Isotopic exchange oxide

V.A. Sobyanin, V.I. Sobolev, V.D. Belyaev, O.A. Mar ina, A.K. Demin, and A.S. Lipilin, On the origin of the Non-Faradaic electrochemical modification of catalytic activity (NEMCA) phenomena. Oxygen isotope exchange on Pt electrode in cell with solid oxide electrolyte, Catal. Lett. 18, 153-164 (1993). 

Kinetic data exist for all these oxidants and some are given in Table 12. The important features are (i) Ce(IV) perchlorate forms 1 1 complexes with ketones with spectroscopically determined formation constants in good agreement with kinetic values (ii) only Co(III) fails to give an appreciable primary kinetic isotope effect (Ir(IV) has yet to be examined in this respect) (/ ) the acidity dependence for Co(III) oxidation is characteristic of the oxidant and iv) in some cases [Co(III) Ce(IV) perchlorate , Mn(III) sulphate ] the rate of disappearance of ketone considerably exceeds the corresponding rate of enolisation however, with Mn(ril) pyrophosphate and Ir(IV) the rates of the two processes are identical and with Ce(IV) sulphate and V(V) the rate of enolisation of ketone exceeds its rate of oxidation. (The opposite has been stated for Ce(IV) sulphate , but this was based on an erroneous value for k(enolisation) for cyclohexanone The oxidation of acetophenone by Mn(III) acetate in acetic acid is a crucial step in the Mn(II)-catalysed autoxidation of this substrate. The rate of autoxidation equals that of enolisation, determined by isotopic exchange , under these conditions, and evidently Mn(III) attacks the enolic form. 

This discovery was quite unexpected, since iron oxide has been never reported as an active catalyst in either partial or full oxidation. The studies of two simplest reactions, i.e. O2 isotopic exchange and N2O decomposition, revealed a dramatic change of Fe properties in the ZSM-5 matrix compared to Fe203 [4]. Fe atoms lose their ability to activate O2 but gain remarkably in their ability to activate N2O. It gives rise to a great effect of the oxidant nature in the reaction of benzene oxidation over the FeZSM-5 zeolite (Table 1). Thus, in the presence of N2O benzene conversion is 27% at 623 K, while in the presence of O2 it is only 0.3% at 773 K. And what is more, there is a perfect change of the reaction route. Instead of selective phenol formation with... 

Relaxation studies have shown that the attachment of an ion to a surface is very fast, but the establishment of equilibrium in wel1-dispersed suspensions of colloidal particles is much slower. Adsorption of cations by hydrous oxides may approach equilibrium within a matter of minutes in some systems (39-40). However, cation and anion sorption processes often exhibit a rapid initial stage of adsorption that is followed by a much slower rate of uptake (24,41-43). Several studies of short-term isotopic exchange of phosphate ions between aqueous solutions and oxide surfaces have demonstrated that the kinetics of phosphate desorption are very slow (43-45). Numerous hypotheses have been suggested for this slow attainment of equilibrium including 1) the formation of binuclear complexes on the surface (44) 2) dynamic particle-particle interactions in which an adsorbing ion enhances contact adhesion between particles (43,45-46) 3) diffusion of ions into adsorbents (47) and 4) surface precipitation (48-50). 

Figure 8. Example of apparent closed-system equilibrium fractionation, where Mo in solution is sorbed to Mn oxides (Barling and Anbar 2004). The 6 Mo values of the Mo remaining in solution during sorption follow die linear trends that are consistent widi closed-system equilibrium fractionation where isotopic equilibrium is continuously maintained between Mo in solution and diat sorbed to die Mn oxides. Three aqueous-solid pairs (shown widi tie lines) are consistent with this interpretation. The isotopic data cannot be ejqilained dirough a Rayleigh process, where die product of die reaction (sorbed Mo) is isolated from isotopic exchange widi aqueous Mo.

The isotopic effects of sorption remain relatively unknown, with disparate interpretations of its significance during DIR. An important avenue of future research will be to quantify the rates of isotopic exchange between sorbed Fe(II) and Fe(II)3q, and to investigate a range of ferric oxide/hydroxide substrates. Because traditional sorption experiments generally... 

Figure 12. Possible isotope fractionation steps during anaerobic photosynthetic Fe(II) oxidation (APIO). It is assumed that the process of oxidation proceeds through an oxidation step, where Fe(II),q is converted to soluble Fe(III) in close proximity to the cell, followed by precipitation as ferric oxides/hydroxides. As in DIR (Fig. 5), the most likely step in which the measured Fe isotope fractionations are envisioned to occur is during oxidation, where isotopic exchange is postulated to occur between pools of Fe(II) and Fe(III) (Aj). As discussed in the text and in Croal et al. (2004), however, it is also possible that significant Fe isotope fractionation occurs between Fe(III), and the ferrihydrite precipitate (Aj) in this case the overall isotopic fractionation measured between Fe(II), and the ferrihydrite precipitate would reflect the sum of A and Aj, assuming the proportion of Fe(III) is small (see text for discussion). Isotopic exchange may also occur between Fe(II),q and the ferric hydroxide precipitate (Aj), although this is considered unlikely.

Figure 8. Results of Mo adsoqjtion experiments of Barling and Anbar (2004). Mo-bearing solutions were exposed to synthetic Mn oxides (5-Mn02) for 2-96 hours at pH 6.5-8.5. Residual Mo in solution ( ) was measured for all experiments. Mo adsorbed to oxide particle surfaces ( ) was either measured or inferred from mass balance. Dissolved Mo was systematically heavier than adsorbed Mo with a fractionation factor of 1.0018 0.0005. The data are consistent with closed system equilibrium, in which isotopes exchange continuously between surface and solution, but incompatible with an irreversible, Rayleigh-type process. Figure modified after Barling and Anbar (2004).

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