Neutral-molecule reactions, ionic products

A major complication in applying radiation chemical techniques to ion-molecule reaction studies is the formation of nonionic initial species by high energy radiation. Another difficulty arises from the neutralization of ions, which may also result in the formation of free radicals and stable products. The chemical effects arising from the formation of ions and their reactions with molecules are therefore superimposed on those of the neutral species resulting from excitation and neutralization. To derive information of ion-molecule reactions, it is necessary to identify unequivocally products typical of such reactions. Progress beyond a speculative rationalization of results is possible only when concrete evidence that ionic species participate in the mechanism of product formation can be presented. This evidence is the first subject of this discussion. 

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. 

Since the ionic states formed by high-energy radiation seem to be the chemically important ones, let us consider their reactions. The reactions between ions and neutral molecules in the gas phase can be studied directly in a mass spectrometer. Under ordinary operating conditions the pressure in the ionizing chamber of the mass spectrometer is about 10 6 mm. and the ions formed have little chance to collide with a molecule during their brief lifetime (10-5 sec.) before collection. Therefore, mainly unimolecular decomposition reactions occur and it is the products of these that are detected. The intensity of these primary ions increases with the first power of the pressure in the ionization chamber. However, when the pressure becomes great enough so that ion molecule collisions can occur readily, additional secondary ions which are the products of these ion molecule Collisions appear. The intensity of these secondary product ions depends on the concentrations of both the molecules and the primary ions, and thus on the square of the pressure. 

Several books and review chapters devoted to the field of ion-neutral reactions in the gas phase have appeared in recent years, la 8, j,k some of which are concerned at least in part with the special topic of interest for the present review chapter—namely, the role of excited states in such interactions. The present review attempts to present a comprehensive survey of the latter subject, and the processes to be discussed include those in which an excited ion interacts with a ground-state neutral, interaction of an excited neutral with a ground-state ion, and on-neutral interactions that produce excited ionic products or excited neutral products. Reactions in which ions are produced by reaction of an excited neutral species with another neutral, for example, Penning ionization, are not included in the present chapter. For a recent review of this topic, the reader is referred to the article by Rundel and Stebbings.1 Electron-molecule interactions and photon-molecule interactions are discussed here only as they relate to the production of ions in excited states, which can then be reacted with neutral species. 

In the gas phase, addition of an ionic electrophile to a neutral (M) is usually accompanied by elimination of a neutral molecule from the reagent ion. This elimination process stabilizes the reaction products by removing excess energy from the initial ion-molecule adduct. Typically, protonation and alkylation reactions normally used in chemical ionization (Cl) and radiolytic experiments are of this type, as shown in equations 3 (HA+ = CH5+, C2H5+, NH4+, etc.) and 4 (R2X+ = an halonium ion, vide infra), respectively. 

Unfortunately, from the point of view of the physical organic chemist, the mass-spectrometric approach suffers from certain intrinsic limitations. In the first place, the range of pressures accessible to the investigator is severely limited, and most of the available data refer to experiments carried out at pressures well below one torr. In the second place, the mass spectrometer detects only charged species, and the neutral molecules, which represent the final products of the carbonium-ion reactions and are of prime concern to the physical organic chemist, cannot be determined at all. Finally, since the structure of the ionic species, that are analysed exclusively according to their m/e ratio, cannot be directly deduced from mass spectra, it is difficult to discriminate isomeric ions, and to study the isomerization reactions of the carbonium ions, which play such an important role in their solution chemistry. 

Chemical ionization. Chemical ionization spectra result from ion-molecule reaction between the ionic products of a high pressure reagent gas, commonly methane, with a low pressure sample gas. Because of the low abundance of the sample, almost all of the initial ionization by electron impact is of the reagent gas. When methane is ionized at a source pressure of 1 mm Hg, the normal El products CHl and CHs react with neutral CH4 molecules producing a plasma in which CH5 (48% 2) and C2H5 (41% 2) are the principal species available for further ion-molecule reaction ... 

Product formation in a radiolysis system is often complex as a result of the many different species present. There are, however, three main types of reactive species excited molecules, ions and free radicals. The excited molecules and ions are generated directly, while the free radicals are formed by dissociation of the excited molecules or ions. The reactions of these three species account for the products. Decomposition or combination and disproportionation are the main reactions of free radicals in the absence of inhibitors. Excited molecules can lead directly to molecular products by dissociation or to higher products by dimerization reactions. Ionic species can yield molecular products by dissociation (if excited) or by ion-molecule reactions with the formation of a new ion in each case. Neutralization of the positive ions by electrons or by negative ions produces additional molecular products. 

We designed a novel three-compartment source (wide-range radiolysis source) for our research mass spectrometer, which was first used to study the radiolysis of methane. The present technique, employing flow, low pressure, localized ionization, and electric fields appears to be a straightforward approach to the problem, and we hoped that this technique would resolve some of the above discrepancies. Our objectives were to (a) determine the percent abundance of the various reactive primary species—ionic and neutral (b) ascertain the percent abundance of stable products under conditions that would minimize subsequent reactions of reactive stable products (c) calculate G values for these products (d) measure the relative contribution of ion-molecule reactions to the formation of stable products (e) obtain the threshold energies and yield curves for such products to assign their precursors and (f) postulate, from the above information and pressure studies, a mechanism for the production of the radiolytic products from methane. 

Implications of Mass Spectrometric Data for Radiation Chemistry. Apart from the positive identification of the ion-molecule reactions in ethyl chloride, the most significant observation from the mass spectrometric studies which has direct application to the radiolysis of this compound is the fact that at pressures greater than ca. 100 /a, essentially the only stable ion in this system is C4Hi0C1+. Therefore, the neutralization of ions as a potential contributor to radiolysis products will be important only for this ion. Moreover, this will hold true even if there are variations in the extent of primary fragmentation with increasing pressure. The radiolysis studies which will now be described assess the contribution of ionic processes to radiolytic yields and provide some indications as to the mode of neutralization of the stable ionic species in the ethyl chloride system. 

Table III also shows that hydrogen and the chlorinated butanes are reduced substantially when ethyl chloride is irradiated in the presence of benzene. The other products are essentially unaffected by this additive. In the radiolysis of certain alkanes (4), benzene, added in small amounts, does not interfere with the fast ion-molecule reactions of primary ionic fragments or with free radical processes, but it will efficiently condense unreactive or long-lived ions in the system. It is reasonable to assume that this is also true for alkyl halide systems and that the reduction in product yields compared with the pure compound upon adding benzene may be attributed to the interception of unreactive ions. Since the rate constants for reactions of the expected primary ions with ethyl chloride are very large (see Table II), the concentration of benzene used in our experiments should not interfere with the initial fast ion-molecule reactions. For ethyl chloride ion-molecule reactions, C4Hi0C1+ is the only unreactive ion of appreciable abundance which is expected in this system at the elevated pressures used in the radiolysis experiments. Thus, the reduced product yields in the presence of benzene additive can be identified tentatively with the removal of this stable ion and the elimination of its resultant neutralization products.

The radiolysis product yields in the presence of ion scavenger (Table III) also show that ethane is not formed from neutralization of stable ions. Therefore, the remainder of the ethane product (above that indicated to result from neutral decomposition) must be produced by an ion-molecule process—i.e., a yield of G = 1.47. The ion-molecule reactions previously listed show that ethylene ions react with ethyl chloride to form ethane. From the relative rates indicated for Reactions 3a-3d and the ethane yield just derived, a relative yield of 2.46 may be deduced for the ionic fragmentation to ethylene ion in the radiolysis. 

Product Excited Neutral Decompositions Ion-Molecule Reactions and Ionic Fragmentation Neutralization... 

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