chloroform chloroform chloroform names preferred iupac name trichloromethane other names chloroformmethane trichloridemethyl trichloridemethenyl trichloridemethenyl chloridetcmfreon 20refrigerant-20r-20un 1888terchloride of formyle(archaic)trichloretum formylicum (latin) identifiers cas number 67-66-3 y 3d model (jsmol) interactive image chebi chebi:35255 y chembl chembl44618 y chemspider 5977 y echa infocard 100.000.603 ec number 200-663-8 kegg c13827 y pubchem cid 6212 rtecs number fs9100000 unii 7v31yc746x y comptox dashboard (epa) dtxsid1020306 inchi inchi=1s/chcl3/c2-1(3)4/h1h ykey: hedrzpfgaczzds-uhfffaoysa-n yinchi=1/chcl3/c2-1(3)4/h1hkey: hedrzpfgaczzds-uhfffaoyag smiles clc(cl)cl properties chemical formula chcl3 molar mass 119.37 g·mol−1 appearance highly refractive colorless liquid odor strong smell reminiscent of dry-cleaner's shops density 1.564 g/cm3 (−20 °c) 1.489 g/cm3 (25 °c) 1.394 g/cm3 (60 °c) melting point −63.5 °c (−82.3 °f; 209.7 k) boiling point 61.15 °c (142.07 °f; 334.30 k) decomposes at 450 °c solubility in water 10.62 g/l (0 °c) 8.09 g/l (20 °c) 7.32 g/l (60 °c) solubility soluble in benzene miscible in diethyl ether, oils, ligroin, alcohol, ccl4, cs2 solubility in acetone ≥ 100 g/l (19 °c) solubility in dimethyl sulfoxide ≥ 100 g/l (19 °c) vapor pressure 0.62 kpa (−40 °c) 7.89 kpa (0 °c) 25.9 kpa (25 °c) 313 kpa (100 °c) 2.26 mpa (200 °c) henry's lawconstant (kh) 3.67 l·atm/mol (24 °c) acidity (pka) 15.7 (20 °c) uv-vis (λmax) 250 nm, 260 nm, 280 nm magnetic susceptibility (χ) −59.30·10−6 cm3/mol thermal conductivity 0.13 w/m·k (20 °c) refractive index (nd) 1.4459 (20 °c) viscosity 0.563 cp (20 °c) structure molecular shape tetrahedral dipole moment 1.15 d thermochemistry heat capacity (c) 114.25 j/mol·k std molarentropy (s⦵298) 202.9 j/mol·k std enthalpy offormation (δfh⦵298) −134.3 kj/mol gibbs free energy (δfg⦵) −71.1 kj/mol std enthalpy ofcombustion (δch⦵298) 473.21 kj/mol pharmacology atc code n01ab02 (who) hazards occupational safety and health (ohs/osh): main hazards decomposes to extremely toxic phosgene and hydrogen chloride in presence of light - suspected carcinogen – reproductive toxicity – specific target organ toxicity (stot) ghs labelling: pictograms signal word danger hazard statements h302, h315, h319, h331, h336, h351, h361d, h372 precautionary statements p201, p202, p235, p260, p264, p270, p271, p280, p281, p301+p330+p331, p302+p352, p304+p340, p305+p351+p338, p308+p313, p310, p311, p314, p332+p313, p337+p313, p362, p403+p233, p405, p501 nfpa 704 (fire diamond) 2 0 0 flash point nonflammable lethal dose or concentration (ld, lc): ld50 (median dose) 704 mg/kg (mouse, dermal) lc50 (median concentration) 9,617 ppm (rat, 4 hr) lclo (lowest published) 20,000 ppm (guinea pig, 2 hr)7,056 ppm (cat, 4 hr)25,000 ppm (human, 5 min) niosh (us health exposure limits): pel (permissible) 50 ppm (240 mg/m3) rel (recommended) ca st 2 ppm (9.78 mg/m3) idlh (immediate danger) 500 ppm safety data sheet (sds) related compounds related chloromethanes chloromethanedichloromethanetetrachloromethane supplementary data page chloroform (data page) except where otherwise noted, data are given for materials in their standard state (at 25 °c , 100 kpa). y verify (what is yn ?) infobox references chloroform, or trichloromethane (often abbreviated as tcm), is an organic compound with the formula chcl3 and a common organic solvent. it is a very volatile, colorless, strong-smelling, dense liquid produced on a large scale as a precursor to ptfe and refrigerants and is a trihalomethane that serves as a powerful anesthetic, euphoriant, anxiolytic, and sedative when inhaled or ingested. chloroform was used as an anesthetic between the 19th century and the first half of the 20th century. chloroform is miscible with many solvents but it is only very slightly soluble in water (only 8 g/l at 20 °c). structure and name the molecule adopts a tetrahedral molecular geometry with c3v symmetry. the chloroform molecule can be viewed as a methane molecule with three hydrogen atoms replaced with three chlorine atoms, leaving a single hydrogen atom. the name "chloroform" is a portmanteau of terchloride (tertiary chloride, a trichloride) and formyle, an obsolete name for the methylidene (ch) radical derived from formic acid. natural occurrence the total global flux of chloroform through the environment is approximately 660000 tonnes per year, and about 90% of emissions are natural in origin. many kinds of seaweed produce chloroform, and fungi are believed to produce chloroform in soil. abiotic processes are also believed to contribute to natural chloroform productions in soils, although the mechanism is still unclear. as chloroform is a volatile organic compound, it dissipates readily from soil and surface water and undergoes degradation in air to produce phosgene, dichloromethane, formyl chloride, carbon monoxide, carbon dioxide, and hydrogen chloride. its half-life in air ranges from 55 to 620 days. biodegradation in water and soil is slow. chloroform does not significantly bioaccumulate in aquatic organisms. history chloroform was synthesized independently by several investigators circa 1831: moldenhawer, a german pharmacist from frankfurt an der oder, appears to have produced chloroform in 1830 by mixing chlorinated lime with ethanol; however, he mistook it for chloräther (chloric ether, 1,2-dichloroethane). samuel guthrie, a u.s. physician from sackets harbor, new york, also appears to have produced chloroform in 1831 by reacting chlorinated lime with ethanol, as well as noting its anaesthetic properties; he also believed that he had prepared chloric ether, however. justus von liebig carried out the alkaline cleavage of chloral. liebig incorrectly states that the empirical formula of chloroform is c2cl5 and names it "chlorkohlenstoff" ("carbon chloride"). eugène soubeiran obtained the compound by the action of chlorine bleach on both ethanol and acetone. in 1834, french chemist jean-baptiste dumas determined chloroform's empirical formula and named it. dumas states chloroform's empirical formula and names it: "es scheint mir also erweisen, dass die von mir analysirte substance, … zur formel hat: c2h2cl6." (thus it seems to me to show that the substance analyzed by me … has as formula: c2h2cl6.) ... "diess hat mich veranlasst diese substanz mit dem namen 'chloroform' zu belegen." (this caused me to bestow this substance with the name "chloroform" .) in 1835, dumas prepared the substance by the alkaline cleavage of trichloroacetic acid. regnault prepared chloroform by chlorination of chloromethane. in 1842, robert mortimer glover in london discovered the anaesthetic qualities of chloroform on laboratory animals. in 1847, scottish obstetrician james y. simpson was the first to demonstrate the anaesthetic properties of chloroform on humans, provided by local pharmacist william flockhart of duncan, flockhart and company, and helped to popularise the drug for use in medicine. by the 1850s, chloroform was being produced on a commercial basis. in britain, about 750,000 doses a week were being produced by 1895 using the liebig procedure, which retained its importance until the 1960s. today, chloroform – along with dichloromethane – is prepared exclusively and on a massive scale by the chlorination of methane and chloromethane. production industrially, chloroform is produced by heating a mixture of chlorine and either methyl chloride (ch3cl) or methane (ch4). at 400–500 °c, a free radical halogenation occurs, converting these precursors to progressively more chlorinated compounds: ch4 + cl2 → ch3cl + hcl ch3cl + cl2 → ch2cl2 + hcl ch2cl2 + cl2 → chcl3 + hcl chloroform undergoes further chlorination to yield carbon tetrachloride (ccl4): chcl3 + cl2 → ccl4 + hcl the output of this process is a mixture of the four chloromethanes: chloromethane, methylene chloride (dichloromethane), trichloromethane (chloroform), and tetrachloromethane (carbon tetrachloride). this can then be separated by distillation. chloroform may also be produced on a small scale via the haloform reaction between acetone and sodium hypochlorite: 3 naclo + (ch3)2co → chcl3 + 2 naoh + ch3coona deuterochloroform deuterated chloroform is an isotopologue of chloroform with a single deuterium atom. cdcl3 is a common solvent used in nmr spectroscopy. deuterochloroform is produced by the reaction of hexachloroacetone with deuterium oxide. the haloform process is now obsolete for the production of ordinary chloroform. deuterochloroform can also be prepared by the reaction of sodium deuteroxide with chloral hydrate. inadvertent formation of chloroform the haloform reaction can also occur inadvertently in domestic settings. bleaching with hypochlorite generates halogenated compounds in side reactions; chloroform is the main byproduct. sodium hypochlorite solution (chlorine bleach) mixed with common household liquids such as acetone, methyl ethyl ketone, ethanol, or isopropyl alcohol can produce some chloroform, in addition to other compounds such as chloroacetone or dichloroacetone. uses in terms of scale, the most important reaction of chloroform is with hydrogen fluoride to give monochlorodifluoromethane (cfc-22), a precursor in the production of polytetrafluoroethylene (teflon) and other fluoropolymers: chcl3 + 2hf → chclf2 + 2 hcl the reaction is conducted in the presence of a catalytic amount of mixed antimony halides. chlorodifluoromethane is then converted into tetrafluoroethylene, the main precursor to teflon. solvent the hydrogen attached to carbon in chloroform participates in hydrogen bonding, thus making it a good solvent for many materials. worldwide, chloroform is also used in pesticide formulations, as a solvent for lipids, rubber, alkaloids, waxes, gutta-percha, and resins, as a cleansing agent, grain fumigant, in fire extinguishers, and in the rubber industry. cdcl3 is a common solvent used in nmr spectroscopy. refrigerant trichloromethane has been used as a precursor to make r-22 (chlorodifluoromethane). this is done by reacting it with a solution of hydrofluoric acid (hf) which will fluorinate the chcl3 molecule and release hydrochloric acid as a byproduct. prior to the enforcement of the montreal protocol, the majority of the trichloromethane produced in the united states, was used for the production of chlorodifluoromethane. although trichloromethane has properties such as its low boiling point and its low global warming potential of only 31 (compared to the 1,760 of r-22) which result in it having good refrigeration properties, there is little information to suggest that it has seen widespread use as a refrigerant in any consumer products. lewis acid in solvents such as ccl4 and alkanes, chloroform hydrogen bonds to a variety of lewis bases. hccl3 is classified as a hard acid and the ecw model lists its acid parameters as ea = 1.56 and ca = 0.44. reagent as a reagent, chloroform serves as a source of the dichlorocarbene :ccl2 group. it reacts with aqueous sodium hydroxide usually in the presence of a phase transfer catalyst to produce dichlorocarbene, :ccl2. this reagent effects ortho-formylation of activated aromatic rings such as phenols, producing aryl aldehydes in a reaction known as the reimer–tiemann reaction. alternatively, the carbene can be trapped by an alkene to form a cyclopropane derivative. in the kharasch addition, chloroform forms the chcl2 free radical in addition to alkenes. anaesthetic antique bottles of chloroform the anaesthetic qualities of chloroform were first described in 1842 in a thesis by robert mortimer glover, which won the gold medal of the harveian society for that year. glover also undertook practical experiments on dogs to prove his theories, and refined his theories and presented them in the thesis for his doctorate at the university of edinburgh in the summer of 1847. the scottish obstetrician james young simpson was one of the persons required to read the thesis, but later claimed to have never read the thesis and to have come to his own conclusions independently. on 4 november 1847, simpson argued that he discovered the anaesthetic qualities of chloroform on humans. he and two colleagues entertained themselves by trying the effects of various substances, and thus revealed the potential for chloroform in medical procedures. a few days later, during the course of a dental procedure in edinburgh, francis brodie imlach became the first person to use chloroform on a patient in a clinical context. in may 1848, robert halliday gunning made a presentation to the medico-chirurgical society of edinburgh following a series of laboratory experiments on rabbits that confirmed glover's findings and also refuted simpson's claims of originality. the laboratory experiments proving the dangers of chloroform were largely ignored. the use of chloroform during surgery expanded rapidly in europe; for instance in the 1850s, chloroform was used by the physician john snow during the birth of queen victoria's last two children. in the united states, chloroform began to replace ether as an anesthetic at the beginning of the 20th century; it was abandoned in favor of ether upon discovery of its toxicity, especially its tendency to cause fatal cardiac arrhythmia analogous to what is now termed "sudden sniffer's death". some people used chloroform as a recreational drug or to attempt suicide. one possible mechanism of action for chloroform is that it increases the movement of potassium ions through certain types of potassium channels in nerve cells. chloroform could also be mixed with other anaesthetic agents such as ether to make c.e. mixture, or ether and alcohol to