Chemistry

IUPAC Name: Aniline Molecular Formula: C6H7N Molecular Weight: 93.13 g/mol EINECS: 200-539-3 Classification Code: Carcinogens; Human Data; Mutation data; Noxae; Reproductive Effect; Skin / Eye Irritant Melting Point: -6.2 C storage temp.: 2-8 C Water Solubility: 36 g/L (20 C) Stability: Stable. Incompatible with oxidizing agents, bases, acids, iron and iron salts, zinc, aluminium. Light sensitive. Combustible. Index of Refraction: 1.579 Molar Refractivity: 30.48 cm3 Molar Volume: 91.7 cm3 Surface Tension: 41.7 dyne/cm Density: 1.015 g/cm3 Flash Point: 70 C Enthalpy of Vaporization: 42.44 kJ/mol Boiling Point: 184.4 C at 760 mmHg Vapour Pressure of Aniline (CAS NO.62-53-3): 0.733 mmHg at 25 C History Aniline was first isolated from the destructive distillation of indigo in 1826 by Otto Unverdorben,who named it crystalline. In 1834, Friedrich Runge isolated from coal tar a substance that produced a beautiful blue colour on treatment with chloride of lime, which he named kyanol or cyanol. In 1841, C. J. Fritzsche showed that, by treating indigo with caustic potash, it yielded an oil, which he named aniline,

from the specific name of one of the indigo-yielding plants, Indigofera anil, anil being derived from the Sanskrit nla, dark-blue, and nl, the indigo plant. About the same time N. N. Zinin found that, on reducing nitrobenzene, a base was formed, which he named benzidam. August Wilhelm von Hofmann investigated these variously-prepared substances, and proved them to be identical (1855), and thenceforth they took their place as one body, under the name aniline or phenylamine. Its first industrial-scale use was in the manufacture of mauveine, a purple dye discovered in 1856 by Hofmann's student William Henry Perkin. At the time of mauveine's discovery, aniline was an expensive laboratory compound, but it was soon prepared "by the ton" using a process previously discovered by Antoine Bchamp. The synthetic dye industry grew rapidly as new aniline-based dyes were discovered in the late 1850s and 1860s. Uses Aniline is the simplest and one of the most important aromatic amines, being used as a precursor to more complex chemicals. Aniline's main application is in the manufacture of polyurethane. It is used to stain neural RNA blue in the Nissl stain. When polymerised, aniline can be used as a type of nanowire for use as a semiconducting electrode bridge, most recently used for nano-scale devices such as biosensors. Aniline is used in the rubber industry for the manufacture of various vulcanization accelerators and age resistors. Aniline is also used in the production of herbicides, dyes and pigments, and specialty fibers. Production Aniline is an important derivative of benzene that can be made in two steps by nitration to nitrobenzene and either catalytic hydrogenation or acidic metal reduction to aniline. C6H6 + HNO3 C6H5NO2 + H2O C6H5NO2 + 3H2 C6H5NH2 + 2H2O Both steps occur in excellent yield. The reaction of ammonia and phenol is also being used for

aniline production. C6H6OH + NH3 C6H5NH2 + H2O Toxicity Data With Reference Test Organism Typ Route e Reported Dose Effect (Normalize d Dose) Source Archives of Environmental Contamination and Toxicology. Vol. 12, Pg. 355, 1983. U.S. Public Health Service, Public Health Bulletin. Vol. 271, Pg. 4, 1941. Gigiena Truda i Professional'nye Zabolevaniya. Labor Hygiene and Occupational Diseases. Vol. 13(5), Pg. 29, 1969. "Abdernalden's Handbuch der Biologischen Arbeitsmethoden." Vol. 4, Pg. 1301, 1935. "Abdernalden's Handbuch der Biologischen

bird - wild

LD5 oral 0

562mg/kg (562mg/kg)

cat

LCLo inhalation

180ppm/8H (180ppm)

cat

LD5 skin 0

254mg/kg (254mg/kg)

cat

LDLo oral

100mg/kg (100mg/kg)

cat

LDLo subcutaneou 100mg/kg s (100mg/kg)

Test Organism Typ Route e

Reported Dose Effect (Normalize d Dose)

Source Arbeitsmethoden." Vol. 4, Pg. 1301, 1935.

child

TDL o

oral

Journal of LUNGS, 3125mg/kg Toxicology, THORAX, OR (3125mg/kg Clinical RESPIRATION ) Toxicology. Vol. : CYANOSIS 26, Pg. 357, 1988. 195mg/kg (195mg/kg) National Technical Information Service. Vol. PB214-270, National Technical Information Service. Vol. PB214-270, National Technical Information Service. Vol. PB214-270, Office of Toxic Substances Report. Vol. OTS, Office of Toxic Substances Report. Vol. OTS, Toxicology and Applied Pharmacology.

dog

LD5 oral 0

dog

LDLo intravenous

200mg/kg (200mg/kg) 1540mg/kg (1540mg/kg ) 100mg/kg (100mg/kg) 400mg/kg (400mg/kg) 1290mg/kg (1290mg/kg )

dog

LDLo skin

LD5 intraperiton guinea pig 0 eal LD5 guinea pig oral 0 guinea pig LD5 skin 0

Test Organism Typ Route e

Reported Dose Effect (Normalize d Dose)

Source Vol. 7, Pg. 559, 1965. Gigiena Truda i Professional'nye Zabolevaniya. Labor Hygiene and Occupational Diseases. Vol. 32(10), Pg. 25, 1988. Gigiena Truda i Professional'nye Zabolevaniya. Labor Hygiene and Occupational Diseases. Vol. 32(10), Pg. 25, 1988. "Poisoning; Toxicology, Symptoms, Treatments," 2nd ed., Arena, J.M., Springfield, IL, C.C. Thomas, 1970Vol. 2, Pg. 73, 1970. Journal of Industrial Hygiene. Vol. 13, Pg. 87, 1931.

mammal (species LC5 unspecifie 0 d)

inhalation

2500mg/m3 (2500mg/m 3)

mammal (species LD5 oral unspecifie 0 d)

500mg/kg (500mg/kg)

man

LDLo unreported

150mg/kg (150mg/kg)

man

LDLo unreported

350mg/kg (350mg/kg)

Test Organism Typ Route e LC5 0

Reported Dose Effect (Normalize d Dose) 175ppm/7H (175ppm)

Source National Technical Information Service. Vol. PB214-270, Izvestiya Sibirskogo Otdeleniya Akademii Nauk SSSR, Seriya Biologomeditsinski kh Nauk. Vol. 3, Pg. 91, 1965. Gigiena Truda i Professional'nye Zabolevaniya. Labor Hygiene and Occupational Diseases. Vol. 13(5), Pg. 29, 1969. ArzneimittelForschung. Drug Research. Vol. 8, Pg. 107, 1958. Archives of Environmental Contamination and Toxicology. Vol. 12, Pg. 355, 1983. National Technical

mouse

inhalation

mouse

LD5 intraperiton 0 eal

492mg/kg (492mg/kg)

mouse

LD5 oral 0

464mg/kg (464mg/kg)

mouse

LD5 subcutaneou 200mg/kg 0 s (200mg/kg)

quail

LD5 oral 0

750mg/kg (750mg/kg)

rabbit

LD5 intravenous 64mg/kg

Test Organism Typ Route e 0

Reported Dose Effect (Normalize d Dose) (64mg/kg)

Source Information Service. Vol. PB214-270, Toxicology and Applied Pharmacology. Vol. 7, Pg. 559, 1965. "Abdernalden's Handbuch der Biologischen Arbeitsmethoden." Vol. 4, Pg. 1301, 1935. Medicina del Lavoro. Industrial Medicine. Vol. 28, Pg. 112, 1937. Journal of Industrial Hygiene and Toxicology. Vol. 31, Pg. 343, 1949. Archiv fuer Gewerbepathologi e und Gewerbehygiene. Vol. 15, Pg. 447, 1957. Journal of

rabbit

LD5 skin 0

820uL/kg (0.82mL/kg)

rabbit

LDLo oral

500mg/kg (500mg/kg)

rabbit

LUNGS, 1gm/kg THORAX, OR subcutaneou LDLo (1000mg/kg RESPIRATION s ) : OTHER CHANGES 250ppm/4H (250ppm)

rat

LCLo inhalation

rat

LD5 intraperiton 0 eal

420mg/kg (420mg/kg)

rat

LD5 oral

250mg/kg

Test Organism Typ Route e

Reported Dose Effect (Normalize d Dose) (250mg/kg)

Source Pharmacology and Experimental Therapeutics. Vol. 90, Pg. 260, 1947. Archiv fuer Gewerbepathologi e und Gewerbehygiene. Vol. 15, Pg. 447, 1957

rat

LD5 skin 0

1400mg/kg (1400mg/kg )

Safety Profile Hazard Codes: T, N, F Risk Statements: 23/24/25-40-41-43-48/23/24/25-50-6848/20/21/22-39/23/24/25-11 R23/24/25:Toxic by inhalation, in contact with skin and if swallowed. R40:Limited evidence of a carcinogenic effect. R41:Risk of serious damage to the eyes. R43:May cause sensitization by skin contact. R48:Danger of serious damage to health by prolonged exposure. R50:Very toxic to aquatic organisms. R68:Possible risk of irreversible effects. R20/21/22:Harmful by inhalation, in contact with skin and if swallowed. R39:Danger of very serious irreversible effects. R11:Highly flammable. Safety Statements: 26-27-36/37/39-45-46-61-36/37 S26: In case of contact with eyes, rinse immediately with plenty of water and seek medical advice. S27:Take off immediately all contaminated clothing. S36/37/39:Wear suitable protective clothing, gloves and eye/face protection. S45:In case of accident or if you feel unwell, seek medical advice immediately (show the label whenever possible.) S46:If swallowed, seek medical advice immediately and show this container or label. S61:Avoid release to the environment. Refer to special instructions / safety data sheets. S36/37:Wear suitable protective clothing and gloves. RIDADR: UN 1547 6.1/PG 2 WGK Germany: 2 RTECS of Aniline (CAS NO.62-53-3): BW6650000 Standards and Recommendations OSHA PEL: TWA 2 ppm (skin) ACGIH TLV: TWA 2 ppm (skin); Animal Carcinogen; BEI: 50 mg/g creatinine of total p-aminophenol in urine at end of shift or 1.5% of hemoglobin for methemoglobin in blood

during or end of shift. DFG MAK: 2 ppm (7.7 mg/m3), Confirmed Animal Carcinogen with Unknown Relevance to Humans; BAT: 1 mg/L in urine at end of shift DOT Classification: 6.1; Label: Poison Analytical Methods For occupational chemical analysis use NIOSH: Amines, Aromatic, 2002. Specification Aniline (CAS NO.62-53-3), its Synonyms are Aminobenzene ; Aminophen ; Anilin ; Aniline and homologs ; Aniline and homologues ; Benzenamine ; Benzene, amino ; Benzidam ; Blue Oil . It is a yellowish to brownish oily liquid with a musty fishy odor. ANILINE 3. Hazards Identification Emergency Overview -------------------------DANGER! MAY BE FATAL IF SWALLOWED, INHALED OR ABSORBED THROUGH SKIN. CAUSES IRRITATION TO SKIN, EYES AND RESPIRATORY TRACT. COMBUSTIBLE LIQUID AND VAPOR. MAY CAUSE METHEMOGLOBINEMIA. AFFECTS BLOOD, CARDIOVASCULAR SYSTEM, CENTRAL NERVOUS SYSTEM, LIVER AND KIDNEYS. Inhalation: Toxic. Affects ability of blood to carry oxygen. Symptoms may include bluish discoloration of lips and tongue, severe headache, nausea, confusion, dizziness, shock, respiratory paralysis, death. Ingestion: Toxic. Lethal dose may be as little as one gram. Symptoms of ingestion parallel those of inhalation exposure. Skin Contact: May be absorbed through skin. Symptoms of skin absorption parallel those from inhalation exposure. May cause skin

irritation. Local contact may cause dermatitis. Eye Contact: Vapor is an eye irritant. May cause tearing, blurred vision. Splashes may cause corneal damage. Chronic Exposure: Aniline is a blood toxin, causing hemoglobin to convert to methemoglobin, resulting in cyanosis. Lengthy or repeated exposures may result in decreased appetite, anemia, weight loss, nervous system affects, and kidney, liver and bone marrow damage. Any exposure may cause an allergic skin reaction. Aggravation of Pre-existing Conditions: Persons with pre-existing skin disorders or eye problems or impaired liver or kidney function may be more susceptible to the effects of the substance. A NIOSH study reported an excess bladder cancer risk in workers exposed to aniline in combination with other dyestuffs and intermediates, although it is not clear which of these materials, or combinations, were responsible for the higher incidence of bladder cancer. Based on the results of this study , historical epidemiology evidence which shows no correlation of pure aniline with bladder cancer, and experimental test results, it was concluded that aniline, most likely, is not responsible for the increased incidence of bladder tumors in the NIOSH study. 4. First Aid Measures Inhalation: If inhaled, remove to fresh air. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Do not give mouth to mouth resuscitation. CALL A PHYSICIAN IMMEDIATELY. Ingestion: Induce vomiting immediately as directed by medical personnel. Never give anything by mouth to an unconscious person. Skin Contact: In case of contact, immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse. Thoroughly clean shoes before reuse. Get medical attention immediately.

Eye Contact: Immediately flush eyes with plenty of water for at least 15 minutes, lifting lower and upper eyelids occasionally. Get medical attention immediately. 5. Fire Fighting Measures Fire: Flash point: 70C (158F) CC Autoignition temperature: 615C (1139F) Flammable limits in air % by volume: lel: 1.3; uel: 11.0 Combustible liquid and vapor. Flammable when exposed to heat or flame. Contact with strong oxidizers may cause fire or explosion. Explosion: Above flash point, vapor-air mixtures are explosive within flammable limits noted above. Sealed containers may rupture when heated. Fire Extinguishing Media: Dry chemical, foam, carbon dioxide, or water spray. Special Information: In the event of a fire, wear full protective clothing and NIOSHapproved self-contained breathing apparatus with full facepiece operated in the pressure demand or other positive pressure mode. Use water spray to blanket fire, cool fire exposed containers, and to flush non-ignited spills or vapors away from fire. 8. Exposure Controls/Personal Protection Airborne Exposure Limits: -OSHA Permissible Exposure Limit (PEL): 5 ppm (TWA) skin -ACGIH Threshold Limit Value (TLV): 2 ppm (TWA) skin Skin Protection: Wear impervious protective clothing, including boots, gloves, lab coat, apron or coveralls, as appropriate, to prevent skin contact.

Eye Protection: Use chemical safety goggles and/or a full face shield where splashing is possible. Maintain eye wash fountain and quickdrench facilities in work area. Other Control Measures: Provide clean work clothes daily to workers who regularly use this material. Wash hands before eating and do not eat, drink, or smoke in workplace.

10. Stability and Reactivity Stability: Stable under ordinary conditions of use and storage. Discolors on exposure to light. Hazardous Decomposition Products: Burning may produce carbon monoxide, carbon dioxide, nitrogen oxides. Hazardous Polymerization: Will not occur. Incompatibilities: Strong acids and strong oxidizers, albumin, solutions of iron, zinc, aluminum, toluene diisocyanate, and alkalis. Ignites spontaneously in the presence of red fuming nitric acid, and with sodium. Conditions to Avoid: Heat, flames, ignition sources and incompatibles.