Rate Constants For Reactions Of Hydroxyl Radicals Research Articles

Iron (III) hydroxocomplex-methyl viologen dication system as a prospective tool for determination of hydroxyl radical reaction rate constants with environmental pollutants.

Reactivity of oxidative species with target pollutants is one of the crucial parameters for application of any system based on advanced oxidation processes (AOPs). This work presents new useful approach how to determine the hydroxyl radical reaction rate constants (kOH) using UVA laser flash photolysis technique. Fe (III) hydroxocomplex at pH 3 was applied as a standard source of hydroxyl radicals and methyl viologen dication (MV2+) was used as selective probe for •OH radical. Application of MV2+ allows to determine kOH values even for compounds which do not generate themselves optically detectable transient species in reaction with hydroxyl radicals. Validity of this approach was tested on a wide range of different persistent pesticides and its main advantages and drawbacks in comparison with existing steady-state and time-resolved techniques were discussed.

Efficacy of ozone for removal of pesticides, metals and indicator virus from reverse osmosis concentrates generated during potable reuse of municipal wastewaters

This study evaluated ozone treatment to address concerns regarding the discharge to marine waters of chemical contaminants and pathogens in reverse osmosis (RO) concentrates generated during the potable reuse of municipal wastewaters. Previous studies indicated that contaminants can be sorted into five groups based on their reaction rate constants with ozone and hydroxyl radical to predict degradation of chemical contaminants during ozonation of municipal effluents. Spiking representatives of each group into five RO concentrate samples, this study demonstrated that the same contaminant grouping scheme could be used to predict contaminant degradation during ozonation of RO concentrates, despite the higher concentrations of ozone and hydroxyl radical scavengers. The predictive capability of the contaminant grouping scheme was further validated for four contaminants of concern in RO concentrates, including the pesticides fipronil and imidacloprid, and the metal chelates Ni-EDTA and Cu-EDTA. After measuring their ozone and hydroxyl radical reaction rate constants, these compounds were assigned to contaminant groups, and their degradation during ozonation matched predictions. Addition of 300 mg/L CaO at pH 11 achieved partial removal of the native nickel and copper by precipitation. Ozone pretreatment further enhanced precipitation of nickel, but not copper. Ozonation achieved 5-log inactivation of MS2 in all five concentrate samples at 1.18 mg O3/mg DOC. Ozonation at 0.9 mg O3/mg DOC formed 139–451 μg/L bromate. Pretreatment of RO concentrates with chlorine and ammonia reduced bromate formation by a maximum of 48% but increased total halogenated DBP concentrations from 20 μg/L to 36 μg/L. Regardless, neither bromate nor trihalomethane concentrations exceeded threshold concentrations of concern for discharge to marine waters.

Modeling the pH and temperature dependence of aqueousphase hydroxyl radical reaction rate constants of organic micropollutants using QSPR approach.

Designing of advanced oxidation process (AOP) requires knowledge of the aqueous phase hydroxyl radical (●OH) reactions rate constants (k OH), which are strictly dependent upon the pH and temperature of the medium. In this study, pH- and temperature-dependent quantitative structure-property relationship (QSPR) models based on the decision tree boost (DTB) approach were developed for the prediction of k OH of diverse organic contaminants following the OECD guidelines. Experimental datasets (n=958) pertaining to the k OH values of aqueous phase reactions at different pH (n=470; 1.4×106 to 3.8×1010M-1s-1) and temperature (n=171; 1.0×107 to 2.6×1010M-1s-1) were considered and molecular descriptors of the compounds were derived. The Sanderson scale electronegativity, topological polar surface area, number of double bonds, and halogen atoms in the molecule, in addition to the pH and temperature, were found to be the relevant predictors. The models were validated and their external predictivity was evaluated in terms of most stringent criteria parameters derived on the test data. High values of the coefficient of determination (R 2) and small root mean squared error (RMSE) in respective training (>0.972, ≤0.12) and test (≥0.936, ≤0.16) sets indicated high generalization and predictivity of the developed QSPR model. Other statistical parameters derived from the training and test data also supported the robustness of the models and their suitability for screening new chemicals within the defined chemical space. The developed QSPR models provide a valuable tool for predicting the ●OH reaction rate constants of emerging new water contaminants for their susceptibility to AOPs.

Hydroxyl radical generation with a high power ultraviolet light emitting diode (UV-LED) and application for determination of hydroxyl radical reaction rate constants

We propose a simple, efficient and selective hydroxyl radical generation system based on the photolysis of submicromolar concentrations of nitrite using a high-power ultraviolet light emitting diode (UV-LED). Hydroxyl radical formation by the 6.75-W UV-LED was at least 10 times greater than that by a 300-W Xe lamp. In the UV-LED system, the hydroxyl radical formation rate from nitrite was about four orders of magnitude larger than that from nitrate and two orders of magnitude larger than that from hydrogen peroxide. Such efficient and selective hydroxyl radical formation can be attributed to the overlap of the emission spectrum of the UV-LED and absorption of nitrite. The system was used to determine the reaction rate constants between hydroxyl radicals and chemicals based on the competition method with terephthalate as the hydroxyl radical probe. The reaction rate constants between hydroxyl radicals and some low-molecular-weight organic compounds and inorganic halide salts with various reaction rate constants were determined. The values obtained ranged from 105 to 1010 M−1 s−1, and agreed well with previously reported values. The potential of the developed method to determine the reaction rate constants of hydroxyl radicals is discussed.

Gas-Phase Reaction of Methyl Isothiocyanate and Methyl Isocyanate with Hydroxyl Radicals under Static Relative Rate Conditions

Gaseous methyl isothiocyanate (MITC), the principal breakdown product of the soil fumigant metam sodium (sodium N-methyldithiocarbamate), is an inhalation exposure concern to persons living near treated areas. Inhalation exposure also involves gaseous methyl isocyanate (MIC), a highly reactive and toxic transformation product of MITC. In this work, gas-phase hydroxyl (OH) radical reaction rate constants of MITC and MIC have been determined using a static relative rate technique under controlled laboratory conditions. The rate constants obtained are 15.36 × 10(-12) cm(3) molecule(-1) s(-1) for MITC and 3.62 × 10(-12) cm(3) molecule(-1) s(-1) for MIC. The average half-lives of MITC and MIC in the atmosphere are estimated to be 15.7 and 66.5 h, respectively. The molar conversion of MITC to MIC for OH radical reactions is 67% ± 8%, which indicates that MIC is the primary product of the MITC-OH reaction in the gas phase.

Development of a model for predicting hydroxyl radical reaction rate constants of organic chemicals at different temperatures

The reaction rate constants of hydroxyl radicals with organic chemicals (kOH) are of great importance for assessing the persistence and fate of organic pollutants in the atmosphere. However, experimental determination of kOH seems fairly unrealistic, due to the soaring number of the emerging chemicals additional to the large number of existing chemicals. Quantitative structure–activity relationship (QSAR) models are excellent choices for evaluating and predicting kOH values. In this study, a QSAR model that can predict kOH at different temperatures was developed by employing quantum chemical descriptors and DRAGON descriptors. The adjusted determination coefficient Radj2 of the model is 0.873, and the external validation coefficient Qext2 is 0.835, implying that the model has satisfactory robustness and good predictability. Additionally, a QSAR model was also built for kOH prediction at room-temperature (298K). The development of the two models followed the guidelines for development and validation of QSAR models proposed by the Organization for Economic Co-operation and Development (OECD). The applicability domains of the current models were extended to several classes of compounds including long-chain alkenes (C8C13), organophosphates, dimethylnaphthalenes, organic selenium and organic mercury compounds that have not been covered in the previous studies.

Radical-based destruction of nitramines in water: kinetics and efficiencies of hydroxyl radical and hydrated electron reactions.

In support of the potential use of advanced oxidation and reduction process technologies for the removal of carcinogenic nitro-containing compounds in water reaction rate constants for the hydroxyl radical and hydrated electron with a series of low molecular weight nitramines (R(1)R(2)-NNO(2)) have been determined using a combination of electron pulse radiolysis and transient absorption spectroscopy. The hydroxyl radical reaction rate constant was fast, ranging from 0.54-4.35 × 10(9) M(-1) s(-1), and seen to increase with increasing complexity of the nitramine alkyl substituents suggesting that oxidation primarily occurs by hydrogen atom abstraction from the alkyl chains. In contrast, the rate constant for hydrated electron reaction was effectively independent of compound structure, (k(av) = (1.87 ± 0.25) × 10(10) M(-1) s(-1)) indicating that the reduction predominately occurred at the common nitramine moiety. Concomitant steady-state irradiation and product measurements under aerated conditions also showed a radical reaction efficiency dependence on compound structure, with the overall radical-based degradation becoming constant for nitramines containing more than four methylene groups. The quantitative evaluation of these efficiency data suggest that some (~40%) hydrated electron reduction also results in quantitative nitramine destruction, in contrast to previously reported electron paramagnetic measurements on these compounds that proposed that this reduction only produced a transient anion adduct that would transfer its excess electron to regenerate the parent molecule.

Reactivity of Aqueous Phase Hydroxyl Radical with Halogenated Carboxylate Anions: Experimental and Theoretical Studies

With concerns about emerging contaminants increasing, advanced oxidation processes have become attractive technologies because of potential mineralization of these contaminants via radical involved reactions that are induced by highly reactive hydroxyl radical. Considering the expensive and time-consuming experimental studies of degradation intermediates and byproduct, there is a need to develop a first-principles computer-based kinetic model that predict reaction pathways and associated reaction rate constants. In this study, we measured temperature-dependent hydroxyl radical reaction rate constants for a series of haloacetate ions and obtained their Arrhenius kinetic parameters. We found a linear correlation between these reaction rate constants and theoretically calculated aqueous-phase free energies of activation. To understand the quantitative effects on entropy of solvation due to solvent water molecules, we calculate each portion of the entropic energies that contribute to the overall aqueous phase entropy of activation; cavity formation is a dominant portion. For the series of reactions of hydroxyl radical with carboxylate ions, the increase in the entropy of activation during the solvation process is approximately 10-15 cal mol(-1)K(-1) because of interactions with solvent water molecules and the transition state. Finally, charge distribution analysis for the aqueous-phase reactions of hydroxyl radical with acetate/haloacetate ions reveals that in the aqueous phase, the degree of polarizability at the transition state is less substantial than those that are in the gaseous phase resulting in a high charge density. In the presence of electronegative halogenated functional groups, the transition state is less polarized and hydrogen bonding interactions are expected to be weaker.

Linear Free Energy Relationships between Aqueous phase Hydroxyl Radical Reaction Rate Constants and Free Energy of Activation

The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs.

Removal of Pharmaceutical and Personal Care Products from Reverse Osmosis Retentate Using Advanced Oxidation Processes

The application of reverse osmosis (RO) in water intended for reuse is promising for assuring high water quality. However, one significant disadvantage is the need to dispose of the RO retentate (or reject water). Studies focusing on Pharmaceutical and Personal Care Products (PPCPs) have raised questions concerning their concentrations in the RO retentate. Advanced oxidation processes (AOPs) are alternatives for destroying these compounds in retentate that contains high concentration of effluent organic matter (EfOM) and other inorganic constituents. Twenty-seven PPCPs were screened in a RO retentate using solid phase extraction (SPE) and UPLC-MS/MS, and detailed degradation studies for 14 of the compounds were obtained. Based on the absolute hydroxyl radical (HO•) reaction rate constants for individual pharmaceutical compounds, and that of the RO retentate (EfOM and inorganic constituents), it was possible to model their destruction. Using excitation-emission matrix (EEM) fluorescence spectroscopy, the HO• oxidation of the EfOM could be observed through decreases in the retentate fluorescence. The decrease in the peak normally associated with proteins correlated well with the removal of the pharmaceutical compounds. These results suggest that fluorescence may be a suitable parameter for monitoring the degradation of PPCPs by AOPs in RO retentates.

Evaluation of parameters influencing removal efficiencies for organic contaminant degradation in advanced oxidation processes

Research Article| March 01 2011 Evaluation of parameters influencing removal efficiencies for organic contaminant degradation in advanced oxidation processes Julie R. Peller; Julie R. Peller 1Department of Chemistry, 3400 Broadway, Indiana University Northwest, Gary, IN 46408, USA Tel: 219-980-6744 Fax: 219-980-6673; E-mail: jpeller@iun.edu Search for other works by this author on: This Site PubMed Google Scholar William J. Cooper; William J. Cooper 2Urban Water Research Center, Department of Civil and Environmental Engineering, University of California, Irvine, CA 96297, USA Search for other works by this author on: This Site PubMed Google Scholar Kenneth P. Ishida; Kenneth P. Ishida 3Research and Development Department, Orange County Water District, Fountain Valley, CA 92708, USA Search for other works by this author on: This Site PubMed Google Scholar Stephen P. Mezyk Stephen P. Mezyk 4Department of Chemistry and Biochemistry, California State University at Long Beach, Long Beach, CA, 90840, USA Search for other works by this author on: This Site PubMed Google Scholar Journal of Water Supply: Research and Technology-Aqua (2011) 60 (2): 69–78. https://doi.org/10.2166/aqua.2011.024 Article history Received: May 19 2010 Accepted: October 18 2010 Views Icon Views Article contents Figures & tables Video Audio Supplementary Data Share Icon Share Facebook Twitter LinkedIn MailTo Tools Icon Tools Cite Icon Cite Permissions Search Site Search Dropdown Menu toolbar search search input Search input auto suggest filter your search All ContentAll JournalsThis Journal Search Advanced Search Citation Julie R. Peller, William J. Cooper, Kenneth P. Ishida, Stephen P. Mezyk; Evaluation of parameters influencing removal efficiencies for organic contaminant degradation in advanced oxidation processes. Journal of Water Supply: Research and Technology-Aqua 1 March 2011; 60 (2): 69–78. doi: https://doi.org/10.2166/aqua.2011.024 Download citation file: Ris (Zotero) Reference Manager EasyBib Bookends Mendeley Papers EndNote RefWorks BibTex Advanced oxidation processes, based on hydroxyl radical chemistry, can be used to successfully destroy chemical contaminants in waters intended for reuse. In determining the effectiveness of these radical oxidative degradations and transformations in water, both reaction rate constants and compound removal efficiencies must be considered. Removal efficiencies are defined as the number of contaminant molecules transformed per 100 hydroxyl radicals reacting. Hydroxyl radical reaction efficiencies have been determined for bisphenol A, caffeine, DEET, and sulfamethazine in different qualities of treated and model laboratory wastewaters. While these four contaminants show similar hydroxyl radical reaction rate constants, their removal efficiencies in deionized water varied significantly at 76±7, 92±8, 95±9, and 56±7%, respectively. Model wastewater studies showed that dissolved oxygen did not appreciably influence these values, and low levels of dissolved organic matter (DOM) reduced the removal efficiencies by an average of approximately 20%. However, the combination of solution alkalinity and DOM had a significant impact in reducing hydroxyl radical reaction efficiencies, although not always in a linear, additive, fashion. These results imply that the effective implementation of advanced oxidation technologies in wastewater treatments might be enhanced by prior removal of organics or alkalinity. advanced oxidation, bisphenol A, caffeine, DEET, removal efficiencies, sulfamethazine This content is only available as a PDF. © IWA Publishing 2011 You do not currently have access to this content.

Estimation of Aqueous‐Phase Reaction Rate Constants of Hydroxyl Radical with Phenols, Alkanes and Alcohols

AbstractA quantitative structure activity relationship (QSAR) model was developed for the aqueous‐phase hydroxyl radical reaction rate constants (kOH) employing quantum chemical descriptors and multiple linear regressions (MLR). The QSAR development followed the OECD guidelines, with special attention to validation, applicability domain (AD) and mechanistic interpretation. The established model yielded satisfactory performance: the correlation coefficient square (R2) was 0.905, the root mean squared error (RMSE) was 0.139, the leave‐many‐out cross‐validated QLMO2 was 0.806, and the external validated QEXT2 was 0.922 log units. The AD of the model covering compounds of phenols, alkanes and alcohols, was analyzed by Williams plot. The main molecular structural factors governing kOH are the energy of the highest occupied molecular orbital (EHOMO), average net atomic charges on hydrogen atoms ($\rm{ \overline {Q_{\rm{H}}^{} } }$), molecular surface area (MSA) and dipole moment (μ). It was concluded that kOH increased with increasing EHOMO and MSA, while decreased with increasing $\rm{ \overline {Q_{\rm{H}}^{} } }$ and μ.

Free Radical-Induced Redox Chemistry of Platinum-Containing Anti-cancer Drugs

Arrhenius parameters for the reactions of oxidizing hydroxyl radicals and reducing hydrated electrons with cisplatin, transplatin and carboplatin in aqueous solution have been determined using pulsed electron radiolysis and absorption spectroscopy techniques. Under physiological pH and chloride concentration conditions, hydroxyl radical reaction rate constants of (9.99 +/- 0.20) x 10(9), (8.38 +/- 0.55) x 10(9), and (6.03 +/- 0.08) x 10(9) M(-1) s(-1) at 24.0, 20.7 and 24.0 degrees C, respectively, with corresponding activation energies of 12.79 +/- 0.57, 13.88 +/- 1.14, and 14.35 +/- 0.56 kJ mol(-1) for these three reactions, were determined. These oxidations of cisplatin and transplatin to form a Pt(III) transient are significantly faster than reported previously at room temperature. The lower rate constant for carboplatin is consistent with hydroxyl radical reaction partitioning between reaction at the platinum center and the cyclobutanedicarboxylate ligand. The equivalent reductive hydrated electron reaction rate constants measured were (1.99 +/- 0.04) x 10(10) (24.0 degrees C), (1.77 +/- 0.08) x 10(10) (22.0 degrees C), and (8.92 +/- 0.06) x 10(9) M(-1) s(-1) (24.0 degrees C), with corresponding activation energies of 15.75 +/- 1.00, 19.74 +/- 1.82, and 19.99 +/- 0.34 kJ mol(-1). Again, the values determined for cisplatin and transplatin are faster than reported; however, all three values are consistent with direct reduction of the platinum center to form a Pt(I) moiety.

Determination of direct photolysis rate constants and OH radical reactivity of representative odour compounds in brewery broth using a continuous flow-stirred photoreactor

A method based on photolysis was developed for the appropriate treatment of organic pollutants in air exhausting from breweries upon wort decoction, and thereby causing smell nuisance. A continuous flow stirred photoreactor was built-up exclusively, allowing OH radicals to react with selected odorous compounds contained in exhaust vapours, such as: 2-methylpropanal, 3-methylbutanal, 2-methylbutanal, 3-methyl-1-butanol, n-hexanal, 2-methylbutyl isobutyrate, 2-undecanone, phenyl acetaldehyde, myrcene, limonene, linalool, humulene, dimethylsulphide, and dimethyltrisulphide. These substances were quantified in brewery broth before and after UV irradiation using high-resolution gas chromatography–mass spectrometry (HRGC–MS). For odour analysis, high-resolution gas chromatography-flame ionisation detection (HRGC-FID) coupled with sensory methods was used. Determined quantum yields of about 10 −3 for phenyl acetaldehyde, myrcene, and humulene pointed out that direct photolysis contributed to their decay. Quantum yields of below 10 −4 for the other substances indicated that UV irradiation did not contribute significantly to their degradation processes. Hydroxyl radical reaction rate constants and Henry constants of organic compounds were also measured. Substances accompanied with low Henry constants converted rapidly, whereas those with higher ones, relatively slowly. Determined aroma values concluded that after UV–H 2O 2 treatment, only dimethylsulphide and myrcene remained as important odorous compounds, but in significantly reduced concentrations. The UV–H 2O 2 treatment of brewery broth has been proved effective to reduce smell-irritating substances formed upon wort decoction.

A QSAR for the hydroxyl radical reaction rate constant: validation, domain of application, and prediction

Abstract A large number of anthropogenic organic chemicals are emitted into the troposphere. Reactions with the hydroxyl radical are a dominant removal pathway for most organic compounds, but experimentally determined gas-phase reaction rate constants are only available for about 750 compounds. The lack of experimental data increases the importance of applying quantitative structure–activity relationships (QSAR) to evaluate and predict reactivities. It is generally acknowledged that these empirical relationships are valid only within the same domain for which they were developed. However, model validation is sometimes neglected and the application domain is not always well defined. The purpose of this paper is to outline how validation and domain definition can facilitate the modeling and prediction of the hydroxyl radical reaction rates for a large database. A substantial number of theoretical descriptors (867) were generated from 2D molecular structures for compounds present in the Syracuse Research Corporation's PhysProp Database. A QSAR model was developed for the hydroxyl radical reaction rate constant using a projection-based regression technique, partial least squares regression (PLSR). The PLSR model was subsequently validated with an external test set. The main factors of variation could be attributed to two reaction pathways, hydrogen atom abstraction and addition to double bonds or aromatic systems. A set of 17 293 compounds, drawn from the PhysProp Database, was projected onto the PLSR model and 74% were inside the applicability domain. The predicted hydroxyl reaction rates for 25% of these compounds were slow or negligible, with atmospheric half-lives in the range from days to years. Finally, the list of persistent organic compounds was matched against the OECD list of high production volume chemicals (HPVC). Together with the experimental data, nearly three hundred compounds were identified as both persistent and in high volume production.

Competitive degradation and detoxification of carbamate insecticides by membrane anodic Fenton treatment.

The competitive degradation of six carbamate insecticides by membrane anodic Fenton treatment (AFT), a new Fenton treatment technology, was carried out in this study. The carbamates studied were dioxacarb, carbaryl, fenobucarb, promecarb, bendiocarb, and carbofuran. The results indicate that AFT can effectively degrade these insecticides in both single component and multicomponent systems. The carbamates compete for hydroxyl radicals, and their kinetics obey the previously developed AFT kinetic model quite well. Hydroxyl radical reaction rate constants were obtained, and they decrease in the following order: dioxacarb approximately carbaryl > fenobucarb > promecarb > bendiocarb > carbofuran. The AFT is shown to have higher treatment efficiency at higher temperature. Degradation products of the carbamates were determined by gas chromatography/mass spectrometry, and it appears that degradation can be initiated by hydroxyl radical attack at different sites in the molecule, depending on the individual structure of the compound. Substituted phenols are the commonly seen degradation products. The AFT treatment can efficiently remove the chemical oxygen demand of the carbamate mixture, significantly increasing the biodegradability. Earthworm studies show that the AFT is also an effective detoxification process.

Method for Predicting Photocatalytic Oxidation Rates of Organic Compounds

In designing a photocatalytic oxidation (PCO) system for a given air pollution source, destruction rates for volatile organic compounds (VOCs) are required. The objective of this research was to develop a systematic method of predicting PCO rate constants by correlating rate constants with physical-chemical characteristics of compounds. Accordingly, reaction rate constants were determined for destruction of volatile organics over a titanium dioxide (TiO2 ) catalyst in a continuous mixed-batch reactor. It was found that PCO rate constants for alkanes and alkenes vary linearly with gas-phase ionization potential (IP) and with gas-phase hydroxyl radical reaction rate constant. The correlations allow rates of destruction of compounds not tested in this research to be predicted based on physical-chemical characteristics.

Uncertainty Analysis for Toxicity Assessment of Chemical Process Designs

There is a growing awareness in the chemical industry that environmental aspects need to be incorporated more fully into the design and operation of chemical processes. There are several recently developed methodologies to perform environmental assessments of chemical process designs. However, the value of the environmental information is dependent upon the level of uncertainty in the predictions of these impacts. This paper presents an uncertainty analysis for toxicity assessment of chemical process designs. This uncertainty analysis generated representative normalized standard errors for several measured environmental properties (Henry's law constant, octanol−water partition coefficient, hydroxyl radical reaction rate constant, and lethal concentration for human inhalation toxicity) from a subset of the high production volume chemicals. Then, the propagation of these property uncertainties in the calculation of an inhalation toxicity index was conducted. This method of uncertainty analysis has been applied to the environmentally conscious design of a process for volatile organic compound recovery and recycle from a gaseous waste stream.

The hydroxyl radical reaction rate constant and atmospheric transformation products of 2-butanol and 2-pentanol

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

The hydroxyl radical reaction rate constants and atmospheric reaction products of three siloxanes

The relative rate technique has been used to measure the hydroxyl radical (OH) reaction rate constant of hexamethyldisiloxane (MM, (CH3)3Si-O-Si(CH3)3), octamethyltrisiloxane (MDM, (CH3)3Si-O-Si(CH3)2-O-Si(CH3)3), and decamethyltetrasiloxane (MD2M, (CH3)3Si-O-Si(CH3)2-O-Si(CH3)2-O-Si(Ch3)3). Hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetrasiloxane react with OH with bimolecular rate constants of 1.32 ± 0.05 × 10−12 cm3molecule−1s−1, 1.83 ± 0.09 × 10−12 cm3 molecule−1s−1, and 2.66 ± 0.13 × 10−12 cm3molecule−1s−1, respectively. Investigation of the OH + siloxane reaction products yielded trimethylsilanol, pentamethyldisiloxanol, heptamethyltetrasiloxanol, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and other compounds. Several of these products have not been reported before because these siloxanes and the proposed reaction mechanisms yielding these products are complicated. Some unusual cyclic siloxane products were observed and their formation pathways are discussed in light of current understanding of siloxane atmospheric chemistry. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 445–451, 1997.