Fuming sulfuric acid

178.14

177.92400

231-639-5

1447

1831

DTXSID5064889

Colorless or slightly colored, viscous liquid|Heavy, oily liquid; colorless to dark brown depending on purity|Heavy, fuming, yellow liquid

2807000090

135

0.71980

Colorless Liquid

1.9 g/cm³

2 °C

~290 °C(lit.)

Miscible with water.

Store below +30°C.

1 mm Hg ( 146 °C)

<0.3 (25 °C, vs air)

Inhalation-Rat LC50: 347 PPM/1 hour

In case of H, the pore-forming agent is flammable; in case of cyanide, it emits highly toxic hydrogen cyanide gas; in the case of flammable organic matter burning or exploding; heat produces toxic sulfur oxide fumes

Risk of fire and explosion on contact with base(s), combustible substances, reducing agents or water.

38 mPa-sec at 25 °C /30% SO3, wt % (% Oleum)/|Fumes strongly in moist air. Extremely hygroscopic. Reacts violently with water.|Consists of sulfuric acid and up to 80% sulfur trioxide|Heat capacity: 1.55 kJ/kg-K at 20 °C /50% SO3, wt % (% Oleum)/|COMBINATION WATER - 18.37% FREE SULFUR TRIOXIDE - 0%, TOTAL SULFUR TRIOXIDE - 81.63%; AMOUNT OF SULFUR TRIOXIDE WITH 100% SULFURIC ACID

Fumes in air. Soluble in water; dissolution generates dangerous amounts of heat that can cause localized boiling and spattering of the acidic mixture and generate heavy fumes, mists. During sulfonation of mononitrobenzene with fuming sulfuric acid, a leak from an internal cooling coil permitted water to enter the reaction tank. A violent eruption occurred due to the heat of solution [MCA Case History 944(1963)].

Acids, Strong Oxidizing

Strong Oxidizing Agent

OLEUM, WITH LESS THAN 30% FREE SULFUR TRIOXIDE reacts as a strong acid, as an oxidizing agent and as a dehydrating agent. Chars wood, sugar and many other organic materials on contact. The heat from these reactions may ignite the wood, sugar or organic matter. May react explosively with acetic acid, acetic anhydride, acetonitrile, acrolein, acrylic acid, acrylonitrile, allyl alcohol, allyl chloride, ammonium hydroxide, aniline, cresol, butyraldehyde, cumene, ethyl acetate, ethylene diamine, ethylene glycol, glyoxal, isoprene, isopropyl alcohol, methyl ethyl ketone, propylene oxide, pyridine, styrene, vinyl acetate; strong bases (sodium hydroxide, potassium hydroxide) or mineral acids (nitric acid, hydrochloric acid, hydrofluoric acid) [Lewis, 3rd ed., 1993, p. 1195]. Mixing in equal molar portions with any of the following substances in a closed container caused the temperature and pressure to increase: 2-aminoethanol, ammonium hydroxide (28%), chlorosulfonic acid, ethylenediamine, ethyleneimine, ethylene cyanohydrin, hydrochloric acid (36%), hydrofluoric acid (48.7%), isopropyl alcohol, nitric acid (70%), 2-nitropropane, propiolactone, propylene oxide, pyridine, styrene monomer, sodium hydroxide, sulfolane, vinyl acetate, vinylidene chloride [NFPA 1991]. Extremely hazardous in contact with carbides, bromates, chlorates, fulminates, picrates, and powdered metals. May induce violent polymerization in polymerizable organic compounds such as allyl chloride. Reacts exothermically with sodium hypochlorite to produce chlorine gas.

Not flammable (USCG, 1999)

The vapour is heavier than air.

Extremely corrosive

II

8

UN 3264 8/PG 3

1

36/38-37-35-14-34

26-30-45-36/37/39

WS5600000

C

Storehouse ventilated at low temperature and dry; stored separately from H pore-forming agent, cyanide, combustible and flammable materials

Explosive when exposed to water

Stable. Incompatible with organic materials, powdered metals, bases, halides. Reacts violently with water. Very hygroscopic.

P260-P280-P284-P305 + P351 + P338-P310

H314-H330-H335

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.

Will react with water or steam to produce heat and toxic and corrosive fumes. Can react vigorously with reducing materials.|Mixing oleum in closed container with following: /acetic acid, acetic anhydride, acetonitrile, acrolein, acrylic acid, acrylonitrile, allyl alc, allyl chloride, 2-aminoethanol, ammonium hydroxide (28%), aniline, n-butyraldehyde, cresol, cumene, dichloroethyl ether, ethylene cyanohydrin, ethyleneimine, hydrochloric acid, hydrofluoric acid, isopropyl alc, nitric acid, 2-nitropropane, propiolactone (beta-), propylene oxide, pyridine, styrene monomer, sulfolane, vinyl acetate, vinylidene chloride, diethylene glycol monomethyl ether, diisobutylene, epichlorohydrin, ethyl acetate, ethylene diamine, ethylene glycol, ethylene glycol monoethyl ether acetate, glyoxal, isoprene, mesityl oxide, methyl ethyl ketone, sodium hydroxide,/ caused temp and pressure to increase.|Sulfuric acid and oleum react violently with water and are corrosive to metals, minerals, and human tissue.

IARC Monographs on the Evaluation of Carcinogenic Risks to Humans. Occupational Exposures to Mists and Vapours from Strong Inorganic Acids and Other Industrial Chemicals (vol 54).336 pp. (1992). IARC Monographs provide critical reviews of data on carcinogenicity for agents to which humans are known to be exposed and on specific exposure situations.[Available from, as of November 18, 2009: http://monographs.iarc.fr/ENG/Monographs/vol54/index.php]|U.S. Dept Health & Human Services/Agency for Toxic Substances & Disease Registry; Toxicological Profile for Sulfur Trioxide and Sulfuric Acid (December 1998). The ATSDR toxicological profile succinctly characterizes the toxicologic and adverse health effects information for a hazardous substance.[Available from, as of October 15, 2009: http://www.atsdr.cdc.gov/toxpro2.html#]|Fire FL; Chemical Data Notebook Series: Sulfuric acid and Oleum; Fire Engineering 139 (6): 30-6 (1986). The physical properties of sulfuric acid and oleum as well as their hazards are discussed.

Special Hazards of Combustion Products: Toxic and irritating vapors are generated. (USCG, 1999)|Not combustible. Many reactions may cause fire or explosion. Gives off irritating or toxic fumes (or gases) in a fire. Risk of fire and explosion on contact with bases, combustible substances, reducing agents, water or organic materials.|Carcinogens, Corrosives, Reactive - 2nd degree

|Danger|H314: Causes severe skin burns and eye damage [Danger Skin corrosion/irritation]|P201, P202, P260, P261, P264, P270, P271, P280, P281, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P308+P313, P309+P311, P310, P311, P314, P321, P363, P403+P233, P405, and P501

Excerpt from ERG Guide 137 [Substances - Water-Reactive - Corrosive]: 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: See ERG Table 1 - Initial Isolation and Protective Action Distances on the UN/NA 1831 datasheet. 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 137 [Substances - Water-Reactive - Corrosive]: 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. (ERG, 2016)

Respirator approved for acid mists; rubber gloves; splashproof goggles; eyewash fountain and safety shower; rubber footwear; face shield. (USCG, 1999)|Workers employed in mfr, handling or use of sulfuric acid should wear suitable personal protective equipment, incl chem goggles, face screens, gloves, neoprene or PVC boots and acid-resistant trousers, legs of which should fall over boots ... /Sulfuric acid/|Protective clothing and safety apparatus needed for spill cleanup rubber gloves and boots, acid-resistant face shields and clothing, and a positive-pressure self-contained breathing apparatus.

A very dangerous fire hazard by chemical reaction with reducing agents and carbohydrates.|Sulfuric acid and oleum are nonflammable liquids, but they can cause or support a fire by reacting with other chemicals.

A severe explosion hazard by chemical reaction ...|Risk of fire and explosion on contact with base(s), combustible substances, reducing agents or water.

NO hydrous agents. NO water. In case of fire in the surroundings: use appropriate extinguishing media ... Cool drums, etc., by spraying with water but avoid contact of the substance with water.

Evacuate danger area! Consult an expert! Ventilation. NEVER direct water jet on liquid. Do NOT absorb in saw-dust or other combustible absorbents. Collect leaking liquid in covered plastic containers. Absorb remaining liquid in dry sand or inert absorbent and remove to safe place. Do NOT let this chemical enter the environment.|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.|Solid remedies react with spilled liq to form skin that supresses fumes to permit close approach or completely solidifies spill.

Extremely corrosive. Handle with great care.|SRP: Contaminated protective clothing should be segregated in a manner so that results in no direct personal contact by personnel who handle, dispose of, or clean the clothing. Quality assurance procedures to confirm the efficacy of the cleaning procedures should be implemented prior to the decontaminated protective clothing being returned for reuse by the workers. Contaminated clothing (including shoes/socks) should not be taken home at end of shift, but should remain at employee's place of work for cleaning.|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.

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. /Sulfuric acid, fuming; Sulfuric acid, fuming, with not less than 30% free Sulfur trioxide/|/GUIDE 137: SUBSTANCES - WATER-REACTIVE - CORROSIVE/ Health: CORROSIVE and/or TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns, or death. Fire will produce irritating, corrosive and/or toxic gases. Reaction with water may generate much heat which will increase the concentration of fumes in the air. Contact with molten substance may cause severe burns to skin and eyes. Runoff from fire control or dilution water may cause pollution. /Sulfuric acid, fuming; Sulfuric acid, fuming, with less than 30% free Sulfur trioxide; Sulfuric acid, fuming, with not less than 30% free Sulfur trioxide/|/GUIDE 137: SUBSTANCES - WATER-REACTIVE - CORROSIVE/ Fire or Explosion: ... 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. 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. /Sulfuric acid, fuming; Sulfuric acid, fuming, with less than 30% free Sulfur trioxide; Sulfuric acid, fuming, with not less than 30% free Sulfur trioxide/|/GUIDE 137: SUBSTANCES - WATER-REACTIVE - CORROSIVE/ 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. /Sulfuric acid, fuming; Sulfuric acid, fuming, with less than 30% free Sulfur trioxide; Sulfuric acid, fuming, with not less than 30% free Sulfur trioxide/|For more DOT Emergency Guidelines (Complete) data for Oleum (9 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.

Evacuate danger area! Consult an expert! Personal protection: chemical protection suit including self-contained breathing apparatus. Do NOT let this chemical enter the environment. Do NOT absorb in saw-dust or other combustible absorbents. Collect leaking liquid in sealable containers. Absorb remaining liquid in dry sand or inert absorbent. Then store and dispose of according to local regulations. Cautiously neutralize remainder with lime or soda ash.

Dry. Separated from food and feedstuffs and incompatible materials. See Chemical Dangers. Store only in original packaging. Ventilation along the floor.

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

The substance is very corrosive to the eyes, skin and respiratory tract. Corrosive on ingestion. Exposure could cause asphyxiation due to swelling in the throat. Inhalation of high concentrations may cause lung oedema, but only after initial corrosive effects on the eyes and the upper respiratory tract have become manifest. Inhalation may cause asthma-like reactions (RADS). Medical observation is indicated.

Repeated or prolonged contact with skin may cause dermatitis. Repeated or prolonged inhalation of the aerosol may cause effects on the lungs. Risk of tooth erosion upon repeated or prolongated exposure to an aerosol of this substance. Mists of this strong inorganic acid are carcinogenic to humans.

NO contact with incompatible materials: See Chemical Dangers

PREVENT GENERATION OF MISTS! AVOID ALL CONTACT! IN ALL CASES CONSULT A DOCTOR!

Use ventilation, local exhaust or breathing protection.

Protective gloves. Protective clothing. Apron.

Wear face shield or eye protection in combination with breathing protection.

Persons in charge of vessels or facilities are required to notify the National Response Center (NRC) immediately, when there is a release of this designated hazardous substance, in an amount equal to or greater than its reportable quantity of 1000 lb or 454 kg. The toll free number of the NRC is (800) 424-8802. The rule for determining when notification is required is stated in 40 CFR 302.4 (section IV. D.3.b).

highly toxic

LC50 Rat/male inhalation 1.4 mg/L 1 hr|LC50 Rat/female inhalation 1.2 mg/L 1 hr|LC50 Rat/male inhalation 420 ppm 1 hr|LC50 Rat/female inhalation 347 ppm 1 hr

NIOSH (NOES Survey 1981-1983) has statistically estimated that 8,071 workers (1,107 of these were female) were potentially exposed to oleum in the US(1).

Acid mist is irritating to eyes, nose and throat. Liquid causes severe burns of skin and eyes. (USCG, 1999)

INGESTION: have victim drink water or milk; do NOT induce vomiting. EYES: flush with plenty of water for at least 15 min.; call a doctor. SKIN: flush with plenty of water. (USCG, 1999)

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

Wear protective gloves when administering first aid. First rinse with plenty of water for at least 15 minutes, then remove contaminated clothes and rinse again. Refer immediately for medical attention.

Rinse with plenty of water for several minutes (remove contact lenses if easily possible). Refer immediately for medical attention.

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. /Inorganic acids 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 respirations if needed. Administer oxygen by nonrebreather mask at 10 to 15 L/min. Monitor for pulmonary edema 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. Activated charcoal is not effective. 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 ... . Do not attempt to neutralize because of exothermic reaction. Cover skin burns with dry, sterile dressings after decontamination ... . /Inorganic acids 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 as 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 ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Inorganic acids and related compounds/

/SIGNS AND SYMPTOMS/ Lungs may be affected by repeated or prolonged exposure to an aerosol of this substance. Risk of tooth erosion upon repeated or prolonged exposure to an aerosol of this substance. Strong inorganic acid mists containing this substance are carcinogenic to humans.|/SIGNS AND SYMPTOMS/ Inhalation of the substance may cause lung edema ... The symptoms of lung edema often do not become manifest until a few hours have passed and they are aggravated by physical effort. Rest and medical observation is therefore essential. Immediate administration of an appropriate inhalation therapy by a doctor or a person authorized by him/her, should be considered.|/SIGNS AND SYMPTOMS/ Potential symptoms of overexposure are eye, skin, nose and throat irritation; pulmonary edema, bronchitis; emphysema; conjunctivitis; stomatis; dental erosion; tracheobronchitis; skin and eye burns; dermatitis.|/SIGNS AND SYMPTOMS/ Symptomatology (...ingestion or skin contact): 1. Corrosion of mucous membranes of mouth, throat and esophagus, with immediate pain and dysphagia. Necrotic areas ... grayish white but soon acquire a blackish discoloration (yellow in case of nitric acid) and sometimes shrunken or wrinkled texture ... 2. Epigastric pain ... may be assoc with nausea and vomiting ... At times, gastric hemorrhage may be intense, and vomitus then contains fresh blood. Profound thirst. 3. Ulceration of all membranes and tissues with which the acid comes in contact. After the ingestion of concn mineral acid, this corrosion may lead within a few hr or a few days to gastric perforation and peritonitis. 4. Circulatory collapse with clammy skin, weak and rapid pulse, shallow resp, and scanty urine. Circulatory shock is often immediate cause of death. /Acids/|For more Human Toxicity Excerpts (Complete) data for Oleum (9 total), please visit the HSDB record page.

Serious local effects by all routes of exposure. The substance can be absorbed into the body by inhalation of its aerosol.

Cough. Sore throat. Burning sensation. Shortness of breath. Laboured breathing.

Redness. Pain. Blisters. Serious skin burns.

Redness. Pain. Blurred vision. Severe burns.

Grades: Commercial (10% to 70% free sulfur trioxide, depending on supplier); CP /chemically pure: a grade designation signifying a minimum of impurities, but not 100% purity/.|Sulfuric acid (100% H2SO4) containing varying amt of sulfur trioxide in soln. Less concentrated sulfuric acid is sometimes erroneously called "oleum".|Avail grades contain up to about 80% free sulfur trioxide.

Explosives manufacturing|Packaging/Delivery: Oleum grades are supplied by railroad tank car or ship. Marketed in Europe only|Oleum strengths are usually reported as weight percent free SO3 or percent equivalent sulfuric acid ... Oleum is generally thought of as a mixture of sulfuric acid and free sulfur trioxide

Fire Hazards -> Carcinogens, Corrosives, Reactive - 2nd degree