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41.
Edges of diffusion flames in a counterflow burner are examined numerically for Lewis greater than unity. When the speed of propagation is plotted against Damköhler for a range of Lewis a fold bifurcation is observed. It is shown that there exist stable positively and negatively propagating edges for some Damköhler and Lewis number pairs. It is further shown that changed local conditions can lead to a transition from positive (advancing into the unburnt gasses) to negative (receding) propagation. 相似文献
42.
Tertiary acyclic allyl amines and tertiary cyclic alpha-vinyl amines undergo conjugate additions to acetylenic sulfones to produce zwitterion intermediates, followed by 3-aza-Cope rearrangements. In the case of cyclic alpha-vinyl amines, the process results in ring-expansion, providing a novel route to 9- to 17-membered cyclic amines. The Hammett plot for the reaction of 8b with 2a- 2f shows rho = +1.19, which is consistent with formation of the proposed zwitterion in the rate-determining step, where electron-withdrawing substituents on the arylsulfonyl moiety stabilize the negative charge and enhance the rate of the reaction. Alternative pathways were observed in methanol in the case of 11, where a methoxy substituent promotes a dissociative mechanism of the corresponding zwitterion via a stabilized allyl cation, whereas the zwitterion derived from amine 12 undergoes ring-opening by direct attack of methanol upon the strained aziridinium moiety instead of by rearrangement. An iterative process was developed, where the product of one ring-expansion is converted into a new cyclic alpha-vinyl amine, followed by a repetition of the conjugate addition and [3,3] rearrangement. This protocol was illustrated by its application to the synthesis of motuporamine A and B. 相似文献
43.
DFT calculations, including the effects of small curvature tunneling, have been performed on the reductive elimination of methane from hydridomethylbis(trimethylphosphine)platinum (1d). The calculations find that at 250 K tunneling results in an increase in the rate constant for reductive elimination by a factor of 4, a lowering of Ea by 1.7 kcal/mol, and a decrease in A by a factor of nearly 10. Tunneling is also calculated to increase the primary H/D kinetic isotope effect (KIE) from k(1d)/k(1f) = 2.26 to k(1d)/k(1f) = 4.12 and to result in a large secondary KIE of k(1d)/k(1e) = 1.35. In addition, tunneling is predicted to result in a violation of the rule of the geometric mean, so that the secondary KIE for reductive elimination of methane-d1 from 1f is calculated to be k(1f)/k(1g) = 1.06, which is much smaller than the secondary KIE of k(1d)/k(1e) = 1.35 for reductive elimination of methane from 1d. Comparison of the measured values of k(1d)/k(1e) and k(1f)/k(1g) is therefore proposed as an experimental test of the prediction that tunneling plays an important role in the reductive elimination of methane from 1d. 相似文献
44.
Berlouis LE Jubin C McMillan BG Morrow J Spicer MD Tang LP Bordelanne O Weston M 《Physical chemistry chemical physics : PCCP》2007,9(45):6032-6039
The properties of dried (but not calcined) coprecipitated nickel ceria systems have been investigated in terms of their hydrogen emission characteristics following activation in hydrogen. XRD and BET data obtained on the powders show similarities to calcined ceria but it is likely that the majority of the material produced by the coprecipitation process is largely of an amorphous nature. XPS data indicate very little nickel is present on the outermost surface of the particles. Nevertheless, the thermal analytical techniques (TGA, DSC and TPD-MS) indicate that the hydrogen has access to the catalyst present and the nickel is able to generate hydrogen species capable of interacting with the support. Both unactivated and activated materials show two hydrogen emission features, viz. low temperature and high temperature emissions (LTE and HTE, respectively) over the temperature range 50 and 500 degrees C. A clear effect of hydrogen interaction with the material is that the activated sample not only emits much more hydrogen than the corresponding unactivated one but also at lower temperatures. H(2) dissociation occurs on the reduced catalyst surface and the spillover mechanism transfers this active hydrogen into the ceria, possibly via the formation and migration of OH(-) species. The amount of hydrogen obtained (~0.24 wt%) is approximately 10x higher than those observed for calcined materials and would suggest that the amorphous phase plays a critical role in this process. The affiliated emissions of CO and CO(2) with that of the HTE hydrogen (and consumption of water) strongly suggests a proportion of the hydrogen emission at this point arises from the water gas shift type reaction. It has not been possible from the present data to delineate between the various hydrogen storage mechanisms reported for ceria. 相似文献
45.
MPW1K density functional calculations, carried out with the 6-31+G(d,p) basis set, have been combined with canonical variational transition state theory (CVT) and small-curvature tunneling (SCT) corrections in order to compute the primary kinetic isotope effects for rearrangement of 5-methyl-1,3-cyclopentadiene (1) to 1-methyl-1,3-cyclopentadiene (2). The Swain-Schaad exponents, SSE = ln(kH/kT)/ln(kD/kT), for this reaction have been computed over the temperature range 100-600 K. Tunneling results in both large positive and large negative deviations from the value of SSE = 3.26, expected from consideration of only the effect of the isotopic mass on passage over the reaction barrier. In the rearrangement of 1 to 2, SSE approximately 3.26, not only at temperatures >400 K, where tunneling is relatively unimportant, but also around 170 K, where tunneling by both H and D is the dominant mode of reaction. Thus, from an experimental finding that SSE approximately 3.26 at a single temperature, it cannot be rigorously concluded that tunneling is unimportant. Measurement of SSEs over a broad temperature range is advisable; but measurement of the temperature dependence of just kH/kD can be used to establish more unequivocally whether tunneling is important, without the necessity of measuring kT. 相似文献
46.
Chelation of vanadium(V) by difluoromethylene bisphosphonate, a structural analogue of pyrophosphate
Crans DC Holder AA Saha TK Prakash GK Yousufuddin M Kultyshev R Ismail R Goodman MF Borden J Florian J 《Inorganic chemistry》2007,46(16):6723-6732
The structural and functional analogy between difluoromethylene bisphosphonate (CF2PP) and pyrophosphate (PPi) is investigated in a reaction with V(V) in the form of vanadate. The reaction of CF2PP with vanadate was investigated using 1.00 M KCl as supporting electrolyte over the ranges 3 < or = [CF2PP] < or = 60 mM and 2.06 < or = pH < or = 11.80. 51V, 19F, and 31P NMR spectroscopic studies showed that a 1:1 species was formed with an H+-dependent formation constant of 110 M-1 at pH 7.22. Results of solution experiments and ab initio calculations are consistent with CF2PP coordinating V(V) in a bidentate manner, as previously reported for PPi. Below pH 4, a minor complex forms, which is consistent with a 1:2 stoichiometry. This complex was also observed with pyrophosphate. The X-ray crystal structure of the monoprotonated difluoromethylene bisphosphonate anion (H[CF2PP]3-)-toludine complex is presented. The H[CF2PP]3- anion crystallized in the triclinic space group P with a = 12.7629(7) A, b = 13.3992(7) A, c = 17.1002(9) A, and V = 2584.4(2) A3, and Z = 2. Sheets of the layers of anions are connected through a network of H-bonds and separated by a layer of toludine cations. The structural features are investigated, and the CF2PP anion was found to be longer and wider than the corresponding PPi. Given the larger size of this anion compared to PPi, the chelation affinity upon CF2 substitution was found to be 4-5-fold reduced at neutral pH. 相似文献
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Experimental data for the photoisomerization of trans-stilbene (S(1)) in thermal bath gases at pressures up to 20 bar obtained previously by Meyer, Schroeder, and Troe (J. Phys. Chem. A 1999, 103, 10528-10539) are modeled by using a full collisional-reaction master equation that includes non-RRKM (Rice-Ramsperger-Kassel-Marcus) effects due to slow intramolecular vibrational energy redistribution (IVR). The slow IVR effects are modeled by incorporating the theoretical results obtained recently by Leitner et al. (J. Phys. Chem. A 2003, 107, 10706-10716), who used the local random matrix theory. The present results show that the experimental rate constants of Meyer et al. are described to within about a factor of 2 over much of the experimental pressure range. However, a number of assumptions and areas of disagreement will require further investigation. These include a discrepancy between the calculated and experimental thermal rate constants near zero pressure, a leveling off of the experimental rate constants that is not predicted by theory and which depends on the identity of the collider gas, the need to use rate constants for collision-induced IVR that are larger than the estimated total collision rate constants, and the choice of barrier-crossing frequency. Despite these unsettled issues, the theory of Leitner et al. shows great promise for accounting for possible non-RRKM effects in an important class of reactions. 相似文献