PHOSGENE

Phosgene is used as an intermediate in manufacturing a number of significant industrial chemicals such as isocyanates (i.e. toluene diisocyanate, polymethylene polyphenylisocyanate, etc.) and their derivatives (i.e. polyurethane and polycarbonate resins), carbamates, and chloroformates (ACGIH, 1996a; Hathaway et al, 1996; HSDB, 2000; ITI, 1995; Lewis, 1997a; Sittig, 1991a; WHO, 1998) .
Phosgene is utilized in production of dyes based on coal tar, triphenylmethane, and urea (ACGIH, 1996a; ITI, 1995; Lewis, 1998; Sittig, 1991a), and as an agent for ore separation by oxide chlorination and volatilization in metallurgy (Hathaway et al, 1996; HSDB, 2000; Lewis, 1998).
This compound is occasionally employed in the manufacture of insecticides, herbicides, and pharmaceuticals (ACGIH, 1996a; ITI, 1995; Lewis, 1998; Sittig, 1991a), specifically in the production of barbiturate drugs (CGA, 1999a).
HISTORICAL USE

Prepared for the first time in 1812, phosgene had a large scale presence in World War I as an asphyxiant war gas (Clayton & Clayton, 1993; HSDB, 2000; Raffle et al, 1994).
The first chemical agent of warfare in modern times was chlorine, used by the German army at Ypres in 1915 against the Allies. Shortly thereafter, the Germans began mixing the chlorine with phosgene, or deployed phosgene alone as a weapon. Phosgene, together with arsenicals, blister agents, and mustard gas (also introduced during World War I) have been estimated to be responsible for approximately 1.3 million casualties during the war, including at least 90,000 fatalities. By the time World War I concluded, mustard gas was the most widely used, but phosgene caused the most deaths (Raffle et al, 1994).

FORMS

At room temperature, phosgene is a colorless, non-combustible, highly toxic gas that is easily liquefied (ACGIH, 1996a; Budavari, 1996; CHRIS, 2000; Grant, 1993a; Hathaway et al, 1996; Harbison, 1998a; Raffle et al, 1994; NIOSH, 2000; Raffle et al, 1994; Sittig, 1991a).

At high concentrations, the gas has an odor described as suffocating (Budavari, 1996), strong and stifling (Lewis, 1997a), and pungent and irritating (Raffle et al, 1994; Sittig, 1991a).
At lower concentrations, the odor has been widely characterized as being "haylike," similar to newly-mown hay, moldy or musty hay, or having an odor that is not pleasant and sweet, like hay (ACGIH, 1996a; Budavari, 1996; Lewis, 1996a; Lewis, 1997a; Raffle et al, 1994; Sittig, 1991a). The dilute gas odor has also been compared to that of green corn (Lewis, 1996a).

Below 0 - 8.3 degrees C or when compressed, phosgene condenses to a colorless to light yellow, non-combustible, highly toxic, fuming/volatile liquid that produces poisonous vapor and sinks in water (ACGIH, 1996a; Budavari, 1996; CHRIS, 2000; Clayton & Clayton, 1993; Harbison, 1998a; Lewis, 1998; NIOSH, 2000).
Phosgene is usually shipped as a liquefied compressed gas (Harbison, 1998a; NIOSH, 2000) in purities of 95% - 100%, dependent on intended use. Impurities may include carbon monoxide, nitrogen, hydrochloric acid, and free sulfur and chlorine compounds (CHRIS, 2000; HSDB , 2000; WHO, 1998).

SOURCES

Phosgene is produced by the following reactions:

Carbon monoxide + chlorine (Ashford, 1994a; Budavari, 1996)
Carbon monoxide + chlorine, passed over activated carbon (Lewis, 1997a)
"Phosgene is produced by reacting equimolar amounts of carbon monoxide and anhydrous chlorine in the presence of a carbon catalyst under appropriate conditions of temperature and pressure" (WHO, 1998).
Carbon monoxide + nitrosyl chloride (Budavari, 1996; HSDB, 2000)
Carbon tetrachloride + oleum (Budavari, 1996)

Phosgene is a combustion product whenever a volatile chlorine compound or its vapor contacts very hot metal or flame (Hathaway et al, 1996; Raffle et al, 1994).

Phosgene may result from decomposition of a number of chlorinated organic chemicals, such as carbon tetrachloride, methylene chloride, and trichloroethylene, in the presence of air or oxygen; the conditions of such decomposition require elevated temperatures and alkaline conditions (ACGIH, 1996a; Harbison, 1998a).
The amount of phosgene created from thermal decomposition reactions differs based on the conditions involved, such as alkalinity, heating, moisture, and hot ferrous surfaces. Enough phosgene may be generated to produce a health hazard when chlorohydrocarbon vapors are thermally decomposed in alkaline conditions and exposed to open flames or arcs that normally accompany welding operations, furnaces, and boilers (Harbison, 1998a; Glass et al, 1974; Gerritsen & Buschmann, 1960).
While usually more hydrochloric acid than phosgene is produced in thermal decomposition reactions involving chlorinated organic substances, phosgene may be the main product in photodecomposition of numerous compounds. For example, vapors of trichloroethylene, mixed with air, may undergo conversion to phosgene when acted upon by short ultraviolet light, which may occur with such processes as aluminum heliarc welding (ACGIH, 1996a).
Endogenous phosgene is produced through metabolism of select chlorinated compounds such as chloroform (Harbison, 1998a).
Phosgene and chlorine may be formed by burning polystyrene (Raffle et al, 1994).

-CLINICAL EFFECTS

GENERAL CLINICAL EFFECTS

USES: Phosgene, also known as carbonyl chloride, is a colorless irritant gas at room temperature. Historically, it was used in chemical warfare during World War I. Today, it is used in the synthesis of organic compounds such as pharmaceuticals, dyes, resins, and pesticides. Welding material cleaned with chlorinated solvents can produce phosgene gas. It can also be released following the combustion of volatile substances that include organochloride compounds (ie, polyvinyl chloride and isocyanates) found frequently in many household items such as solvents, paint removers, dry cleaning fluids, home and office furnishings, floor coverings and electrical insulation. In low concentrations, its odor is described as resembling freshly cut hay or grass, and at high concentrations the odor can be sharp and suffocating.

TOXICOLOGY: Phosgene injury caused by inhalation are dependent on phosgene concentration and/or the inhaled dose. Of note, determining the actual dose inhaled is very difficult. Phosgene is a lower respiratory tract irritant. Its low water solubility leads to less upper respiratory tract irritation. It then hydrolyzes in the lungs on contact with water to form hydrochloric acids. Phosgene initiates a cascade of inflammatory cytokines and pulmonary vascular permeability, resulting in gas diffusion abnormalities and pulmonary edema. Cases of high concentration but short-duration exposures may result in initial symptoms but no long-term effects; conversely low concentrations but longer exposures may have no immediate symptoms but result in fatal outcomes.

EPIDEMIOLOGY: Reports of phosgene poisonings are very rare. However, there has been historical use of phosgene as a chemical weapon and continued concern for this potential use in the future. In addition, fatalities have occurred due to industrial release of phosgene.

WITH POISONING/EXPOSURE

ROUTES OF EXPOSURE: Inhalation is the most common route of exposure to phosgene and may result in irritant and pulmonary effects. Dermal and/or ocular contact with phosgene gas may cause irritation and reddening of the skin and/or eyes. Severe burns may result from contact with liquid phosgene. Contamination (eg, clothing) of phosgene in solvent solution can lead to significant off-gassing and potentially continuous (ie, inhalation) exposure to the individual or to others (eg, coworkers, first-responders). Ingestion of phosgene is unlikely.
MILD TO MODERATE TOXICITY: IRRITANT EFFECTS: Immediate onset of symptoms are usually due to the irritant effects of phosgene. Severity is based on vapor concentrations of the gas and not the exposure dose. Contact with gas concentrations greater than 3 ppm can cause immediate irritation and pain of the mucous membranes (ie, eyes, nose, throat and bronchi). Symptoms may include conjunctivitis, rhinitis, pharyngitis, bronchitis, lacrimation, blepharospasm, conjunctival hyperemia, and upper respiratory tract irritation. Levels greater than 3 ppm causes throat irritation, levels greater than 4 ppm cause eye irritation, and levels of greater than 4.8 ppm can induce cough and chest tightness.
SEVERE TOXICITY: PULMONARY EFFECTS: Based on the inhaled dose (not the exposure concentration), severe pulmonary toxicity (including pulmonary edema) may occur. Although signs and symptoms of inhalation exposure can be divided into 3 phases (ie, reflex, latency, terminal), patients may NOT develop distinct phases of exposure or the phases may be clinically unrecognizable.

REFLEX PHASE: Following inhalation concentrations of greater than 3 ppm, patients develop shallow, rapid breathing due to a vagal reflex action that can cause decreased vital capacity and volume producing mild hypoxemia and mild respiratory acidosis. During this phase, patients can experience pain in the eyes and throat, chest tightness, shortness of breath, wheezing, coughing, hypotension, bradycardia and possible dysrhythmias.
DELAYED (LATENCY PHASE) EFFECTS: Depending on the inhaled dose (ie, higher exposure doses usually result in a shorter symptom-free period) there can be a symptom free period of up to 48 hours. However, biochemical effects (ie, histologic changes) start immediately after exposure. Following the symptom-free period, symptoms of cough, chest tightness, dyspnea, tachypnea and pulmonary edema can develop. INHALATION DOSE: Inhalation dose of less than 50 ppm-min: no clinical pulmonary effects; 50 to 150 ppm-min: subclinical pulmonary reactions (edema unlikely); 150 ppm-min or above: pulmonary edema probable; 300 ppm-min or above: life-threatening pulmonary edema anticipated. PROGNOSTIC INDICATOR: Generally, the shorter the latency period, the worse the prognosis.
CLINICAL (TERMINAL PHASE) EFFECTS: Progressive dyspnea, crackles throughout the lung fields and cyanosis are present. Symptoms can include pulmonary edema, cough, choking sensation, tachypnea, and production of foaming bloody sputum. Secondary to severe pulmonary edema, cardiac failure has also occurred.

OTHER CLINICAL EFFECTS: Phosgene-induced hypoxia/anoxia and hypotension can cause injury to the heart, brain, kidneys and liver, and metabolic acidosis. Hematologic events (ie, intravascular hemolysis and coagulopathy, leukocytosis) have been associated with very high concentrations of phosgene (ie, greater than 200 ppm).
DERMAL EXPOSURE: Severe dermal burns or frostbite may develop from skin exposure. Vapor contact (greater than 3 ppm) with moist or wet skin can produce mild irritation and erythema, however, serious injury has not been reported from this type of exposure. Liquid phosgene can be a frostbite hazard.
OCULAR EXPOSURE: Contact with splashed liquid phosgene has produced complete corneal opacification, perforation, and symblepharon in one case. Exposure to phosgene gas has caused conjunctival inflammation.
NON-SPECIFIC EFFECTS: Headache, anxiety, and nausea may be reported.

POTENTIAL HEALTH HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)

TOXIC; may be fatal if inhaled, ingested or absorbed through skin.
Vapors are extremely irritating and corrosive.
Contact with gas or liquefied gas may cause burns, severe injury and/or frostbite.
Fire will produce irritating, corrosive and/or toxic gases.
Runoff from fire control may cause pollution.

-FIRST AID

FIRST AID AND PREHOSPITAL TREATMENT

SUMMARY

INHALATION: For inhalational exposures, the mainstay of treatment is removal of the patient(s) from phosgene exposure to fresh air. Phosgene may be fatal if inhaled or absorbed through the skin in sufficient amounts. Remove clothing suspected of being contaminated with liquid or gaseous phosgene or solvents containing phosgene to avoid contamination of other individuals by direct contact or through off-gassing of phosgene. Double-bag all items for disposal. Begin oxygen therapy after phosgene inhalation, if the victim shows signs of hypoxemia or respiratory distress or has a pulse oximetry reading of less than 94%.
DERMAL: Remove clothing as described above. Skin contamination with liquid or gaseous phosgene or solvents containing phosgene, should be washed copiously with warm water for at least 15 minutes.
OCULAR: Copiously irrigate eyes with plain water or saline following exposure to liquids containing phosgene.
FROSTBITE: Frostbite has not been commonly reported but is a potential risk following contact with liquid phosgene. If frostbite has developed after exposure, seek medical attention immediately and do NOT flush exposed area with water. Carefully observe patients for signs of systemic symptoms and administer treatment as necessary.

-MEDICAL TREATMENT

LIFE SUPPORT

Support respiratory and cardiovascular function.

SUMMARY

FIRST AID - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)

Move victim to fresh air.
Call 911 or emergency medical service.
Give artificial respiration if victim is not breathing.
Do not use mouth-to-mouth method if victim ingested or inhaled the substance; give artificial respiration with the aid of a pocket mask equipped with a one-way valve or other proper respiratory medical device.
Administer oxygen if breathing is difficult.
Remove and isolate contaminated clothing and shoes.
In case of contact with liquefied gas, thaw frosted parts with lukewarm water.
In case of contact with substance, immediately flush skin or eyes with running water for at least 20 minutes.
In case of contact with Hydrogen fluoride, anhydrous (UN1052), flush skin and eyes with water for 5 minutes; then, for skin exposures rub on a calcium/jelly combination; for eyes flush with a water/calcium solution for 15 minutes.
Keep victim warm and quiet.
Keep victim under observation.
Effects of contact or inhalation may be delayed.
Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves.

FIRST AID

FIRST AID

EYE EXPOSURE (LIQUID): Immediately wash the eyes with large amounts of water, occasionally lifting the lower and upper lids. Get medical attention immediately. Contact lenses should not be worn when working with this chemical.
DERMAL EXPOSURE (LIQUID): Immediately flush the contaminated skin with water. If this chemical penetrates the clothing, immediately remove the clothing and flush the skin with water. Get medical attention promptly.
INHALATION EXPOSURE: Move the exposed person to fresh air at once. If breathing has stopped, perform artificial respiration. Keep the affected person warm and at rest. Get medical attention as soon as possible.
TARGET ORGANS: Eyes, skin, and respiratory system (National Institute for Occupational Safety and Health, 2007).

SUMMARY

Phosgene may be fatal if inhaled or absorbed through the skin in sufficient amounts. Move victims of inhalation exposure from the toxic environment. Remove clothing suspected of being contaminated with liquid or gaseous phosgene or solvents containing phosgene to avoid contamination of other individuals by direct contact or through off-gassing of phosgene. Double-bag all items for disposal. Begin oxygen therapy after phosgene inhalation, if the victim shows signs of hypoxemia or respiratory distress or has a pulse oximetry reading of less than 94%.
DERMAL: Skin contamination with liquid or gaseous phosgene or solvents containing phosgene, should be washed copiously with warm water for at least 15 minutes (American Chemical Council, 2014).
OCULAR: Copiously irrigate eyes with plain water or saline following exposure to liquids containing phosgene (American Chemical Council, 2014).
FROSTBITE: Frostbite has not been commonly reported but is a potential risk following contact with liquid phosgene (Vaish et al, 2013). If frostbite has developed after exposure, seek medical attention immediately and do NOT flush exposed area with water. Carefully observe patients for signs of systemic symptoms and administer treatment as necessary.
Obtain dosimetry reading from the victim's phosgene badge following an occupational exposure to estimate exposure dose, if possible. To decrease the risk of secondary contamination, a phosgene badge or detector tape can verify if off-gassing is present prior to transport of the patient (American Chemical Council, 2014).

INHALATION EXPOSURE

Carefully observe patients with inhalation exposure for the development of any systemic signs or symptoms and administer symptomatic treatment as necessary.
Begin oxygen therapy after phosgene inhalation, if the victim shows signs of hypoxemia or respiratory distress or has a pulse oximetry reading of less than 94%.
If oxygen is needed, use the lowest concentration of oxygen to maintain the SaO2 in the normal range (Grainge & Rice, 2010).
ACUTE LUNG INJURY: Maintain ventilation and oxygenation and evaluate with frequent arterial blood gases and/or pulse oximetry monitoring. Early use of positive pressure airway ventilation and mechanical ventilation may be needed.

DERMAL EXPOSURE

DECONTAMINATION: Remove contaminated clothing and jewelry and place them in plastic bags. Wash exposed areas with soap and water for 10 to 15 minutes with gentle sponging to avoid skin breakdown. A physician may need to examine the area if irritation or pain persists (Burgess et al, 1999).
FROSTBITE: Frostbite has not been commonly reported but is a potential risk following contact with liquid phosgene (Vaish et al, 2013). If frostbite has developed after exposure, seek medical attention immediately and do NOT flush exposed area with water. Carefully observe patients for signs of systemic symptoms and administer treatment as necessary.

EYE EXPOSURE

DECONTAMINATION: Remove contact lenses and irrigate exposed eyes with copious amounts of room temperature 0.9% saline or water for at least 15 minutes. If irritation, pain, swelling, lacrimation, or photophobia persist after 15 minutes of irrigation, the patient should be seen in a healthcare facility.
If contact with escaping gas may have caused frostbite of the eyes, DO NOT flush with water; early ophthalmologic consultation should be obtained.

ORAL EXPOSURE

Oral exposure to escaping gas might cause frostbite injury to the upper gastrointestinal and respiratory tracts. Assess and maintain airway clinically indicated.
Observe patients with ingestion carefully for the possible development of esophageal or gastrointestinal tract irritation or burns. If signs or symptoms of esophageal irritation or burns are present, consider endoscopy to determine the extent of injury.

-RANGE OF TOXICITY

MINIMUM LETHAL EXPOSURE

The lowest published lethal concentration for a human is 50 ppm for 5 minutes ((RTECS, 2000)).

Breathing phosgene concentrations exceeding 0.25 mg/L of air, or 62 ppm, for greater than or equal to 0.5 hours may prove fatal. Death occurs within a few minutes of exposure to 3 to 5 mg/L (HSDB , 2000).

Inhalation exposure to 500 ppm for 1 minute has been reported to be the LC50 for a human. It has also been reported that exposure levels of 3 ppm for 170 minutes were equally fatal to 30 ppm for 17 minutes (ACGIH, 1996; Hathaway et al, 1996).

CASE REPORT: A 58-year-old man was inadvertently exposed to 300 ppm/min of phosgene in less than a tenth of a second (based on later findings from his dosimetry badge) and died approximately 30 hours after exposure from profound hypoxemia with respiratory acidosis along with fulminant pulmonary edema. Despite early aggressive measures including intubation, IV methylprednisolone, nebulized N-acetylcysteine and albuterol and IV terbutaline and ibuprofen, the patient continued to be hypoxic and developed overwhelming acute respiratory distress syndrome (Hardison et al, 2014).

MAXIMUM TOLERATED EXPOSURE

WORKPLACE EXPOSURE

The NIOSH TLV TWA is 0.1 ppm (American Conference of Governmental Industrial Hygienists, 2010) and 2 ppm is considered immediately dangerous to life and health (IDLH) (National Institute for Occupational Safety and Health, 2007).

DOSE AND CONCENTRATION

Phosgene injury caused by inhalation are dependent on phosgene concentration and/or the inhaled dose (American Conference of Governmental Industrial Hygienists, 2010).
IRRITANT EFFECTS: Severity of immediate symptoms is based on vapor concentrations of the gas and not the exposure dose (American Conference of Governmental Industrial Hygienists, 2010; Grainge & Rice, 2010; Borak & Diller, 2001).
PULMONARY EFFECTS: Based on the inhaled dose (not the exposure concentration), severe pulmonary toxicity (including pulmonary edema) may occur (American Conference of Governmental Industrial Hygienists, 2010; Vaish et al, 2013; Gutch et al, 2012; Borak & Diller, 2001).

PHOSGENE CONCENTRATION AND EFFECT

Greater than 0.125 ppm: Odor perception (American Conference of Governmental Industrial Hygienists, 2010)
Greater than 1.5 ppm: Recognition of odor (American Conference of Governmental Industrial Hygienists, 2010)
IRRITANT EFFECTS: Greater than 3 ppm: Irritation of eyes, nose, throat and bronchi (American Conference of Governmental Industrial Hygienists, 2010)
Olfactory fatigue occurs with exposure to phosgene. The odor threshold for this compound can rise from 0.4 ppm to 1.5 ppm with adaption recognition, thus phosgene is considered to have poor odor warning properties (WHO, 1998).

INHALATION EXPOSURE

PULMONARY EFFECTS

An inhalation dose of less than 50 ppm-min: No clinical pulmonary effect (American Conference of Governmental Industrial Hygienists, 2010; Borak & Diller, 2001).
An inhalation dose of 50 to 150 ppm-min: Subclinical pulmonary reactions; pulmonary edema unlikely (American Conference of Governmental Industrial Hygienists, 2010).
An inhalation dose of 150 ppm-min or above: Pulmonary edema probable (American Conference of Governmental Industrial Hygienists, 2010; Borak & Diller, 2001).
An inhalation dose of 300 ppm-min or above: Life-threatening pulmonary edema expected (American Conference of Governmental Industrial Hygienists, 2010; Borak & Diller, 2001).

SUMMARY

There are varied reports of human phosgene exposure concentration levels:

Short term exposure to phosgene levels of 12 mg/m(3) results in throat irritation;
Short term exposure to concentrations of 16 mg/m(3) results in eye irritation;
No permanent adverse effects occur at doses below 100 mg/m(3);
Exposure to air concentrations of greater than 600 mg/m(3)-minute results in pulmonary edema;
There have been fatalities reported at concentrations greater than 400 mg/m(3)-minute;
Severe tissue damage and death may occur with a several-hour exposure to 6 mg/m(3) (the odor threshold for phosgene).
Reference: (WHO, 1998)

According to WHO (1998)

Short term exposure to phosgene levels of 12 mg/m(3) results in throat irritation;
Short term exposure to concentrations of 16 mg/m(3) results in eye irritation;
No permanent adverse effects occur at doses below 100 mg/m(3);
Exposure to air concentrations of greater than 600 mg/m(3)-minute results in pulmonary edema;
There have been fatalities reported at concentrations greater than 400 mg/m(3)-minute;
Severe tissue damage and death may occur with a several-hour exposure to 6 mg/m(3) (the odor threshold for phosgene).
Reference: (WHO, 1998)

At concentrations of 3 ppm, there is an immediate irritation of the throat;
Immediate irritation of the eyes occurs at 4 ppm;
A concentration of 4.8 ppm causes coughing;
An exposure of over 50 ppm may cause rapid death.
Reference: (Hathaway et al, 1996)

According to Hathaway et al (1996)

At concentrations of 3 ppm, there is an immediate irritation of the throat;
Immediate irritation of the eyes occurs at 4 ppm;
A concentration of 4.8 ppm causes coughing;
An exposure of over 50 ppm may cause rapid death.
Reference: (Hathaway et al, 1996)

Acute phosgene exposures of 25 ppm/minute rarely cause human lower respiratory tract problems;
Exposure of 2 to 50 ppm/minute have been responsible for chemical bronchitis;
Exposures of 50 to 150 ppm/minute may result in pulmonary edema.
Reference: (Clayton & Clayton, 1994a)

Clayton & Clayton (1994) Reports

Acute phosgene exposures of 25 ppm/minute rarely cause human lower respiratory tract problems;
Exposure of 2 to 50 ppm/minute have been responsible for chemical bronchitis;
Exposures of 50 to 150 ppm/minute may result in pulmonary edema.
Reference: (Clayton & Clayton, 1994a)

Carcinogenicity Ratings for CAS75-44-5 :

ACGIH (American Conference of Governmental Industrial Hygienists, 2010): Not Listed ; Listed as: Phosgene
EPA (U.S. Environmental Protection Agency, 2011): Inadequate information to assess carcinogenic potential. ; Listed as: Phosgene
IARC (International Agency for Research on Cancer (IARC), 2016; International Agency for Research on Cancer, 2015; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2010a; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2008; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2007; IARC Working Group on the Evaluation of Carcinogenic Risks to Humans, 2006; IARC, 2004): Not Listed
NIOSH (National Institute for Occupational Safety and Health, 2007): Not Listed ; Listed as: Phosgene
MAK (DFG, 2002): Not Listed
NTP (U.S. Department of Health and Human Services, Public Health Service, National Toxicology Project ): Not Listed

TOXICITY AND RISK ASSESSMENT VALUES

EPA IRIS

EPA Risk Assessment Values for CAS75-44-5 (U.S. Environmental Protection Agency, 2011):

Oral:

Slope Factor:
RfD: Information reviewed but value not estimated.

Inhalation:

Unit Risk:
RfC: 3x10(-4) mg/m3

Drinking Water:

Unit Risk:

TOXICITY VALUES

References: ITI, 1995 Lewis, 1996 RTECS, 2000 WHO, 1998
- LC- (INHALATION)GUINEA_PIG:
- LC50- (INHALATION)CAT:
- LC50- (INHALATION)GUINEA_PIG:
- LC50- (INHALATION)HUMAN:
- LC50- (INHALATION)MOUSE:
- LC50- (INHALATION)PRIMATE:
- LC50- (INHALATION)RABBIT:
- LC50- (INHALATION)RAT:
- LCLo- (INHALATION)CAT:
- LCLo- (INHALATION)DOG:
- LCLo- (INHALATION)HUMAN:
- TCLo- (INHALATION)HUMAN:
- TCLo- (INHALATION)RAT:

CALCULATIONS

AMBIENT CONVERSIONS

1 ppm = 4.05 mg phosgene/m(3) air (at 68 degrees F and 760 mmHg) (NIOSH , 2000; WHO, 1998)
1 mg phosgene/m(3) = 0.25 ppm (at 25 degrees C and 101.3 kPa) (WHO, 1998)

-STANDARDS AND LABELS

WORKPLACE STANDARDS

ACGIH TLV Values for CAS75-44-5 (American Conference of Governmental Industrial Hygienists, 2010):

Editor's Note: The listed values are recommendations or guidelines developed by ACGIH(R) to assist in the control of health hazards. They should only be used, interpreted and applied by individuals trained in industrial hygiene. Before applying these values, it is imperative to read the introduction to each section in the current TLVs(R) and BEI(R) Book and become familiar with the constraints and limitations to their use. Always consult the Documentation of the TLVs(R) and BEIs(R) before applying these recommendations and guidelines.

Adopted Value

Phosgene

TLV:

TLV-TWA: 0.1 ppm
TLV-STEL:
TLV-Ceiling:

Notations and Endnotes:

Carcinogenicity Category: Not Listed
Codes: Not Listed
Definitions: Not Listed

TLV Basis - Critical Effect(s): URT irr; pulm edema; pulm emphysema
Molecular Weight: 98.92

For gases and vapors, to convert the TLV from ppm to mg/m(3):

[(TLV in ppm)(gram molecular weight of substance)]/24.45

For gases and vapors, to convert the TLV from mg/m(3) to ppm:

[(TLV in mg/m(3))(24.45)]/gram molecular weight of substance

AIHA WEEL Values for CAS75-44-5 (AIHA, 2006):

Not Listed

NIOSH REL and IDLH Values for CAS75-44-5 (National Institute for Occupational Safety and Health, 2007):

Listed as: Phosgene
REL:

TWA: 0.1 ppm (0.4 mg/m(3))
STEL:
Ceiling: 0.2 ppm (0.8 mg/m(3)) [15-minute]
Carcinogen Listing: (Not Listed) Not Listed
Skin Designation: Not Listed
Note(s):

IDLH:

IDLH: 2 ppm
Note(s): Not Listed

OSHA PEL Values for CAS75-44-5 (U.S. Occupational Safety, and Health Administration (OSHA), 2010):

Listed as: Phosgene (Carbonyl chloride)
Table Z-1 for Phosgene (Carbonyl chloride):

8-hour TWA:

ppm: 0.1

Parts of vapor or gas per million parts of contaminated air by volume at 25 degrees C and 760 torr.

mg/m3: 0.4

Milligrams of substances per cubic meter of air. When entry is in this column only, the value is exact; when listed with a ppm entry, it is approximate.

Ceiling Value:
Skin Designation: No
Notation(s): Not Listed

OSHA List of Highly Hazardous Chemicals, Toxics, and Reactives for CAS75-44-5 (U.S. Occupational Safety and Health Administration, 2010):

Threshold Quantity, in pounds:100
Threshold Quantity, in pounds:100

ENVIRONMENTAL STANDARDS

EPA CERCLA, Hazardous Substances and Reportable Quantities for CAS75-44-5 (U.S. Environmental Protection Agency, 2010):

Listed as: Phosgene
Final Reportable Quantity, in pounds (kilograms):

10 (4.54)

Additional Information:
Listed as: Carbonic dichloride
Final Reportable Quantity, in pounds (kilograms):

10 (4.54)

Additional Information:

EPA CERCLA, Hazardous Substances and Reportable Quantities, Radionuclides for CAS75-44-5 (U.S. Environmental Protection Agency, 2010):

Not Listed

EPA RCRA Hazardous Waste Number for CAS75-44-5 (U.S. Environmental Protection Agency, 2010b):

Listed as: Carbonic dichloride
P or U series number: P095
Footnote:
Listed as: Phosgene
P or U series number: P095
Footnote:
Editor's Note: The D, F, and K series waste numbers and Appendix VIII to Part 261 -- Hazardous Constituents were not included. Please refer to 40 CFR Part 261.

EPA SARA Title III, Extremely Hazardous Substance List for CAS75-44-5 (U.S. Environmental Protection Agency, 2010):

Listed as: Phosgene
Reportable Quantity, in pounds: 10

Only the statutory or final RQ is shown. For more information, see 40 CFR table 302.4.

Threshold Planning Quantity, in pounds:

10
Amount necessary to be covered by this standard. See 40 CFR 355.30.

Note(s): f

f: Chemicals on the original list that do not meet toxicity criteria but because of their acute lethality, high production volume and known risk are considered chemicals of concern ("Other chemicals"). (November 17, 1986, and February 15, 1990.)

EPA SARA Title III, Community Right-to-Know for CAS75-44-5 (40 CFR 372.65, 2006; 40 CFR 372.28, 2006):

Listed as: Phosgene
Effective Date for Reporting Under 40 CFR 372.30: 1/1/87
Lower Thresholds for Chemicals of Special Concern under 40 CFR 372.28:

DOT List of Marine Pollutants for CAS75-44-5 (49 CFR 172.101 - App. B, 2005):

Not Listed

EPA TSCA Inventory for CAS75-44-5 (EPA, 2005):

Listed as: Carbonic dichloride

SHIPPING REGULATIONS

SURFACE

DOT -- Table of Hazardous Materials and Special Provisions for UN/NA Number 1076 (49 CFR 172.101, 2005):

Hazardous materials descriptions and proper shipping name: Phosgene

Symbol(s): Not Listed
Hazard class or Division: 2.3

2.3: Poisonous gas. See 49 CFR section 173.115 for definitions.

Identification Number: UN1076
Packing Group: Not Listed
Label(s) required (if not excepted): 2.3, 8

2.3: Poison Gas.
8: Corrosive.

Special Provisions: 1, B7, B46

1: This material is poisonous by inhalation (see sxn. 171.8 of this subchapter) in Hazard Zone A (see sxn. 173.116(a) or sxn. 173.133(a) of this subchapter), and must be described as an inhalation hazard under the provisions of this subchapter.
B7: Safety relief devices are not authorized on multi-unit tank car tanks. Openings for safety relief devices on multi-unit tank car tanks shall be plugged or blank flanged.
B46: The detachable protective housing for the loading and unloading valves of multi-unit tank car tanks must withstand tank test pressure and must be approved by the Associate Administrator.

Packaging Authorizations (refer to 49 CFR 173.***):

Exceptions: None
Non-bulk packaging: 192
Bulk packaging: 314

Quantity Limitations:

Passenger aircraft or railcar: Forbidden
Cargo aircraft only: Forbidden

Vessel Stowage Requirements:

Vessel stowage location: D

D: The material must be stowed "on deck only" on a cargo vessel and on a passenger vessel carrying a number of passengers limited to not more than the larger of 25 passengers or one passenger per each 3 m of overall vessel length, but the material is prohibited on passenger vessels in which the limiting number of passengers is exceeded.

Vessel stowage other: 40

40: Stow "clear of living quarters".

ICAO International Shipping Name for UN1076 (ICAO, 2002):

Proper Shipping Name: Phosgene
UN Number: 1076

LABELS

NFPA

NFPA Hazard Ratings for CAS75-44-5 (NFPA, 2002):

Not Listed

-HANDLING AND STORAGE

SUMMARY

INDUSTRIAL CHEMICALS

Phosgene is listed as a Class A poison and classified as "extremely dangerous" by the U.S. Department of Transportation. This compound should be handled and stored with extreme caution, and every action should be taken to ensure safety, as with all poison gases (CGA, 1999).
Avoiding or minimizing exposure to phosgene is the most effective way to prevent contamination and the toxicity and other dangers involved. As suggested by standard industrial hygiene practices, control measures such as substituting a less hazardous compound for phosgene, engineering and administrative controls, and personal protective equipment may all be utilized to prevent contamination/exposure (Clayton & Clayton, 1994).

HANDLING

Phosgene is listed as a Class A poison and classified as "extremely dangerous" by the U.S. Department of Transportation (CGA, 1999).

Prevent the possibility of exposure to phosgene vapors. Wear a positive pressure breathing apparatus when exposure potential exists (AAR, 1998; CHRIS , 2000; ITI, 1995). Persons with the potential for phosgene exposure should be supplied with personal monitors (WHO, 1998).

For any place with the potential for phosgene gas to be present above safe limits, it is strongly recommended to have automatic continuous monitors with alarm systems installed (Sittig, 1991). Preferably, such alarms should emit warning when a phosgene concentration of 0.8 mg/m(3) is detected (WHO, 1998).

Measures should be taken to maintain workplace phosgene concentration levels below 0.4 to 0.5 mg/m(3). At these levels, phosgene is not detectable by paper strip monitors (WHO, 1998).

Bodily contact with this compound should be avoided. People handling liquid phosgene should always be equipped with the appropriate personal protective equipment to prevent possibility of skin or eye contact (AAR, 1998; NIOSH , 2000; Sittig, 1991).

Appropriate chemical protective gloves, goggles, boots, body shield, etc., should be employed (ITI, 1995).
Contact lenses should not be worn where phosgene is handled (HSDB , 2000).
For more detailed information on the appropriate personal protective equipment for phosgene, see the "Personal Protection" section.

Emergency showers should be present within the immediate handling area. Workers should immediately wash skin contaminated with phosgene and remove contaminated, non-impervious clothing (AAR, 1998; NIOSH , 2000; Sittig, 1991).

It is highly recommended for phosgene handling to take place within high efficiency draft chambers or outdoors within a protective wall (ITI, 1995).

In buildings where phosgene is handled, ventilation systems should exist that remove the gas from personal breathing zones, prevent build-up or recirculation of the gas, and ensure concentrations of gas within the standards (HSDB , 2000).

STORAGE

CONTAINER

Phosgene should be stored in tightly closed, corrosion-resistant steel containers, which should be inspected for leaks on a frequent basis (Sittig, 1991; WHO, 1998).
Protect the containers from physical damage that may result from falling, hitting, or rolling (ITI, 1995; WHO, 1998).
It is absolutely necessary to take all precautions to guard closed phosgene containers against the entrance of moisture. The compound's reaction with moisture, which produces hydrochloric acid and carbon dioxide, may lead to corrosion and rupture of containers. Containers should also be protected against heat and direct sunlight (CGA, 1999; ITI, 1995; WHO, 1998).
Phosgene should only be present in the minimum quantities necessary to maintain operations. Containers of phosgene should not be stored full, and should be used according to a "first-in, first-out" practice. If full containers do exist, they should be clearly labeled as such, and containers in use should likewise be clearly marked as "In Use" (HSDB , 2000).

ROOM/CABINET RECOMMENDATIONS

Store phosgene in a dry, cool, well-ventilated and fireproof area, out of direct sunlight (ITI, 1995; Sittig, 1991).
Storage must provide for phosgene's mandatory isolation from water, moisture, or steam to prevent possible violent reactions. Phosgene should be stored away from all other materials (Sittig, 1991; WHO, 1998).
Complete isolation should exist between phosgene storage areas and work areas. If a common wall separates the two area types, all possible pathways (such as ducts, pass-throughs, doors, and holes) for phosgene to escape from the storage area to other areas should be sealed and secured (HSDB , 2000; Sittig, 1991).
Ventilation for the storage area should be at floor level, and phosgene should be stored away from cooling and heating ducts (Sittig, 1991; WHO, 1998).

INCOMPATIBILITIES

Phosgene reacts with water, moisture, and steam, producing hydrochloric acid and carbon dioxide (CGA, 1999; Pohanish & Greene, 1997; Raffle et al, 1994; WHO, 1998).
Protect the substance from sources of ignition (AAR, 1998) and heat. At high temperatures, phosgene dissociates into carbon monoxide and chlorine (CGA, 1999; WHO, 1998).
Violent reactions result from phosgene's interaction with strong oxidizers, chemically active metals, isopropyl alcohol, and anhydrous ammonia (Pohanish & Greene, 1997).
In moist conditions, phosgene will attack most metals (Pohanish & Greene, 1997).
For more information regarding compounds/materials that are incompatible/reactive in relation to phosgene, see the "Reactivity Hazard" section.

-PERSONAL PROTECTION

SUMMARY

RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)

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.

RESPIRATORY PROTECTION

Refer to "Recommendations for respirator selection" in the NIOSH Pocket Guide to Chemical Hazards on TOMES Plus(R) for respirator information.

PROTECTIVE CLOTHING

CHEMICAL PROTECTIVE CLOTHING. Search results for CAS 75-44-5.

All data are compiled from published sources and are NOT recommended specifically by Truven Health Analytics. The appearance of specific manufacturers or products in this section does not represent an endorsement by Truven Health Analytics. No attempt has been made to verify the data presented. All product recommendations should be confirmed with the specific manufacturer for verification of product performance.
CLOTHING

Chlorinated Polyethylene

Standard Safety Equipment Company

ChemMaster

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: Not Listed
Citation: (Standard Safety Equipment, 1995)

Plastic Laminate

DuPont Personal Protection

Reflector

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: Not Listed
Citation: (DuPont, 2002)

Responder

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): None detected
Notes: Not Listed
Citation: (DuPont, 2002)

Responder Plus

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): None detected
Notes: Not Listed
Citation: (DuPont, 2002)

Tychem 10,000

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): 0.002
Notes: gas
Citation: (DuPont, 2002)

Tychem 7500

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: gas
Citation: (DuPont, 2002)

Tychem 9400

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: gas
Citation: (DuPont, 2002)

Tychem BR

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: Not Listed
Citation: (DuPont, 2002)

Tychem F

Degradation Rating: Not Listed
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.02
Notes: Not Listed
Citation: (DuPont, 2003)

Tychem LV

Degradation Rating: Not Listed
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: Not Listed
Citation: (DuPont, 2003)

Tychem QC

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: gas
Citation: (DuPont, 2002)

Tychem SL

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): Not Tested
Permeation Rate (mcg/cm2/min): Not Tested
Notes: gas
Citation: (DuPont, 2002)

Tychem ThermoPro

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.02
Notes: Not Listed
Citation: (DuPont, 2003)

Tychem TK

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: gas
Citation: (DuPont, 2002)
Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: Not Listed
Citation: (DuPont, 2002)

Teflon Laminate

Mar-Mac Manufacturing, Inc.

Commander Ultrapro

Degradation Rating: No Degradation Rating provided
Breakthrough Time (minutes): >480
Permeation Rate (mcg/cm2/min): <0.1
Notes: Not Listed
Citation: (Mar-Mac Manufacturing, Inc, 1995)

FOOTWEAR

Specific recommendations and test data for this product type were not found in the available manufacturers' product literature.

GLOVES

Specific recommendations and test data for this product type were not found in the available manufacturers' product literature.

GENERAL INFORMATION

This section provides a compilation of chemical resistance information and test data for specific protective clothing products. Chemical resistance information includes both degradation resistance ratings and permeation resistance data. This information is designed to assist in the selection of appropriate protective clothing. Only data on specific products and manufacturers are included. Generic information or recommendations are not provided since significant differences can exist in the chemical resistance for apparent similar product types.
Specific product information is organized by general product type (gloves, garments, and footwear), material type, and manufacturer. The category 'garments' may include totally encapsulating suits, splash suits, as well as other items (e.g., coveralls, jackets, and aprons). Specific manufacturers should be contacted to determine the features of available styles/models.
In addition to chemical resistance information, there are many critical variables in the selection of protective clothing which cannot be represented in this summary of the literature. Some factors to be considered in choosing protective clothing include, but are not limited to: overall clothing integrity, physical hazard resistance, durability, human factors, ease of decontamination, and cost. Overall clothing integrity refers to a specific design's ability to offer consistent protection for all clothing-covered areas of the body. Physical hazards include resisting the effects of abrasion, cuts, tears, and punctures. Human factors entail effects on wearer mobility, visibility, and hearing for garments; dexterity, tactility, and grip for gloves; ankle support and weight for footwear; and, any effect of the clothing on the function of the wearer. There are several variations in the design for gloves, garments, and footwear that affect these factors. Protective clothing must properly be sized and correctly fit the wearer to ensure its proper use and function.
As required in the U.S.A., protective clothing should be selected based on a risk assessment of the workplace. This risk assessment must account for the identification of existing as well as potential hazards and involve the recommendation of protective clothing appropriate for the identified hazards. Therefore, the recommendations in this section should not be used as the sole basis for decisions on choice of protective clothing, but rather should be used as a tool by qualified occupational health and safety professionals or other technically qualified persons in conjunction with a review of all mitigating factors. Consult the OSHA PPE Standard (29 CFR 1910.132 - 1910.138) for regulations and additional guidance regarding the selection and use of protective clothing and equipment. For general information on protective clothing selection, refer to the "PERSONAL PROTECTIVE EQUIPMENT - OSHA PUB 3077" document.
PROTECTIVE CLOTHING SELECTION

Determine the type of protective clothing item needed based on a risk assessment (e.g., gloves, garments, footwear).
For high risk situations, choose clothing that covers all parts of the body that may be exposed. In many cases, multiple clothing items will be required. Low risk situations may permit partial body protective clothing. Select protective clothing products that have reported chemical resistance data. High risk situations involving full body clothing or extended chemical contact often require permeation resistance data to determine the barrier effectiveness of materials used in the construction of clothing. Relatively low risk situations, where only splash or incidental exposure occur, may allow use of protective clothing based on degradation or penetration resistance data. Specifics on the interpretation of chemical resistance data are presented below.
Other factors must be considered in addition to chemical resistance. The selected chemical protective clothing item should offer the optimal combination of protection against identified hazards while allowing maximum function and comfort.

INTERPRETATION OF DEGRADATION RATINGS

Degradation refers to physical changes in a material as the result of chemical exposure. Degradation may become evident in visible changes, such as discoloration, swelling, delamination, deterioration, or disintegration. Degradation effects may also be measured by weight change or other changes in a material's physical properties (e.g., strength, elasticity, hardness).
Degradation resistance ratings are provided by manufacturers to rate the amount of degradation that occurs for a particular protective clothing material when contacted by a chemical. All degradation ratings are qualitative and include ratings, such as "EXCELLENT," "GOOD," "FAIR," "POOR," and "NOT RECOMMENDED." There is no standard test method for the measurement of chemical degradation resistance; therefore, manufacturer ratings may be based on different testing approaches. This makes comparison of degradation ratings between manufacturers unreliable.
The use of degradation resistance ratings alone to recommend protective clothing, particularly for high hazard situations, should be avoided. Degradation resistance testing does not directly assess the barrier quality of protective clothing, since materials can show relatively little degradation but still allow either permeation or penetration by a chemical. Degradation resistance ratings can be used to exclude protective clothing materials from consideration. Protective clothing materials with a "NOT RECOMMENDED" degradation resistance rating should never be used.
For some products, the rating "NO PENETRATION" is provided. This refers to penetration resistance test results that are based on a different procedure (American Society for Testing and Materials (ASTM) Standard Test Method F 903). Penetration resistance testing involves placing a material sample in a test cell, exposing the exterior side of the material to a chemical, and then observing the interior side of the material for visible signs of liquid penetration. Part of the test is conducted at an elevated pressure. Test results are reported as pass (no penetration) or fail (penetration detected). Unlike degradation testing, penetration testing provides an assessment of protective clothing material barrier performance. Since penetration resistance testing examines only observable amounts of liquid penetration, permeation may still occur. The use of penetration resistance data must be restricted to liquid chemicals, and should be limited to scenarios where there is no reasonable vapor exposure hazard under the conditions of exposure.

INTERPRETATION OF PERMEATION DATA

Permeation is the process of chemical movement through a material on a molecular level. Permeation resistance refers to the ability of a material to retard or prevent chemical movement through it. Permeation may occur without any visible signs of degradation.
Permeation resistance is measured using a test cell which is divided into two halves by a protective clothing specimen. Chemical is placed on the challenge side, while the collection side is periodically monitored for permeating chemical. Permeation data were obtained in accordance with the American Society for Testing and Materials (ASTM) Standard Test Method F 739 (Resistance of Materials Used in Protective Clothing to Permeation by Liquids and Gases), unless stated otherwise. In the case of chemicals that are classified as warfare agents, the data were obtained in accordance with the Military Standard 282 (MIL-STD-282) (Military Standard, Filter Units, Protective Clothing, Gas-Mask Components, and Related Products: Performance Test Methods).
Permeation rate is the amount of chemical that passes through a material for a measured surface area per unit time. In this section, permeation rate is expressed in micrograms per square centimeter per minute (mcg/cm(2)/min). The reported permeation rate is either the steady-state rate or the maximum rate observed during testing. In some cases, very large permeation rates exceed measurement techniques and are reported as ">" (greater than) or "HIGH."
Breakthrough time is the elapsed time, in minutes, from the time the chemical comes in contact with the material exterior surface, to the time that chemical is detected on the interior surface. When no breakthrough is detected, the breakthrough time is report as ">" the testing period. If permeation breakthrough is rapid, results are reported as "<" (less than) the earlier sampling time or as "IMMEDIATELY" (which usually means breakthrough in less than 4 minutes).
The breakthrough time should exceed the expected use period of the selected protective clothing. Additionally, there are several other factors that must be taken into account to provide appropriate protection.
Permeation testing is usually conducted with full strength, undiluted chemical for the duration of the test period. Actual exposures may involve diluted chemical for short or intermittent exposure periods.
Permeation testing is usually conducted at room temperature. Permeation occurs faster at elevated temperatures (short breakthrough times and higher permeation rates) and slower at reduced temperatures (long breakthrough times and lower permeation rates).
Permeation resistance of mixtures cannot usually be determined on the basis of the individual chemicals making up the mixture. Synergistic effects may occur and result in more rapid permeation than accounted for by the individual mixture chemicals.
Permeation rates may be used to calculate potential wearer exposure; however, several assumptions must be made about the extent of exposure and condition of clothing wear. Furthermore, there are few chemicals with dermal exposure limits, making it difficult to determine an acceptable skin exposure level.

COMPANY INFORMATION

DuPont Personal Protection P. O. Box 80705 Wilmington, DE 19880-0705 USA Phone: (302) 774-1000 Toll-Free: (800) 931-3456 Website: http://personalprotection.dupont.com Email: personalprotection@usa.dupont.com
Mar-Mac Manufacturing, Inc. P. O. Box P.O. Box 278 McBee, SC 29101 USA Phone: (843) 335-8211 Fax: (843) 355-8599 Toll-Free: (843) 335-8211 Website: http://www.marmac.com Email: info@marmac.com
Standard Safety Equipment Company 1407 Ridgeview Drive McHenry, IL 60050 USA Phone: (815) 363-8565 Fax: (815) 363-8633 Toll-Free: (815) 363-8565 Website: http://www.standardsafety.com Email: solson@standardsafety.com

REFERENCES

CHEMICAL PROTECTIVE CLOTHING CITATIONS

The following sources were consulted for chemical protective clothing data:

(Ansell-Edmont, 2001)
(Bata Shoe Company, 1995)
(Best Manufacturing, 2002)
(Best Manufacturing, 2004)
(Boss Manufacturing Company, 1998)
(ChemFab Corporation, 1993)
(Comasec Safety, Inc., 2003)
(Comasec Safety, Inc., 2003a)
(DuPont, 2002)
(DuPont, 2002)
(DuPont, 2003)
(Guardian Manufacturing Group, 2001)
(ILC Dover, Inc., 1998)
(Kappler Inc., 2001)
(Kimberly-Clark, 2002)
(LaCrosse-Rainfair, 1997)
(MAPA Professional, 2003)
(MAPA Professional, 2004)
(Mar-Mac Manufacturing, Inc, 1995)
(Marigold Industrial, 2003)
(Memphis Glove Company, 2001)
(Montgomery Safety Products, 1995)
(Nat-Wear, 2001)
(Neese Industries, Inc., 2003)
(North, 2002)
(North, 2002)
(Playtex, 1995)
(River City, 1995)
(Safety 4, 2002)
(Servus, 1995)
(Standard Safety Equipment, 1995)
(Tingley, 2002)
(Trelleborg-Viking, Inc., 2001)
(Trelleborg-Viking, Inc., 2002)
(Wells Lamont Industrial, 2002)
(Workrite, 1997)

-PHYSICAL HAZARDS

FIRE HAZARD

SUMMARY

POTENTIAL FIRE OR EXPLOSION HAZARDS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)
- Some may burn, but none ignite readily.
- Vapors from liquefied gas are initially heavier than air and spread along ground.
- Some of these materials may react violently with water.
- Cylinders exposed to fire may vent and release toxic and/or corrosive gas through pressure relief devices.
- Containers may explode when heated.
- Ruptured cylinders may rocket.
Phosgene is a non-combustible material, belonging to the "Non-flammable Gas" flammability class (AAR, 1998; CHRIS , 2000; ITI, 1995; Lewis, 1997; NIOSH , 2000; WHO, 1998). However, exposure of phosgene to fire, high temperatures, and water can present serious dangers.
- Phosgene reacts with water, moisture, and steam, producing hydrochloric acid and carbon dioxide (CGA, 1999; Pohanish & Greene, 1997; Raffle et al, 1994; WHO, 1998). At high temperatures, phosgene dissociates into carbon monoxide and chlorine (CGA, 1999; WHO, 1998). Also, heat and water may cause rupture and possibly violent rocketing of vessels containing the compound, leading to release of phosgene in both liquid and gaseous states (AAR, 1998; WHO, 1998).
Use water as a fog and to cool affected phosgene containers, taking care to apply water from as far away as possible and to prevent water from entering containers (AAR, 1998; CHRIS , 2000; ITI, 1995; Sittig, 1991). When feasible, move containers away from the fire. Keep the fire area isolated until well after the fire is out (Sittig, 1991).

FLAMMABILITY CLASSIFICATION

NFPA Flammability Rating for CAS75-44-5 (NFPA, 2002):

Not Listed

FIRE CONTROL/EXTINGUISHING AGENTS

SMALL FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)

Dry chemical or CO2.

LARGE FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)

Water spray, fog or regular foam.
Move containers from fire area if you can do it without risk.
Do not get water inside containers.
Damaged cylinders should be handled only by specialists.

TANK FIRE PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)

Fight fire from maximum distance or use unmanned hose holders or monitor nozzles.
Cool containers with flooding quantities of water until well after fire is out.
Do not direct water at source of leak or safety devices; icing may occur.
Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank.
ALWAYS stay away from tanks engulfed in fire.

NFPA Extinguishing Methods for CAS75-44-5 (NFPA, 2002):

Not Listed

If the fire is small, use carbon dioxide or dry chemical as an extinguishing agent. If the fire is large, employ fog, water spray, or foam (AAR, 1998; Sittig, 1991; WHO, 1998).

COMBUSTION TOXICITY

At high temperatures (above 300 degrees C), phosgene dissociates into the toxic gases of carbon monoxide, hydrochloric acid, and chlorine (CGA, 1999; CHRIS , 2000; WHO, 1998).

EXPLOSION HAZARD

Heat and water may cause rupture and possibly violent rocketing of vessels containing the compound, leading to release of phosgene in both liquid and gaseous states (AAR, 1998; WHO, 1998).

Incompatible and reactive with alcohols, alkalis, ammonia, and copper (NIOSH , 2000).

Violent reactions result from phosgene's interaction with strong oxidizers, chemically active metals, isopropyl alcohol, and anhydrous ammonia (Pohanish & Greene, 1997).

Shock-sensitive material is formed between potassium and phosgene (Pohanish & Greene, 1997).

The reaction of phosgene and 2,4-hexadiyn-1,6-diol produces 2,4-hexadiyn-1,6-bischloroformate, a shock-sensitive material (HSDB , 2000).

Phosgene and isopropyl alcohol react to form hydrogen chloride and isopropyl chloroformate. Thermal decomposition is possible if iron salts are present, presenting a possibility for explosion (HSDB , 2000).

DUST/VAPOR HAZARD

Phosgene gas is a severe respiratory and eye irritant (AAR, 1998; Hathaway et al, 1996) and can be extremely toxic and poisonous if inhaled (AAR, 1998; CHRIS , 2000; Lewis, 1997) ERG, 2000).

Powdered aluminum will burn in phosgene vapor (HSDB , 2000).

REACTIVITY HAZARD

Phosgene reacts with water, moisture, and steam, producing hydrochloric acid and carbon dioxide (CGA, 1999; Pohanish & Greene, 1997; Raffle et al, 1994; WHO, 1998).

Protect the substance from sources of ignition (AAR, 1998) and heat. At high temperatures, phosgene dissociates into carbon monoxide and chlorine (CGA, 1999; WHO, 1998).

Containers of phosgene may rupture and rocket when exposed to water or elevated temperatures. This may release phosgene, both in gaseous and liquid forms, in addition to toxic reaction and thermal degradation products such as carbon monoxide, chlorine, and hydrochloric acid (WHO, 1998).

In moist conditions, phosgene will attack most metals (Pohanish & Greene, 1997).

Violent reactions result from phosgene's interaction with strong oxidizers, chemically active metals, isopropyl alcohol, and anhydrous ammonia (Pohanish & Greene, 1997).

Incompatible and reactive with alcohols, alkalis, ammonia, copper, and moisture (NIOSH , 2000).

Shock-sensitive material is formed between potassium and phosgene (Pohanish & Greene, 1997).

Powdered aluminum will burn in phosgene vapor (HSDB , 2000).

At approximately 260 degrees C, phosgene and sodium vapors react with luminescence (HSDB , 2000).

The reaction of phosgene and 2,4-hexadiyn-1,6-diol produces 2,4-hexadiyn-1,6-bischloroformate, a shock-sensitive material (HSDB , 2000).

Phosgene and isopropyl alcohol react to form hydrogen chloride and isopropyl chloroformate. Thermal decomposition is possible if iron salts are present, presenting a possibility for explosion (HSDB , 2000).

"In formation of tert-butyl azidoformate by addition of phosgene to alcohols followed by addition of sodium nitride or hydrazoic acid in presence of pyridine, reaction of phosgene with azide causes formation of explosive carbazide. To prevent the reaction complete removal of excess phosgene is advocated by passing nitrogen into solution prior to addition of azide" (HSDB , 2000).

EVACUATION PROCEDURES

SUMMARY

Initial Isolation and Protective Action Distances (ERG, 2004)

Data presented from the Emergency Response Guidebook Table of Initial Isolation and Protective Action Distances are for use when a spill has occurred and there is no fire. If there is a fire, or if a fire is involved, evacuation information presented under FIRE - PUBLIC SAFETY EVACUATION DISTANCES should be used.
Generally, a small spill is one that involves a single, small package such as a drum containing up to approximately 200 liters, a small cylinder, or a small leak from a large package. A large spill is one that involves a spill from a large package, or multiple spills from many small packages.
Suggested distances to protect from vapors of toxic-by-inhalation and/or water-reactive materials during the first 30 minutes following the spill.

DOT ID No. 1076 - CG

when used as a weapon
SMALL SPILLS

First isolate in all directions: 150 meters (500 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 1.3 kilometers (0.8 miles); or
during the NIGHT for: 3.3 kilometers (2 miles).

LARGE SPILLS

First isolate in all directions: 800 meters (2500 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 7.3 kilometers (4.5 miles); or
during the NIGHT for: 11.0+ kilometers (7.0+ miles).

DOT ID No. 1076 - Phosgene

SMALL SPILLS

First isolate in all directions: 90 meters (300 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 0.9 kilometers (0.6 miles); or
during the NIGHT for: 4.1 kilometers (2.6 miles).

LARGE SPILLS

First isolate in all directions: 800 meters (2500 feet).
Note wind direction.
Then protect persons downwind:

during the DAY for: 6.6 kilometers (4.1 miles); or
during the NIGHT for: 11.0+ kilometers (7.0+ miles).

SPILL - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)

Increase, in the downwind direction, as necessary, the isolation distance of at least 100 meters (330 feet) in all directions.

FIRE - PUBLIC SAFETY EVACUATION DISTANCES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)

If tank, rail car or tank truck is involved in a fire, ISOLATE for 1600 meters (1 mile) in all directions; also, consider initial evacuation for 1600 meters (1 mile) in all directions.

PUBLIC SAFETY MEASURES - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)

CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number:

MEXICO:

SETIQ:

01-800-00-214-00 in the Mexican Republic;
For calls originating in Mexico City and the Metropolitan Area: 5559-1588;
For calls originating elsewhere, call: 011-52-555-559-1588.

CENACOM:

01-800-00-413-00 in the Mexican Republic;
For calls originating in Mexico City and the Metropolitan Area: 5550-1496, 5550-1552, 5550-1485, or 5550-4885;
For calls originating elsewhere, call: 011-52-555-550-1496, or 011-52-555-550-1552; 011-52-555-550-1485, or 011-52-555-550-4885.

ARGENTINA:

CIQUIME:

0-800-222-2933 in the Republic of Argentina;
For calls originating elsewhere, call: +54-11-4613-1100.

BRAZIL:

PRÓ-QUÍMICA:

0-800-118270 (Toll-free in Brazil);
For calls originating elsewhere, call: +55-11-232-1144 (Collect calls are accepted).

COLUMBIA:

CISPROQUIM:

01-800-091-6012 in Colombia;
For calls originating in Bogotá, Colombia, call: 288-6012;
For calls originating elsewhere, call: 011-57-1-288-6012.

CANADA:

CANUTEC:

613-996-6666 (Collect calls are accepted);
*666 cellular (in Canada only).

UNITED STATES:

CHEMTREC®:

1-800-424-9300 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
703-527-3887 for calls originating elsewhere (Collect calls are accepted).

CHEM-TEL, INC.:

1-800-255-3924 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
813-248-0585 for calls originating elsewhere (Collect calls are accepted).

INFOTRAC:

1-800-535-5053 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
352-323-3500 for calls originating elsewhere (Collect calls are accepted).

3E COMPANY:

1-800-451-8346 (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
760-602-8703 for calls originating elsewhere (Collect calls are accepted).

NATIONAL RESPONSE CENTER (NRC):

1-800-424-8802 - (24 hours) (Toll-free in the U.S., Canada, and the U.S. Virgin Islands);
202-267-2675 for calls in the District of Columbia.

MILITARY SHIPMENTS:

703-697-0218 - Explosives/ammunition incidents (Collect calls are accepted);
1-800-851-8061 - All other dangerous goods incidents.

NATIONWIDE POISON CONTROL CENTER (United States only):

1-800-222-1222 (Toll-free in the U.S.).

For additional details see the section entitled "WHO TO CALL FOR ASSISTANCE" under the ERG Instructions.
As an immediate precautionary measure, isolate spill or leak area for at least 100 meters (330 feet) in all directions.
Keep unauthorized personnel away.
Stay upwind.
Many gases are heavier than air and will spread along ground and collect in low or confined areas (sewers, basements, tanks).
Keep out of low areas.
Ventilate closed spaces before entering.

Consider evacuating an area of one-third (1/3) mile radius if a fire involving phosgene becomes out of control or containers of the compound are exposed to direct flame. If there is no fire involved, but phosgene is leaking, downwind evacuation should be considered based upon the quantity involved in the spill, weather conditions, and location (AAR, 1998).

AIHA ERPG Values for CAS75-44-5 (AIHA, 2006):

Listed as Phosgene
ERPG-1 (units = ppm): Not appropriate
ERPG-2 (units = ppm): 0.2
ERPG-3 (units = ppm): 1
Under Ballot, Review, or Consideration: No
Definitions:

ERPG-1: The ERPG-1 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing more than mild, transient adverse health effects or perceiving a clearly defined objectionable odor.
ERPG-2: The ERPG-2 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing or developing irreversible or other serious health effects or symptoms that could impair an individual's ability to take protective action.
ERPG-3: The ERPG-3 is the maximum airborne concentration below which it is believed nearly all individuals could be exposed for up to one hour without experiencing or developing life-threatening health effects.

DOE TEEL Values for CAS75-44-5 (U.S. Department of Energy, Office of Emergency Management, 2010):

Listed as Phosgene
TEEL-0 (units = ppm): 0.1
TEEL-1 (units = ppm): 0.1
TEEL-2 (units = ppm): 0.3
TEEL-3 (units = ppm): 0.75
Definitions:

TEEL-0: The threshold concentration below which most people will experience no adverse health effects.
TEEL-1: The airborne concentration (expressed as ppm [parts per million] or mg/m(3) [milligrams per cubic meter]) of a substance above which it is predicted that the general population, including susceptible individuals, could experience notable discomfort, irritation, or certain asymptomatic, nonsensory effects. However, these effects are not disabling and are transient and reversible upon cessation of exposure.
TEEL-2: The airborne concentration (expressed as ppm or mg/m(3)) of a substance above which it is predicted that the general population, including susceptible individuals, could experience irreversible or other serious, long-lasting, adverse health effects or an impaired ability to escape.
TEEL-3: The airborne concentration (expressed as ppm or mg/m(3)) of a substance above which it is predicted that the general population, including susceptible individuals, could experience life-threatening adverse health effects or death.

AEGL Values for CAS75-44-5 (National Research Council, 2010; National Research Council, 2009; National Research Council, 2008; National Research Council, 2007; NRC, 2001; NRC, 2002; NRC, 2003; NRC, 2004; NRC, 2004; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; United States Environmental Protection Agency Office of Pollution Prevention and Toxics, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2009; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2008; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2007; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2005; National Advisory Committee for Acute Exposure Guideline Levels for Hazardous Substances, 2006; 62 FR 58840, 1997; 65 FR 14186, 2000; 65 FR 39264, 2000; 65 FR 77866, 2000; 66 FR 21940, 2001; 67 FR 7164, 2002; 68 FR 42710, 2003; 69 FR 54144, 2004):

Listed as: Phosgene
Proposed Value:

AEGL-1

10 min exposure:

ppm: Not recommended
mg/m3:

30 min exposure:

ppm: Not recommended
mg/m3:

1 hr exposure:

ppm: Not recommended
mg/m3:

4 hr exposure:

ppm: Not recommended
mg/m3:

8 hr exposure:

ppm: Not recommended
mg/m3:

Definitions:

AEGL-1 is the airborne concentration of a substance above which it is predicted that the general population, including susceptible individuals, could experience notable discomfort, irritation, or certain asymptomatic non-sensory effects. However, the effects are not disabling, are transient, and are reversible upon cessation of exposure.

Listed as: Phosgene
Proposed Value:

AEGL-2

10 min exposure:

ppm: 2.3 ppm
mg/m3: 9.5 mg/m(3)

30 min exposure:

ppm: 0.77 ppm
mg/m3: 3.2 mg/m(3)

1 hr exposure:

ppm: 0.38 ppm
mg/m3: 1.6 mg/m(3)

4 hr exposure:

ppm: 0.096 ppm
mg/m3: 0.39 mg/m(3)

8 hr exposure:

ppm: 0.048 ppm
mg/m3: 0.19 mg/m(3)

Definitions:

AEGL-2 is the airborne concentration of a substance above which it is predicted that the general population, including susceptible individuals, could experience irreversible or other serious, long-lasting adverse health effects or an impaired ability to escape.

Listed as: Phosgene
Proposed Value:

AEGL-3

10 min exposure:

ppm: 7.8 ppm
mg/m3: 32 mg/m(3)

30 min exposure:

ppm: 2.6 ppm
mg/m3: 11 mg/m(3)

1 hr exposure:

ppm: 1.3 ppm
mg/m3: 5.3 mg/m(3)

4 hr exposure:

ppm: 0.33 ppm
mg/m3: 1.4 mg/m(3)

8 hr exposure:

ppm: 0.16 ppm
mg/m3: 0.66 mg/m(3)

Definitions:

AEGL-3 is the airborne concentration of a substance above which it is predicted that the general population, including susceptible individuals, could experience life-threatening health effects or death.

NIOSH IDLH Values for CAS75-44-5 (National Institute for Occupational Safety and Health, 2007):

IDLH: 2 ppm
Note(s): Not Listed

CONTAINMENT/WASTE TREATMENT OPTIONS

SUMMARY

SPILL OR LEAK PRECAUTIONS - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)
- Fully encapsulating, vapor protective clothing should be worn for spills and leaks with no fire.
- Do not touch or walk through spilled material.
- Stop leak if you can do it without risk.
- If possible, turn leaking containers so that gas escapes rather than liquid.
- Prevent entry into waterways, sewers, basements or confined areas.
- Do not direct water at spill or source of leak.
- Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to conact spilled material.
- Isolate area until gas has dispersed.
RECOMMENDED PROTECTIVE CLOTHING - EMERGENCY RESPONSE GUIDEBOOK, GUIDE 125 (ERG, 2004)
- 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.
Isolate the spill area immediately. Prevent physical contact with phosgene liquid and prevent inhalation of phosgene gas. Persons not essential to spill containment or clean-up and those not wearing appropriate personal protective equipment should be restricted from the spill area. Persons in the vicinity of the spill should be moved upwind until exposure to the gas is no longer possible (Sittig, 1991; WHO, 1998).
Persons involved in the spill containment/clean-up should wear appropriate personal protective equipment (Sittig, 1991; WHO, 1998).
- In larger spills not involving fire, a self-contained breathing apparatus and fully encapsulated clothing should be worn. Limited protection is afforded by normal protective fire-fighter's clothing, in short-term exposures only (WHO, 1998).
- For detailed information on the appropriate personal protective equipment for phosgene, see the "Personal Protection" section.
Sources of ignition (such as flames, sparks, etc.) should be kept away from the spill. Ensure that water and moisture do not contact phosgene and do not enter phosgene containers. Prevent the spill from entering sewers or water sources (AAR, 1998).
If safe and feasible, make an effort to stop the leak (AAR, 1998; Sittig, 1991). If a leaking container cannot be repaired in place, transport the container to a safe, open-air location and either fix the leak or allow the container to empty safely (Sittig, 1991).
The area of the spill should be well-ventilated to disperse any gas (Sitting, 1991). Water spray can be used to knock-down vapors in the area (AAR, 1998).
If present in water intakes, phosgene poses a possible danger. Notify nearby water intake operators and local health and wildlife officials in the event of a phosgene spill (CHRIS , 2000).
- In large liquid phosgene spill situations, create a dike well in advance of the spill for the purposes of containment and later disposal. Ensure that no water is allowed to contact the spill (WHO, 1998). Dikes can be constructed using sand bags, soil, foamed polyurethane, or foamed concrete. A holding area, such as a pond, pit, or lagoon may also be dug for the same purpose (AAR, 1998).
- In case of a liquid spill, phosgene may be covered with sodium hydrogen carbonate or equal parts slake lime and soda ash or crystallized urea. After carefully adding water from an atomizer, the mixture can be added to a large quantity of water (WHO, 1998).
- In case of a phosgene gas spill, apply aqueous ammonia, gaseous ammonia, or an ammonia steam curtain or sprays (WHO, 1998).

WASTE TREATMENT OPTIONS

CHEMICAL TREATMENT

The best way to handle dilute aqueous phosgene waste is through scrubbing in towers containing water and activated carbon or through caustic scrubbing in packed columns (WHO, 1998).
- Controlled amounts of phosgene may be passed through a 10% solution of NaOH in a scrubbing tower (Sittig, 1991).
In land and air spills involving phosgene, the spill may be neutralized with sodium bicarbonate (NaHCO3), agricultural lime (CaO), or crushed limestone (CaCO3) (AAR, 1998; CGA, 1999). Alkali solutions may also be employed to neutralize phosgene. Always dispose of the resulting product observing all applicable regulations (CGA, 1999).
- To treat waste/spilled liquid phosgene absorb in earth, dry sand, vermiculite, or like material and place in sealed containers. To neutralize, cover the material with an equal mixture of soda ash and slaked lime or sodium bicarbonate and mix. Using an atomizer, carefully spray with water then slowly transfer the material into a large container of water. DO NOT use water directly on a phosgene spill (ITI, 1995; Sittig, 1991).
- Emergency field neutralization of phosgene can be achieved through alkali or alkali solutions; an especially effective option is to apply ammonia solution to phosgene, which results in formation of urea (CGA, 1999).
- To treat gaseous phosgene, direct the flow of gas through a mixed solution of slaked lime and caustic soda. Keep this process in a hood until all phosgene has been treated, if possible (ITI, 1995).
- Waste phosgene may be absorbed in a caustic soda solution. Use 2,480 pounds of caustic soda dissolved in 1000 gallons of water for one ton of phosgene (CHRIS , 2000).
Waste management activities associated with material disposition are unique to individual situations. Proper waste characterization and decisions regarding waste management should be coordinated with the appropriate local, state, or federal authorities to ensure compliance with all applicable rules and regulations.

PHYSICAL TREATMENT

Incineration should not be employed in the treatment of phosgene, and phosgene should not be allowed to enter an incinerator. However, if a product containing phosgene or capable of producing phosgene is introduced into an incinerator, scrubbing equipment capable of removing phosgene and/or HCl from the issueing gases must be present. All regulations must be observed (WHO, 1998).

-ENVIRONMENTAL HAZARD MANAGEMENT

POLLUTION HAZARD

ENVIRONMENTAL EXPOSURE

Environmental release of phosgene may occur in waste streams from its production or large-scale use as an intermediate in organic chemical production. (HSDB, 2005).
Environmental release of phosgene may also occur from its use as a choking gas (CG) (e.g., chemical warfare agent [CWA]) (HSDB, 2005).
Atmospheric release of phosgene also occurs through photooxidation of chlorinated solvents such as tetrachloroethylene, trichloroethylene, carbon tetrachloride, and chloroform (HSDB, 2005).

OCCUPATIONAL EXPOSURE

Inhalation is the primary exposure route for workers at chemical production sites, as well as the general population. Other primary exposure routes are ingestion and dermal contact (HSDB, 2005).
Occupational exposure to phosgene may occur at industrial facilities that manufacture chemical solvents (e.g., toluene di-isocyanate [TDI], methylene di-isocyanate [MDI], dyestuffs, polymeric isocyanates), polycarbonate resins, plastics, and dyes, as well as facilities that produce pesticides, herbicides, and metal oxides (HSDB, 2005).
Thermal decomposition (above 300 degrees C) of chlorinated solvents and polymers caused by nearby fires, heaters, or welding activities can generate hazardous quantities of phosgene and become a potential exposure source for workers, welders, and fire-fighters. Phosgene is also released in flue gas from incinerators used to burn municipal refuse, coal, or plastics (HSDB, 2005; WHO, 1998).
Inhalation of phosgene choking gas (CG) is the principal exposure route of concern for military personnel (HSDB, 2005).

GENERAL POPULATION EXPOSURE

Atmospheric phosgene concentrations detected at urban, suburban, and rural sites range from 31.7 ppb (mean) in urban Los Angeles to 22 ppt (median) from three rural sites (HSDB, 2005). Reported ambient air values range from 80-130 ng/m(3) (WHO, 1998).

ENVIRONMENTAL FATE AND KINETICS

In the ambient atmosphere, phosgene likely exists solely in its gas phase, given its vapor pressure of 1418 mm Hg at 25 degrees C (HSDB, 2005).
Photochemically-produced hydroxyl radicals can degrade phosgene, although this is a slow and unimportant environmental fate process. The estimated half-life for this reaction is 44 years, based on a rate constant of 1 x 10(-15) cm(3)/molecule-sec at 25 degrees C and an average atmospheric hydroxyl radical concentration of 5 x 10(5) radicals/cm(3) (HSDB, 2005).
Phosgene has an estimated hydrolytic atmospheric half-life of 113 years at sea level (extrapolated from high temperature data, assuming 10 torr of water vapor) (HSDB, 2005).
- Phosgene's estimated atmospheric half-life can range from 989,880 hours (113 years) to 7.2 x 10(14) hours (8.2 x 10(10) years) (based on hydrolysis rate constant in air) (Howard et al, 1991).

WATER

SURFACE WATER
- Phosgene rapidly volatilizes from surface water, given a Henry's Law constant of 0.02 atm-m(3)/mole (HSDB, 2005).
- Phosgene undergoes rapid hydrolysis with liquid water; hydrolysis is slower with water vapor. Complete hydrolysis of a 1% phosgene solution can occur within 20 seconds at 0 degrees C. Phosgene's hydrolytic by-products are hydrochloric acid and carbon dioxide (HSDB, 2005; DOD (Department of Defense), 2005).
GROUND WATER
- Phosgene's environmental half-life in ground water (based on hydrolysis half-life at -20 degrees C in 89% acetone solution) ranges from 0.05 hours (3 minutes) to 1 hour (Howard et al, 1991).

SOIL

TERRESTRIAL
- Phosgene readily volatilizes and hydrolyzes from moist soil, given a Henry's Law constant of 0.02 atm-m(3)/mole and vapor pressure of 1418 mm Hg (HSDB, 2005).
- Phosgene's potential mobility in soil is considered high, given an estimated organic carbon partition coefficient (Koc) of 2.2 (HSDB, 2005).
- Phosgene typically undergoes abiotic degradation in the terrestrial environment (soil and vegetation) and is not readily detectable in these media (WHO, 1998).
- Phosgene's environmental half-life in soil ranges from 0.05 hours to 1 hour (based on hydrolysis half-life at -20 degrees C in 89% acetone solution) (Howard et al, 1991).

ABIOTIC DEGRADATION

If released to the ambient atmosphere, phosgene will exist solely in its vapor phase. Gas-phase hydrolysis is the principal degradation pathway in ambient air. Degradation by reaction with photochemically-produced hydroxyl radicals is a slow process. Phosgene may persist in the atmosphere at high humidity levels and undergo long distance transport. Phosgene only absorbs UV radiation at wavelengths less than 290 nm. While degradation by direct photolysis is a negligible environmental fate process at lower altitudes, photolysis may occur at higher stratospheric altitudes. Phosgene readily volatilizes and hydrolyzes in both surface water and moist soil environments. Phosgene also volatilizes from dry soils (HSDB, 2005; WHO, 1998).

BIODEGRADATION

Phosgene's estimated aqueous biodegradation half-life ranges from 168 hours (7 days) to 672 hours (4 weeks) under aerobic, unacclimated conditions (Howard et al, 1991).

Phosgene's estimated aqueous anaerobic biodegradation half-life ranges from 672 hours (28 days) to 2,688 hours (16 weeks) (based on aerobic aqueous biodegradation half-life) (Howard et al, 1991).

BIOACCUMULATION

FISH

An estimated bioconcentration factor (BCF) of 3 suggests phosgene's bioconcentration potential in fish and aquatic organisms is low (HSDB, 2005).

BIOCONCENTRATION FACTOR

Phosgene's calculated bioconcentration factor (BCF) of 3, based on an estimated log octanol water partition coefficient (Kow) of -0.71(1), suggests its bioconcentration potential in aquatic organisms is low (HSDB, 2005).
Phosgene is considered unlikely to bioaccumulate or biomagnify based on its physico-chemical properties and hazard profile data from GESAMP (Group of Experts on the Scientific Aspects of Marine Pollution) (CHRIS, 2005; WHO, 1998).

ENVIRONMENTAL TOXICITY

No toxicity data are currently available regarding phosgene's direct potential to adversely affect the environment (WHO, 1998).

At low concentrations, phosgene is considered unlikely to adversely affect aquatic organisms. However, phosgene in water readily degrades to hydrochloric acid, which can be toxic and adversely impact aquatic organisms and their environment (WHO, 1998).

-PHYSICAL/CHEMICAL PROPERTIES

MOLECULAR WEIGHT

98.91

DESCRIPTION/PHYSICAL STATE

At room temperature, phosgene is a colorless, non-combustible, highly toxic gas that is easily liquefied (ACGIH, 1996)(Budavari, 1996; CHRIS , 2000; Grant, 1993; Hathaway et al, 1996; Harbison, 1998; Lewis, 1998; NIOSH , 2000; Raffle et al, 1994; Sittig, 1991).

At high concentrations, the gas has an odor described as suffocating (Budavari, 1996), strong and stifling (Lewis, 1997), and pungent and irritating (Raffle et al, 1994; Sittig, 1991).

At lower concentrations, the odor has been widely characterized as being haylike, similar to newly-mown hay, moldy or musty hay, or having an odor that is not pleasant and sweet, like hay (ACGIH, 1996) (Budavari, 1996; Lewis, 1996; Lewis, 1997; Raffle et al, 1994; Sittig, 1991). The dilute gas odor has also been compared to that of green corn (Lewis, 1996).

Below 0-8.3 degrees C or when compressed, phosgene condenses to a colorless to light yellow, non-combustible, highly toxic, fuming/volatile liquid that produces poisonous vapor and sinks in water (ACGIH, 1996) (Budavari, 1996; CHRIS , 2000; Clayton & Clayton, 1994; Harbison, 1998; Lewis, 1998; NIOSH , 2000).

VAPOR PRESSURE

161.6 kPa (at 20 degrees C) (WHO, 1998)

161.6 kPa (ILO, 1998)

1.6 atm (NIOSH , 2000)

1215 mmHg (at 20 degrees C) (ACGIH, 1996) (Budavari, 1996)

1420 mmHg (at 25 degrees C, calculated from experimentally derived coefficients) (HSDB , 2000)

586 mm Hg (at 0 degrees C) (HSDB , 2000)

9.1 psig; 63 kPa (at 21.1 degrees C, 70 degrees F) (CGA, 1999)

29.9 psig; 206 kPa (at 40.6 degrees C, 105 degrees F) (CGA, 1999)

38.1 psig; 263 kPa (at 46.1 degrees C, 115 degrees F) (CGA, 1999)

52.1 psig; 359 kPa (at 54.4 degrees C, 130 degrees F)(CGA, 1999)

SPECIFIC GRAVITY

OTHER TEMPERATURE AND/OR PRESSURE

1.381 (at 20/4 degrees C) (HSDB , 2000)
1.392 (at 19/4 degrees C) (ITI, 1995; Lewis, 1997)
1.419 (at 0/4 degrees C) (Lewis, 1996)

DENSITY

STANDARD TEMPERATURE AND PRESSURE

(0 degrees C; 32 degrees F and 760 mmHg)
LIQUID: 1.43 kg/L (at 32 degrees F) (NIOSH , 2000)

OTHER TEMPERATURE AND/OR PRESSURE

GAS: 0.26 lb/ft(3); 4.16 kg/m(3) (at 21.1 degrees C, 1 atm) (CGA, 1999)
LIQUID: 1.38 kg/L (at 20 degrees C) (CHRIS , 2000)
1.388 kg/L (WATER = 1) (at 20 degrees C) (CGA, 1999)
1.381 kg/L (at 20 degrees C) (ACGIH, 1996)
1.39 kg/L (at 20 degrees C) (Ashford, 1994)
86.65 lb/ft (3); 1388 kg/m(3) (at 20 degrees C; 68 degrees F) (CGA, 1999)
86.47 lb/ft(3); 1385 kg/m(3) (at 21.1 degrees C; 70 degrees F) (CGA, 1999)
83.47 lb/ft(3); 1337 kg/m(3) (at 40.6 degrees C; 105 degrees F) (CGA, 1999)
82.66 lb/ft(3); 1324 kg/m(3) (at 46.1 degrees C; 115 degrees F) (CGA, 1999)
81.41 lb/ft(3); 1304 kg/m(3) (at 54.4 degrees C; 130 degrees F) (CGA, 1999)

TEMPERATURE AND/OR PRESSURE NOT LISTED

1.4 kg/L (WATER = 1) (WHO, 1998)
1.381 kg/L (WATER = 1) (ILO, 1998)

BOILING POINT

7 degrees C (Ashford, 1994)

7.56 degrees C (WHO, 1998)

7.6 degrees C (Lewis, 1996)

8 degrees C (ILO, 1998)

8.2 degrees C; 46.8 degrees F; 281.4 degrees K (1 atm) (ACGIH, 1996) (Budavari, 1996; CGA, 1999; CHRIS , 2000; Clayton & Clayton, 1994; ITI, 1995; Lewis, 1997)

47 degrees F (NIOSH , 2000)

SOLUBILITY

IN WATER

Phosgene is slightly soluble in water (ACGIH, 1996) (Ashford, 1994; Budavari, 1996; ILO, 1998; Lewis, 1996; Lewis, 1997; NIOSH , 2000).
Phosgene is soluble in water (ITI, 1995).
In water, phosgene is slowly hydrolyzed (ACGIH, 1996) (Budavari, 1996; ITI, 1995; Lewis, 1997).
Phosgene decomposes to hydrochloric acid and carbon dioxide in water (Clayton & Clayton, 1994; WHO, 1998)
The compound undergoes slight decomposition in water (Lewis, 1996).
Phosgene reacts with water (Ashford, 1994).

IN ORGANIC SOLVENTS

Phosgene reacts with ethanol and is soluble unaltered in toluene, benzene, the majority of liquid hydrocarbons, and glacial acetic acid (WHO, 1998).
This compound is "freely soluble" in toluene, glacial acetic acid, benzene, and most liquid hydrocarbons (ACGIH, 1996) (Budavari, 1996)
Phosgene is "very soluble" in acetic acid and benzene (Lewis, 1996)
Phosgene is soluble in organic solvents such as toluene and benzene (Clayton & Clayton, 1994; ITI, 1995; Lewis, 1997).
Soluble in ester, hydrocarbon, and organic acid solvents (Ashford, 1994).
Phosgene is soluble in chloroform (HSDB , 2000).

SPECTRAL CONSTANTS

2858 (Coblentz Society Spectral Collection) (HSDB , 2000)

MASS

215 (Atlas of Mass Spectral Data, John Wiley & Sons, New York) (HSDB , 2000)

OTHER/PHYSICAL

CRITICAL PRESSURE

823 psia; 56.0 atm; 5.67 MN/m(2); 5674 kPa abs (CHRIS , 2000; CGA, 1999)

IONIZATION POTENTIAL

11.55 eV (NIOSH , 2000)

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