Ethylene radiolysis

Assigning a mechanism for the formation of products resulting from ionic intermediates is aided by our knowledge of the probable primary ions and the elementary ion-molecule reactions which they may undergo. The second subject to be examined is the applicability of fragmentation patterns and mass spectrometric ion-molecule reaction studies to radiolysis conditions. Lastly, the formation and the chemistry of the ionic species in ethylene radiolysis will be summarized. 

Two of the many products of ethylene radiolysis—methane and propane—show no or only negligible variation with field strength. Methane is produced by a molecular elimination process, as evidenced by the inability of oxygen or nitric oxide to quench its formation even when these additives are present in 65 mole % concentration (34). Propane is completely eliminated by trace amounts of the above scavengers, suggesting methyl and ethyl radicals as precursors ... 

Application to Ethylene Radiolysis. The predominant ions in the mass spectrum of ethylene (1) are ethylene, vinyl, and acetylene ions, which together account for over 85% of the total ionization. A total of 38% of all ions are C2H4+, and since kF(ethylene) = 25.9 e.v./ion pair, the parent ion should be produced with a yield of at least 1.5 ions/100 e.v. absorbed in ethylene. Similar calculations for the probable yields of the other major ions lead to estimates of 0.96 vinyl ions/100 e.v. and 0.94 acetylene ions/100 e.v. Successive dissociations are relatively unimportant in ethylene. 

Enhancement of the total butene yield is observed when various additives whose ionization potential falls below about 9.4 e.v. are present during ethylene radiolysis (35). This is consistent with the above interpretation (Figure 2). In the vacuum ultraviolet photolysis of cyclobutane the yield of butenes varies with the ionization potential of the additives in the same way as observed here (12). The maximum enhancement corresponds closely to the yield of C4H8+, as expected from our mechanism. 

Acetylene Ion. No evidence for the contribution of ion-molecule reactions originating with acetylene ion to product formation has been obtained to date. By analogy with the two preceding sections, we may assume that the third-order complex should dissociate at pressures below about 50 torr. Unfortunately, the nature of the dissociation products would make this process almost unrecognizable. The additional formation of hydrogen and hydrogen atoms would be hidden in the sizable excess of the production of these species in other primary acts while the methyl radical formation would probably be minor compared with that resulting from ethylene ion reactions. The fate of the acetylene ion remains an unanswered question in ethylene radiolysis. 

The eventual fate of any ion is its neutralization, either by a free electron or by a negative ion formed by electron attachment. In ethylene radiolysis at high dose rates, electron capture processes should be insignificant (29), and the recombination energy of the positive ion will become available on neutralization, a portion of which may be in the form of excitation (59). 

Ethylene. The radiolysis and photolysis of ethylene have been studied extensively, and again both dissociation and free radical processes are well established. A review by Meisels (28) and the references therein discuss the mechanisms in detail. In our experiment the detection of ethyl radicals clearly indicates the prior formation of H atoms, a major primary radical in ethylene radiolysis (27). 

Both this and previous studies demonstrate the existence of rather long chains of consecutive ion-molecule reactions in methane, ethylene, and acetylene, and thus they provide direct evidence for ionic mechanisms of condensation or polymerization in these gases. Polymers have been found in relatively high yields among the radiolysis products of these... 

Proceeding in this manner one finds that some 4.5 ethylene molecules are used up per ion formed. Using the established value of 3.88 ion pairs per 100 e.v. we find a G value for ethylene used up by ionic reactions at 5 torr pressure G( — AC2H4) 17. This shows that ionic mechanisms account for the major part of the ethylene consumed in gas phase radiolysis. 

Phenomenological evidence for the participation of ionic precursors in radiolytic product formation and the applicability of mass spectral information on fragmentation patterns and ion-molecule reactions to radiolysis conditions are reviewed. Specific application of the methods in the ethylene system indicates the formation of the primary ions, C2H4+, C2i/3+, and C2H2+, with yields of ca. 1.5, 1.0, and 0.8 ions/100 e.v., respectively. The primary ions form intermediate collision complexes with ethylene. Intermediates [C4iZ8 + ] and [CJH7 + ] are stable (<dissociation rate constants <107 sec.-1) and form C6 intermediates which dissociate rate constants <109 sec. l). The transmission coefficient for the third-order ion-molecule reactions appears to be less than 0.02, and such inefficient steps are held responsible for the absence of ionic polymerization. 

Considerable support exists for Reaction 18a (35). The application of an electrostatic field during radiolysis of ethylene-nitric oxide (I.P. 9.25 e.v.) mixtures showed no enhancement of the butene yields, consistent with an ionic mechanism. When mixtures of C2D4 and C2H4 are irradiated in the presence of nitric oxide, product butene consists almost entirely of C4H8, C4D4H4, and C4D8—evidence for a molecular association mechanism. 

The conclusions on the occurrence of ion-molecule reaction in the radiolysis of ethylene are not seriously affected by the uncertainties in the neutralization mechanism. It must be assumed that neutralization results in the complex species which constitute the ionic polymer, — i.e., the fraction of the ethylene disappearance which cannot be accounted for by the lower molecular weight products containing up to six carbon atoms. 

On the other hand, the formation of ethylene was ascribed mainly to the unimolecular decomposition of a neutral excited propane molecule. These interpretations were later confirmed (4) by examining the effect of an applied electrical field on the neutral products in the radiolysis of propane. The yields of those products which were originally ascribed to ion-molecule reactions remained unchanged when the field strength was increased in the saturation current region while the yields of hydrocarbon products, which were ascribed to the decomposition of neutral excited propane molecules, increased several fold because of increased excitation by electron impact. In various recent radiolysis 14,17,18,34) and photoionization studies 26) of hydrocarbons, the origins of products from ion-molecule reactions or neutral excited molecule decompositions have been determined using the applied field technique. However, because of recent advances in vacuum ultraviolet photolysis and ion-molecule reaction kinetics, the technique used in the above studies has become somewhat superfluous. 

The ion-molecule reaction between thiirane and its radical cation to form a thiirane sulfide radical cation and ethylene has been studied by Qin, Meng and WiUiams [134]. ESR studies using a low-temperature sohd-state Freon radiolysis technique provided compeUing evidence that the hemibonded dimer radical cation of thiirane is an intermediate in this so-called sulfur-transfer reaction see Scheme 2. 

Temperature dependence (related to the temperature dependence of the conformational structure and the morphology of polymers) of the radiation effect on various fluoropolymers e.g., poly (tetrafluoroethylene-co-hexafluoropropylene), poly(tetrafluoroethylene-co-perfluoroalkylvinylether), and poly(tetrafluoroethylene-co-ethylene) copolymers has been reported by Tabata [419]. Hill et al. [420] have investigated the effect of environment and temperature on the radiolysis of FEP. While the irradiation is carried out at temperatures above the glass transition temperature of FEP, cross-linking reactions predominate over chain scission or degradation. Forsythe et al. [421]... 

The most radiation-stable poly(olefin sulfone) is poly(ethylene sulfone) and the most radiation-sensitive is poly(cyclohexene sulfone). In the case of poly(3-methyl-1-butene sulfone) there is very much isomerization of the olefin formed by radiolysis and only 58.5% of the olefin formed is 3-methyl-l-butene. The main isomerization product is 2-methyl-2-butene (37.3% of the olefin). Similar isomerization, though to a smaller extent, occurs in poly(l-butene sulfone) where about 10% of 2-butene is formed. The formation of the olefin isomer may occur partly by radiation-induced isomerization of the initial olefin, but studies with added scavengers do not support this as the major source of the isomers. The presence of a cation scavenger, triethylamine, eliminates the formation of the isomer of the parent olefin in both cases of poly(l-butene sulfone) and poly(3-methyl-l-butene sulfone) indicating that the isomerization of the olefin occurred mainly by a cationic mechanism, as suggested previously . ... 

Absorption due to main intermediates such as polymer cation radicals and excited states, electrons, and alkyl radicals of saturated hydrocarbon polymers had not been observed for a long time by pulse radiolysis [39]. In 1989, absorption due to the main intermediates was observed clearly in pulse radiolysis of saturated hydrocarbon polymer model compounds except for electrons [39,48]. In 1989, the broad absorption bands due to polymer excited states in the visible region and the tail parts of radical cation and electrons were observed in pulse radiolysis of ethylene-propylene copolymers and the decay of the polymer radical cations were clearly observed [49]. Recently, absorption band due to electrons in saturated hydrocarbon polymer model compounds was observed clearly by pulse radiolysis [49] as shown in Fig. 2. In addition, very broad absorption bands in the infrared region were observed clearly in the pulse radiolysis of ethylene-propylene copolymers [50] as shown in Fig. 3. Radiation protection effects [51] and detailed geminate ion recombination processes [52] of model compounds were studied by nano-, pico-, and subpicosecond pulse radiolyses. 

Benzvalene (18) is a tricyclic benzene isomer containing a bicyclobutane ring system bridged by an ethylene moiety its radical cation is accessible by PET or radiolysis. CIDNP indicated negative hfcs for the alkene protons (H ), strong positive hfcs for the non-allylic bridgehead protons (Hy), and negligible hfcs for the... 

Complexes with organic compounds have been reported. Solubility studies with tributyl phosphate (TBP) indicate the formation of a complex PoC14-2TBP (IS). Weighable amounts of polonium tetrachloride in dilute hydrochloric acid can be titrated to a colorless end point with ethylene-diamine tetra-acetic acid (EDTA) the results suggest a complex with two molecules of EDTA, but solubility studies favor a 1 1 complex. The EDTA complex is soluble in alkali and is more stable in alkaline than in acid media, but the ligand is rapidly destroyed by the radiation and solvent radiolysis products 12). However, EDTA can apparently be used to complex trace polonium in the separation of radium D-E-F mixtures (129). 

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