Analysis of multiple gas solid reactions

Multiple gas solid reactions involving one solid and N gaseous reactants are investigated in this study by using a matched asymptotic expansion technique. Two cases are particularly studied. In the first case all N chemical reaction rates are faster than the diffusion rate. While in the second case only M (M < N) chemical reaction rates are faster than the diffusion rate and the rates of the remaining (N-M) chemical reactions are comparable to that of diffusion. For these two cases the solid concentration profile behaves like a travelling wave. In the first case the wave front velocity is contributed linearly by all gaseous reactants (additive law) while in the second case this law does not hold.

Gas-solid reactions of single crystals: a study of reactions of NH3 and NO2 with single crystalline organic substrates by infrared microspectroscopy

Reaction of single crystals of benzoic and trans-cinnamic acids with 200 Torr pressure of ammonia gas in a sealed glass bulb at 20 degrees C generates the corresponding ammonium salts; there is no sign of any 1:2 adduct as has been reported previously for related systems. Isotopic substitution using ND3 has been used to aid identification of the products. Adipic acid likewise reacts with NH3 gas to form a product in which ammonium salts are formed at both carboxylic acid groups. Reaction of 0.5 Torr pressure of NO2 gas with single crystals of 9-methylanthracene and 9-anthracenemethanol in a flow system generates nitrated products where the nitro group appears to be attached at the 10-position, i.e. the position trans to the methyl or methoxy substituent on the central ring. Isotopic substitution using (NO2)-N-15 has been used to confirm the identity of the bands arising from the coordinated NO2 group. The products formed when single crystals of hydantoin are reacted with NO2 gas under similar conditions depend on the temperature of the reaction. At 20 degrees C, a nitrated product is formed, but at 65 degrees C this gives way to a product containing no nitro groups. The findings show the general applicability of infrared microspectroscopy to a study of gas-solid reactions of organic single crystals. (c) 2005 Elsevier B.V. All rights reserved.

Gas-solid reactions of single crystals: a study of the reaction of bromine with single crystals of trans-cinnamic acid and a range of its derivatives by infrared and Raman microspectroscopy

Single crystals of trans-cinnamic acid and of a range of derivatives of this compound containing halogen substituents on the aromatic ring have been reacted with 165 Torr pressure of bromine vapour in a sealed desiccator at 20 degrees C for 1 week. Infrared and Raman microspectroscopic examination of the crystals shows that bromination of the aliphatic double bond, but not of the aromatic ring, has occurred. It is demonstrated also that the reaction is truly gas-solid in nature. A time-dependent study of these reactions shows that they do not follow a smooth diffusion-controlled pathway. Rather the reactions appear to be inhomogeneous and to occur at defects within the crystal. The reaction products are seen to flake from the surface of the crystal. It is shown, therefore, that these are not single crystal to single crystal transitions, as have been observed previously for the photodimerisation of trans-cinnamic acid and several of its derivatives. It is shown that there are no by-products of the reaction and that finely ground samples react to form the same products as single crystals.

On the validity of the shrinking core model in noncatalytic gas solid reaction

By using a matched asymptotic expansion technique, the shrinking core model (SCM) used in non-catalytic gas solid reactions with general kinetic expression is rigorously justified in this paper as a special case of the homogeneous model when the reaction rate is much faster than that of diffusion. The time-pendent velocity of the moving reacted-unreacted interface is found to be proportional to the gas flux at that interface for all geometries of solid particles, and the thickness order of the reaction zone and also the degree of chemical reaction at the interface is discussed in this paper.

Solution techniques for transport problems involving steep concentration gradients: application to noncatalytic fluid solid reactions

Some efficient solution techniques for solving models of noncatalytic gas-solid and fluid-solid reactions are presented. These models include those with non-constant diffusivities for which the formulation reduces to that of a convection-diffusion problem. A singular perturbation problem results for such models in the presence of a large Thiele modulus, for which the classical numerical methods can present difficulties. For the convection-diffusion like case, the time-dependent partial differential equations are transformed by a semi-discrete Petrov-Galerkin finite element method into a system of ordinary differential equations of the initial-value type that can be readily solved. In the presence of a constant diffusivity, in slab geometry the convection-like terms are absent, and the combination of a fitted mesh finite difference method with a predictor-corrector method is used to solve the problem. Both the methods are found to converge, and general reaction rate forms can be treated. These methods are simple and highly efficient for arbitrary particle geometry and parameters, including a large Thiele modulus. (C) 2001 Elsevier Science Ltd. All rights reserved.

On the accuracy of two-fluid model predictions for a particular gas-solid riser flow

Literature presents a huge number of different simulations of gas-solid flows in risers applying two-fluid modeling. In spite of that, the related quantitative accuracy issue remains mostly untouched. This state of affairs seems to be mainly a consequence of modeling shortcomings, notably regarding the lack of realistic closures. In this article predictions from a two-fluid model are compared to other published two-fluid model predictions applying the same Closures, and to experimental data. A particular matter of concern is whether the predictions are generated or not inside the statistical steady state regime that characterizes the riser flows. The present simulation was performed inside the statistical steady state regime. Time-averaged results are presented for different time-averaging intervals of 5, 10, 15 and 20 s inside the statistical steady state regime. The independence of the averaged results regarding the time-averaging interval is addressed and the results averaged over the intervals of 10 and 20 s are compared to both experiment and other two-fluid predictions. It is concluded that the two-fluid model used is still very crude, and cannot provide quantitative accurate results, at least for the particular case that was considered. (C) 2009 Elsevier Inc. All rights reserved.

Comparative analysis of the gas-phase reactions of cylindrospermopsin and the difference in the alkali metal cation mobility

Cylindrospermopsin (CYN) belongs to a group of toxins produced by several strains of freshwater cyanobacteria. It is a compact zwitterionic molecule composed of a uracil section and a tricyclic guanidinium portion with a primarily hepatotoxic effect. Using low multi-stage and high-resolution mass spectrometry, the gas-phase reactions of this toxin have been investigated. Our data show that collision-induced dissociation (CID) spectra of CYN are dominated by neutral losses, and three major initial fragmentation pathways are clearly distinguishable. Interestingly, comparative analysis of protonated and cationizated molecules showed a significant difference in the balance of the SO(3) and terminal ring elimination. These data indicate that the differential ion mobility of H(+), Li(+), Na(+) and K(+) leads to different fragmentation pathways, giving rise to mass spectra with different profiles. Copyright (C) 2008 John Wiley & Sons, Ltd.

Analysis and validation of space averaged drag model for numerical simulations of gas-solid flows in fluidized beds

This thesis presents an approach for formulating and validating a space averaged drag model for coarse mesh simulations of gas-solid flows in fluidized beds using the two-fluid model. Proper modeling for fluid dynamics is central in understanding any industrial multiphase flow. The gas-solid flows in fluidized beds are heterogeneous and usually simulated with the Eulerian description of phases. Such a description requires the usage of fine meshes and small time steps for the proper prediction of its hydrodynamics. Such constraint on the mesh and time step size results in a large number of control volumes and long computational times which are unaffordable for simulations of large scale fluidized beds. If proper closure models are not included, coarse mesh simulations for fluidized beds do not give reasonable results. The coarse mesh simulation fails to resolve the mesoscale structures and results in uniform solids concentration profiles. For a circulating fluidized bed riser, such predicted profiles result in a higher drag force between the gas and solid phase and also overestimated solids mass flux at the outlet. Thus, there is a need to formulate the closure correlations which can accurately predict the hydrodynamics using coarse meshes. This thesis uses the space averaging modeling approach in the formulation of closure models for coarse mesh simulations of the gas-solid flow in fluidized beds using Geldart group B particles. In the analysis of formulating the closure correlation for space averaged drag model, the main parameters for the modeling were found to be the averaging size, solid volume fraction, and distance from the wall. The closure model for the gas-solid drag force was formulated and validated for coarse mesh simulations of the riser, which showed the verification of this modeling approach. Coarse mesh simulations using the corrected drag model resulted in lowered values of solids mass flux. Such an approach is a promising tool in the formulation of appropriate closure models which can be used in coarse mesh simulations of large scale fluidized beds.

Gas-solid two-phase flow in the riser of circulating fluidized beds: mathematical modelling and numerical simulation

A mathematical model is developed for gas-solids flows in circulating fluidized beds. An Eulerian formulation is followed based on the two-fluids model approach where both the fluid and the particulate phases are treated as a continuum. The physical modelling is discussed, including the formulation of boundary conditions and the description of the numerical methodology. Results of numerical simulation are presented and discussed. The model is validated through comparison to experiment, and simulation is performed to investigate the effects on the flow hydrodynamics of the solids viscosity.

Direct time-resolved study of the gas-phase reactions of germylene with ethyl- and diethylgermane: absolute rate constants, temperature dependences, and mechanism

Time-resolved studies of germylene, GeH2, generated by the 193 nm laser flash photolysis of 3,4-dimethyl-1-germacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reactions with ethyl- and diethylgermanes in the gas phase. The reactions were studied over the pressure range 1-100 Torr with SF6 as bath gas and at five temperatures in the range 297-564 K. Only slight pressure dependences were found for GeH2 + EtGeH3 (399, 486, and 564 K). The high pressure rate constants gave the following Arrhenius parameters: for GeH2 + EtGeH3, log A = -10.75 +/- 0.08 and E-a = -6.7 +/- 0.6 kJ mol(-1); for GeH2 + Et2GeH2, log A = -10.68 +/- 0.11 and E-a = -6.95 +/- 0.80 kJ mol(-1). These are consistent with fast, near collision-controlled, association processes at 298 K. RRKM modeling calculations are, for the most part, consistent with the observed pressure dependence of GeH2 + EtGeH3. The ethyl substituent effects have been extracted from these results and are much larger than the analogous methyl substituent effects in the SiH2 + methylsilane reaction series. This is consistent with a mechanistic model for Ge-H insertion in which the intermediate complex has a sizable secondary barrier to rearrangement.

The gas-phase reactions Of SiCl4 and Si2Cl6 with CH3OH and C2H5OH: an investigation by mass spectrometry and matrix-isolation infrared spectroscopy

The gas phase reactions Of SiCl4 and Si2Cl6 With CH3OH and C2H5OH have been investigated using both mass spectrometry and matrix isolation techniques. SiCl4 reacts with both CH3OH and C2H5OH upon mixing of the vapours for times in excess of 3 h to generate the HCl-elimination products SiCl3OR (R = CH3 or C2H5). The identity of these products is confirmed by deuteration experiments and by ab initio calculations at the HF/6-31G(d) level. Further products are generated when the mixture is passed through a tube heated to 750degreesC. Si2Cl6 reacts with CH3OH and C2H5OH via a different mechanism in which the Si-Si bond is cleaved to yield SiCl3OR and HCl. Other products of the type SiCl4-n(OCH3)(n) are tentatively identified by a combination of mass spectrometric and matrix isolation measurements. These latter products indicate further replacement of Cl atoms by OR groups as a result of reaction of CH3OH or C2H5OH with the initial product.

Gas-phase reactions of NO3 and N2O5 with (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol

The night-time atmospheric chemistry of the biogenic volatile organic compounds (Z)-hex-4-en-1-ol, (Z)-hex-3-en-1-ol ('leaf alcohol'), (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO3) with these stress-induced plant emissions were measured using the discharge-flow technique. We employed off-axis continuous-wave cavity-enhanced absorption spectroscopy (CEAS) for the detection of NO3, which enabled us to work in excess of the hexenol compounds over NO3. The rate coefficients determined were (2.93 +/- 0.58) x 10(-13) cm(3) molecule(-1) s(-1), (2.67 +/- 0.42) x 10(-13) cm(3) molecule(-1) s(-1), (4.43 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1), (1.56 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1), and (1.30 +/- 0.24) x 10(-13) cm(3) molecule(-1) s(-1) for (Z)-hex-4-en-1-ol, (Z)-hex-3en-1-ol, (E)-hex-3-en-1-ol, (Z)-hex-2-en-1-ol and (E)-hex-2-en-1-ol. The rate coefficient for the reaction of NO3 with (Z)-hex-3-en-1-ol agrees with the single published determination of the rate coefficient using a relative method. The other rate coefficients have not been measured before and are compared to estimated values. Relative-rate studies were also performed, but required modification of the standard technique because N2O5 (used as the source of NO3) itself reacts with the hexenols. We used varying excesses of NO2 to determine simultaneously rate coefficients for reactions of NO3 and N2O5 with (E)-hex-3-en-1-ol of (5.2 +/- 1.8) x 10(-13) cm(3) molecule(-1) s(-1) and (3.1 +/- 2.3) x 10(-18) cm(3) molecule(-1) s(-1). Our new determinations suggest atmospheric lifetimes with respect to NO3-initiated oxidation of roughly 1-4 h for the hexenols, comparable with lifetimes estimated for the atmospheric degradation by OH and shorter lifetimes than for attack by O-3. Recent measurements of [N2O5] suggest that the gas-phase reactions of N2O5 with unsaturated alcohols will not be of importance under usual atmospheric conditions, but they certainly can be in laboratory systems when determining rate coefficients.

Structure–activity relations (SARs) for gas-phase reactions of NO3, OH and O3 with alkenes: an update

We present updated structure-activity relations (SARs) for the prediction of rate coefficients for gas-phase reactions with alkenes of the major atmospheric oxidants NO3, OH and O-3. Such SARs provide one way of incorporating essential information about reactivity into atmospheric models. Rate coefficients obtained from correlations relating the logarithms of the rate coefficients to the energies of the highest occupied molecular orbitals (HOMOs) of the alkenes were used to refine the SARs. SARs have an advantage for the user over the direct application of the correlations in that knowledge of the structure of the alkene of interest is sufficient to estimate rate coefficients, and no quantum-mechanical calculations need to be performed. A comparison of the values predicted by the SARs with experimental data where they exist allowed us to assess the reliability of our method.

Correlations for gas-phase reactions of NO3, OH and O3 with alkenes: an update

Methods are developed for predicting rate coefficients for reactions of initiators of tropospheric oxidation with unsaturated compounds that are abundant in the atmosphere; prognostic tools of this kind are essential for atmospheric chemists and modellers. To pursue the aim of exploring such tools, the kinetics of reactions of NO3, OH and O-3 with a series of alkenes are examined for correlations relating the logarithms of the rate coefficients to the energies of the highest occupied molecular orbitals (HOMOs) of the alkenes. A comparison of the values predicted by the correlations with experimental data (where the latter exist) allowed us to assess the reliability of our method. We used a series of theoretical methods to calculate the HOMO energies, and found that higher computational effort improves the agreement of the predicted rate coefficients with experimental values, especially for reactions of NO3 with alkenes that possess vinyllic halogen substituents. As a consequence, it is expedient to suggest new correlations to replace those presented by us and others that were based on the lower level of theory. We propose the following correlations for the reactions of NO3, OH and O-3 with alkenes: ln(k(NO3)/cm(3) molecule(-1) s(-1)) = 6.40(E-HOMO/eV) + 31.69, ln(k(OH)/cm(3) molecule(-1) s(-1)) = 1.21 (E-HOMO/eV)-12.34 and ln(k(O3)/cm(3) molecule(-1) s(-1)) = 3.28(E-HOMO/eV)-6.78. These new correlations have been developed using the larger experimental data sets now available, and the impact of the extended data on the quality of the correlations is examined in the paper. Atmospheric lifetimes have been calculated from both experimental and estimated rate coefficients to provide an overview of removal efficiencies for different classes of alkenes with respect to oxidative processes initiated by NO3, OH and O-3. A figure is presented to show the spatial scales over which alkenes may survive transport in competition with attack by NO3, OH and O-3. Removal by NO3 or OH is always more important than removal by O-3, and reactions with NO3 dominate for scales up to a few hundred metres.

The kinetics of the gas-phase reactions of selected monoterpenes and cyclo-alkenes with ozone and the NO3 radical

The relative rate method has been used to measure the room-temperature rate constants for the gasphase reactions of ozone and NO3 with selected monoterpenes and cyclo-alkenes with structural similarities to monoterpenes. Measurements were carried out at 298 ! 2 K and 760 ! 10 Torr. The following rate constants (in units of 10"18 cm3 molecule"1 s"1) were obtained for the reaction with ozone: methyl cyclohexene (132 ! 17), terpinolene (1290 ! 360), ethylidene cyclohexane (223 ! 57), norbornene (860 ! 240), t-butyl isopropylidene cyclohexane (1500 ! 460), cyclopentene (543 ! 94), cyclohexene (81 ! 18), cyclooctene (451 ! 66), dicyclopentadiene (1460 ! 170) and a-pinene (107 ! 13). For the reaction with NO3 the rate constants obtained (in units of 10"12 cm3 molecule"1 s"1) were: methyl cyclohexene (7.92 ! 0.95), terpinolene (47.9 ! 4.0), ethylidene cyclohexane (4.30 ! 0.24), norbornene (0.266 ! 0.029), cyclohexene (0.540 ! 0.017), cyclooctene (0.513 ! 0.029), dicyclopentadiene (1.20 ! 0.10) and a-pinene (5.17 ! 0.62). Errors are quoted as the root mean square of the statistical error (95% con!dence) and the quoted error in the rate constant for the reference compound. Combining these results with previous studies, new recommendations for the rate constants are presented. Molecular orbital energies were calculated for each alkene and the kinetic data are discussed in terms of the deviation from the structureeactivity relationship obtained from the rate constants for a series of simple alkenes. Lifetimes with respect to key initiators of atmospheric oxidation have been calculated suggesting that the studied reactions play dominant roles in the night-time removal of these compounds from the atmosphere.