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Correlations redox potentials

Correlating Redox Potential with Equilibrium Constant for Atom Transfer. 242... [Pg.221]

Under appropriate conditions, analysis of cychc voltanuno-grams such as that shown in Figure 1 provide simple measures of the solution redox potentials of transition metal complexes, derived as 1/2. Extensive tabulations of redox potentials are available, and provide a key resource for inorganic chemistry. The correlation redox potentials with parameters such as ligand field strength, ligand hardness, and ionization energy of the transition metal forms an important theoretical framework for transition metal chemistry. [Pg.1172]

Many of the electrochemical studies of metal carbonyl derivatives, and indeed of other species, have sought to correlate redox potentials with other physical or spectroscopic properties. These studies will be described briefly where appropriate but the reader may wish to refer to a review (33) of such correlations in coordination chemistry. A more theoretical basis has also been provided for the often noted relationship between ° and infrared carbonyl, nitrosyl, or isocyanide stretching frequencies (34). [Pg.4]

Williams (64) has correlated redox potential in iron-porphyrin protein complexes with increasing basicity of the ligand. [Pg.281]

Based on correlations between energy level positions and electrochemical redox potentials, it has been estabHshed that polymethine dyes with reduction potentials less than —1.0 V (vs SCE) can provide good spectral sensitization (95). On the other hand, dyes with oxidation potentials lower than +0.2 V ate strong desensitizets. [Pg.496]

An effective method for localizing causes of redox potentials is to plot the total backbone and side chain contributions to ( ) per residue for homologous proteins as functions of the residue number using a consensus sequence, with insertions treated by summing the contribution of the entire insertion as one residue. The results for homologous proteins should be examined for differences in the contributions to ( ) per residue that correlate with observed redox potential differences. These differences can then be correlated with any other sequence-redox potential data for proteins that lack crystal or NMR structures. In addition, any sequences of homologous proteins that lack both redox potentials and structures should be examined, because residues important in defining the redox potential are likely to have semi-sequence conservation of a few key amino acid types. [Pg.407]

The absolute rate constants for attack of carbon-centered radicals on p-benzoquinone (38) and other quinones have been determined to be in the range I0M08 M 1 s 1.1 -04 This rate shows a strong dependence on the electrophilicity of the attacking radical and there is some correlation between the efficiency of various quinones as inhibitors of polymerization and the redox potential of the quinone. The complexity of the mechanism means that the stoichiometry of inhibition by these compounds is often not straightforward. Measurements of moles of inhibitor consumed for each chain terminated for common inhibitors of this class give values in the range 0.05-2.0.176... [Pg.271]

As a simplification, it was assumed that the interactions between charged oligomeric segments were negligible. These redox data correlate well with potential values obtained by extrapolation from quantum ma hanical calculations and redox potential measurements on oligomers of defined chain length. As expected,... [Pg.20]

Fig. 5.14 Inoue et al. carried out a systematic study of the photocatalytic reduction of CO2 by different semiconductor powders in aqueous suspensions. Shown here is the energy correlation between semiconductor catalysts and redox couples in water, as presented in their paper. In principle, the solution species with more positive redox potential with respect to the conduction band level of the semiconductor is preferably reduced at the electrode. Photoexcited electrons in the more negative conduction band certainly have greater ability to reduce CO2 in the solution. (Reproduced from [240])... Fig. 5.14 Inoue et al. carried out a systematic study of the photocatalytic reduction of CO2 by different semiconductor powders in aqueous suspensions. Shown here is the energy correlation between semiconductor catalysts and redox couples in water, as presented in their paper. In principle, the solution species with more positive redox potential with respect to the conduction band level of the semiconductor is preferably reduced at the electrode. Photoexcited electrons in the more negative conduction band certainly have greater ability to reduce CO2 in the solution. (Reproduced from [240])...
An attempt to correlate reduction rate with redox potential of the metal ion... [Pg.478]

The single-electron reduction and oxidation of Co(salen) is solvent dependent as a result of the available coordination sites perpendicular to the CoN202 plane.1220 Furthermore, substituents on the phenyl rings modulate the observed redox potentials and subsequently the 02 binding constants. Hammett correlations are obtained.1221 Potentiometric titrations were performed to determine the 02 binding constants and species distribution as a function of pH for a variety of Schiff base Co complexes.1222... [Pg.110]

With respect to the ring size, it has been stated that neither the redox potentials nor the half-lives of the Ni species are directly correlated to the cavity of the macrocyclic ligand, but the redox potentials are dependent on solvation effects.139 The effect of fused benzene rings and ring conformation has been monitored.140 In Ni complexes of fluorine-containing cyclams (25) the higher oxidation state becomes successively destabilized with respect to Ni, while the lower oxidation state (i.e., Ni1) becomes successively stabilized.141... [Pg.256]

The half-wave redox potentials can be satisfactorily correlated to the energy of the highest occupied molecular orbitals in quinocyclopropenes 118—125 by calculations according to the simple HMO model7S ... [Pg.97]

Although no good quantitative correlation between redox potentials of flavonoids and their prooxidant activities still was not documented, a relationship between the prooxidant toxicity of flavonoids to HL-60 cells and redox potentials apparently takes place [176]. However, there is a simple characteristic of possible prooxidant activity of flavonoids, which increases with an increase in reactive hydroxyl groups in the B ring. From this point of view, the prooxidant activity of flavonoids should increase in the range kaempferol < quercetin < myricetin (Figure 29.7). Thus, for many flavonoids the ratio of their antioxidant and prooxidant activities must depend on the competition between Reactions (14) and (15) and Reaction (17). [Pg.870]

Aquatic plants can sequester As from soils, sediments and directly from water. Temperature, pH, redox potential and nutrient availability affect this sequestration (Robinson et al. 2006), but aquatic plants can control the local conditions. Arsenic is adsorbed to the surface of plant roots via physiochemical reactions. A positive correlation between As and Fe concentrations is consistent with As being incorporated into HFO on the surface of plants. Plant roots at NBM generally have >1000 mg/kg dw As. Plant roots contain 4-5 orders of magnitude more As than surface water or sediments at the same location. [Pg.374]

In Fig.26, the energy correlation is schematically presented. The potential-controlled modulation of the molecular-interfaced enzymes may be interpreted by Fig.26. The enzyme and its substrate molecule have their intrinsic redox potentials. The redox potentials of oxidases and dehydrogenases are determined by an electron transferring molecule, i.e. a cofactor such as FAD, which is located at the active site of the enzyme. Due to potential gradient, an electron can be transferred from the substrate molecule to the active site of the enzyme, if the substrate molecule is accepted by the molecular space of the enzyme active site. However, the electron transfer between the active site of the enzyme and the electrode is regulated by the electrode potential, even if the molecule wire could be completed. It should be reasonable that the enzyme activity is electrically modulated at a threshold of the redox potential of the enzyme. [Pg.356]

Electrochemistry. The redox potentials, as measured by cyclic voltammetry, of 76 (trans) and 77 (cis) porphyrazines are given in Table XXII, where they are compared to all other isomeric products (A4, B4, A3B, AB3). These redox processes show no obvious correlations between the amount of thioether functionality and redox potential. [Pg.522]


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See also in sourсe #XX -- [ Pg.217 , Pg.309 , Pg.334 ]




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