The mechanisms and kinetics of the gas phase reactions that the hydrogen atom in formyl fluoride （FCHO） abstracted by OH in the presence of water, formic acid （FA）, or sulfuric acid （SA） are theoretically invest...The mechanisms and kinetics of the gas phase reactions that the hydrogen atom in formyl fluoride （FCHO） abstracted by OH in the presence of water, formic acid （FA）, or sulfuric acid （SA） are theoretically investigated at the CCSD（T）/6-311＋＋G（3df, 3pd）//MO6-2X/6- 311＋＋G（3df, 3pd） level of theory. The calculated results show that the barriers of the transition states involving catalysts are lowered to -2.89, -6.25, and -7.76 kcal/mol from 3.64 kcal/mol with respect to the separate reactants, respectively, which reflects that those catalysts play an important role in reducing the barrier of the hydrogen abstraction reaction of FCHO with OH. Additionally, using conventional transition state theory with Eckart tun- neling correction, the kinetic data demonstrate that the entrance channel X…FCHO＋OH （X=H2O, FA, or SA） is significantly more favorable than the pathway X…OH＋FCHO. More- over, the rate constants of the reactions of FCHO with OH radical with H2O, FA, or SA introduced are computed to be smaller than that of the naked OH＋FCHO reaction because the concentration of the formed X…FCHO or X…OH complex is quite low in the atmosphere.展开更多
To investigate the hydrogen permeability of calcium fluoride used for electroslag remelting （ESR） process, ＂Gas-slag- metal＂ osmosis process under argon atmosphere saturated with water vapor at 318 K was used to s...To investigate the hydrogen permeability of calcium fluoride used for electroslag remelting （ESR） process, ＂Gas-slag- metal＂ osmosis process under argon atmosphere saturated with water vapor at 318 K was used to study the hydrogen permeability of slag containing calcium fluoride. The results indicate that the conventional slag, consisting of 70% CaF2 and 30% A1203, has the lowest hydrogen permeability. A parameter EH was proposed for evaluation of the hydrogen permeability of slags containing calcium fluoride. The hydrogen permeability decreases with increasing EH to a certain extent. An appropriate choice of slag for the ESR process can be obtained. These results also suggest that the hydrogen pick-up in steel after remelting might be reduced when a slag with low hydrogen permeability is used.展开更多
<div style="text-align:justify;"> An organogelator named N-[3-(hydroxy)-4-(dodecyloxy)-benzoyl]-N’ (4’-nitro-benzoyl) hydrazide (D12) was synthesized. It could form stable gels in some of the tested ...<div style="text-align:justify;"> An organogelator named N-[3-(hydroxy)-4-(dodecyloxy)-benzoyl]-N’ (4’-nitro-benzoyl) hydrazide (D12) was synthesized. It could form stable gels in some of the tested organic solvent. SEM images revealed that the molecules self- assembled into fibrous aggregates in the xerogels. The X-ray diffraction analysis showed that the xerogel exhibited a layered structure. FT-IR studies confirmed that intermolecular hydrogen bonding between C=O and N-H groups was the major driving force for gelation of organic solvents. The gel exhibited gel-sol transition and color change upon addition of F<span style="font-size:10px;"><sup>- </sup></span>. An extended conjugated system formed through the phenyl group and a five-membered ring based on intramolecular hydro-gen bonding between the oxygen atom near the deprotonation nitrogen atom and the other NH, which is responsible for the dramatic color change upon addition of <span style="text-align:justify;white-space:normal;">F</span><span style="font-size:10px;text-align:justify;white-space:normal;"><sup>- </sup></span>. </div>展开更多
A new complex C（18）H（24）CoF6N（12）Si has been synthesized by the reaction of cobalt（II） fluoride tetrahydrate with imidazole in a glass vessel. SiF62-was generated by in situ reaction of fluoride on silica. Thi...A new complex C（18）H（24）CoF6N（12）Si has been synthesized by the reaction of cobalt（II） fluoride tetrahydrate with imidazole in a glass vessel. SiF62-was generated by in situ reaction of fluoride on silica. This complex has been characterized by different techniques such as elemental analysis, IR studies, magnetic measurements, electronic absorption measurements and single-crystal X-ray structure determination. The crystals are hexagonal in the R-3 space group, with a = 13.225（6）, b = 13.225（6）, c = 12.517（11） A, and g = 120°. In complex [Co（im）6]SiF6, the cobalt atom is six-coordinated to adopt a regular octahedral geometry and the SiF62-ion acts as the counter anion. The crystal displays a network structure and SiF62- bridging hexagram formation by N-（39）···F-Si interactions between imdazole and SiF62-. SiF62-plays an important role in assembling the supramolecular aggregates.展开更多
Almost half of the total rural area of Guizhou Province and many regions within the 11 adjacent provinces in southwestern China have a long history(at least 70 years) of endemic fluorosis,including dental fluorosis an...Almost half of the total rural area of Guizhou Province and many regions within the 11 adjacent provinces in southwestern China have a long history(at least 70 years) of endemic fluorosis,including dental fluorosis and osteofluorosis along with its associated deformities and disabilities.Over decades of research,this specific type of endemic fluorosis has been defined as coal-burning fluorosis,which is distinct from drinking-water fluorosis.It is generally acknowledged that indoor burning and combustion of high-fluorine coal leads to food contamination,and fluorine then enters the human body.However,the exact chemical form of fluorine during its release and transfer to the body is still unknown.In the present study,21 domestic coal samples from outcrop and semi-outcrop coal collected in five villages with fluorosis were analyzed by time-of-flight secondary ion mass spectrometry(TOF-SIMS).The total mass fraction of sulfur in the samples ranged from 0.24%-5.58% and total fluorine content ranged 90.2-149.2 mg/kg.H3O+,H2SO4+ and HSO4-were detected in the samples by TOF-SIMS,which indicated that sulfuric acid hydrate(H2SO4.H2O) was present in the samples.F-was detected in all of these,which suggested the samples contain ionic fluorine compounds.Under certain circumstances,such as heating or burning,the prevalence and coexistence of the acid(H2SO4.H2O) and base(F-) would lead to a neutralization reaction producing volatile hydrogen fluoride(HF,bp = 19.5℃).This would be the chemical form of fluorine released from the coal.Further studies using HF and SO2 test tubes on headspace gas over coal samples heated to 200℃ in the laboratory and on headspace gas over stoves or chimney tops at rural residences confirmed the release of HF.展开更多
文摘The mechanisms and kinetics of the gas phase reactions that the hydrogen atom in formyl fluoride （FCHO） abstracted by OH in the presence of water, formic acid （FA）, or sulfuric acid （SA） are theoretically investigated at the CCSD（T）/6-311＋＋G（3df, 3pd）//MO6-2X/6- 311＋＋G（3df, 3pd） level of theory. The calculated results show that the barriers of the transition states involving catalysts are lowered to -2.89, -6.25, and -7.76 kcal/mol from 3.64 kcal/mol with respect to the separate reactants, respectively, which reflects that those catalysts play an important role in reducing the barrier of the hydrogen abstraction reaction of FCHO with OH. Additionally, using conventional transition state theory with Eckart tun- neling correction, the kinetic data demonstrate that the entrance channel X…FCHO＋OH （X=H2O, FA, or SA） is significantly more favorable than the pathway X…OH＋FCHO. More- over, the rate constants of the reactions of FCHO with OH radical with H2O, FA, or SA introduced are computed to be smaller than that of the naked OH＋FCHO reaction because the concentration of the formed X…FCHO or X…OH complex is quite low in the atmosphere.
基金Project(50904015) supported by the National Natural Science Foundation of ChinaProject(N090402012) supported by the Fundamental Research Funds for Central Universities of China
文摘To investigate the hydrogen permeability of calcium fluoride used for electroslag remelting （ESR） process, ＂Gas-slag- metal＂ osmosis process under argon atmosphere saturated with water vapor at 318 K was used to study the hydrogen permeability of slag containing calcium fluoride. The results indicate that the conventional slag, consisting of 70% CaF2 and 30% A1203, has the lowest hydrogen permeability. A parameter EH was proposed for evaluation of the hydrogen permeability of slags containing calcium fluoride. The hydrogen permeability decreases with increasing EH to a certain extent. An appropriate choice of slag for the ESR process can be obtained. These results also suggest that the hydrogen pick-up in steel after remelting might be reduced when a slag with low hydrogen permeability is used.
文摘<div style="text-align:justify;"> An organogelator named N-[3-(hydroxy)-4-(dodecyloxy)-benzoyl]-N’ (4’-nitro-benzoyl) hydrazide (D12) was synthesized. It could form stable gels in some of the tested organic solvent. SEM images revealed that the molecules self- assembled into fibrous aggregates in the xerogels. The X-ray diffraction analysis showed that the xerogel exhibited a layered structure. FT-IR studies confirmed that intermolecular hydrogen bonding between C=O and N-H groups was the major driving force for gelation of organic solvents. The gel exhibited gel-sol transition and color change upon addition of F<span style="font-size:10px;"><sup>- </sup></span>. An extended conjugated system formed through the phenyl group and a five-membered ring based on intramolecular hydro-gen bonding between the oxygen atom near the deprotonation nitrogen atom and the other NH, which is responsible for the dramatic color change upon addition of <span style="text-align:justify;white-space:normal;">F</span><span style="font-size:10px;text-align:justify;white-space:normal;"><sup>- </sup></span>. </div>
基金financially supported by Higher Education Commission of Pakistan under Indigenous PhD 5000 Fellowship Program and International Research Support Initiative Program(IRSIP)
文摘A new complex C（18）H（24）CoF6N（12）Si has been synthesized by the reaction of cobalt（II） fluoride tetrahydrate with imidazole in a glass vessel. SiF62-was generated by in situ reaction of fluoride on silica. This complex has been characterized by different techniques such as elemental analysis, IR studies, magnetic measurements, electronic absorption measurements and single-crystal X-ray structure determination. The crystals are hexagonal in the R-3 space group, with a = 13.225（6）, b = 13.225（6）, c = 12.517（11） A, and g = 120°. In complex [Co（im）6]SiF6, the cobalt atom is six-coordinated to adopt a regular octahedral geometry and the SiF62-ion acts as the counter anion. The crystal displays a network structure and SiF62- bridging hexagram formation by N-（39）···F-Si interactions between imdazole and SiF62-. SiF62-plays an important role in assembling the supramolecular aggregates.
基金supported by the State Scholarship Fund by China Scholarship Council (2007106398)the Key Project of the National Science & Technology Pillar Program (2006BAK03A21)
文摘Almost half of the total rural area of Guizhou Province and many regions within the 11 adjacent provinces in southwestern China have a long history(at least 70 years) of endemic fluorosis,including dental fluorosis and osteofluorosis along with its associated deformities and disabilities.Over decades of research,this specific type of endemic fluorosis has been defined as coal-burning fluorosis,which is distinct from drinking-water fluorosis.It is generally acknowledged that indoor burning and combustion of high-fluorine coal leads to food contamination,and fluorine then enters the human body.However,the exact chemical form of fluorine during its release and transfer to the body is still unknown.In the present study,21 domestic coal samples from outcrop and semi-outcrop coal collected in five villages with fluorosis were analyzed by time-of-flight secondary ion mass spectrometry(TOF-SIMS).The total mass fraction of sulfur in the samples ranged from 0.24%-5.58% and total fluorine content ranged 90.2-149.2 mg/kg.H3O+,H2SO4+ and HSO4-were detected in the samples by TOF-SIMS,which indicated that sulfuric acid hydrate(H2SO4.H2O) was present in the samples.F-was detected in all of these,which suggested the samples contain ionic fluorine compounds.Under certain circumstances,such as heating or burning,the prevalence and coexistence of the acid(H2SO4.H2O) and base(F-) would lead to a neutralization reaction producing volatile hydrogen fluoride(HF,bp = 19.5℃).This would be the chemical form of fluorine released from the coal.Further studies using HF and SO2 test tubes on headspace gas over coal samples heated to 200℃ in the laboratory and on headspace gas over stoves or chimney tops at rural residences confirmed the release of HF.
