Negative ion transfers

Various types of negative ion transfers have been observed in the gas phase as well as in the condensed phase. For example, the transfer of the H ion is a fast process, provided that the reaction is exothermic ... 

Several processes are unique to ions. A common reaction type in which no chemical rearrangement occurs but rather an electron is transferred to a positive ion or from a negative ion is tenued charge transfer or electron transfer. Proton transfer is also conunon in both positive and negative ion reactions. Many proton- and electron-transfer reactions occur at or near the collision rate [72]. A reaction pertaining only to negative ions is associative detaclunent [73, 74],... 

Molecular Interaction. The examples of gas lasers described above involve the formation of chemical compounds in their excited states, produced by reaction between positive and negative ions. However, molecules can also interact in a formally nonbonding sense to give complexes of very short lifetimes, as when atoms or molecules collide with each other. If these sticky collisions take place with one of the molecules in an electronically excited state and the other in its ground state, then an excited-state complex (an exciplex) is formed, in which energy can be transferred from the excited-state molecule to the ground-state molecule. The process is illustrated in Figure 18.12. 

The second class of atomic manipulations, the perpendicular processes, involves transfer of an adsorbate atom or molecule from the STM tip to the surface or vice versa. The tip is moved toward the surface until the adsorption potential wells on the tip and the surface coalesce, with the result that the adsorbate, which was previously bound either to the tip or the surface, may now be considered to be bound to both. For successful transfer, one of the adsorbate bonds (either with the tip or with the surface, depending on the desired direction of transfer) must be broken. The fate of the adsorbate depends on the nature of its interaction with the tip and the surface, and the materials of the tip and surface. Directional adatom transfer is possible with the apphcation of suitable junction biases. Also, thermally-activated field evaporation of positive or negative ions over the Schottky barrier formed by lowering the potential energy outside a conductor (either the surface or the tip) by the apphcation of an electric field is possible. FIectromigration, the migration of minority elements (ie, impurities, defects) through the bulk soHd under the influence of current flow, is another process by which an atom may be moved between the surface and the tip of an STM. 

Because both positive and negative ions move under the influence of an electric field, albeit in opposite directions, the fraction of the current carried by an ion is given by the ratio of the mobiUty of the ion and the total mobiUty of all the ions in solution. This ratio is called the transference number t of the ion. Thus ... 

A type of molecular resonance scattering can also occur from the formation of short-lived negative ions due to electron capture by molecules on surfrices. While this is frequently observed for molecules in the gas phase, it is not so important for chemisorbed molecules on metal surfaces because of extremely rapid quenching (electron transfer to the substrate) of the negative ion. Observations have been made for this scattering mechanism in several chemisorbed systems and in phys-isorbed layers, with the effects usually observed as smaU deviations of the cross section for inelastic scattering from that predicted from dipole scattering theory. 

In any pure liquid, the transfer of a proton from one molecule to another (distant) molecule has been named autoprololysis. I11 any solvent this process creates a positive and a negative ion and must clearly belong to class II it will not differ from other proton transfers of class II except for the fact that the relation between Kx and K will be different. On the left-hand side of (127) and (128) there is no solute particle hence the increase in the cratic term is greater than in (119) or (121). In (128) we have Aq — +2, and... 

On closing the external circuit between the two Ag electrodes, when a current flows, the net result will be simply to transfer an amount of solute from one solvent to the other, and the measured e.m.f. will be equal to the change in free energy associated with the transfer of a kome of ions from one solvent to the other. This quantity will contain, in addition to the usual communal term, a unitary term arising from the fact that, in the co-sphere of each positive ion and each negative ion, the amount of free energy lost by the dipoles of one solvent will be different from that lost by the dipoles of the other solvent. 

It was pointed out in Sec. 126 that in any proton transfer of class I the number of negative ions remains unchanged and the number of positive ions remains unchanged and consequently there is the possibility that the contribution from the interionic forces shall remain unchanged. Whether this is so or not can be decided only by experiment. Consider what result should be obtained if (218) and (219) are applicable. In this case, if experimental values of the left-hand side of (218) are plotted... 

Whether the second step does take place depends on a number of factors. The electron affinity of the M ion must be sufficiently great, and this point can be appreciated by considering a few examples. Electron transfer to stilbene or tetraphenyl ethylene leads to the formation of negative ions which in turn rapidly ac-... 

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. 

Reactions of D with D20 and of 0 with 02, N20, and N02 have been studied with a magnetic sector mass spectrometer. Competition between electron transfer and ion-atom interchange has been observed in the production of 02 by reaction of 0 with 02, an endothermic reaction. The negative ion of the reacting neutral molecule is formed in 02, N2Of and N02 but not in D20. Rate constants have been estimated as a function of repeller potential. 

As expected, the addition to the flame of the electronegative species Cl (from HC1) or CN (from CH3CN) produces Cl or CN. At low pressures, the total negative ion population may be increased (9) while at 1 atm. all the negative ions can be replaced by Cl (14). Thus, both direct attachment and charge transfer are involved. 

Direct Electron Transfer. We have already met some reactions in which the reduction is a direct gain of electrons or the oxidation a direct loss of them. An example is the Birch reduction (15-14), where sodium directly transfers an electron to an aromatic ring. An example from this chapter is found in the bimolecular reduction of ketones (19-55), where again it is a metal that supplies the electrons. This kind of mechanism is found largely in three types of reaction, (a) the oxidation or reduction of a free radical (oxidation to a positive or reduction to a negative ion), (b) the oxidation of a negative ion or the reduction of a positive ion to a comparatively stable free radical, and (c) electrolytic oxidations or reductions (an example is the Kolbe reaction, 14-36). An important example of (b) is oxidation of amines and phenolate ions ... 

Description glycosidic cleavage with a hydrogen transfer charge retained on reducing end positive- and negative-ion modes often referred to as )S-cleavage. 

Within the potential range where Ru(bpy)3 remains in the aqueous phase, photocurrent responses are clearly observed with a slow rising time of the order of 10 s as shown in Fig. 14(a). According to the convention employed by these authors, positive currents correspond to the transfer of a negative charge from water to DCE. No photoresponses were observed in the absence of either the dye in the aqueous phase or TCNQ in DCE. Further analysis of the interfacial behavior of the product TCNQ revealed that the ion transfer occurred outside of the polarizable window [cf. Fig. 14(d)], confirming that these photoresponses are not affected by coupled ion-transfer processes. An earlier report also showed photoeffects for the photoreduction of the viologen under similar conditions [131]. 

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