Library

Notes: From a study of the complexation of FeIII with 2,6-dimethyl-3,5-heptanedione in aqueous solution, thermodynamic and kinetic parameters have been obtained. Results obtained for this system and a series of structurally similar iron(III) diketonates at different temperatures, establishes isokinetic behaviors of these kinds of reactions.Analytical correlations obtained may be useful to predict, for analogous ligands in similar experimental conditions, an essential mechanism, that pathways involving reaction of metal-hydrolyzed species with the enol tautomer are faster than pathways involving hexa-aqua species. Additionally, thermodynamic parameters associated with the monochelated complexations may be predicted. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 121-127, 1998.

Notes: This article is concerned with the application of a new method to recover the rate constants in chemical reactions. The method is based on treating the unknown parameters as time dependent. With appropriate experimental data the unknown rate constants are guided from an arbitrary initial condition to their true value at a final time. An explicit equation describing the time evolution of the parameters is obtained by minimizing the error along the trajectory. The method leads to an iterative algorithm which is described in detail. Numerical results with the method indicate that accurate estimates of the rate constants can be obtained directly from experimental data. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 151-159, 1998.

Notes: Ab initio calculations have been used to characterize the transition states for halogen abstraction by CH3 in reactions with CF4, CF3Cl, CF3Br, and CF3I (1-4). Geometries and frequencies were obtained at the HF/6-31G(d) and MP2=full/6-31G(d) levels of theory. Energy barriers were computed via the Gaussian-2 methodology, and the results were employed in transition state theory analyses to obtain the rate constants over 298-2500 K. There is good accord with literature measurements in the approximate temperature range 360-500 K for reactions (2-4), and the computed activation energies are accurate to within ±6 kJ mol-1. Recommended rate constant expressions for use in combustion modeling are k;1=1.6×10-19 (T/K)2.41 exp(-13150 K/T), k2=8.4×10-20(T/K)2.34 exp(-5000 K/T), k3=4.6×10-19 (T/K)2.05 exp(-3990 K/T), and k4=8.3×10-19 (T/K)2.18 exp(-1870 K/T) cm3 molecule-1 s-1. The results are discussed in the context of flame suppression chemistry. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 179-184, 1998.

Notes: Upper limits of 4×10-20 and 7×10-20 cm3 molecule-1 s-1 were established for the gas-phase reactions of H2O2 with O3 and NO, respectively. These reactions are too slow to explain features observed in the atmospheric vertical profile of H2O2. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 707-709, 1998

Notes: The influence of the mass transfer phenomena on the thermal decomposition of calcium carbonate powders under vacuum was investigated through a detailed kinetic analysis by the constant transformation rate thermal analysis (CRTA). Reliable kinetic curves, free from the mass transfer problems, can be obtained by CRTA under vacuum, but within a restricted range of small sample sizes, 〈10 mg. The influence of mass transfer phenomena on the apparent kinetic parameters is discussed in relation to the distribution of fractional reaction α of the individual particles in a sample assemblage. Only when the distribution of α is maintained constant among a series of experimental kinetic curves, can a reliable activation energy, E, be obtained by one of the isoconversion methods. In this respect, a single cyclic CRTA permits the α distribution to be maintained constant between the two adjacent data points with different decomposition rates. In the present study, an apparent E value of about 223 kJ mol-1 was obtained by the Friedman method from a series of CRTA curves with sample sizes less than 10 mg and by the rate jump method from a single cyclic CRTA curve with sample size of about 40 mg. The first-order (F1) law was determined to be the most appropriate kinetic model function, from a series of CRTA curves, instead of the ideal contracting geometry (R3) law formalized for the three-dimensional shrinkage of the reaction interface in the respective particles. The particle size distribution of the sample particles is suggested to be one possible reason for the apparent agreement with the F1 law. A kinetic exponent n of the nth-order law that deviated from unity was obtained from the CRTA curves with sample sizes larger than 10 mg, due to an additional distribution of α produced by mass transfer phenomena. Because the α distribution due to the mass and heat transfer phenomena cannot be expressed practically in an analytical function, a meaningful kinetic model and preexponential factor are difficult to estimate from kinetic data that are influenced by the transfer phenomena. © 1998 John Wiley & Sons, Inc. Int. J Chem Kinet: 30: 737-744, 1998

Notes: The reaction of 2-phenoxyquinoxaline (1) with hydroxide ion is accelerated by reactive counter-ion micelles of cetyltrialkylammonium hydroxides (alkyl=Me, Et, n-Pr, and n-Bu), cetylmethylpiperidinium hydroxide, and cetylquinuclidinium hydroxide containing bulky head groups. First-order rate constants for reaction of (1) with OH- increase with increasing bulk of the head group and are associated with an increase in nucleophile reactivity as water is squeezed away from the micelle surface. Micellar effects upon the alkaline hydrolysis of compound (1) were analyzed by using a model that describes micelle-ion interactions in terms of Langmuir isotherms. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 777-783, 1998

Notes: The time-resolved total emission of SO2 (B1B1→X1A1) at 354.9 nm were monitored following the direct excitation by a 266 nm laser pulse. A three-level model was proposed to deal with SO2 (X1A1, A1A2, B1B1) system. From a kinetic treatment of these measurements, the coupling coefficient, ξ, and the relaxation time, τ, relating to the high vibronic levels of A1A2 and B1B1 states were first obtained. It is found that ξ and τ values keep basically constant, reflecting the characteristics of the studied system. In addition, the quenching rate constants of SO2 (A1A2, B1B1) by some alkane and chloromethane molecules were measured at room temperature. The formation cross sections of complexes of SO2 (A1A2, B1B1) and quenchers were calculated by means of a collision complex model. It is shown that the dependence of the formation cross section of complex on the number of C(SINGLEBOND)H or C(SINGLEBOND)Cl bonds is generally in agreement with that of the measured quenching cross section. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 831-837, 1998

Notes: The products of the gas-phase reaction of the OH radical with 3-methyl-1-butene in the presence of NO have been investigated at room temperature and 740 torr total pressure of air by gas chromatography with flame ionization detection, in situ Fourier transform infrared absorption spectroscopy, and direct air sampling atmospheric pressure ionization tandem mass spectrometry. The products identified and quantified by GC-FID and in situ FT-IR absorption spectroscopy were HCHO, 2-methylpropanal, acetone, glycolaldehyde, and methacrolein, with formation yields of 0.70±0.06, 0.58±0.08, 0.17±0.02, 0.18±0.03, and 0.033±0.007, respectively. In addition, IR absorption bands due to organic nitrates were observed, consistent with API-MS observations of product ion peaks attributed to the β-hydroxynitrates (CH3)2CHCH(ONO2)CH2OH and/or (CH3)2CHCH(OH)CH2ONO2 formed from the reactions of the corresponding β-hydroxyalkyl peroxy radicals with NO. A formation yield of ca. 0.15 for these nitrates was estimated using IR absorption band intensities for known organic nitrates. These products account for essentially all of the reacted 3-methyl-1-butene. Analysis of the potential reaction pathways involved shows that H-atom abstraction from the allylic C(SINGLEBOND)H bond in 3-methyl-1-butene is a minor pathway which accounts for 5-10% of the overall OH radical reaction. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 577-587, 1998

Notes: The kinetics of the reaction between glycolaldehyde (GA) and tetrachloroaurate(III) in acetic acid-sodium acetate buffer has been studied. The reaction is first-order with respect to [AuIII] as well as [GA]. Both H+ and Cl- ions retard the rate of reaction. AuCl4-, AuCl3(OH2), and AuCl3(OH)- are the reactive species of gold(III) with gradually increasing reactivity. A reaction mechanism involving two-electron transfer rate determining steps has been proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 613-619, 1998

Notes: Detailed modeling of the oxidation of n-octane and n-decane in the gas phase was performed by using mechanisms written by means of a software recently developed in our laboratory. This computer-aided design of mechanisms permits the automatic generation of detailed oxidation and combustion kinetic models in the case of paraffins and isoparaffins [1]. For n-octane, the predictions of the model were compared with experimental results obtained by Dryer and Brezinsky by means of a turbulent plug flow reactor (1080 K, 1 atm) [2]. The experimental study of Balès-Guéret et al., performed in a perfectly stirred reactor (922-1033 K, 1 atm) [3], was used as a basis of comparison for the modeling of the oxidation of n-decane. Considering that no fitting of any kinetic parameter was done, the agreement between the computed and the experimental values is satisfactory both for conversions and for the distribution of the products formed. This modeling has required improvement in the generation of the secondary reactions of alkenes, which are the main primary products obtained during the oxidation of these two alkanes in the range of temperature studied and for which reaction paths are detailed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 949-959, 1998

Notes: Decomposition studies of trichlorosilane, dichlorosilane, and monochlorosilane at 921 K, 872 K, and 806 K, respectively, are reported. The studies were made at fixed reactant pressures over a range of total pressures in a wall conditioned, quartz reactor connected to a quadrupole mass-spectrometer. Products were monitored sequentially and continuously in time. The dichlorosilane decomposition was also studied by the comparative-rate single-pulse shock-tube method at temperatures around 1250 K. Two mechanisms of decomposition are considered: a silylene based mechanism initiated by molecular elimination reactions (Scheme I), and a free radical based mechanism initiated by bond fission reactions (Scheme V). Modeling tests of these mechanisms show that only the former is consistent with the experimental data. The decompositions are shown to be essentially nonchain processes initiated by the following pressure dependent reactions: HSiCl3(SINGLEBOND)4→ SiCl2+HCl, H2SiCl2(SINGLEBOND)1→ SiCl2+H2 and H3SiCl(SINGLEBOND)5→ HSiCl+H2. High pressure Arrhenius parameters recommended for these reactions are A4,∞=A1,∞=A5,∞=1014.5±0.5 s-1, E4,∞=71.9±2.1 kcal/mol, E1,∞=69.2±2.0 kcal/mol, and E5,∞=60.6±1.8 kcal/mol. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 69-88, 1998.

Notes: The formation of 3-azabicyclo[3,3,0]oct-2-ene in the course of the synthesis of N-amino-3-azabicyclo[3,3,0]octane using the Raschig process results from the following two consecutive reactions: chlorine transfer between the monochloramine and the 3-azabicyclo[3,3,0]octane followed by a dehydrohalogenation of the substituted haloamine. The kinetics of the reaction were studied by HPLC and UV as a function of temperature (15 to 44°C), and the concentrations of NaOH (0.1 to 1 M) and the chlorinated derivative (1 to 4×10-3 M). The reaction is bimolecular (k=103×10-6 M-1 s-1; ΔH0#=89 kJ mol-1; and ΔS0#=-33.6 J mol-1 K-1) and has an E2 mechanism. The spectral data of 3-azabicyclo[3,3,0]oct-2-ene were determined. IR, NMR, and ES/MS analysis show dimerization of the water-soluble monomer into a white insoluble dimer. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 129-136, 1998.

Notes: A high-pressure, high-temperature reactor unit was developed to test batch-wise inter-conversions of hydrocarbons. A major ambiguity characterizes this reactor, as it does all similar units that have been described, determination of the time-temperature profile for the reacting mixture. Here we report on a solution to this problem - use of a “chemical thermometer,” based on the kinetics of dissociation of C4F8. We propose a revised set of rate constants that permit calibration of the reactor operation. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 171-177, 1998.

Notes: Transient absorption spectra of 1-naphthylseleno (1-NaphSe·), and 2-naphthylseleno (2-NaphSe·) radicals, which are generated by laser-flash photolysis of the corresponding diselenides, were observed. The reactions of 1-NaphSe·, and 2-NaphSe· with 2-methyl-1,3-butadiene and α-methylstyrene were investigated by following the decay rates of these seleno radicals. By both steady-state and laser-flash photolysis, it is proved that these seleno radicals add to alkenes in a reversible manner. The reaction rate constants for such reversible addition reactions were determined by conducting the reaction in the presence of O2, which traps selectively the carbon-centered radicals formed by the addition reaction of the seleno radicals to the alkenes. The reactivity of 2-NaphSe· is higher than that of 1-NaphSe·, both of which are less reactive than PhSe·. These reactivities were interpreted with the properties of SOMO calculated by MO method. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 193-200, 1998.

Notes: Using stationary-point information from a BAC-MP4 potential-energy surface and statistical-dynamical methods, we have calculated the total rate coefficient for the two-channel reaction,\documentclass{article}\pagestyle{empty}\begin{document}$ CH3+NO\rightarrow HCN+H2O\quad (R1) $\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$ \rightarrow H2CN+OH,\quad (R2) $\end{document}in the temperature range 1000 K≥T≥2500 K. The result obtained,\documentclass{article}\pagestyle{empty}\begin{document}$ kT=3.0 \times 10-1T3.52exp(-3950/RT) cm3/mole s, $\end{document}is in excellent agreement with recent shock-tube measurements of kT by Braun-Unkhoff, et al. and Hennig and Wagner. Qualitative considerations suggest that the radical channel (R2) is dominant in this temperature range. The analysis and the results are discussed in some detail. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 223-228, 1998.

Notes: The kinetics and mechanisms of the reactions of aluminium(III) with pentane-2,4-dione (Hpd), 1,1,1-trifluoro pentane-2,4-dione (Htfpd) and heptane-3,5-dione (Hhptd) have been investigated in aqueous solution at 25°C and ionic strength 0.5 mol dm-3 sodium perchlorate. The kinetic data are consistent with a mechanism in which aluminium(III) reacts with the β-diketones by two pathways, one of which is acid independent while the second exhibits a second-order inverse-acid dependence. The acid-independent pathway is ascribed to a mechanism in which [Al(H2O)6]3+ reacts with the enol tautomers of Hpd, Htfpd, and Hhptd with rate constants of 1.7(±1.3)×10-2, 0.79(±0.21), and 7.5(±1.6)×10-3 dm3 mol-1 s-1, respectively. The inverse acid pathway is consistent with a mechanism in which [Al(H2O)5(OH)]2+ reacts with the enolate ions of Hpd, Htfpd, and Hhptd with rate constants of 4.32(±0.18)×106, 5.84(±0.24)×103, and 1.67(±0.05)×107 dm3 mol-1 s-1, respectively. An alternative formulation involves a pathway in which [Al(H2O)4(OH)2]+ reacts with the protonated enol tautomers of the ligands. This gives rate constants of 2.79(±0.12)×104, 3.86(±0.16)×105, and 8.98(±0.25)×103 dm3 mol-1 s-1 for reaction with Hpd, Htfpd, and Hhptd, respectively. Consideration of the kinetic data reported here together with data from the literature, suggest that [Al(H2O)5(OH)]2+ reacts by an associative or associative-interchange mechanism. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 257-266, 1998.

Notes: The oscillatory behavior of a [Fe(phen)3]2+-catalyzed/bromomalonic acid/acidic bromate Belousov-Zhabotinsky system in aerated batch conditions has been reinvestigated. An 18-step skeleton mechanism is proposed. Reactions involving oxygen in the aqueous phase as well as reactions involving organic radicals are included in the skeleton mechanism. The numerical treatment of the corresponding differential equations leads to simulated behaviors in satisfactory agreement with the experimental ones. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 291-300, 1998.

Notes: No abstract.

Notes: The thermal decomposition of acetonitrile in the temperature range 1350-1950 K is modeled with a reaction scheme containing 23 species and 43 elementary reactions. Values of {[product]t/[CH3CN]0}/t, which were reported in a previous investigation are computed with this scheme at 50 K intervals and are compared with the values reported in the literature. Except for acrylonitrile and propyl nitrile at the high-temperature end of the study, very good agreement between the calculation and the experiment is obtained. A sensitivity spectrum of the kinetic scheme is shown and a discussion of the overall mechanism is presented. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 341-347, 1998

Notes: Vacuum line kinetic studies of the reaction of p-toluenesulfonyl chloride and benzene or toluene, using aluminum chloride as the catalyst and dichloromethane as the solvent were determined at 25°C by means of gas chromatography. The reaction is first-order in arene, tosyl chloride, and in AlCl3 as catalyst. Noncompetitive results are kT/kB=22±7 with a product sulfone isomer distribution: ortho, 14±1%; meta, 4.3±0.2%; and para 82±1%. With hexadeuteriobenzene kH/kD was determined to be 1.8±0.1. Rate constant ratios and product isomer distributions were also determined competitively: with AlCl3, kT/kB=30±2; % ortho, 13±1; % meta, 4.0±0.5; % para, 84±3; with SbCl5, kT/kB=40±4; % ortho 10.3±0.4; % meta, 4.7±0.2; and % para, 85.0±0.5. The kT/kB ratio for AlCl3 and the meta sulfone product percentages for both AlCl3 and SbCl5 are considerably higher than those reported in the literature. NMR and Raman studies suggest a molecular complex between p-tosyl chloride and AlCl3, with coordination through oxygen as the dominant species and the probable electrophile in CH2Cl2. A reaction mechanism consistent with the kinetic and spectroscopic results is proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 367-372,1998

Notes: The aminolysis reactions of O-ethyl S-(Z-phenyl) dithiocarbonates (Z=p-CH3, H, p-Cl, and p-NO2) with anilines (AN) and N,N-dimethylanilines (DMA) in acetonitrile at 30.0°C are investigated. Relatively small values of βX (βnuc,0.4 ca. 0.7) and βZ (βlg -0.1 ca. -0.4) for both ANs and DMAs, significantly large kH/kD values (1.1 ca. 1.9) involving deuterated anilines, and large negative ρXZ values for ANs (-0.56) are interpreted to indicate a concerted mechanism for both ANs and DMAs but with a hydrogen bonded four-center type transition state (TS) for ANs. The relative leaving ability, k(Z=p-NO2)/k(Z=p-CH3), is smaller for ANs than for DMAs, especially for a weaker nucleophile (1.9 and 4.7 for AN and DMA, respectively, with X=p-Cl). This suggests that the rate enhancement by the hydrogen-bond formation in the four-center type TS for AN is greater for a weaker nucleofuge (Z=p-CH3), especially when the nucleophile (X=p-Cl) is weaker. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 419-423,1998

Notes: Six analogues and derivatives (1-6) of 3-phenylhydrazonopentane-2,4-dione (7) were subjected to gas-phase thermolysis. The Arrhenius log A (s-1) and Ea (kJ mol-1) of the analogues (1-5) are, respectively: 10.42 and 140.8 for 1-cyano-1-phenyl-hydrazonopropanone (1), 11.19 and 135.4 for 1-cyano-1-(\documentclass{article}\pagestyle{empty}\begin{document}$ \underline{\rm{p}} $\end{document}-nitrophenylhydrazono)-propanone (2) , 10.68 and 144.9 for 1-cyano-1-(\documentclass{article}\pagestyle{empty}\begin{document}$ \underline{\rm{p}} $\end{document}-methoxyphenylhydrazono)propanone (3), 11.76 and 137.8 for 1-cyano-3-phenyl-1-phenylhydrazonopropanone (4), and 11.29 and 145.9 for 1-cyano-1-phenylhydrazonobutanone (5). The corresponding values for ethyl 3-oxo-2-phenylhydrazonobutanoate (6) are 11.90 s-1 and 143.3 kJ mol-1. The rates of reaction at 600 K are compared with those of the title diketone (7) and of pentane-2,4-dione (8) and rationalized in terms of a plausible elimination pathway involving a semiconcerted six-membered transition state. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 457-462, 1998

Notes: The gas-phase reaction of bornyl acetate (bicyclo[2,2,1]-heptan-2-ol-1,7,7-trimethyl-acetate) with hydroxyl radical has been studied. A relative method was used to determine the rate constant for this reaction, with n-octane as reference compound.Methyl nitrite photolysis experiments were carried out in an environmental smog chamber at atmospheric pressure and (294±2) K. The rate constant determined for bornyl acetate is k=(13.9±2.2)×10-12 cm3 molecule-1 s-1.The experimental rate constant has been compared with the rate constants calculated with the structure-activity relationship (SAR) and with the evolution trend of the acetate rate constants. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 497-502, 1998

Notes: Pulse radiolysis was used to study the kinetics of the reactions of CH3C(O)CH2O2 radicals with NO and NO2 at 295 K. By monitoring the rate of formation and decay of NO2 using its absorption at 400 and 450 nm the rate constants k(CH3C(O)CH2O2+NO)=(8±2)×10-12 and k(CH3C(O)CH2O2+NO2)=(6.4±0.6)×10-12 cm3 molecule-1 s-1 were determined. Long path length Fourier transform infrared spectrometers were used to investigate the IR spectrum and thermal stability of the peroxynitrate, CH3C(O)CH2O2NO2. A value of k-6≈3 s-1 was determined for the rate of thermal decomposition of CH3C(O)CH2O2NO2 in 700 torr total pressure of O2 diluent at 295 K. When combined with lower temperature studies (250-275 K) a decomposition rate of k-6=1.9×1016 exp (-10830/T) s-1 is determined. Density functional theory was used to calculate the IR spectrum of CH3C(O)CH2O2NO2. Finally, the rate constants for reactions of the CH3C(O)CH2 radical with NO and NO2 were determined to be k(CH3C(O)CH2+NO)=(2.6±0.3)×10-11 and k(CH3C(O)CH2+NO2)=(1.6±0.4)×10-11 cm3 molecule-1 s-1. The results are discussed in the context of the atmospheric chemistry of acetone and the long range atmospheric transport of NOx. © John Wiley & Sons, Inc. Int J Chem Kinet: 30: 475-489, 1998

Notes: Experiments have been carried out on the oxidation of CF3CFH2 (HFC-134a). Reaction was initiated by continuous photolysis of F2 in the near-ultraviolet. The F atoms produced abstracted a hydrogen atom from CF3CFH2 initiating oxidation in gas mixtures containing O2 and made up to a total pressure of 700 torr with N2. Product yields were measured using Fourier-transform infrared (FTIR) spectroscopy. Experiments were performed with several different partial pressures of O2 present, and at three temperatures; 298, 323, and 357 K. The major products were HC(O)F, CF3C(O)F, and CF3O3CF3, consistent with H atom abstraction by O2 and CC bond scission being the dominant loss processes for CF3CFHO radicals:\documentclass{article}\pagestyle{empty}\begin{document}$ CF3CFHO+O2 \rightarrow CF3C(O)F+HO2 (4a) $\end{document}\documentclass{article}\pagestyle{empty}\begin{document}$ CF3CFHO+M \rightarrow CF3+HC(O)F+M (4b) $\end{document}The following expression was derived for the ratio of rate constants for these reactions:k4a/k4b=(3.8±1.6)×10-24 exp[(2400±500)/T]cm3 molecule-1 (viii)The main fate of the CF3 radicals was formation of CF3O3CF3 and small amounts of CF3OH were detected. The results of the present experiments in which F atoms were used to initiate reaction are in good agreement with those of previous studies in which Cl atoms were employed to initiate the oxidation of HFC-134a. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 541-554, 1998

Notes: The room temperature rate coefficient for the reaction Br+Br2O→Br2+BrO (3) has been measured using the technique of pulse-laser photolysis with long-path transient absorption detection of the BrO reaction product. A value of k3=(2.0±0.5)×10-10 cm3 molecule-1 s-1 was determined. The photolysis products of Br2O at 308 nm were also examined. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 571-576, 1998

Notes: The kinetics of the oxidation of diazepam (DZ) by Chloramine-B (CAB) has been studied in aqueous hydrochloric acid medium. The oxidation reaction follows the rate law:\documentclass{article}\pagestyle{empty}\begin{document}$ \it{-d[\rm{CAB}]\over\it dt_{\ .}}=k\rm{[CAB][DZ]^{0.6}[HCl]^{0.6}} $\end{document}The dependence of the reaction rate on temperature is studied and activation parameters for the rate-determining step are evaluated. The dielectric constant of the medium has a small effect on the rate. Ionic strength and the reaction product benzenesulfonamide have no effect on the reaction rate. The solvent isotope effect is studied. A probable mechanism for the observed kinetic data is proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 605-611, 1998

Notes: Kinetics and mechanism of the reaction of Cr(VI) with oxalic acid have been studied in presence and absence of H2SO4, HClO4, and CH3COOH by monitoring the formation of Cr(III)-oxalic acid complex at 560 nm. The effect of total [oxalic acid], [Cr(VI)], [H2SO4], [HClO4], and [CH3COOH] on the reaction rate was determined at 30°C. Formation of carbon dioxide was also confirmed. The oxidation rate increases with [oxalic acid] and [CH3COOH] while it decreases with [H2SO4], [HClO4], and pH. The rate law governing the oxidation of oxalic acid over a wide range of conditions is rate=k1 Kes1 [oxalic acid]T [Cr(VI)]T 1+Kes1 [oxalic acid]T, where only undissociated oxalic acid is kinetically active. Kinetic evidence for the formation of a Cr(VI)(SINGLEBOND)oxalic acid 1:1 complex has been obtained and the equilibrium constant for their formation has been determined. The 1:1 complex exists most likely in an open chain form. The rate-limiting step of the oxidation reaction involves the breaking of the C(SINGLEBOND)C bond in the 1:2 complex. Oxidizing ability of Cr(VI) species have been discussed. Mechanism with the associated reaction kinetics is assigned. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 335-340, 1998

Notes: The reaction of trans-[Cr(Salen)(OH2)2]+ with aqueous sulfite yields trans-[Cr(Salen)(OH2)(OSO2(SINGLEBOND)O)]- (O-bonded isomer). The rate and activation parameter data for the formation of the sulfito complex are consistent with a mechanism involving rate-limiting addition of SO2 to the CrIII(SINGLEBOND)OH bond. The complex ions, trans-[(OH2)Cr(Salen)(OSO2(SINGLEBOND)O)]-, and trans-[(OH)Cr(Salen)(OSO2(SINGLEBOND)O)]2-, undergo reversible anation by NCS-, N3-, imidazole, and pyridine resulting in the formation of trans-[XCr(Salen)(OSO2(SINGLEBOND)O)](N+1)-(n=1 for X=N3-,NCS-, and 0 for X=imidazole and pyridine) predominantly via dissociative interchange mechanism. The labilizing action of the coordinated sulfite on the trans-CrIII-X bond in trans-[XCr(Salen)(OSO2)](n+1)- follows the sequence: NCS-pyridine ca. N3- ca. imidazole. Data analysis indicated that the coordinated sulfite has little trans activating influence. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 373-384, 1998

Notes: The photochemistry of IrCl62- complex in simple alcohols have been studied using laser-flash photolysis. Single electron transfer from the solvent molecule to the light-excited complex has been shown to be the primary photochemical process. Quantum yields of the photoreduction of IrCl62- complex and the rate constants of its reaction with hydroxyalkyl radicals were determined at 200-330 K. Deviations of the rate constants from Debye-Smoluchowski equation for diffusion-controlled reactions are discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 711-719, 1998

Notes: The relative rate technique has been used to measure the hydroxyl radical (OH) reaction rate constant of +2-butanol (2BU, CH3CH2CH(OH)CH3) and 2-pentanol (2PE, CH3CH2CH2CH(OH)CH3). 2BU and 2PE react with OH yielding bimolecular rate constants of (8.1±2.0)×10-12 cm3molecule-1s-1 and (11.9±3.0)×10-12 cm3molecule-1s-1, respectively, at 297±3 K and 1 atmosphere total pressure. Both 2BU and 2PE OH rate constants reported here are in agreement with previously reported values [1-4]. In order to more clearly define these alcohols' atmospheric reaction mechanisms, an investigation into the OH+alcohol reaction products was also conducted. The OH+2BU reaction products and yields observed were: methyl ethyl ketone (MEK, (60±2)%, CH3CH2C((DOUBLEBOND)O)CH3) and acetaldehyde ((29±4)% HC((DOUBLEBOND)O)CH3). The OH+2PE reaction products and yields observed were: 2-pentanone (2PO, (41±4)%, CH3C((DOUBLEBOND)O)CH2CH2CH3), propionaldehyde ((14±2)% HC((DOUBLEBOND)O)CH2CH3), and acetaldehyde ((40±4)%, HC((DOUBLEBOND)O)CH3). The alcohols' reaction mechanisms are discussed in light of current understanding of oxygenated hydrocarbon atmospheric chemistry. Labeled (18O) 2BU/OH reactions were conducted to investigate 2BU's atmospheric transformation mechanism details. The findings reported here can be related to other structurally similar alcohols and may impact regulatory tools such as ground level ozone-forming potential calculations (incremental reactivity) [5]. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 745-752, 1998

Notes: The rate constant of the title reaction is determined during thermal decomposition of di-n-pentyl peroxide C5H11O(—)OC5H11 in oxygen over the temperature range 463-523 K. The pyrolysis of di-n-pentyl peroxide in O2/N2 mixtures is studied at atmospheric pressure in passivated quartz vessels. The reaction products are sampled through a micro-probe, collected on a liquid-nitrogen trap and solubilized in liquid acetonitrile. Analysis of the main compound, peroxide C5H10O3, was carried out by GC/MS, GC/MS/MS [electron impact EI and NH3 chemical ionization CI conditions]. After micro-preparative GC separation of this peroxide, the structure of two cyclic isomers (3S*,6S*)3α-hydroxy-6-methyl-1,2-dioxane and (3R*,6S*)3α-hydroxy-6-methyl-1,2-dioxane was determined from 1H NMR spectra. The hydroperoxy-pentanal OHC(—)(CH2)2(—)CH(OOH)(—)CH3 is formed in the gas phase and is in equilibrium with these two cyclic epimers, which are predominant in the liquid phase at room temperature. This peroxide is produced by successive reactions of the n-pentoxy radical: a first one generates the CH3C·H(CH2)3OH radical which reacts with O2 to form CH3CH(OO·)(CH2)3OH; this hydroxyperoxy radical isomerizes and forms the hydroperoxy HOC·H(CH2)2CH(OOH)CH3 radical. This last species leads to the pentanal-hydroperoxide (also called oxo-hydroperoxide, or carbonyl-hydroperoxide, or hydroperoxypentanal), by the reaction HOC·H(CH2)2CH(OOH)CH3+O2→O(=)CH(CH2)2CH(OOH)CH3+HO2.The isomerization rate constant HOCH2CH2CH2CH(OO·)CH3→HOC·HCH2CH2CH(OOH)CH3 (k3) has been determined by comparison to the competing well-known reaction RO2+NO→RO+NO2 (k7). By adding small amounts of NO (0-1.6×1015 molecules cm-3) to the di-n-pentyl peroxide/O2/N2 mixtures, the pentanal-hydroperoxide concentration was decreased, due to the consumption of RO2 radicals by reaction (7). The pentanal-hydroperoxide concentration was measured vs. NO concentration at ten temperatures (463-523 K). The isomerization rate constant involving the H atoms of the CH2(—)OH group was deduced:\documentclass{article}\pagestyle{empty}\begin{document}$ k_{3}\rm =(6.4\pm 0.6)\times 10^{10}\hbox{exp}\{-(16,900\pm 700)\hbox{cal mol}^{-1}/RT\}s^{-1} $\end{document}or per H atom:\documentclass{article}\pagestyle{empty}\begin{document}$ k_{3\rm (H)}\rm =(3.2\pm 0.3)\times 10^{10}\hbox{exp}\{-(16,900\pm 700)\hbox{cal mol}^{-1}/RT\}s^{-1} $\end{document}The comparison of this rate constant to thermokinetics estimations leads to the conclusion that the strain energy barrier of a seven-member ring transition state is low and near that of a six-member ring. Intramolecular hydroperoxy isomerization reactions produce carbonyl-hydroperoxides which (through atmospheric decomposition) increase concentration of radicals and consequently increase atmospheric pollution, especially tropospheric ozone, during summer anticyclonic periods. Therefore, hydrocarbons used in summer should contain only short chains (〈C4) hydrocarbons or totally branched hydrocarbons, for which isomerization reactions are unlikely. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 875-887, 1998

Notes: The mechanism of the thermal decomposition of smithsonite has been determined from a comparison of the results obtained from isothermal, linear heating rate (TG), and Constant Rate Thermal Analysis (CRTA) experiments. Two important precautions have been taken in this work. Firstly, the chemical composition of the sample has been checked in order to be sure that pure anhydrous zinc carbonate has been used. Secondly, the experimental conditions have been selected in such a way to avoid the influence of heat and mass transfer phenomena on the forward reaction. It has been shown that the mechanism for the thermal decomposition of smithsonite depends upon temperature. Thus, at temperatures lower than 650 K, approximately, an A0.5 kinetic model describes the reaction, whereas, at temperatures roughly higher than 690 K the above reaction obeys a F1 kinetic law. An interpretation of this behavior is given. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 647-655, 1998

Notes: The pulse-radiolysis technique has been employed to produce and study the kinetics of hydrated electrons (eaq-) in a quaternary micro emulsion (Sodium Lauryl Sulfate (NaLS)/water/cyclohexane/1-pentanol) system. Two orders of magnitude higher life time (20 μs) of the eaq- has been obtained as compared to that in reverse micelles reported earlier. Several probes including a biomolecule have been used to determine the water pool concentrations and quenching constants (kq). The observed yield and half life (t1/2) of the hydrated electrons vary smoothly as the water droplet sizes are changed. The bimolecular rate constants for the reaction of eaq- with different solutes have been determined. It has been observed that the measured bimolecular rate constants for the reaction of hydrated electrons with different solutes are indicative of the solubilization sites, the water core sizes, and the surrounding environment. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 699-705, 1998

Notes: Potential-energy surfaces for various channels of the HNO+NO2 reaction have been studied at the G2M(RCC,MP2) level. The calculations show that direct hydrogen abstraction leading to the NO+cis-HONO products should be the most significant reaction mechanism. Based on TST calculations of the rate constant, this channel is predicted to have an activation energy of 6-7 kcal/mol and an A factor of ca. 10-11 cm3 molecule-1 s-1 at ambient temperature. Direct H-abstraction giving NO+trans-HONO has a high barrier on PES and the formation of trans-HONO would rather occur by the addition/1,3-H shift mechanism via the HN(O)NO2 intermediate or by the secondary isomerization of cis-HONO. The formation of NO+HNO2 can take place by direct hydrogen transfer with the barrier of ca. 3 kcal/mol higher than that for the NO+cis-HONO channel. The formation of HNO2 by oxygen abstraction is predicted to be the least significant reaction channel. The rate constant calculated in the temperature range 300-5000 K for the lowest energy path producing NO+cis-HONO gave rise to\documentclass{article}\pagestyle{empty}\begin{document}$ k_{a}=7.34\cdot 10^{-20}\ \rm{T}^{2.64}\ \rm{exp}(-2034/T)\ \rm{cm}^{3}\ \rm{molecule}^{-1}\ \rm{s}^{-1}. $\end{document}© 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 729-736, 1998

Notes: Collisional deactivation of I(2P1/2) by the title compounds was investigated through the use of the time-resolved atomic absorption of excited iodine atoms at 206.2 nm. Rate constants for atomic spin-orbit relaxation by CH3Cl, CH2Cl2, CHCl3, CCl3F, and CCl4 are 3.1±0.3×10-13, 1.28±0.08×10-13, 5.7±0.3×10-14, 3.9±0.4×10-15, and 2.3±0.3×10-15cm3 molecule-1 s-1, respectively, at room temperature (298 K).The higher efficiency observed for relaxation by CH3Cl, CH2Cl2, and CHCl3 reveals a contribution in the deactivation process of the first overtone corresponding to the C(SINGLEBOND)H stretching of the deactivating molecule (which lies close to 7603 cm-1) as well as the number of the contributing modes and certain molecular properties such as the dipole moment. It is believed that, for these molecules, a quasi-resonant (E-v,r,t) energy transfer mechanism operates. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 799-803, 1998

Notes: Using a pulse-radiolysis transient UV-VIS absorption system, rate constants for the reactions of F atoms with CH3CHO (1) and CH3CO radicals with O2 (2) and NO (3) at 295 K and 1000 mbar total pressure of SF6 was determined to be k1=(1.4±0.2)×10-10, k2=(4.4±0.7)×10-12, and k3=(2.4±0.7)×10-11 cm3 molecule-1 s-1. By monitoring the formation of CH3C(O)O2 radicals (λ〉250nm) and NO2 (λ=400.5nm) following radiolysis of SF6/CH3CHO/O2 and SF6/CH3CHO/O2/NO mixtures, respectively, it was deduced that reaction of F atoms with CH3CHO gives (65±9)% CH3CO and (35±9)% HC(O)CH2 radicals. Finally, the data obtained here suggest that decomposition of HC(O)CH2O radicals via C—C bond scission occurs at a rate of 〈4.7×105 s-1. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 913-921, 1998

Notes: Ascorbic acid present in natural products is often analyzed by its reducing effect on 2,6-dichlorophenolindophenol (DCPI). In case of coexistence of Fe(II) in natural samples and if oxalic acid is used for their extraction and stabilization, a significant interference is observed. The reaction of Fe2+ with 2,6-dichlorophenolindophenol (DCPI) in acidic solutions in the presence or absence of oxalate ions was investigated. The reaction was studied with a Stopped-Flow Spectrophotometer (S.F.S) equiped with a data acquisition system, which allows the determination of initial rates and reaction rate constants. Results for the effect of the concentrations of all the reagents of the reaction are presented. During the experimental work all concentrations of the reagents were kept in such levels to make the reaction first-order in respect of DCPI. An interesting finding is, that, although Fe2+ and C2O42- ions do not react separately with DCPI (or react very slowly), they react very rapidly in mixtures and show a strong synergetic effect. The experimental data fit with the mechanism of the formation of intermediates FeC2O4 and [Fe(C2O4)2]2-. The proposed rate law agrees with the above mechanism and the experimental results. The value kc=(1.6±0.2)×105 M-1·s-1 was calculated for the second-order rate constant of the reaction of FeC2O4 and DCPI. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 941-948, 1998

Notes: A detailed chemical kinetic model has been used to study dimethyl ether (DME) oxidation over a wide range of conditions. Experimental results obtained in a jet-stirred reactor (JSR) at 1 and 10 atm, 0.2≤φ≤2.5, and 800≤T≤1300 K were modeled, in addition to those generated in a shock tube at 13 and 40 bar, φ=1.0 and 650≤T≤1300 K. The JSR results are particularly valuable as they include concentration profiles of reactants, intermediates, and products pertinent to the oxidation of DME. These data test the kinetic model severely, as it must be able to predict the correct distribution and concentrations of intermediate and final products formed in the oxidation process. Additionally, the shock-tube results are very useful, as they were taken at low temperatures and at high pressures, and thus undergo negative temperature dependence (NTC) behavior. This behavior is characteristic of the oxidation of saturated hydrocarbon fuels, (e.g., the primary reference fuels, n-heptane and iso-octane) under similar conditions. The numerical model consists of 78 chemical species and 336 chemical reactions. The thermodynamic properties of unknown species pertaining to DME oxidation were calculated using THERM. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 229-241, 1998.

Notes: Cationic micelles of cetyltrimethylammonium bromide, CTABr, speed attack of hydroxide ion upon coumarin by a factor of c.a-2, due to a concentration effect. The first-order rate constants, kobs, at a given hydroxide ions concentration go through maxima with increasing surfactant concentration. The overall micellar effects in these cationic micelles can be treated in terms of the pseudo-phase ion exchange model. Analysis of the data shows that second-order rate constant at the micellar surface is smaller than the second-order rate constant in water. Anionic micelles of sodium dodecyi sulfate, SDS, inhibit the same reaction. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 273-276, 1998.

Notes: The kinetics of oxidation of four vicinal diols, four nonvicinal diols, and one of their monoethers by pyridinium bromochromate (PBC) have been studied in dimethyl sulfoxide. The main product of oxidation is the corresponding hydroxyaldehyde. The reaction is first-order with respect to each the diol and PBC. The reaction is acid-catalyzed and the acid dependence has the form: kobs=a+b[H+]. The oxidation of [1,1,2,2-2H4]ethanediol exhibited a primary kinetic isotope effect (kH/k D=6.70 at 298 K). The reaction has been studied in 19 organic solvents including dimethyl sulfoxide and the solvent effect has been analyzed using multiparametric equations. The temperature dependence of the kinetic isotope effect indicates the presence of a symmetrical transition state in the rate-determining step. A suitable mechanism has been proposed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 285-290, 1998.

Notes: Models that simulate atmospheric photochemistry require the use of a stiff ordinary differential equations (ODEs) solver. Since the simulation of the chemical transformations taking place in the system takes up to 80 percent of the CPU time, the numerical solver must be computationally fast. Also, the residual error from the solver must be small. Because most accurate solvers are relatively slow, modelers continue to search for timely, yet accurate integration methods. Over the past years an extensive number of articles have been dedicated to this subject. One of the highly debated questions is whether one should construct specialized algorithms or instead use general methods for stiff ODEs. In the present article we use the second alternative. We apply three linearly (semi-)implicit methods from the classical stiff ODE literature which we modified to implement the sparse routines to solve the system of equations describing a complex kinetic mechanism. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 349-358, 1998

Notes: The investigation of high-pressure autoignition of combustible mixtures is of importance in providing both practical information in the design of combustion systems and fundamental measurements to verify and develop chemical kinetic models. The autoignition characteristics of hydrogen-oxygen mixtures at low pressures have been explored extensively, whereas few measurements have been made at high pressures. The present measurements extend the range of pressures up to 4 MPa, where few measurements have yet been reported.Using a rapid compression machine equipped with a specially designed piston head, hydrogen autoignition pressure traces were measured at pressures above the second explosion limit (p=0.6-4 MPa, T=950-1050 K). The measured pressure records show a more gradual pressure increase during induction time in this regime than in the low-pressure regime, indicating that the energy release becomes significant at conditions over the second explosion limit.By comparing the measurements and a thermodynamic model which incorporates the heat transfer and energy release, a modified reaction rate constant for H2O2+H=HO2+H2, one of the most important reactions for hydrogen oxidation at high pressure, and the reaction with the largest uncertainty, is suggested in this work as k17=2.3 . 1013exp(-4000/T) cm3/mol-s. The modeled pressure history with the modified reaction rate agrees well with the measured values during the induction period over the range of conditions tested. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 385-406, 1998

Notes: Isobutane pyrolysis has been studied at 20-200 torr initial pressures and 773-793 K, in a packed reactor treated with PbO and in a reactor packed with platinum foils. These packings strongly inhibit product formation and this effect is explained by the occurrence of the heterogeneous termination step:\documentclass{article}\pagestyle{empty}\begin{document}$ \rm H\cdot\mathrel{\mathop{\relbar\joinrel\longrightarrow}^{walls}} product $\end{document}at the reactor walls. The reaction has been modeled in the temperature and pressure range on the basis of a kinetic scheme which has been proposed for the homogeneous reaction and step (w) with the following values of kw:$$\eqalign{(k_{_{w}})_{_{\rm{PbO}}}&=3.7\ 10^{8}\ \rm{exp} \left[-{9000\over \rm{T}}\right]\rm{S}^{-1}\cr(k_{_{w}})_{_{\rm{Pt}}}&=15000\ \rm{S}^{-1}\ \rm{at\ any\ temperature}\cr}$$for both types of packing. The corresponding sticking coefficients of hydrogen atoms are:$$\eqalign{\gamma _{_{\rm{PbO}}} &=160\ \rm{exp} \left[-{9000\over \rm{T}}\right]\cr\gamma _{_{\rm{Pt}}} &=0.03\cr}$$© 1998 John Wiley & Sons, Inc. Int J Chem. Kinet 30: 439-450,1998

Notes: The kinetics of Zn(II), Cd(II), and Hg(II) incorporation into meso tetrameta-tolueneporphyri n (H2T(m-CH3)PP) in acetone have been studied by means of stopped-flow method. A unified reaction mechanism was proposed and the kinetic parameters were obtained by nonlinear least-square methods. The effect of ionic strength (I) on Cd(II)/H2T(m-CH3)PP was investigated. It has been found that there is a negative kinetic salt effect and the relationship of rate constants with ionic strength was obtained. Some solvent effects have also been investigated in this article. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 277-283, 1998.

Notes: The thermal reaction of propene was examined around 800 K in the presence of less than 20% oxygen. At initial time, the production of H2, CH4, C2H4, C2H6, allene, C3H8, 1,3-butadiene, butenes, 3- and 4-methylcyclopentene, a mixture of 1,4- and 1,5-hexadienes, methylcyclopentane (or dimethylcyclobutane), 4-methylpent-1-ene, and hex-1-ene, was observed along with hydrogen peroxide, CO, and small quantities of ethanal and CO2. Oxygen increases the initial production of hydrogen and of most hydrocarbons and, particularly, that of C6 dienes and of cyclenes. However, the production of allene, methylcyclopentane (or dimethylcyclobutane), and 4-methylpent-1-ene is practically not affected. A kinetic study confirms the mechanism proposed for the thermal reaction of propene. Formation of allene, thus, involves a four-center-unimolecular dehydrogenation of propene, that of 4-methylpent-1-ene is explained by an ene bimolecular reaction while methylcyclopentane (or dimethylcyclobutane) probably arises from a bimolecular process involving a biradical intermediate. Other products arise from a conventional chain radical mechanism.A kinetic scheme is proposed in which chains are primarily initiated by the bimolecular step:C3H6+O2→HO2·+C3H5·which competes with the second-order initiation of propene pyrolysis. Since allene production is not affected by oxygen, it is concluded that allyl radicals are not dehydrogenated by oxygen; but they oxidize in a branching step involving allylperoxyl radicals; r. radicals other than methyl, and allyl are dehydrogenated according to the conventional process:r·+O2→unsaturated+HO2·and account for the production of a large excess of C6 diolefins, methylcyclopentenes, and hydrogen peroxide, when r. stands for C6H11, the allyl adduct. Hydrogen peroxide gives rise to a degenerate branching of chains. Based on the proposed scheme, a modeling of the reaction is shown to account fairly well for the concentration-time profiles. Rate constants of many steps are evaluated and discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 503-522, 1998

Notes: Laser-flash photolysis of RBr/O3/SF6/He mixtures at 248 nm has been coupled with BrO detection by time-resolved UV absorption spectroscopy to measure BrO product yields from O(1D) reactions with HBr, CF3Br, CH3Br, CF2ClBr, and CF2HBr at 298±3 K. The measured yields are: HBr, 0.20±0.04; CF3Br, 0.49±0.07; CH3Br, 0.44±0.05; CF2ClBr, 0.31±0.06; and CF2HBr, 0.39±0.07 (uncertainties are 2σ and include estimates of both random and systematic errors). The results are discussed in light of other available information or O(1D)+RBr reactions. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 555-563, 1998

Notes: Isobutane pyrolysis has been studied in the presence of oxygen at about 773 K in unpacked and in PbO-coated packed Pyrex reactors. The reaction is shown to be accelerated by oxygen in reactors of low surface-to-volume ratio and strongly inhibited in packed PbO-coated reactors. These oxygen effects are explained in terms of interaction between two radical chain systems, one of pyrolysis, the other of oxidation. Oxygen introduces additional chain initiations and a degenerate chain branching step due to H2O2 while oxygenated radicals are efficiently removed at the reactor wall. All experimental results have been modeled and many rate constants of elementary steps were evaluated. The collision efficiency of HO2 radicals on a PbO-coated Pyrex surface has been determined in the temperature range of this study. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 657-671, 1998

Notes: The kinetics of the substitution reactions of Fe(CN)5H2O3- ion with a series of nitrogen and sulfur containing heterocycles were studied in aqueous media. In the presence of excess ligand, varied over a large range of concentrations, second-order rate constants were calculated at μ = 0.100 M NaClO4. Activation parameters for the formation reactions were found, ΔH*ast; and ΔS*, 28 ± 6 kJ/mol and 135±20 J/mol, respectively. The results are interpreted as being consistent with dissociative, SN1 mechanism. The kinetics of formation and dissociation were studied by stopped-flow technique at several temperatures. An investigation of the kinetics of exchange of coordinated heterocycles for 1,3,5-triazine, yielded rate saturation that is typical of a limiting SN1 mechanism. Activation parameters of the limiting first-order specific rate of dissociations were found with ΔH* and ΔS* 53±2 kJ/mol and 105±5 J/mol, respectively. From the specific rates of formation and dissociation reactions the equilibrium constants were calculated. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 415-418, 1998

Notes: N-cyanomethyl-N-ethyl aniline (CEAN) and N-cyanomethyl-N-ethyl-p-anisidine (CEPA) have been thermolyzed in a stirred-flow reactor, in the range of 510-560 °C, pressures of 7-11 torr and residence times of 0.5-0.9 s, using toluene as carrier gas. N-cyanomethyl-N-ethyl-p-nitroaniline (ECNA) was thermolyzed at 640°C and 13% conversion. Ethylene and HCN formed in 43% yield each as products from all three starting materials. Phenyl methanaldimine and p-anisidyl methanaldimine were also products of CEAN and CEPA, respectively. The consumption of CEAN and CEPA showed first-order kinetics for a three-fold increase of reactant inflow and initial conversions of up to 40 percent. The following Arrhenius equations were obtained from the rate coefficients for the production of ethylene: CEAN: k=1015.10±0.74 exp(-238±11 kJ/mol·RT); CEPA: k=1015.61±0.29 exp(-246±4 kJ/mol·RT). The results are explained by means of radical, nonchain thermolysis mechanisms. The thermochemistry of relevant reaction steps has been estimated from thermochemical parameters calculated by using the semiempirical AM1 method. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 451-456, 1998

Notes: Photolysis of S2O8= in strong alkaline solutions (pH 〉 13) in the presence of molecular oxygen yields ozonide radical ions, \documentclass{article}\pagestyle{empty}\begin{document}$ \rm{O^{\textstyle{\cdot}-}_{3}} $\end{document}. These radicals show a complex decay rate sensitive to the peroxodisulfate concentration. A reaction mechanism, which includes the reaction of O•- and S2O8= with a rate constant k=(3-6)×106M-1s-1 and accounts for the experimental results is discussed. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 491-496, 1998

Notes: Using a relative rate method, rate constants have been measured for the gas-phase reactions of the OH radical with 1-hexanol, 1-methoxy-2-propanol, 2-butoxyethanol, 1,2-ethanediol, and 1,2-propanediol at 296±2 K, of (in units of 10-12 cm3 molecule-1 s-1): 15.8±3.5; 20.9±3.1; 29.4±4.3; 14.7±2.6; and 21.5±4.0, respectively, where the error limits include the estimated overall uncertainties in the rate constants for the reference compounds. These OH radical reaction rate constants are higher than certain of the literature values, by up to a factor of 2. Rate constants were also measured for the reactions of 1-methoxy-2-propanol and 2-butoxyethanol with NO3 radicals and O3, with respective NO3 radical and O3 reaction rate constants (in cm3 molecule-1 s-1 units) of: 1-methoxy-2-propanol, (1.7±0.7)×10-15, and 〈1.1×10-19; and 2-butoxyethanol, (3.0±1.2)×10-15, and 〈1.1×10-19. The dominant tropospheric loss process for the alcohols, glycols, and glycol ethers studied here is calculated to be by reaction with the OH radical, with lifetimes of 0.4-0.8 day for a 24 h average OH radical concentration of 1.0×106 molecule cm-3. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 533-540, 1998

Notes: Ligand substitution kinetics for the reaction [PtIVMe3(X)(NN)]+NaY=[PtIVMe3(Y)(NN)]+NaX, where NN=bipy or phen, X=MeO-, CH3COO-, or HCOO-, and Y=SCN- or N3-, has been studied in methanol at various temperatures. The kinetic parameters for the reaction are as follows. The reaction of [PtMe3(OMe)(phen)] with NaSCN: k1=36.1±10.0 s-1; ΔH1≠=65.9±14.2 kJ mol-1; ΔS1≠=6±47 J mol-1 K-1; k-2=0.0355±0.0034 s-1; ΔH-2≠=63.8±1.1 kJ mol-1; ΔS-2≠=-58.8±3.6 J mol-1 K-1; and k-1/k2=148±19. The reaction of [PtMe3(OAc)(bipy)] with NaN3: k1=26.2±0.1 s-1; ΔH1≠=60.5±6.6 kJ mol-1; ΔS1≠=-14±22 J mol-1K-1; k-2=0.134±0.081 s-1; ΔH-2≠=74.1±24.3 kJ mol-1; ΔS-2≠=-10±82 J mol-1K-1; and k-1/k2=0.479±0.012. The reaction of [PtMe3(OAc)(bipy)] with NaSCN: k1=26.4±0.3 s-1; ΔH1≠=59.6±6.7 kJ mol-1; ΔS1≠=-17±23 J mol-1K-1; k-2=0.174±0.200 s-1; ΔH-2≠=62.7±10.3 kJ mol-1; ΔS-2≠=-48±35 J mol-1K-1; and k-1/k2=1.01±0.08. The reaction of [PtMe3(OOCH)(bipy)] with NaN3: k1=36.8±0.3 s-1; ΔH1≠=66.4±4.7 kJ mol-1; ΔS1≠=7±16 J mol-1K-1; k-2=0.164±0.076 s-1; ΔH-2≠=47.0±18.1 kJ mol-1; ΔS-2≠=-101±61 J mol-1 K-1; and k-1/k2=5.90±0.18. The reaction of [PtMe3(OOCH)(bipy)] with NaSCN: k1 =33.5±0.2 s-1; ΔH1≠=58.0±0.4 kJ mol-1; ΔS1≠=-20.5±1.6 J mol-1 K-1; k-2=0.222±0.083 s-1; ΔH-2≠=54.9±6.3 kJ mol-1; ΔS-2≠=-73.0±21.3 J mol-1 K-1; and k-1/k2=12.0±0.3. Conditional pseudo-first-order rate constant k0 increased linearly with the concentration of NaY, while it decreased drastically with the concentration of NaX. Some plausible mechanisms were examined, and the following mechanism was proposed. [Note to reader: Please see article pdf to view this scheme.] © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 523-532, 1998

Notes: Diffuse Interface Model (DIM) is introduced to describe the mechanism of high-temperature corrosion/internal oxidation. The zone has dissolved oxygen and metal atoms diffuse and react resulting in the inward movement of zone. The high-temperature oxidation data for cobalt, iron, and nickel, which are for metal deficit (p-type), have been analyzed using a nonlinear optimization method to obtain the optimal values for different parameters, diffusivity of metal atoms in metal oxide, diffiusivity of gaseous species in the corrosion product, diffusivity of oxidant in the unreacted solid (metal or alloy), the rate constant for the reaction and the fraction of the zone reacted. The expression for diffusivity in the reaction zone has been modified by relating diffusivities of the product layer and the core as function of fraction of zone reacted. The model was applied to the experimental data for the high-temperature oxidation of cobalt, iron, and nickel by pure oxygen at an atmospheric pressure. The model predicts the values of diffusion coefficients, preexponential factors, and activation energies for diffusion process, which are generally compared favorably with those reported in the literature. Linear relationship are derived relating the diffusion coefficient in the core and product layer to the parabolic rate constant which is valid for iron, cobalt, and nickel for high-temperature oxidation (900-1350°C) by oxygen at an atmospheric pressure according to the following equations:\scriptfont4=\seveni \scriptscriptfont4=\fivei $$D_{\rm P}=1.4\times 10^{-8}\ \it k_{g}$$ $$D_{\rm C}=6.9\times 10^{-9}\ \it k_{g}$$The results of the model have been successfully used to predict the experimentally determined parabolic rate constants for the oxidation of cobalt at high temperatures for two different investigators [6,7] under similar conditions. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 903-912, 1998

Notes: The kinetics of the title reactions have been studied using the discharge-flow mass spectrometic method at 296 K and 1 torr of helium. The rate constant obtained for the forward reaction Br+IBr→I+Br2 (1), using three different experimental approaches (kinetics of Br consumption in excess of IBr, IBr consumption in excess of Br, and I formation), is: k1=(2.7±0.4)×10-11 cm3 molecule-1s-1. The rate constant of the reverse reaction: I+Br2→Br+IBr (-1) has been obtained from the Br2 consumption rate (with an excess of I atoms) and the IBr formation rate: k-1=(1.65±0.2)×10-13 cm3molecule-1s-1. The equilibrium constant for the reactions (1,-1), resulting from these direct determinations of k1 and k-1 and, also, from the measurements of the equilibrium concentrations of Br, IBr, I, and Br2, is: K1=k1/k-1=161.2±19.7. These data have been used to determine the enthalpy of reaction (1), ΔH298°=-(3.6±0.1) kcal mol-1 and the heat of formation of the IBr molecule, ΔHf,298°(IBr)=(9.8±0.1) kcal mol-1. © 1998 John Wiley & sons, Inc. Int J Chem Kinet 30: 933-940, 1998

Notes: A rigorous approach was developed for the simulation of the decoking of an industrial cracking furnace. A one-dimensional heterogeneous reactor model, which accounts for the interfacial gradients between the process gas and the coke surface, was used to simulate reactor coils. Both the combustion and steam gasification of the coke layer were taken into account. The reactor model for the decoking was coupled with a detailed firebox simulation model. The initial profile of the coke layer thickness, required for the decoking calculations, was obtained by a run-length simulation. The evolution with time of the temperature distribution inside the cracking coil and in the furnace was generated simultaneously, which made it possible to understand the decoking operation in detail and to predict its duration accurately.

Notes: A semibatch flow scheduling strategy proposed by Teymour and Ray (1989, 1996) is evaluated for a polymerization reaction conducted in a pilot-plant reactor. The reaction used is the free radical terpolymerization of styrene, α-methyl styrene, and acrylic acid monomers initiated by an organic peroxide initiator and carried out in the presence of a reactive glycol ether solvent. This strategy was tested in both single batch and sequential semibatch modes. The process was shown to produce polymer of constant molecular weight properties and composition as inferred from acid number and monomer conversion measurements. This process could be used for obtaining polymer products from a semibatch reactor that are of comparable quality to CSTR products. Results indicate success of this process at meeting this objective; however, practical considerations relating to agitation and temperature control need to be properly addressed to ensure this success.

Notes: Diffusion coefficients measured by holographic interferometry are presented for two globular proteins and three nonionic surfactant species in agarose gels. The cloud points for the surfactants in agarose solutions are also given. In all cases, rates of diffusion in the gel are smaller than those in bulk solution, with the hindering effect of the gel increasing both with increasing gel concentration and with increasing solute size. It is shown that the diffusion rate of the surfactant micelles is very similar to that of proteins having similar hydrodynamic radii; it would therefore appear that the size and shape of the micelles in the solution and gel phases are similar. In addition, the measured rates of hindered diffusion agree very well with rates predicted by a rigorous hydrodynamic theory in which the solutes are modeled as hard spheres and the gel fibers are modeled as straight, cylindrical fibers. Hence, for the range of conditions considered, rates of hindered diffusion for both the globular proteins and the micellar species are determined primarily by hard-sphere hydrodynamic and steric interactions between the solute and the gel matrix.

Notes: Equations were derived that describe the dynamics of cake growth in cake filtration, and methods for their solutions were developed. In deriving the equations, the moving boundary nature of the cake formation process and the effect of fine particle retention were considered. It was shown that fine particle retention may contribute significantly to the decrease of cake permeability and thus alters the performance of cake filtration even if the amount of fine particles involved is small. Through numerical examples, it was also demonstrated that fine particle retention in filter cakes may cause serious errors in determining the constitutive relationships from filter test data.

Notes: Fundamental characteristics of liquid-solid fluidization at high pressures (up to 21 MPa) and moderate temperatures (up to 89°C) are investigated. Properties under study include minimum fluidization velocity (umf), bed voidage at minimum fluidization, and bed expansion. Devices for in-situ measurements of physical properties of the liquid in the bed are developed, and measurements are carried out to quantify the pressure and temperature effects on the fluidization behavior. The results indicate that under high pressures and moderate temperatures, liquid-solid fluidization behavior is affected significantly by the variation of liquid density and viscosity with pressure. As the pressure increases, the liquid viscosity and density increase, yielding an increased drag force and buoyancy force on the particles, and hence a decreasing umf and an increasing bed expansion for a given liquid flow rate. An increase in temperature has an opposite effect on the physical properties of the liquid, increasing umf and decreasing the bed expansion for a given liquid flow rate. Various correlations proposed in the literature for umf and bed expansion, including those by Richardson and Zaki (1954) and Chitester et al. (1984), are applicable to high-pressure and high-temperature conditions when proper account is made of the liquid physical properties under bed operating conditions.

Notes: Asymptotic power series solutions for the mass-transfer enhancement factor for absorption of a gas component into a liquid where it undergoes irreversible instantaneous chemical reaction(s) with one and two liquid-phase reactants are developed in this work. The Padé technique is used to extend the region of applicability (accelerate the convergence) of the four-term asymptotic power series solutions. The resulting modified asymptotic expressions for the enhancement factor show excellent accuracy over a wide range and can be used to predict enhancement factors as low as 2 with an error of about 5% compared to the exact numerical solution. Predictions of these new asymptotic solutions are compared with experimental absorption data for H2S absorption into aqueous methyldiethanolamine and H2S absorption into aqueous mixtures of methyldiethanolamine and diethanolamine obtained in a laminar-jet absorber. The absolute mean deviations of the predictions from the experimental absorption data for the single and mixed amine solutions were 4.6% and 2.4%, respectively.

Notes: When a trickle-bed reactor (TBR) is operated periodically, the bed is fed with liquid on and off, while the gas phase passes continuously. Rates and conversions could be higher than those corresponding to the steady-state operation. In the “dry cycles” the heat generated by the reaction can drive the vaporization of the liquid phase, and a much more rapid “gas phase” reaction may occur. There is a trade-off between the potential for hot-spot formation and the fact that overall rates are higher during cycling. A qualitative understanding of the phase transition in TBRs is obtained by a simple phenomenological model that takes into account different transport and reaction mechanisms occurring in a catalytic particle under different cycling conditions. A mathematical model is used to predict results.

Notes: Theoretical and engineering models for the thermodynamic properties of strong electrolyte solutions have advanced significantly since 1985. This progress is notable in the ability to calculate selected properties of single and mixed strong electrolyte solutions over a wide range of temperatures and compositions, including effects of various nonelectrolytes, solvents and supercritical components. Theoretical studies have begun to consider more realistic fundamental interactions between various components in these systems. There have been several successful conversions of theories based on the mean spherical approximation and perturbation methods into engineering equations, without large numbers of empirical parameters. Other theoretical models seem almost ready for application to real systems. The capability to estimate a wide variety of thermodynamic properties accurately with a consistent set of equations and a small number of adjustable parameters has been achieved by several groups over limited temperature and composition ranges. Much work remains to be done, however, to understand completely the interplay and relative importance of various contributing energy effects.

Notes: Centrifugal partition chromatography (CPC) is a relatively new preparative chromatographic technique. To understand, predict, and optimize CPC separations a model is needed, describing the effluent concentration profile as a function of the phenomena that determine the separation efficiency (mass transfer, mixing, and partitioning). The model presented in this article describes experimental effluent concentration profiles accurately. Partition coefficients, Stanton numbers, and Péclet numbers were obtained by comparing model simulations to experimental pulse-response data. The fitted partition coefficients agree well with those obtained from shake-flask experiments. Mass-transfer limitation is the major reason for peak broadening. The inverse mass-transfer coefficient is a linear function of the partition coefficient. The model will be a valuable tool in determining the influence of mass transfer as a function of various experimental conditions.

Notes: In this article we present a method for the on-line identification and modeling of full profile disturbance models for sheet forming processes. A particular principal components analysis technique called the Karhunen-Loève expansion is used to adaptively identify the significant features of the profile. In addition, we show how the temporal modes of the reconstructed profile can be modeled using low-order linear autoregressive (AR) processes. By simulation examples, the effect of the order of the AR model is studied, as well as the window size of the data used in the on-line application of the KL expansion, the effect of data weighting, the importance of the correct selection of the number of modes, and the frequency of updating the parameters of the AR models. Identified disturbance models can be easily incorporated into model-predictive control algorithms.

Notes: A pure culture of Pseudomonas putida was grown as a film on carbon particles in a differential fluidized bed biofilm reactor, a new experimental system for the application of diffusion-reaction models. In the active biofilm, effective diffusion coefficients of the essential substrates - phenol and oxygen - were simultaneously calculated. The multisubstrate biokinetic expression used in the model solution was derived by nonlinear regression analysis of the data of continuous system fermenter experiments. The determined biokinetic equations were utilized to solve the diffusion-reaction model for effective diffusion coefficients in the active biofilm. The ratio of the evaluated effective diffusion coefficient through active biofilm to that of water varied between 17-44% and 9-24% for phenol and oxygen, respectively, for different biofilm densities. Results of the study showed a fair agreement with the literature at low biofilm densities.

Notes: The convective diffusion equations were used to obtain mean concentrations and concentration fluctuation covariances during turbulent reactive mixing of fast reversible reactions. The mean concentrations are directly applicable to reactions that are much faster than the mixing, while the covariances can serve as a first approximation closure for slower reactions. The covariances should also be useful for testing more general closure models. Numerical examples are presented for the simple mass-action rate law with stoichiometric coefficients of unity.

Notes: Electrophoresis of a solute through a column in which its transport is governed by the convection - diffusion equation is described. Approximate solutions to the convection - diffusion equation in the limit of small diffusion are developed using perturbation methods. The diffusion coefficient and velocity are assumed to be functions of space and time such that both undergo a sudden change from one constant value to another within a thin transition zone that itself translates with a constant velocity. Two cases are considered: (1) the thickness ∊f of the transition zone is negligible compared to the diffusional length scale, so the zone may be treated as a singular boundary across which the diffusion constant and velocity suffer discontinuous changes; (2) the transition zone is considerably wider than the diffusional length scale, so the diffusion coefficient and velocity, although sharply varying, are smooth functions of position and time. A systematic perturbation expansion of the concentration distribution is presented for case 1 in terms of the small parameter ∊ = 1/Pe. A lowest order approximation is given for case 2. A suitably configured system analyzed here can lead to progressive accumulation, or focusing, of the transported solute. The degree of focusing in case 1 scales with ∊-1, whereas in case 2 it scales with (∊f∊)-1/2, and thus increases much more weakly with increasing Pe. A separation based on this concept requires development of materials and devices that allow dynamic tuning of the mass-transport properties of a medium. This would make it possible to achieve progressive focusing and separation of solutes, such as proteins and DNA fragments, in electrophoretic media with an unprecedented degree of control.

Notes: The influence on drying selectivity of the continuous-contact mode between a solid wetted with ternary mixtures and a gas stream was theoretically studied. The liquid mixtures, ethanol-isopropanol-water and water-ethanol-acetone, were used. A mathematical model describing a gas-phase-controlled process was developed, and the influence of the process variables was studied by simulations. In addition to the inlet composition of the moisture and temperature of the solid, gas composition has the most important effect on selectivity. Small changes of gas composition, either imposed or spontaneous, may modify completely the process trajectory. The extent of these effects depends on the ratio between the flow rates of inlet gas and liquid contained in the solid. Because of their effects on the evolution of temperature and composition, the operating pressure and energy sources other than convection are also useful in controlling the selectivity. Since all these variables determine the composition of the remaining liquid and thereby product quality, their influence should be predictable. The model may be a valuable tool for exploring the process, provided that drying is gas-phase-controlled.

Notes: A novel, physically based kernel for population balance modeling of granule growth by coalescence is presented. This kernel is size-independent in that all collisions with an effective average granule size less than a critical value are successful. Simulations based on this kernel show that a variety of contradictory experimental observations can be modeled. In the limiting case of viscoelastic collisions, the kernel can be related to the governing group of the Stokes number (Ennis et al., 1991), representing the ratio of granule collisional kinetic energy to viscous dissipation brought about by the binder. In more general cases, material properties that control deformability, such as interparticle friction, binder viscosity, and liquid content, strongly affect this critical size. The kernel clearly demonstrates the three regimes of drum granulation originally proposed by Kapur and Fuerstenau in 1964 and compares favorably with the two-stage sequential kernel developed by Adetayo et al. in 1995 for the drum granulation of fertilizers.

Notes: Complex mixing flows and mixing parameters are calculated to evaluate mixing quality on the basis of kinematic parameters together with a statistical analysis. The results allow for a comparative evaluation in terms of geometry and flow parameters. The evaluation is limited to two-dimensional flows with moving boundaries in periodic motion such as the flow in the cross section of a twin-cam mixer. The finite-element calculation requires a remeshing procedure for every time step with special techniques to upgrade mixing variables from one time step to the next. The relative mixing quality of single cam and co: or counterrotating cam devices are compared by evaluating segregation scale, length stretch, and efficiency. The numerical results exhibit a good correspondence with their experimental counterpart.

Notes: Numerical tools for the analysis of complex 3-D mixing devices were developed. Calculations are based on the finite-element method. The flow calculation is combined with that of pathlines for a fairly large number of material points; along these pathlines, relevant kinematic variables, which are then subjected to a statistical treatment, are evaluated. These numerical techniques are applied to the analysis of a Kenics mixer. It is assumed that the geometry is periodic in the axial direction, that is, that the mixer contains an infinite number of blades; the finite-element analysis may then be completed on a single wavelength of the geometry. To test the accuracy of the three-dimensional calculation, a Kenics device was mounted in order to mix clays of different colors, and photographs of experimental cross-sections were compared with numerical results showing concentration maps. A statistical treatment was performed on some 8,000 material points crossing the entry section to evaluate mixing quality.

Notes: A cold model of a circulating fluidized bed with a 0.030-m-ID, 2.77-m-high riser was operated in a wide range of operating conditions. Several solids were tested, from 57 μm to 1,830 μm in size and from 1,100 kg/m3 to 2,540 kg/m3 in density. Pressure fluctuations were measured at several points along the riser, and time series were processed to evaluate chaotic invariants (Kolmogorov entropy and correlation dimesion). Axial profiles of average values of pressure and voidage were also evaluated. At fixed operating conditions, the Kolmogorov entropy changed along the riser, which appeared to be a fuction of the local voidage and showed a minimum when voidage decreases from 1.00 until about 0.90. Changes of the Kolmogorov entropy with local voidage were interpreted based on interactions among solids and gas turbulence structure. Three regions were identified in the voidage range investigated: particles-controlled region, clusters-controlled region, and bottom-bed-controlled region.

Notes: The prototype of an integrated hazard-analysis system (IHAS) was developed. Essentially any process can be analyzed with this software if the system topology is correctly supplied by the user. Since all altorithms adopted are digraph-based, the system digraph must be constructed first with IHAS. The embedded feedforward and feedback loops are then identified and classified. On the basis of this information, three widely accepted hazard-assessment procedures - FTA, ETA, and HAZOP - can be performed automatically. From the results obtained in practical applications, one can see that the quality. From the results obtained in practical applications, one can see that the quality of hazard analysis is indeed improved if IHAS can be used as an aid to the human experts.

Notes: The problem of analyzing the stability of chemical process plants is considered. The idea of exchange plants has been extended with more general binary transfer terms and binary equilibrium, resulting in the idea of binary exchange-equilibrium plants. Their structural stability is analyzed using results on conservation matrices. It was found that binary exchange-equilibrium plants with no azeotropes are stable irrespective of the connections of their operating units. The general results are illustrated in examples of practical importance: heat-exchanger networks and binary distillation columns with constant molar flows.

Notes: An electrochemically modulated complexation (EMC) process was designed to selectively extract and concentrate ethylene from a feed-phase mixture with ethane. Unlike previous EMC processes, where the separation was based on equilibrium solubility differences, this separation was based on differences in the rate of complexing with copper(I) solution between the two gases. The EMC process employed flowthrough electrolysis cells that electrochemically modulate aqueous-phase copper chlorides between high, copper(I), and low, copper(II), affinity states. The liquid phase in the high affinity form contracts a feed gas phase in a hollow-fiber membrane module for selective extraction and contacts the receiving gas phase in the low affinity form for concentration. Experimental results and modeling of the process are reported.

Notes: A systematic method to synthesize crystallization-distillation hybrid separation processes is presented. Two classes of hybrids are identified for binary mixtures. The first bypasses azeotropes and tangent pinches, while the second bypasses eutectics. Guidelines for flow-sheet selection are proposed based on an analysis of simple eutectic, constant relative volatility systems. In addition, the hybrids are compared to both extractive and adductive crystallization in order to determine the conditions under which solvent-based crystallization techniques outperform the proposed hybrid configurations. The method is extended to ternary mixture. The use of stream combination and complex distillation columns is also considered.

Notes: Back-and-forth-moving temperature fronts separating regions with high and low temperatures (amplitudes up to 100 K) formed on a Pd on alumina ring during the atmospheric oxidation of carbon monoxide. The back-and-forth front movement reflects the intrinsic nonuniformity of the catalytic system and the impact of global coupling. The ignition and extinction fronts usually moved at different velocities, in agreement with theoretical predictions. Complex spatiotemporal patterns were observed due to small-amplitude temperature fronts that moved on the high-temperature region at a much higher velocity than the high-amplitude fronts. The qualitative motion features were affected by changes in the excess oxygen concentration. The nonuniform states existed mainly for feed conditions for which the only uniform state was an extinguished one.

Notes: Parameters of wetting dry fibers with non-Newtonian liquids are studied experimentally. Rheological tests show that seven of the 13 test liquids adhere to Newtonian behavior with a wide range of viscosities 3 〈 μ 〈 30,000 mPa·s. The other six liquids show shear-thinning behavior with different flow indices. Some of the liquids exhibited viscoelastic behavior. Diameters of the fibers are in the range 0.033 〈 D 〈 0.071 cm. Experimental measurements cover contact angles, interfacial depths and diameters, as well as the critical wetting speed of entraining visible small air bubbles in the liquid volume. Dynamic contact angles are strong functions of the apparent viscosity of the liquid at the particular wetting speed regardless of whether the liquid is Newtonian or non-Newtonian. Higher values of contact angles correspond to wetting of fiber with larger diameter for less viscous liquid are generally higher than those for Newtonian liquids. Depressions created in the surface of different test liquids can be classified into three different scales, corresponding to three scales of liquid viscosities.

Notes: The role of swelling clays in hindering the compressional dewatering characteristics of coal-mine tailings is examined. The effects of electrolyte concentration and ion exchange in improving the shear and compressional rheology are compared. Suspensions studies include actual mine tailings (thickener feed and thickener underflow) as well as synthetic clay dispersions made from clay collected from the coal seam. It was shown that the most important parameter in controlling the properties of the tailings suspension is “controlled” dispersion in the presence of a Ca2+ electrolyte concentration in excess of that required to (1) prevent initial swelling and (2) provide full cation exchange of the clay. Under these electrolyte conditions, complete delamination of the clay did not occur, and both the dewatering and handling characteristics of the resultant suspensions improved dramatically.

Notes: A simplified exponential (SEXP) approximation, combining the exponential approximation and the first-order mean spherical approximation, is proposed to improve the equation of state for the Lennard-Jones (LJ) fluid. The SEXP approximation, which can be implemented in an analytical manner, yields better radial distribution functions of the LJ fluid. Extensive comparisons with two typical perturbation theories show that the SEXP approximation is more appropriate to describe the behaviors of the LJ fluid. The latest 33-parameter modified Benedict-Webb-Rubin equation, also calculated, is inadequate in the region of phase coexistence. The SEXP approximation is applied to the calculation of methane properties with much better results than the Peng-Robinson equation of state for saturated liquid densities and second virial coefficients.

Notes: One of the challenges in building reaction mechanisms using algorithms for automated model construction is to describe the essential chemistry and enable prediction of experimental data over wide ranges of reaction conditions while maintaining a manageable model size. Two complementary methodologies for building compact reaction mechanisms were developed and combined with existing algorithms based on graph theory and bond-electron matrix operations. Each strategy was developed using pentadecylbenzene pyrolysis as an illustrative example. The first approach used a radical lumping strategy to group radicals according to their reactivity. The mechanism was reduced from 719 to 215 species and successfully predicted the experimentally observed initial reactivity. However, implementation of the radical lumping criteria alone was insufficient to allow for secondary reactions to higher-rank products. Therefore, on-the-fly sensitivity analysis was incorporated to identify the important and necessary species as the mechanism was generated to guide the mechanism building process. The generic algorithms developed can be applied to generate compact reaction mechanisms for a wide array of higher molecular-weight reactants.

Notes: In this work, the bimodal/film model is compared with the cell model based on a case study using polystyrene/styrene devolatilization. It shows improvements over the cell model: (1) it requires a lower initial number of bubbles, which is more physically realistic and (2) it takes into account the observation of a limiting foam volume growth for a specific polymer in devolatilization. A stripper dispersion experiment was designed to investigate the effect of dispersed nitrogen stripper bubbles on the foam dynamics and devolatilization efficiency. The variables examined include polymer viscosity, initial volatile concentration, and the initial number and size of dispersed stripper bubbles. Polymer viscosity was the dominant factor in limiting the maximum foam volume expansion. The number and size of dispersed stripper bubbles show positive and negative effects (which are only secondary) on the maximum foam volume expansion, respectively. The initial volatile concentration has no effect on limiting the maximum foam volume expansion.

Notes: Mathematical models developed describe the unfolding of polymeric crystals in the presence of a solvent followed by their subsequent disentanglement. A thermodynamic model considering the free energy changes during crystal unfolding was proposed to obtain an expression for the unfolding rate. A simplified version of this expression, assuming uniform crystal size, was incorporated into a continuum model to predict the dissolution kinetics of a semicrystalline polymer slab. The model yielded predictions of the crystalline and solvent volume fractions as a function of position within the slab, in addition to changes in the fraction of polymer dissolved as well as the degree of crystallinity of the polymer as a function of time. The degree of crystallinity of the polymer decreased with time and the plot of the fraction of the polymer dissolved as a function of time exhibited Case II behavior. The model predictions agreed will with experimental results obtained during dissolution of semicrystalline poly(vinyl alcohol) in water.

Notes: The hydrodynamics of two-dimensional bubble columns operated in various flow regimes are studied using particle image velocimetry. Both averaged velocity profiles and Reynolds stress profiles are obtained and discussed in relation to large-scale structures present in the flow. The normal stresses, dominated by large-scale structures, are an order of magnitude higher than the shear stress. It is found that the contribution from the bubbles to the shear to the normal stresses is negligible. A time series of the flow field is studied, demonstrating that the flow could be split into a low-frequency contribution due to the vortical structures and a high-frequency fluctuating part. The latter gives rise to flat normal stress profiles, and the former is responsible for the original form of the normal stress profiles. The shear stress in the smaller columns investigated can be related to the averaged vertical velocity profile according to a Boussinesq approximation. Data on the eddy viscosity are presented.

Notes: A modified CaCO3 sorbent with an open internal pore structure is prepared and its sulfation characteristics are investigated in an entrained flow reactor at high temperatures (900-1,100°C) and short contact times (20-600 ms) using small particle sizes (〈 5 μm). The most distinguishing feature of this modified carbonate (MC) is its 70-75% sulfation conversion within 0.5 s, which is substantially higher than any other sorbents published. The MC is prepared by carbonation-precipitation from a calcium hydroxide suspension by optimizing the operating parameters to generate carbonate particles of the desired pore structural properties. The high initial surface area combined with its open pore structure and pore-size distribution of its calcine contribute to its high reactivity. The calcined MC possesses a significant portion of its pore volume in the 50-200 Å range. This size range represents an optimum pore size for sulfation since it provides a reasonably high surface area and is less susceptible than 〈 50 Å pore sizes, to pore filling, or pore-mouth plugging due to the formation of higher molar volume CaSO4. Investigation with other carbonates reveals that a much higher portion of their calcines' porosity lies in the smaller pores, which leads to premature termination of sulfation. Results show the impact of internal pore structure on initial reactivity and ultimate sorbent conversion.

Notes: This work determines the rate constant of hydrogen peroxide decomposition in supercritical water. Experiments were conducted at pressures ranging from 5.0 to 34.0 MPa and for temperatures up to 450°C. The rate of the homogeneous decomposition reaction is distinguished from the rate of the catalytic decomposition on the reactor surface by conducting experiments at different surface-to-volume ratios. The rate constant of H2O2 decomposition follows the expression k(s-1) = 1013.4 ± 1.2 exp[(- 180 ± 16 kJ/mol)/RT], providing a higher value than that derived from RRKM calculations. Comparison between experiments at supercritical conditions (P = 24.5 and 34.0 MPa) and experiments in high-pressure steam (P = 5.0 and 10.0 MPa) show that the efficiency of the catalytic surface reactions decreases significantly under supercritical conditions. The rate constant just mentioned was incorporated into a methanol oxidation model and the new prediction is compared with the experimental data of Rice et al. (1996), showing a distinct improvement compared to the original prediction.