Ion-molecule reactions / chemistry

We are being somewhat disingenuous here. If performed and interpreted correctly and with the appropriate ancillary phase-change enthalpy information, the enthalpy of formation of an arbitrary species by ion-molecule reaction chemistry and by combustion calorimetry must be the same. That the ionization potential of quinuclidine is higher than l,4-diazabicyclo[2.2.2]octane simply says that there is a stabilizing effect in the radical cation of the latter not found in the former. This information does not say that there is a stabilizing effect in the neutral molecular form of the latter not found in the former. After all, we trust the reader is not bothered by the fact that the ionization potential order of the cyclohexenes increases in the order 1,3-diene < 1,4-diene < 1-ene < 1,3,5-triene (benzene). 

H O A H20/He MW discharge results in a high conversion of H2O to ionic and neutral association products [77-79], The ion/molecule reaction chemistry plays an important role. Primary ion production in the H2O MW plasma is observed under any plasma condition and is given by,... 

Knewstubb, P.F., Mass Spectrometry and Ion-Molecule Reactions, Cambridge University Press, London, 1969. Laeter, J.R. di. Applications of Inorganic Chemistry, Wiley, New York, 2001. 

The sophistication of the concepts being considered by this symposium points up the impressive advances which have been made in recent years in the understanding of ion-molecule reactions. Unfortunately, this knowledge is confined to that fraction of the scientific population which reads the current literature of mass spectrometry or radiation chemistry since writers of textbooks on kinetics have not yet discovered ion-molecule reaction kinetics as an area worthy of more than cursory mention. It is hoped that this symposium will help in some small way to remedy that situation. 

Ton-molecule reactions are of great interest and importance in all areas of kinetics where ions are involved in the chemistry of the system. Astrophysics, aeronomy, plasmas, and radiation chemistry are examples of such systems in which ion chemistry plays a dominant role. Mass spectrometry provides the technique of choice for studying ion-neutral reactions, and the phenomena of ion-molecule reactions are of great intrinsic interest to mass spectrometry. However, equal emphasis is deservedly placed on measuring reaction rates for application to other systems. Furthermore, the energy dependence of ion-molecule reaction rates is of fundamental importance in assessing the validity of current theories of ion-molecule reaction rates. Both the practical problem of deducing rate parameters valid for other systems and the desire to provide input to theoretical studies of ion-molecule reactions have served as stimuli for the present work. 

One of the chief reasons for the recent extensive work in this field has been the recognition that ion-molecule reactions are highly relevant to radiation chemistry. The possibility that certain simple reactions, such as the formation of H3+, participate in the mechanism of product formation was appreciated much earlier 14), but wider applicability of this concept required that the generality of such reactions be demonstrated by an independent, unequivocal method. Mass spectrometry has been the predominant means of investigating ion-molecule reactions. The direct identification of reactant and product ions is appealing, at least in part, because of the conceptual simplicity of this approach. However, the neutral products of ion-molecule reactions cannot be determined directly and must be inferred. Gross chemical measurements can serve as an auxiliary technique since they allow identification of un-... 

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. 

The first complication to be considered is the presence of an electrostatic field during the mass spectrometric study of the reaction. Only few quantitative studies have allowed for the possible contribution of hard collisions to cross-section (25), and the possibility that competitive reactions of the same ion may depend on ion energy is generally neglected in assigning ion-molecule reaction sequences. These effects, however, do not preclude qualitative application of mass spectrometric results to radiation chemistry. 

Radiolytic ethylene destruction occurs with a yield of ca. 20 molecules consumed/100 e.v. (36, 48). Products containing up to six carbons account for ca. 60% of that amount, and can be ascribed to free radical reactions, molecular detachments, and low order ion-molecule reactions (32). This leaves only eight molecules/100 e.v. which may have formed ethylene polymer, corresponding to a chain length of only 2.1 molecules/ ion. Even if we assumed that ethylene destruction were entirely the result of ionic polymerization, only about five ethylene molecules would be involved per ion pair. The absence of ionic polymerization can also be demonstrated by the results of the gamma ray initiated polymerization of ethylene, whose kinetics can be completely explained on the basis of conventional free radical reactions and known rate constants for these processes (32). An increase above the expected rates occurs only at pressures in excess of ca. 20 atmospheres (10). The virtual absence of ionic polymerization can be regarded as one of the most surprising aspects of the radiation chemistry of ethylene. 

The choice of a particular type of gas discharge for quantitative studies of ion-molecule reactions is essential if useful information is to be obtained from ion abundance measurements. Generally, two types of systems have been used to study ion-molecule reactions. The pulsed afterglow technique has been used successfully by Fite et al. (3) and Sayers et al. (1) to obtain information on several exothermic reactions including simple charge transfer processes important in upper atmosphere chemistry. The use of a continuous d.c. discharge was initiated in our laboratories and has been successful in both exothermic and endothermic ion-molecule reactions which occur widely within these systems. 

A second major class of ion-molecule reactions that is relatively poorly studied consists of systems involving very unsaturated hydrocarbon neutrals, especially radicals. The unsaturated nature of the organic chemistry in interstellar clouds leads to sizeable abundances of very unsaturated hydrocarbons such as the polyacetylenes HC H, the carbenes H2C , the radicals C H, and the clusters Cn. Although some work has been done on the chemistry of such species, much of the relevant ion-molecule chemistry involving ions such as C+, CH3, and even C2H2 must be guessed at from generalizations based on a small number of studied systems. 

The first systematic measurements of the reactions of ions with molecules in the gas phase were initiated largely by workers associated with analytical mass spectrometry.4-6 It was the rapidly expanding area of ion-molecule reactions which led to the origin of Gas-Phase Ion Chemistry as a distinct field.7 The discovery that ion-molecule equilibria in the gas phase can be determined by mass spectrometric techniques8 led to an explosion of thermochemical measurements based on determination of equilibria by a variety of techniques.9 Significantly, for the first time, information could be obtained on the thermochemistry of reactions which had solution counterparts of paramount importance such as acidities and basicities. These were obtained from proton transfer equilibria such as,... 

The extension of analytical mass spectrometry from electron ionization (El) to chemical ionization (Cl) and then to the ion desorption (probably more correctly ion desolvation ) techniques terminating with ES, represents not only an increase of analytical capabilities, but also a broadening of the chemical horizon for the analytical mass spectrometrist. While Cl introduced the necessity for understanding ion—molecule reactions, such as proton transfer and acidities and basicities, the desolvation techniques bring the mass spectrometrist in touch with ions in solution, ion-ligand complexes, and intermediate states of ion solvation in the gas phase. Gas-phase ion chemistry can play a key role in this new interdisciplinary integration. 

Techniques for the Study of Ion-Molecule Reactions Farrar, J. M. Saunders, W. H. Jr. (Eds.). Part of series Techniques of Chemistry, Weissbeiger, Ed. Wiley-Interscience New York, 1988. 

Gas-phase ion chemistry is a broad field which has many applications and which encompasses various branches of chemistry and physics. An application that draws together many of these branches is the synthesis of molecules in interstellar clouds (Herbst). This was part of the motivation for studies on the neutralization of ions by electrons (Johnsen and Mitchell) and on isomerization in ion-neutral associations (Adams and Fisher). The results of investigations of particular aspects of ion dynamics are presented in these association studies, in studies of the intermediates of binary ion-molecule Sn2 reactions (Hase, Wang, and Peslherbe), and in those of excited states of ions and their associated neutrals (Richard, Lu, Walker, and Weisshaar). Solvation in ion-molecule reactions is discussed (Castleman) and extended to include multiply charged ions by the application of electrospray techniques (Klassen, Ho, Blades, and Kebarle). These studies also provide a wealth of information on reaction thermodynamics which is critical in determining reaction spontaneity and availability of reaction channels. More focused studies relating to the ionization process and its nature are presented in the final chapter (Harland and Vallance). 

Table 2.1 summarizes some of the events that occur in radiation chemistry through the various stages. The earliest discernible time, obtained from uncertainty principle, AE At - fi, is 1CH7 s, which accounts for the production of fast secondary electrons with energy > 100 eV Times shorter than these are just computed values. It has been suggested that, following ionization in liquid water, the dry hole H20+ can move by exact resonance until the ion-molecule reaction H20+ + H20 — H30+ + OH localizes the hole. The... 

The formation of carbon chains seems to be a natural consequence of the ion-molecule reactions and would be expected to have low activation energies. We have already mentioned the neutral-neutral radical chemistry that may also lead to carbon chain chemistry. 

Essentially, all reactions that require the formation of a chemical bond with an activation energy of around 100 kJ mol-1 are frozen out at the surface of Titan but are considerably faster in the stratosphere, although still rather slow compared with the rates of reaction at 298 K. Chemistry in the atmosphere of Titan will proceed slowly for neutral reactions but faster for ion-molecule reactions and radical-neutral reactions, both of which have low activation barriers. The Arrhenius equation provides the temperature dependence of rates of reactions but we also need to consider the effect of cold temperatures on thermodynamics and in particular equilibrium. 

The quadrupole ion trap traps ions in an electric field generally in the presence of a buffer gas (He). The theory and some of its uses have been discussed by March (26). Ion molecule reactions in ion traps have been reviewed (27). The quadrupole ion trap is a relatively new instrument commercialized <20 years ago and the new generation of instruments has only been available since 1995. Thus gas-phase inorganic chemistry using a quadrupole ion trap is as yet relatively hard to find, but on the increase. 

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