Measurements of three chlorofluorocarbons (CFCs): trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and trichlorotrifluoroethane (CFC-113), along with methyl chloroform (CH 3CCl 3) and carbon tetrachlo...Measurements of three chlorofluorocarbons (CFCs): trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and trichlorotrifluoroethane (CFC-113), along with methyl chloroform (CH 3CCl 3) and carbon tetrachloride (CCl 4) were made in water samples from Lake Washington, using Electron Capture-Gas Chromatography (EC-GC). The samples were collected in mid-autumn, a period when the lake’s upper layer undergoes rapid cooling. At the time of sampling, a strong vertical temperature gradient was present in the lake, with surface temperatures of ~14℃, and near bottom (50 meters) temperatures of ~8℃. The concentrations of dissolved CFC-12 and CFC-11 increased with depth, as expected from the higher solubilities of these gases at lower temperatures. Atmospheric measurements made at the sampling site at the time of the cruise, showed that CFC-11 and CFC-12 saturations in the near surface samples were 100 % and 106%, respectively. For the deepest sample (52 meters) CFC-11 and CFC-12 saturations were 102 % and 126 %. Because the surface layer of the lake responds to changes in atmospheric CFCs on a time scale of several weeks, the higher than equilibrium concentrations of CFC-12 observed at the time of sampling may reflect earlier episodes of elevated levels of atmospheric CFC-12 in this urban area. High concentrations of dissolved CFCs in runoff or industrial effluent might also lead to elevated CFC levels in the lake. The cold, deep water of Lake Washington is relatively isolated from the effects of surface gas exchange except during winter, and the supersaturations observed in the deep layer may reflect periods of elevated atmospheric CFC-12 levels from the previous winter season. These results were compared to summertime profiles of CFC-11 and CFC-12 made in 1994.展开更多
Functional-group-transfer strategies that avoid the use of unsustainable chemicals are attractive for the development of green methodologies.Chlorofluorocarbons(CFCs)not only contribute to the depletion of the stratos...Functional-group-transfer strategies that avoid the use of unsustainable chemicals are attractive for the development of green methodologies.Chlorofluorocarbons(CFCs)not only contribute to the depletion of the stratospheric ozone layer,but their gaseous nature also poses a serious threat in scientific laboratories.Hence,the design of effective and sustainable alternatives to CFCs is highly desirable.Herein,a practical CFC transfer platform for the addition of both a fluoroalkyl group and a chlorine substituent across alkenes by a photomediated redox-neutral manifold using bench-stable and easy-to-handle oxime-based surrogates is reported.The distinct reactivity of these tunable reagents allows for their single-electron reduction to trigger fragmentation driven by benzonitrile formation and loss of carbon dioxide.The other fragments released in that step,namely an electrophilic fluoroalkyl radical and a nucleophilic chloride anion,are subsequently transferred onto alkenes by a radical-ionic mechanism to deliver the desired chlorofluorocarbon products.展开更多
Fluorinated porous organic networks(F-PONs)have demonstrated unique properties and applications,but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free...Fluorinated porous organic networks(F-PONs)have demonstrated unique properties and applications,but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free and easy handling conditions are still rarely reported.Herein,using polydivinylbenzene(PDVB)as an easily available precursor,a novel and straightforward approach was developed to afford F-PONs via a dehydrative Friedel-Crafts reaction using perfluorinated benzylic alcohols as the cross-linking agent promoted by Bronsted acid(trifluoromethanesulfonic acid).The afforded material(F-PDVB)featured high fluorine content(22 at.%),large surface area(771 m^(2)·g^(-1)),and good chemical/thermal stability,rendering them as promising candidates for the adsorption of CO_(2),hydrocarbons,fluorocarbons,and chlorofluorocarbons,with weight capacities up to 520 wt.%being achieved.This simple methodology can be extended to fabricate fluorinated hyper-crosslinked polymers(F-HCPs)from rigid aromatic monomers.The progress made in this work will open new opportunities to further expand the involvement of fluorinated materials in large scale applications.展开更多
Ozone (O3) is a stratospheric layer that plays important role in providing support to humans for their survival. It is an essential factor for many global, biological and environmental phenomena. The ultra-violet (UV)...Ozone (O3) is a stratospheric layer that plays important role in providing support to humans for their survival. It is an essential factor for many global, biological and environmental phenomena. The ultra-violet (UV) rays emitted from sun are captured by ozone and thereby provide a stable ontological structure in the biosphere. Various anthropogenic activities such as emissions of CFCs, HCFCs and other organo-halogens lead to the depletion of ozone. The ozone depletion resulted in secondary production of an ozone layer near the ground (terrestrial ozone layer), which is responsible for adverse effects on plants, humans and environment with increased number of bronchial diseases in humans. The mutations caused by UV rays result in variation in morphogenic traits of plants which ultimately decreases crop productivity. However, UV radiation is required in optimum intensity for both plants and animals. This review takes into an account the wide ranging effects of ozone depletion with a majority of them being detrimental to the plant system.展开更多
The catalytic hydrolysis of dichlorodifluoromethane (CFC-12) was investigated over solid acid Ti(SO_4)_2. The catalytic activity decreased with the calcination temperature. When space velocity was 6 1 h^(-1) g-cat^(-1...The catalytic hydrolysis of dichlorodifluoromethane (CFC-12) was investigated over solid acid Ti(SO_4)_2. The catalytic activity decreased with the calcination temperature. When space velocity was 6 1 h^(-1) g-cat^(-1). the CPC-12 conversion at 310C over Ti(SO_4)_2 calcined at 350C remained about 98.5% during 360 h on stream. and the selectivity to by-products remained zero. The findings enlarged the scope of traditional catalyst systems for the CFCs decomposition.展开更多
The Miami Isopycnic Coordinate Ocean Model (MICOM) is used to investigate the effect of diapycnal mixing on the oceanic uptake of CFC-11 and the ventilation of the surface waters in the Southern Ocean (south of 45...The Miami Isopycnic Coordinate Ocean Model (MICOM) is used to investigate the effect of diapycnal mixing on the oceanic uptake of CFC-11 and the ventilation of the surface waters in the Southern Ocean (south of 45°S). Three model experiments are performed: one with a diapycnal mixing coefficientK d (m2 s?1) of 2 × 10?7/N (Expt. 1), one withK d = 0 (Expt. 2), and one withK d = 5 × 10?8/N (Expt. 3),N (s?1) is the Brunt-V?is?l? frequency. The model simulations indicate that the observed vertical distribution of CFC-11 along 88°W (prime meridian at 0°E) in the Southern Ocean is caused by local ventilation of the surface waters and westward-directed (eastward-directed) isopycnic transport and mixing from deeply ventilated waters in the Weddell Sea region. It is found that at the end of 1997, the simulated net ocean uptake of CFC-11 in Expt. 2 is 25% below that of Expt. 1. The decreased uptake of CFC-11 in the Southern Ocean accounts for 80% of this difference. Furthermore, Expts. 2 and 3 yield far more realistic vertical distributions of the ventilated CFC-waters than Expt. 1. The experiments clearly highlight the sensitivity of the Southern Ocean surface water ventilation to the distribution and thickness of the simulated mixed layer. It is argued that inclusion of CFCs in coupled climate models could be used as a test-bed for evaluating the decadal-scale ocean uptake of heat and CO2.展开更多
Until recently, CFC-11 and CFC-12 were the most widely used refrigerant gases in air conditioning systems. Environmental agencies around the world, however, have specifical concern for these gases as a direct cause of...Until recently, CFC-11 and CFC-12 were the most widely used refrigerant gases in air conditioning systems. Environmental agencies around the world, however, have specifical concern for these gases as a direct cause of the depletion of the Earth’s ozone layer. Consequently, the world’s industrial nations are taking concerted action to decrease the use of CFCs, calling for attention of the engineers and designers involved in the manufacture and application of refrigeration systems for air conditioning. This paper analyses the available alternatives of CFCs in the industry and examines the problem found in process application.展开更多
文摘Measurements of three chlorofluorocarbons (CFCs): trichlorofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12) and trichlorotrifluoroethane (CFC-113), along with methyl chloroform (CH 3CCl 3) and carbon tetrachloride (CCl 4) were made in water samples from Lake Washington, using Electron Capture-Gas Chromatography (EC-GC). The samples were collected in mid-autumn, a period when the lake’s upper layer undergoes rapid cooling. At the time of sampling, a strong vertical temperature gradient was present in the lake, with surface temperatures of ~14℃, and near bottom (50 meters) temperatures of ~8℃. The concentrations of dissolved CFC-12 and CFC-11 increased with depth, as expected from the higher solubilities of these gases at lower temperatures. Atmospheric measurements made at the sampling site at the time of the cruise, showed that CFC-11 and CFC-12 saturations in the near surface samples were 100 % and 106%, respectively. For the deepest sample (52 meters) CFC-11 and CFC-12 saturations were 102 % and 126 %. Because the surface layer of the lake responds to changes in atmospheric CFCs on a time scale of several weeks, the higher than equilibrium concentrations of CFC-12 observed at the time of sampling may reflect earlier episodes of elevated levels of atmospheric CFC-12 in this urban area. High concentrations of dissolved CFCs in runoff or industrial effluent might also lead to elevated CFC levels in the lake. The cold, deep water of Lake Washington is relatively isolated from the effects of surface gas exchange except during winter, and the supersaturations observed in the deep layer may reflect periods of elevated atmospheric CFC-12 levels from the previous winter season. These results were compared to summertime profiles of CFC-11 and CFC-12 made in 1994.
基金by the Alexander von Humboldt Foundation(postdoctoral fellowship to M.Z.,2021-2023)in part by the Deutsche Forschungsgemeinschaft(grant no.Oe 249/26-1)is gratefully acknowledged+1 种基金M.Z.is also grateful for financial support from the University of Science and Technology of China(grant no.KY9990000197)M.O.is indebted to the Einstein Foundation Berlin for an endowed professorship.
文摘Functional-group-transfer strategies that avoid the use of unsustainable chemicals are attractive for the development of green methodologies.Chlorofluorocarbons(CFCs)not only contribute to the depletion of the stratospheric ozone layer,but their gaseous nature also poses a serious threat in scientific laboratories.Hence,the design of effective and sustainable alternatives to CFCs is highly desirable.Herein,a practical CFC transfer platform for the addition of both a fluoroalkyl group and a chlorine substituent across alkenes by a photomediated redox-neutral manifold using bench-stable and easy-to-handle oxime-based surrogates is reported.The distinct reactivity of these tunable reagents allows for their single-electron reduction to trigger fragmentation driven by benzonitrile formation and loss of carbon dioxide.The other fragments released in that step,namely an electrophilic fluoroalkyl radical and a nucleophilic chloride anion,are subsequently transferred onto alkenes by a radical-ionic mechanism to deliver the desired chlorofluorocarbon products.
基金supported financially by the Division of Chemical Sciences,Geosciences,and Biosciences,Office of Basic Energy Sciences,US Department of Energy.
文摘Fluorinated porous organic networks(F-PONs)have demonstrated unique properties and applications,but approaches capable of affording F-PONs with high fluorine content and robust nanoporous architecture under metal-free and easy handling conditions are still rarely reported.Herein,using polydivinylbenzene(PDVB)as an easily available precursor,a novel and straightforward approach was developed to afford F-PONs via a dehydrative Friedel-Crafts reaction using perfluorinated benzylic alcohols as the cross-linking agent promoted by Bronsted acid(trifluoromethanesulfonic acid).The afforded material(F-PDVB)featured high fluorine content(22 at.%),large surface area(771 m^(2)·g^(-1)),and good chemical/thermal stability,rendering them as promising candidates for the adsorption of CO_(2),hydrocarbons,fluorocarbons,and chlorofluorocarbons,with weight capacities up to 520 wt.%being achieved.This simple methodology can be extended to fabricate fluorinated hyper-crosslinked polymers(F-HCPs)from rigid aromatic monomers.The progress made in this work will open new opportunities to further expand the involvement of fluorinated materials in large scale applications.
文摘Ozone (O3) is a stratospheric layer that plays important role in providing support to humans for their survival. It is an essential factor for many global, biological and environmental phenomena. The ultra-violet (UV) rays emitted from sun are captured by ozone and thereby provide a stable ontological structure in the biosphere. Various anthropogenic activities such as emissions of CFCs, HCFCs and other organo-halogens lead to the depletion of ozone. The ozone depletion resulted in secondary production of an ozone layer near the ground (terrestrial ozone layer), which is responsible for adverse effects on plants, humans and environment with increased number of bronchial diseases in humans. The mutations caused by UV rays result in variation in morphogenic traits of plants which ultimately decreases crop productivity. However, UV radiation is required in optimum intensity for both plants and animals. This review takes into an account the wide ranging effects of ozone depletion with a majority of them being detrimental to the plant system.
文摘The catalytic hydrolysis of dichlorodifluoromethane (CFC-12) was investigated over solid acid Ti(SO_4)_2. The catalytic activity decreased with the calcination temperature. When space velocity was 6 1 h^(-1) g-cat^(-1). the CPC-12 conversion at 310C over Ti(SO_4)_2 calcined at 350C remained about 98.5% during 360 h on stream. and the selectivity to by-products remained zero. The findings enlarged the scope of traditional catalyst systems for the CFCs decomposition.
文摘The Miami Isopycnic Coordinate Ocean Model (MICOM) is used to investigate the effect of diapycnal mixing on the oceanic uptake of CFC-11 and the ventilation of the surface waters in the Southern Ocean (south of 45°S). Three model experiments are performed: one with a diapycnal mixing coefficientK d (m2 s?1) of 2 × 10?7/N (Expt. 1), one withK d = 0 (Expt. 2), and one withK d = 5 × 10?8/N (Expt. 3),N (s?1) is the Brunt-V?is?l? frequency. The model simulations indicate that the observed vertical distribution of CFC-11 along 88°W (prime meridian at 0°E) in the Southern Ocean is caused by local ventilation of the surface waters and westward-directed (eastward-directed) isopycnic transport and mixing from deeply ventilated waters in the Weddell Sea region. It is found that at the end of 1997, the simulated net ocean uptake of CFC-11 in Expt. 2 is 25% below that of Expt. 1. The decreased uptake of CFC-11 in the Southern Ocean accounts for 80% of this difference. Furthermore, Expts. 2 and 3 yield far more realistic vertical distributions of the ventilated CFC-waters than Expt. 1. The experiments clearly highlight the sensitivity of the Southern Ocean surface water ventilation to the distribution and thickness of the simulated mixed layer. It is argued that inclusion of CFCs in coupled climate models could be used as a test-bed for evaluating the decadal-scale ocean uptake of heat and CO2.
文摘Until recently, CFC-11 and CFC-12 were the most widely used refrigerant gases in air conditioning systems. Environmental agencies around the world, however, have specifical concern for these gases as a direct cause of the depletion of the Earth’s ozone layer. Consequently, the world’s industrial nations are taking concerted action to decrease the use of CFCs, calling for attention of the engineers and designers involved in the manufacture and application of refrigeration systems for air conditioning. This paper analyses the available alternatives of CFCs in the industry and examines the problem found in process application.