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Equilibrium charge-transfer

Comparison of thermal and photochemical activation. The identical color changes that accompany the thermal and photochemical methyl transfer in various [Py+, BMe ] salts suggests that pre-equilibrium charge-transfer complexation is common to both processes. Moreover, the methyl transfer either by charge-transfer photolysis or by thermal activation of [Py+, BMeT] leads to the same products, which strongly suggests common reactive intermediates (i.e., the radical pair in equation (46)) for both thermal and photochemical processes. [Pg.250]

The question now arises as to what factors are responsible for determining the rates at which the various cell processes occur. Thermodynamic arguments permit the feasibility of overall cell reactions to be predicted, but give no information on rates. To understand the latter it is necessary to consider the effects on various parts of the cell of forcing the cell voltage to assume a value different from that of the equilibrium emf. It has been shown above that in the Daniell cell at equilibrium, charge transfer across the zinc/solution interface can be described in terms of processes... [Pg.38]

This formula represents the difference between the logarithm of the anode and cathode concentrations, each of which are referenced to the equilibrium value Cq. The result derives from the Nernst equation under the assumption that the current in the fluid may be considered small in comparison with the equilibrium charge transfer rate that takes place at the electrodes. [Pg.369]

These charge-transfer structures have been studied [4] in terms a very limited number of END trajectories to model vibrational induced electron tiansfer. An electronic 3-21G-1- basis for Li [53] and 3-21G for FI [54] was used. The equilibrium structure has the geometry with a long Li(2)—FI bond (3.45561 a.u.) and a short Li(l)—H bond (3.09017 a.u.). It was first established that only the Li—H bond stietching modes will promote election transfer, and then initial conditions were chosen such that the long bond was stretched and the short bond compressed by the same (%) amount. The small ensemble of six trajectories with 5.6, 10, 13, 15, 18, and 20% initial change in equilibrium bond lengths are sufficient to illustrate the approach. [Pg.245]

Recently the solvent effect on the [4+2] cycloaddition of singlet oxygen to cyclic dienes has been subjected to a multiparameter analysis. A pre-equilibrium with charge-transfer character is involved, which is affected by the solvent through dipolarity-polarisability (n ) and solvophobic interactions ( Sjf and Another multiparameter analysis has been published by Gajewski, demonstrating the... [Pg.9]

It should be noted that dative bonds, like metal complexes and charge transfer species, in general have RHF wave functions which dissociate correctly, and the equilibrium bond lengths in these cases are normally too long. [Pg.112]

The region of immunity [Fig. 1.15 (bottom)] illustrates how corrosion may be controlled by lowering the potential of the metal, and this zone provides the thermodynamic explanation of the important practical method of cathodic protection (Section 11.1). In the case of iron in near-neutral solutions the potential E = —0-62 V for immunity corresponds approximately with the practical criterion adopted for cathodically protecting the metal in most environments, i.e. —0-52 to —0-62V (vs. S.H.E.). It should be observed, however, that the diagram provides no information on the rate of charge transfer (the current) required to depress the potential into the region of immunity, which is the same (< —0-62 V) at all values of pH below 9-8. Consideration of curve//for the Hj/HjO equilibrium shows that as the pH... [Pg.71]

Fig. 1.20 Cell consisting of two reversible Ag /Ag electrodes (Ag in AgN03 solution). The rate and direction of charge transfer is indicated by the length and arrow-head as follows gain of electrons by Ag -he- Ag—> loss of electrons by Ag - Ag + e- —. (o) Both electrodes at equilibrium and (f>) electrodes polarised by an external source of e.m.f. the position of the electrodes in the vertical direction indicates the potential change. (K, high-impedance voltmeter A, ammeter R, variable resistance)... Fig. 1.20 Cell consisting of two reversible Ag /Ag electrodes (Ag in AgN03 solution). The rate and direction of charge transfer is indicated by the length and arrow-head as follows gain of electrons by Ag -he- Ag—> loss of electrons by Ag - Ag + e- —. (o) Both electrodes at equilibrium and (f>) electrodes polarised by an external source of e.m.f. the position of the electrodes in the vertical direction indicates the potential change. (K, high-impedance voltmeter A, ammeter R, variable resistance)...
For simplicity a cell consisting of two identical electrodes of silver immersed in silver nitrate solution will be considered first (Fig. 1.20a), i.e. Agi/AgNOj/Ag,. On open circuit each electrode will be at equilibrium, and the rate of transfer of silver ions from the metal lattice to the solution and from the solution to the metal lattice will be equal, i.e. the electrodes will be in a state of dynamic equilibrium. The rate of charge transfer, which may be regarded as either the rate of transfer of silver cations (positive charge) in one direction, or the transfer of electrons (negative charge) in the opposite direction, in an electrochemical reaction is the current I, so that for the equilibrium at electrode I... [Pg.77]

If the areas of the electrodes are assumed to be 1 cm, and taking the equilibrium exchange current density /g for the Ag /Ag equilibrium to be 10 A cm", then /g will be 10 A, which is a very high rate of charge transfer. A similar situation will prevail at electrode II, and rates of exchange of silver ions and the potential will be the same as for electrode I. [Pg.77]

Consider now the transfer of electrons from electrode II to electrode I by means of an external source of e.m.f. and a variable resistance (Fig.. 20b). Prior to this transfer the electrodes are both at equilibrium, and the equilibrium potentials of the metal/solution interfaces will therefore be the same, i.e. Ey — Ell = E, where E, is the reversible or equilibrium potential. When transfer of electrons at a slow rate is made to take place by means of the external e.m.f., the equilibrium is disturbed and Uie rat of the charge transfer processes become unequal. At electrode I, /ai.i > - ai.i. 3nd there is... [Pg.77]

In the previous example of an electrolytic cell the two electrodes were immersed in the same solution of silver nitrate, and the system was therefore thermodynamically at equilibrium. However, if the activities of Ag at the electrodes differ, the system is unstable, and charge transfer will occur in a direction that tends to equalise the activities, and equilibrium is achieved only when they are equal. [Pg.78]

It is apparent (Fig. 1.21) that at potentials removed from the equilibrium potential see equation 1.30) the rate of charge transfer of (a) silver cations from the metal to the solution (anodic reaction), (b) silver aquo cations from the solution to the metal (cathodic reaction) and (c) electrons through the metallic circuit from anode to cathode, are equal, so that any one may be used to evaluate the rates of the others. The rate is most conveniently determined from the rate of transfer of electrons in the metallic circuit (the current 1) by means of an ammeter, and if / is maintained constant it can eilso be used to eveduate the extent. A more precise method of determining the quantity of charge transferred is the coulometer, in which the extent of a single well-defined reaction is determined accurately, e.g. by the quantity of metal electrodeposited, by the volume of gas evolved, etc. The reaction Ag (aq.) -t- e = Ag is utilised in the silver coulometer, and provides one of the most accurate methods of determining the extent of charge transfer. [Pg.80]

Equilibrium constants for complex formation (A") have been measured for many donor-acceptor pairs. Donor-acceptor interaction can lead to formation of highly colored charge-transfer complexes and the appearance of new absorption bands in the UV-visible spectrum may be observed. More often spectroscopic evidence for complex formation takes the font) of small chemical shift differences in NMR spectra or shifts in the positions of the UV absorption maxima. In analyzing these systems it is important to take into account that some solvents might also interact with donor or acceptor monomers. [Pg.352]

Zollinger and coworkers (Nakazumi et al., 1983) therefore supposed that the diazonium ion and the crown ether are in a rapid equilibrium with two complexes as in Scheme 11-2. One of these is the charge-transfer complex (CT), whose stability is based on the interaction between the acceptor (ArNj) and donor components (Crown). The acceptor center of the diazonium ion is either the (3-nitrogen atom or the combined 7r-electron system of the aryl part and the diazonio group, while the donor centers are one or more of the ether oxygen atoms. The other partner in the equilibrium is the insertion complex (IC), as shown in structure 11.5. Scheme 11-2 is intended to leave the question open as to whether the CT and IC complexes are formed competitively or consecutively from the components. ... [Pg.300]

An ideally polarized electrode is rigorously defined as the electrode at which no charge transfer across the metal/solution interface can occur, regardless of the potential externally imposed on the electrode. At any fixed potential, such an electrode system attains a true state of equilibrium. [Pg.258]

On the other hand, the electrochemical potentials of electrons, pe, oxygen ions, jIo2, and gaseous oxygen, po2 are related via the charge transfer equilibrium at the three-phase-boundaries (tpb) metal-support-gas38"40 ... [Pg.497]

Because of the dependence of the dissociation on the polarity of the solvent medium, in the less polar acetone solvent the dissolution of [3-2] does not give rise to the green colour of the Kuhn s carbanion [2 ] but simply the pale yellow colour of the hydrocarbon [3-2]. However, when pyrene, which forms a charge-transfer complex with the tropylium ion (Dauben and Wilson, 1968), is added to the acetone solution, it turns green, indicating that the dissociation is induced by pyrene and that the equilibrium is shifted to the ionic side (Okamoto et al., 1985). [Pg.192]


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