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C6H6

Benzene, with the chemical formula C₆H₆, is a colorless, volatile, and highly flammable liquid at room temperature, exhibiting a characteristic sweet odor and serving as the simplest and most fundamental aromatic hydrocarbon.^[1] Its molecular structure consists of six carbon atoms arranged in a planar hexagonal ring, with each carbon atom bonded to one hydrogen atom and featuring delocalized π electrons across alternating double bonds, which imparts remarkable chemical stability and defines the aromaticity of the compound.^[2] This unique ring system makes benzene the parent compound for a vast array of derivatives in organic chemistry.^[3] Physically, benzene has a boiling point of 80.1°C, a melting point of 5.5°C, a density of 0.879 g/cm³ at 20°C, and is only slightly soluble in water (approximately 1.8 g/L at 25°C) but highly miscible with organic solvents.^[4] It evaporates rapidly into the air, is heavier than air vapors, and floats on water, contributing to its environmental persistence and potential for widespread dispersal.^[5] Chemically, benzene is relatively unreactive due to its aromatic stability but undergoes electrophilic substitution reactions, such as nitration and sulfonation, which are key to its industrial applications.^[3] Benzene is primarily produced through catalytic reforming of petroleum naphtha fractions, a process that converts low-octane hydrocarbons into high-value aromatics, accounting for the majority of global production of approximately 60 million metric tons annually as of 2022.^[6]^[7] It also occurs naturally in crude oil and is obtained as a byproduct of steam cracking for ethylene production. Industrially, benzene ranks among the top 20 most produced chemicals worldwide and serves as a critical feedstock for manufacturing styrene, phenol, cyclohexane, aniline, detergents, synthetic fibers like nylon, and various plastics, resins, dyes, lubricants, and pesticides.^[5]^[3] Despite its utility, benzene is a well-established human carcinogen, classified as Group 1 by the International Agency for Research on Cancer, primarily linked to acute myeloid leukemia and other blood disorders through bone marrow toxicity and chromosomal damage.^[3] Exposure occurs via inhalation or skin contact in occupational settings, gasoline, tobacco smoke, and environmental sources like vehicle exhaust, with regulatory limits such as 1 ppm for an 8-hour workday enforced by agencies like OSHA to mitigate risks.^[5]

Structure and bonding

Molecular geometry

Benzene (C₆H₆) features a planar, hexagonal ring structure composed of six carbon atoms positioned at the vertices, with each carbon atom bonded to a single hydrogen atom. In the classical Kekulé representation, the molecule is depicted with alternating single and double bonds around the ring, reflecting an early model proposed by Friedrich August Kekulé in 1865.^[8] This structure establishes the foundational symmetry of benzene, though experimental evidence reveals equal bond lengths, indicating a resonance hybrid rather than fixed alternation. All carbon-carbon (C-C) bonds in benzene are equivalent, with a length of approximately 1.39 Å (139 pm), which is intermediate between the typical C-C single bond length of 1.54 Å found in ethane and the C=C double bond length of 1.34 Å observed in ethene.^[9]/01%3A_Structure_and_Bonding/1.13%3A_Ethane_Ethylene_and_Acetylene) These uniform bond lengths, confirmed through X-ray crystallography, arise from the delocalized electron distribution and contribute to the molecule's overall planarity.^[10] Additionally, the carbon-hydrogen (C-H) bonds lie in the same plane as the ring, maintaining the flat geometry. The bond angles in benzene are all 120° for the C-C-C angles within the ring, consistent with the sp² hybridization of each carbon atom, where three sp² hybrid orbitals form sigma bonds in a trigonal planar arrangement.^[9] Each carbon also possesses an unhybridized p orbital perpendicular to the ring plane, which overlaps with adjacent p orbitals to form the pi bonding framework. This results in a delocalized pi electron system encompassing all six carbon atoms, with six pi electrons distributed across the ring.^[11] The sigma bonds provide the skeletal framework, while the pi system enhances the stability of this geometry.

Aromaticity and stability

Benzene is the prototypical aromatic compound, characterized by a cyclic, planar structure with a conjugated system of six π-electrons that satisfies Hückel's rule for aromaticity, which states that a planar, monocyclic, fully conjugated hydrocarbon is aromatic if it contains 4n + 2 π-electrons, where n is a non-negative integer (n = 1 for benzene). This delocalization of π-electrons over the ring leads to enhanced stability compared to non-aromatic analogs. The rule, derived from quantum mechanical calculations on the benzene molecule, predicts that such systems exhibit unique chemical and physical properties due to the symmetric distribution of electrons in molecular orbitals.^[12] The aromatic stabilization of benzene is quantified by its resonance energy, approximately 36 kcal/mol lower than that of hypothetical localized Kekulé structures with alternating single and double bonds. This energy difference arises from the equal contribution of multiple resonance forms, where the actual molecule is a hybrid with equivalent C-C bonds, rather than distinct single and double bonds. Experimental determination of this value comes from comparing the heat of hydrogenation of benzene to that expected for a triene with three isolated double bonds.^[13] In contrast to benzene, the hypothetical non-aromatic 1,3,5-cyclohexatriene, which would feature localized double bonds without delocalization, is unstable and has never been isolated or observed experimentally, as computational studies show it to be a transition state rather than a stable minimum on the potential energy surface. Benzene's stability stems from its molecular orbital configuration, where the six π-electrons fill the three lowest-energy bonding orbitals, forming a closed-shell system with no unpaired electrons, as predicted by Hückel molecular orbital theory.^[12]^[14] Thermodynamically, benzene's aromaticity manifests in its hydrogenation behavior: the experimental heat of hydrogenation is 49.8 kcal/mol, far less exothermic than the 85.8 kcal/mol anticipated for three alkene-like double bonds, with the 36 kcal/mol difference directly attributable to aromatic stabilization. This reduced reactivity toward addition reactions, preferring substitution to preserve the aromatic system, underscores benzene's exceptional thermodynamic stability relative to typical alkenes or polyenes. The planar geometry of the molecule facilitates this π-orbital overlap and delocalization.^[13]

Physical properties

Appearance and phase behavior

Benzene appears as a clear, colorless liquid at room temperature and standard pressure, with a distinctive sweet, aromatic odor often described as gasoline-like. This odor is detectable at concentrations as low as 1.5 to 4.7 parts per million in air. The compound remains liquid under typical ambient conditions but readily evaporates due to its volatility. Benzene has a melting point of 5.53 °C and a normal boiling point of 80.1 °C at 1 atm. Its liquid density is 0.8765 g/cm³ at 20 °C, making it less dense than water. The vapor pressure of benzene is 95.2 mmHg at 25 °C, which contributes to its high tendency to vaporize and form explosive mixtures with air. In its phase diagram, benzene exhibits three phases: solid, liquid, and gas. The solid phase consists of orthorhombic crystals at temperatures below the melting point under atmospheric pressure. The triple point, where all three phases coexist in equilibrium, occurs at 5.53 °C and approximately 36 mmHg. The molar heat capacity of liquid benzene is 136.2 J/mol·K at 25 °C. The standard enthalpy of fusion is 9.87 kJ/mol at the melting point, while the enthalpy of vaporization is 30.8 kJ/mol at the boiling point. These values reflect the energy required for phase transitions and are consistent with benzene's relatively low polarity, which limits its miscibility with water to about 1.8 g/L at 25 °C.

Spectroscopic properties

Benzene is characterized by distinct ultraviolet-visible (UV-Vis) absorption due to electronic transitions within its conjugated π system. The primary π to π* transition occurs as a series of weak bands around 255 nm, corresponding to the promotion of an electron from the highest occupied molecular orbital to the lowest unoccupied molecular orbital in the aromatic ring.^[15] This absorption, with a molar absorptivity (ε) of approximately 230 M⁻¹ cm⁻¹, is indicative of the delocalized nature of the benzene ring and is used for quantitative analysis in solutions.^[15] Infrared (IR) spectroscopy provides vibrational signatures for benzene's functional groups. The aromatic C-H stretching mode appears as a sharp band at about 3030 cm⁻¹, distinguishing it from aliphatic C-H stretches below 3000 cm⁻¹.^[16] Additionally, the C=C stretching vibrations of the ring manifest as multiple bands in the 1450–1600 cm⁻¹ region, typically at 1480 cm⁻¹, 1580 cm⁻¹, and 1600 cm⁻¹, reflecting the symmetric deformation and stretching of the aromatic skeleton.^[16] These features confirm the presence of the unsubstituted benzene moiety in samples. Nuclear magnetic resonance (NMR) spectroscopy highlights benzene's high symmetry. In ¹H NMR, all six protons are chemically equivalent, producing a singlet at 7.27 ppm (relative to tetramethylsilane), a shift typical for aromatic protons deshielded by the ring current.^[17] The ¹³C NMR spectrum similarly shows a single resonance at 128.3 ppm for the six equivalent carbon atoms, underscoring the D_{6h} symmetry that equates all positions. This proton equivalence arises from the molecule's planar, hexagonal geometry with rapid π-electron delocalization.^[17] Mass spectrometry of benzene yields a molecular ion peak at m/z 78 (C₆H₆⁺•), which is the base peak and stable due to the aromatic structure.^[18] Major fragmentation includes loss of a hydrogen atom to form the phenyl cation at m/z 77 (C₆H₅⁺, ~6–8% relative intensity), and further breakdown to the C₄H₃⁺ ion at m/z 51 via ring cleavage.^[18] These patterns aid in identifying benzene and its derivatives in complex mixtures. Raman spectroscopy complements IR by probing symmetric vibrations inactive in IR due to benzene's center of symmetry. The totally symmetric modes include two A_{1g} stretches (breathing and C-H symmetric stretch near 992 cm⁻¹ and 3060 cm⁻¹), an E_{1g} mode, and four E_{2g} deformations, all confirming the D_{6h} point group symmetry. These Raman-active bands, such as the strong line at 992 cm⁻¹ for ring breathing, are used to verify molecular integrity in non-polar environments.

Chemical properties

General reactivity

Benzene exhibits remarkable inertness toward addition reactions that are characteristic of alkenes, such as halogenation or hydrogenation under mild conditions, owing to the exceptional stability imparted by its aromatic π-electron delocalization. This aromatic stabilization energy, approximately 36 kcal/mol relative to hypothetical cyclohexatriene, renders addition across the double bonds energetically unfavorable, as it would disrupt the conjugated system and lead to a loss of resonance energy.^[2] Instead, benzene preferentially undergoes substitution reactions that preserve the aromatic sextet of electrons.^[19] Benzene demonstrates resistance to oxidation under ambient conditions, reflecting its chemical stability, though it combusts readily in air with a characteristic luminous sooty flame due to incomplete oxidation and deposition of carbon particles. This sooty combustion contrasts with the cleaner blue flames of alkanes and alkenes, highlighting the role of the aromatic ring in producing higher soot yields during burning.^[20] In free radical reactions, benzene does not undergo ring halogenation without a catalyst, but alkyl-substituted derivatives, such as toluene, readily experience side-chain halogenation at the benzylic position in the presence of light or heat, facilitated by the stability of the resultant resonance-stabilized radical intermediate.^[21] Hydrogenation of benzene to cyclohexane requires a metal catalyst, such as platinum or nickel, along with elevated temperature and pressure to overcome the activation barrier and disrupt aromaticity, with the overall reaction being exothermic by -49.8 kcal/mol.^[22] Benzene functions as a very weak acid, with the pKa of its C-H bond approximately 43 in DMSO, indicating negligible deprotonation under typical conditions due to the instability of the phenyl anion lacking resonance stabilization.^[23] Similarly, benzene is an extremely weak base, as evidenced by the pKa of its protonated form (benzenium ion) around -23, which underscores its reluctance to accept a proton without strong acid catalysis.^[24]

Electrophilic substitution reactions

Electrophilic aromatic substitution (EAS) is the primary mode of reactivity for benzene, involving the replacement of a hydrogen atom by an electrophile while preserving the aromatic π-system. The general mechanism proceeds via an addition-elimination pathway: the electrophile adds to one of the delocalized π-electrons of the benzene ring, forming a carbocation intermediate known as the Wheland intermediate or σ-complex, in which the ring temporarily loses its aromaticity and adopts sp³ hybridization at the attacked carbon. This intermediate then loses a proton from the same carbon, regenerating the aromatic ring and yielding the substituted product. Nitration of benzene introduces a nitro group (-NO₂) and is achieved by treating benzene with a mixture of concentrated nitric acid (HNO₃) and concentrated sulfuric acid (H₂SO₄) at approximately 50 °C, producing nitrobenzene as the main product. The sulfuric acid acts as a catalyst by protonating nitric acid, generating the nitronium ion (NO₂⁺) as the active electrophile that attacks the benzene ring.^[25] Halogenation substitutes a halogen atom onto the benzene ring and requires a Lewis acid catalyst to generate a potent electrophile from the halogen. For bromination, benzene reacts with bromine (Br₂) in the presence of iron(III) bromide (FeBr₃), yielding bromobenzene; the FeBr₃ coordinates with Br₂ to form a bromonium-like species (Br⁺ equivalent) that serves as the electrophile. Chlorination follows a similar mechanism using chlorine (Cl₂) and iron(III) chloride (FeCl₃) to produce chlorobenzene.^[26] The Friedel-Crafts alkylation attaches an alkyl group to benzene using an alkyl chloride (RCl) and aluminum chloride (AlCl₃) as a Lewis acid catalyst, forming alkylbenzenes such as ethylbenzene from ethyl chloride. However, this reaction often leads to polyalkylation because the initial alkyl-substituted product is more reactive than benzene toward further electrophilic attack, resulting in multiple substitutions unless excess benzene is used. In contrast, the Friedel-Crafts acylation introduces an acyl group (-COR) using an acyl chloride (RCOCl) and AlCl₃, producing acylbenzenes such as acetophenone from acetyl chloride. This reaction is preferred over alkylation for synthetic control, as the deactivating carbonyl group in the product prevents polyacylation and avoids carbocation rearrangements that can occur in alkylation. Sulfonation adds a sulfonic acid group (-SO₃H) to benzene by reaction with fuming sulfuric acid (H₂SO₄ containing SO₃), generating sulfur trioxide (SO₃) as the electrophile to form benzenesulfonic acid. Unlike most EAS reactions, sulfonation is reversible; heating the product with dilute aqueous acid or steam removes the sulfonic group, a property exploited for protecting the benzene ring during multi-step syntheses or for purification purposes.^[27]

Synthesis and production

Laboratory synthesis

Benzene can be synthesized in the laboratory through the decarboxylation of sodium benzoate using soda lime, a historical method suitable for educational demonstrations. In this process, a mixture of sodium benzoate (C₆H₅COONa) and soda lime (a 3:1 mixture of NaOH and CaO) is heated strongly in a dry distillation setup to 220–230 °C, resulting in the elimination of carbon dioxide and formation of benzene vapor, which is collected by condensation.^[28]^[29] The reaction proceeds via the sodium salt decomposing to the free carboxylic acid intermediate, followed by decarboxylation to replace the -COOH group with hydrogen. Typical laboratory yields for this method range from 70% to 90%, depending on the purity of starting materials and heating efficiency, producing 5–10 grams of crude benzene from 20–30 grams of sodium benzoate.^[29] Another approach involves the catalytic trimerization of acetylene (C₂H₂), where three molecules cyclize to form benzene under controlled conditions. This reaction employs catalysts such as nickel complexes or Ziegler-Natta systems (e.g., TiCl₄ with AlEt₃), typically at elevated temperatures of 60–100 °C and moderate pressure to promote selectivity over polymerization side products. The process is exothermic and requires careful handling of acetylene due to its explosiveness, making it less routine but valuable for studying cycloaddition mechanisms; yields can reach 80–95% with optimized catalysts.^[30] Catalytic dehydrogenation of cyclohexane (C₆H₁₂) or cyclohexene provides a reversible route to benzene in laboratory vapor-phase flow reactors. Cyclohexane is passed over supported metal catalysts like platinum or palladium on alumina or ceria at 150–300 °C, facilitating stepwise hydrogen elimination to yield benzene as the primary product, with hydrogen gas as a byproduct.^[31] For cyclohexene, lower temperatures around 150–200 °C suffice, achieving over 80% selectivity to benzene at conversions of 20–50%, though equilibrium limitations require continuous removal of hydrogen to drive the reaction forward.^[32] This method mimics industrial processes but on a microgram-to-gram scale, emphasizing catalyst preparation and reactor design in research settings. Purification of laboratory-synthesized benzene is essential to remove impurities like unreacted starting materials or byproducts. Simple distillation under reduced pressure exploits benzene's boiling point of 80 °C to isolate it from higher-boiling contaminants, often achieving 95–99% purity in a single pass.^[33] For enhanced purity, crystallization can be performed by cooling molten benzene to its freezing point of 5.5 °C in a suitable solvent like acetic acid, though this is less common due to benzene's liquid state at room temperature; alternatively, the sulfonation-desulfonation cycle involves treating crude benzene with fuming sulfuric acid to form water-soluble benzenesulfonic acid, which is isolated, purified by recrystallization, and then desulfonated by heating with dilute aqueous acid or steam at 150–200 °C to regenerate pure benzene.^[34]^[35] These techniques ensure analytical-grade benzene with yields of 85–95% recovery, prioritizing safety given benzene's toxicity.^[33] Unlike large-scale industrial production, laboratory methods emphasize high purity over volume, often integrating multiple purification steps for spectroscopic or synthetic applications.

Industrial production methods

Benzene is primarily produced on an industrial scale through petroleum-derived processes, with global output reaching approximately 62 million metric tons in 2023. Leading producers include China, the United States, and European countries such as Germany and the Netherlands, where integrated refineries and petrochemical complexes dominate manufacturing.^[7]^[36] The principal modern method is catalytic reforming of naphtha fractions from petroleum, which accounts for roughly 45% of benzene production. In this process, low-octane naphtha is heated to about 500 °C in the presence of hydrogen and passed over platinum-rhenium catalysts supported on alumina, promoting dehydrogenation of cycloalkanes, isomerization of alkylcyclopentanes, and cyclization of paraffins to form aromatic compounds. The resulting reformate contains 40-60% aromatics, from which benzene is extracted via solvent processes like sulfolane extraction followed by distillation, co-producing toluene and xylenes (BTX) that enhance overall energy efficiency in aromatics recovery.^[37]^[38] Hydrodealkylation of toluene (HDA) represents another key route, contributing about 25% of global supply. Toluene, often a byproduct from reforming or steam cracking, is reacted with hydrogen at 500-700 °C and 20-60 atmospheres pressure over catalysts such as chromium, molybdenum, or nickel oxides, achieving up to 90% conversion per pass and yielding benzene along with methane as the primary byproduct, which is separated by distillation.^[37]^[38] A smaller portion, approximately 22%, derives from pyrolysis gasoline produced during ethylene steam cracking of naphtha or gas oils, where benzene is recovered through hydrogenation to saturate olefins and subsequent extractive distillation. Coal tar distillation, the original commercial source since the mid-19th century, now supplies only 2-3% worldwide via fractional distillation of light oil fractions from coke ovens, yielding a crude benzene stream containing 60-85% of the target compound.^[37]^[38]

Uses and applications

Solvent and extractant roles

Benzene functions as a nonpolar solvent due to its aromatic structure and low dielectric constant, effectively dissolving nonpolar substances such as fats, oils, waxes, resins, and organic polymers like rubber and plastics.^[1] This solvency arises from its ability to interact via weak van der Waals forces with similar hydrophobic molecules, making it suitable for applications requiring the dissolution of lipophilic materials without promoting ionization.^[39] In industrial extraction processes, benzene plays a key role in dewaxing lubricating oils, where it is combined with ketones such as acetone to selectively separate wax crystals from oil fractions, improving viscosity and pour point characteristics.^[40] It is also employed in the recovery of hydrocarbons from natural sources, including the extraction of essential oils from seeds and nuts, leveraging its miscibility with oily components to facilitate isolation.^[1] Within the paint and varnish industry, benzene historically served as a diluent for drying oils and alkyd resins, aiding in viscosity reduction and uniform application during formulation, though its direct use in consumer products has been largely phased out in favor of less toxic alternatives like toluene.^[41]^[42] In laboratory contexts, benzene is utilized as a recrystallization solvent for purifying organic compounds, where its boiling point and solubility profile allow controlled precipitation upon cooling, as seen in the purification of substances like benzoic acid.^[43] Additionally, it acts as a reaction medium for nonaqueous chemistry, enabling acid-base and other reactions that are incompatible with water, such as proton transfer studies in aprotic environments.^[44] Historically, approximately 12% of benzene production was dedicated to solvent applications, including rubber processing and adhesives, but regulatory restrictions on its carcinogenic potential have significantly reduced this share.^[45]

Chemical precursor applications

Benzene serves as an essential precursor in the chemical industry for synthesizing a wide array of derivatives, with these applications accounting for over 90% of its global consumption. In 2024, worldwide benzene consumption was approximately 51 million metric tons, primarily driven by demand for downstream products in plastics, resins, fibers, and surfactants.^[46] A significant portion of benzene is converted to styrene through the ethylbenzene intermediate. The process begins with the Friedel-Crafts alkylation of benzene using ethylene over a zeolite catalyst to yield ethylbenzene, followed by catalytic dehydrogenation at high temperatures to produce styrene. Styrene is chiefly polymerized to form polystyrene and other copolymers like ABS and SBR, which are used in packaging, automotive parts, and consumer goods. Ethylbenzene represents approximately 48% of global benzene consumption, equivalent to roughly 24 million metric tons annually, supporting a styrene market of about 29 million metric tons in 2024.^[36]^[47] The cumene process utilizes around 20% of benzene production to generate phenol and acetone. Benzene undergoes alkylation with propylene in the presence of a phosphoric acid or zeolite catalyst to form cumene (cumene hydroperoxide intermediate), which is then air-oxidized and cleaved to phenol and acetone. These compounds are critical feedstocks for phenolic resins, polycarbonates, and methyl methacrylate production. Global cumene output reached approximately 17.1 million metric tons in 2024.^[36]^[48] Benzene is also hydrogenated to cyclohexane, comprising about 12% of its usage. This exothermic reaction occurs over a nickel or platinum catalyst at elevated temperatures and pressures, yielding cyclohexane that is subsequently oxidized to cyclohexanone and further to adipic acid via nitric acid oxidation. Adipic acid is a key monomer for nylon-6,6, employed in textiles, carpets, and automotive components. Worldwide cyclohexane production stood at roughly 7.2 million metric tons in 2024.^[36]^[49] Nitrobenzene production involves the nitration of benzene using a mixed acid (nitric and sulfuric) system, followed by selective hydrogenation or reduction to aniline. Aniline serves as a building block for polyurethane foams, rubber chemicals, dyes, and pharmaceuticals such as paracetamol. This pathway consumes about 3% of global benzene, corresponding to nitrobenzene output of approximately 1.2 million metric tons annually.^[50]^[51] In detergent manufacturing, benzene is alkylated with linear C10-C13 olefins using HF or solid acid catalysts to produce linear alkylbenzene (LAB), which is then sulfonated to linear alkylbenzene sulfonates (LAS). LAS acts as the primary surfactant in household and industrial detergents due to its biodegradability and cleaning efficacy. LAB production totaled around 4.4 million metric tons in 2024, accounting for about 10% of benzene consumption.^[52] These transformations largely rely on electrophilic aromatic substitution reactions, enabling selective functionalization of the benzene ring while preserving its stability. As of 2025, emerging trends include exploration of bio-based benzene production to reduce reliance on petroleum feedstocks amid sustainability goals.^[53]^[54]

Health, safety, and environmental impact

Toxicity and health effects

Benzene exposure in humans occurs primarily via inhalation, accounting for about 95% of total uptake, while dermal absorption through intact skin is minimal and ingestion is rare except in cases of contaminated water or food. Acute inhalation at concentrations of 300 to 3,000 ppm can induce central nervous system effects including dizziness, headache, nausea, tremors, and confusion, with higher levels above 10,000 ppm leading to severe CNS depression, unconsciousness, and potentially fatal respiratory arrest.^[55]^[56]^[55] Chronic exposure to benzene, even at low levels above 1 ppm over months to years, suppresses bone marrow function, causing hematological disorders such as leukopenia, anemia, thrombocytopenia, pancytopenia, and aplastic anemia. The American Conference of Governmental Industrial Hygienists recommends a threshold limit value of 0.02 ppm (8-hour time-weighted average) to prevent these non-cancer health effects, reflecting updated evidence of risks at lower concentrations.^[55]^[56]^[57] Benzene undergoes hepatic metabolism primarily via cytochrome P450 2E1 to form benzene oxide, a reactive epoxide that isomerizes to oxepin or is further oxidized to muconaldehyde, a genotoxic dialdehyde that forms DNA adducts and contributes to bone marrow toxicity. These reactive intermediates are key to benzene's myelotoxic effects, as they accumulate in target tissues like the bone marrow.^[58]^[55] Benzene is classified by the International Agency for Research on Cancer as a Group 1 carcinogen, with sufficient evidence from human studies linking it to acute myeloid leukemia and other leukemias through no safe threshold mechanism. Occupational cohort studies, such as those of rubber workers in the Pliofilm production (exposed to cumulative doses exceeding 200 ppm-years), demonstrate a clear dose-response relationship for leukemia risk, with standardized mortality ratios increasing with exposure intensity.^[59]^[60]

Environmental occurrence and regulation

Benzene occurs naturally in the environment from sources such as volcanic emissions and forest fires.^[5] It is also produced through microbial processes in soil, where certain bacteria contribute to its breakdown under aerobic conditions.^[61] Anthropogenic sources dominate overall emissions, including incomplete combustion in vehicle exhaust, evaporation from gasoline (which contains approximately 0.5-2.0% benzene by volume), and industrial processes such as petrochemical manufacturing.^[62]^[63] Benzene exhibits limited persistence in the environment due to rapid volatilization and degradation. In air, it evaporates quickly with a half-life of less than one day, primarily through photooxidation by hydroxyl radicals.^[45] In water and soil, it degrades via microbial activity or photooxidation, with half-lives ranging from 7 to 25 days depending on conditions like oxygen availability and temperature.^[64] These processes help maintain low ambient levels despite ongoing releases. Regulatory measures worldwide aim to limit benzene exposure due to its environmental mobility. In the European Union, the annual average air concentration is capped at 5 µg/m³ to protect human health.^[65] In the United States, benzene is designated as a hazardous air pollutant under the Clean Air Act, subjecting industrial sources to emission controls.^[66] To reduce gasoline-related releases, reformulated gasoline standards implemented in the 1990s limit average benzene content to less than 1% by volume, with current federal averages at 0.62 volume percent.^[62] Environmental monitoring involves national air quality networks that track benzene levels against standards, such as the U.S. Air Quality System database.^[45] For contaminated sites, remediation techniques include bioremediation, where indigenous microbes degrade benzene in soil, and air stripping, which removes volatile benzene from groundwater by transferring it to air for subsequent treatment.^[67]^[68] These methods are often combined with soil vapor extraction to enhance efficiency at petroleum-impacted locations.

References

[1]
Benzene
Insufficient relevant content. The provided text only includes a PubChem page header with a logo and a JavaScript requirement notice, lacking specific details about benzene (C6H6). No chemical formula, molecular weight, structure, properties, uses, production methods, or toxicity/safety information is present.
[2]
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Organic_Chemistry_(Morsch_et_al.)/15:_Benzene_and_Aromaticity/15.02:_Structure_and_Stability_of_Benzene
[3]
BENZENE - Chemical Agents and Related Occupations - NCBI - NIH
Benzene is mainly used to make styrene, phenol, cyclohexane, aniline, maleic anhydride, alkylbenzenes and chlorobenzenes.
[4]
[PDF] Toxicological Profile for Benzene, Draft for Public Comment
Information regarding the physical and chemical properties of benzene is presented in Table 4-2. ... Melting point. 5.558°C. NLM 2023. Boiling point. 80.08°C.
[5]
Benzene | Chemical Emergencies - CDC
Sep 6, 2024 · Benzene is a liquid chemical at room temperature. It either has no color or is light-yellow. It has a sweet smell and is very flammable.Missing: C6H6 properties structure
[6]
Sustainable production of benzene from lignin - PMC
Currently, benzene is dominantly produced from petroleum and coal via catalytic reforming, steam cracking and toluene disproportionation processes, as well as ...
[7]
Bonding in Benzene: the Kekulé Structure - Chemistry LibreTexts
Jan 22, 2023 · Kekulé was the first to suggest a sensible structure for benzene. The carbons are arranged in a hexagon, and he suggested alternating double and single bonds ...Missing: source | Show results with:source
[8]
https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Supplemental_Modules_%28Organic_Chemistry%29/Fundamentals/Bonding_in_Organic_Compounds/Bonding_in_Benzene%253A_the_Kekule_Structure
[9]
Bonding in Benzene - a Modern Orbital View - Chemistry LibreTexts
Jan 22, 2023 · Each carbon atom uses the sp2 hybrids to form sigma bonds with two other carbons and one hydrogen atom. The next diagram shows the sigma ...
[10]
Quantentheoretische Beiträge zum Benzolproblem
Quantentheoretische Beiträge zum Benzolproblem. I. Die Elektronenkonfiguration des Benzols und verwandter Verbindungen. Published: March 1931. Volume 70, pages ...Missing: benzene | Show results with:benzene
[11]
Heats of Organic Reactions. IV. Hydrogenation of Some Dienes and ...
The Resonance Energy of Benzene: A Revisit. The Journal of Physical Chemistry A 2009, 113 (17) , 5163-5169. https://doi.org/10.1021/jp808941h. Arkadiusz ...
[12]
1,3,5-Cyclohexatriene captured in computro; the importance of ...
Jul 30, 2002 · Since 1,3,5-cyclohexatriene as such does not exist, it was proposed to compare the energy of benzene with that of a polyene-like 1,3,5- ...Missing: unstable | Show results with:unstable
[13]
UV-Visible Spectroscopy - MSU chemistry
Benzene exhibits very strong light absorption near 180 nm (ε > 65,000) , weaker absorption at 200 nm (ε = 8,000) and a group of much weaker bands at 254 nm (ε = ...
[14]
15.7 Spectroscopy of Aromatic Compounds - Organic Chemistry
Sep 20, 2023 · The aromatic C–H band at 3030 cm–1 generally has low intensity and occurs just to the left of a typical saturated C–H band. As many as four ...
[15]
Benzene
**Summary of Benzene Mass Spectrum Peaks:**
[16]
Benzene and Other Aromatic Compounds - MSU chemistry
The enhanced stability, often referred to as aromatic stabilization, ranges (in the above cases) from a low of 16 kcal/mol for furan to 36 kcal/mol for benzene.Missing: original source
[17]
[PDF] ARENES. ELECTROPH AROMAT C SUBST - Caltech Authors
The electron pair of this C-H bond then becomes part of the aromatic n-electron system and a substitution product of benzene, C,H,X, is formed. electrophilic ...Missing: inertness | Show results with:inertness
[18]
[PDF] Ch17 Reactions of Aromatic Compounds
Side Chain Halogenation Alkyl benzenes undergo free radical halogenation very easily at the benzylic position, since the required intermediate radical is a ...
[19]
Bordwell pKa Table - Organic Chemistry Data
pKa is an acid dissociation constant describing acidity, related to a molecule's structure. The Bordwell pKa table is a compilation of pKa values in DMSO.
[20]
[PDF] values to know 1. Protonated carbonyl pKa
Protonated carbonyl pKa = -7, carboxylic acid pKa = 4-5, phenol pKa = 10, alcohol pKa = 16-18, and amine pKa = 38-40.
[21]
The Nitration of Benzene - Chemistry LibreTexts
Jan 22, 2023 · Benzene is treated with a mixture of concentrated nitric acid and concentrated sulfuric acid at a temperature not exceeding 50°C.
[22]
The Halogenation of Benzene - Chemistry LibreTexts
Jan 22, 2023 · The reaction with bromine. The reaction between benzene and bromine in the presence of either aluminum bromide or iron gives bromobenzene.
[23]
Nitration and Sulfonation of Benzene - Chemistry LibreTexts
Jan 22, 2023 · The first step in the nitration of benzene is to activate HNO 3 with sulfuric acid to produce a stronger electrophile, the nitronium ion.Nitration of Benzene · Sulfonation of Benzene · Further Applications of...
[24]
https://pubs.acs.org/doi/10.1021/ja012613x
[25]
[PDF] Preparation of benzene, compiled by CHROMIUM, special ...
This experiment was repeated with other members. Ordenblitz used 7 g of NaOH and 25g sodium benzoate that were roughly crushed together in a mortar and pestle.
[26]
Catalytic Reactions of Acetylene: A Feedstock for the Chemical ...
Although the reaction itself is very exothermic and forms a stable molecule, temperatures around 600–700 °C are required for it to proceed in the absence of a ...
[27]
Page not found | Nature
Insufficient relevant content.
[28]
Reversible dehydrogenation and rehydrogenation of cyclohexane ...
Mar 1, 2022 · Here we used the as-prepared Pt1/CeO2 single-site catalyst for the catalytic cyclohexane dehydrogenation reaction (Supplementary Fig. 2).
[29]
[PDF] Purification of Laboratory Chemicals, Sixth Edition - Neilson Lab
To help in applying this information, two chapters describe the more common processes currently used for purification in chemical laboratories and give fuller ...
[30]
Desulfonation - an overview | ScienceDirect Topics
Desulfonation is defined as the process of removing a sulfonic acid group from a compound, which can occur in dilute aqueous acid as part of the reversible ...
[31]
https://www.nature.com/articles/s41467-022-28888-4
[32]
Benzene Market Report | Forecast [2033]
In 2023, the region produced approximately 6.5 million metric tons of benzene, with Germany, the Netherlands, and Belgium as key producers. Demand is led by ...
[33]
[PDF] Locating and Estimating Air Emissions from Sources of Benzene pt. 1
This report has been reviewed by the Office of Air Quality Planning and Standards, U.S.. Environmental Protection Agency, and has been approved for publication.
[34]
[PDF] Benzene, Toluene, Xylene - eere.energy.gov
The new production methods were based on the catalytic reforming of naphtha, and by 1980 they had gradually eliminated the use of coal tar.
[35]
BENZENE - Ataman Kimya
Benzene is used as a constituent in motor fuels; as a solvent for fats, waxes, resins, oils, inks, paints, plastics, and rubber; in the extraction of oils from ...
[36]
Recent Advances in Solvent Dewaxing
SOLVENT DEWAXING OF LUBRICATING oils found its first commercial application in. 1927 when Indian Refining Company started its original acetone-benzene ...
[37]
7 Types of Solvents for Coatings&Paints - Doxu Chemical
Jan 25, 2024 · Benzene: Used in combination with butyl acetate, acetone, and butanol; benzene vapor is highly toxic to the human body and tends to be phased ...
[38]
http://www1.eere.energy.gov/manufacturing/resources/chemicals/pdfs/profile_chap4.pdf
[39]
[PDF] RECRYSTALLISATION Never heat organic solvents with a Bunsen ...
The purification of a solid by recrystallisation depends upon the fact that different substances have different solubilities in different solvents.
[40]
[PDF] Acid-base reactions in benzene and other organic solvents
Benzene was used as reference solvent for CHaOD or DzO. Nitrobenzene was found to produce a small but measurable shift, and acetonitrile, oxygen com- pounds ...
[41]
[PDF] Benzene - Withdrawn provided for historical reference only - OSHA
About 87% is used chiefly as an intermediate in producing other chemicals such as phenol, cyclohexane, and styrene. The remaining 13% is used primarily in the ...
[42]
[PDF] Toxicological Profile for Benzene, Draft for Public Comment
Benzene is released to the environment by both natural and industrial sources, although the anthropogenic emissions are undoubtedly the most important.
[43]
Benzene and its Derivatives Market Size & Share [2034]
Oct 24, 2025 · In 2024, global benzene consumption exceeded 41 million metric tons, with derivatives like ethylbenzene accounting for 28 million metric tons.
[44]
Styrene Market Size, Share, Growth, and Forecast, 2035
The global Styrene market stood at approximately 42 million tonnes in 2024 and is expected to grow at a CAGR of 4.37% during the forecast period until 2035.
[45]
Cumene Supply and Demand 2025-2034 - Expert Market Research
The global cumene market stood at a volume of around 17100.00 Kilo Tons in 2024. The market is estimated to grow at a CAGR of 3.50% between 2025 and 2034.
[46]
Cyclohexane Market Size, Share, Trends, Growth & Forecast 2035
The global Cyclohexane market had a size of roughly at approximately 7236 thousand tonnes in 2024 and is anticipated to grow at a CAGR of 3.9% during the ...
[47]
Nitrobenzene Market Size, Share | Global Industry Report, 2032
The global Nitro Benzene market stood at approximately 1170 thousand tonnes in 2022 and is anticipated to grow at a CAGR of 5% during the forecast period ...
[48]
Nitrobenzene | C6H5NO2 | CID 7416 - PubChem - NIH
9.1 Uses. The majority of nitrobenzene is used to manufacture aniline, which is a chemical used in the manufacture of polyurethane. Nitrobenzene is also used ...
[49]
Linear Alkyl Benzene Market Size, Share and Forecast, 2035
The global Linear Alkyl Benzene (LAB) market has expanded remarkably to reach approximately 4406 thousand tonnes in 2024 and is expected to grow at a CAGR of 4 ...
[50]
None
### Summary of Benzene Uses, Derivatives, Production Methods, and Statistics
[51]
HEALTH EFFECTS - Toxicological Profile for Benzene - NCBI - NIH
These findings suggest that benzene may induce toxic effects on the nervous system involving peripheral nerves and/or spinal cord. The limitations of this study ...DISCUSSION OF HEALTH... · TOXICOKINETICS · BIOMARKERS OF...
[52]
[PDF] Benzene | EPA
Benzene has a sweet odor with an ASTDR reported odor threshold of 1.5 ppm (5 mg/m. 3. ). The vapor pressure for benzene is 95.2 mm Hg at 25 °C, and it has a ...Missing: appearance | Show results with:appearance
[53]
BENZENE - ACGIH
BENZENE. CAS number: 71-43-2. Synonyms: Benzol; Coal naphtha; Cyclohexatriene; Phenyl hydride. Molecular formula: C6H6. Structural formula: TLV®-TWA ...Missing: 0.5 | Show results with:0.5
[54]
The Fate of Benzene Oxide - PMC - NIH
Benzene is initially metabolized via cytochromes P450 (primarily CYP2E1 in liver) to benzene oxide, which subsequently gives rise to a number of secondary ...
[55]
IARC Monographs Volume 120: Benzene
Dec 19, 2018 · ... carcinogenicity of benzene, updating the most recent ... An IARC Monographs Working Group reviewed epidemiological evidence, animal cancer ...
[56]
Leukemia in benzene workers - PubMed
Among 748 workers who had at least one day of exposure to benzene between 1940 and 1950, seven deaths from leukemia occurred.
[57]
PUBLIC HEALTH STATEMENT - Toxicological Profile for Benzene
Lower levels (700–3,000 ppm) can cause drowsiness, dizziness, rapid heart rate, headaches, tremors, confusion, and unconsciousness. In most cases, people will ...
[58]
Gasoline Mobile Source Air Toxics | US EPA
Sep 19, 2025 · Air toxics include benzene and other hydrocarbons such as 1,3-butadiene, formaldehyde, acetaldehyde, acrolein, and naphthalene.Missing: EU quality Clean phase- out
[59]
Benzene Exposure and Cancer Risk from Commercial Gasoline ...
Feb 15, 2021 · Generally, gasoline in the United States is likely to contain 0.5%–2.0% benzene by volume [14,15].
[60]
POTENTIAL FOR HUMAN EXPOSURE - NCBI - NIH
A half-life of 16.9 days was reported for photolysis of benzene ... Additional data characterizing the concentration of benzene in drinking water, air, and soil ...
[61]
EU air quality standards - Environment - European Commission
EU air quality standards ; 0.5 µg/m · 1 year, Limit value to be met as of 1.1.2005 (or 1.1.2010 in the immediate vicinity of specific, notified industrial sources ...
[62]
Initial List of Hazardous Air Pollutants with Modifications | US EPA
Under the Clean Air Act, EPA is required to regulate emissions of hazardous air pollutants. ... Benzene (including benzene from gasoline). 92875, Benzidine.
[63]
Remediation of soils combining soil vapor extraction and ...
This work reports the study of the combination of soil vapor extraction (SVE) with bioremediation (BR) to remediate soils contaminated with benzene.Missing: stripping | Show results with:stripping
[64]
[PDF] Groundwater Fact Sheet Benzene
It also occurs naturally in volcanic gases and smoke resulting from forest fires. Benzene can get into drinking water from industrial discharge, gas storage ...Missing: emissions | Show results with:emissions