formaldehyde

Formaldehyde
IUPAC name	formaldehyde
Other names	formol, methyl aldehyde, methylene oxide, methanal
Identifiers
CAS number	50-00-0 Y
EC-number	200-001-8
RTECS number	LP8925000
ATCvet code	QP53AX19
SMILES	C=O
InChI	1/CH2O/c1-2/h1H2
ChemSpider ID	692
Properties[1]
Molecular formula	CH2O
Molar mass	30.026 g/mol
Appearance	colorless gas
Melting point	−92 °C
Boiling point	−21 °C
Solubility in water	very high (see text)
Dipole moment	2.33 D
Structure
Molecular shape	trigonal planar
Hazards
MSDS	ICSC 0275
EU Index	605-001-00-5
EU classification	Toxic (T) Carc. Cat. 3
R-phrases	R23/24/25, R34, R40, R43
S-phrases	(S1/2), S26, S36/37/39, S45, S51
NFPA 704	2 3 2
Flash point	flammable gas
Autoignition temperature	430 ºC (806 ºF)
Explosive limits	7–73%
Related compounds
Related aldehydes	acetaldehyde propionaldehyde
Related compounds	methanol formic acid
Y (what is this?)  (verify) Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)
Infobox references

Formaldehyde (systematic name: methanal) is a chemical compound with the formula CH₂O. It is the simplest aldehyde. Formaldehyde also exists as the cyclic trimer trioxane and the polymer paraformaldehyde. It exists in water as the hydrate H₂C(OH)₂. Aqueous solutions of formaldehyde are referred to as formalin. "100%" formalin consists of a saturated solution of formaldehyde (this is about 40% by volume or 37% by mass) in water, with a small amount of stabilizer, usually methanol to limit oxidation and polymerization. A typical commercial grade formalin may contain 10–12% methanol in addition to metallic impurities such as aluminium (3 ppm), iron (1 ppm) and copper (1 ppm). Annual world production of formaldehyde (about 2005) was 21 million tonnes (46 billion pounds).^[2]

In view of its widespread use, toxicity, and volatility, exposure to formaldehyde is a significant consideration for human health.^[3]

Occurrence

Formaldehyde is an intermediate in the oxidation (or combustion) of methane as well as other carbon compounds, e.g. forest fires, in automobile exhaust, and in tobacco smoke. When produced in the atmosphere by the action of sunlight and oxygen on atmospheric methane and other hydrocarbons, it becomes part of smog.

Formaldehyde, as well as its oligomers and hydrates are rarely encountered in living organisms. Methanogenesis proceeds via the equivalent of formaldehyde, but this one-carbon species is masked as a methylene group in methanopterin. Formaldehyde is the primary cause of methanol's toxicity, since methanol is metabolised into toxic formaldehyde by alcohol dehydrogenase. Formaldehyde is converted to formic acid in the body. Formaldehyde has been detected in outer space (see below).

Synthesis and industrial production

Formaldehyde was first reported by the Russian chemist Aleksandr Butlerov (1828–86), but was conclusively identified by August Wilhelm von Hofmann.^[4]

Formaldehyde is produced industrially by the catalytic oxidation of methanol. The most common catalysts are silver metal or a mixture of an iron and molybdenum or vanadium oxides. In the more commonly used FORMOX process methanol and oxygen react at ca. 250–400 °C in presence of iron oxide in combination with molybdenum and/or vanadium to produce formaldehyde according to the chemical equation:^[3]

2CH₃OH + O₂ → 2CH₂O + 2H₂O

The silver-based catalyst is usually operated at a higher temperature, about 650 °C. Two chemical reactions on it simultaneously produce formaldehyde: that shown above and the dehydrogenation reaction:

CH₃OH → H₂CO + H₂

In principle formaldehyde could be generated by oxidation of methane, but this route is not industrially viable because the methanol is more easily oxidized than methane.^[3]

Organic chemistry

Formaldehyde is a building block in the synthesis of many other compounds of specialised and industrial significance. It exhibits most of the chemical properties of other aldehydes but is more reactive. For example it is more readily oxidized by atmospheric oxygen to formic acid (formic acid is found in ppm levels in commercial formaldehyde). Formaldehyde is a good electrophile, participating in electrophilic aromatic substitution reactions with aromatic compounds, and can undergo electrophilic addition reactions with alkenes and aromatics. Formaldehyde undergoes a Cannizzaro reaction in the presence of basic catalysts to produce formic acid and methanol.

Examples of organic synthetic applications

Condensation with acetaldehyde affords pentaerythritol, a chemical necessary in synthesizing PETN, a high explosive.^[5] Condensation with phenols gives phenol-formaldehyde resins. With 4-substituted phenols one obtains calixarenes.^[6]

When combined with hydrogen sulfide it forms trithiane.^[7]

3CH₂O + 3H₂S → (CH₂S)₃ + 3H₂O

Industrial applications

Formaldehyde is a common building block for the synthesis of more complex compounds and materials. In approximate order of decreasing consumption, products generated from formaldehyde include urea formaldehyde resin, melamine resin, phenol formaldehyde resin, polyoxymethylene plastics, 1,4-butanediol, and methylene diphenyl diisocyanate.^[3]

When reacted with phenol, urea, or melamine formaldehyde produces, respectively, hard thermoset phenol formaldehyde resin, urea formaldehyde resin, and melamine resin, which are commonly used in permanent adhesives such as those used in plywood or carpeting. It is used as the wet-strength resin added to sanitary paper products such as (listed in increasing concentrations injected into the paper machine headstock chest) facial tissue, table napkins, and roll towels. They are also foamed to make insulation, or cast into moulded products. Production of formaldehyde resins accounts for more than half of formaldehyde consumption.

Formaldehyde is also a precursor to polyfunctional alcohols such as pentaerythritol, which is used to make paints and explosives. Other formaldehyde derivatives include methylene diphenyl diisocyanate, an important component in polyurethane paints and foams, and hexamine, which is used in phenol-formaldehyde resins as well as the explosive RDX.

The textile industry uses formaldehyde-based resins as finishers to make fabrics crease-resistant.^[8]

Formaldehyde has been found as a contaminant in several bath products, at levels from 54–610 ppm: it is thought to arise from the breakdown of preservatives in the products.^[9]

Miscellaneous applications

Formaldehyde is a common component of many uses. Formaldehyde, along with 18 M (concentrated) sulfuric acid (the entire solution often called the Marquis reagent), is used as an MDMA "testing kit" by such groups as Dancesafe as well as MDMA consumers. The solution alone cannot verify the presence of MDMA but reacts with many other chemicals that the MDMA tablet itself may be adulterated with. The reaction itself produces colors that correlate with these components.

As a disinfectant and biocide

An aqueous solution of formaldehyde can be useful as a disinfectant as it kills most bacteria and fungi (including their spores). It is also used as a preservative in vaccines. Formaldehyde solutions are applied topically in medicine to dry the skin, such as in the treatment of warts. Many aquarists use formaldehyde as a treatment for the parasites Ichthyophthirius multifiliis and Cryptocaryon irritans.^[10]

Formaldehyde preserves or fixes tissue or cells by irreversibly cross-linking primary amino groups in proteins with other nearby nitrogen atoms in protein or DNA through a -CH₂- linkage. This is exploited in ChIP-on-chip transcriptomics experiments. Formaldehyde is also used as a denaturing agent in RNA gel electrophoresis, preventing RNA from forming secondary structures.

In photography

Formaldehyde is still used in low concentrations for process C-41 (color negative film) stabilizer in the final wash step,^[11] as well as in the process E-6 pre-bleach step, to obviate the need for it in the final wash.

Tissue fixative and embalming agent

Formaldehyde solutions are used as a fixative for microscopy and histology. Formaldehyde-based solutions are also used in embalming to disinfect and temporarily preserve human and animal remains. It is the ability of formaldehyde to fix the tissue that produces the tell-tale firmness of flesh in an embalmed body. In post mortem examinations a procedure known as the "sink test" involves placing the lungs of an animal in an aqueous solution of fomaldehyde; if the lungs float it suggests the animal was probably breathing or able to breathe at the time of death.

Several European countries restrict the use of formaldehyde, including the import of formaldehyde-treated products and embalming. The European Union is considering a complete ban on the use of formaldehyde as a biocide (including embalming) under the Biocidal Products Directive (98/8/EC).^[12][13] Countries with a strong tradition of embalming corpses, such as Ireland and other colder-weather countries, have raised concerns. Despite reports to the contrary,^[14] no decision on the inclusion of formaldehyde on Annex I of the Biocidal Products Directive for product-type 22 (embalming and taxidermist fluids) had been made as of September 2009.^[15]

Interstellar formaldehyde

Formaldehyde was the first polyatomic organic molecule detected in the interstellar medium^[16] and since its initial detection has been observed in many regions of the galaxy. Because of the widespread interest in interstellar formaldehyde it has recently been extensively studied, yielding new extragalactic sources.^[17] A proposed mechanism for the formation is the hydrogenation of CO ice, shown below.^[18]

H + CO → HCO

HCO + H → H₂CO (rate constant = 9.2 × 10⁻³ s⁻¹)

Formaldehyde appears to be a useful probe for astrochemists due to its low reactivity in the gas phase and to the fact that the 1₁₀←1₁₁ and 2₁₁←2₁₂ K-doublet transitions are rather clear.

Safety

Occupational exposure to formaldehyde by inhalation is mainly from three types of sources: thermal or chemical decomposition of formaldehyde-based resins, formaldehyde emission from aqueous solutions (for example, embalming fluids), and the production of formaldehyde resulting from the combustion of a variety of organic compounds (for example, exhaust gases). Formaldehyde can be toxic, allergenic, and carcinogenic.^[2] Because formaldehyde resins are used in many construction materials it is one of the more common indoor air pollutants.^[19] At concentrations above 0.1 ppm in air formaldehyde can irritate the eyes and mucous membranes, resulting in watery eyes.^[20] Formaldehyde inhaled at this concentration may cause headaches, a burning sensation in the throat, and difficulty breathing, as well as triggering or aggravating asthma symptoms.^[21][22]

Formaldehyde is classified as a probable human carcinogen by the U.S. Environmental Protection Agency. The International Agency for Research on Cancer (IARC) has determined that there is "sufficient evidence" that occupational exposure to formaldehyde causes nasopharyngeal cancer in humans.^[2] The United States Environmental Protection Agency (EPA) allows no more than 16 ppb formaldehyde in the air in new buildings constructed for that agency.^[23] The Federal Emergency Management Agency (FEMA) has also announced limits on the formaldehyde levels in trailers purchased by that agency.^[24]

Formaldehyde can cause allergies and is part of the standard patch test series. People with formaldehyde allergy are advised to avoid formaldehyde releasers as well (e.g., Quaternium-15, imidazolidinyl urea, and diazolidinyl urea).^[25] Formaldehyde has been banned in cosmetics in both Sweden and Japan.^{[citation needed]}

FEMA trailer incidents

Hurricane Katrina & Rita

In the U.S. the Federal Emergency Management Agency (FEMA) provided travel trailers and mobile homes starting in 2006 for habitation by residents of the U.S. gulf coast displaced by Hurricane Katrina and Hurricane Rita. Some of the people who moved into the trailers complained of breathing difficulties, nosebleeds, and persistent headaches. Formaldehyde-catalyzed resins were used in the production of these homes.

The United States Centers For Disease Control and Prevention (CDC) performed indoor air quality testing for formaldehyde^[26] in some of the units. On February 14, 2008 the CDC announced that potentially hazardous levels of formaldehyde were found in many of the travel trailers and mobile homes provided by the agency.^[27][28] The CDC's preliminary evaluation of a scientifically established random sample of 519 travel trailers and mobile homes tested between Dec. 21, 2007 and Jan. 23, 2008 (2+ years after manufacture) showed average levels of formaldehyde in all units of about 77 parts per billion (ppb). Long-term exposure to levels in this range can be linked to an increased risk of cancer and, at levels above this range, there can also be a risk of respiratory illness. These levels are higher than expected in indoor air, where levels are commonly in the range of 10-20 ppb, and are higher than the Agency for Toxic Substance Disease Registry (ATSDR, division of the CDC) Minimal Risk Level (MRL) of 8 ppb.^[29] Levels measured ranged from 3 ppb to 590 ppb.^[30]

FEMA, which requested the testing by the CDC, said it would work aggressively to relocate all residents of the temporary housing as soon as possible. Lawsuits are being filed against FEMA as a result of the exposures.^[31]

Iowa Floods of 2008

Also in the U.S., problems arose in trailers again provided by FEMA to residents displaced by the Iowa floods of 2008. A couple months after moving to the trailers, occupants reported violent coughing, headaches, as well as Asthma, Bronchitis, and other problems. Tests showed that in some trailers, levels of formaldehyde exceeded the limits recommended by the U.S. Environmental Protection Agency and American Lung Association.^[32][33] The associated publicity has resulted in additional testing to begin in November.^[34]

Contaminant in Food

Scandals have broken in both the 2005 Indonesia food scare and 2007 Vietnam food scare regarding the addition of formaldehyde to foods to extend shelf life. Foods known to be contaminated include noodles, salted fish, tofu, and rumors of chicken and beer. In humans, it is known to cause a number of detrimental effects and there is limited evidence of a carcinogenic effect.^[2]

See also

• 1,3-dioxetane
• Interstellar formaldehyde

References

External links

• International Chemical Safety Card 0275 (gas)
• International Chemical Safety Card 0695 (solution)
• NIOSH Pocket Guide to Chemical Hazards 0293
• Entry for "Formaldehyde" on the Australian National Pollutant Inventory
• Formaldehyde Council (grouping of producers and industrial users in North America)
• Formaldehyde from ChemSub Online
• Prevention guide—Formaldehyde in the Workplace from the Institut de recherche Robert-Sauvé en santé et en sécurité du travail (IRSST)
• Formaldehyde from the National Institute for Occupational Safety and Health
• SIDS Initial Assessment Report for Formaldehyde from the Organisation for Economic Co-operation and Development (OECD)
• IPCS Health and Safety Guide 57: Formaldehyde
• IPCS Environmental Health Criteria 89: Formaldehyde