^m radionuclides is discussed.     

Condensation of 2-(1-ethoxyvinyl)oxiranes with sodiomalonic ester and decarboxylation of the reaction products obtained

-(1-Ethoxyvinyl)- and -(1-ethoxyvinyl)--ethoxycarbonyl--butyrolactones were obtained by the reaction of 2-(1-ethoxyvinyl)oxiranes with sodiomalonic ester. Decarboxylation of the -(1-ethoxyvinyl)--ethoxycarbonyl-butyrolactones in DMSO leads to -(1-ethoxyvinyl)--butyrolactones, the hydrolysis of which gives -acetyl-butyrolactones. Ethyl trans-3-acetyl-3-pentenoate was obtained by decarboxylation of -methyl--(1-ethoxyvinyl)--ethoxycarbonyl--butyrolactone in DMSO.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 22–25, January, 1992.     

Studies in dipyridyl chemistry. VII. Sulfur trioxide sulfonation of γ,γ′-dipyridyl

Reaction of ,-dipyridyl with sulfur trioxide at room temperature gives ,-dipyridyld'isulfotrioxide, which latter on heating at 200° gives ,-dipyridyl-sulfonic acid. Salts of ,-dipyridyl-3-sulfonic acid are prepared, among them the potassium, sodium, barium, and 3-cyano-,-dipyridyl salts.For Part VI see [1].     

Thermal Decomposition of Secondary N-nitramines Having 1,2,4-Triasole and Tetrazole Substituents

Thermal decomposition of secondary N-nitramines having azole substituents in the position is faster by almost two orders of magnitude than the decomposition of -substituted analogs. The rate-determining stage is homolytic dissociation of the NÄNO₂ bond. An alternative route of thermal decomposition of -tetrazolyl-substituted N-nitramines involves initial clavage of the tetrazole ring.     

Quantitative extraction of uranium(VI) in aqueous solutions with n-alkylamine intercalates of γ-titanium phosphate

The intercalation compounds Ti(C₃H₇NH₂)(HPO₄)₂·H₂O (18.4 Å) (-TiP/n-Pr) and Ti(C₄H₉NH₂)(HPO₄)₂·H₂O (20.5 Å) (-TiP/n-Bu) have been prepared using -titanium phosphate, Ti(HPO₄)₂·2H₂O (11.6 Å), as precursor. The retention of UO ₂ ²⁺ , in aqueous solutions by -TiP is very low being only a superficial adsorption phenomenon. When the intercalated materials are used, the retention is quantitative until 95% of the cation exchange capacity in the -TiP/n-Pr case (c.e.c.=6.30 mequiv./g), and over 80% for the -TiP/n-Bu compound (c.e.c.=6.04 mequiv./g).     

The effect of outer sphere cations on the thermal stability of nitritocuprates(II)

Thermal analyses by Derivatograph were made for salts of the general formula M ₂ ^I M^II[Cu(NO₂)₆] where M^I=K⁺, Rb⁺ or Cs⁺; and M^II=Ca²⁺, Sr²⁺, Ba²⁺ or Pb²⁺. From the results and the chemical and diffractometric analysis of sinters of chosen salts, the mechanism of thermal decomposition was established. Some conclusions concerning the effects of outer sphere cations on the thermal stabilities of these salts are also drawn.

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Zusammenfassung Es wurden thermische Analysen mit einem Derivatographen für die Salze der allgemeinen Formel M₂ ^IM^II [Cu(NO₂)₆] durchgeführt [M^I=K⁺, Rb⁺, Cs⁺; M^II=Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺]. Aus den Ergebnissen dieser sowie der chemischen und diffraktometrischen Analysen der Sinterprodukte der jeweiligen Salze wurde der Mechanismus ihrer chemischen Zersetzung ermittelt. Einige Folgerungen bezüglich der Wirkung von Kationen der äusseren Sphäre auf die thermische Stabilität konnten ebenfalls gemacht werden.

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Résumé Le mécanisme de la décomposition thermique des sels de formule générale M₂ ^IM^II [Cu(NO₂)₆] où M^I=K⁺, Rb⁺, Cs⁺ et M^II=Ca²⁺, Sr²⁺, Ba²⁺, Pb²⁺ a été établi à partir des données thermiques obtenues à l'aide d'un Derivatograph, ainsi que par des analyses thermiques et diffractométriques sur les produits frittés. L'effet des cations de la couche externe sur la stabilité thermique de ces sels est discuté.

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M ₂ ^I M^II[Cu(NO₂)₆], M^I=K⁺, Rb⁺, Cs⁺; M^II=Ca²⁺, Sr²⁺, Ba²⁺, b²⁺. , , . , .

     

The role of induced secondary radiation in in situ sorption studies using β-, γ-emitting radionuclides

This article is focused on the effect of -induced radiation in in situ sorption measurements of⁶⁰Co (emitting -and -radiation). The results presented show that the intensity of solution background is primarily due to the -induced radiation (possibly caused by photoeffect and Compton-scattering) and does not change during cobalt accumulation. Experiments were carried out with a pure -emitting isotope (⁹⁹Tc) in order to elaborate a method for the separation of the intensities originating from -and -induced radiations. Various methods of evaluation of sorption measurements are discussed. The extension of the method to application of different radioactive nuclides is considered.     

188Os Low Excited Levels

The -ray spectra of ¹⁸⁸Re decay have been studied by using a compton-suppressed spectrometer and a three parameters --T list coincidence system. Six -rays at 557, 810, 1463, 1867, 1936 and 2022 keV and three levels at 1443, 1936 and 2022 keV are confirmed again. Eight new -rays at 309.60±0.04, 826.90±0.02, 979.29±0.08, 1086.13±0.03, 1103.7±0.4, 1828.2±0.1, 1842.5±0.2, 1982.5±0.2 keV have been identified, three new levels at 309.60, 1828.2 and 1982.5 keV are assigned. The ^–-decay branching ratio is deduced.     

Microcalorimetric Evaluation of Precipitation in Cu–2Be–0.2Mg

Beryllium precipitation from the Cu-rich matrix in a Cu–2 mass% Be–0.2 mass% Mg alloy homogenized and quenched from 1073 K was studied by differential scanning calorimetry (DSC). The DSC traces showed two main exothermic effects, A and B, each comprising two subeffects: A₁ and A₂ , and B₁ and B₂ respectively. Effects A₁ and A₂ correspond to the precipitation of GP zones and subsequent overlapping and independent precipitation of the phase. Only at very low heating rates can be inherited from GP zones. Effects B₁ and B₂ correspond to heat evolved during transitions to the states with and phases, respectively. Heat effect A can be quantitatively described in terms of solid solubilities before and after precipitation, and of the precipitation heats of the phases involved. The heat content of the combined GP zone/ phase precipitation effect was proportional to the number of beryllium atoms precipitated, yielding an average value of 21 kJ mol^–1 beryllium for beryllium precipitation. It was shown that the phase arises from the combined transition from states with GP zones and phases, whereas arises from the transition of states with and phases. The apparent activation energies associated with GP zones and , and phases are 1.16±0.08, 1.18±0.07, 1.37±0.08 and 1.74±0.09 eV, respectively. These values are discussed in terms of the mobility of dissolved atoms related to the concentrations of excess vacancies and solute-vacancy complexes, and the direction of plate-like precipitate growth (either normal or perpendicular to the plate). It is inferred that the main roles of magnesium are to decrease the amount and rate of GP formation, to enhance the volume fraction of and to suppress the discontinuous precipitation of .This revised version was published online in November 2005 with corrections to the Cover Date.