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T J Wallington

Publications and source records attributed to T J Wallington.

15 recordsLinked to original sources
PubMed2006

Atmospheric chemistry of n-C(x)F(2)(x)(+1)CHO (x = 1, 2, 3, 4): fate of n-C(x)F(2)(x)(+1)C(O) radicals.

Smog chamber/FTIR techniques were used to study the atmospheric fate of n-C(x)F(2)(x)(+1)C(O) (x = 1, 2, 3, 4) radicals in 700 Torr O(2)/N(2) diluent at 298 +/- 3 K. A competition is observed between reaction with O(2) to form n-C(x)()F(2)(x)()(+1)C(O)O(2) radicals and decomposition to form n-C(x)F(2)(x)(+1) radicals and CO. In 700 Torr O(2)/N(2) diluent at 298 +/- 3 K, the rate constant ratio, k(n-C(x)F(2)(x)(+1)C(O) + O(2) --> n-C(x)F(2)(x)(+1)C(O)O(2))/k(n-C(x)F(2)(x)(+1)C(O) --> n-C(x)F(2)(x)(+1) + CO) = (1.30 +/- 0.05) x 10(-17), (1.90 +/- 0.17) x 10(-19), (5.04 +/- 0.40) x 10(-20), and (2.67 +/- 0.42) x 10(-20) cm(3) molecule(-1) for x = 1, 2, 3, 4, respectively. In one atmosphere of air at 298 K, reaction with O(2) accounts for 99%, 50%, 21%, and 12% of the loss of n-C(x)F(2)(x)(+1)C(O) radicals for x = 1, 2, 3, 4, respectively. Results are discussed with respect to the atmospheric chemistry of n-C(x)F(2)(x)(+1)C(O) radicals and their possible role in contributing to the formation of perfluorocarboxylic acids in the environment.

Air Pollutants↗
PubMed2006

Atmospheric chemistry of perfluorinated aldehyde hydrates (n-C(x)F(2x+1)CH(OH)2, x = 1, 3, 4): hydration, dehydration, and kinetics and mechanism of Cl atom and OH radical initiated oxidation.

Smog chamber/Fourier transform infrared (FTIR) techniques were used to measure k(Cl+C(x)F(2x+1)CH(OH)(2)) (x = 1, 3, 4) = (5.84 +/- 0.92) x 10(-13) and k(OH+C(x)F(2x+1)CH(OH)(2)) = (1.22 +/- 0.26) x 10(-13) cm(3) molecule(-1) s(-1) in 700 Torr of N(2) or air at 296 +/- 2 K. The Cl initiated oxidation of CF(3)CH(OH)(2) in 700 Torr of air gave CF(3)COOH in a molar yield of 101 +/- 6%. IR spectra of C(x)F(2x+1)CH(OH)(2) (x = 1, 3, 4) were recorded and are presented. An upper limit of k(CF(3)CHO+H(2)O) < 2 x 10(-23) cm(3) molecule(-1) s(-1) was established for the gas-phase hydration of CF(3)CHO. Bubbling CF(3)CHO/air mixtures through liquid water led to >80% conversion of CF(3)CHO into the hydrate within the approximately 2 s taken for passage through the bubbler. These results suggest that OH radical initiated oxidation of C(x)F(2x+1)CH(OH)(2) hydrates could be a significant source of perfluorinated carboxylic acids in the environment.

Journal Article↗
PubMed2006

Atmospheric chemistry of perfluoroalkanesulfonamides: kinetic and product studies of the OH radical and Cl atom initiated oxidation of N-ethyl perfluorobutanesulfonamide.

Perfluorooctanesulfonamides [C8F17SO2N(R1)(R2)] are present in the atmosphere and may, via atmospheric transport and oxidation, contribute to perfluorocarboxylates (PFCA) and perfluorooctanesulfonate (PFOS) pollution in remote locations. Smog chamber experiments with the perfluorobutanesulfonyl analogue N-ethyl perfluorobutanesulfonamide [NEtFBSA; C4F9SO2N(H)CH2CH3] were performed to assess this possibility. By use of relative rate methods, rate constants for reactions of NEtFBSA with chlorine atoms (296 K) and OH radicals (301 K) were determined to be kCL) = (8.37 +/- 1.44) x 10(-12) and kOH = (3.74 +/- 0.77) x 10(-13) cm3 molecule(-1) s(-1), indicating OH reactions will be dominant in the troposphere. Simple modeling exercises suggestthat reaction with OH radicals will dominate removal of perfluoroalkanesulfonamides from the gas phase (wet and dry deposition will not be important) and that the atmospheric lifetime of NEtFBSA in the gas phase will be 20-50 days, thus allowing substantial long-range atmospheric transport. Liquid chromatography/tandem mass spectrometry (LC/MS/MS) analysis showed that the primary products of chlorine atom initiated oxidation were the ketone C4F9SO2N(H)COCH3; aldehyde 1, C4F9SO2N(H)CH2CHO; and a product identified as C4F9SO2N(C2H5O)- by high-resolution MS but whose structure remains tentative. Another reaction product, aldehyde 2, C4F9SO2N(H)CHO, was also observed and was presumed to be a secondary oxidation product of aldehyde 1. Perfluorobutanesulfonate was not detected above the level of the blank in any sample; however, three perfluoroalkanecarboxylates (C3F7CO2-, C2F5CO2-, and CF3CO2-) were detected in all samples. Taken together, results suggest a plausible route by which perfluorooctanesulfonamides may serve as atmospheric sources of PFCAs, including perfluorooctanoic acid.

Chlorine↗
PubMed2006

Formation of C7F15COOH (PFOA) and other perfluorocarboxylic acids during the atmospheric oxidation of 8:2 fluorotelomer alcohol.

Calculations using a three-dimensional global atmospheric chemistry model (IMPACT) indicate that n-C8F17CH2CH2OH (widely used in industrial and consumer products) degrades in the atmosphere to give perfluorooctanoic acid (PFOA) and other perfluorocarboxylic acids (PFCAs). PFOA is persistent, bioaccumulative, and potentially toxic. Molar yields of PFOA depend on location and season, are in the range of 1-10%, and are of the correct order of magnitude to explain the observed levels in Arctic fauna. Fluorotelomer alcohols such as n-C8F17CH2CH2OH appear to be a significant global source of persistent bioaccumulative perfluorocarboxylic acid pollution. This is the first modeling study of the atmospheric chemistry of a fluorotelomer alcohol.

Alcohols↗
PubMed2006

Automotive fuels and internal combustion engines: a chemical perspective.

Commercial transportation fuels are complex mixtures containing hundreds or thousands of chemical components, whose composition has evolved considerably during the past 100 years. In conjunction with concurrent engine advancements, automotive fuel composition has been fine-tuned to balance efficiency and power demands while minimizing emissions. Pollutant emissions from internal combustion engines (ICE), which arise from non-ideal combustion, have been dramatically reduced in the past four decades. Emissions depend both on the engine operating parameters (e.g. engine temperature, speed, load, A/F ratio, and spark timing) and the fuel. These emissions result from complex processes involving interactions between the fuel and engine parameters. Vehicle emissions are comprised of volatile organic compounds (VOCs), CO, nitrogen oxides (NO(x)), and particulate matter (PM). VOCs and NO(x) form photochemical smog in urban atmospheres, and CO and PM may have adverse health impacts. Engine hardware and operating conditions, after-treatment catalysts, and fuel composition all affect the amount and composition of emissions leaving the vehicle tailpipe. While engine and after-treatment effects are generally larger than fuel effects, engine and after-treatment hardware can require specific fuel properties. Consequently, the best prospects for achieving the highest efficiency and lowest emissions lie with optimizing the entire fuel-engine-after-treatment system. This review provides a chemical perspective on the production, combustion, and environmental aspects of automotive fuels. We hope this review will be of interest to workers in the fields of chemical kinetics, fluid dynamics of reacting flows, atmospheric chemistry, automotive catalysts, fuel science, and governmental regulations.

Journal Article↗
PubMed2005

Atmospheric chemistry of CF3OCF2CF2H and CF3OC(CF3)2H: reaction with Cl atoms and OH radicals, degradation mechanism, global warming potentials, and empirical relationship between k(OH) and k(Cl) for organic compounds.

Using FTIR smog chamber techniques, k(Cl + CF3OCF2CF2H) = (2.70 +/- 0.52) x 10(-16), k(OH + CF3OCF2CF2H) = (2.26 +/- 0.18) x 10(-15), k(Cl + CF3OC(CF3)2H) = (1.58 +/- 0.27) x 10(-18) and k(OH + CF3OC(CF3)2H) = (3.26 +/- 0.95) x 10(-16) cm3 molecule(-1) s(-1) were measured. The atmospheric lifetimes of CF3OCF2CF2H and CF3OC(CF3)2H are estimated to be 27 and 216 years, respectively. Chlorine atom initiated oxidation of CF3OCF2CF2H in 700 Torr of air in the presence of NO(x) gives CF3OC(O)F in a molar yield of 36 +/- 5% and COF2 in a molar yield of 174 +/- 9%, whereas oxidation of CF3OC(CF3)2H gives CF3OC(O)CF3 and COF2 in molar yields that are indistinguishable from 100%. Quantitative infrared spectra were recorded and used to estimate global warming potentials of 3690 and 8230 (100 year time horizon, relative to CO2) for CF3OCF2CF2H and CF3OC(CF3)2H, respectively. All experiments were performed in 700 Torr of N2/O2 diluent at 296 +/- 2 K. An empirical relationship can be used to estimate the preexponential factor, which can be combined with k(298 K) to give the temperature dependence of reactions of OH radicals with organic compounds proceeding via H-atom abstraction: log(A/n) = (0.239 +/- 0.027) log(k(OH)/n) - (8.69 +/- 0.372), k(OH) is the rate constant at 298 K and n is the number of H atoms. The rates of H-atom abstraction by OH radicals and Cl atoms at 298 K from organic compounds are related by the expression log(k(OH)) = (0.412 +/- 0.049) log(k(Cl)) - (8.16 +/- 0.72). The utility of these expressions and the atmospheric chemistry of the title hydrofluoroethers are discussed.

Journal Article↗
PubMed2005

Atmospheric chemistry of 4:2 fluorotelomer alcohol (n-C4F9CH2CH2OH): products and mechanism of Cl atom initiated oxidation in the presence of NOx.

Smog chamber/FTIR techniques were used to study the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (C(4)F(9)CH(2)CH(2)OH, 4:2 FTOH) in the presence of NO(x) in 700 Torr of N(2)/O(2) diluent at 296 K. Chemical activation effects play an important role in the atmospheric chemistry of the peroxy, and possibly the alkoxy, radicals derived from 4:2 FTOH. Cl atoms react with C(4)F(9)CH(2)CH(2)OH to give C(4)F(9)CH(2)C(*)HOH radicals which add O(2) to give chemically activated alpha-hydroxyperoxy radicals, [C(4)F(9)CH(2)C(OO(*))HOH]*. In 700 Torr of N(2)/O(2) at 296 K, approximately 50% of the [C(4)F(9)CH(2)C(OO(*))HOH]* radicals decompose "promptly" to give HO(2) radicals and C(4)F(9)CH(2)CHO, the remaining [C(4)F(9)CH(2)C(OO(*))HOH]* radicals undergo collisional deactivation to give thermalized peroxy radicals, C(4)F(9)CH(2)C(OO(*))HOH. Decomposition to HO(2) and C(4)F(9)CH(2)CHO is the dominant atmospheric fate of the thermalized peroxy radicals. In the presence of excess NO, the thermalized peroxy radicals react to give C(4)F(9)CH(2)C(O(*))HOH radicals which then decompose at a rate >2.5 x 10(6) s(-1) to give HC(O)OH and the alkyl radical C(4)F(9)CH(2)(*). The primary products of 4:2 FTOH oxidation in the presence of excess NO(x) are C(4)F(9)CH(2)CHO, C(4)F(9)CHO, and HCOOH. Secondary products include C(4)F(9)CH(2)C(O)O(2)NO(2), C(4)F(9)C(O)O(2)NO(2), and COF(2). In contrast to experiments conducted in the absence of NO(x), there was no evidence (<2% yield) for the formation of the perfluorinated acid C(4)F(9)C(O)OH. The results are discussed with regard to the atmospheric chemistry of fluorotelomer alcohols.

Journal Article↗
PubMed2004

CO2 emission benefit of diesel (versus gasoline) powered vehicles.

Concerns regarding global warming have increased the pressure on automobile manufacturers to decrease emissions of CO2 from vehicles. Diesel vehicles have higher fuel economy and lower CO2 emissions than their gasoline counterparts. Increased penetration of diesel powered vehicles into the market is a possible transition strategy toward a more sustainable transportation system. To facilitate discussions regarding the relative merits of diesel vehicles it is important to have a clear understanding of their CO2 emission benefits. Based on European diesel and gasoline certification data, this report quantifies such CO2 reduction opportunities for cars and light duty trucks in today's vehicles and those in the year 2015. Overall, on a well-to-wheels per vehicle per mile basis, the CO2 reduction opportunity for today's vehicles is approximately 24-33%. We anticipate that the gap between diesel and gasoline well-to-wheel vehicle CO2 emissions will decrease to approximately 14-27% by the year 2015.

Air Pollutants↗
PubMed2004

Methane emissions from vehicles.

Methane (CH4) is an important greenhouse gas emitted by vehicles. We report results of a laboratory study of methane emissions using a standard driving cycle for 30 different cars and trucks (1995-1999 model years) from four different manufacturers. We recommend the use of an average emission factor for the U.S. on-road vehicle fleet of (g of CH/g of CO2) = (15 +/- 4) x 10(-5) and estimate that the global vehicle fleet emits 0.45 +/- 0.12 Tg of CH4 yr(-1) (0.34 +/- 0.09 Tg of C yr(-1)), which represents < 0.2% of anthropogenic CH4 emissions. This estimate includes the effects of vehicle aging, cold start, and hot running emissions. The contribution of CH4 emissions from vehicles to radiative forcing of climate change is 0.3-0.4% of that of CO2 emissions from vehicles. The environmental impact of CH4 emissions from vehicles is negligible and is likely to remain so for the foreseeable future.

Air Pollutants↗
PubMed2003

Formation of methyl nitrite and methyl nitrate during plasma treatment of diesel exhaust.

FTIR spectroscopy was used to identify CH3ONO and CH3ONO2 as products of the nonthermal plasma treatment of simulated diesel exhaust. This is the first observation of CH3ONO formation in such systems. The yield of CH3ONO relativeto CH3ONO2 scaled linearly with the average [NO]/ [NO2] ratio in the system. A plot of [CH3ONO]/[CH3ONO2] versus [NO]/[NO2] gives a slope of 1.81 +/- 0.30. This result is indistinguishable from the literature value of the rate constant ratio k(CH3O + NO)/k(CH3O + NO2) = (2.6 x 10(-11))/ (1.5 x 10(-11)) = 1.73 +/- 0.37. The experimental observations suggest that reactions of CH3O radicals with NO and NO2 are the sources of CH3ONO and CH3ONO2 in such systems. The linear relationship between the yields of CH3ONO and CH3ONO2 provides a means of estimating the yield of these compounds during nonthermal plasma treatment of diesel exhaust.

Air Pollution↗
PubMed2003

Atmospheric lifetime of fluorotelomer alcohols.

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with a series of fluorotelomer alcohols, F(CF2CF2)nCH2CH2OH (n = 2, 3, 4), in 700 Torr of N2 or air, diluent at 296 +/- 2K. The length of the F(CF2CF2)n- group had no discernible impact on the reactivity of the molecule. For n = 2, 3, or 4, k(Cl + F(CF2CF2)nCH2CH2OH) = (1.61 +/- 0.49) x 10(-11) and k(OH + F(CF2CF2)nCH2CH2OH) = (1.07 +/- 0.22) x 10(-12) cm3 molecule(-1) s(-1). Consideration of the likely rates of other possible atmospheric loss mechanisms leads to the conclusion that the atmospheric lifetime of F(CF2CF2)nCH2CH2OH (n > or = 2) is determined by reaction with OH radicals and is approximately 20 d.

Air Pollutants↗
PubMed2002

Atmospheric chemistry of HFE-7500 [n-C3F7CF(OC2H5)CF(CF3)2]: reaction with OH radicals and Cl atoms and atmospheric fate of n-C3F7CF(OCHO*)CF(CF3)2 and n-C3F7CF(OCH2CH2O*)CF(CF3)2 radicals.

Relative rate techniques were used to measure k(OH + HFE-7500) = (2.6+/-0.6) x 10(-14), k(Cl + HFE-7500) = (2.3+/-0.7) x 10(-12), k[Cl + n-C3F7CF(OC(O)H)CF(CF3)2] = (9.7+/-1.4) x 10(-15), and k[Cl + n-C3F7CF(OC(O)CH3)CF(CF3)2] < 6 x 10(-17) cm3 molecule(-1) s(-1) at 295 K [HFE-7500 = n-C3F7-CF(OC2H5)CF(CF3)2]. From the value of k(OH + HFE-7500) an estimate of 2.2 years for the atmospheric lifetime of HFE-7500 is obtained. Two competing loss mechanisms for n-C3F7-CF(OCHO.CH3)CF(CF3)2 radicals were identified in 700 Torr of N2/O2 diluent at 295 K; reaction with O2 and decomposition via C-C bond scission with kO2/k(decomp) = 0.013+/-0.006 Torr(-1). The Cl atom initiated oxidation of HFE-7500 in N2/O2 diluent gives n-C3F7CF(OC(O)CH3)CF(CF3)2 as the major product and n-C3F7CF(OC(O)H)CF(CF3)2 as a minor product. The atmospheric oxidation of HFE-7500 gives n-C3F7-CF(OC(O)CH3)CF(CF3)2 and n-C3F7CF(OC(O)H)CF(CF3)2 as oxidation products. The results are discussed with respect to the atmospheric chemistry and environmental impact of HFE-7500.

Air Pollutants↗
PubMed2002

R-134a emissions from vehicles.

We report the first study of R-134a (also known as HFC-134a and CF3CFH2) refrigerant leakage from air conditioning (AC) systems of modern vehicles. Twenty-eight light duty vehicles from five manufacturers (Ford, Toyota, Daimler Chrysler, General Motors, and Honda) were tested according to the USEPA (Federal) extended diurnal test procedure using the Sealed Housing for Evaporative Determination (SHED) apparatus. All tests were conducted using stationary vehicles with the motor and air conditioning system turned off. R-134a was measured using gas chromatography (GC) with a flame ionization detector (FID). All vehicles exhibited measurable R-134a leakage over the 2-day diurnal test. Leak rates of R-134a ranged from 0.01 to 0.36 g/day with an average of 0.07+/-0.07 g/day. When combined with leakage associated with vehicle operation, servicing, and disposal we estimate that the lifetime average R-134a emission rate from an AC equipped vehicle is 0.41+/-0.27 g/day (the majority of emissions are associated with vehicle servicing and disposal). Assuming that the average vehicle travels 10 000 miles per year we estimate that the global warming impact of R-134a leakage from an AC equipped vehicle is approximately 4-5% of that of the CO2 emitted by the vehicle. The results are discussed with respect to the contribution of vehicle emissions to global climate change.

Aerosol Propellants↗
PubMed2001

Organic aerosol formation during the atmospheric degradation of toluene.

Organic aerosol formation during the atmospheric oxidation of toluene was investigated using smog chamber systems. Toluene oxidation was initiated by the UV irradiation of either toluene/air/NOx or toluene/air/CH3ONO/NO mixtures. Aerosol formation was monitored using scanning mobility particle sizers and toluene loss was monitored by in-situ FTIR spectroscopy or GC-FID techniques. The experimental results show that the reaction of OH radicals, NO3 radicals and/or ozone with the first generation products of toluene oxidation are sources of organic aerosol during the atmospheric oxidation of toluene. The aerosol results fall into two groups, aerosol formed in the absence and presence of ozone. An analytical expression for aerosol formation is developed and values are obtained for the yield of the aerosol species. In the absence of ozone the aerosol yield, defined as aerosol formed per unit toluene consumed once a threshold for aerosol formation has been exceeded, is 0.075 +/- 0.004. In the presence of ozone the aerosol yield is 0.108 +/- 0.004. This work provides experimental evidence and a simple theory confirming the formation of aerosol from secondary reactions.

Aerosols↗