Thionyl Chloride

H302: Harmful if swallowed [Warning Acute toxicity, oral]

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

H332: Harmful if inhaled [Warning Acute toxicity, inhalation]

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

H302 (85.1%): Harmful if swallowed [Warning Acute toxicity, oral]

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

H318 (29.4%): Causes serious eye damage [Danger Serious eye damage/eye irritation]

H331 (45.7%): Toxic if inhaled [Danger Acute toxicity, inhalation]

H332 (48.7%): Harmful if inhaled [Warning Acute toxicity, inhalation]

H335 (38.4%): May cause respiratory irritation [Warning Specific target organ toxicity, single exposure; Respiratory tract irritation]

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

Aggregated GHS information provided per 727 reports by companies from 29 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.

H315 (100%): Causes skin irritation [Warning Skin corrosion/irritation]

H319 (100%): Causes serious eye irritation [Warning Serious eye damage/eye irritation]

H332 (100%): Harmful if inhaled [Warning Acute toxicity, inhalation]

H334 (100%): May cause allergy or asthma symptoms or breathing difficulties if inhaled [Danger Sensitization, respiratory]

H335 (100%): May cause respiratory irritation [Warning Specific target organ toxicity, single exposure; Respiratory tract irritation]

P233, P260, P261, P264, P264+P265, P271, P280, P284, P302+P352, P304+P340, P305+P351+P338, P317, P319, P321, P332+P317, P337+P317, P342+P316, P362+P364, P403, P403+P233, P405, and P501 (click each P-code to see the statement)

Aggregated GHS information provided per 59 reports by companies from 1 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.

H301: Toxic if swallowed [Danger Acute toxicity, oral]

H318: Causes serious eye damage [Danger Serious eye damage/eye irritation]

H330: Fatal if inhaled [Danger Acute toxicity, inhalation]

H370: Causes damage to organs [Danger Specific target organ toxicity, single exposure]

P260, P264, P264+P265, P270, P271, P280, P284, P301+P316, P301+P330+P331, P302+P361+P354, P304+P340, P305+P354+P338, P308+P316, P316, P317, P320, P321, P330, P363, P403+P233, P405, and P501 (click each P-code to see the statement)

H331: Toxic if inhaled [Danger Acute toxicity, inhalation]

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

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 NIOSH Pocket Guide for Thionyl chloride:

Eye: IRRIGATE IMMEDIATELY - If this chemical contacts the eyes, immediately wash (irrigate) the eyes with large amounts of water, occasionally lifting the lower and upper lids. Get medical attention immediately.

Skin: WATER FLUSH IMMEDIATELY - If this chemical contacts the skin, 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.

Breathing: RESPIRATORY SUPPORT - If a person breathes large amounts of this chemical, 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.

Swallow: MEDICAL ATTENTION IMMEDIATELY - If this chemical has been swallowed, get medical attention immediately. (NIOSH, 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.

· Removal of solidified molten material from skin requires medical assistance.

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

(General first aid procedures)

Eye: Irrigate immediately - If this chemical contacts the eyes, immediately wash (irrigate) the eyes with large amounts of water, occasionally lifting the lower and upper lids. Get medical attention immediately.

Skin: Water flush immediately - If this chemical contacts the skin, 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.

Breathing: Respiratory support

Swallow: Medical attention immediately - If this chemical has been swallowed, get medical attention immediately.

Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]:

When material is not involved in fire, do not use water on material itself.

SMALL FIRE: Dry chemical or CO2. If it can be done safely, move undamaged containers away from the area around the fire.

LARGE FIRE: Flood fire area with large quantities of water, while knocking down vapors with water fog. If insufficient water supply, responders should withdraw.

FIRE INVOLVING TANKS, RAIL TANK CARS OR HIGHWAY TANKS: Cool containers with flooding quantities of water until well after fire is out. Do not get water inside containers. 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)

In case of fire in the surroundings, use appropriate extinguishing media. NO water. In case of fire: keep drums, etc., cool by spraying with water. NO direct contact with water.

Suitable extinguishing media: Dry powder.

Advice for firefighters: Wear self-contained breathing apparatus for firefighting if necessary.

Extinguish fire using agent suitable for surrounding fire. DO NOT use water. Violent reaction may result. Fight fire from protected location or maximum possible distance.

Use dry chemical, carbon dioxide, or alcohol foam extinguishers. Notify local health and fire officials and pollution control agencies. From a secure, explosion-proof location, use water spray to cool exposed containers. Keep water out of open containers. If cooling streams are ineffective (venting sound increases in volume and pitch, tank discolors, or shows any signs of deforming), withdraw immediately to a secure position. ... The only respirators recommended for firefighting are self-contained breathing apparatuses that have full face-pieces and are operated in a pressure-demand or other positive-pressure mode.

If material involved in fire: Use dry chemical, dry sand, or carbon dioxide. Do not use water on material itself. If large quantities of combustibles are involved, use water in flooding quantities as spray and fog. Use water spray to knock-down vapors. Cool all affected containers with flooding quantities of water. Apply water from as far a distance as possible.

Container explosion may occur under fire conditions.

... Interaction with water violently decomposes the /thionyl/ chloride to hydrogen chloride (2 mol) and sulfur dioxide (1 mol), the total expansion ratio from liquid to gas being 993:1 at 20 °C, so very high pressures may be generated.

... Closed containers may rupture violently when heated.

· 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.

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

· Stop leak if you can do it without risk.

· Use water spray to reduce vapors; do not put water directly on leak, spill area or inside container.

· Keep combustibles (wood, paper, oil, etc.) away from spilled material.

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.

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

HCl SO2 - when spill Thionyl chloride into water.

Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]:

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: See ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 1836 datasheet.

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.

When spilled in water

Small spill:

- ISOLATE in all directions: 100 m (300 ft)

Large spill:

- ISOLATE in all directions: 600 m (2000 ft)

When spilled on land

- ISOLATE in all directions: 30 m (100 ft)

- PROTECT people from downwind during DAY time: 0.1 km (0.1 mi)

- PROTECT people from downwind during NIGHT time: 0.2 km (0.2 mi)

- PROTECT people from downwind during DAY time: 0.3 km (0.2 mi)

- PROTECT people from downwind during NIGHT time: 0.5 km (0.4 mi)

- PROTECT people from downwind during DAY time: 0.9 km (0.6 mi)

- PROTECT people from downwind during NIGHT time: 2.9 km (1.8 mi)

- PROTECT people from downwind during DAY time: 7.6 km (4.7 mi)

- PROTECT people from downwind during NIGHT time: 11.0+ km (7.0+ mi)

Ventilation. 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. Personal protection: complete protective clothing including self-contained breathing apparatus.

Fully encapsulating, vapor-protective clothing should be worn for spills and leaks with no fire. Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. Use water spray to reduce vapors; do not put water directly on leak, spill area or inside container. Keep combustibles (wood, paper, oil, etc.) away from spilled material. 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. Prevent entry into waterways, sewers, basements or confined areas.

ACCIDENTAL RELEASE MEASURES: Personal precautions, protective equipment and emergency procedures: Wear respiratory protection. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Environmental precautions: Prevent further leakage or spillage if safe to do so. Do not let product enter drains. Methods and materials for containment and cleaning up: Soak up with inert absorbent material and dispose of as hazardous waste. Do not flush with water. Keep in suitable, closed containers for disposal.

Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]:

Do not touch damaged containers or spilled material unless wearing appropriate protective clothing. Stop leak if you can do it without risk. Use water spray to reduce vapors; do not put water directly on leak, spill area or inside container. Keep combustibles (wood, paper, oil, etc.) away from spilled material.

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. Prevent entry into waterways, sewers, basements or confined areas. (ERG, 2024)

Ventilation along the floor. Separated from food and feedstuffs. See Chemical Dangers. Dry. Well closed.

Keep container tightly closed in a dry and well-ventilated place. Containers which are opened must be carefully resealed and kept upright to prevent leakage. Keep away from water. Never allow product to get in contact with water during storage. Handle and store under inert gas. Storage class (TRGS 510): 6.1D: Non-combustible, acute toxic Cat.3 / toxic hazardous materials or hazardous materials causing chronic effects.

Thionyl chloride is classified as a corrosive material; it is shipped and stored in glass-lined steel tanks, zinc-coated (galvanized) steel drums, or special plastic drums having a DOT permit. Stainless steel (304L or 316L) may be used if all traces of moisture are excluded. Thionyl chloride stored in tanks or drums should be kept cool and away from direct sunlight and water.

Store separately in a corrosive-resistant location. Prior to working with thionyl chloride you should be trained on its proper handling and storage. Store in tightly closed containers in a cool, well-ventilated area away from water, acids, alkalis, ammonia, chloryl perchloride. Where possible, automatically pump liquid from drums or other storage containers to process containers.

Thionyl chloride should be stored in a cool, dry, well-ventilated area in tightly sealed containers that are labeled in accordance with OSHA's Hazard Communication Standard [29 CFR 1910.1200]. Containers of thionyl chloride should be protected from physical damage and contact with moisture and should be stored separately from ammonia or other bases, and dimethyl sulfoxide.

· 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.

TIH (Toxic Inhalation Hazard) - Term used to describe gases and volatile liquids that are toxic when inhaled. Some are TIH materials themselves, e.g., chlorine, and some release TIH gases when spilled in water, e.g., chlorosilanes. [ERG 2016].

AEGL 1: Notable discomfort, irritation, or certain asymptomatic non-sensory effects. However, the effects are not disabling and are transient and reversible upon cessation of exposure (Unit: ppm)

AEGL 2: Irreversible or other serious, long-lasting adverse health effects or an impaired ability to escape (Unit: ppm)

AEGL 3: Life-threatening health effects or death (Unit: ppm)

NR = Not recommended due to insufficient data

AEGLs Status: Interim

0.20 [ppm]

2.4 [ppm]

14 [ppm]

1 ppm (5 mg/m³)

C 1 ppm (5 mg/m3)

none See Appendix G

See: IDLH INDEX

0.2 [ppm]

Ceiling Limit: 0.2 ppm.

0.2 ppm as STEL

0.2 ppm [2009]

· When material is not involved in fire, do not use water on material itself.

Small Fire

· Dry chemical or CO2.

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

Large Fire

· Flood fire area with large quantities of water, while knocking down vapors with water fog. If insufficient water supply, responders should withdraw.

Fire Involving Tanks, Rail Tank Cars or Highway Tanks

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

· Do not get water inside containers.

· 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.

ERPG-1: 0.2 ppm - one hour exposure limit: 1 = mild transient health effects or objectionable odor [AIHA]

ERPG-2: 2 ppm - one hour exposure limit: 2 = impaired ability to take protective action [AIHA]

ERPG-3: 10 ppm - one hour exposure limit: 3 = life threatening health effects [AIHA]

Emergency Response Planning Guidlines (ERPGs) for thionyl chloride:[Table#2289]

Chemical Weapons Convention Schedule 3 B. Precursors chemical

The current /2001/ MAC for thionyl chloride in the Netherlands is 5 mg/cu m (1 ppm) as a ceiling value. /Based on a review of the existing literature /The committee considered that the toxicological database on thionyl chloride was too poor to justify the recommendation of a health-based limit. The committee concluded that there was insufficient information to comment on the level of the present MAC-value.

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

The substance is very corrosive to the eyes, skin and respiratory tract. Corrosive on ingestion. Inhalation may cause lung oedema. The substance may cause effects on the lungs. This may result in inflammation and blockage of the airways. Exposure far above the OEL could cause death. The effects may be delayed. Medical observation is indicated.

Excerpt from NIOSH Pocket Guide for Thionyl chloride:

Thionyl chloride appears as a colorless to yellow fuming liquid with a suffocating pungent odor. Boiling point 79 °C. A lachrymator. Highly corrosive and toxic. Long-term inhalation of low concentrations or short-term inhalation of high concentrations has adverse health effects.

Colorless to yellow to reddish liquid with a pungent odor like sulfur dioxide. [Note: Fumes form when exposed to moist air.]; [NIOSH]

COLOURLESS-TO-YELLOW OR REDDISH FUMING LIQUID WITH PUNGENT ODOUR.

Colorless to yellow to reddish liquid with a pungent odor like sulfur dioxide.

Colorless to yellow to reddish liquid with a pungent odor like sulfur dioxide. [Note: Fumes form when exposed to moist air.]

Colorless to pale yellow or reddish liquid

Pale yellow to red liquid

Colorless to pale yellow, fuming, refractive liquid

Colorless to yellow to reddish liquid [Note: Fumes form when exposed to moist air]

Suffocating odor

Pungent odor like sulfur dioxide.

169 °F at 760 mmHg (NIOSH, 2024)

76 °C at 760 mm Hg

78.8 °C @760 [mm Hg]

-156 °F (NIOSH, 2024)

-104.5 °C

Reacts with water (NIOSH, 2024)

Decomposes (fumes) in water

Decomp in acids, alc, alkalies; in cold and hot water

Miscible with benzene, chloroform, carbon tetrachloride

Solubility in water: reaction

1.64 (NIOSH, 2024) - Denser than water; will sink

1.676 at 0 °C/4 °C; 1.655 at 10 °C/4 °C; 1.638 at 20 °C/4 °C

Percent in saturated air: 14.5 at 26 °C; density of saturated air: 1.5 at 26 °C (air= 1); 1 mg/cu m is equiv to 0.2 ppm and 1 ppm is equiv to 4.87 mg/cu m at 25 °C, 760 mm Hg

Relative density (water = 1): 1.64

1.640 @ 15.5°C

4.1 (Air = 1)

Relative vapor density (air = 1): 4.1

100 mmHg at 70 °F (NIOSH, 2024)

119.0 [mmHg]

Vapor pressure = 110 mm Hg at 26 °C

Vapor pressure, kPa at 25 °C: 16

100 mmHg at 70 °F

100 [mm Hg] @21.4 °C

(70 °F): 100 mmHg

Stable under recommended storage conditions.

... It fumes upon exposure to air.

Hazardous decomposition products formed under fire conditions - Sulfur oxides, hydrogen chloride gas.

When heated to decomposition it emits toxic fumes of /sulfur oxides and chloride/.

Decomposes when heated above 140 °C forming chlorine, sulfur dioxide, and disulfur dichloride ...

Emits dense corrosive fumes in moist air. Violently reacts with water to liberate hydrochloric acid and sulfur dioxide [NFPA 10th ed. 1991].

Thionyl chloride reacts vigorously with water to generate gaseous HCl and SO2. Based on a scenario where the chemical is spilled into an excess of water (at least 5 fold excess of water), half of the maximum theoretical yield of Sulfur Dioxide gas will be created in 0.25 minutes. Experimental details are in the following: "Development of the Table of Initial Isolation and Protective Distances for the 2008 Emergency Response Guidebook", ANL/DIS-09-2, D.F. Brown, H.M. Hartmann, W.A. Freeman, and W.D. Haney, Argonne National Laboratory, Argonne, Illinois, June 2009.

Acyl Halides, Sulfonyl Halides, and Chloroformates

Water-Reactive

Air-Reactive

CSL00031

N,N-DIMETHYLFORMAMIDE + THIONYL CHLORIDE

Health Hazard

Harmful,Toxic

Chlorination

Generation of dimethylcarbamoyl chloride (carcinogen). DMCC is also toxic and a severe irritant.

User-Reported

CSL00034

THIONYL CHLORIDE + 1,4-DIOXANE

Explosive decomposition when heated in a steel vessel

Explosive

CSL00035

ACETONITRILE + THIONYL CHLORIDE

Thermal runaway from 25°C to >100°C

CSL00036

THIONYL CHLORIDE + ETHYL ACETATE + IRON

Galvanised drums burst when used for storing thionyl chloride in ethyl acetate

Gas Under Pressure

Bretherick's

CSL00063

THIONYL CHLORIDE + DIMETHYL SULFOXIDE

Potentially explosive

CSL00081

SODIUM AZIDE + THIONYL CHLORIDE

highly explosive

CSL00199

2-Nitroacetonitrile + 2-Nitroacetaldehyde + Thionyl chloride + Diethyl ether

" The Chemistry Group at the National Institutes of Health Chemical Genomics Center wishes to alert readers on the volatile nature of nitroacetonitrile (CAS No. 13218-13-8), which caused a recent explosion in our laboratories that, fortunately, did not result in harm to individuals or property. A chemist was performing a dehydration of 2-nitroacetaldehyde oxime to nitroacetonitrile using thionyl chloride in diethyl ether (diethyl ether was from a freshly opened bottle) at 40 ºC for one hour (following a reported literature procedure: J. Org. Chem. 1960, 25, 266; J. Med. Chem. 1986, 29, 1046, but working on a substantially smaller scale). The reaction mixture was subsequently filtered to remove precipitate, and the filtrate was washed with water. The diethyl ether layer was separated, dried with sodium sulfate, filtered, and concentrated under reduced pressure. Note: Some diethyl ether remained at this point. The round-bottom flask remained vented and was placed in the back of the hood. Approximately one hour later, an explosion occurred. Numerous reports do not advise on the explosive nature of nitroacetonitrile, and we have noted only one report that suggests reagents of this type are potentially explosive (Can. J. Chem. 1959, 37, 1266). The mechanism of the violent decomposition has not been determined." (reprint of the full-text)

Not Available

10.1021/cen-v087n032.p004

Literature Reference

10/15/2022

THIONYL CHLORIDE reacts, potentially explosively, with dimethyl sulfoxide or dimethylformamide containing traces of iron or zinc [Spitulnik, M. J., Chem. Eng. News, 1977, 55(31), p. 31]. Undergoes violent reactions with bases (ammonia, sodium hydroxide, potassium hydroxide, amines), alkali metals (sodium, potassium), esters (ethyl acetate), toluene mixed with ethanol / water [Bretherick, 5th ed., 1995, p. 1325]. Has an expansion ratio from gas to liquid of nearly 1000:1. Hence may cause an explosion if heated while contained [MCA Case History No. 1808]. 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]. Perchloric acid ignites on contact with sulfinyl chloride. (Bailar, 1973, Vol. 2, 1442). SOCl2 reacts with esters, such as ethyl acetate, forming toxic SO2 gas and water soluble/toxic acyl chlorides, catalyzed by Fe or Zn (Spagnuolo, C.J. et al. 1992. Chemical and Engineering News 70(22):2.).

Incompatible materials: Alcohols, amines, metals, reacts violently with water.

Violent reaction with water releases hydrogen chloride and sulfur dioxide. Both these decomposition products constitute serious toxicity hazards. ... A powerful chlorinating agent. Potentially explosive reaction with ammonia, bis(dimethylamino)sulfoxide (above 800 °C), chloryl perchlorate, 1,2,3-cyclohexanetrione trioxime + sulfur dioxide, dimethyl sulfoxide, hexafluoroisopropy-lideneaminolithium. Violent reaction or ignition with 2,4-hexadiyn-1-6-diol, o-nitrobenzoyl acetic acid, o-nitrophen-yl-acetic acid, sodium (ignites at 300 °C). Incompatible with ammonia, dimethyl formamide + trace iron it zinc, linseed oil + quinoline, toluene + ethanol + water.

IDENTIFICATION AND USE: Thionyl chloride is a colorless to pale yellow or reddish liquid. Thionyl chloride is an industrially produced liquid used to make acyl chlorides and to synthesize pharmaceuticals including drugs and vitamins. It is used to make dyes, to prepare organic chlorine compounds, as a solvent in the production of herbicides, and as an electrolyte in lithium batteries. Thionyl chloride is also used to prepare polyacrylate-type engineering thermoplastics made from iso- and tere-phthaloyl chlorides. It is required in the manufacture of methylphosphonic dichloride, a key precursor for the nerve gas Sarin. HUMAN STUDIES: Potential symptoms of overexposure are irritation of eyes, skin, mucous membranes, as well as eye and skin burns. Symptoms of exposure range from mild irritation to death and include dyspnea, burns, pulmonary edema, and inflammation. Cases of thionyl chloride-induced lung injury have been noted. ANIMAL STUDIES: A 20-min exposure to 17.5 ppm proved fatal to cats. Male rats were exposed to 99% pure thionyl chloride in a whole-body inhalation chamber. Two of five males died at 1239 ppm, three of five died at 1509 ppm, and four of five died at 1989 ppm. All deaths occurred within 48 hours of exposure. Severe lung irritation and edema were reported as the cause of death.

The substance can be absorbed into the body by inhalation and by ingestion.

inhalation, ingestion, skin and/or eye contact

Sore throat. Cough. Burning sensation. Shortness of breath. Laboured breathing. Symptoms may be delayed.

Pain. Redness. Serious skin burns.

Pain. Redness. Severe deep burns.

Burning sensation. Abdominal pain. Shock or collapse.

irritation eyes, skin, mucous membrane; eye, skin burns

Eyes, skin, respiratory system

Dermatotoxin - Skin burns.

Lacrimator (Lachrymator) - A substance that irritates the eyes and induces the flow of tears.

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

Fibrogenic - Inducing tissue injury and fibrosis (scarring).

LC50 (rat) = 500 ppm/1h

LC50 Rat inhalation 736 ppm/1 hr

LC50 Rat inhalation 1277 ppm/1 hr

LC50 Rat inhalation 500 ppm/1 hr

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 if 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 ... . Monitor for shock 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. Early intubation at the first sign of upper airway obstruction may be necessary. 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 bronchospasm ... . 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 (Valium) or lorazepam (Ativan) ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Sulfur and related compounds/

If this chemical gets into the eyes, remove any contact lenses at once and irrigate immediately for at least 15 min, occasionally lifting upper and lower lids. Seek medical attention immediately. If this chemical contacts the skin, remove contaminated clothing and wash immediately with soap and water. Seek medical attention immediately. If this chemical has been inhaled, remove from exposure, begin rescue breathing (using universal precautions, including resuscitation mask) if breathing has stopped and CPR if heart action has stopped. Transfer promptly to a medical facility. When this chemical has been swallowed, get medical attention. If victim is conscious, administer water or milk. Do not induce vomiting. Medical observation is recommended for 24-48 hr after breathing overexposure, as pulmonary edema may be delayed. As first aid for pulmonary edema, a doctor of authorized paramedic may consider administering a corticosteroid spray.

/SIGNS AND SYMPTOMS/ Potential symptoms of overexposure are irritation of eyes, skin, mucous membranes; eye, skin burns.

/SIGNS AND SYMPTOMS/ Symptoms of exposure range from mild irritation to death and include dyspnea, burns, pulmonary edema, and inflammation.

/CASE REPORTS/ ... A case /was reported/ of a pharmaceutical production plant worker exposed for two minutes to an unknown amount of thionyl chloride vapor during repair of a vent pipe. The worker experienced burning of the eyes, upper airway, and chest followed by feelings of suffocation. He began coughing with expulsion of blood. He was hospitalized ... with cough, sero-mucosal excretion, pharyngeal and chest burning. His respiratory function test showed insufficient ventilation and examination revealed vesicular murmur with wheezing at end of expiration. He was diagnosed with acute asthmatic tracheal bronchitis, was treated with bronchodilators and antibiotics, and recovered.

/CASE REPORTS/ /An/ employee suffered CNS effects after an acute exposure to an unknown concentration of what was believed to be thionyl chloride. The employee was not wearing any respiratory protection, inhaled 2-3 breaths of thionyl chloride vapor, and began suffering from rhinitis, lacrimation, sore throat, and coughing. The employee also exhibited signs of impaired hand-eye coordination, memory, judgment, and slurred speech. These clinical signs had improved six hours post exposure and no symptoms were present 72 hours post exposure.

For more Human Toxicity Excerpts (Complete) data for Thionyl chloride (6 total), please visit the HSDB record page.

/LABORATORY ANIMALS: Acute Exposure/ /A study/ exposed male Fischer 344 rats to 99% pure thionyl chloride in a 60-liter whole-body inhalation chamber for one hour and observed the animals for at least two weeks post exposure. Analytical concentrations were measured by IR analysis. Moisture from the rats increased the humidity of the chamber to around 50% and caused almost complete hydrolysis of thionyl chloride to a mixture of sulfur dioxide and hydrogen chloride, and rats were exposed to this mixture more than to thionyl chloride. Exposure concentrations were reported as the mixture of sulfur dioxide and hydrogen chloride concentrations (906, 1080, 1239, 1509, or 1983 ppm). Five animals were exposed per group and no deaths were reported at 906 or 1080 ppm of the mixture. Two of five males died at 1239 ppm, three of five died at 1509 ppm, and four of five died at 1989 ppm of the mixture. All deaths occurred within 48 hours of exposure. Examination of the animals revealed mild to moderate multifocal congestion and alveolar damage. Severe lung irritation and edema were reported as the cause of death. The BMCL05 /benchmark concentration, 95% lower confidence limit with 5% response/ and BMC01 /benchmark concentration with 1% response/ were 663 and 830 ppm, respectively.

/LABORATORY ANIMALS: Acute Exposure/ ... Five male and five female Wistar rats /were exposed/ in an OECD Guideline study to 71, 407, 769, 2121, or 3441 ppm of thionyl chloride vapor for one hour and observed ... for 14 days post exposure. The thionyl chloride used for the study was reported to be 99.8% pure, and rats were exposed head/nose only in a chamber 30 x 28 cm that prevented expired air from mixing with test atmosphere. Analytical concentration was determined using spectrophotometry. The LC50 was calculated to be 1277 ppm. Four of five males and four of five females died at 2121 ppm, and five of five males and four of five females died at 3441 ppm prior to sacrifice. Prior to death, labored breathing was observed in the animals. The author noted opacity of cornea, lung distention, necrotic changes in the nose, and pulmonary edema in the animals that died. The BMCL05 /benchmark concentration, 95% lower confidence limit with 5% response/ and BMC01 /benchmark concentration with 1% response/ were 507 and 671 ppm, respectively.

/LABORATORY ANIMALS: Acute Exposure/ ... 6 male and 6 female Wistar rats /were exposed/ to 196, 371, 593, 954, or 1241 ppm to 99.9% pure (a.i.) thionyl chloride vapor in a nose-only chamber for one hour and observed ... 14 days post exposure. Gas chromatography was used to analyze thionyl chloride during exposure. The LC50 was 736 ppm for males and females combined. No deaths were recorded in the 196 or 371 ppm exposure groups. Five of six males and two of six females died at 593 ppm. Five of six males and two of six females died at 954 ppm. Six of six males and four of six females died at 1241 ppm. Prior to death, audible respiration was observed. Hyperinflation of the lungs, perinasal and periocular encrustation were noted in some of the animals that died in the 954 and 1241 ppm exposure groups. One control male rat died during exposure and it was thought to be due to incorrect positioning in the chamber. The BMCL05 BMCL05 /benchmark concentration, 95% lower confidence limit with 5% response/ and BMC01 BMC01 /benchmark concentration with 1% response/ were 193 and 222 ppm, respectively.

/LABORATORY ANIMALS: Acute Exposure/ A 20-min exposure to 17.5 ppm is said to have proved fatal to cats.

Thionyl chloride's production and use in the manufacture of pesticides, engineering plastics, as a chlorinating agent, catalyst(1) and in the synthesis of various nerve agents(2) may result in its release to the environment through various waste streams(SRC).

TERRESTRIAL FATE: Thionyl chloride reacts rapidly and violently with water, water vapor or moisture to form sulfur dioxide and hydrogen chloride(1). Therefore, soil adsorption, volitilization, and biodegradation in soil are not expected to be environmental fate processes(SRC).

AQUATIC FATE: Thionyl chloride reacts rapidly and violently with water, water vapor or moisture to form sulfur dioxide and hydrogen chloride(1). Therefore, sediment adsorprion, volitilization, bioconcentration, and biodegradation in water are not expected to be environmental fate processes(SRC).

TERRESTRIAL FATE: Thionyl chloride reacts rapidly and violently with water, water vapor or moisture to form sulfur dioxide and hydrogen chloride(1). Therefore, reaction with hyrdroxyl radicals is not expected to be an environmental fate process(SRC).

Thionyl chloride reacts rapidly and violently with water, water vapor or moisture to form sulfur dioxide and hydrogen chloride(1).

According to the 2016 TSCA Inventory Update Reporting data, 4 reporting facilities estimate the number of persons reasonably likely to be exposed in the manufacturing, processing, or use of thionyl chloride in the United States may be as low as 10-25 workers up to the range of 100-500 workers per plant; the data may be greatly underestimated due to confidential business information (CBI) or unknown values(1).

NIOSH (NOES Survey 1981-1983) has statistically estimated that 7082 workers (1223 of these are female) were potentially exposed to thionyl chloride in the US(1).

Thionyl chloride's production and use in the manufacture of pesticides, engineering plastics, as a chlorinating agent, catalyst(1) and in the synthesis of various nerve agents(2) may result in its release to the environment through various waste streams(SRC).

TERRESTRIAL FATE: Thionyl chloride reacts rapidly and violently with water, water vapor or moisture to form sulfur dioxide and hydrogen chloride(1). Therefore, soil adsorption, volitilization, and biodegradation in soil are not expected to be environmental fate processes(SRC).

AQUATIC FATE: Thionyl chloride reacts rapidly and violently with water, water vapor or moisture to form sulfur dioxide and hydrogen chloride(1). Therefore, sediment adsorprion, volitilization, bioconcentration, and biodegradation in water are not expected to be environmental fate processes(SRC).

TERRESTRIAL FATE: Thionyl chloride reacts rapidly and violently with water, water vapor or moisture to form sulfur dioxide and hydrogen chloride(1). Therefore, reaction with hyrdroxyl radicals is not expected to be an environmental fate process(SRC).

Thionyl chloride reacts rapidly and violently with water, water vapor or moisture to form sulfur dioxide and hydrogen chloride(1).

According to the 2016 TSCA Inventory Update Reporting data, 4 reporting facilities estimate the number of persons reasonably likely to be exposed in the manufacturing, processing, or use of thionyl chloride in the United States may be as low as 10-25 workers up to the range of 100-500 workers per plant; the data may be greatly underestimated due to confidential business information (CBI) or unknown values(1).

NIOSH (NOES Survey 1981-1983) has statistically estimated that 7082 workers (1223 of these are female) were potentially exposed to thionyl chloride in the US(1).

SRP: 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 air, soil or water; effects on animal, aquatic and plant life; and conformance with environmental and public health regulations. If it is possible or reasonable use an alternative chemical product with less inherent propensity for occupational harm/injury/toxicity or environmental contamination.

SRP: Wastewater from contaminant suppression, cleaning of protective clothing/equipment, or contaminated sites should be contained and evaluated for subject chemical or decomposition product concentrations. Concentrations shall be lower than applicable environmental discharge or disposal criteria. Alternatively, pretreatment and/or discharge to a permitted wastewater treatment facility is acceptable only after review by the governing authority and assurance that "pass through" violations will not occur. Due consideration shall be given to remediation worker exposure (inhalation, dermal and ingestion) as well as fate during treatment, transfer and disposal. If it is not practicable to manage the chemical in this fashion, it must be evaluated in accordance with EPA 40 CFR Part 261, specifically Subpart B, in order to determine the appropriate local, state and federal requirements for disposal.

Product: Offer surplus and non-recyclable solutions to a licensed disposal company. Contact a licensed professional waste disposal service to dispose of this material. Dissolve or mix the material with a combustible solvent and burn in a chemical incinerator equipped with an afterburner and scrubber; Contaminated packaging: Dispose of as unused product.

Spray on a thick layer of a (1:1) mixture of dry soda ash and slaked lime behind a shield. After mixing, spray water from an atomizer with great precaution. Transfer slowly into a large amount of water. Neutralize ...

/Laboratory Quantities/ Package Lots: Place in a separate labeled container for recycling or disposal. Small Quantities: Wear butyl rubber gloves, laboratory coat, and eye protection. In the fume hood, pour the thionyl chloride into a large evaporating dish. Cover the thionyl chloride with excess solid sodium carbonate or calciun carbonate. When the reaction has subsided, very slowly add the mixture to a pail of cold water. Allow to stand for 24 hr. Test the pH of the solution and neutralize if necessary. ...

If ... THERE IS NO FIRE, go directly to the Table of Initial Isolation and Protective Action Distances /(see table below)/ ... to obtain initial isolation and protective action distances. IF THERE IS A FIRE, or IF A FIRE IS INVOLVED, go directly to the appropriate guide /(see guide(s) below)/ and use the evacuation information shown under PUBLIC SAFETY.

Table: Table of Initial Isolation and Protective Action Distances for Thionyl chloride (when spilled in water) ID: 1836 [Table#2286]

Table: Table of Initial Isolation and Protective Action Distances for Thionyl chloride (when spilled on land) ID: 1836 [Table#2287]

Table of Water-Reactive Materials Which Produce Toxic Gases.

Table: Materials Which Produce Large Amounts of Toxic-by-Inhalation (TIH) Gas(es) When Spilled in Water [Table#2288]

/GUIDE 137 SUBSTANCES - WATER-REACTIVE - CORROSIVE/ Fire or Explosion: EXCEPT FOR ACETIC ANHYDRIDE (UN1715), THAT IS FLAMMABLE, some of these materials may burn, but none ignite readily. May ignite combustibles (wood, paper, oil, clothing, etc.). Substance will react with water (some violently), releasing corrosive and/or toxic gases and runoff. Flammable/toxic gases may accumulate in confined areas (basement, tanks, hopper/tank cars, etc.). Contact with metals may evolve flammable hydrogen gas. Containers may explode when heated or if contaminated with water. Substance may be transported in a molten form.

For more DOT Emergency Guidelines (Complete) data for Thionyl chloride (11 total), please visit the HSDB record page.

UN 1836; Thionyl chloride

IMO 8.0; Thionyl chloride

49 300 60; Thionyl 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. Thionyl chloride is included on the dangerous goods list.

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. Thionyl chloride is included on the dangerous goods list.

Corrosive

Unbreakable packaging. Put breakable packaging into closed unbreakable container. Do not transport with food and feedstuffs.

Symbol: C; R: 14-20/22-29-35; S: (1/2)-26-36/37/39-45

UN Hazard Class: 8; UN Pack Group: I