Dichloromethane

Dichloromethane (DCM or methylene chloride, methylene bichloride[14]) is an organochlorine compound with the formula CH2Cl2. This colorless, volatile liquid with a chloroform-like, sweet odour is widely used as a solvent. Although it is not miscible with water, it is slightly polar, and miscible with many organic solvents.[15]

"Di-clo" redirects here. For the anti-inflammatory drug trade named Diclo, see Diclofenac.
Dichloromethane
Names
Preferred IUPAC name
Dichloromethane
Other names
Methylene bichloride;[1], Methylene chloride gas,[2] Methylene dichloride, Solmethine; Narkotil; Dichloromethylene,[3] Solaesthin; Di-clo; Refrigerant-30; Freon-30; R-30; DCM; MDC
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.000.763
EC Number
  • 200-838-9
KEGG
RTECS number
  • PA8050000
UNII
UN number 1593
CompTox Dashboard (EPA)
InChI
  • InChI=1S/CH2Cl2/c2-1-3/h1H2 Y
    Key: YMWUJEATGCHHMB-UHFFFAOYSA-N Y
  • InChI=1/CH2Cl2/c2-1-3/h1H2
    Key: YMWUJEATGCHHMB-UHFFFAOYAG
SMILES
  • ClCCl
Properties
CH2Cl2
Molar mass 84.93 g·mol−1
Appearance Colorless liquid
Odor Faint, chloroform-like[4]
Density 1.3266 g/cm3 (20 °C)[5]
Melting point −96.7 °C (−142.1 °F; 176.5 K)
Boiling point 39.6 °C (103.3 °F; 312.8 K)
decomposes at 720 °C[6]
39.75 °C (103.55 °F; 312.90 K)
at 760 mmHg[7]
Solubility in water
 25.6 g/L (15 °C)
17.5 g/L (25 °C)
15.8 g/L (30 °C)
5.2 g/L (60 °C)[6]
Solubility Miscible in ethyl acetate, alcohol, hexanes, benzene, CCl4, diethyl ether, CHCl3
log P 1.19[8]
Vapor pressure 0.13 kPa (−70.5 °C)
2 kPa (−40 °C)
19.3 kPa (0 °C)
57.3 kPa (25 °C)[9]
79.99 kPa (35 °C)[6]
3.25 L·atm/mol[7]
−46.6·10−6 cm3/mol
1.4244 (20 °C)[7][10]
Viscosity 0.43 cP (20 °C)[7]
0.413 cP (25 °C)
Structure
1.6 D
Thermochemistry
102.3 J/(mol·K)[9]
Std molar
entropy (S⦵298)
 174.5 J/(mol·K)[9]
Std enthalpy of
formation (ΔfH⦵298)
 −124.3 kJ/mol[9]
Std enthalpy of
combustion (ΔcH⦵298)
 -454.0 kJ/mol (from standard enthalpies of formation)[9]
Hazards
Occupational safety and health (OHS/OSH):
Eye hazards
 Irritant
GHS labelling:[10]
Pictograms
Signal word
 Warning
Hazard statements
 H315, H319, H335, H336, H351, H373
Precautionary statements
 P261, P281, P305+P351+P338
NFPA 704 (fire diamond)
2
1
0
Flash point None, but can form flammable vapour-air mixtures above ≈100 °C[11]
Autoignition
temperature
 556 °C (1,033 °F; 829 K)
Explosive limits 13%-23%[4]
Lethal dose or concentration (LD, LC):
LD50 (median dose)
 1.25 g/kg (rats, oral)
2 g/kg (rabbits, oral)[6]
LC50 (median concentration)
 24,929 ppm (rat, 30 min)
14,400 ppm (mouse, 7 h)[12]
LCLo (lowest published)
 5000 ppm (guinea pig, 2 h)
10,000 ppm (rabbit, 7 h)
12,295 ppm (cat, 4.5 h)
14,108 ppm (dog, 7 h)[12]
NIOSH (US health exposure limits):
PEL (Permissible)
 25 ppm over 8 hours (time-weighted average), 125 ppm over 15 minutes (STEL)[4][13]
REL (Recommended)
 Ca[4]
IDLH (Immediate danger)
 Ca [2300 ppm][4]
Supplementary data page
Dichloromethane (data page)
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Y verify (what is YN ?)
Infobox references

Occurrence

Natural sources of dichloromethane include oceanic sources, macroalgae, wetlands, and volcanoes.[16] However, the majority of dichloromethane in the environment is the result of industrial emissions.[16]

Production

DCM is produced by treating either chloromethane or methane with chlorine gas at 400–500 °C. At these temperatures, both methane and chloromethane undergo a series of reactions producing progressively more chlorinated products. In this way, an estimated 400,000 tons were produced in the US, Europe, and Japan in 1993.[15]

CH4 + Cl2 → CH3Cl + HCl
CH3Cl + Cl2 → CH2Cl2 + HCl
CH2Cl2 + Cl2 → CHCl3 + HCl
CHCl3 + Cl2 → CCl4 + HCl

The output of these processes is a mixture of chloromethane, dichloromethane, chloroform, and carbon tetrachloride as well as hydrogen chloride as a byproduct. These compounds are separated by distillation.

DCM was first prepared in 1839 by the French chemist Henri Victor Regnault (1810–1878), who isolated it from a mixture of chloromethane and chlorine that had been exposed to sunlight.[17]

Uses

DCM's volatility and ability to dissolve a wide range of organic compounds makes it a useful solvent for many chemical processes.[15] In the food industry, it is used to decaffeinate coffee and tea as well as to prepare extracts of hops and other flavourings.[18][19] Its volatility has led to its use as an aerosol spray propellant and as a blowing agent for polyurethane foams.

Hydrogen bonding

Methylene chloride is a Lewis acid that can hydrogen bond to electron donors. It is classified as a hard acid and is included in the ECW model. It is a solvent that has been used in many thermodynamic studies of donor-acceptor bonding. The donor hydrogen-bonding corrections of methylene chloride in these thermodynamic studies has been reported.[20][21]

Specialized uses
Near IR absorption spectrum of dichloromethane showing complicated overlapping overtones of mid IR absorption features.

The chemical compound's low boiling point allows the chemical to function in a heat engine that can extract mechanical energy from small temperature differences. An example of a DCM heat engine is the drinking bird. The toy works at room temperature.[22] It is also used as the fluid in jukebox displays and holiday bubble lights that have a colored bubbling tube above a lamp as a source of heat and a small amount of rock salt to provide thermal mass and a nucleation site for the phase changing solvent.

DCM chemically welds certain plastics. For example, it is used to seal the casing of electric meters. Often sold as a main component of plastic welding adhesives, it is also used extensively by model building hobbyists for joining plastic components together. It is commonly referred to as "Di-clo."

It is used in the garment printing industry for removal of heat-sealed garment transfers.

DCM is used in the material testing field of civil engineering; specifically it is used during the testing of bituminous materials as a solvent to separate the binder from the aggregate of an asphalt or macadam to allow the testing of the materials.[23]

Dichloromethane extract of Asparagopsis taxiformis, a seaweed fodder for cattle, has been found to reduce their methane emissions by 79%.[24]

It has been used as the principal component of paint stripper, but its use for this purpose is now prohibited in the United States and the European Union.

Chemical reactions

Dichloromethane is widely used as a solvent in part because it is relatively inert. It does participate in reactions with certain strong nucleophiles however. Tert-butyllithium deprotonates DCM:[25]

H2CCl2 + RLi → HCCl2Li + RH

Hydride reagents convert dichloromethane to methyl chloride.

Toxicity

Even though DCM is the least toxic of the simple chlorohydrocarbons, it has serious health risks. Its high volatility makes it an acute inhalation hazard.[26][27] It can also be absorbed through the skin.[4][28] Symptoms of acute overexposure to dichloromethane via inhalation include difficulty concentrating, dizziness, fatigue, nausea, headaches, numbness, weakness, and irritation of the upper respiratory tract and eyes. More severe consequences can include suffocation, loss of consciousness, coma, and death.[4][28]

DCM is also metabolized by the body to carbon monoxide potentially leading to carbon monoxide poisoning.[29] Acute exposure by inhalation has resulted in optic neuropathy[30] and hepatitis.[31] Prolonged skin contact can result in DCM dissolving some of the fatty tissues in skin, resulting in skin irritation or chemical burns.[32]

It may be carcinogenic, as it has been linked to cancer of the lungs, liver, and pancreas in laboratory animals.[33] Other animal studies showed breast cancer and salivary gland cancer. Research is not yet clear as to what levels may be carcinogenic.[4][28] DCM crosses the placenta but fetal toxicity in women who are exposed to it during pregnancy has not been proven.[34] In animal experiments, it was fetotoxic at doses that were maternally toxic but no teratogenic effects were seen.[33]

In people with pre-existing heart problems, exposure to DCM can cause abnormal heart rhythms and/or heart attacks, sometimes without any other symptoms of overexposure.[28] People with existing liver, nervous system, or skin problems may worsen after exposure to methylene chloride.[13]

Regulation

In many countries, products containing DCM must carry labels warning of its health risks.

In February 2013, the U.S. Occupational Safety and Health Administration (OSHA) and the National Institute for Occupational Safety and Health warned that at least 14 bathtub refinishers have died since 2000 from DCM exposure. These workers had been working alone, in poorly ventilated bathrooms, with inadequate or no respiratory protection, and no training about the hazards of DCM.[13][28][35] OSHA has since then issued a DCM standard.[36] In the European Union, the European Parliament voted in 2009 to ban the use of DCM in paint-strippers for consumers and many professionals.[37] The ban took effect in December 2010.[38]

In Europe, the Scientific Committee on Occupational Exposure Limit Values (SCOEL) recommends for DCM an occupational exposure limit (8 h time-weighted average) of 100 ppm and a short-term exposure limit (15 min) of 200 ppm.[39]

Concerns about its health effects have led to a search for alternatives in many of these applications.[15][40]

On March 15, 2019, the U.S. Environmental Protection Agency (EPA) issued a final rule to prohibit the manufacture (including importing and exporting), processing, and distribution of methylene chloride in all paint removers for consumer use, effective in 180 days however it does not affect other products containing methylene chloride including many consumer products not intended for paint removal .

Environmental effects

Ozone
CH2Cl2 measured by the Advanced Global Atmospheric Gases Experiment (AGAGE) in the lower atmosphere (troposphere) at stations around the world. Abundances are given as pollution free monthly mean mole fractions in parts-per-trillion.

Dichloromethane is not classified as an ozone-depleting substance by the Montreal Protocol.[41] The U.S. Clean Air Act does not regulate dichloromethane as an ozone depleter.[42] Recent research shows that dichloromethane and other halogenated very short-lived substances (VSLSs), despite their short atmospheric lifetimes of less than 0.5 year, can contribute to stratospheric ozone depletion, particularly if emitted in regions where rapid transport to the stratosphere occurs. [43] Atmospheric abundances of dichloromethane have been increasing in recent years.

Ozone concentrations measured at the midlatitudes from the ground up through the stratosphere from 1998 to 2016 have declined by 2.2 Dobson units,[44] just under 1%.[45] The reasons for this decline are unclear, but one unverified hypothesis is the presence of short-lived substances such as dichloromethane in the lower atmosphere.[46]

See also

References
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  3. Dichloromethane (freon)
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    Reprinted in German in:
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