organic chemistry Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...

, peroxyacyl nitrates (also known as Acyl peroxy nitrates, APN or PANs) are powerful respiratory and eye irritants present in

photochemical smog Smog, or smoke fog, is a type of intense air pollution. The word "smog" was coined in the early 20th century, and is a portmanteau of the words ''smoke'' and ''fog'' to refer to smoky fog due to its opacity, and odor. The word was then inten ...

. They are

nitrates Nitrate is a polyatomic ion with the chemical formula . Salts containing this ion are called nitrates. Nitrates are common components of fertilizers and explosives. Almost all inorganic nitrates are soluble in water. An example of an insoluble ...

produced in the

thermal equilibrium Two physical systems are in thermal equilibrium if there is no net flow of thermal energy between them when they are connected by a path permeable to heat. Thermal equilibrium obeys the zeroth law of thermodynamics. A system is said to be in ...

between organic

peroxy In chemistry, peroxides are a group of compounds with the structure , where R = any element. The group in a peroxide is called the peroxide group or peroxo group. The nomenclature is somewhat variable. The most common peroxide is hydrogen ...

radical Radical may refer to: Politics and ideology Politics *Radical politics, the political intent of fundamental societal change *Radicalism (historical), the Radical Movement that began in late 18th century Britain and spread to continental Europe and ...

s by the

gas Gas is one of the four fundamental states of matter (the others being solid, liquid, and plasma). A pure gas may be made up of individual atoms (e.g. a noble gas like neon), elemental molecules made from one type of atom (e.g. oxygen), or ...

-phase

oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a d ...

of a variety of

volatile organic compound Volatile organic compounds (VOCs) are organic compounds that have a high vapour pressure at room temperature. High vapor pressure correlates with a low boiling point, which relates to the number of the sample's molecules in the surrounding air, a ...

s (VOCs), or by

aldehyde In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl grou ...

s and other oxygenated VOCs oxidizing in the presence of . For example,

peroxyacetyl nitrate Peroxyacetyl nitrate is a peroxyacyl nitrate. It is a secondary pollutant present in photochemical smog. It is thermally unstable and decomposes into peroxyethanoyl radicals and nitrogen dioxide gas. It is a lachrymatory substance, meaning tha ...

, : :Hydrocarbons + O2 + NO2 + light -> CH3COOONO2 The general equation is: :C_\mathitH_\mathitO3 + NO2 -> C_\mathitH_\mathitO3NO2 They are good markers for the source of VOCs as either biogenic or anthropogenic, which is useful in the study of global and local effects of pollutants. PANs are both toxic and irritating, as they dissolve more readily in water than

ozone Ozone (), or trioxygen, is an inorganic molecule with the chemical formula . It is a pale blue gas with a distinctively pungent smell. It is an allotrope of oxygen that is much less stable than the diatomic allotrope , breaking down in the lo ...

. They are

lachrymator Tear gas, also known as a lachrymator agent or lachrymator (), sometimes colloquially known as "mace" after the early commercial aerosol, is a chemical weapon that stimulates the nerves of the lacrimal gland in the eye to produce tears. In ad ...

s, causing eye irritation at concentrations of only a few parts per billion. At higher concentrations they cause extensive damage to vegetation. Both PANs and their

chlorinated In chemistry, halogenation is a chemical reaction that entails the introduction of one or more halogens into a compound. Halide-containing compounds are pervasive, making this type of transformation important, e.g. in the production of polymers, ...

derivates are said to be

mutagen In genetics, a mutagen is a physical or chemical agent that permanently changes nucleic acid, genetic material, usually DNA, in an organism and thus increases the frequency of mutations above the natural background level. As many mutations can ca ...

ic, as they can be a factor causing

skin cancer Skin cancers are cancers that arise from the skin. They are due to the development of abnormal cells that have the ability to invade or spread to other parts of the body. There are three main types of skin cancers: basal-cell skin cancer (BCC) ...

. PANs are secondary pollutants, which means they are not directly emitted as exhaust from

power plants A power station, also referred to as a power plant and sometimes generating station or generating plant, is an industrial facility for the generation of electric power. Power stations are generally connected to an electrical grid. Many pow ...

internal combustion engines An internal combustion engine (ICE or IC engine) is a heat engine in which the combustion of a fuel occurs with an oxidizer (usually air) in a combustion chamber that is an integral part of the working fluid flow circuit. In an internal combus ...

, but they are formed from other pollutants by chemical reactions in the atmosphere.

Free radical A daughter category of ''Ageing'', this category deals only with the biological aspects of ageing. Ageing Ailments of unknown cause Biogerontology Biological processes Causes of death Cellular processes Gerontology Life extension Metabo ...

reactions catalyzed by

ultraviolet light Ultraviolet (UV) is a form of electromagnetic radiation with wavelength from 10 nm (with a corresponding frequency around 30 PHz) to 400 nm (750 THz), shorter than that of visible light, but longer than X-rays. UV radiation i ...

from the sun oxidize unburned

hydrocarbons In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic, and their odors are usually weak or ex ...

aldehydes In organic chemistry, an aldehyde () is an organic compound containing a functional group with the structure . The functional group itself (without the "R" side chain) can be referred to as an aldehyde but can also be classified as a formyl group ...

ketones In organic chemistry, a ketone is a functional group with the structure R–C(=O)–R', where R and R' can be a variety of carbon-containing substituents. Ketones contain a carbonyl group –C(=O)– (which contains a carbon-oxygen double bon ...

, and

dicarbonyl compounds In organic chemistry, a dicarbonyl is a molecule containing two carbonyl () groups. Although this term could refer to any organic compound containing two carbonyl groups, it is used more specifically to describe molecules in which both carbonyls ...

, whose secondary reactions create peroxyacyl radicals, which combine with

nitrogen dioxide Nitrogen dioxide is a chemical compound with the formula . It is one of several nitrogen oxides. is an intermediate in the industrial synthesis of nitric acid, millions of tons of which are produced each year for use primarily in the producti ...

to form peroxyacyl nitrates. The most common peroxyacyl radical is peroxyacetyl, which can be formed from the free radical oxidation of

acetaldehyde Acetaldehyde (IUPAC systematic name ethanal) is an organic chemical compound with the formula CH3 CHO, sometimes abbreviated by chemists as MeCHO (Me = methyl). It is a colorless liquid or gas, boiling near room temperature. It is one of the mos ...

, various ketones, or the

photolysis Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by photons. It is defined as the interaction of one or more photons with one target molecule. ...

of dicarbonyl compounds such as

methylglyoxal Methylglyoxal (MGO) is the organic compound with the formula CH3C(O)CHO. It is a reduced derivative of pyruvic acid. It is a reactive compound that is implicated in the biology of diabetes. Methylglyoxal is produced industrially by degradation ...

diacetyl Diacetyl (IUPAC systematic name: butanedione or butane-2,3-dione) is an organic compound with the chemical formula (CH3CO)2. It is a yellow liquid with an intensely buttery flavor. It is a vicinal diketone (two C=O groups, side-by-side). Diacet ...

. Since they dissociate quite slowly in the atmosphere into

s and , PANs are able to transport these unstable compounds far away from the urban and industrial origin. This is important for

tropospheric ozone Ground-level ozone (O3), also known as surface-level ozone and tropospheric ozone, is a trace gas in the troposphere (the lowest level of the Earth's atmosphere), with an average concentration of 20–30 parts per billion by volume (ppbv), with cl ...

production as PANs transport NO_''x'' to regions where it can more efficiently produce

References

{{DEFAULTSORT:Peroxyacyl Nitrates Organic peroxides Pollutants Smog