In organic chemistry, peroxyacyl nitrates (also known as Acyl peroxy nitrates, APN or PANs) are powerful respiratory and eye irritants present in photochemical smog. They are nitrates produced in the thermal equilibrium between organic peroxy radicals by the gas-phase oxidation of a variety of volatile organic compounds (VOCs), or by aldehydes and other oxygenated VOCs oxidizing in the presence of NO2. [1] [2] [3]
For example, peroxyacetyl nitrate, CH3C(O)OONO2:
The general equation is:
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. [4] [5]
PANs are both toxic and irritating, as they dissolve more readily in water than ozone. They are lachrymators, 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 derivates are said to be mutagenic, as they can be a factor causing skin cancer.
PANs are secondary pollutants, which means they are not directly emitted as exhaust from power plants or internal combustion engines, but they are formed from other pollutants by chemical reactions in the atmosphere. Free radical reactions catalyzed by ultraviolet light from the sun oxidize unburned hydrocarbons to aldehydes, ketones, and dicarbonyl compounds, whose secondary reactions create peroxyacyl radicals, which combine with nitrogen dioxide to form peroxyacyl nitrates.
The most common peroxyacyl radical is peroxyacetyl, which can be formed from the free radical oxidation of acetaldehyde, various ketones, or the photolysis of dicarbonyl compounds such as methylglyoxal or diacetyl.
Since they dissociate quite slowly in the atmosphere into radicals and NO2, PANs are able to transport these unstable compounds far away from the urban and industrial origin. This is important for tropospheric ozone production as PANs transport NOx to regions where it can more efficiently produce ozone.
In organic chemistry, a ketone is an organic compound 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)−. The simplest ketone is acetone, with the formula (CH3)2CO. Many ketones are of great importance in biology and industry. Examples include many sugars (ketoses), many steroids, and the solvent acetone.
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 intended to refer to what was sometimes known as pea soup fog, a familiar and serious problem in London from the 19th century to the mid-20th century, where it was commonly known as a London particular or London fog. This kind of visible air pollution is composed of nitrogen oxides, sulfur oxide, ozone, smoke and other particulates. Man-made smog is derived from coal combustion emissions, vehicular emissions, industrial emissions, forest and agricultural fires and photochemical reactions of these emissions.
An oxidizing agent is a substance in a redox chemical reaction that gains or "accepts"/"receives" an electron from a reducing agent. In other words, an oxidizer is any substance that oxidizes another substance. The oxidation state, which describes the degree of loss of electrons, of the oxidizer decreases while that of the reductant increases; this is expressed by saying that oxidizers "undergo reduction" and "are reduced" while reducers "undergo oxidation" and "are oxidized". Common oxidizing agents are oxygen, hydrogen peroxide, and the halogens.
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 that it irritates the lungs and eyes.
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 close to 100 ppbv in polluted areas. Ozone is also an important constituent of the stratosphere, where the ozone layer (2 to 8 parts per million ozone) exists which is located between 10 and 50 kilometers above the Earth's surface. The troposphere extends from the ground up to a variable height of approximately 14 kilometers above sea level. Ozone is least concentrated in the ground layer (or planetary boundary layer) of the troposphere. Ground-level or tropospheric ozone is created by chemical reactions between NOx gases (oxides of nitrogen produced by combustion) and volatile organic compounds (VOCs). The combination of these chemicals in the presence of sunlight form ozone. Its concentration increases as height above sea level increases, with a maximum concentration at the tropopause. About 90% of total ozone in the atmosphere is in the stratosphere, and 10% is in the troposphere. Although tropospheric ozone is less concentrated than stratospheric ozone, it is of concern because of its health effects. Ozone in the troposphere is considered a greenhouse gas, and as such contribute to global warming. as reported in IPCC reports. Actually, tropospheric ozone is considered the third most important greenhouse gas after CO2 and CH4, as indicated by estimates of its radiative forcing.
Nitrogen dioxide is a chemical compound with the formula NO2. One of several nitrogen oxides, nitrogen dioxide is a reddish-brown gas. It is a paramagnetic, bent molecule with C2v point group symmetry. Industrially, NO2 is an intermediate in the synthesis of nitric acid, millions of tons of which are produced each year, primarily for the production of fertilizers.
The following outline is provided as an overview of and topical guide to organic chemistry:
An enamine is an unsaturated compound derived by the condensation of an aldehyde or ketone with a secondary amine. Enamines are versatile intermediates.
Dinitrogen pentoxide is the chemical compound with the formula N2O5. It is one of the binary nitrogen oxides, a family of compounds that contain only nitrogen and oxygen. It exists as colourless crystals that sublime slightly above room temperature, yielding a colorless gas.
In organic chemistry, nitro compounds are organic compounds that contain one or more nitro functional groups. The nitro group is one of the most common explosophores used globally. The nitro group is also strongly electron-withdrawing. Because of this property, C−H bonds alpha (adjacent) to the nitro group can be acidic. For similar reasons, the presence of nitro groups in aromatic compounds retards electrophilic aromatic substitution but facilitates nucleophilic aromatic substitution. Nitro groups are rarely found in nature. They are almost invariably produced by nitration reactions starting with nitric acid.
Volatile organic compounds (VOCs) are organic compounds that have a high vapor pressure at room temperature. They are common and exist in a variety of settings and products, not limited to house mold, upholstered furniture, arts and crafts supplies, dry cleaned clothing, and cleaning supplies. VOCs are responsible for the odor of scents and perfumes as well as pollutants. They play an important role in communication between animals and plants, such as attractants for pollinators, protection from predation, and even inter-plant interactions. Some VOCs are dangerous to human health or cause harm to the environment, often despite the odor being perceived as pleasant, such as "new car smell".
Non-methane volatile organic compounds (NMVOCs) are a set of organic compounds that are typically photochemically reactive in the atmosphere—marked by the exclusion of methane. NMVOCs include a large variety of chemically different compounds, such as benzene, ethanol, formaldehyde, cyclohexane, 1,1,1-trichloroethane and acetone. Essentially, NMVOCs are identical to volatile organic compounds (VOCs), but with methane excluded. Methane is excluded in air-pollution contexts because it is not toxic. It is however a very potent greenhouse gas, with low reactivity and thus a long lifetime in the atmosphere. An important subset of NMVOCs are the non-methane hydrocarbons (NMHCs).
In organic chemistry, ozonolysis is an organic reaction where the unsaturated bonds are cleaved with ozone. Multiple carbon–carbon bond are replaced by carbonyl groups, such as aldehydes, ketones, and carboxylic acids. The reaction is predominantly applied to alkenes, but alkynes and azo compounds are also susceptible to cleavage. The outcome of the reaction depends on the type of multiple bond being oxidized and the work-up conditions.
A peroxy acid is an acid which contains an acidic −OOH group. The two main classes are those derived from conventional mineral acids, especially sulfuric acid, and the peroxy derivatives of organic carboxylic acids. They are generally strong oxidizers.
Organic reductions or organic oxidations or organic redox reactions are redox reactions that take place with organic compounds. In organic chemistry oxidations and reductions are different from ordinary redox reactions, because many reactions carry the name but do not actually involve electron transfer. Instead the relevant criterion for organic oxidation is gain of oxygen and/or loss of hydrogen. Simple functional groups can be arranged in order of increasing oxidation state. The oxidation numbers are only an approximation:
In atmospheric chemistry, NOx is shorthand for nitric oxide and nitrogen dioxide, the nitrogen oxides that are most relevant for air pollution. These gases contribute to the formation of smog and acid rain, as well as affecting tropospheric ozone.
Autoxidation refers to oxidations brought about by reactions with oxygen at normal temperatures, without the intervention of flame or electric spark. The term is usually used to describe the gradual degradation of organic compounds in air at ambient temperatures. Many common phenomena can be attributed to autoxidation, such as food going rancid, the 'drying' of varnishes and paints, and the perishing of rubber. It is also an important concept in both industrial chemistry and biology. Autoxidation is therefore a fairly broad term and can encompass examples of photooxygenation and catalytic oxidation.
Denitrifying bacteria are a diverse group of bacteria that encompass many different phyla. This group of bacteria, together with denitrifying fungi and archaea, is capable of performing denitrification as part of the nitrogen cycle. Denitrification is performed by a variety of denitrifying bacteria that are widely distributed in soils and sediments and that use oxidized nitrogen compounds such as nitrate and nitrite in the absence of oxygen as a terminal electron acceptor. They metabolize nitrogenous compounds using various enzymes, including nitrate reductase (NAR), nitrite reductase (NIR), nitric oxide reductase (NOR) and nitrous oxide reductase (NOS), turning nitrogen oxides back to nitrogen gas or nitrous oxide.
In an oil and gas production, flash-gas is a spontaneous vapor that is produced from the heating or depressurization of the extracted oil mixture during different phases of production. Flash evaporation, or flashing, is the process of volatile components suddenly vaporizing from their liquid state. This often happens during the transportation of petroleum products through pipelines and into vessels, such as when the stream from a common separation unit flows into an on-site atmospheric storage tank. Vessels that are used to intentionally “flash” a mixture of gas and saturated liquids are aptly named "flash drums." A type of vapor-liquid separator. A venting apparatus is used in these vessels to prevent damage due to increasing pressure, extreme cases of this are referred to as boiling liquid expanding vapor explosion (BLEVE).
α,β-Unsaturated carbonyl compounds are organic compounds with the general structure (O=CR)−Cα=Cβ-R. Such compounds include enones and enals, but also carboxylic acids and the corresponding esters and amides. In these compounds, the carbonyl group is conjugated with an alkene. Unlike the case for carbonyls without a flanking alkene group, α,β-unsaturated carbonyl compounds are susceptible to attack by nucleophiles at the β-carbon. This pattern of reactivity is called vinylogous. Examples of unsaturated carbonyls are acrolein (propenal), mesityl oxide, acrylic acid, and maleic acid. Unsaturated carbonyls can be prepared in the laboratory in an aldol reaction and in the Perkin reaction.