Residence times of intermediates

Figure 9. Proportions of species overtime for the process of oxidation of Fe(II),( to Fe(III), followed by precipitation of ferrihydrite (Eqn. 5), as calculated using the first-order rate laws of Equations (6)-(8), and the rate constant from Figure 8. (A) Proportion of species calculated from Equations (6)-(8), assuming a kilki ratio of 10. Ferrihydrite represented as Fe(OH)3 for simplicity. (B) The residence time of intermediate species Fe(III),q, as calculated using Equation (10), for various kjh ratios.

A prototype study for this issue was performed for the conversion of ethane to acetic acid [71] and the same group highlighted in an earlier comparative study of C3 oxidation [54] that, although initial propane activation is a difficult step, subsequent reactions associated with either excessive residence times of intermediates or with branching of reaction sequences into total oxidation may interfere with the overall selectivity to partial oxidation products. 

Future developments in Accelerator Mass Spectrometry might enable development of Ar to a routine tool in oceanography. If the technical difficulties in measuring this noble gas isotope on small water samples can be mastered, it would offer a unique tool for studies of ocean circulation on time scales ranging from decades to the order of one thousand years, a good match for mean residence times of intermediate and deep waters (e.g., Loosli 1989). 

Since SSITKA can decouple the apparent rate of reaction into the contribution from the intrinsic activity ( the reciprocal of surface residence time of intermediates) and the nrnnber of active sites ( surface concentration of intermediates), the cause of deactivation of a catalyst during reaction can often be revealed. SSITKA has been used in a number of studies for this purpose. Catalyst deactivation during n-butane isomerization and selective CO oxidation are good examples. Deactivation studies are conducted by collecting isotopic transient data at particular times-on-stream as deactivation occurs. 

In a caustic scmbbing system, caustic potash, KOH, is preferred to caustic soda, NaOH, because of the higher solubiUty of the resulting potassium fluoride. Adequate solution contact and residence time must be provided in the scmb tower to ensure complete neutralization of the intermediate oxygen difluoride, OF2. Gas residence times of at least one minute and caustic concentrations in excess of 5% are recommended to prevent OF2 emission from the scmb tower. 

Figure 2 illustrates the three-step MIBK process employed by Hibernia Scholven (83). This process is designed to permit the intermediate recovery of refined diacetone alcohol and mesityl oxide. In the first step acetone and dilute sodium hydroxide are fed continuously to a reactor at low temperature and with a reactor residence time of approximately one hour. The product is then stabilized with phosphoric acid and stripped of unreacted acetone to yield a cmde diacetone alcohol stream. More phosphoric acid is then added, and the diacetone alcohol dehydrated to mesityl oxide in a distillation column. Mesityl oxide is recovered overhead in this column and fed to a further distillation column where residual acetone is removed and recycled to yield a tails stream containing 98—99% mesityl oxide. The mesityl oxide is then hydrogenated to MIBK in a reactive distillation conducted at atmospheric pressure and 110°C. Simultaneous hydrogenation and rectification are achieved in a column fitted with a palladium catalyst bed, and yields of mesityl oxide to MIBK exceeding 96% are obtained. 

Whether the first or the second factor dominates depends on the type of polymerization process involved. If the period during which the polymer molecule is growing is short compared to the residence time of the molecule in the reactor, the first factor dominates. This situation holds for many free radical and ionic polymerization processes where the reaction intermediates are extremely short-lived. Figure 9.11, taken from Denbigh (10), indicates the types of behavior expected for systems of this type. 

The heating and cooling system ensures rapid heating and cooling of the heat-transfer medium. The installation of additional intermediate silos for cooling the final polymer shortens the residence time of the polymer in the reactor and helps to increase its capacity. 

In this paper selectivity in partial oxidation reactions is related to the manner in which hydrocarbon intermediates (R) are bound to surface metal centers on oxides. When the bonding is through oxygen atoms (M-O-R) selective oxidation products are favored, and when the bonding is directly between metal and hydrocarbon (M-R), total oxidation is preferred. Results are presented for two redox systems ethane oxidation on supported vanadium oxide and propylene oxidation on supported molybdenum oxide. The catalysts and adsorbates are stuped by laser Raman spectroscopy, reaction kinetics, and temperature-programmed reaction. Thermochemical calculations confirm that the M-R intermediates are more stable than the M-O-R intermediates. The longer surface residence time of the M-R complexes, coupled to their lack of ready decomposition pathways, is responsible for their total oxidation. 

Flow coulometry experiments were performed to study the reduction of U02 in nitric, perchloric, and sulfuric acid solutions [56]. The results of these studies show a single two-electron reduction wave attributed to the U02 /U + couple. The direct two-electron process is observed without evidence for the intermediate U02" " species because of the relatively long residence time of the uranium ion solution at the electrode surface in comparison to the residence time typically experienced at a dropping mercury working electrode. The implication here is that as the UO2 is produced at the electrode surface, it is immediately reduced to the ion. As the authors note a simplified equation for this process can be written, Eq. (7), but the process is more complicated. Once the U02" species is produced it experiences homogeneous reactions comprising Eqns (8) and (9) or (8) and (10) followed by chemical decomposition of UOOH+ or UO + to [49]. 

When the overpotential becomes increasingly negative, the residence time of the intermediate adion concentration decreases according to ... 

Cant and Hall (13) suggest a mechanism of leaking D into the zeolite by exchange with acidic OH via 1 1 complex of ethylene. For D2, D is presumably leaking into the pool of rapidly moving H. Imanaka et al. (12) suggest that a triatomic intermediate is formed with the hydroxyls. If this is true for the supercage hydroxyls, the residence time of D2 on the surface site occupied by a proton should be on the order of 10-6 sec to have a chance to capture the proton (23, 25). 

Zeolites are somewhat like silica in their surface characteristics. Ketones and hydroxy-1,4-biradicals have very polar groups which can interact favorably with metal cations located along zeolite walls. The potential effect of the metal ions on the position of the reacting ketones is twofold. First, the cations may force a ketone molecule into a conformation or a site which it would normally not occupy based solely upon free-volume considerations. Second, the diffusion coefficient of a ketone or a hydroxy-1,4-biradical is probably much more than an order of magnitude smaller than that of benzene [289] so that the residence time of a ketone and its Norrish II intermediates in a zeolite site with at least one metal ion is expected to be closer to 100 ns than to 1 ns. 

A library of 35 different catalysts fixed on electrochemically oxidized aluminum either in oxalic acid (Lib 1) or sulfuric add (lib 2) was tested at 450 °C and 1.1 bar. The methane-to-oxygen ratio was set to 1 in order to establish the potential of the catalyst to form intermediates. Figure 3.20 shows experimental results for a residence time of 550 ms and a screening time of 60 s. The conversion rate followed directly the platinum content in the catalysts. The higher the platinum content, the higher is the degree of conversion. Catalyst carrier formed by anodization of... 

Betzer et al. (1984, 1986) studied the sedimentation of pteropods and foraminifera in the North Pacific. Their sediment trap results confirmed that considerable dissolution of pteropods was taking place in the water column. They calculated that approximately 90% of the aragonite flux was remineralized in the upper 2.2 km of the water column. Dissolution was estimated to be almost enough to balance the alkalinity budget for the intermediate water maximum of the Pacific Ocean. It should be noted that the depth for total dissolution in the water column is considerably deeper than the aragonite compensation depth. This is probably due to the short residence time of pteropods in the water column because of their rapid rates of sinking. 

Most likely, this competition between solvent and the other organic molecules is responsible for the decrease in the initial selectivity for 2-AMN and in deacylation with the increase of solvent polarity there is a decrease in the residence time of 1-AMN molecules within the zeolite pores with consequently less secondary reactions. However at long reaction times, the highest yield in 2-AMN is obtained with nitrobenzene, a solvent of intermediate polarity, and not with the less polar solvents. It is probably because competition with solvent plays a role in both the residence times of 1-AMN and 2-AMN.25... 

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