Formaldehyde

Formaldehyde (systematic name: methanal) is an organic compound with the formula CH₂O. As the simplest aldehyde, it is an important precursor to many other chemical compounds, especially for polymers. In 2005, annual world production of formaldehyde was estimated to be 23 million tons (50 billion pounds).In view of its widespread use, toxicity and volatility, exposure to formaldehyde is a significant consideration for human health.

Formaldehyde is more complicated than many simple carbon compounds because it adopts different forms. Formaldehyde is a gas at room temperature, but the gas readily converts to a variety of derivatives. These derivatives generally behave similarly to gaseous formaldehyde and are used in industry. One important derivative is the cyclic compound trioxane, the "trimer" of formaldehyde with formula is (CH₂O)₃. When dissolved in water, formaldehyde converts to H₂C(OH)₂, a diol (i.e. a compound with two hydroxy groups). 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 degree of polymerization. A typical commercial grade formalin may contain 10–12% methanol in addition to various metallic impurities. The diol also exists in equilibrium with a series of short polymers (called oligomers), depending on the concentration and temperature. The infinite polymer formed from formaldehyde is called paraformaldehyde. The cyclic trimer is called metaformaldehyde (or 1,3,5-trioxane).

Formaldehyde is a naturally occurring substance in the environment made of carbon, hydrogen and oxygen. Natural processes in the upper atmosphere may contribute up to 90 percent of the total formaldehyde in the environment. 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 has also been detected in outer space (see below).
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 does not accumulate in the environment, because it is broken down within a few hours by sunlight or by bacteria present in soil or water. Humans metabolize formaldehyde quickly, so it does not accumulate, and is converted to formic acid in the body.
Small amounts of formaldehyde are produced in case of incomplete combustion of methane gas.

Formaldehyde was the first polyatomic organic molecule detected in the interstellar medium 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.A proposed mechanism for the formation is the hydrogenation of CO ice, shown below.

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.

Formaldehyde was first reported by the Russian chemist Aleksandr Butlerov (1828–86) and was conclusively identified by August Wilhelm von Hofmann.
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:

2 CH₃OH + O₂ → 2 CH₂O + 2 H₂O

The silver-based catalyst usually operates 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 formaldehyde is more easily oxidized than methane.

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.Condensation with phenols gives phenol-formaldehyde resins. With 4-substituted phenols one obtains calixarenes.
When combined with hydrogen sulfide it forms trithiane.

3CH₂O + 3H₂S → (CH₂S)₃ + 3H₂O

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.The textile industry uses formaldehyde-based resins as finishers to make fabrics crease-resistant.Formaldehyde-based materials are key to the manufacture of automobiles, and used to make components for the transmission, electrical system, engine block, door panels, axles and brake shoes. The value of sales of formaldehyde and derivative products was over $145 billion in 2003, about 1.2% of the Gross Domestic Product (GDP) of the United States and Canada. Including indirect employment, over 4 million work in the formaldehyde industry across approximately 11,900 plants in the U.S. and Canada.
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. 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.

^{Formaldehyde preserves or fixes tissue or cells by reversibly 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.
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 formaldehyde; if the lungs float it suggests the animal was probably breathing or able to breathe at the time of death.
Formaldehyde solutions are commonly used as a biological preserving medium, usually for smaller specimens.
Several European countries restrict the use of formaldehyde, including the import of formaldehyde-treated products and embalming. Starting September 2007, the European Union banned the use of formaldehyde due to its carcinogenic properties as a biocide (including embalming) under the Biocidal Products Directive (98/8/EC).Countries with a strong tradition of embalming corpses, such as Ireland and other colder-weather countries, have raised concerns. Despite reports to the contrary, 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.}