Thiophosphoryl chloride

H302 (100%): Harmful if swallowed [Warning Acute toxicity, oral]

H314 (100%): Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]

H318 (72.3%): Causes serious eye damage [Danger Serious eye damage/eye irritation]

H330 (100%): Fatal if inhaled [Danger Acute toxicity, inhalation]

H335 (71.6%): May cause respiratory irritation [Warning Specific target organ toxicity, single exposure; Respiratory tract irritation]

H412 (70.3%): Harmful to aquatic life with long lasting effects [Hazardous to the aquatic environment, long-term hazard]

P260, P261, P264, P264+P265, P270, P271, P273, P280, P284, P301+P317, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P316, P317, P319, P320, P321, P330, P363, P403+P233, P405, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 148 reports by companies from 6 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

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

Fresh air, rest. Half-upright position. Artificial respiration may be needed. Refer for medical attention.

Remove contaminated clothes. Rinse skin with plenty of water or shower. Refer for medical attention .

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

Rinse mouth. Do NOT induce vomiting. Refer for medical attention .

Excerpt from ERG Guide 157 [Substances - Toxic and/or Corrosive (Non-Combustible / Water-Sensitive)]:

Refer to the "General First Aid" section. Specific First Aid: For corrosives, in case of contact, immediately flush skin or eyes with running water for at least 30 minutes. Additional flushing may be required. In case of skin contact with Hydrofluoric acid (UN1790), if calcium gluconate gel is available, rinse 5 minutes, then apply gel. Otherwise, continue rinsing until medical treatment is available. (ERG, 2024)

General First Aid:

· Call 911 or emergency medical service.

· Ensure that medical personnel are aware of the material(s) involved, take precautions to protect themselves and avoid contamination.

· Move victim to fresh air if it can be done safely.

· Administer oxygen if breathing is difficult.

· If victim is not breathing:

-- DO NOT perform mouth-to-mouth resuscitation; the victim may have ingested or inhaled the substance.

-- If equipped and pulse detected, wash face and mouth, then give artificial respiration using a proper respiratory medical device (bag-valve mask, pocket mask equipped with a one-way valve or other device).

-- If no pulse detected or no respiratory medical device available, provide continuous compressions. Conduct a pulse check every two minutes or monitor for any signs of spontaneous respirations.

· Remove and isolate contaminated clothing and shoes.

· For minor skin contact, avoid spreading material on unaffected skin.

· In case of contact with substance, remove immediately by flushing skin or eyes with running water for at least 20 minutes.

· For severe burns, immediate medical attention is required.

· Effects of exposure (inhalation, ingestion, or skin contact) to substance may be delayed.

· Keep victim calm and warm.

· Keep victim under observation.

· For further assistance, contact your local Poison Control Center.

· Note: Basic Life Support (BLS) and Advanced Life Support (ALS) should be done by trained professionals.

Specific First Aid:

· For corrosives, in case of contact, immediately flush skin or eyes with running water for at least 30 minutes. Additional flushing may be required.

· In case of skin contact with Hydrofluoric acid (UN1790), if calcium gluconate gel is available, rinse 5 minutes, then apply gel. Otherwise, continue rinsing until medical treatment is available.

In Canada, an Emergency Response Assistance Plan (ERAP) may be required for this product. Please consult the shipping paper and/or the "ERAP" section.

Excerpt from ERG Guide 157 [Substances - Toxic and/or Corrosive (Non-Combustible / Water-Sensitive)]:

Note: Some foams will react with the material and release corrosive/toxic gases.

SMALL FIRE: CO2 (except for Cyanides), dry chemical, dry sand, alcohol-resistant foam.

LARGE FIRE: Water spray, fog or alcohol-resistant foam. If it can be done safely, move undamaged containers away from the area around the fire. Avoid aiming straight or solid streams directly onto the product. Dike runoff from fire control for later disposal.

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

Use powder, carbon dioxide. NO water. In case of fire: keep drums, etc., cool by spraying with water. NO direct contact with water. Combat fire from a sheltered position.

If material /is/ involved in /a/ fire extinguish fire using agent suitable for type of surrounding fire. (Material itself does not burn or burns with difficulty.) Use water in flooding quantities as fog. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible.

· CALL 911. Then call emergency response telephone number on shipping paper. If shipping paper not available or no answer, refer to appropriate telephone number listed on the inside back cover.

· Keep unauthorized personnel away.

· Stay upwind, uphill and/or upstream.

· Ventilate closed spaces before entering, but only if properly trained and equipped.

· ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area.

· All equipment used when handling the product must be grounded.

· Do not touch damaged containers or spilled material unless wearing appropriate protective clothing.

· Stop leak if you can do it without risk.

· A vapor-suppressing foam may be used to reduce vapors.

· DO NOT GET WATER INSIDE CONTAINERS.

· Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material.

· Prevent entry into waterways, sewers, basements or confined areas.

Small Spill

· Cover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain.

· Use clean, non-sparking tools to collect material and place it into loosely covered plastic containers for later disposal.

Excerpt from ERG Guide 157 [Substances - Toxic and/or Corrosive (Non-Combustible / Water-Sensitive)]:

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

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

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

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.

· For highlighted materials: see Table 1 - Initial Isolation and Protective Action Distances.

· For non-highlighted materials: increase the immediate precautionary measure distance, in the downwind direction, as necessary.

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

Evacuate danger area! Consult an expert! Personal protection: chemical protection suit including self-contained breathing apparatus. Ventilation. Do NOT let this chemical enter the environment. Do NOT wash away into sewer. Collect leaking and spilled liquid in sealable containers as far as possible. Absorb remaining liquid in sand or inert absorbent. Then store and dispose of according to local regulations. NEVER direct water jet on liquid.

If material /is/ not involved in /a/ fire keep material out of water sources and sewers. Build dikes to contain flow as necessary. Use water spray to knock- down vapors. Do not use water on material itself. Neutralize spilled material with crushed limestone, soda ash, or lime.

Avoid breathing vapors. 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.

SRP: The scientific literature for the use of contact lenses in industry is conflicting. The benefit 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.

Excerpt from ERG Guide 157 [Substances - Toxic and/or Corrosive (Non-Combustible / Water-Sensitive)]:

ELIMINATE all ignition sources (no smoking, flares, sparks or flames) from immediate area. All equipment used when handling the product must be grounded. Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. A vapor-suppressing foam may be used to reduce vapors. DO NOT GET WATER INSIDE CONTAINERS. Use water spray to reduce vapors or divert vapor cloud drift. Avoid allowing water runoff to contact spilled material. Prevent entry into waterways, sewers, basements or confined areas.

SMALL SPILL: Cover with DRY earth, DRY sand or other non-combustible material followed with plastic sheet to minimize spreading or contact with rain. Use clean, non-sparking tools to collect material and place it into loosely covered plastic containers for later disposal. (ERG, 2024)

Fireproof. Provision to contain effluent from fire extinguishing. Cool. Dry.

· Wear positive pressure self-contained breathing apparatus (SCBA).

· Wear chemical protective clothing that is specifically recommended by the manufacturer when there is NO RISK OF FIRE.

· Structural firefighters' protective clothing provides thermal protection but only limited chemical protection.

0.013 [mg/m3]

0.15 [mg/m3]

0.88 [mg/m3]

· Note: Some foams will react with the material and release corrosive/toxic gases.

Small Fire

· CO2 (except for Cyanides), dry chemical, dry sand, alcohol-resistant foam.

Large Fire

· Water spray, fog or alcohol-resistant foam.

· If it can be done safely, move undamaged containers away from the area around the fire.

· Avoid aiming straight or solid streams directly onto the product.

· Dike runoff from fire control for later disposal.

Fire Involving Tanks, Rail Tank Cars or Highway Tanks

· Fight fire from maximum distance or use unmanned master stream devices or monitor nozzles.

· Do not get water inside containers.

· Cool containers with flooding quantities of water until well after fire is out.

· Withdraw immediately in case of rising sound from venting safety devices or discoloration of tank.

· ALWAYS stay away from tanks in direct contact with flames.

A harmful contamination of the air can be reached very quickly on evaporation of this substance at 20 °C.

The substance is corrosive to the eyes, skin and respiratory tract. The vapour is corrosive to the eyes, skin and respiratory tract. Corrosive on ingestion. Inhalation of the vapour may cause lung oedema. If this liquid is swallowed, aspiration into the lungs may result in chemical pneumonitis. Exposure could cause death. The effects may be delayed. Medical observation is indicated.

Excerpt from ERG Guide 157 [Substances - Toxic and/or Corrosive (Non-Combustible / Water-Sensitive)]:

Wear positive pressure self-contained breathing apparatus (SCBA). Wear chemical protective clothing that is specifically recommended by the manufacturer when there is NO RISK OF FIRE. Structural firefighters' protective clothing provides thermal protection but only limited chemical protection. (ERG, 2024)

... Wear positive pressure self-contained breathing apparatus. ... Wear appropriate chemical protective gloves, boots, and goggles. ...

Respiratory protection (supplied-air respirator with full facepiece or self-contained breathing apparatus) should be available where these compounds are manufactured or used and should be worn in case of emergency and overexposure. /Phosphorus compounds/

NO open flames, NO sparks and NO smoking. NO contact with water or moisture.

AVOID ALL CONTACT! IN ALL CASES CONSULT A DOCTOR!

Use ventilation, local exhaust or breathing protection.

Protective gloves. Protective clothing.

Wear safety goggles, face shield or eye protection in combination with breathing protection.

Do not eat, drink, or smoke during work.

Thiophosphoryl chloride appears as a colorless fuming liquid. Boiling point 257 °F (125 °C). Irritates the eyes and mucous membranes. Corrosive to metals and tissue.

Colorless fuming liquid with pungent odor; [ICSC]

FUMING COLOURLESS LIQUID WITH PUNGENT ODOUR.

Colorless liquid

CRYSTALLIZES AS ALPHA-FORM @ -40.8 °C OR AS BETA-FORM @ -36.2 °C

Penetrating

125 °C @ 760 MM HG

125 °C @760 [mm Hg]

SOL IN BENZENE, CARBON TETRACHLORIDE, CARBON DISULFIDE, CHLOROFORM

Solubility in water: reaction

Relative density (water = 1): 1.6

1.635 @25 °C

5.86 (AIR= 1)

Relative vapor density (air = 1): 5.8

16.35 [mmHg]

vapor pressure = 16.35 mm Hg at 25 °C/ calculated from experimentally derived coefficients/

Vapor pressure, kPa at 25 °C: 2.9

Decomposed by water producing hydrochloric and phosphoric acids ... and hydrogen sulfide ... .

Dangerous; when heated to decomp ... emits highly toxic fumes of /phosphorus oxides, sulfur oxides and hydrogen chloride/.

INDEX OF REFRACTION: 1.635 @ 25 °C/D

INDEX OF REFRACTION: 1.563 (COLD)

HYDROLIZES SLOWLY IN WATER, RAPIDLY IN ALKALINE SOLN

IN WATER, HYDROLYSIS PRODUCTS ARE ORTHOPHOSPHORIC ACID, HYDROCHLORIC ACID & HYDROGEN SULFIDE

vapor pressure = 22 MM HG AT 25 °C

Schoenflies notation

Bond type

Chemical bond

Corrosion

Excitation energy

Internuclear distance

Molecular structure

Nuclear quadrupole resonance spectroscopy

Point group

Quadrupole coupling

Reaction coordinate

Rotational excitation cross section

Toxic Gases & Vapors -> Other Toxic Gases & Vapors

Corrosives

Reactive agents - 2nd degree

Fumes in air. The liquid decomposes in water to form phosphoric acid and hydrochloric acid (hydrogen chloride). It can also form hydrogen sulfide (H2S), a toxic flammable gas, in reaction with water.

Acyl Halides, Sulfonyl Halides, and Chloroformates

Water-Reactive

Air-Reactive

THIOPHOSPHORYL CHLORIDE is acidic. Incompatible with bases (including amines), with strong oxidizing agents, and with alcohols. May react vigorously or explosively if mixed with diisopropyl ether or other ethers in the presence of trace amounts of metal salts [J. Haz. Mat., 1981, 4, 291].

Water or steam will react to produce toxic and corrosive fumes, pentaerythritol.

The substance can be absorbed into the body by inhalation.

Burning sensation. Cough. Headache. Laboured breathing. Shortness of breath. Sore throat. Unconsciousness. Vomiting. Wheezing. Symptoms may be delayed.

Redness. Skin burns. Pain. Blisters.

Redness. Pain. Loss of vision. Severe deep burns.

Abdominal pain. Burning sensation. Nausea. Shock or collapse. Further see Inhalation.

Dermatotoxin - Skin burns.

Toxic Pneumonitis - Inflammation of the lungs induced by inhalation of metal fumes or toxic gases and vapors.

LC50 (rat) = 20 ppm/4h

This substance may be hazardous to the environment. Special attention should be given to water quality.

Thiophosphoryl chloride may be released to the environment during its manufacture and use. It is a volatile chemical and would therefore tend to volatilize from water and soil and partition in the atmosphere. Its atmospheric half-life is estimated to be 0.3 days as a result of its reaction with photochemically produced hydroxyl radicals. Although no rate data are available, it is expected to hydrolyze slowly in water and moist soil. The rate of hydrolysis will increase with increasing pH. Exposure would be occupational. (SRC)

TERRESTRIAL FATE: If released on land thiophosphoryl chloride will be lost by volatilization and hydrolysis. No estimates of half-lives of these processes are available. (SRC)

AQUATIC FATE: If released in water, thiophosphoryl chloride will be lost by hydrolysis; the rate of hydrolysis is unknown. It may also be lost by volatilization; however, lack of physical chemical constants does not permit an estimation of the rate of volatilization. (SRC)

ATMOSPHERIC FATE: Because of its high vapor pressure, thiophosphoryl chloride may accumulate in the atmosphere. Its rate of reaction with atmospheric constituents is unknown. (SRC)

Thiophosphoryl chloride is a fuming liquid that hydrolyzes slowly in water and rapidly in base to form orthophosphoric acid, hydrochloric acid and hydrogen sulfide(1). No rates of hydrolysis were located. In the atmosphere thiophosphoryl chloride will react with photochemically produced hydroxyl radicals at a estimated rate of 5.5X10-11 cu cm/molecule sec(2). Assuming a hydroxyl radical concn of 5X10+5/cu cm, the half life of thiophosphoryl chloride would be 0.3 days(SRC).

Thiophosphoryl chloride has a relatively high vapor pressure, 16.35 mm Hg at 25 °C(1) and it should volatilize rapidly from soil. No experimental Henry's Law constant is available and the value cannot be estimated from structural considerations because of lack of structural fragments nor calculated from the vapor pressure and water solubility because of the lack of an experimental water solubility(SRC).

The probable route of exposure to thiophosphoryl chloride is by inhalation. (SRC)

NIOSH (NOES Survey 1981-1983) has statistically estimated that 1944 workers are exposed to thiophosphoryl chloride in the USA(1).

Occupational exposure involves acetyl cellulose makers, bronze alloy makers, munitions workers, smoke bomb and incendiary makers, pesticide rat poison worker, fertilizer makers, electroluminescent-coating makers, and semiconductor workers. /Phosphorus/

This substance may be hazardous to the environment. Special attention should be given to water quality.

Thiophosphoryl chloride may be released to the environment during its manufacture and use. It is a volatile chemical and would therefore tend to volatilize from water and soil and partition in the atmosphere. Its atmospheric half-life is estimated to be 0.3 days as a result of its reaction with photochemically produced hydroxyl radicals. Although no rate data are available, it is expected to hydrolyze slowly in water and moist soil. The rate of hydrolysis will increase with increasing pH. Exposure would be occupational. (SRC)

TERRESTRIAL FATE: If released on land thiophosphoryl chloride will be lost by volatilization and hydrolysis. No estimates of half-lives of these processes are available. (SRC)

AQUATIC FATE: If released in water, thiophosphoryl chloride will be lost by hydrolysis; the rate of hydrolysis is unknown. It may also be lost by volatilization; however, lack of physical chemical constants does not permit an estimation of the rate of volatilization. (SRC)

ATMOSPHERIC FATE: Because of its high vapor pressure, thiophosphoryl chloride may accumulate in the atmosphere. Its rate of reaction with atmospheric constituents is unknown. (SRC)

Thiophosphoryl chloride is a fuming liquid that hydrolyzes slowly in water and rapidly in base to form orthophosphoric acid, hydrochloric acid and hydrogen sulfide(1). No rates of hydrolysis were located. In the atmosphere thiophosphoryl chloride will react with photochemically produced hydroxyl radicals at a estimated rate of 5.5X10-11 cu cm/molecule sec(2). Assuming a hydroxyl radical concn of 5X10+5/cu cm, the half life of thiophosphoryl chloride would be 0.3 days(SRC).

Thiophosphoryl chloride has a relatively high vapor pressure, 16.35 mm Hg at 25 °C(1) and it should volatilize rapidly from soil. No experimental Henry's Law constant is available and the value cannot be estimated from structural considerations because of lack of structural fragments nor calculated from the vapor pressure and water solubility because of the lack of an experimental water solubility(SRC).

The probable route of exposure to thiophosphoryl chloride is by inhalation. (SRC)

NIOSH (NOES Survey 1981-1983) has statistically estimated that 1944 workers are exposed to thiophosphoryl chloride in the USA(1).

Occupational exposure involves acetyl cellulose makers, bronze alloy makers, munitions workers, smoke bomb and incendiary makers, pesticide rat poison worker, fertilizer makers, electroluminescent-coating makers, and semiconductor workers. /Phosphorus/

/GUIDE 157: SUBSTANCES - TOXIC AND/OR CORROSIVE (NON-COMBUSTIBLE/WATER -SENSITIVE)/ Health: TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns, or death. Reaction with water or moist air will release toxic, corrosive or flammable gases. Reaction with water may generate much heat which will increase the concentration of fumes in the air. Fire will produce irritating, corrosive and/or toxic gases. Runoff from fire control or dilution water may be corrosive and/or toxic and cause pollution.

/GUIDE 157: SUBSTANCES - TOXIC AND/OR CORROSIVE (NON-COMBUSTIBLE/WATER -SENSITIVE)/ Fire or Explosion: Non-combustible, substance itself does not burn but may decompose upon heating to produce corrosive and/or toxic fumes. Vapors may accumulate in confined areas (basement, tanks, hopper/tank cars etc.). Substance will react with water (some violently), releasing corrosive and/or toxic gases. Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated or contaminated with water.

/GUIDE 157: SUBSTANCES - TOXIC AND/OR CORROSIVE (NON-COMBUSTIBLE/WATER -SENSITIVE)/ Public Safety: CALL Emergency Response Telephone Number ... . As an immediate precautionary measure, isolate spill or leak area in all directions for at least 50 meters (150 feet) for liquids and at least 25 meters (75 feet) for solids. Keep unauthorized personnel away. Stay upwind. Keep out of low areas. Ventilate enclosed areas.

/GUIDE 157: SUBSTANCES - TOXIC AND/OR CORROSIVE (NON-COMBUSTIBLE/WATER -SENSITIVE)/ 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.

For more DOT Emergency Guidelines (Complete) data for THIOPHOSPHORYL CHLORIDE (8 total), please visit the HSDB record page.

UN 1837; Thiophosphoryl chloride

IMO 8.0; Thiophosphoryl chloride

49 302 64; Thiophosphoryl chloride

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.

Corrosive

Airtight.

UN Hazard Class: 8; UN Pack Group: II