Chemical Determination of Free‐Ion Yields in Irradiated Liquid Hydrocarbons

1968 ◽  
Vol 49 (6) ◽  
pp. 2861-2863 ◽  
Author(s):  
Stefan J. Rzad ◽  
John M. Warman
1972 ◽  
Vol 50 (16) ◽  
pp. 2697-2698 ◽  
Author(s):  
G. R. Freeman ◽  
J.-P. Dodelet

Two seemingly unrelated phenomena in liquid hydrocarbons have similar trends in their dependences upon the molecular structure of the hydrocarbon. The phenomena are the annihilation half-life of triplet positronium and the radiolysis free ion yield. In n-alkanes the effect of increasing the molecular chain length, upon both phenomena, appears to be simply to increase the density of interacting sites. Branching the alkane chain decreases the strength of molecular interaction with both electrons and positronium, although the relative decrease is much greater for the former than for the latter. The effects of double bonds on the phenomena, after separating out the density effect, are different from each other.


1970 ◽  
Vol 48 (15) ◽  
pp. 2429-2432 ◽  
Author(s):  
N. H. Sagert ◽  
J. A. Reid

The room temperature, liquid phase radiolysis of n-hexane, 3-methylpentane, and 2,2,4-trimethyl-pentane has been examined using perfluorocyclohexane as an electron scavenger. Yields of C6F11H and C6F11CH3 were determined for scavenger concentrations below 5 × 10−3 M, and from these results free ion yields of 0.08, 0.17, and 0.37 G units were deduced for n-hexane, 3-methylpentane, and 2,2,4-trimethylpentane, respectively. These results are in good agreement with those obtained by other methods.


1969 ◽  
Vol 47 (6) ◽  
pp. 885-892 ◽  
Author(s):  
D. W. Brazier ◽  
G. R. Freeman

An attempt was made to test the cavity model of electron localization in liquid hydrocarbons by measuring the effect of pressures up to 4000 bars on the radiation induced conductance of n-pentane, n-hexane, n-octane, cyclopentane, methylcyclohexane, and 2,2-dimethylbutane at 30°. Measurements at 3 and 56° were also made on n-hexane and n-octane. The relative induced conductance, i.e. the ratio of the induced conductance at pressure p to that at 1 bar, decreased with increasing pressure. The amount of decrease was slightly greater at low than at high temperatures. The behavior of 2,2-dimethylbutane was complex and is not understood. For the other liquids, it was concluded that the free ion yields remained constant or decreased somewhat with increasing pressure. An appreciable increase in the free ion yields, which is a possible implication of the cavity model of electron localization, did not occur. Therefore, either (a) the cavity model of electron localization in hydrocarbons is wrong, or (b) application of pressures up to 4000 bars did not appreciably alter the cavity concentrations in the liquids. Perhaps the cavity concentration is greatly reduced only by pressures great enough to cause a solid phase (glass or crystal) to form.


1957 ◽  
Vol 24 (3_Suppl) ◽  
pp. S319-S323 ◽  
Author(s):  
Heinz Breuer ◽  
Wolfgang Nocke

1963 ◽  
Vol 44 (1) ◽  
pp. 47-66 ◽  
Author(s):  
W. Nocke ◽  
H. Breuer

ABSTRACT A method for the chemical determination of 16-epi-oestriol in the urine of nonpregnant women with a qualitative sensitivity of less than 0.5 μg/24 h is described. The separation of 16-epi-oestriol and oestriol is accomplished by converting 16-epi-oestriol into its acetonide, a reaction which is stereoselective for cis-glycols and therefore not undergone by oestriol as a trans-glycol. Following partition between chloroform and aqueous alkali, the acetonide of 16-epi-oestriol is completely separated with the organic layer whereas oestriol as a strong phenol remains in the alkaline phase. 16-epi-oestriol is chromatographed on alumina as the acetonide and determined as a Kober chromogen. This procedure can easily be incorporated into the method of Brown et al. (1957 b) thus making possible the simultaneous routine assay of oestradiol-17β, oestrone, oestriol and 16-epi-oestriol from one sample of urine. The specificity of the method was established by separation of 16-epi-oestriol from nonpregnancy urine as the acetonide, hydrolysis of the acetonide by phosphoric acid, isolation of the free compound by microsublimation and identification by micro melting point, colour reactions and chromatography. The accuracy of the method is given by a mean recovery of 64% for pure crystalline 16-epi-oestriol when added to hydrolysed urine in 5–10 μg amounts. The precision is given by s = 0.24 μg/24 h. For the duplicate determination of 16-epi-oestriol the qualitative sensitivity is 0.44 μg/24 h, the maximum percentage error being ± 100% The quantitative sensitivity (±25% error) is 1.7 μg/24 h.


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