Transferable potential

H.J.C. Towards phase transferable potential fnaf -2 . plication to nitrogen. J. Chem. Phys. 103 C ... 

Martin M G and J I Siepmann 1999. Novel Configurational-bias Monte Carlo Method for Blanche Molecules. Transferable Potentials for Phase Equilibria. 2. United-atom Description of Branchi Alkanes. Journal of Physical Chemistry 103 4508-4517. 

Countereurrent bubble flow with liquid-supported solids, whieh ean be affeeted by downward liquid fluidization of partieles having a density lower than that of the liquid, has been referred to as inverse three-phase fluidization. The mass transfer potential of sueh a eountercurrent operation is worthy of study, especially for cases in whieh dispersion of the gas rather than the liquid is ealled for and the required gas-liquid ratio and throughput ean be effected without flooding. In contrast, the eorresponding eoeurrent mode has reeeived more attention than all other eases and eonstitutes the majority of the literature on three-phase fluidization. 

The concept of group transfer potential is not particularly novel. Other kinds of transfer (of hydrogen ions and electrons, for example) are commonly... 

The free energy change, which we henceforth call the group transfer potential, is given by... 

Even this set of equations represents an approximation, because ATP, ADP, and Pi all exist in solutions as a mixture of ionic species. This problem is discussed in a later section. For now, it is enough to note that the free energy changes listed in Table 3.3 are the group transfer potentials observed for transfers to water. 

Several additional points should be made. First, although oxygen esters usually have lower group-transfer potentials than thiol esters, the O—acyl bonds in acylcarnitines have high group-transfer potentials, and the transesterification reactions mediated by the acyl transferases have equilibrium constants close to 1. Second, note that eukaryotic cells maintain separate pools of CoA in the mitochondria and in the cytosol. The cytosolic pool is utilized principally in fatty acid biosynthesis (Chapter 25), and the mitochondrial pool is important in the oxidation of fatty acids and pyruvate, as well as some amino acids. 

Similarly, blocked intake screens caused by aquatic weeds, mussels, or floating debris reduce the heat transfer potential of the condenser. 

Figure 30-17. Formation of S-adenosylmethionine. -CHj represents the high group transfer potential of "active methionine."...

Nucleoside Triphosphates Have High Group Transfer Potential... 

Nucleoside triphosphates have high group transfer potential and participate in covalent bond syntheses. The cyclic phosphodiesters cAMP and cGMP function as intracellular second messengers. 

The many redox reactions that take place within a cell make use of metalloproteins with a wide range of electron transfer potentials. To name just a few of their functions, these proteins play key roles in respiration, photosynthesis, and nitrogen fixation. Some of them simply shuttle electrons to or from enzymes that require electron transfer as part of their catalytic activity. In many other cases, a complex enzyme may incorporate its own electron transfer centers. There are three general categories of transition metal redox centers cytochromes, blue copper proteins, and iron-sulfur proteins. 

A relative scale of the standard Gibbs energies of ion transfer or the standard ion transfer potentials can be established based on partition and solubility measurements. The partition eqnilibrium of the electrolyte can be characterized by a measnrable parameter, the partition coefficient P x-... 

The standard Gibbs energy of electrolyte transfer is then obtained as the difference AG° x ° = AG° ° - AG° x. To estabfish the absolute scale of the standard Gibbs energies of ion transfer or ion transfer potentials, an extrathermodynamic hypothesis must be introduced. For example, for the salt tetraphenylarsonium tetraphenyl-borate (TPAs TPB ) it is assumed that the standard Gibbs energies of transfer of its ions are equal. 

TABLE 32.2 Standard Gibbs Energy of Transfer and Standard Ion Transfer Potentials for Ion Transfer Between Water and Nitrobenzene Derived from Partition Measurements... 

FIGURE 32.4 Potential dependence of the interfacial tension J and the capacity C for the interface between solutions of 5mM tetrabutylammonium tetraphenylborate in 1,2-dichloroethane and lOOmM LiCl in water. The potential scale E represents the Galvani potential difference relative to the standard ion transfer potential for tetraethylammonium ion, cP o EA+ = 0.02 V. 

Previously, Osaka and coworkers [29-31] employed ion-transfer voltammetry to determine the standard ion-transfer potentials (Aq 4> ) of heteropoly- and isopolyoxome-talate anions (in short, polyanions) at the nitrobenzene (NB)/W and 1,2-dichloroethane (1,2-DCE)/W interfaces is directly related to the transfer energy by... 

Accordingly, the contribution of the CT interaction to the ion-transfer potential [being given by Eq. (7)] can be expressed as... 

Calculated from the standard ion-transfer potentials compiled previously [33]. 

Thus, the HLB of an ionic surface-active substance is balanced at the standard ion-transfer potential. This is simply a reinterpretation of the definition of Aq P, but is a very important relation, which is valid no matter what the actual form of the adsorption... 

Heterogeneous ET reactions at polarizable liquid-liquid interfaces have been mainly approached from current potential relationships. In this respect, a rather important issue is to minimize the contribution of ion-transfer reactions to the current responses associated with the ET step. This requirement has been recognized by several authors [43,62,67-72]. Firstly, reactants and products should remain in their respective phases within the potential range where the ET process takes place. In addition to redox stability, the supporting electrolytes should also provide an appropriate potential window for the redox reaction. According to Eqs. (2) and (3), the redox potentials of the species involved in the ET should match in a way that the formal electron-transfer potential occurs within the potential window established by the transfer of the ionic species present at the liquid-liquid junction. The results shown in Figs. 1 and 2 provide an example of voltammetric ET responses when the above conditions are fulfilled. A difference of approximately 150 mV is observed between Ao et A" (.+. ... 

Aq ° is the standard ion-transfer potential (these values for some ions can be found in Ref. 74), z is the number of the charge of the potential-determining ion, and are the activities of the potential-determining ion in the oil and water phases, respectively. 

The concentration of the transferred ion in organic solution inside the pore can become much higher than its concentration in the bulk aqueous phase [15]. (This is likely to happen if r <5c d.) In this case, the transferred ion may react with an oppositely charged ion from the supporting electrolyte to form a precipitate that can plug the microhole. This may be one of the reasons why steady-state measurements at the microhole-supported ITIES are typically not very accurate and reproducible [16]. Another problem with microhole voltammetry is that the exact location of the interface within the hole is unknown. The uncertainty of and 4, values affects the reliability of the evaluation of the formal transfer potential from Eq. (5). The latter value is essential for the quantitative analysis of IT kinetics [17]. Because of the above problems no quantitative kinetic measurements employing microhole ITIES have been reported to date and the theory for kinetically controlled CT reactions has yet to be developed. 

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