We use a regional-scale, three-dimensional atmospheric model to evaluate U.S. air quality effects that would result from replacing HFC-134a in automobile air conditioners in the U.S. with HFO-1234yf. Although HFO-1234yf produces tropospheric ozone, the incremental amount is small, averaging less than 0.01% of total ozone formed during the simulation. We show that this production of ozone could be compensated for by a modest improvement in air conditioner efficiency. Atmospheric decomposition of HFO-1234yf produces trifluoroacetic acid (TFA), which is subject to wet and dry deposition. Deposition and concentrations of TFA are spatially variable due to HFO-1234yf's short atmospheric lifetime, with more localized peaks and less global transport when compared to HFC-134a. Over the 2.5 month simulation, deposition of TFA in the continental U.S. from mobile air conditioners averages 0.24 kg km(-2), substantially higher than previous estimates from all sources of current hydrofluorocarbons. Automobile air conditioning HFO-1234yf emissions are predicted to produce concentrations of TFA in Eastern U.S. rainfall at least double the values currently observed from all sources, natural and man-made. Our model predicts peak concentrations in rainfall of 1264 ng L(-1), a level that is 80x lower than the lowest level considered safe for the most sensitive aquatic organisms.

Vapor pressure and aqueous solubility are important parameters used to estimate the potential for transport of chemical substances in the atmosphere. For fluorotelomer alcohols (FTOHs), currently under scrutiny by environmental scientists as potential precursors of persistent perfluorocarboxylates (PFCAs), vapor pressure is the more significant property since these compounds are only very sparingly soluble in water. We have measured the vapor pressures of a homologous series of fluorotelomer alcohols, F(CF2CF2)nCH2CH2OH (n = 2-5), in the temperature range 21-250 degrees C by three independent methods: (a) a method suitable for very low vapor pressures at ambient temperatures (gas-saturation method), (b) an improved boiling point method at controlled pressures (Scott method), and (c) a novel method, requiring milligram quantities of substance, based on gas-phase NMR, a technique largely unfamiliar to chemists and holding promise for studies of relevance to environmental chemistry. The concordant values obtained indicate that recently published vapor pressure data overestimate the vapor pressure at ambient temperature, and therefore the volatility, of this series of fluorinated compounds. It was suggested that substantial intramolecular -O-H...F- hydrogen bonding between the hydroxylic proton and the two fluorines next to the ethanol moiety was responsible for their putative high volatility. Therefore, we have used gas-phase NMR, gas-phase FTIR, 2D NMR heteronuclear Overhauser effect measurements, and high-level ab initio computations to investigate the intramolecular hydrogen bonding in fluorotelomer alcohols. Our studies unequivocally show that hydrogen bonding of this type is not significant and cannot contribute to and cause unusual volatility. The substantially lower vapor pressure at ambient temperatures than previously reported resulting from our work is important in developing a valid understanding of the environmental transport behavior of this class of compounds.

A high spatial and temporal resolution atmospheric model is used to evaluate the potential contribution of fluorotelomer alcohol (FTOH) and perfluorocarboxylate (PFCA) emissions associated with the manufacture, use, and disposal of DuPont fluorotelomer-based products in North America to air concentrations of FTOH, perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) in North America and the Canadian Arctic. A bottom-up emission inventory for PFCAs and FTOHs was developed from sales and product composition data. A detailed FTOH atmospheric degradation mechanism was developed to simulate FTOH degradation to PFCAs and model atmospheric transport of PFCAs and FTOHs. Modeled PFCA yields from FTOH degradation agree with experimental smog-chamber results supporting the degradation mechanism used. Estimated PFCA and FTOH air concentrations and PFCA deposition fluxes are compared to monitoring data and previous global modeling. Predicted FTOH air concentrations are generally in agreement with available monitoring data. Overall emissions from the global fluorotelomer industry are estimated to contribute approximately 1-2% of the PFCAs in North American rainfall, consistent with previous global emissions estimates. Emission calculations and modeling results indicate that atmospheric inputs of PFCAs in North America from fluorotelomer-based products will decline by an order of magnitude in the near future as a result of current industry commitments to reduce manufacturing emissions and lower the residual fluorotelomer alcohol raw material and trace PFCA product content.

In response to recent regulations and concern over climate change, the global automotive community is evaluating alternatives to the current refrigerant used in automobile air conditioning units, 1,1,1,2-tetrafluoroethane, HFC-134a. One potential alternative is 2,3,3,3-tetrafluoropropene (HFC-1234yf, also known as HFO-1234yf). We have developed a spatially and temporally resolved inventory of likely future HFC refrigerant emissions from the U.S. vehicle fleet in 2017, considering regular, irregular, servicing, and end-of-life leakages. We estimate the annual leak rate emissions for each leakage category for a projected 2017 U.S. vehicle fleet by state, and spatially apportion these leaks to a 36 km square grid over the continental United States. This projected inventory is a necessary first step in analyzing for potential atmospheric and ecosystem effects, such as ozone and trifluoroacetic acid production, that might result from widespread replacement of HFC-134a with HFC-1234yf.

Articles you may be interested inThe semiclassical regime of the chaotic quantum-classical transition Chaos 15, 033302 (2005); 10. 1063/1.1979227 Comparison of quantum mechanical and semiclassical methods for the determination of transport cross sections and collision integrals AIP Conf.We examine the classical, semiclassical, and quantum mechanics of the Hamiltonian H = ~(p; + p; + x 2 y2). The dynamics of this system are globally chaotic. However, the classical and quantum mechanical problems can be solved analytically by assuming an adiabatic separation of the x and y motion. We construct the canonical transformation to adiabatic action-angle variables and investigate the connection between this integrable approximation and the exact dynamics. In addition, we present a simple semiclassical formula that predicts energy levels in excellent agreement with the exact energy spectrum. The quantum adiabatic potential curves of this system have a very unusual structure-infinitely many curves cross at one point.2328

Three-dimensional quantum close-coupling calculations are presented for the vibrational predissociation of He-ICI B state complexes containing two quanta of ICI vibrational excitation. The dynamics are evaluated for the lowest quasibound van der Waals levels of He-ICI with total angular momentum J = 0 and 1. The vibrational predissociation lifetime and final ICI B(v = l,j ) rotational distribution are calculated using the golden rule approximation. The calculated ICI product rotational distributions are broadly bimodal with maxima atj = 7 and 15, as experimentally observed. The computed rotational distributions exhibit pronounced oscillations, which are expected to be suppressed when averaged over the ini~ial angular mo~entum distribution sampled in the experiment. The theoretical analysis pomts to the dommant role of final-state interactions in determining the rotational distribution of the ICI fragments. The zero-point bending motion of the He-ICI complex and the coupling between the initial and final vibrational states make only small contributions to the final ICI rotational-state distributions. The extensive rotational excitation of the ICI product is primarily due to the anisotropic intermolecular interaction between the separating ICI and He fragments.The peaks of the rotational distributions from the av = -1 channel scale directly with E 1/2. In the B state, a compari-J. Chern. Phys. 92 (7).

The UV absorption spectra of CF(3)CHO, C(2)F(5)CHO, C(3)F(7)CHO, C(4)F(9)CHO, CF(3)CH(2)CHO, and C(6)F(13)CH(2)CHO were recorded over the range 225-400 nm at 249-297 K. C(x)F(2)(x)(+1)CHO and C(x)F(2)(x)(+1)CH(2)CHO have broad absorption features centered at 300-310 and 290-300 nm, respectively. The strength of the absorption increases with the size of the C(x)F(2)(x)(+1) group. There was no discernible (<5%) effect of temperature on the UV spectra. Quantum yields for photolysis at 254 and 308 nm were measured. Quantum yields at 254 nm were 0.79 +/- 0.09 (CF(3)CHO), 0.81 +/- 0.09 (C(2)F(5)CHO), 0.63 +/- 0.09 (C(3)F(7)CHO), 0.60 +/- 0.09 (C(4)F(9)CHO), 0.74 +/- 0.08 (CF(3)CH(2)CHO), and 0.55 +/- 0.09 (C(6)F(13)CH(2)CHO). Quantum yields at 308 nm were 0.17 +/- 0.03 (CF(3)CHO), 0.08 +/- 0.02 (C(4)F(9)CHO), and 0.04 +/- 0.01 (CF(3)CH(2)CHO). The quantum yields decrease with increasing size of the C(x)F(2)(x)(+1) group and with increasing wavelength of the photolysis light. The photolysis quantum yield at 308 nm for CF(3)CHO measured here is a factor of at least 8 greater than that reported previously. Photolysis is probably the dominant atmospheric fate of C(x)F(2)(x)(+1)CHO (x = 1-4) and is an important fate of C(x)F(2)(x)(+1)CH(2)CHO (x = 1 and 6). These results have important ramifications concerning the yield of perfluorocarboxylic acids in the atmospheric oxidation of fluorotelomer alcohols.

No abstract