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UV Photolysis (uv + photolysi)

Distribution by Scientific Domains

Chemistry	60%

Selected Abstracts

Kinetics of the gas-phase reaction of CF3OC(O)H with OH radicals at 242,328 K

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2004
L. Chen
The rate constants, k1, of the reaction of CF3OC(O)H with OH radicals were measured by using a Fourier transform infrared spectroscopic technique in an 11.5-dm3 reaction chamber at 242,328 K. OH radicals were produced by UV photolysis of an O3,H2O,He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during UV irradiation. With CF3OCH3 as a reference compound, k1 at 298 K was (1.65 ± 0.13) × 10,14 cm3 molecule,1 s,1. The temperature dependence of k1 was determined as (2.33 ± 0.42) × 10,12 exp[,(1480 ± 60)/T] cm3 molecule,1 s,1; possible systematic uncertainty could add an additional 20% to the k1 values. The atmospheric lifetime of CF3OC(O)H with respect to reaction with OH radicals was calculated to be 3.6 years. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 337,344 2004 [source]

Rate constants for the gas-phase reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals at 250,430 K

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 1 2004
L. Chen
The rate constants k1 for the reaction of CF3CF2CF2CF2CF2CHF2 with OH radicals were determined by using both absolute and relative rate methods. The absolute rate constants were measured at 250,430 K using the flash photolysis,laser-induced fluorescence (FP-LIF) technique and the laser photolysis,laser-induced fluorescence (LP-LIF) technique to monitor the OH radical concentration. The relative rate constants were measured at 253,328 K in an 11.5-dm3 reaction chamber with either CHF2Cl or CH2FCF3 as a reference compound. OH radicals were produced by UV photolysis of an O3,H2O,He mixture at an initial pressure of 200 Torr. Ozone was continuously introduced into the reaction chamber during the UV irradiation. The k1 (298 K) values determined by the absolute method were (1.69 ± 0.07) × 10,15 cm3 molecule,1 s,1 (FP-LIF method) and (1.72 ± 0.07) × 10,15 cm3 molecule,1 s,1 (LP-LIF method), whereas the K1 (298 K) values determined by the relative method were (1.87 ± 0.11) × 10,15 cm3 molecule,1 s,1 (CHF2Cl reference) and (2.12 ± 0.11) × 10,15 cm3 molecule,1 s,1 (CH2FCF3 reference). These data are in agreement with each other within the estimated experimental uncertainties. The Arrhenius rate constant determined from the kinetic data was K1 = (4.71 ± 0.94) × 10,13 exp[,(1630 ± 80)/T] cm3 molecule,1 s,1. Using kinetic data for the reaction of tropospheric CH3CCl3 with OH radicals [k1 (272 K) = 6.0 × 10,15 cm3 molecule,1 s,1, tropospheric lifetime of CH3CCl3 = 6.0 years], we estimated the tropospheric lifetime of CF3CF2CF2CF2CF2CHF2 through reaction with OH radicals to be 31 years. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 36: 26,33, 2004 [source]

Removal of organic contaminants in paper pulp effluents by AOPs: an economic study

JOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 5 2002
Montserrat Pérez
Abstract The degradation of the organic content of a bleaching Kraft mill effluent was carried out using Advanced Oxidation Processes (AOPs). The study was focused on the identification of the AOP, or combination of AOPs, that showed the highest efficiency together with the lowest cost. Direct UV photolysis (UV), TiO2 assisted-photocatalysis (TiO2/UV), Fenton, Fenton-like, and photo-Fenton reactions (Fe(II)/H2O/UV), UV-assisted ozonation (O3/UV) and addition of Fe2+ and/or H2O2 to the TiO2/UV and the O3/UV systems, were used for the degradation of a conventional cellulose bleaching effluent. The effluent was characterized by the general parameters TOC, COD and color, and analyzed for chlorinated low molecular weight compounds using GC,MS. The costs of the systems per unit of TOC reduction were compared. Fenton, Fenton-like and photo-Fenton reactions achieved better levels of TOC degradation than photocatalysis and with lower cost's than photocatalytic treatments. Ozonation is an effective but rather expensive process. The use of UVA light, however, increased the effectiveness of ozonation with a significant decrease (>25%) in the operational cost. © 2002 Society of Chemical Industry [source]

Laser Flash Photolysis in a O3/Cl2 Mixture at 266 nm in a Very Low-Pressure Flow System,

PHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 4 2005
Jorge Codnia
ABSTRACT The laser flash photolysis in a very low-pressure flow system with mass spectrometry detection technique was developed for the study of oxidation reactions of chlorofluorocarbons. In this work, we have studied the UV photolysis of O3 in the presence of Cl2 at room temperature, which presents two catalytic cycles of O3 depletion with efficiencies dependent on the partial pressures in the photoreactor. The ozone dissociation was initiated with fourth harmonic pulses of a Nd:YAG laser. The detection of the reactants and the final and intermediate reaction products was performed with real-time mass spectrometry. The variations of the O3, Cl2 and ClO concentration were measured. The equations system associated to a proposed kinetic scheme was solved numerically and excellent agreement with the experimental results was obtained. The results from this work allowed the determination of the wall loss rates of the O(1D), Cl and ClO radicals. [source]

013 Effect of UV on the susceptibility of acid-soluble Skh-1 hairless mouse collagen to collagenase

PHOTODERMATOLOGY, PHOTOIMMUNOLOGY & PHOTOMEDICINE, Issue 2 2002
J.M. Menter
To test the hypothesis that UV could alter collagen susceptibility to interstitial collagenase, acid-extracted Skh-1 hairless mouse collagen samples were (un)irradiated with 0,140 J/cm2 of radiation from bank of filtered FS lamp (UVB/UVA = 0.33, fluence rate = 0.81 mW/cm2). Subsequent to UV irradiation, collagen samples were coupled with fluorescein isothiocyanate (FITC) and assayed for its susceptibility to bacterial collagenase by monitoring the appearance of supernatant FITC fluorescence (a measure of lysed collagen) over time of incubation. As a reference. unirradiated commercial FITC , labeled collagen (Elastin Products) was similarly analyzed. Mouse collagen had a lower rate of cleavage than did the calf skin sample. Mouse collagen initial cleavage followed a quasi-linear time course over the first 5 h. Calf-skin collagen displayed a ,sigmoidal' time course, reminiscent of a cooperative mechanism. UV irradiation afforded no significant effect on the ability of collagenase to cleave mouse collagen, although a small effect could be discerned after 48 h (140 J/cm2). On the other hand, these samples exhibited significant chain degradation. cross-linking and loss of intrinsic collagen fluorescence on UV photolysis. It appears that the rate of cleavage depends on the superstructure of the collagen, and that the collagen fluorophores are not in proximity to the specific site of collagenase cleavage. Supported in part by NIH/MBRS Grant #GM 08248 and RCMI Grant #RR 03034. [source]