Fluoroform
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| Names | |||
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| IUPAC name
Trifluoromethane
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| Other names
Fluoroform, Carbon trifluoride, Methyl trifluoride, Fluoryl, Freon 23, Arcton 1, HFC 23, R-23, FE-13, UN 1984
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| Identifiers | |||
3D model (JSmol)
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| ChEBI | |||
| ChemSpider | |||
| ECHA InfoCard | 100.000.794 | ||
| EC Number |
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PubChem CID
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| RTECS number |
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| UNII | |||
CompTox Dashboard (EPA)
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| Properties | |||
| CHF3 | |||
| Molar mass | 70.01 g/mol | ||
| Appearance | Colorless gas | ||
| Density | 2.946 kg·m−3 (gas, 1 bar, 15 °C) | ||
| Melting point | −155.2 °C (−247.4 °F; 118.0 K) | ||
| Boiling point | −82.1 °C (−115.8 °F; 191.1 K) | ||
| 1 g/l | |||
| Solubility in organic solvents | Soluble | ||
| Vapor pressure | 4.38 MPa at 20 °C | ||
Henry's law
constant (kH) |
0.013 mol.kg−1.bar−1 | ||
| Acidity (pKa) | 25 - 28 | ||
| Structure | |||
| Tetrahedral | |||
| Hazards | |||
| Occupational safety and health (OHS/OSH): | |||
Main hazards
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Nervous system depression | ||
| NFPA 704 (fire diamond) | |||
| Flash point | Non-flammable | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Fluoroform is the chemical compound with the formula CHF3. It is one of the "haloforms", a class of compounds with the formula CHX3 (X = halogen). Fluoroform is used in diverse niche applications and is produced as a by-product of the manufacture of Teflon. It is also generated biologically in small amounts apparently by decarboxylation of trifluoroacetic acid.[1]
Structure
The molecule adopts tetrahedral molecular geometry with C3v symmetry.
Synthesis
Fluoroform was first obtained by Maurice Meslans in the violent reaction of iodoform with dry silver fluoride in 1894.[2] The reaction was improved by Otto Ruff by substitution of silver fluoride by a mixture of mercury fluoride and calcium fluoride.[3] The exchange reaction works with iodoform and bromoform, and the exchange of the first two halogen atoms by fluorine is vigorous. By changing to a two step process, first forming a bromodifluoro methane in the reaction of antimony trifluoride with bromoform and finishing the reaction with mercury fluoride the first efficient synthesis method was found by Henne.[3]
Industrial applications
CHF3 is used in the semiconductor industry in plasma etching of silicon oxide and silicon nitride. Known as R-23 or HFC-23, it is also a useful refrigerant, sometimes as a replacement for chlorotrifluoromethane (cfc-13) and is a byproduct of its manufacture.
When used as a fire suppressant, the fluoroform carries the DuPont trade name, FE-13. CHF3 is recommended for this application because of its low toxicity, its low reactivity, and its high density. HFC-23 has been used in the past as a replacement for Halon 1301[cfc-13b1] in fire suppression systems as a total flooding gaseous fire suppression agent.
Organic chemistry
The molecule is weakly acidic with a pKa = 25–28 and quite inert. The main synthetic methods to use CHF3 as a reagent are based on its deprotonation to generate the "CF3−" anion, which is highly reactive and undergoes defluorination to generate F- and CHF2. Recently, some approaches activating it by assisted metallation with copper organometallic species are able to effect the site-selective trifluoromethylation arene halides.[4] It is a precursor of Ruppert's reagent CF3Si(CH3)3 which is the most useful source of the nucleophilic CF3−" anion. More recently, the direct preparation of Ruppert's reagent from fluoroform has been reported [5] [6]
Greenhouse gas
CHF3 is a potent greenhouse gas. The secretariat of the Clean Development Mechanism estimates that a ton of HFC-23 in the atmosphere has the same effect as 11,700 tons of carbon dioxide. More recent work (IPCC, 2007) suggests that this equivalency, also called a 100-yr global warming potential, is slightly larger at 14,800 for HFC-23.[7] The atmospheric lifetime is 270 years.[7]
According to the 2007 IPCC climate report, HFC-23 was the most abundant HFC in the global atmosphere until around 2001, which is when the global mean concentration of HFC-134a (1,1,1,2-tetrafluoroethane), the chemical now used extensively in automobile air conditioners, surpassed those of HFC-23. Global emissions of HFC-23 have in the past been dominated by the inadvertent production and release during the manufacture of the refrigerant HCFC-22 (chlorodifluoromethane).
Data reported to the United Nations Framework Convention on Climate Change (UNFCCC) greenhouse gas emissions databases [8] indicate substantial decreases in developed or Annex 1 countries HFC-23 emissions from the 1990s to the 2000s (UNFCCC greenhouse gas emissions databases). The UNFCCC Clean Development Mechanism projects have provided funding and facilitated the destruction of HFC-23 co-produced from a portion of HCFC-22 produced in developing or non-Annex 1 countries since 2003. Developing countries have become the largest producers of HCFC-22 in recent years according to data compiled by the Ozone Secretariat of the World Meteorological Organization.[9][10][11] Emissions of all HFCs are included in the UNFCCCs Kyoto Protocol. To mitigate its impact, CHF3 can be destroyed with electric plasma arc technologies or by high temperature incineration.
References
- ^ Kirschner, E., Chemical and Engineering News 1994, 8.
- ^ Meslans M. M. (1894). "Recherches sur quelques fluorures organiques de la série grasse". Annales de chimie et de physique. 7 (1): 346–423.
- ^ a b Henne A. L. (1937). "Fluoroform". Journal of the American Chemical Society. 59 (7): 1200–1202. doi:10.1021/ja01286a012.
- ^ Zanardi, Alessandro; Novikov, Maxim A.; Martin, Eddy; Benet-Buchholz, Jordi; Grushin, Vladimir V. (2011-12-28). "Direct Cupration of Fluoroform". Journal of the American Chemical Society. 133 (51): 20901–20913. doi:10.1021/ja2081026. ISSN 0002-7863.
- ^ Rozen, S.; Hagooly, A. "Fluoroform" in Encyclopedia of Reagents for Organic Synthesis (Ed: L. Paquette) 2004, J. Wiley & Sons, New York. doi:10.1002/047084289X.rn00522
- ^ Prakash, G. K. Surya; Jog, Parag V.; Batamack, Patrice T. D.; Olah, George A. (2012-12-07). "Taming of Fluoroform: Direct Nucleophilic Trifluoromethylation of Si, B, S, and C Centers". Science. 338 (6112): 1324–1327. doi:10.1126/science.1227859. ISSN 0036-8075.
- ^ a b Forster, P., V. Ramaswamy, P. Artaxo, T. Berntsen, R. Betts, D.W. Fahey, J. Haywood, J. Lean, D.C. Lowe, G. Myhre, J. Nganga, R. Prinn, G. Raga, M. Schulz and R. Van Dorland (2007). "Changes in Atmospheric Constituents and in Radiative Forcing." (PDF). Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change.
{{cite conference}}: Unknown parameter|booktitle=ignored (|book-title=suggested) (help)CS1 maint: multiple names: authors list (link) - ^ http://unfccc.int/di/FlexibleQueries.do
- ^ http://ozone.unep.org/Data_Reporting/Data_Access/
- ^ Profits on Carbon Credits Drive Output of a Harmful Gas August 8, 2012 New York Times
- ^ Subsidies for a Global Warming Gas
Literature
- McBee E. T. (1947). "Fluorine Chemistry". Industrial & Engineering Chemistry. 39 (3): 236–237. doi:10.1021/ie50447a002.
- Oram D. E.; Sturges W. T.; Penkett S. A.; McCulloch A.; Fraser P. J. (1998). "Growth of fluoroform (CHF3, HFC-23) in the background atmosphere". Geophysical Research Letters. 25 (1): 236–237. Bibcode:1998GeoRL..25...35O. doi:10.1029/97GL03483.
- McCulloch A. (2003). "Fluorocarbons in the global environment: a review of the important interactions with atmospheric chemistry and physics". Journal of Fluorine Chemistry. 123 (1): 21–29. doi:10.1016/S0022-1139(03)00105-2.
External links
- International Chemical Safety Card 0577
- MSDS at Oxford University
- MSDS at mathesontrigas.com
- Coupling of fluoroform with aldehydes using an electrogenerated base
Additional physical properties
| Property | Value |
|---|---|
| Density (ρ) at -100 °C (liquid) | 1.52 g/cm3 |
| Density (ρ) at -82.1 °C (liquid) | 1.431 g/cm3 |
| Density (ρ) at -82.1 °C (gas) | 4.57 kg/m3 |
| Density (ρ) at 0 °C (gas) | 2.86 kg/m3 |
| Density (ρ) at 15 °C (gas) | 2.99 kg/m3 |
| Dipole moment | 1.649 D |
| Critical pressure (pc) | 4.816 MPa (48.16 bar) |
| Critical temperature (Tc) | 25.7 °C (299 K) |
| Critical density (ρc) | 7.52 mol/l |
| Compressibility factor (Z) | 0.9913 |
| Acentric factor (ω) | 0.26414 |
| Viscosity (η) at 25 °C | 14.4 μPa.s (0.0144 cP) |
| Molar specific heat at constant volume (CV) | 51.577 J.mol−1.K−1 |
| Latent heat of vaporization (lb) | 257.91 kJ.kg−1 |