p-phenylenediamine

H301: Toxic if swallowed [Danger Acute toxicity, oral]

H311: Toxic in contact with skin [Danger Acute toxicity, dermal]

H317: May cause an allergic skin reaction [Warning Sensitization, Skin]

H319: Causes serious eye irritation [Warning Serious eye damage/eye irritation]

H331: Toxic if inhaled [Danger Acute toxicity, inhalation]

H400: Very toxic to aquatic life [Warning Hazardous to the aquatic environment, acute hazard]

H410: Very toxic to aquatic life with long lasting effects [Warning Hazardous to the aquatic environment, long-term hazard]

P261, P262, P264, P264+P265, P270, P271, P272, P273, P280, P301+P316, P302+P352, P304+P340, P305+P351+P338, P316, P321, P330, P333+P317, P337+P317, P361+P364, P362+P364, P391, P403+P233, P405, and P501 (click each P-code to see the statement)

H301+H311+H331 (43.2%): Toxic if swallowed, in contact with skin or if inhaled [Danger Acute toxicity, oral; acute toxicity, dermal; acute toxicity, inhalation]

H301 (99.7%): Toxic if swallowed [Danger Acute toxicity, oral]

H311 (99.7%): Toxic in contact with skin [Danger Acute toxicity, dermal]

H317 (99.8%): May cause an allergic skin reaction [Warning Sensitization, Skin]

H319 (99.7%): Causes serious eye irritation [Warning Serious eye damage/eye irritation]

H331 (99.7%): Toxic if inhaled [Danger Acute toxicity, inhalation]

H370 (38.9%): Causes damage to organs [Danger Specific target organ toxicity, single exposure]

H400 (98.3%): Very toxic to aquatic life [Warning Hazardous to the aquatic environment, acute hazard]

H410 (99.7%): Very toxic to aquatic life with long lasting effects [Warning Hazardous to the aquatic environment, long-term hazard]

P260, P261, P262, P264, P264+P265, P270, P271, P272, P273, P280, P301+P316, P302+P352, P304+P340, P305+P351+P338, P308+P316, P316, P321, P330, P333+P317, P337+P317, P361+P364, P362+P364, P391, P403+P233, P405, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 597 reports by companies from 32 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

Information may vary between notifications depending on impurities, additives, and other factors. The percentage value in parenthesis indicates the notified classification ratio from companies that provide hazard codes. Only hazard codes with percentage values above 10% are shown. For more detailed information, please visit ECHA C&L website.

H320: Causes eye irritation [Warning Serious eye damage/eye irritation]

H334: May cause allergy or asthma symptoms or breathing difficulties if inhaled [Danger Sensitization, respiratory]

H370: Causes damage to organs [Danger Specific target organ toxicity, single exposure]

H372: Causes damage to organs through prolonged or repeated exposure [Danger Specific target organ toxicity, repeated exposure]

P233, P260, P261, P264, P264+P265, P270, P271, P272, P273, P280, P284, P301+P316, P302+P352, P304+P340, P305+P351+P338, P308+P316, P316, P319, P321, P330, P333+P317, P337+P317, P342+P316, P362+P364, P391, P403, P403+P233, P405, and P501 (click each P-code to see the statement)

H315: Causes skin irritation [Warning Skin corrosion/irritation]

H373: May causes damage to organs through prolonged or repeated exposure [Warning Specific target organ toxicity, repeated exposure]

P233, P260, P261, P264, P264+P265, P270, P271, P272, P273, P280, P284, P301+P316, P302+P352, P304+P340, P305+P351+P338, P308+P316, P316, P319, P321, P330, P332+P317, P333+P317, P337+P317, P342+P316, P362+P364, P391, P403, P403+P233, P405, and P501 (click each P-code to see the statement)

H318: Causes serious eye damage [Danger Serious eye damage/eye irritation]

H333: May be harmful if inhaled [Warning Acute toxicity, inhalation]

P233, P260, P261, P264, P264+P265, P270, P271, P272, P280, P284, P301+P316, P302+P352, P304+P317, P304+P340, P305+P354+P338, P308+P316, P317, P319, P321, P330, P332+P317, P333+P317, P342+P316, P362+P364, P403, P405, and P501 (click each P-code to see the statement)

Fresh air, rest. Half-upright position. Refer for medical attention.

First rinse with plenty of water for at least 15 minutes, then remove contaminated clothes and rinse again. Refer for medical attention .

First rinse with plenty of water for several minutes (remove contact lenses if easily possible), then refer for medical attention.

Rinse mouth. Give a slurry of activated charcoal in water to drink. Refer for medical attention .

EYES: First check the victim for contact lenses and remove if present. Flush victim's eyes with water or normal saline solution for 20 to 30 minutes while simultaneously calling a hospital or poison control center. Do not put any ointments, oils, or medication in the victim's eyes without specific instructions from a physician. IMMEDIATELY transport the victim after flushing eyes to a hospital even if no symptoms (such as redness or irritation) develop.

SKIN: IMMEDIATELY flood affected skin with water while removing and isolating all contaminated clothing. Gently wash all affected skin areas thoroughly with soap and water. If symptoms such as redness or irritation develop, IMMEDIATELY call a physician and be prepared to transport the victim to a hospital for treatment.

INHALATION: IMMEDIATELY leave the contaminated area; take deep breaths of fresh air. If symptoms (such as wheezing, coughing, shortness of breath, or burning in the mouth, throat, or chest) develop, call a physician and be prepared to transport the victim to a hospital. Provide proper respiratory protection to rescuers entering an unknown atmosphere. Whenever possible, Self-Contained Breathing Apparatus (SCBA) should be used; if not available, use a level of protection greater than or equal to that advised under Protective Clothing.

INGESTION: DO NOT INDUCE VOMITING. If the victim is conscious and not convulsing, give 1 or 2 glasses of water to dilute the chemical and IMMEDIATELY call a hospital or poison control center. Be prepared to transport the victim to a hospital if advised by a physician. If the victim is convulsing or unconscious, do not give anything by mouth, ensure that the victim's airway is open and lay the victim on his/her side with the head lower than the body. DO NOT INDUCE VOMITING. IMMEDIATELY transport the victim to a hospital. (NTP, 1992)

(General first aid procedures)

Eye: Irrigate immediately - If this chemical contacts the eyes, immediately wash (irrigate) the eyes with large amounts of water, occasionally lifting the lower and upper lids. Get medical attention immediately.

Skin: Soap wash promptly - If this chemical contacts the skin, promptly wash the contaminated skin with soap and water. If this chemical penetrates the clothing, promptly remove the clothing and wash the skin with soap and water. Get medical attention promptly.

Breathing: Respiratory support

Swallow: Medical attention immediately - If this chemical has been swallowed, get medical attention immediately.

Excerpt from ERG Guide 153 [Substances - Toxic and/or Corrosive (Combustible)]:

SMALL FIRE: Dry chemical, CO2 or water spray.

LARGE FIRE: Dry chemical, CO2, alcohol-resistant foam or water spray. If it can be done safely, move undamaged containers away from the area around the fire. Dike runoff from fire control for later disposal.

FIRE INVOLVING TANKS, RAIL TANK CARS OR HIGHWAY TANKS: Fight fire from maximum distance or use unmanned master stream devices or monitor nozzles. Do not get water inside containers. Cool containers with flooding quantities of water until well after fire is out. Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank. ALWAYS stay away from tanks in direct contact with flames. (ERG, 2024)

Use water spray, powder.

WATER, CARBON DIOXIDE, DRY CHEM ... .

Excerpt from ERG Guide 153 [Substances - Toxic and/or Corrosive (Combustible)]:

IMMEDIATE PRECAUTIONARY MEASURE: Isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids.

SPILL: Increase the immediate precautionary measure distance, in the downwind direction, as necessary.

FIRE: If tank, rail tank car or highway tank is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. (ERG, 2024)

Personal protection: particulate filter respirator adapted to the airborne concentration of the substance. Do NOT let this chemical enter the environment. Sweep spilled substance into covered containers. If appropriate, moisten first to prevent dusting. Carefully collect remainder. Then store and dispose of according to local regulations. Do NOT absorb in saw-dust or other combustible absorbents.

The following wastewater treatment technologies have been investigated for p-phenylenediamine: biological treatment.

SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices.

SRP: Contaminated protective clothing should be segregated in such a manner so that there is no direct personal contact by personnel who handle, dispose, or clean the clothing. Quality assurance to ascertain the completeness of the cleaning procedures should be implemented before the decontaminated protective clothing is returned for reuse by the workers. Contaminated clothing should not be taken home at end of shift, but should remain at employee's place of work for cleaning.

The worker should immediately wash the skin when it becomes contaminated.

The worker should wash daily at the end of each work shift.

Work clothing that becomes wet or significantly contaminated should be removed and replaced.

For more Preventive Measures (Complete) data for 1,4-BENZENEDIAMINE (6 total), please visit the HSDB record page.

Excerpt from ERG Guide 153 [Substances - Toxic and/or Corrosive (Combustible)]:

ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area. Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. Prevent entry into waterways, sewers, basements or confined areas. Absorb or cover with dry earth, sand or other non-combustible material and transfer to containers. DO NOT GET WATER INSIDE CONTAINERS. (ERG, 2024)

Separated from strong oxidants, strong acids, acid anhydrides and food and feedstuffs. Keep in the dark. Well closed.

Keep well closed and protected from light.

IN GENERAL MATERIALS ... TOXIC AS STORED OR WHICH CAN DECOMP INTO TOXIC COMPONENTS ... SHOULD BE STORED IN COOL ... VENTILATED PLACE, OUT OF ... SUN, AWAY FROM ... FIRE HAZARD ... /AND/ BE PERIODICALLY INSPECTED & MONITORED. INCOMPATIBLE MATERIALS SHOULD BE ISOLATED.

0.1 [mg/m3], inhalable fraction[German Research Foundation (DFG)]

0.30 [mg/m3]

4.2 [mg/m3]

25 [mg/m3]

0.1 mg/m³

TWA 0.1 mg/m3 [skin]

0.1 [mg/m3]

25 mg/m3 (NIOSH, 2024)

25.0 [mg/m3]

Excerpts from Documentation for IDLHs: Basis for revised IDLH: No inhalation toxicity data are available on which to base an IDLH for p­phenylene diamine. Therefore, based on health considerations and acute oral toxicity data in animals [Burnett et al. 1977; Hanzlik 1923; Lloyd et al. 1977], a value of about 50 mg/m3 would have been appropriate. However, the revised IDLH for p­phenylene diamine is 25 mg/m3 based on the concentration recommended originally in the Standards Completion Program for deciding when the most protective respirators should be used. Because sensitized workers may be affected by concentrations far below occupational exposure limits, exacerbation of asthma cannot be used to set an IDLH.

25 mg/cu m

25 mg/m³

25 mg/m3

See: 106503

8 hr Time Weighted Avg (TWA): 0.1 mg/cu m.

Excursion Limit Recommendation: Excursions in worker exposure levels may exceed three times the TLV-TWA for no more than a total of 30 min during a work day, and under no circumstances should they exceed five times the TLV-TWA, provided that the TLV-TWA is not exceeded.

A4; Not classifiable as a human carcinogen.

0.1 mg/m

(inhalable fraction): 0.1 mg/m

Australia: 0.1 mg/cu m, skin designation (1900); Federal Republic of Germany: 0.1 mg/cu m (total dust), short term level 0.2 mg/cu m, 30 min TWA, 4 times per work shift (1991); Sweden: 0.1 mg/cu m, short term limit, 0.3 mg/cu m, skin, sensitizer (1990); United Kingdom: 0.1 mg/cu m, skin (1991).

A harmful contamination of the air will not or will only very slowly be reached on evaporation of this substance at 20 °C; on spraying or dispersing, however, much faster.

The substance is irritating to the eyes. Inhalation of dust may cause asthmatic reactions. Ingestion could cause swelling of mouth and throat. The substance may cause effects on the blood. This may result in the formation of methaemoglobin. Exposure could cause death.

Repeated or prolonged contact may cause skin sensitization. Repeated or prolonged inhalation may cause asthma. The substance may have effects on the kidneys. This may result in kidney impairment.

Excerpt from NIOSH Pocket Guide for p-Phenylene diamine:

Skin: PREVENT SKIN CONTACT - Wear appropriate personal protective clothing to prevent skin contact.

Eyes: PREVENT EYE CONTACT - Wear appropriate eye protection to prevent eye contact.

Wash skin:

• WHEN CONTAMINATED - The worker should immediately wash the skin when it becomes contaminated.

• DAILY - The worker should wash daily at the end of each work shift, and prior to eating, drinking, smoking, etc.

Remove: WHEN WET OR CONTAMINATED - Work clothing that becomes wet or significantly contaminated should be removed and replaced.

Change: DAILY - Workers whose clothing may have become contaminated should change into uncontaminated clothing before leaving the work premises. (NIOSH, 2024)

Employees should be provided with and required to use impervious clothing, gloves, face shields (eight-inch minimum), and other protective clothing necessary to prevent skin contact ... .

Wear appropriate personal protective clothing to prevent skin contact.

Wear appropriate eye protection to prevent eye contact.

Recommendations for respirator selection. Max concn for use: 2.5 mg/cu m. Respirator Class(es): Any supplied-air respirator operated in a continuous flow mode. Eye protection needed.

For more Personal Protective Equipment (PPE) (Complete) data for 1,4-BENZENEDIAMINE (8 total), please visit the HSDB record page.

NIOSH/OSHA

Up to 2.5 mg/m3 :

(APF = 25) Any supplied-air respirator operated in a continuous-flow mode

Up to 5 mg/m3 :

P-phenylenediamine appears as a white to purple crystalline solid (melting point 234 F) that turns purple to black in air. Flash point 309 F. Toxic by skin absorption, inhalation or ingestion. Used for production of aramid fiber, antioxidants, as a laboratory reagent, in photographic developing, and as a dye for hair and furs.

Large Crystals; Liquid

White to slightly red, crystalline solid; [NIOSH]

WHITE-TO-SLIGHTLY-RED CRYSTALS. TURNS DARK ON EXPOSURE TO AIR.

White to slightly red, crystalline solid.

WHITE TO SLIGHTLY RED CRYSTALS

WHITE PLATES FROM BENZENE, ETHER

513 °F at 760 mmHg (NTP, 1992)

267 °C @760 [mm Hg]

284 °F (NTP, 1992)

145-147 °C

139-147 °C

141.1 °C

311 °F (NTP, 1992)

156 °C c.c.

4 % at 75 °F (NIOSH, 2024)

SOL IN 100 PARTS COLD WATER; SOL IN ALCOHOL, CHLOROFORM, ETHER

SOL IN HOT BENZENE

Water solubility= 38,000 ppm

Solubility in water, g/100ml at 25 °C: 4

(75 °F): 4%

Greater than 1 (water= 1)

Relative density (water = 1): 1.1

>1 no temp

3.72 (NTP, 1992) - Heavier than air; will sink (Relative to Air)

3.72 (AIR= 1)

Relative vapor density (air = 1): 3.7

less than 1 mmHg (NIOSH, 2024)

0.005 [mmHg]

<1 mm Hg at 21 °C (technical product)

Vapor pressure, Pa at 100 °C: 144

log Kow= -0.25

ON STANDING IN AIR, OXIDIZES TO PURPLE AND BLACK /COLOR/.

Toxic gases and vapors (such as oxides of nitrogen and carbon monoxide) may be released in a fire involving p-phenylenediamine.

When heated to decomposition it emits acrid smoke and irritating fumes.

The pKa value of the conjugate acid is 6.2

13C nuclear magnetic resonance spectrum

15N nuclear magnetic resonance spectrum

Schoenflies notation

Boiling point

Oxidizes on exposure to air. The finely powdered base if suspended in air poses a significant dust explosion hazard. Soluble in water. Even as a solid will spot downwind areas purple/black (Roger Patrick, DuPont Engineer).

Amines, Aromatic

P-PHENYLENEDIAMINE is the stongest of the weak aromatic bases. It neutralizes acids in weak exothermic reactions to form salts. May be incompatible with isocyanates, halogenated organics, peroxides, phenols (acidic), epoxides, anhydrides, and acid halides. Reacts readily with oxidizing agents (NTP, 1992).

Contact with strong oxidizers may cause fires and explosions.

Strong oxidizers.

Strong oxidizers

Safe in the present practices of use and concentration. Ingredient, concentration, and use information are available in documents discoverable at https://cir-reports.cir-safety.org

No data are available in humans. Inadequate evidence of carcinogenicity in animals. OVERALL EVALUATION: Group 3: The agent is not classifiable as to its carcinogenicity to humans.

A4; Not classifiable as a human carcinogen.

para-Phenylenediamine

Group 3: Not classifiable as to its carcinogenicity to humans

Volume 16: (1978) Some Aromatic Amines and Related Nitro Compounds – Hair Dyes, Colouring Agents and Miscellaneous Industrial Chemicals

Volume Sup 7: Overall Evaluations of Carcinogenicity: An Updating of IARC Monographs Volumes 1 to 42, 1987; 440 pages; ISBN 92-832-1411-0 (out of print)

The substance can be absorbed into the body by inhalation, through the skin and by ingestion.

inhalation, skin absorption, ingestion, skin and/or eye contact

Cough. Dizziness. Headache. Laboured breathing. See Ingestion.

MAY BE ABSORBED! Redness.

Redness. Pain. Swelling of the eyelids. Blurred vision. Loss of vision.

Abdominal pain. Blue lips, fingernails and skin. Convulsions. Drowsiness. Laboured breathing. Shortness of breath. Vomiting. Weakness.

irritation pharynx, larynx; bronchial asthma; sensitization dermatitis

respiratory system, skin

Occupational hepatotoxin - Secondary hepatotoxins: the potential for toxic effect in the occupational setting is based on cases of poisoning by human ingestion or animal experimentation.

Nephrotoxin - The chemical is potentially toxic to the kidneys in the occupational setting.

Methemoglobinemia - The presence of increased methemoglobin in the blood; the compound is classified as secondary toxic effect

Skin Sensitizer - An agent that can induce an allergic reaction in the skin.

Asthma - Reversible bronchoconstriction (narrowing of bronchioles) initiated by the inhalation of irritating or allergenic agents.

ACGIH Carcinogen - Not Classifiable.

p-Phenylenediamine

PDF Document

Inadequate information to assess carcinogenic potential

SCREEN Current

PPRTV Current

LC50 (rat) = 920 mg/m3/4H

LDLo Rat oral 100 mg/kg

LDLo Rat ip 50 mg/kg

LDLo Rat sc 170 mg/kg

LD50 Dog iv 17 mg/kg

For more Non-Human Toxicity Values (Complete) data for 1,4-BENZENEDIAMINE (8 total), please visit the HSDB record page.

Flush eyes with water. Wash contaminated areas of body with soap and water.

For immediate first aid: Ensure that adequate decontamination has been carried out. If victim is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask as trained. Perform CPR if necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep victim quiet and maintain normal body temperature. Obtain medical attention. /Organic bases, amines, and related compounds/

For basic treatment: Establish a patent airway. Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... Monitor for shock and treat if necessary ... Anticipate seizures and treat if necessary ... For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with normal saline during transport ... Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool. Administer activated charcoal ... Cover skin burns with sterile dressings after decontamination ... . /Organic bases, amines, and related compounds/

/Annual/ physical examinations of exposed personnel, including blood counts and studies of liver function. Those persons with allergy and with diseases of skin, liver, blood, and lungs should avoid exposure. Sensitized persons should avoid re-exposure.

EXPOSED WORKMEN ... SUFFER FROM ALLERGIC ASTHMA & FREQUENTLY SHOW INFLAMMATORY REACTIONS OF THE LARYNX & PHARYNX, EVIDENTLY CAUSED BY DIRECT IRRITATION. ... VERY SMALL QUANTITIES ... COULD CAUSE ASTHMA IN PERSONS AFTER 3 MO TO 10 YR OF EXPOSURE. THESE EPISODES WERE CVHARACTERIZED BY THE IMMEDIATE ONSET OF SYMPTOMS WHICH PROMPTLY DISAPPEARED UPON DISCONTINUATION OF THE EXPOSURE.

Potential symptoms of overexposure are irritation of pharynx and larynx; bronchial asthma; sensitization dermatitis.

/HYPERSENSITIVITY/ REACTIONS WHICH HAVE FOLLOWED APPLICATION OF DYES CONTAINING P-PHENYLENEDIAMINE TO HAIR ... CHARACTERISTICALLY HAVE CONSISTED OF DERMATITIS OF HEAD, FOREHEAD, & NECK, ASSOC WITH EDEMA OF LIDS & CONJUNCTIVA, WITH TEARING & EXOPHTHALMOS.

Produces severe local reactions and systemic effects from percutaneous absorption and from ingestion. Local actions incl severe dermatitis and urticaria; in the eye, chemosis, lacrimation, exophthalmos, ophthalmia, and even permanent blindness. Systemic actions incl asthma, gastritis (regardless of portal of entry), rise in blood pressure, transudation into serous cavities, vertigo, tremors, convulsions and coma. ... The ortho isomer (diolene) is less toxic than the para (orsin).

LC50 Goldfish 5.75 mg/L/48 hr /Conditions of bioassay not specified/

6.30e+01

8.20e+02

2.00e+01

1.5E+01(G)

5.40e-03

1.00e-03

Volatile

1.90e+02

2.50e+03

6.00e+01

1.5E+01 (G)

The substance is very toxic to aquatic organisms.

1,4-Benzenediamine's production and use as an intermediate in the manufacture of diisocyanates for polyurethane; antioxidants and accelerators for rubber, and its use in dye mixtures for hair, fur and photographic developing chemicals may result in its release to the environment through a variety of waste streams. Based on an extrapolated vapor pressure of 0.005 mm Hg at 25 °C, 1,4-benzenediamine is expected to exist primarily as a vapor in the ambient atmosphere. Vapor-phase 1,4-benzenediamine is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals with an estimated atmospheric half-life of about 2 hours. If released to soil, 1,4-benzenediamine is expected to have high mobility based on an estimated Koc value of 16; however it may form covalent bonds to humic material which would limit its movement through soil. Volatilization from dry soil surfaces is not expected based upon the vapor pressure of this compound. Volatilization from moist soil surfaces is not expected based on an estimated Henry's Law constant of 6.7X10-10 atm-cu m/mol. Biodegradation is expected to occur slowly in moist and dry soils. In water, 1,4-benzenediamine is not expected to adsorb to sediment or particulate matter based on its estimated Koc value. Volatilization from water surfaces is not expected based upon the estimated Henry's Law constant for this compound. Abiotic degradation of 1,4-benzenediamine by photochemically produced peroxy radicals is an important environmental fate process in surface waters. The half-life of this reaction has been estimated as about 1 day. The potential for bioconcentration in aquatic organisms is low based on an estimated BCF value of 0.3. A measured pKb value of 6.2 indicates that the protonated form of 1,4-benzenediamine will exist at environmentally significant pH and this may affect the environmental fate of this compound in aquatic environments. Occupational exposure may occur through inhalation and dermal contact with this compound at workplaces where 1,4-benzenediamine is produced or used. The general population may be exposed to this compound by dermal contact, primarily through the use of hair dyes containing 1,4-benzenediamine. (SRC)

1,4-Benzenediamine is not known to occur as a natural product(1).

1,4-Benzenediamine may be released in emissions and wastewater during its production and use in the manufacture of diisocyanates for polyurethanes (largest volume use) such as Kevlar(1) and as an intermediate in manufacture of antioxidants and accelerators for rubber. It is used in manufacture of azo dyes and as a component of dye mixtures for hair and fur(2). Its derivatives are also used as developers for black-and-white and color photographs(3).

TERRESTRIAL FATE: Based on a recommended classification scheme(1), an estimated Koc value of 16(SRC), determined from a measured log Kow of -0.30(2), and a recommended regression-derived equation(3), indicates that 1,4-benzenediamine is expected to have high mobility in soil(SRC); however it may form covalent bonds to humic material which would limit movement through soil(4). Volatilization of 1,4-benzenediamine is not expected from moist soil surfaces(SRC) given an estimated Henry's Law constant of 6.7X10-10 atm-cu m/mole(SRC), using a fragment constant estimation method(5). Volatilization of 1,4-benzenediamine from dry soil surfaces is not expected(SRC) based on an extrapolated vapor pressure of 0.005 mm Hg(SRC) at 25 °C(6). Biodegradation is expected to occur slowly in soils based on standard biodegradability tests conducted with activated sludge(7-11).

AQUATIC FATE: Based on a recommended classification scheme(1), an estimated Koc value of 16(SRC), determined from a measured log Kow of -0.30(2), and a recommended regression-derived equation(3), indicates that 1,4-benzenediamine is not expected to adsorb to suspended solids and sediment in water(SRC). 1,4-benzenediamine is not expected to volatilize from water surfaces(3,SRC) based on an estimated Henry's Law constant of 6.7X10-10 atm-cu m/mole(SRC), developed using a fragment constant estimation method(4). Degradation of 1,4-benzenediamine by photochemically produced peroxy radicals will be an important environmental fate process in surface waters(5,SRC). The half-life of this reaction is estimated as 1 day for a solution concentration of 1X10-9 M of peroxy radicals and an estimated rate constant of 1X10+4 L/mol-s(5). According to a classification scheme(6), an estimated BCF value of 0.3(3,SRC), from a measured log Kow of -0.3(2,SRC), suggests that bioconcentration in aquatic organisms is low(SRC). Biodegradation in aquatic environments is not expected to be an important environmental fate process(SRC). A 0% theoretical oxygen demand was observed for 1,4-benzenediamine in a Warburg apparatus during a 5 day incubation period(7). A measured pKb value of 6.2 indicates that the protonated form of 1,4-benzenediamine will exist at environmentally significant pH and this may affect the environmental fate of this compound in aquatic environments(8).

ATMOSPHERIC FATE: According to a model of gas/particle partitioning of semivolatile organic compounds in the atmosphere(1), 1,4-benzenediamine, which has an extrapolated vapor pressure of 0.005 mm Hg at 25 °C(2,SRC), is expected to exist primarily as a vapor in the ambient atmosphere. Vapor-phase 1,4-benzenediamine is degraded in the atmosphere by reaction with photochemically-produced hydroxyl radicals(SRC); the half-life for this reaction in air is estimated to be about 2 hours(3,SRC).

Biodegradation of 1,4-benzenediamine (60 ng/l) with an adapted mixed culture from soil, compost or mud from a waste lagoon capable of rapid degradation of phenol led to a 9% theoretical BOD in 3hr at 30 °C (phenol reference - 70% theoretical BOD)(1). An 80% degradation of 1,4-benzenediamine (25-30 mg/l) with acclimated activated sludge in 120 hr at 20 °C has been reported(2). Aniline-acclimated activated sludge led to 8% theoretical BOD in 190 hr at 20 °C(3). No degradation of 500 mg/l 1,4-benzenediamine was observed with 3 activated sludges in 24 hr at 20 °C, the test compound was toxic to the 3 sludges(4). A 0% theoretical BOD was observed for 1,4-benzenediamine in a Warburg apparatus during a 5 day incubation period(5). 3.8% Biodegradation was observed when 1,4-diaminobenzene dihydrochloride (initial concentration unspecified) was incubated with an activated sludge inoculum obtained from a municipal sewage treatment facility over a 5 day incubation period(6).

The rate constant for the vapor-phase reaction of 1,4-benzenediamine with photochemically-produced hydroxyl radicals has been estimated as 2.3X10-10 cu cm/molecule-sec at 25 °C(SRC) using a structure estimation method(1,SRC). This corresponds to an atmospheric half-life of about 2 hours at an atmospheric concentration of 5X10+5 hydroxyl radicals per cu cm(1,SRC). A measured pKb value of 6.2 indicates that 1,4-benzenediamine is expected to exist in the protonated form at environmentally significant pH values(2,SRC). Abiotic degradation of 1,4-benzenediamine by photochemically produced peroxy radicals is an important environmental fate process in surface waters(3,SRC). The rate constant for this reaction has been estimated as 1X10+4 L/mol-s at 25 °C(3). This corresponds to a half-life of about 1 day for a solution concentration of 1X10-9 M of peroxy radicals(3). 1,4-Benzenediamine adsorbs UV light above 290 nm (UV maximum 308 nm(4)) and therefore may undergo direct photolysis in the environment by sunlight. 53.7% Photooxidation of a 1,4-diaminobenzene dihydrochloride sample (initial concentration unspecified) on a silica gel substrate was observed when irradiated with light above 290 nm for 17 hours(5).

An estimated BCF value of 0.3 was calculated for 1,4-benzenediamine(SRC), using a measured log Kow of -0.3(1,SRC) and a recommended regression-derived equation(2). According to a classification scheme(3), this BCF value suggests that bioconcentration in aquatic organisms is low(SRC). An experimental BCF value of 450 was measured for algae exposed to 1,4-diaminobenzene dihydrochloride for 24 hours(4). An experimental BCF value of 6 was measured for fish (golden ide) exposed to 1,4-diaminobenzene dihydrochloride for 3 days(4).

Based on a recommended classification scheme(1), an estimated Koc value of 16(SRC), determined from a measured log Kow of -0.3(2) and a recommended regression-derived equation(3), indicates that 1,4-benzenediamine is expected to have high mobility in soil(SRC); however it may form covalent bonds to humic material which would limit movement through soil(4).

The Henry's Law constant for 1,4-benzenediamine is estimated as 6.7X10-10 atm-cu m/mole(SRC) using a fragment constant estimation method(1). This value indicates that 1,4-benzenediamine will be essentially nonvolatile from water surfaces(2,SRC). 1,4-Benzenediamine is not expected to volatilize from dry soil surfaces based on an extrapolated vapor pressure of 0.005 mm Hg at 25 °C(3).

Occupational exposure to 1,4-benzenediamine may occur through inhalation and dermal contact with this compound at workplaces where 1,4-benzenediamine is produced or used(1,SRC). NIOSH (NOES Survey 1981-83) has statistically estimated that 104 workers are potentially exposed to 1,4-benzenediamine in the USA(2). The general population may be exposed to this compound by dermal contact, primarily through the use of hair dyes containing 1,4-benzenediamine(1,3).

The following wastewater treatment technologies have been investigated for p-phenylenediamine: biological treatment.

SRP: At the time of review, criteria for land treatment or burial (sanitary landfill) disposal practices are subject to significant revision. Prior to implementing land disposal of waste residue (including waste sludge), consult with environmental regulatory agencies for guidance on acceptable disposal practices.

/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Health: TOXIC; inhalation, ingestion, or skin contact with material may cause severe injury or death. Contact with molten substance may cause severe burns to skin and eyes. Avoid any skin contact. Effects of contact or inhalation may be delayed. Fire may produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution. /Phenylenediamines/

/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Fire or Explosion: Combustible material: may burn but does not ignite readily. When heated, vapors may form explosive mixtures with air: indoors, outdoors, and sewers explosion hazards. Those substances designated with a "P" may polymerize explosively when heated or involved in a fire. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated. Runoff may pollute waterways. Substance may be transported in a molten form. /Phenylenediamines/

/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Public Safety: CALL Emergency Response Telephone Number ... . As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate enclosed areas. /Phenylenediamines/

/GUIDE 153: SUBSTANCES - TOXIC AND/OR CORROSIVE (COMBUSTIBLE)/ Protective Clothing: Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible. /Phenylenediamines/

For more DOT Emergency Guidelines (Complete) data for 1,4-BENZENEDIAMINE (8 total), please visit the HSDB record page.

UN 1673; Phenylenediamines

IMO 6.1; Phenylenediamines

No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that person is registered in conformance ... and the hazardous material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./

The International Air Transport Association (IATA) Dangerous Goods Regulations are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and constitute a manual of industry carrier regulations to be followed by all IATA Member airlines when transporting hazardous materials.

The International Maritime Dangerous Goods Code lays down basic principles for transporting hazardous chemicals. Detailed recommendations for individual substances and a number of recommendations for good practice are included in the classes dealing with such substances. A general index of technical names has also been compiled. This index should always be consulted when attempting to locate the appropriate procedures to be used when shipping any substance or article.

Airtight. Do not transport with food and feedstuffs.

Symbol: T+, N; R: 23/24/25-36-43-50/53; S: (1/2)-28-36/37-45-60-61

UN Hazard Class: 6.1; UN Pack Group: III