Oxidation states experimental differentiation

Sulphur isotopes (32,33,34,36S) fractionate strongly in the earth s crust because (1) the element occurs in different oxidation states with differential preference for heavy isotopes, (2) the existence of volatile and easily soluble compounds favors kinetic separations, and (3) it is involved in biogenic cycles where the oxidation state is easily changed and kinetic processes are important. From theoretical calculations of Bigeleisen (1961) and data on the isotopic properties of sulphur compounds by Sakai (1957, 1968), the amount of S isotope fractionation and its temperature dependence is known. The information on experimental inorganic isotope fractionation in coexisting sulphide minerals which occur naturally was summarized by Thode (1970), who also discussed the application of S isotopes from sulphides for geo thermometry (cf. also Sakai, 1971). Analytical work on all types of sulphur compounds which occur in nature has been reviewed by Nielsen (1973). 

The complexation of Pu(IV) with carbonate ions is investigated by solubility measurements of 238Pu02 in neutral to alkaline solutions containing sodium carbonate and bicarbonate. The total concentration of carbonate ions and pH are varied at the constant ionic strength (I = 1.0), in which the initial pH values are adjusted by altering the ratio of carbonate to bicarbonate ions. The oxidation state of dissolved species in equilibrium solutions are determined by absorption spectrophotometry and differential pulse polarography. The most stable oxidation state of Pu in carbonate solutions is found to be Pu(IV), which is present as hydroxocarbonate or carbonate species. The formation constants of these complexes are calculated on the basis of solubility data which are determined to be a function of two variable parameters the carbonate concentration and pH. The hydrolysis reactions of Pu(IV) in the present experimental system assessed by using the literature data are taken into account for calculation of the carbonate complexation. 

Equation (10) shows that the isomer shift IS is a direct measure of the total electronic density at the probe nucleus. This density derives almost exclusively from 5-type orbitals, which have non-zero electron densities at the nucleus. Band electrons, which have non-zero occurrence probabilities at the nucleus and 5-type conduction electrons in metals may also contribute, but to a lesser extent. Figure 3 shows the linear correlation that is observed between the experimental values of Sb Mossbauer isomer shift and the calculated values of the valence electron density at the nucleus p (0). The total electron density at the nucleus p C ) (Eq. 10) is the sum of the valence electron density p (0) and the core electron density p (0), which is assumed to be constant. This density is not only determined by the 5-electrons themselves but also by the screening by other outer electrons p-, d-, or /-electrons) and consequently by the ionicity or covalency and length of the chemical bonds. IS is thus a probe of the formal oxidation state of the isotope under investigation and of the crystal field around it (high- and low-spin Fe may be differentiated). The variation of IS with temperature can be used to determine the Debye temperature of a compound (see Eq. (13)). 

If a chemical reaction is operated in a flow reactor under fixed external conditions (temperature, partial pressures, flow rate etc.), usually also a steady-state (i.e., time-independent) rate of reaction will result. Quite frequently, however, a different response may result The rate varies more or less periodically with time. Oscillatory kinetics have been reported for quite different types of reactions, such as with the famous Belousov-Zha-botinsky reaction in homogeneous solutions (/) or with a series of electrochemical reactions (2). In heterogeneous catalysis, phenomena of this type were observed for the first time about 20 years ago by Wicke and coworkers (3, 4) with the oxidation of carbon monoxide at supported platinum catalysts, and have since then been investigated quite extensively with various reactions and catalysts (5-7). Parallel to these experimental studies, a number of mathematical models were also developed these were intended to describe the kinetics of the underlying elementary processes and their solutions revealed indeed quite often oscillatory behavior. In view of the fact that these models usually consist of a set of coupled nonlinear differential equations, this result is, however, by no means surprising, as will become evident later, and in particular it cannot be considered as a proof for the assumed underlying reaction mechanism. 

The stoicheiometric number concept has been applied to butane dehydrogenation, the isobutane-isobutene-H2 system, SO2 oxidation and ethanol dehydrogenation. Experimentally it is desirable to operate in a differential mode, using a reactor either of the recirculating or once-through continuous flow type. Since the method is based on the assumption that a steady state exists as regards the concentration of surface intermediates, pulsed flow reactors are not suitable for this type of experiment. 

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