Unstationary film model for the determination of absolute gas-liquid kinetic rate constants: ozonation of Acid Red 27, Acid Orange 7, and Acid Blue 129

A method for the determination of absolute kinetic rate constants is proposed using an unstationary film model. This methodology avoids the experimental determination of parameters like the enhancement factor or the Hatta number which are usually model-dependent. The mathematical model is general for gas-liquid systems with irreversible second order reactions. An optimization procedure based on artificial neural networks is used to estimate the initial guess of the parameters and the subsequent application of Gauss-Newton algorithm for the final nonlinear parameter estimation. The model is tested with the ozonation reaction of Acid Red 27, Acid Orange 7 and Acid Blue 129. The second-order kinetic rate constants for the direct reaction with O3 are 1615±93, 609±83, and 49±2M−1s−1, respectivelyJF acknowledges the support of the doctoral fellowship from the Universitat Politecnica de Valencia (UPV-PAID-FPI-2010-04).Ferre Aracil, J.; Cardona Navarrete, SC.; López Pérez, MF.; Abad Sempere, A.; Navarro-Laboulais, J. (2013). Unstationary film model for the determination of absolute gas-liquid kinetic rate constants: ozonation of Acid Red 27, Acid Orange 7, and Acid Blue 129. Ozone: Science and Engineering. 35(6):423-437. https://doi.org/10.1080/01919512.2013.815104S423437356Biń, A. K. (2006). Ozone Solubility in Liquids. Ozone: Science & Engineering, 28(2), 67-75. doi:10.1080/01919510600558635Cardona, S. C., López, F., Abad, A., & Navarro-Laboulais, J. (2010). On bubble column reactor design for the determination of kinetic rate constants in gas-liquid systems. The Canadian Journal of Chemical Engineering, 88(4), 491-502. doi:10.1002/cjce.20327Chang, C. S., & Rochelle, G. T. (1982). Mass transfer enhanced by equilibrium reactions. Industrial & Engineering Chemistry Fundamentals, 21(4), 379-385. doi:10.1021/i100008a011Dachipally, P., & Jonnalagadda, S. B. (2011). Kinetics of ozone-initiated oxidation of textile dye, Amaranth in aqueous systems. Journal of Environmental Science and Health, Part A, 46(8), 887-897. doi:10.1080/10934529.2011.580201Danckwerts, P. V., & Lannus, A. (1970). Gas-Liquid Reactions. Journal of The Electrochemical Society, 117(10), 369C. doi:10.1149/1.2407312Das, A. K., & Das, P. K. (2009). Bubble Evolution through a Submerged Orifice Using Smoothed Particle Hydrodynamics: Effect of Different Thermophysical Properties. Industrial & Engineering Chemistry Research, 48(18), 8726-8735. doi:10.1021/ie900350hFerrell, R. T., & Himmelblau, D. M. (1967). Diffusion coefficients of nitrogen and oxygen in water. Journal of Chemical & Engineering Data, 12(1), 111-115. doi:10.1021/je60032a036Gerlach, D., Alleborn, N., Buwa, V., & Durst, F. (2007). Numerical simulation of periodic bubble formation at a submerged orifice with constant gas flow rate. Chemical Engineering Science, 62(7), 2109-2125. doi:10.1016/j.ces.2006.12.061Glasscock, D. A., & Rochelle, G. T. (1989). Numerical simulation of theories for gas absorption with chemical reaction. AIChE Journal, 35(8), 1271-1281. doi:10.1002/aic.690350806Gomes, A. C., Nunes, J. C., & Simões, R. M. S. (2010). Determination of fast ozone oxidation rate for textile dyes by using a continuous quench-flow system. Journal of Hazardous Materials, 178(1-3), 57-65. doi:10.1016/j.jhazmat.2010.01.043Gupta, P., Al-Dahhan, M. H., Duduković, M. P., & Mills, P. L. (2000). A novel signal filtering methodology for obtaining liquid phase tracer responses from conductivity probes. Flow Measurement and Instrumentation, 11(2), 123-131. doi:10.1016/s0955-5986(99)00025-4Hoigné, J., & Bader, H. (1983). Rate constants of reactions of ozone with organic and inorganic compounds in water—I. Water Research, 17(2), 173-183. doi:10.1016/0043-1354(83)90098-2Jamialahmadi, M., Zehtaban, M. R., Müller-Steinhagen, H., Sarrafi, A., & Smith, J. M. (2001). Study of Bubble Formation Under Constant Flow Conditions. Chemical Engineering Research and Design, 79(5), 523-532. doi:10.1205/02638760152424299Johnson, P. N., & Davis, R. A. (1996). Diffusivity of Ozone in Water. Journal of Chemical & Engineering Data, 41(6), 1485-1487. doi:10.1021/je9602125King, C. J. (1966). Turbulent Liquid Phase Mass Transfer at Free Gas-Liquid Interface. Industrial & Engineering Chemistry Fundamentals, 5(1), 1-8. doi:10.1021/i160017a001Ledakowicz, S., Maciejewska, R., Perkowski, J., & Bin, A. (2001). Ozonation of Reactive Blue 81 in the bubble column. Water Science and Technology, 44(5), 47-52. doi:10.2166/wst.2001.0248Lewis, W. K., & Whitman, W. G. (1924). Principles of Gas Absorption. Industrial & Engineering Chemistry, 16(12), 1215-1220. doi:10.1021/ie50180a002Lopez, A., Benbelkacem, H., Pic, J. ‐S., & Debellefontaine, H. (2004). Oxidation pathways for ozonation of azo dyes in a semi‐batch reactor: A kinetic parameters approach. Environmental Technology, 25(3), 311-321. doi:10.1080/09593330409355465Meldon, J. H., Olawoyin, O. O., & Bonanno, D. (2007). Analysis of Mass Transfer with Reversible Chemical Reaction†. Industrial & Engineering Chemistry Research, 46(19), 6140-6146. doi:10.1021/ie0705397Navarro-Laboulais, J., Cardona, S. C., Torregrosa, J. I., Abad, A., & López, F. (2006). Structural identifiability analysis of the dynamic gas–liquid film model. AIChE Journal, 52(8), 2851-2863. doi:10.1002/aic.10901Navarro-Laboulais, J., Cardona, S. C., Torregrosa, J. I., Abad, A., & López, F. (2008). Practical identifiability analysis in dynamic gas–liquid reactors. Computers & Chemical Engineering, 32(10), 2382-2394. doi:10.1016/j.compchemeng.2007.12.004Rapp, T., & Wiesmann, U. (2007). Ozonation of C.I. Reactive Black 5 and Indigo. Ozone: Science & Engineering, 29(6), 493-502. doi:10.1080/01919510701617959Tanaka, M., Girard, G., Davis, R., Peuto, A., & Bignell, N. (2001). Recommended table for the density of water between 0  C and 40  C based on recent experimental reports. Metrologia, 38(4), 301-309. doi:10.1088/0026-1394/38/4/3Tizaoui, C., & Grima, N. (2011). Kinetics of the ozone oxidation of Reactive Orange 16 azo-dye in aqueous solution. Chemical Engineering Journal, 173(2), 463-473. doi:10.1016/j.cej.2011.08.014Von Gunten, U. (2003). Ozonation of drinking water: Part I. Oxidation kinetics and product formation. Water Research, 37(7), 1443-1467. doi:10.1016/s0043-1354(02)00457-

Kinetic detection of osmium(VI) ester intermediates during the OsO4‐mediated aqueous dihydroxylation of chloroethylenes

The kinetics and mechanism of the cis dihydroxylation of cis‐1,2‐ dichloroethylene, trans‐1,2‐dichloroethylene, and trichloroethylene by osmium tetroxide was studied systematically in aqueous solution. The stoichiometry of the process was determined based on the principle of continuous variation of reactant ratios with spectrophotometric detection. The results always showed 1:1 stoichiometry, which is in agreement with dihydroxylation. All three reactions were found to proceed in two distinct steps. The first step occurred on a time scale of seconds and was associated with a minor change in absorbance and was identified as the formation of a 1:1 adduct between the two reagents, which is the osmium(VI) ester that plays a decisive role in catalytic applications. This species is formed in an equilibrium that is very much shifted toward the reactants, so the osmium(VI) complex is a short‐lived intermediate of the process, which is detected kinetically, but its concentration is never high enough for structural characterization. The second reaction is accompanied by major spectral changes; it involves the formation of the final products. Our results clearly show that it is possible to detect the intermediate of the process by careful kinetic studies. It is also possible that the same strategy might be successful in other OsO4‐dependent dihydroxylation processes

Controlled Radical Polymerization of Vinyl Acetate Mediated by a Bis(imino)pyridine Vanadium Complex

Source type: Prin

Water-Soluble Mo3S4 Clusters Bearing Hydroxypropyl Diphosphine Ligands: Synthesis, Crystal Structure, Aqueous Speciation, and Kinetics of Substitution Reactions

The [Mo3S4Cl3(dhprpe)3]+ (1+) cluster cation has been prepared by reaction between Mo3S4Cl4(PPh3)3 (solvent)2 and the watersoluble 1,2-bis(bis(hydroxypropyl)phosphino)ethane (dhprpe, L) ligand. The crystal structure of [1]2[Mo6Cl14] has been determined by X-ray diffraction methods and shows the typical incomplete cuboidal structure with a capping and three bridging sulfides. The octahedral coordination around each metal center is completed with a chlorine and two phosphorus atoms of the diphosphine ligand. Depending on the pH, the hydroxo group of the functionalized diphosphine can substitute the chloride ligands and coordinate to the cluster core to give new clusters with tridentate deprotonated dhprpe ligands of formula [Mo3S4(dhprpe-H)3]+ (2+). A detailed study based on stopped-flow, 31P{1H} NMR, and electrospray ionization mass spectrometry techniques has been carried out to understand the behavior of acid−base equilibria and the kinetics of interconversion between the 1+ and the 2+ forms. Both conversion of 1+ to 2+ and its reverse process occur in a single kinetic step, so that reactions proceed at the three metal centers with statistically controlled kinetics. The values of the rate constants under different conditions are used to discuss on the mechanisms of opening and closing of the chelate rings with coordination or dissociation of chloride