Electron/molecule reactions

Table 12.1. Electron-molecule reactions and parameters of their rate constants...

Figure 5.10 Electron-ion and electron-molecule reactions. (Adapted with permission from Fraser, 2002)...

In the first half of the twentieth century, positive-ion molecule reactions and the interaction of hyperthermal electrons with molecules were emphasized. Some thermal electron molecule reactions in flames and electron swarms were investigated [3]. Prior to 1950 only the electron affinities of hydrogen and the halogen atoms had been measured. A 1953 review on electron affinities noted... 

In the late 1960s several major advances were made in the study of thermal electron reactions. These were based on the ECD, the extension of the magnetron method of studying electron molecule reactions to determine equilibrium constants for electron molecule reactions, and the invention of high-pressure thermal electron negative-ion sources for mass spectrometry [5-7], Electron swarms were also used to determine rate constants for thermal electron reactions [8, 9]. The electron affinities of molecules were measured using electron and alkali metal beams [10, 11]. Relative electron affinities were obtained from the direction of the reaction of a negative ion with a molecule [12, 13], Other major advances were photodetachment and photoelectron spectroscopy [14—17],... 

Qan ratio of unity. This was one of the first determinations of a Qan ratio for electron molecule reactions. The ECD values of the excited-state electron affinity, Qlm, and A i and E agree with the swarm values. The low-temperature response of the ECD can be calculated from parameters measured in swarm experiments. 

Electron-molecule reactions This process is also referred to as electron capture detection mass spectrometry (ECD-MS), and is amenable to compounds containing electrophilic moieties (such as compounds with positive electron affinities). ECD-MS has been investigated and used extensively for analyses of many classes of environmental contaminants and for forensic toxicological applications. 

When studying an electron-molecule reaction one must consider two different temperatures the temperature of the gas (Tg) and the temperature of the electrons (Te), assuming they have a Maxwell-Boltzmann velocity... 

In our simple model, the expression in A2.4.135 corresponds to the activation energy for a redox process in which only the interaction between the central ion and the ligands in the primary solvation shell is considered, and this only in the fonn of the totally synnnetrical vibration. In reality, the rate of the electron transfer reaction is also infiuenced by the motion of molecules in the outer solvation shell, as well as by other... 

Kebarle P 1988 Pulsed electron high pressure mass spectrometer Techniques for the Study of Ion-Molecule Reactions ed J M Farrar and W FI Saunders (New York Wiley-Interscience)... 

Sauer M, Drexhage K H, Lieberwirth U, Muller R, Nerd S and Zander C 1998 Dynamics of the electron transfer reaction between an oxazine dye and DNA oligonucleotides motored on the single-molecule level Chem. Phys. Lett. 284 153-63... 

The concept of biradicals and biradicaloids was often used in attempts to account for the mechanism of photochemical reactions [2,20,129-131]. A biradical (or diradical) may be defined as [132] an even-electron molecule that has one bond less than the number permitted by the standard rules of valence. 

Thus two electrons exit the reaction zone, leaving a positively charged species (M ) called an ion (in this case, a molecular ion). Strictly, M" is a radical-cation. This electron/molecule interaction (or collision) was once called electron impact (also El), although no impact actually occurs. 

Metal oxide electrodes have been coated with a monolayer of this same diaminosilane (Table 3, No. 5) by contacting the electrodes with a benzene solution of the silane at room temperature (30). Electroactive moieties attached to such silane-treated electrodes undergo electron-transfer reactions with the underlying metal oxide (31). Dye molecules attached to sdylated electrodes absorb light coincident with the absorption spectmm of the dye, which is a first step toward simple production of photoelectrochemical devices (32) (see Photovoltaic cells). 

Metal-Catalyzed Oxidation. Trace quantities of transition metal ions catalyze the decomposition of hydroperoxides to radical species and greatiy accelerate the rate of oxidation. Most effective are those metal ions that undergo one-electron transfer reactions, eg, copper, iron, cobalt, and manganese ions (9). The metal catalyst is an active hydroperoxide decomposer in both its higher and its lower oxidation states. In the overall reaction, two molecules of hydroperoxide decompose to peroxy and alkoxy radicals (eq. 5). 

Among the dynamical properties the ones most frequently studied are the lateral diffusion coefficient for water motion parallel to the interface, re-orientational motion near the interface, and the residence time of water molecules near the interface. Occasionally the single particle dynamics is further analyzed on the basis of the spectral densities of motion. Benjamin studied the dynamics of ion transfer across liquid/liquid interfaces and calculated the parameters of a kinetic model for these processes [10]. Reaction rate constants for electron transfer reactions were also derived for electron transfer reactions [11-19]. More recently, systematic studies were performed concerning water and ion transport through cylindrical pores [20-24] and water mobility in disordered polymers [25,26]. 

Equation (5-69) is an important result. It was first obtained by Marcus " in the context of electron-transfer reactions. Marcus derivation is completely different from the one given here. In electron transfer from one molecule (or ion) to another, no bonds are broken or formed, so the transition state theory does not seem to be applicable. Marcus assumed negligible orbital overlap in the electron-transfer transition state, but he later obtained the same equation for group transfer reactions requiring significant overlap. Many applications have been made to proton transfers and nucleophilic displacements. ... 

Nitric oxide is the simplest thermally stable odd-electron molecule known and, accordingly, its electronic structure and reaction chemistry have been very extensively studied. The compound is an intermediate in the production of nitric acid and is prepared industrially by the catalytic oxidation of ammonia (p. 466). On the laboratory scale it can be synthesized from aqueous solution by the mild reduction of acidified nitrites with iodide or ferrocyanide or by the disproportionation of nitrous acid in the presence of dilute sulfuric acid ... 

Recently, Weissman and his colleagues52 showed that the product is paramagnetic indicating that it results from an electron transfer process giving one unpaired electron to the hydrocarbon ion. Furthermore, they demonstrated30 that electron transfer reactions easily proceed in systems containing aromatic" ions and neutral aromatic hydrocarbon molecules, e.g., naphthalene" + phenathrene - naphthalene -j- phenanthrene". 

Addition of methane to the ion source at a pressure of about 0.5 Torr causes almost all of the electrons entering the ion source to collide with methane molecules. The first event is the expected production of a molecular ion (eq. 3). The molecular ion can then undergo fragmentation (eq. 4) or because of the high pressure of neutral methane, ion-molecule reactions can occur (eqs. 5 and 6). 

Chemical ionization (Cl) The formation of new ionized species when gaseous molecules interact with ions. This process may involve the transfer of an electron, proton, or other charged species between the reactants in an ion-molecule reaction. Cl refers to positive ions, and negative Cl is used for negative ions. 

Hamiltonian operator, 2,4 for many-electron systems, 27 for many valence electron molecules, 8 semi-empirical parametrization of, 18-22 for Sn2 reactions, 61-62 for solution reactions, 57, 83-86 for transition states, 92 Hammond, and linear free energy relationships, 95... 

Method (b) corresponds to the usual method of investigating ion-molecule reactions in a high pressure mass spectrometer although charge exchange with slow ions is used instead of electron impact. After preliminary work (9, 23), the method was fully developed by Szabo 20, 21, 22). 

Some of the problems encountered in the mass spectrometric study of ion-molecule reactions are illustrated in a review of the H2-He system (25). If the spectrometer ion source is used as a reaction chamber, a mixture of H2 and He are subjected to electron impact ionization, and both H2+ and He+ are potential reactant ions. The initial problem is iden-... 

---