Zirconium chloride (ZrCl4)

233.04

319.684814

233-058-2

2503

DTXSID1044142

Lustrous monoclinic crystals|White monoclinic crystals; hygroscopic

2827399000

0

2.75800

White powder

2.803 g/cm³ @ Temp: 15 °C

436 °C

331 °C

Reacts with water.soluble in alcohol, ether, hydrochloric acid.

Store below +30°C.

1 mm Hg ( 190 °C)

Oral-Rat LD50: 1688 mg/kg; Oral-Mouse LD50: 489 mg/kg

In case of H, the pore-forming agent is combustible; in case of cyanide, it emits toxic hydrogen cyanide gas; when heated, it produces toxic chloride and zirconium-containing fumes

Instantly hydrolyzed in water to zirconium oxide dichloride octahydrate|Tetrahedral symmetry in gas phase with a Zr-Cl distance of 2.33 angstoms; Lewis acid. Extremely hygroscopic, forms HCL vapor and gives off fumes in moist iar. Sublimes at 331 °C. MP 437 °C under its own pressure which is about 25 atm at this temperature.|Enthalpy of formation at 298.15 K: -980.5 kJ/mol (crystal); molar heat capacity at 298.15 K: 119.8 J/mol K (crystal)|Enthalpy of fusion: 29 kJ/mol at 437 °C (triple point)|Critical volume: 319 cu cm/mol

Reacts vigorously with water forming hydrochloric acid with the evolution of heat.

Acids, Strong Non-oxidizing

Water-Reactive

ZIRCONIUM TETRACHLORIDE is corrosive to metals in the presence of moisture and to tissue. Behavior in Fire: Will not burn - sublimes above 626°F (331°C). May give off HCl fumes (USCG, 1999). It is incompatible with alcohols (ethanol), lithium metal, and tetrahydrofuran.

Not flammable (USCG, 1999)

Ignites spontaneously in air.

Corrosive

Critical temperature: 778 K (505 °C); critical pressure: 5.77 MPa (4.33X10+4 mm Hg)

III

8

UN 2503 8/PG 3

3

14-22-34-35

26-36/37/39-45-8

ZH7175000

C

The warehouse is ventilated and dried at low temperature; stored separately from oxidants, cyanides, H pore-forming agents and alkalis.

Forms hydrochloric acid vapor and gives off fumes in moist air.

P280-P305 + P351 + P338-P310

H290-H314

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.|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.|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.

Incompatible materials: Acids, alcohols, amines. Reacts violently with water.|/Zirconium tetrachloride/ reacts vigorously with water forming hydrogen chloride (irritating vapor) ans zirconium oxychloride.|Reacts with water producing heat, hydrogen chloride, dense white clouds.|Ethanol, or water: Interaction with either is violent.|For more Hazardous Reactivities and Incompatibilities (Complete) data for ZIRCONIUM TETRACHLORIDE (6 total), please visit the HSDB record page.

Behavior in Fire: Will not burn - sublimes above 626°F (331°C). May give off HCl fumes. (USCG, 1999)|Corrosives, Reactive - 2nd degree

|Danger|H290 (59.15%): May be corrosive to metals [Warning Corrosive to Metals]|P234, P260, P261, P264, P270, P271, P272, P280, P285, P301+P312, P301+P330+P331, P302+P352, P303+P361+P353, P304+P312, P304+P340, P304+P341, P305+P351+P338, P310, P312, P321, P322, P330, P333+P313, P342+P311, P363, P390, P404, P405, and P501|Aggregated GHS information provided by 71 companies from 9 notifications to the ECHA C&L Inventory. Each notification may be associated with multiple companies.|H290: May be corrosive to metals [Warning Corrosive to Metals]|P234, P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P390, P404, P405, and P501|Warning|H302: Harmful if swallowed [Warning Acute toxicity, oral]|P264, P270, P273, P280, P301+P312, P302+P352, P305+P351+P338, P321, P330, P332+P313, P337+P313, P362, 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: Increase, in the downwind direction, as necessary, the isolation distance shown above. FIRE: If tank, rail car or tank truck is involved in a fire, ISOLATE for 800 meters (1/2 mile) in all directions; also, consider initial evacuation for 800 meters (1/2 mile) in all directions. (ERG, 2016)

Excerpt from ERG Guide 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)

Helmet, self-contained breathing apparatus, rubber boots, gloves, bands around legs, arms and waist. Facemask as well as covering rest of head. (USCG, 1999)|Eye/face protection: Face shield and safety glasses. Use equipment for eye protection tested and approved under appropriate government standards such as NIOSH (US) or EN 166(EU).|Skin protection: Handle with gloves.|Body Protection: Complete suit protecting against chemicals. Flame retardant protective clothing. The type of protective equipment must be selected according to the concentration and amount of the dangerous substance at the specific workplace.|Respiratory protection: Where risk assessment shows air-purifying respirators are appropriate use a full-face particle respirator type N100 (US) or type P3 (EN 143) respirator cartridges as a backup to engineering controls. If the respirator is the sole means of protection, use a full-face supplied air respirator. Use respirators and components tested and approved under appropriate government standards such as NIOSH (US) or CEN (EU).|For more Personal Protective Equipment (PPE) (Complete) data for ZIRCONIUM TETRACHLORIDE (13 total), please visit the HSDB record page.

Not combustible but if involved in a fire decomposes to produce hydrogen chloride fumes of zirconium, and zirconium oxides.

Suitable extinguishing media: Dry powder.|Advice for firefighters: Wear self contained breathing apparatus for fire fighting if necessary.|Dry chemical, "alcohol resistant" foam, or carbon dioxide preferred. Water may cause violent reaction.|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.

Poisonous gas produced on contact with water. Wear chemical protective suit with self contained breathing apparatus. Do not use water on adjacent fires. Extinguish adjacent fires with carbon dioxide or dry chemical.

Accidental release measures: Personal precautions, protective equipment and emergency procedures: Wear respiratory protection. Avoid dust formation. Avoid breathing vapors, mist or gas. Ensure adequate ventilation. Evacuate personnel to safe areas. Avoid breathing dust.; Environmental precautions: Do not let product enter drains.; Methods and materials for containment and cleaning up: Pick up and arrange disposal without creating dust. Sweep up and shovel. Do not flush with water. Keep in suitable, closed containers for disposal.|Environmental considerations: land spill: Dig a pit, pond, lagoon, holding area to contain liquid or solid material. ... Cover solids with a plastic sheet to prevent dissolving in rain or fire fighting water. /SRP: If time permits, pits, ponds, lagoons, soak holes, or holding areas should be sealed with an impermeable flexible membrane liner./|Environmental considerations: water spill: Neutralize with agricultural lime (CaO), crushed limestone (CaCO3), or sodium bicarbonate (NaHCO3). ... Use mechanical dredges or lifts to remove immobilized masses of pollutants and precipitates.|1. Ventilate area of spill. 2. Collect spilled material in the most convenient and safe manner and deposit in sealed containers for reclamation... . /Zirconium compound (as Zr)/

Precautions for safe handling: Avoid formation of dust and aerosols. Further processing of solid materials may result in the formation of combustible dusts. The potential for combustible dust formation should be taken into consideration before additional processing occurs. Provide appropriate exhaust ventilation at places where dust is formed.|Appropriate engineering controls: Handle in accordance with good industrial hygiene and safety practice. Wash hands before breaks and at the end of workday.|Gloves must be inspected prior to use. Use proper glove removal technique (without touching glove's outer surface) to avoid skin contact with this product. Dispose of contaminated gloves after use in accordance with applicable laws and good laboratory practices. Wash and dry hands.|SRP: The scientific literature for the use of contact lenses by industrial workers is inconsistent. The benefits or detrimental effects of wearing contact lenses depend not only upon the substance, but also on factors including the form of the substance, characteristics and duration of the exposure, the uses of other eye protection equipment, and the hygiene of the lenses. However, there may be individual substances whose irritating or corrosive properties are such that the wearing of contact lenses would be harmful to the eye. In those specific cases, contact lenses should not be worn. In any event, the usual eye protection equipment should be worn even when contact lenses are in place.|For more Preventive Measures (Complete) data for ZIRCONIUM TETRACHLORIDE (7 total), please visit the HSDB record page.

/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.|/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 that 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.|/GUIDE 137 SUBSTANCES - WATER-REACTIVE - CORROSIVE/ Public Safety: CALL Emergency Response Telephone Number on Shipping Paper first. If Shipping Paper not available or no answer, refer to appropriate telephone number listed on the inside back cover. 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 137 SUBSTANCES - WATER-REACTIVE - CORROSIVE/ 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 ZIRCONIUM TETRACHLORIDE (8 total), please visit the HSDB record page.

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

A corrosive irritant to skin, eyes, and mucous membranes.|Irritating to skin, eyes, and respiratory system.

Permissible Exposure Limit: Table Z-1 8-hr Time Weighted Avg: 5 mg/cu m. /Zirconium compounds (as Zr)/|Vacated 1989 OSHA PEL TWA 5 mg/cu m; STEL 10 mg/cu m is still enforced in some states. /Zirconium compounds (as Zr)/

| 3 - Materials that, under emergency conditions, can cause serious or permanent injury.| 0 - Materials that will not burn under typical fire conditions, including intrinsically noncombustible materials such as concrete, stone, and sand.| 2 - Materials that readily undergo violent chemical changes at elevated temperatures and pressures.|W - No water: Materials that react violently or explosively with water.

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 5000 lb or 2270 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).

moderately toxic

IDENTIFICATION AND USE: Zirconim tetrachloride forms white monoclinic crystals. It is used to form zirconium nitride coatings, to react electrochemically to form zirconia in high-temperature fuel cells, to react with alcohols to form alkoxides, and to produce zirconium organometallic compounds. Zirconium tetrachloride is reduced by molten alkali and alkaline earth metals, yielding zirconium metal. HUMAN EXPOSURE AND TOXICITY: Exposure to zirconium tetrachloride may cause corrosive injury. Common early features of corrosive ingestion include immediate pain in the mouth, pharynx and abdomen, intense thirst, vomiting, hematemesis and diarrhea. Gastric and esophageal perforation and chemical peritonitis may also occur. Late features include antral or pyloric stenosis, jejunal stricture formation, achlorhydria, protein-losing gastroenteropathy and gastric carcinoma. Pulmonary edema has been reported after exposure to zirconium tetrachloride and may be delayed for up to 36 hours. Allergic reactions have been reported in dental patients with crowns or bridges that contain zirconium tetrachloride resulting in eosinophilic gastritis that resolved when artificial dentition was replaced. ANIMAL STUDIES: Inhalation of ZrCl4 mist at an airborne concentration of 6 mg of Zr/cu m was perceptibly toxic after a 2-month exposure, as shown by slight decreases in hemoglobin and erythrocyte count in dogs. There was some increase in mortality over that of controls. Salmonella typhimurium TA 98, TA 100, TA 102, TA 1537, TA 2637 were negative. When tested in combination with 9-aminoacridine, the mutation rate was higher than that for 9-aminoacridine alone (zirconium tetrachloride). ECOTOXICITY STUDIES: The inactivation of phosphorus by zirconium tetrachloride reduced phytoplankton production in the experimental side, as a possible approach to eutrophication control, in a eutrophic farm pond study.

LD50 Rat oral 1688 mg/kg|LD50 Mouse oral 489 mg/kg

/FIELD STUDIES/ The inactivation of /phosphorus/ (P) by zirconium tetrachloride, as a possible approach to eutrophication control, was studied in a eutrophic farm pond divided into experimental and control sides. Dramatic differences in phytoplankton production between the 2 sides occurred during the 1st summer. An intensive bloom of Anabaena circinalis developed in the control, along with elevated total P. Phytoplankton peaks were over 6 times higher in the control. Benthic macroinvertebrates were not affected. Reduced phytoplankton production in the experimental side seemed to be caused by inhibition of P cycling from the sediments. An absence of pronounced differences in the 2nd year was caused by leakage of Zr from the experimental side into the control.|/OTHER TERRESTRIAL SPECIES/ ... In this study, ...the effects of different TiO2 and Zr materials on the soil oligochaete Enchytraeus crypticus /were investigated/, using exposure via soil, via water, and via soil-water extracts, and studied the effects combined with UV radiation. The results showed that ZrO2 (bulk and nano) were not toxic, while zirconium tetrachloride (ZrCl4) reduced the enchytraeids reproduction in soil (EC50=502 mg/kg). ...

According to the 2012 TSCA Inventory Update Reporting data, 2 reporting facilities estimate the number of persons reasonably likely to be exposed during the manufacturing, processing, or use of zirconium tetrachloride in the United States may be as low as 50 workers and as high as 99 workers; the data may be greatly underestimated due to confidential business information (CBI) or unknown values(1).

Deposition and retention of zirconium in lung and pulmonary lymph nodes following inhalation of zirconium oxide dust are typical of that of insol substance; however, deposition of sol zirconyl chloride in lung following inhalation of zirconium tetrachloride mist was equally great and showed similar distribution in othertissues....|Tracer studies of oral absorption of zirconium tetrachloride with the stable chloride as carrier, show less than 0.001% of dose passed from GI tract to blood stream.

INHALATION: Irritating to upper respiratory tract; presumably caused by liberated HCl. EYES: Irritating. SKIN: Irritating. INGESTION: Burning pain in the mouth and throat, vomiting, watery or bloody diarrhea, retching, collapse, and convulsions. (USCG, 1999)

Call a physician. INHALATION: Remove from exposure. EYES: Flush with water. SKIN: Wash with soap and plenty of water. INGESTION: Dilute with water or milk. Give milk of magnesia. (USCG, 1999)

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 the 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. /Poisons A and B/|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 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 ... . Anticipate seizures and treat if necessary ... . For eye contamination, flush eyes immediately with water. Irrigate each eye continuously with 0.9% saline (NS) during transport ... . Do not use emetics. For ingestion, rinse mouth and administer 5 mL/kg up to 200 mL of water for dilution if the patient can swallow, has a strong gag reflex, and does not drool ... . Cover skin burns with dry sterile dressings after decontamination ... . /Poisons A and B/|Advanced treatment: Consider orotracheal or nasotracheal intubation for airway control in the patient who is unconscious, has severe pulmonary edema, or is in severe respiratory distress. Positive-pressure ventilation techniques with a bag valve mask device may be beneficial. Consider drug therapy for pulmonary edema ... . Consider administering a beta agonist such as albuterol for severe bronchospasm ... . Monitor cardiac rhythm and treat arrhythmias as necessary ... . Start IV administration of D5W TKO /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. Watch for signs of fluid overload ... . Treat seizures with diazepam (Valium) or lorazepam (Ativan) ... . Use proparacaine hydrochloride to assist eye irrigation ... . /Poisons A and B/|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/|For more Antidote and Emergency Treatment (Complete) data for ZIRCONIUM TETRACHLORIDE (6 total), please visit the HSDB record page.

/SIGNS AND SYMPTOMS/ Most zirconium compounds are absorbed poorly from the gastrointestinal tract although some salts such as zirconium tetrachloride may cause corrosive injury. Common early features of corrosive ingestion include immediate pain in the mouth, pharynx and abdomen, intense thirst, vomiting, hematemesis and diarrhea. Gastric and esophageal perforation and chemical peritonitis may also occur. Late features include antral or pyloric stenosis, jejunal stricture formation, achlorhydria, protein-losing gastroenteropathy and gastric carcinoma.|/SIGNS AND SYMPTOMS/ Pulmonary edema has been reported after exposure to zirconium tetrachloride and may be delayed for up to 36 hours.|/CASE REPORTS/ Only a few cases of contact allergic gastritis in patients with nickel allergy have been reported. We report a case of probable contact-allergic gastritis in a 46-year-old woman. Clinical examination revealed lichenoid mucosal lesions of the gums adjacent to bridges and crowns that had been implanted several weeks back. Since implantation, the patient had suffered from gastrointestinal complaints (including stomach pain). Gastroscopy showed eosinophilic gastritis. Patch testing done under the diagnosis of contact allergic stomatitis showed positive reactions to: gold sodium thiosulphate; manganese (II) chloride; nickel (II) sulphate; palladium chloride; vanadium (III) chloride and zirconium (IV) chloride. The crowns and bridge contained gold, palladium and zirconium chloride, hence they were replaced by titan-based dentition. Shortly after replacing the artificial dentition, all gastrointestinal symptoms resolved spontaneously without further treatment. Delayed-type allergy against the components of artificial dentition seemed to be the cause of gastritis.

zirconium chloride

Technical|Available in 99.9% purity grade; crude reactor grade and spectrograde.

All other basic inorganic chemical manufacturing|Zirconium chloride (ZrCl4), (T-4)-: ACTIVE|Naturally occurring zirconium contains five isotopes. Thirty-one other radioactive isotopes and isomers are known to exist.

Method 4500-chloride ion C. Mercuric Nitrate Method for the determinatin of chloride ions in water and wastewater. Chloride can be titrated with mercuric nitrate because of the formation of soluble and slightly dissociated mercuric chloride. In the pH range 2.3 to 2.8 diphenylcarbazone indicates the titration end point by formation of a purple complex with the excess mercuric ions. Chromate, ferric, and sulfite ions interfere when present in excess of 10 mg/l. A synthetic sample containing 241 mg chloride/1 ... in distilled water was analyzed in 10 laboratories, with a relative standard deviation of 3.3% and a relative error of 2.9%. /Chloride/|Method 4500-Chloride ion D. Potentiometric method for the determination of chloride ions in water and wastewater. The method is suitable for colored or turbid samples in which color-indicated end point might be difficult to observe. Chloride is determined by potentiometric titration with silver nitrate solution with a glass and silver-silver chloride electrode sytem. In the absence of interfering substances, the precision and accuracy are estimated to be about 0.12 mg for 5 mg chloride, or 2.5% of the amount present. When pretreatment is required to remove interfering substances, the precision and accuracy are reduced to about 0.25 mg for 5 mg chloride, or 5% of the amount present. /Chloride/

Fire Hazards -> Corrosives, Reactive - 2nd degree