Uninhibited Formalin Solution
The document provides information on
uninhibited formalin solution (37% formaldehyde, no methanol stabilizer). Much of the information provided is general;
however, some information is specific for formalin. The precise hazards associated with exposure to formaldehyde
depend both on the form (solid, liquid, or gas) of the material and the
concentration present. For example,
37-50 percent solutions of formaldehyde present a much greater hazard to the
skin and eyes from spills or splashes than solutions containing less than 1
percent formaldehyde.
Substance Identification
Chemical Name:
Formaldehyde
Chemical
Family: Aldehyde
Chemical
Formula: HCHO
Molecular
Weight: 30.03
Chemical
Abstracts Service Number (CAS Number): 50-00-0
Synonyms: Formalin;
Formic Aldehyde; Paraform; Formol; formalin (Methanol-free); Fyde; Formalith;
Methanal; Methyl Aldehyde; Methylene Glycol; Methylene Oxide;
Tetraoxymethalene: Oxomethane; Oxymethylene.
Components and Contaminants
Percent: 37.0
Formaldehyde
Percent: 63.0
Water
(Note.-Inhibited
solutions contain methanol).
Other
Contaminants: Formic acid (alcohol free)
Exposure
Limits:
OSHA TWA-
0.75ppm
OSHA STEL- 2
.00ppm
Physical Data
Description:
Colorless liquid, pungent odor
Boiling point:
214 F (101 C)]
Specific
Gravity: 1.08 (H20=1 @ 20 C)
pH: 2.8-4.0
Solubility in
Water: Miscible
Solvent
Solubility: Soluble in alcohol and acetone
Vapor Density:
1.04 (Air =1 @ 20 C)
Odor
Threshold: 0.8-1ppm
Fire and Explosion Hazard
Moderate fire and explosion hazard when exposed to heat or flame. The flash point of 37% formaldehyde solutions is above normal room temperature, but the explosion range is very wide, from 7 to 73% by volume in air. Reaction of formaldehyde with nitrogen dioxide, nitromethane, perchloric acid and aniline, or peroxyformic acid yields explosive compounds.
Flash Point:
185 F (85 C) closed cup
Lower
Explosion Limit: 7%
Upper
Explosion Limit: 73%
Autoignition
Temperature: 806 F (430 C)
Flammability
Class (OSHA): III A
Extinguishing
Media: Use dry chemical "alcohol
foam", carbon dioxide, or water in flooding amounts as fog. Solid streams
may not be effective.
Reactivity
Stability: Formaldehyde
solutions may self-polymerize to form white precipitates.
Incompatibility (Materials to
Avoid): Strong oxidizing agents, caustics, strong alkalis, isocyanates,
anhydrides, oxides, and inorganic acids. Formaldehyde reacts with hydrochloric acid to form the potent
carcinogen, bis-chloromethyl ether. Formaldehyde
reacts with nitrogen dioxide, nitromethane, perchloric acid and aniline, or
peroxyformic acid to yield explosive compounds. A violent reaction occurs when formaldehyde is mixed with strong
oxidizers. Hazardous Combustion or
Decomposition Products: Oxygen from the air can oxidize formaldehyde to formic
acid, especial when heated. Formic acid
is corrosive.
Health Hazard Data
Acute Effects
of Exposure
Ingestion (Swallowing):
Liquids containing 10 to 40% formaldehyde cause severe irritation and
inflammation to the mouth, throat, and stomach. Severe stomach pains will follow ingestion with possible loss of
consciousness and death. Ingestion of
dilute formaldehyde solutions (0.03-0.04%) may cause discomfort in the stomach
and pharynx.
Inhalation (Breathing):
Formaldehyde is highly irritating to the upper respiratory tract and eyes.
Concentrations of 0.5 to 2.0 ppm may irritate the eyes, nose, and throat of
some individuals. Concentrations of 3 to 5 ppm also cause tearing of the eyes
and are intolerable to some persons. Concentrations of 10 to 20 ppm cause difficulty
in breathing, burning of the nose and throat, cough, and heavy tearing of the
eyes; 25 to 30 ppm causes severe respiratory tract injury leading to pulmonary
edema and pneumonitis. A concentration of 100 ppm is immediately dangerous to
life and health. Deaths from accidental
exposure to high concentrations of formaldehyde have been reported.
Skin (Dermal):
Formalin is a severe skin irritant and a sensitizer. Contact with formalin causes white discoloration, smarting,
drying, cracking, and scaling. Prolonged
and repeated contact can cause numbness and a hardening or tanning of the skin.
Previously exposed persons may react to
future exposure with an allergic eczematous and dermatitis or hives.
Eye Contact: Formaldehyde
solutions splashed in the eye can cause injuries ranging from transient
discomfort to severe, permanent corneal clouding and loss of vision. The severity of the effect depends on the
concentration of formaldehyde in the solution and whether or not the eyes are
flushed with water immediately after the accident.
Note.-The
perception of formaldehyde by odor and eye irritation becomes less sensitive
with time as one adapts to formaldehyde. This can lead to overexposure if a worker is relying on
formaldehyde's warning properties to alert him or her to the potential for
exposure.
Acute Animal
Toxicity:
Oral, rats:
LD50=800 mg/kg
Oral, mouse:
LD50=42 mg/kg
Inhalation,
rats: LCLo=250 mg/kg
Inhalation,
mouse: LCLo=900 mg/kg
Inhalation,
rats: LC50=590 mg/kg
Chronic Effects of Exposure
Carcinogenicity: Formaldehyde
has the potential to cause cancer in humans. Repeated and prolonged exposure increases the risk. Various animal experiments have conclusively
shown formaldehyde to be a carcinogen in rats. In humans, formaldehyde exposure had been associated with cancers
of the lung, nasopharynx and oropharynx, and nasal passages.
Mutagenicity: Formaldehyde
is genotoxic in several in vitro test systems showing properties of both an
initiator and a promoter.
Toxicity: Prolonged or repeated exposure to formaldehyde may result in respiratory impairment. Rats exposed to formaldehyde at 2 ppm developed benign nasal tumors and changes of the cell structure in the nose as well as inflamed mucous membranes of the nose. Structural changes in the epithelial cells in the human nose have also been observed. Some persons have developed asthma or bronchitis following exposure to formaldehyde, most often as the result of an accidental spill involving a single exposure to a high concentration of formaldehyde.
Emergency and First Aid Procedures
Employees and students must notify their immediate supervisor or instructor of all illness and injuries related to exposure to hazardous chemicals. Contact your supervisor if you have any questions regarding the procedure for treating a non-serious injury or illness.
Ingestion (Swallowing):
If the victim is conscious, dilute, inactivate, or absorb the ingested
formaldehyde by giving milk, activated charcoal, or water. Any organic material will inactivate the
formaldehyde. Keep affected person warm
and at rest. Get medical attention
immediately. If vomiting occurs, keep head lower than hips.
Inhalation (Breathing): Remove
the victim from the exposure area to fresh air immediately. Do not enter areas with high levels of
formaldehyde. Wait for rescuers with
appropriate respiratory protection equipment. If breathing has stopped, give artificial respiration. Keep the affected person warm and at rest
until ambulance arrives.
Skin Contact: Remove
contaminated clothing (including shoes) immediately. Wash the affected area of your body with soap or mild detergent
and large amounts of water until no evidence of the chemical remains (at least
15 to 20 minutes). Get medical attention
after washing affected area.
Eye Contact: Wash the
eyes immediately with large amounts of water occasionally lifting lower and
upper lids, until no evidence of chemical remains (at least 15 to 20 minutes). Get medical attention immediately. If you have experienced appreciable eye
irritation from a splash or excessive exposure, you should be referred promptly
to an ophthalmologist for evaluation.
Spill, Leak, and Disposal Procedures
Occupational Spill: Take up small spills with absorbent material and place the waste into properly labeled containers for later disposal. In the event of a large spill alert personnel in the area that a spill has occurred. Do not attempt to handle a large spill of formaldehyde. Vacate the laboratory immediately and call for assistance.
Monitoring and Measurement Procedures
Monitoring
Requirements: If your exposure to formaldehyde exceeds the 0.5 ppm
action level or the 2 ppm STEL, your employer must monitor your exposure. Your employer need not measure every exposure
if a "high exposure" employee can be identified. This person usually spends the greatest
amount of time nearest the process equipment. If you are a "representative employee", you will be
asked to wear a sampling device to collect formaldehyde. This device may be a passive badge, a sorbent
tube attached to a pump, or an impinger containing liquid. You should perform your work as usual, but
inform the person who is conducting the monitoring of any difficulties you are
having wearing the device.
Evaluation of
8-hour Exposure: Measurements taken for the purpose of determining
time-weighted average (TWA) exposures are best taken with samples covering the
full shift. Samples collected must be
taken from the employee's breathing zone air.
Short-term
Exposure Evaluation: If there are tasks that involve brief but intense exposure
to formaldehyde, employee exposure must be measured to assure compliance with
the STEL. Sample collections are for
brief periods, only 15 minutes, but several samples may be needed to identify
the peak exposure.
Monitoring
Techniques:
OSHA's only requirement for selecting a method for sampling and analysis is
that the methods used accurately evaluate the concentration of formaldehyde in
employees' breathing zones. Sampling
and analysis may be performed by collection of formaldehyde on liquid or solid
sorbents with chemical analysis. Sampling
and analysis may also be performed by passive diffusion monitors and short-term
exposure may be measured by instruments such as real-time continuous monitoring
systems and portable direct reading instruments.
Notification
of Results:
Your employer must inform you of the results of exposure monitoring
representative of your job. You may be
informed in writing, but posting the results where you have ready access to
them constitutes compliance with the standard.
Protective Equipment and Clothing
Clothing: Material impervious to formaldehyde is needed if the employee handles formaldehyde solutions of 1% or more. Other employees may also require protective clothing or equipment to prevent dermatitis.
Respiratory
Protection:
Contact Supervision if you believe respirators are required.
Protective
Gloves:
Wear protective (impervious) gloves provided by your employer, at no cost, to
prevent contact with formalin. Y our employer should select these gloves based
on the results of permeation testing and in accordance with the ACGIH
Guidelines for Selection of Chemical Protective Clothing.
Eye protection: If you might
be splashed in the eyes with formalin, it is essential that you wear goggles or
some other type of complete protection for the eye. You may also need a face shield if your face is likely to be
splashed with formalin, but you must not substitute face shields for eye
protection. (This section pertains to formaldehyde solutions of 1% or
more.) Other Protective Equipment:
You must wear protective (impervious) clothing and equipment provided by your
employer at no cost to prevent repeated or prolonged contact with formaldehyde
liquids. If you are required to change
into whole-body chemical protective clothing, your employer must provide a
change room for your privacy and for storage of your street clothing. If you are splashed with formaldehyde, use
the emergency showers and eyewash fountains provided by your employer
immediately to prevent serious injury. Report
the incident to your supervisor and obtain necessary medical support.
Engineering Controls
Ventilation is the most widely applied engineering control method of reducing the concentration of airborne substances in the breathing zones of workers. There are two distinct types of ventilation.
Local Exhaust: Local ventilation is designed to capture airborne contaminants as near to the point of generation as possible. To protect you, the direction of contaminant flow must always be toward the local exhaust system inlet and away from you.
General (Mechanical): General dilution ventilation involves continuous introduction of fresh air into the workroom to mix with the contaminated air and lower your breathing zone concentration of formaldehyde. Effectiveness depends on the number of air changes per hour. Where devices emitting formaldehyde are spread out over a large area, general dilution ventilation may be the only practical method of control. Work Practices: Work practices are an important part of a control system. If you are asked to perform a task in a certain manner to limit your exposure to formaldehyde, it is extremely important that you follow these procedures.
Medical Surveillance
Medical surveillance helps to protect employees' health. Your employer must make a medical surveillance program available at no expense to you and at a reasonable time and place if you are exposed to formaldehyde at concentrations above 0.5 ppm as an 8-hour average or 2 ppm over any 15 minute period. You will be offered medical surveillance at the time of your initial assignment and once a year afterward as long as your exposure is at least 0.5 ppm (TWA) or 2 ppm (STEL). Even if your exposure is below these levels, you should inform your employer if you have signs and symptoms that you suspect, through your training, are related to your formaldehyde exposure because you may need medical surveillance to determine if your health is being impaired by your exposure. The surveillance plan includes: (a) A medical disease questionnaire. (b) A physical examination if the physician determines this is necessary. If you are required to wear a respirator, your employer must offer you a physical examination and a pulmonary function test every year. The physician must collect all information needed to determine if you are at increased risk from your exposure to formaldehyde. At the physician's discretion, the medical examination may include other tests, such as a chest x-ray, to make this determination. After a medical examination the physician will provide your employer with a written opinion which includes any special protective measures recommended and any restrictions on your exposure. The physician must inform you of any medical conditions you have which would be aggravated by exposure to formaldehyde. All records from your medical examinations, including disease surveys, must be retained at your employer's expense.