Subchapter 7. General Industry Safety Orders
Group 16. Control of Hazardous Substances
Article 110. Regulated Carcinogens

§5213. Acrylonitrile, Appendix B

Substance Technical Guidelines for Acrylonitrile

I. Physical and Chemical Data

A. Substance Identification:

1. Synonyms: AN; VCN; vinyl cyanide; acrylic nitrile; cyanoethylene; Acrylon; Carbacryl; Fumigrain; Ventox; propenenitrile.

2. Formula: CH₂ = CHCN

3. Molcular Weight: 53.1.

B. Physician Data:

1. Boiling Point (760 mm Hg): 77.3° C (171° F)

2. Specific Gravity (water = 1): 0.81 (at 20° C or 68° F)

3. Vapor Density (air = 1) at boiling point of acrylonitrile: 1.83.

4. Melting Point: -83° F (-117° F)

5. Vapor Pressure at 20° C (68° F): 83 mm Hg.

6. Solubility in Water: Percent by weight at 20° C (68° F): 7.35.

7. Evaporation Rate (Butyl Acetate = 1): 4.54.

8. Appearance and Odor: Colorless to pale yellow liquid with a pungent odor at concentrations above the permissible exposure level. Any detectable odor of acrylonitrile may indicate overexposure.

II. Fire, Explosion, and Reactivity Hazard Data

A. Fire:

1. Flash Point: -1° C (30° F) (open cup)

2. Autoignition Temperature: 481° C (898° F).

3. Flammable Limits in Air, Percent by Volume: Lower: 3; Upper: 17.

4. Extinguishing Media: Alcohol foam, carbon dioxide, dry chemical.

5. Special Fire-fighting Procedures: Do not use a solid stream of water, since the stream will scatter and spread the fire. Use water spray to cool containers exposed to a fire.

6. Fire and Explosion Hazards: Acrylonitrile is a flammable liquid. Its vapors can easily form explosive mixtures with air. All ignition sources must be controlled where acrylonitrile is handled, used, or stored in a manner that could create a potential fire or explosion hazard. Acrylonitrile vapors are heavier than air and may travel along the ground and be ignited by open flames or sparks at locations remote from the site at which acrylonitrile is being handled.

7. For purposes of compliance with the requirements of Articles 141 through 148 of the General Industry Safety Orders, acrylonitrile is classified as a Class 1B flammable liquid. For example, 7500 ppm, approximately one-fourth of the lower flammable limit, would be considered to pose a potential fire and explosion hazard.

8. For purposes of compliance with the regulations for fire protection, acrylonitrile is classified as a Class B fire hazard.

9. For purpose of compliance with the Electrical Safety Orders (California Administrative Code, Chapter 4, Subchapters 5 and 6) locations classified as hazardous due to the presence of acrylonitrile shall be Class I Group D.

B. Reactivity.

1. Conditions Contributing to Instability: Acrylonitrile will polymerize when hot, and the additional heat liberated by the polymerization may cause containers to explode. Pure AN may self-polymerize with a rapid build-up of pressure resulting in an explosive hazard. Inhibitors are added to the commercial product to prevent self-polymerization.

2. Incompatibilities: Contact with strong oxidizers (especially bromine) and strong bases may cause fires and explosions. Contact with copper, copper alloys, ammonia, and amines may start serious decomposition.

3. Hazardous Decomposition Products: Toxic gases and vapors (such as hydrogen cyanide, oxides of nitrogen, and carbon monoxide) may be released in a fire involving acrylonitrile and certain polymers made from acrylonitrile.

4. Special Precautions: Liquid acrylonitrile will attack some forms of plastics, rubbers, and coatings.

III. Spill, Leak, and Disposal Procedures

A. If acrylonitrile is spilled or leaked, the following steps should be taken:

1. Remove all ignition sources.

2. The area should be evacuated at once and reentered only after the area has been thoroughly ventilated and washed down with water.

3. If liquid acrylonitrile or polymer intermediate, collect for reclamation or absorb in paper, vermiculite, dry sand, earth, or similar material, or wash down with water into process sewer system.

B. Persons not wearing protective equipment should be restricted from areas of spills or leaks until cleanup has been completed.

C. Waste Disposal Methods: Waste material shall be disposed of in a manner that is not hazardous to employees or to the general population. Spills of acrylonitrile and flushing of such spills shall be channeled for appropriate treatment or collection for disposal. They shall not be channeled directly into the sanitary sewer system. In selecting the method of waste disposal, applicable local, state, and federal regulations should be consulted.

IV. Monitoring and Measurement Procedures

A. Exposure Above the Permissible Exposure Limit:

1. Eight-hour Exposure Evaluation: Measurements taken for the purpose of determining employee exposure under this section are best taken so that the average eight-hour exposure may be determined from a single 8-hour sample or two (2) 4-hour samples. Air samples should be taken in the employee's breathing zone (air that would most nearly represent that inhaled by the employee).

2. Ceiling Evaluation: Measurements taken for the purpose of determining employee exposure under this section must be taken during periods of maximum expected concentrations of acrylonitrile in the employee's breathing zone. A minimum of three (3) measurements should be taken on one work shift. The average of all measurement taken is an estimate of the employee's ceiling exposure.

3. Monitoring Techniques: The sampling and analysis under this section may be performed by collecting the acrylonitrile vapor on charcoal adsorption tubes or other composition adsorption tubes, with subsequent chemical analysis. Sampling and analysis may also be performed by instruments such as real-time continuous monitoring systems, portable direct-reading instrument or passive dosimeters. Analysis of resultant samples should be by gas chromatography.

Appendix D lists methods of sampling and analysis which have been tested by NIOSH and OSHA for use with acrylonitrile. NIOSH and OSHA have validated modifications of NIOSH Method S-156 (see Appendix D) under laboratory conditions for concentrations below 1 ppm. The employer has the obligation of selecting a monitoring method which meets the accuracy and precision requirements of the standard under his unique field conditions. The standard requires that methods of monitoring must be accurate, to 95-percent confidence level, to +35 percent for concentrations of AN at or above 2 ppm, and to +50 percent for concentrations below 2 ppm. In addition to the methods described in Appendix D, there are numerous other methods available for monitoring for AN in the workplace.

Since many of the duties relating to employee exposure are dependent on the results of monitoring and measuring procedures, employers shall assure that the evaluation of employee exposures is performed by a competent industrial hygienist or other technically qualified person.

V. Protective Clothing

Employees shall be provided with, and required to wear appropriate protective clothing to prevent any possibility of skin contact with liquid AN. Because acrylonitrile is absorbed through the skin, it is important to prevent skin contact with the liquid. Protective clothing shall include impermeable coveralls or similar full-body work clothing, gloves, head-coverings, and workshoes or shoe coverings, as appropriate, to protect areas of the body which may come in contact with liquid AN.

Employers should ascertain that the protective garments are impermeable to acrylonitrile. Non-impermeable clothing and shoes should not be allowed to become contaminated with acrylonitrile. If permeable clothing does become contaminated, it should be promptly removed, placed in a regulated area for removal of the AN, and not worn again until the AN is removed. If leather footwear or other leather garments become wet from acrylonitrile, they should be replaced and not worn again, due to the ability of leather to absorb acrylonitrile and hold it against the skin. Since there is no pain associated with the blistering, it is essential that the employee be informed of this hazard so that he or she can be protected.

Any protective clothing which has developed leaks or is otherwise found to be defective should be repaired or replaced. Clean protective clothing shall be provided to the employee, as necessary to assure adequate protection. Whenever impervious clothing becomes wet with liquid AN, it shall be washed down with water before being removed by the employee. Employees are also required to wear splash-proof safety goggles where there is any possibility of acrylonitrile contacting the eyes.

VI. Housekeeping and Hygiene Facilities

For purposes of complying with Article 9 of the General Industry Safety Orders the following items should be emphasized

A. The workplace should be kept clean, orderly, and in a sanitary condition. The employer is required to institute a leak and spill detection program for operations involving liquid AN in order to detect sources of fugitive AN emissions.

B. Dry sweeping and the use of compressed air is unsafe for the cleaning of floors and other surfaces where liquid AN may be found.

C. Adequate washing facilities with hot and cold water are to be provided, and maintained in a sanitary condition. Suitable cleansing agents are also to be provided to assure the effective removal of acrylonitrile from the skin.

D. Change or dressing rooms with individual clothes-storage facilities must be provided to prevent the contamination of street clothes with acrylonitrile. Because of the hazardous nature of acrylonitrile, contaminated protective clothing must be placed in a regulated area designated by the employer for the removal of the AN before the clothing is laundered or disposed of.

VII. Miscellaneous Precautions

A. Store acrylonitrile in tightly-closed containers in a cool, well-ventilated area and take the necessary precautions to avoid an explosion hazard.

B. High exposure to acrylonitrile can occur when transferring the liquid from one container to another.

C. Non-sparking tools must be used to open and close metal acrylonitrile containers. These containers must be effectively grounded and bonded prior to pouring.

D. Never store uninhibited acrylonitrile.

E. Acrylonitrile vapors are not inhibited. They may clog vents of storage tanks through the formation of polymer.

F. Use of supplied-air suits or other impervious coverings may be necessary to prevent skin contact as well as to provide respiratory protection where the concentration of acrylonitrile is unknown or is above the ceiling limit. Supplied-air suits should be selected, used, and maintained under the immediate supervision of persons knowledgeable in the limitations and potential life-endangering characteristics of supplied-air suits.

G. Employers shall advise employees of all areas and operations where exposure to acrylonitrile could occur.

VIII. Common Operations

Common operations in which exposure to acrylonitrile is likely to occur include the following: manufacture of acrylonitrile monomer; synthesis of acrylic fibers, ABS, SAN and nitrile barrier plastics and resins, nitrile rubber, surface coatings, specialty chemicals, use as a chemical intermediate, use as a fumigant and in the cyanoethylation of cotton.