Product isotopic transient

During steady-state isotopic transient kinetic analysis, the 12CO was switched to 13CO and the carbon-containing adsorbed and gas phase species were monitored in the IR as they exchanged from the 12C to the 13C label. Particular attention was made to those species that exchanged on a timescale similar to that of the exchange of the product C02, as that species could be a likely intermediate to the water-gas... 

Shen et al. (142) used an isotopic transient technique and XPS to investigate the partial oxidation of CH4 to synthesis gas on a Ni/Al203 catalyst at 973 K. The results show that CH4 can decompose easily and quickly to give H2 and Ni C on the reduced catalyst, and that Ni vC can react rapidly with NiO, formed by the oxidation of nickel by 02 to give CO or C02, depending on the relative concentration of Ni,C around NiO on the catalyst surface. The conclusion drawn by the authors (142) was not only that H2 and CO are primary products in the partial oxidation of CH4, but also that most of the CO2 is also the primary product of the surface reaction between Ni,C and NiO. In contrast, the kinetics results of Verykios et al. (143) indicated that the reaction on the Ni/La203 catalyst mainly takes place via the sequence of total oxidation to CO2 and H20, followed by... 

SLIDER is a Fortran IV computer program for investigating the diffusion of a single fission-product isotope in a multilayered spherical fuel particle. This code enables one to compute, on the basis of Fick s law of diffusion, the transient and steady-state fission product concentrations and releases in multilayered spherical geometry. 

Buyevskaya et al, 1994 Mallens et al, 1994) and SSITKA (Steady-State Isotopic Transient Kinetic Analysis) (Nibbelke et al, 1995) techniques. It was demonstrated that ethane—the primary OCM product—is leaving the reactor with the same characteristic time as an inert tracer. This surely indicates that no intermediates noticeably residing on the surface participate in its formation. 

The overall catalytic activity of a catalyst is the product of two independent properties the total number of active sites on the catalyst and the intrinsic activity per site (turnover frequency) of each of these sites. The only technique capable of measuring both the number of active sites and their turnover frequency simultaneously under actual operating conditions is the Isotope Transient Kinetics (ITK) technique. This makes it one of the most powerful techniques available to the catalytic chemist today. 

Kinetics and diffusion Steady-state isotopic transient kinetic analysis (SSITKA) Temporal analysis of products (TAP) Tapered element oscillating microbalance (TEOM) Temperature scanning reactor (TSR) Zero length chromatography (ZLC) Pulsed field gradient NMR... 

Steady-state isotopic transient kinetic analysis (SSITKA) involves the replacement of a reactant by its isotopically labelled counterpart, typically in the form of a step or pulse input function. Producing an input function with isotope-labelled reactants permits the monitoring of isotopic transient responses, while maintaining the total concentration of labelled plus nonlabelled reactants, adsorbates, and products at steady-state conditions. It is assumed that there are no effects due to differences in kinetic behavior of the isotopic species from unmarked atomic species. However, for instance, deuterium substitution exhibits isotopic effects that can not be neglected. 

In the present communication we report on the influence of water on the FT synthesis studied by SSITKA and conventional kinetic experiments. Steady-state isotopic transient kinetic analysis (SSITKA) has proved to be a powerful technique for this work. The technique involves switching between CO and " CO in the feed gas and analyzing the transients with respect to the formation of products containing C and C. This technique allows the determination of the true turnover frequency of the active site, decoupled from site coverage. Applied to the FTS over metal promoted cobalt catalysts SSITKA has shown that the true turnover frequency of cobalt always remains the same, regardless of the second metal [6-8]. 

Accordingly, transient kinetic techniques which are able to provide unique information on the actual state of a working catalyst within a very short period of time [13,14] were applied to this complex and unstable catalytic system. Non-steady-state and steady-state isotopic transient kinetics (NSSTK and SSITK) combined with in situ diffuse reflectance infrared Fourier transformed spectroscopy (DRIFT) and temporal analysis of product (TAP) were performed in order to analyse some of the above mentioned key steps of the aromatisation process. 

IN SSITKA, Np and the mean surface residence time of these most active reaction intermediates (xp) are determined. After a step-change between two reactant streams containing different isotopes of a reactant without disturbing other reaction conditions or reaction (as long as an H2/D2 switch is not used), the distributions of isotopically labeled products are monitored using a mass spectrometer. Tp is first determined by integration of the normalized isotopic transient of a product relative to an inert tracer (usually Ar) that delineates gas phase hold-up (see Figure 1 for the case of methanation). Np is then calculated from... 

The growing evidence (for example. References 36, 117, 118) that the hydrogenation of CO on various metals proceeds via the carbon formed by dissociative adsorption of CO led to the use of the hydrogen/deuterium isotope effect as one attempt to better define that the synthesis follows this reaction pathway. Another reason was to modify the mass of the hydrocarbon peaks so that interference from gases such as H2O, CO2, N2, etc., would not prevent analysis of products from transient isotope studies by mass spectrometry. However, the evidence from the early studies with H2/D2 led to conflicting viewpoints. Sakharoff and Dokukina obtained kjj/ku = 0.77 for a Co catalyst, whereas McKee reported a value of 2.2. 

The utility of the isotopic transient kinetic studies can be illustrated by considering a simple reaction of A giving product B through a single adsorbed intermediate I ... 

Since the isotopic transient technique involves the number and type of intermediates on the catalyst surface, independent transient experiments (with or without the use of isotopes) have also been used to determine these parameters. The simplest reaction for analysis by the isotopic transient kinetic technique for the conversion of syngas is the production of methane. Studies of methanation provide a background to the isotopic transient kinetic studies and independent justification for the number and type of adsorbed species involved in FTS. Furthermore, the production of methane is undesirable for FTS and an understanding of the mode of its production will aid in FTS catalyst and process design. 

Transient Isotopic Kinetic Studies of Methanation. - The Fischer-Tropsch reaction results in the formation of a wide distribution of hydrocarbons containing different numbers of carbon atoms. In contrast, the related reaction of methanation of CO/H2 mixtures involves only one product and is easier to study using isotope transient kinetic techniques. The results of the methanation reaction have a direct relevance to the Fischer-Tropsch reaction and are reviewed below. 

In summary, the isotopic transient studies have shown the existence of two intermediates and their parallel conversion is involved in the production of methane from adsorbed CO. These intermediates can be connected in various overall reaction schemes which cannot be distinguished from each other by isotopic transient studies alone. The ratio of the rate constant of the more active intermediate to the less active intermediate lies between two and seven for the catalysts studied and is dependent on the catalyst. The absolute values of the rate constants are also dependent on the catalyst used. 

Isotopic Transient Kinetic Studies of the FTS. - Unlike methanation, the Fischer-Tropsch reaction produces a variety of hydrocarbon products having multiple carbon... 

As stated earlier, SSITKA is carried out by tracking the change in the isotopic labelled product(s), following a step change in the isotopic label on a reactant. To maintain isothermal and isobaric reaction conditions, flow rate and pressure of the two isotopic labelled reactant flows are adjusted to be identical, prior to switching. A typical reaction system for isotopic transient studies is shown in Fig. 1. 

Fig. 4. Typical normalized isotopic transient responses in product species P following an isotopic switch in reactant R— R. An inert tracer, I, is introduced to determine the gas-phase holdup of the reactor system.

The ILT method is based on the fact that the isotopic transient of the product formation rate [r (t)] represents the Laplace transform of Np k f(k). For a pseudo-first order reaction, the transient of the product formation rate can be expressed as... 

Equations (11) and (12) enable the generation of the total isotopic transient responses of a product species given (a) the transient response that characterises hypothesized catalyst-surface behaviour and (b) an inert-tracer transient response that characterises the gas-phase behaviour of the reactor system. Use of the linear-convolution relationships has been suggested as an iterative means to verify a model of the catalyst surface reaction pathway and kinetics. I This is attractive since the direct determination of the catalyst-surface transient response is especially problematic for non-ideal PFRs, since a method of complete gas-phase behaviour correction to obtain the catalyst-surface transient response is presently unavailable for such reactor systems.1 1 Unfortunately, there are also no corresponding analytical relationships to Eqs. (11) and (12) which permit explicit determination of the catalyst-surface transient response from the measured isotopic and inert-tracer transient responses, and hence, a model has to be assumed and tested. The better the model of the surface reaction pathway, the better the fit of the generated transient to the measured transient. 

The greater activity of Pd for methanol decomposition reaction was also found by using the steady state isotopic transient kinetic analysis (SSITKA) method over noble metal (Pt, Pd, Rh)/ceria catalysts. Their activity increased in the order Rh < Pt < Pd, while the by-products were (i) methane, carbon dioxide, water, methyl formate and formaldehyde in most cases and (ii) ethylene and propylene, formed only over Rh/Ce02, at 553 K. SSITKA measurements indicated that two parallel pools exist for the formation of CO (via formation and decomposition of formaldehyde and methyl formate). The difference in the activity order of noble metal/ceria catalysts seems to correlate with the surface coverage of active carbon containing species, which followed the same order. The latter implies that a part of these species is formed on the ceria surface or/and metal-ceria interface. ... 

Since the 1980s, SSITKA has been widely used to understand the formation mechanism of methane as the first paraffin in the chain. The study of the dynamics of the entire complex of reactions involved in the Fischer-Tropsch process became possible only after the development of the GC-MS technique with high resolution time. A review of field suggests that the cycle of papers by van Dijk et al. [18-21] describes the results that were obtained using the full potential of the SSITKA technique. First, a comparison of C, O, and H labeling on different Co-based catalyst formulations and in different conditions was made. For the first time, a substantial part of the product spectrum (both hydrocarbons and alcohols) was included in the isotopic transient analysis. After the qualitative interpretation of the experimental data, extensive mathematical modeling was performed for the identification and discrimination of reaction mechanisms. 

Temperature-prograimned reduction, oxidation and desorption (TPR, TPO, TPD), belong probably to the most widely used in situ techiuques for the characterization of oxidation catalysts and are discussed in more detail in Section 19.4. While TPD (with ammonia as the probe molecule) is frequently used to examine surface acid sites, TPR and TPO (with H2 or O2, respectively) provide information on the redox properties of oxide catalysts being crucial for their performance in catalytic oxidation reactions. Important information on reaction mechanisms can be obtained when the catalysts are heated in the presence of reactants combined with mass spectrometric product analysis. This is called temperature-programmed reaction spectroscopy (TPRS). As far as reaction mechanisms and kinetics are concerned, transient techniques which reflect the response of the catalytic system to a sudden change of reactant are inevitable tools. Two such techiuques, namely the temporal analysis of products (TAP) reactor and steady-state isotopic transient kinetic analysis (SSITKA) will be described in more detail in Section 19.5. 

However, the carbonate mechanism is favored by some authors. Using a combination of DRIFTS and steady-state isotopic transient kinetic analysis (SSITKA) Meunier et al. assessed the reactivity of the species formed at the surface of an Au/Ce(La)02 catalyst during the WGS reaction. The analysis revealed that surface formates are not important factors in the WGS reaction mechanism. Their role is ascribed to minor reaction intermediates but not spectators because they nevertheless participate in the formation of reaction product. 

The basic principle of SSITKA is the following. Under steady-state isothermal and isobaric operating conditions, an isotopic transient is introduced by an isotope switch or, in other words, a sudden replacement of one labeled compound with its isotope. Analysis is done by GC and MS. The amount of adsorbed intermediates Np converted in products is defined as... 

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