The f nmr spectra of the trifluoroacetates of poly /alkylene oxides/
Fluorine-19 nuclear magnetic resonance spectra of trifluoroacetates of polyalkylene oxides
FLUORINE↗
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Trifluoroacetic Acid from Degradation of HCFCs and HFCs: A Three-dimensional Modeling Study
Trifluoroacetic acid (TFA; CF3 COOH) is produced by the degradation of the halocarbon replacements HFC-134a, HCFC-124, and HCFC-123. The formation of TFA occurs by HFC/HCFC reacting with OH to yield CF3COX (X = F or CI), followed by in-cloud hydrolysis of CF3COX to form TFA. The TFA formed in the clouds may be reevaporated but is finally deposited onto the surface by washout or dry deposition. Concern has been expressed about the possible long-term accumulation of TFA in certain aquatic environments, pointing to the need to obtain information on the concentrations of TFA in rainwater over scales ranging from local to continental. Based on projected concentrations for HFC-134a, HCFC-124, and HCFC-123 of 80, 10, and 1 pptv in the year 2010, mass conservation arguments imply an annually averaged global concentration of 0.16 microg/L if washout were the only removal mechanism for TFA. We present 3-D simulations of the HFC/HCFC precursors of TFA that include the rates of formation and deposition of TFA based on assumed future emissions. An established (GISS/Harvard/ UCI) but coarse-resolution (8 deg latitude by 10 deg longitude) chemical transport model was used. The anually averaged rainwater concentration of 0.12 gg/L (global) was calculated for the year 2010, when both washout and dry deposition are included as the loss mechanism for TFA from the atmosphere. For some large regions in midnorthern latitudes, values are larger, 0.15-0.20 microg/L. The highest monthly averaged rainwater concentrations of TFA for northern midlatitudes were calculated for the month of July, corresponding to 0.3-0.45 microg/L in parts of North America and Europe. Recent laboratory experiments have suggested that a substantial amount of vibrationally excited CF3CHFO is produced in the degradation of HFC-134a, decreasing the yield of TFA from this compound by 60%. This decrease would reduce the calculated amounts of TFA in rainwater in the year 2010 by 26%, for the same projected concentrations of precursors.
Kotamarthi, V. R.↗
Trifluoroacetic Acid from Degradation of HCFCs and HFCs: A Three-Dimensional Modeling Study
Trifluoroacetic acid (TFA; CF3COOH) is produced by the degradation of the halocarbon replacements HFC-134a, HCFC-124, and HCFC-123. The formation of TFA occurs by HFC/HCFC reacting with OH to yield CF3COX (X = F or CI), followed by in-cloud hydrolysis of CF3COX to form TFA. The TFA formed in the clouds may be reevaporated but is finally deposited onto the surface by washout or dry deposition. Concern has been expressed about the possible long-term accumulation of TFA in certain aquatic environments, pointing to the need to obtain information on the concentrations of TFA in rainwater over scales ranging from local to continental. Based on projected concentrations for HFC-134a, HCFC-124, and HCFC-123 of 80, 10, and 1 pptv in the year 2010, mass conservation arguments imply an annually averaged global concentration of 0.16 micro g/L if washout were the only removal mechanism for TFA. We present 3-D simulations of the HFC/HCFC precursors of TFA that include the rates of formation and deposition of TFA based on assumed future emissions. An established (GISS/Harvard/ UCI) but coarse-resolution (8 deg latitude by 10 deg longitude) chemical transport model was used. The annually averaged rainwater concentration of 0.12 micro g/L (global) was calculated for the year 2010, when both washout and dry deposition are included as the loss mechanism for TFA from the atmosphere. For some large regions in midnorthern latitudes, values are larger, 0.15-0.20 micro g/L. The highest monthly averaged rainwater concentrations of TFA for northern midlatitudes were calculated for the month of July, corresponding to 0.3-0.45 micro g/L in parts of North America and Europe. Recent laboratory experiments have suggested that a substantial amount of vibrationally excited CF3CHFO is produced in the degradation of HFC-134a, decreasing the yield of TFA from this compound by 60%. This decrease would reduce the calculated amounts of TFA in rainwater in the year 2010 by 26%, for the same projected concentrations of precursors.
Kotamarthi, V. R.↗
Trifluoroacetic Acid from Degradation of HCFCs and HFCs: A Three-Dimensional Modeling Study
Trifluoroacetic acid (TFA; CF3 COOH) is produced by the degradation of the halocarbon replacements HFC-134a, HCFC-124, and HCFC-123. The formation of TFA occurs by HFC/HCFC reacting with OH to yield CF3COX (X = F or CI), followed by in-cloud hydrolysis of CF to form TFA. The TFA formed in the clouds may be reevaporated but is finally deposited onto the surface by washout or dry deposition. Concern has been expressed about the possible long-term accumulation of TFA in certain aquatic environments, pointing to the need to obtain information on the concentrations of TFA in rainwater over scales ranging from local to continental. Based on projected concentrations for HFC-134a, HCFC-124, and HCFC-123 of 80, 10, and 1 pptv in the year 2010, mass conservation arguments imply an annually averaged global concentration of 0.16 micro g/L if washout were the only removal mechanism for TFA. We present 3-D simulations of the HFC/HCFC precursors of TFA that include the rates of formation and deposition of TFA based on assumed future emissions. An established (GISS[Harvard/ UCI) but coarse-resolution (8 deg latitude by 10 deg longitude) chemical transport model was used. The annually averaged rainwater concentration of 0.12 micro g/L (global) was calculated for the year 2010, when both washout and dry deposition are included as the loss mechanism for TFA from the atmosphere. For some large regions in midnorthern latitudes, values are larger. 0.15-0.20 micro g/L. The highest monthly averaged rainwater concentrations of TFA for northern midlatitudes were calculated for the month of July, corresponding to 0.3 - 0.45 micro g/L in parts of North America and Europe. Recent laboratory experiments have suggested that a substantial amount of vibrationally excited CF3CHFO is produced in the degradation of HFC-134a, decreasing the yield of TFA from this compound by 60%. This decrease would reduce the calculated amounts of TFA in rainwater in the year 2010 by 26%, for the same projected concentrations of precursors.
Kotamarthi, V. R.↗
New methods for preparing N,N-dialkyltrifluoroacetamides
The customary preparative methods for N,N-dialkyltrifluoroacetamides involve the acylation of an amine by trifluoroacetic acid or its derivatives. The synthesis of N,N-dialkyltrifluoroacetamides by reacting trifluoroacetic anhydride or acid with disubstituted formamides and acetamides is discussed. These reactions were interpreted with the aid of gas chromatographic analysis. Different reaction mechanisms are proposed for the reactions of formamides and acetamides with trifluoroacetic anhydride or acid. The use of the proposed reaction mechanisms for the synthesis of other fluorinated compounds is discussed.
Hsu, L.↗
New methods for preparing n, n-dialkyltrifluoroacetamides
The customary preparative methods for N,N-dialkyltrifluoroacetamides involve the acylation of an amine by trifluoroacetic acid or its derivatives. In this report the synthesis of N,N-dialkyltrifluoroacetamides by reacting trifluoroacetic anhydride or acid with disubstituted formamides and acetamides is discussed. These reactions are interpreted with the aid of gas chromatographic analysis. Different reaction mechanisms are proposed for the reactions of formamides and acetamides with trifluoroacetic anhydride or acid. The use of the proposed reaction mechanisms for the synthesis of other fluorinated compounds is discussed.
Hsu, L.↗
NMR characterization of functional groups: 9--isomer ratios of available chloromethylstyrene mixtures
From the assignments of the 1H and 13C 11.7 tesla NMR spectra of available mixtures of m- and p-chloromethylstyrene, the proportion of the meta and para compounds are easily determined. For these materials from two common commercial sources, proportions of 72 and 28% and 68 and 32% were found. These concentrations are substantially different from the often assumed 60 and 40% for the meta and para compounds, respectively. The influence of this difference on the desired properties of copolymers made from such mixtures is discussed. An alternative quantitative procedure for determining the chloromethyl group isomer ratios is also described which employs silver trifluoroacetate in acetone displacement of chloride and 19F NMR examination of the resulting ester mixture with a 2.3 tesla spectrometer.
Polystyrenes/analysis/chemistry↗
Toxicology of atmospheric degradation products of selected hydrochlorofluorocarbons
Trifluoroacetic acid (TFA) is a liquid with a sharp biting odor. It has been proposed as the product of environmental degradation of the hydrochlorofluorocarbons HCFC-123, HCFC-124, HFC-134a, and HFC-125. Compounds HCFC-141b and HCFC-142b could yield mixed fluorochloroacetic acids, for which there is no available toxicologic data. The release of hydrochlorofluorocarbons into the environment could also give rise to HF, but the additional fluoride burden (1 to 3 ppb) in rainwater is trivial compared to levels in fluoridated drinking water (1 ppm), and would provide an insignificant risk to humans. Thus, in this paper only the toxocologic data on TFA is reviewed to assess the potential risks of environmental exposure.
Kaminsky, Laurence S.↗
Stability of Trifluoromethane in Forest Soils and Methanotrophic Cultures
Trifluoromethane (TFM) has been reported as an endproduct of trifluoroacetate degradation under oxic conditions. Although other halomethanes, such as chloroform, methyl bromide, and methyl fluoride, inhibit methane oxidation or are degraded by methanotrophs, the fate of TFM is unknown. TFM had no affect on atmospheric methane consumption when added to forest soils at either 10 ppm or 10,000 ppm. No degradation of TFM was observed at either concentration for incubations of 6 days. Cultures of Methylobacter albus BG8 and Methylosinus trichosporium OB3b grown With and without added copper were also used to assay TFM degradation at 10 10000 ppm levels. TFM did not inhibit methane oxidation under any growth conditions, including those inducing expression of soluble methane monooxygenase, nor was it degraded at measurable rates. In contrast, parallel assays showed that both methyl fluoride and chloroform inhibited methane oxidation in M. trichosporium OB3b. Our results suggest that TFM may be relatively inert with respect to methanotrophic degradition. Although TFM has a negligible ozone depletion potential, it absorbs infrared radiation and has a relatively long atmospheric residence time. Thus, accumulation of TFM in the atmosphere as a consequence of the decomposition of hydrochlorofluorocarbons may have significant unpredicted climate impacts.
King, Gary M.↗
Fluoroester Co-Solvents for Low-Temperature Li+ Cells
Electrolytes comprising LiPF6 dissolved in alkyl carbonate/fluoroester mixtures have been found to afford improved low-temperature performance and greater high-temperature resilience in rechargeable lithium-ion electrochemical cells. These and other electrolytes comprising lithium salts dissolved mixtures of esters have been studied in continuing research directed toward extending the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. The purpose of the present focus on high-temperature resilience in addition to low-temperature performance is to address issues posed by the flammability of the esters and, at temperatures near the upper end (about 55 C) of their intended operating temperature range, by their high chemical reactivity. As used here, high-temperature resilience signifies, loosely, a desired combination of low flammability of an electrolyte mixture and the ability of a cell that contains the mixture to sustain a relatively small loss of reversible charge/discharge capacity during storage in the fully charged condition at high temperature. The selection of fluoroesters for study as candidate electrolyte solvent components to increase high-temperature resilience was prompted in part by the observation that like other halogenated compounds, fluoroesters have low flammability. The fluoroesters investigated in this study include trifluoroethyl butyrate (TFEB), ethyl trifluoroacetate (ETFA), trifluoroethyl acetate (TFEA), and methyl pentafluoropropionate (MPFP). Solvent mixtures were prepared by mixing these fluoroesters with two other esters: ethylene carbonate (EC) and ethyl methyl carbonate (EMC).
Smart, Marshall↗
Inorganic salt mixtures as electrolyte media in fuel cells
Fuel cell designs and techniques for converting chemical energy into electrical energy uses a fuel cell are disclosed. The designs and techniques include an anode to receive fuel, a cathode to receive oxygen, and an electrolyte chamber in the fuel cell, including an electrolyte medium, where the electrolyte medium includes an inorganic salt mixture in the fuel cell. The salt mixture includes pre-determined quantities of at least two salts chosen from a group consisting of ammonium trifluoromethanesulfonate, ammonium trifluoroacetate, and ammonium nitrate, to conduct charge from the anode to the cathode. The fuel cell includes an electrical circuit operatively coupled to the fuel cell to transport electrons from the cathode.
Angell, Charles Austen↗
Lithium-Ion Electrolytes with Fluoroester Co-Solvents
An embodiment lithium-ion battery comprising a lithium-ion electrolyte of ethylene carbonate; ethyl methyl carbonate; and at least one solvent selected from the group consisting of trifluoroethyl butyrate, ethyl trifluoroacetate, trifluoroethyl acetate, methyl pentafluoropropionate, and 2,2,2-trifluoroethyl propionate. Other embodiments are described and claimed.
Smart, Marshall C.↗