3,5,7-Trithia-1,2,4,6-tetraphosphatricyclo[2.2.1.02,6]heptane

226.13800

220.09

215-245-0

8V5Q0M194Y

1341

DTXSID4074562

Yellow-green orthogonal crystals|Yellowish-green, long, rhombic needles from benzene|Yellow, crystalline mass

79.03000

3.78320

Phosphorus sesquisulfide, free from yellow and white phosphorus appears as a yellow crystalline solid. Easily ignited by friction. Forms sulfur dioxide and phosphorus pentaoxide during combustion. Reacts with water to form phosphoric acid, a corrosive material. Used to make matches and in the manufacture of other chemicals.

2.03 g/cm³ @ Temp: 20 °C

172.5 °C

407.5 °C

Insoluble in cold water; decomposed by hot water, yielding H2S; Soluble in carbon disulfide (60% w/w at 20 deg C); soluble in benzene, similar hydrocarbons, phorphorus trichloride

Protect against physical damage. Store in cool, ventilated place. Separate from other materials.

Flammable by spontaneous ignition.

Stable to air|Heat of fusion: -154 kJ/mol|Phosphorus sesquisulfide decomposes (hydrolyzes) in water with the hydrolysis reaction relatively slow in cold water but becoming faster upon heating producing mainly hydrogen sulfide and orthophosphoric acid, H3PO4; in neutral solutions, the hydrolysis products include PH3 (3%), H3PO2 (38%), H3PO3 (49%) and H3PO4 (6)(1); in alkaline solutions, the hydrolysis products include PH3 (5%), H3PO2 (15%), H3PO3 (75%)

Highly flammable.Slowly decomposed by water to form phosphoric acid and toxic hydrogen sulfide gas (H2S). May ignite on contact with water or moist air.

Sulfides, Inorganic

Highly Flammable

PHOSPHORUS SESQUISULFIDE is a reducing agent.

212 °F (100 °C)

63.6 kJ/mol

II

4.1

UN 1341

11-22-50

7-16-24/25-61

TH4330000

F,Xn,N

Stable in air.

P210, P223, P231+P232, P240, P241, P264, P270, P273, P280, P301+P312, P330, P335+P334, P370+P378, P391, P402+P404, P501

H228

SRP: The most favorable course of action is to use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination. Recycle any unused portion of the material for its approved use or return it to the manufacturer or supplier. Ultimate disposal of the chemical must consider: the material's impact on air quality; potential migration in soil or water; effects on animal and plant life; and conformance with environmental and public health regulations.

Decomp by hot water, yielding hydrogen sulfide (H2S)

Excerpt from ERG Guide 139 [Substances - Water-Reactive (Emitting Flammable and Toxic Gases)]: Produce flammable and toxic gases on contact with water. May ignite on contact with water or moist air. Some react vigorously or explosively on contact with water. May be ignited by heat, sparks or flames. May re-ignite after fire is extinguished. Some are transported in highly flammable liquids. Containers may explode when heated. Runoff may create fire or explosion hazard. (ERG, 2016)|Flammable - 2nd degree, Reactive - 2nd degree

|Danger|H228: Flammable solid [Danger Flammable solids]|P210, P223, P231+P232, P240, P241, P264, P270, P273, P280, P301+P312, P330, P335+P334, P370+P378, P391, P402+P404, and P501|H228 (100%): Flammable solid [Danger Flammable solids]|Aggregated GHS information provided by 42 companies from 2 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.|Warning|P210, P240, P241, P280, and P370+P378

Excerpt from ERG Guide 139 [Substances - Water-Reactive (Emitting Flammable and Toxic Gases)]: As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. SPILL: Increase, in the downwind direction, as necessary, the isolation distance shown above. FIRE: If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. (ERG, 2016)

Excerpt from ERG Guide 139 [Substances - Water-Reactive (Emitting Flammable and Toxic Gases)]: Fully encapsulating, vapor-protective clothing should be worn for spills and leaks with no fire. ELIMINATE all ignition sources (no smoking, flares, sparks or flames in immediate area). Do not touch or walk through spilled material. Stop leak if you can do it without risk. DO NOT GET WATER on spilled substance or inside containers. Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material. FOR CHLOROSILANES, use AFFF alcohol-resistant medium-expansion foam to reduce vapors. SMALL SPILL: Cover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain. Dike for later disposal; do not apply water unless directed to do so. POWDER SPILL: Cover powder spill with plastic sheet or tarp to minimize spreading and keep powder dry. DO NOT CLEAN-UP OR DISPOSE OF, EXCEPT UNDER SUPERVISION OF A SPECIALIST. (ERG, 2016)

Excerpt from ERG Guide 139 [Substances - Water-Reactive (Emitting Flammable and Toxic Gases)]: 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. (ERG, 2016)|Personnel protection: Wear appropriate chemical protective gloves, boots, and goggles.|In fire condition wear self-contained breathing apparatus.

HIGHLY FLAMMABLE.

Flammable by spontaneous ignition.

If material on fire or involved in fire: Do not use water. Use dry chemical or carbon dioxide. When fire is out, cover all suspected material with dry sand or earth to prevent re-ignition until material can be permanently disposed of.|Personnel protection: Wear positive pressure self-contained breathing apparatus when fighting fires involving this material.|Flood with water.

SRP: The scientific literature for the use of contact lenses by industrial workers is inconsistent. The benefits or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.|Personnel protection: Avoid breathing dusts, and fumes from burning material. Keep upwind. Avoid bodily contact with the material. Do not handle broken packages unless wearing appropriate personal protective equipment. Wash away any material which may have contacted the body with copious amounts of water or soap and water. If contact with the material anticipated, wear appropriate chemical protective clothing.|If material is not on fire and not involved in fire: Do not use water. Keep sparks, flames, and other sources of ignition away. Keep material out of water sources and sewers. Keep material dry.|All possible sources of ignition and friction should be eliminated. Good housekeeping, maintenance of gateways & exits, the provision of ... fire resisting personal protective equipment & training in fire drills are all necessary to minimize risks & to deal swiftly with any outbreak.|Hand protection, barrier creams and strict cleanliness are necessary. A high standard of sanitary and washing facilities is necessary for all workers; shower baths are particularly required for workers in storeroom & paste-making processes.

/GUIDE 139: SUBSTANCES - WATER-REACTIVE (EMITTING FLAMMABLE AND TOXIC GASES)/ Fire or Explosion: Produce flammable and toxic gases on contact with water. May ignite on contact with water or moist air. Some react vigorously or explosively on contact with water. May be ignited by heat, sparks or flames. May re-ignite after fire is extinguished. Some are transported in highly flammable liquids. Containers may explode when heated. Runoff may create fire or explosion hazard. /Phosphorus sesquisulfide, free from yellow and white Phosphorus/|/GUIDE 139: SUBSTANCES - WATER-REACTIVE (EMITTING FLAMMABLE AND TOXIC GASES)/ Health: Highly toxic: contact with water produces toxic gas, may be fatal if inhaled. Inhalation or contact with vapors, substance, or decomposition products may cause severe injury or death. May produce corrosive solutions on contact with water. Fire will produce irritating, corrosive and/or toxic gases. Runoff from fire control may cause pollution. /Phosphorus sesquisulfide, free from yellow and white Phosphorus/|/GUIDE 139: SUBSTANCES - WATER-REACTIVE (EMITTING FLAMMABLE AND TOXIC GASES)/ Public Safety: CALL Emergency Response Telephone Number ... As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate the area before entry. /Phosphorus sesquisulfide, free from yellow and white Phosphorus/|/GUIDE 139: SUBSTANCES - WATER-REACTIVE (EMITTING FLAMMABLE AND TOXIC GASES)/ Protective Clothing: Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer. It may provide little or no thermal protection. Structural firefighters' protective clothing provides limited protection in fire situations ONLY; it is not effective in spill situations where direct contact with the substance is possible. /Phosphorus sesquisulfide, free from yellow and white Phosphorus/|For more DOT Emergency Guidelines (Complete) data for PHOSPHORUS SESQUISULFIDE (8 total), please visit the HSDB record page.

No person may /transport,/ offer or accept a hazardous material for transportation in commerce unless that person is registered in conformance ... and the hazardous material is properly classed, described, packaged, marked, labeled, and in condition for shipment as required or authorized by ... /the hazardous materials regulations (49 CFR 171-177)./|The International Air Transport Association (IATA) Dangerous Goods Regulations are published by the IATA Dangerous Goods Board pursuant to IATA Resolutions 618 and 619 and constitute a manual of industry carrier regulations to be followed by all IATA Member airlines when transporting hazardous materials.|The International Maritime Dangerous Goods Code lays down basic principles for transporting hazardous chemicals. Detailed recommendations for individual substances and a number of recommendations for good practice are included in the classes dealing with such substances. A general index of technical names has also been compiled. This index should always be consulted when attempting to locate the appropriate procedures to be used when shipping any substance or article.

The dust or fume is irritant to the eyes, the respiratory tract, and the skin.

| 0 - Materials that, under emergency conditions, would offer no hazard beyond that of ordinary combustible materials.| 1 - Materials that must be preheated before ignition can occur. Materials require considerable preheating, under all ambient temperature conditions, before ignition and combustion can occur.| 1 - Materials that in themselves are normally stable but that can become unstable at elevated temperatures and pressures.

Phosphorus sesquisulfide's production and use in strike-anywhere matches and in organic synthesis(1) may result in its release to the environment through various waste streams(SRC).

TERRESTRIAL FATE: Phosphorus sesquisulfide decomposes (hydrolyzes) in water forming hydrogen sulfide and orthophosphoric acids(1). Therefore, hydrolysis is expected to be the dominant fate process in moist soil. Leaching and volatilization in moist soil are not expected to be important fate processes becuase of rapid hydrolysis(SRC). Biodegradation data were not available(SRC).|AQUATIC FATE: Phosphorus sesquisulfide decomposes (hydrolyzes) in water forming hydrogen sulfide and orthophosphoric acids(1). Therefore, volatilization from surface waters, bioconcentration in aquatic organisms, and adsorption to sediment are not expected to be important fate processes with respect to phosphorus sesquisulfide(SRC).|ATMOSPHERIC FATE: Appropriate estimation methods are not available to adequately predict vapor pressure or atmospheric reaction rates of phosphorus sesquisulfide. (SRC)

Phosphorus sesquisulfide decomposes (hydrolyzes) in water with the hydrolysis reaction slower in cold water but becoming faster upon heating, producing mainly hydrogen sulfide and orthophosphoric acid, H3PO4(1). In neutral solutions, the hydrolysis products include PH3 (3%), H3PO2 (38%), H3PO3 (49%) and H3PO4 (6)(1); in alkaline solutions, the hydrolysis products include PH3 (5%), H3PO2 (15%), H3PO3 (75%)(1).

Phosphorus sesquisulfide decomposes (hydrolyzes) in water forming hydrogen sulfide and orthophosphoric acids(1). This suggests the potential for bioconcentration of phosphorus sesquisulfide in aquatic organisms is low(SRC).

Phosphorus sesquisulfide decomposes (hydrolyzes) in water forming hydrogen sulfide and orthophosphoric acids(1). This suggests that leaching of phosphorus sesquisulfide in moist soil will not be an important fate process(SRC).

Phosphorus sesquisulfide decomposes (hydrolyzes) in water forming hydrogen sulfide and orthophosphoric acids(1). This suggests that volatilization of phosphorus sesquisulfide from surface waters or moist soil will not be an important fate process(SRC).

NIOSH (NOES Survey 1981-1983) has statistically estimated that 1,663 workers (298 of these were female) were potentially exposed to phosphorus sesquisulfide in the US(1). Occupational exposure to phosphorus sesquisulfide may occur through dermal contact with this compound at workplaces where phosphorus sesquisulfide is produced or used(SRC). Strike-anywhere matches may contain phosphorus sesquisulfide(2), therefore, the general population may be exposed to phosphorus sesquisulfide via dermal contact with these matches(SRC).|/IN MATCH INDUSTRY/ THERE IS HIGH FIRE & EXPLOSION RISK IN MIXING OF PASTES & IN HANDLING OF HEADED MATCHES. THIS RISK IS GREATER WHERE BOXES ARE HAND FILLED OR MATERIALS & BOXES ARE MANUALLY HANDLED. ...DUST & FUMES...PRESENT A HAZARD...IN STOREROOMS & IN PREPN OF PASTE.

Excerpt from ERG Guide 139 [Substances - Water-Reactive (Emitting Flammable and Toxic Gases)]: Highly toxic: contact with water produces toxic gas, may be fatal if inhaled. Inhalation or contact with vapors, substance or decomposition products may cause severe injury or death. May produce corrosive solutions on contact with water. Fire will produce irritating, corrosive and/or toxic gases. Runoff from fire control may cause pollution. (ERG, 2016)

Excerpt from ERG Guide 139 [Substances - Water-Reactive (Emitting Flammable and Toxic Gases)]: Ensure that medical personnel are aware of the material(s) involved and take precautions to protect themselves. 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 substance, wipe from skin immediately; flush skin or eyes with running water for at least 20 minutes. Keep victim calm and warm. (ERG, 2016)

Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Sulfur and related compounds/|Basic treatment: Establish a patent airway (oropharyngeal or nasopharyngeal airway, if needed). Suction if necessary. Watch for signs of respiratory insufficiency and assist ventilations if necessary. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema and treat if necessary ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool ... . Administer activated charcoal ... . Cover skin burns with dry sterile dressings after decontamination ... . /Sulfur and related compounds/|Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag-valve-mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasms ... . Monitor cardiac rhythm and treat arrhythmias if necessary ... . Start IV administration of D5W /SRP: "To keep open", minimal flow rate/. Use 0.9% saline (NS) or lactated Ringer's (LR) if signs of hypovolemia are present. For hypotension with signs of hypovolemia, administer fluid cautiously. Consider vasopressors if patient is hypotensive with a normal fluid volume. Watch for signs of fluid overload ... . Treat seizures with diazepam or lorazepam ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Sulfur and related compounds/|Immediate first aid: Ensure that adequate decontamination has been carried out. If patient is not breathing, start artificial respiration, preferably with a demand-valve resuscitator, bag-valve-mask device, or pocket mask, as trained. Perform CPR as necessary. Immediately flush contaminated eyes with gently flowing water. Do not induce vomiting. If vomiting occurs, lean patient forward or place on left side (head-down position, if possible) to maintain an open airway and prevent aspiration. Keep patient quiet and maintain normal body temperature. Obtain medical attention. /Phosphorus and related compounds/|For more Antidote and Emergency Treatment (Complete) data for PHOSPHORUS SESQUISULFIDE (6 total), please visit the HSDB record page.

/HUMAN EXPOSURE STUDIES/ Patch testing was performed with phosphorus sesquisulfide P4S3 in 2 groups containing equal numbers of patients using different concentrations (0.5% P4S3 in pet. and 1% P4S3 in pet., the usual suggested test concentration as recommended by the International Contact Dermatitis Research Group). /Investigators/ found that there was a statistically significant increase in the number of clinically irrelevant irritant reactions in the group tested with the concentration (X2= 16, P < 0.0004). /The authors/ recommend that patch testing with phosphorous sesquisulfide should be at a reduced concentration of 0.5% pet.|/HUMAN EXPOSURE STUDIES/ The results of patch testing with a series containing components of cigarettes and matches were reviewed. Two years were reviewed, 1987 and 1997. 314 patients were patch tested to this series, 203 in 1987 and 111 in 1997. 31 patients had clinically relevant positive reactions to the series, 25 in 1987 and 6 in 1997. 26 patients had relevant positive tests to cigarette components in the series. There were 14 relevant positive reactions to phosphorus sesquisulfide in 1987 and one in 1997. All patients with relevant positive reactions to red match tips also had reactions to phosphorus sesquisulfide. There was a significant association between cigarette and fragrance hypersensitivity. The eczema in 3 of 4 patients who stopped smoking improved. A series containing match heads, smoked cigarette filters and remnants of tobacco from smoked cigarettes may be useful in smokers with eczema of the face, neck or hands.|/SIGNS AND SYMPTOMS/ ...A rapidly developing erythema with formation of vesicles or pustules accompanied by pain and pruritis in handling phosphorus sesquisulfide /is reported among industrial workers/. Greasy skins were said to be most susceptible.|/CASE REPORTS/ Two months ago, a 32-year-old male waiter developed red, edematous, exudative and infiltrated plaques on the antero-lateral sides of both thighs, which were quite resistant to topical therapy. Scaly erythematous lesions on the eyelids and backs of the hands were also present. He used safety matches which he usually carried in his trouser pockets. The standard Spanish patch test series was negative. A test with the striking surface of his match box and with 0.5% phosphorus sesquisulphide produced an immediate, severe, urticarial response (at 20 min). Inspite of the fact that the tests had been removed immediately after the reading, there was an eczematous reaction at 48 hr, which lasted several days. The patient volunteered the information that he noticed and intense "taste of matches" in his mouth, several minutes after the patch test had been applied. When interviewed again, he mentioned that on lighting matches, he frequently observed an erythema and edema with itching on his hands and face. A biopsy showed a round cell infiltrate with slight acanthosis, exocytosis and spongiosis of the epidermis but no "lymphomatoid" appearance. On eliminating the use of matches the lesions cleared up with conventional local treatment, but persistent hypo-chromic plaques remained.|For more Human Toxicity Excerpts (Complete) data for PHOSPHORUS SESQUISULFIDE (12 total), please visit the HSDB record page.

phosphorus sesquisulfide

MODERN MATCHES THAT CAN BE STRUCK ON ANY ROUGH SURFACE CONTAIN EITHER RED PHOSPHORUS OR PHOSPHORUS SESQUISULFIDE, TOGETHER WITH POTASSIUM CHLORATE & GLUE. SAFETY MATCHES...STRIKING SURFACE CONSISTS OF RED PHOSPHORUS (OR THE SESQUISULFIDE), SAND & GLUE.

Fire Hazards -> Flammable - 2nd degree, Reactive - 2nd degree