Category → Accidents
“A batch of the protic ionic liquid pyrrolidinium nitrate exploded while drying it under reduced pressure at 110 °C, using a rotary evaporator with an oil bath.”
While ionic liquids typically have low vapor pressures and high flash points, that doesn’t mean they’re hazard-free, as the documented experience indicates. KU Leuven chemistry professor Koen Binnemans and colleagues were investigating a series of pyrrolidium ionic liquids with different coordinating groups, one of which was nitrate. The researchers report:
After stirring at room temperature for 4 hours, the remaining pyrrolidine, water and nitric acid were removed on a rotary evaporator under reduced pressure (16 mbar) at 70 °C. Heating of the flask on the rotary evaporator was done by means of a hot silicon oil bath. Not all of the water could be distilled off, and the temperature was increased stepwise to 110 °C. Suddenly an explosion occurred. The glass round-bottom flask was scattered and part of the hot silicon oil in the heating bath was blasted by the shock to the walls and ceiling in the neighborhood of the rotary evaporator. At the same time, a cloud of reddish-brown nitrogen dioxide gas was visible. Luckily, nobody was injured and there was only material damage.
The explosion can be attributed to the strong oxidizing properties of concentrated nitric acid under the anhydrous conditions, resulting in a violent oxidative decomposition of the organic compounds. A search of the literature revealed that mixing of nitric acid with secondary amines like pyrrolidine
has been reported to cause violent reactions. Clark described secondary and tertiary amines as hypergolic with nitric acid.
If you need to dry a nitrate-containing protic ionic liquid, they recommend vacuum freeze-drying rather than heating.
This also seems like an opportune time to remind people of what Prudent Practices has to say about nitric acid generally:
Nitric acid is a strong acid, very corrosive, and decomposes to produce nitrogen oxides. The fumes are very irritating, and inhalation may cause pulmonary edema. Nitric acid is also a powerful oxidant and reacts violently, sometimes explosively [with] reducing agents (e.g., organic compounds) with liberation of toxic nitrogen oxides. Contact with organic matter must be avoided. Extreme caution must be taken when cleaning glassware contaminated with organic solvents or material with nitric acid. Toxic fumes of NOx are generated and explosion may occur.
Chemical health and safety news from the past few weeks:
- On Nov. 20, UCLA chemistry professor Patrick Harran had a status check with the judge regarding felony charges of labor code violations that led to the death of researcher Sheharbano (Sheri) Sangji. The result of that status check was another status check scheduled for Jan. 10, 2014. Harran’s preliminary hearing concluded on April 26. We’re going on two years since charges were filed on Dec. 27, 2011, and five years since the Dec. 29, 2008, fire.
- On Nov. 1, former UC Davis chemist David Snyder was arraigned on felony charges of reckless disposal of hazardous waste, possession of a destructive device or explosive, possession of materials with intent to make a destructive device, and possession of firearms on university property. The charges relate to an explosion in his campus apartment nearly one year ago. Snyder’s preliminary hearing concluded on Oct. 10. Snyder is scheduled for a trial-setting conference on March 17, 2014, and a jury trial to start on March 24, 2014.
Tweets of the month from @Free_Radical1:
First synthesis lab of the semester, and 3 students not wearing goggles. Lab uses conc. phosphoric/sulfuric acid. Meh, vision is over-rated.
— Free Radical (@Free_Radical1) November 11, 2013
Idea for post-lab question: do a Google Image Search for “sulfuric acid in eyes”, screen cap the first page of hits, email to TA. #tempting
— Free Radical (@Free_Radical1) November 11, 2013
I think our safety committee would have an issue with 450 undergrads synthesizing TNT: http://t.co/xYphFEXxMh
— Free Radical (@Free_Radical1) November 21, 2013
Came across a J Chem Ed lab where the students used lithium aluminum hydride. Um…yeah. And by “yeah”, I mean “no”.
— Free Radical (@Free_Radical1) November 21, 2013
Other items of interest
- The president-elect of ACS, Diane Grob Schmidt, is currently the chair of the Division of Chemical Health & Safety
- NIOSH released new recommendations for controlling worker exposure to nanomaterials
- BioRAFT will hold a webinar on Proactive EHS Management & Communications on Dec. 12
- Residents near an Allenco Energy oil field in Southern California have been complaining for three years about fumes from the site. At Sen. Barbara Boxer’s request, EPA investigators visited the site in October. “I’ve been to oil and gas production facilities throughout the region, but I’ve never had an experience like that before,” [EPA regional administrator Jared] Bumenfeld said. “We suffered sore throats, coughing and severe headaches that lingered for hours.” No word on what’s happened since.
- Also in California, state regulators are supposed to match hazardous material origin paperwork with what arrives at disposal sites. They don’t. “These so-called lost loads include more than 20,000 tons of lead, a neurotoxin; 520 tons of benzene, a carcinogen; and 355 tons of methyl ethyl ketone, a flammable solvent some in the industry call ‘methyl ethyl death.’” (I’m curious to know what chemists think of that nickname. It’s flammable, yes, but it’s not ranked category 1 for any GHS hazard class.)
- And, er, ALSO in California, a waste mystery: “more than 100 metric tons of the banned pesticide DDT and industrial compounds known as polychlorinated biphenyls, or PCBs, have vanished from one of the country’s most hazardous sites, almost a 90% drop in just five years. Scientists are at a loss to explain the decline across the 17-square-mile site, which sits about 200 feet below the ocean surface and two miles off the Los Angeles County coast.” The chemicals wound up there from industrial waste dumped into sewers.
Fires and explosions
- A Sinopec oil pipeline in China ruptured, then “oil that entered local rain drainage pipes exploded“;
so far reports say that 35 people have died and 166 are injuredMONDAY UPDATE: CNN reported late Friday that 44 people were killed and at least another 135 were injured
- An explosion and fire in a cracking unit at a Chevron refinery in Mississippi killed operator Tonya Graddy
- A massive fire at a Southern Energy facility in Tennessee seems to have started when a methanol tank overflowed and something sparked
- “Accidental ignition” was reportedly the cause of an explosion at Aerojet Rocketdyne in California; one employee is hospitalized
- An employee “moving chemicals” may have caused a spark that led to a fire at Chemical Technology in Michigan; no one was injured but homes, a school, and other businesses were evacuated
Leaks, spills, and other exposures
- A 20,000-gal tank of liquid…something…overpressurized and launched itself through the roof of American Vinyl Company in Florida; one employee died and was found covered in a yellow liquid, while five others were injured
- More than a pound of mercury spilled onto the ground and into a deep well at an Archer Daniels Midland site in Iowa, “when a contractor was pulling a submersible pump from the well and the mercury seal in the pump broke”
- Sulfuric acid leaked from a Solvay plant in California, the cause was a malfunctioning scrubber; 13 people in the area were treated for nose and throat irritation and vomiting
- Chlorine dioxide leaked at Nucor Steel in Arkansas; 18 employees and contractors were treated for exposure
- Two workers at dental implant manufacturer Hiossen in Pennsylvania were pouring nitric acid from one container into another when some sort of reaction occurred; the workers were wearing gloves but no other PPE, and suffered burns to their airways and upper bodies
- Gluteraldehyde spilled at an office building in Texas; the chemical was possibly intended to disinfect health care equipment that cannot be heat sterilized
- Five University of Illinois, Urbana-Champaign, students got to experience safety showers after a plastic waste container ruptured, likley from “nitric acid mixing with a reducing agent to produce a nitrogen oxide gas“; two containers of ammonium hydroxide also broke
- A mixture of ammonia and sulfuric acid spilled at the University of Connecticut; two students were evaluated for exposure
- A Syracuse University student dropped a bottle of ethylenediamine and got an emergency shower and trip to the hospital for evaluation
- A Melbourne University chemical engineering student “was mixing chemicals when a glass container exploded in front of him“; he suffered cuts to his face and arms
Not covered (usually): meth labs; incidents involving floor sealants, cleaning solutions, or pool chemicals; transportation spills; things that happen at recycling centers (dispose of your waste properly, people!); and fires from oil, natural gas, or other fuels
The U.S. Chemical Safety & Hazard Investigation Board last week released its report on a 2009 explosion at a quartz crystal manufacturing plant in Illinois operated by NDK America. CSB determined that a corrosive environment led to cracks in a pressure vessel’s steel walls, resulting in its failure. The blast blew a piece of steel 650 feet to a nearby gas station, where it fatally injured one truck driver.
When they were in operation, the six 50-foot tall crystallization vessels at the plant were loaded with raw mined quartz, 800 gallons of 4% sodium hydroxide in water, a “small amount” of lithium nitrate, and seed crystals of pure quartz, the CSB report says. Once sealed, they were heated to 370 °C and pressurized to 29,000 psig for 100 to 150 days.
The vessels’ steel walls were eight inches thick. Sodium hydroxide and silica will react with iron in steel to produce a layer of sodium iron silicate, or acmite. ADK believed that the acmite layer would prevent corrosion of the steel, but neither the company nor the state ever inspected the vessels’ interiors. In 2007, one of the vessels leaked through a connection in its lid. A consultant hired by NDK determined that the leak was caused by stress corrosion cracking and found cracks in three other lids. The company continued to operate the remaining vessels without inspections, the CSB report says.
For more detail and for CSB’s recommendations to the American Society of Mechanical Engineers, the National Board of Boiler & Pressure Vessel Inspectors, the Office of the Illinois State Fire Marshal, and NDK, see CSB’s report. The agency also produced its usual excellent summary video:
The preliminary hearing for former University of California, Davis chemist David Snyder concluded on Oct. 4. Yolo County Superior Court Judge David Reed determined that there was enough evidence to send Snyder to trial on 17 felony counts of reckless disposal of hazardous waste, possession of a destructive device or explosive, possession of materials with intent to make a destructive device, and possession of firearms on university property. The charges stem from a January explosion in Snyder’s campus apartment.
The preliminary hearing began on July 30 and was supposed to continue on Sept. 6 but was postponed to Oct. 4. In the first part of the hearing, deputy district attorney Martha Holzapfel called eight witnesses, the last of whom was Jason Winger, a West Sacramento police sergeant and member of the Yolo County bomb squad. Holzapfel completed direct questioning of Winger on July 30, and the hearing resumed on Oct. 4 with cross-examination by defense attorney Linda Parisi.
In cross-examining Winger, Parisi generally focused on amounts of materials, whether they were in forms that could be effectively used as explosives, and how authorities had tested them. For example, she asked about a vial that had tested positive for triacetone triperoxide (TATP) by a portable Raman spectrometer. Winger testified that the vial was about 1.75 inches tall and 0.75 to 1 inch in diameter, and that it probably contained about 10 to 14 g of material.
She also asked whether potassium perchlorate found in Snyder’s apartment was finely ground. Winger testified that it was more granular, and that reponders find it in both granular and finely ground forms in clandestine labs. Winger said that a finer powder would make for a more effective explosive.
Parisi next asked about a portable Raman device used for field testing and how it was calibrated. Winger said that he didn’t know about the calibration since it wasn’t his agency’s device. Parisi also asked about one Raman unit that authorities were trying to use to test a device in Snyder’s bedroom when the device exploded. Parisi asked whether that Raman unit was subsequently used to test other things in the apartment. Winger said that it was. The Raman unit has a glass shield to protect it from damage, and while the shield was damaged and removed, the technician operating the unit ran diagnostics that indicated the spectrometer was functioning all right after the explosion.
Parisi also asked whether the Raman unit used a single wavelength and whether it used “UV spectroscopy” (these appear to be the instrument specifications, although the instrument used may be an older model). She also asked if the investigators used gas chromatography or gas chromatography-mass spectrometry, and whether the forensic lab tested for materials other than what came up positive. Winger said that he didn’t know the details of what the forensic lab does.
Parisi next asked how investigators avoided cross-contamination. Winger said that in the field, items were spread out on tarps. The primary purpose of separating materials was to avoid having them react with each other, but it also serves to prevent cross-contamination. Also, the Raman unit can test the materials in clear containers without opening them, which also limits contamination.
Parisi asked Winger about whether he’d investigated other clandestine labs that involved chemists with Ph.D. degrees. Winger said he hadn’t. She asked whether Winger thought that more training would decrease the danger of a clandestine lab. Winger said that in his opinion, more training wouldn’t improve safety, because more training and experience could increase someone’s comfort level such that they’d be less cautious and not take safety precautions.
Among the items found in Snyder’s apartment was a solution of explosive propellant called double base smokeless powder (DBSP), as well as ingredients to make it. On redirect questioning, Holzapfer asked whether it was safe to make DBSP in Snyder’s apartment. Winger said no. As for whether Snyder could have safely stored the material, Winger said that while the state does not require specialized storage, it can’t be present on a university campus. Holzapfer also asked whether there was any safe way to make explosives in Snyder’s apartment. Winger said no.
Cross-examining Winger again, Parisi explored the safety question further. Winger said it is not safe to manufacture explosives or other illegal substances in an apartment. Parisi asked if that was true even given a very small amount. Winger responded that it depends on the circumstances, but even half to one ounce of a high explosive could inflict significant damage. He pointed out that Snyder himself was injured.
That concluded Winger’s testimony.
Parisi asked the judge to dismiss counts 7-10, those for possession of materials with intent to make a destructive device. Parisi said that while tests indicated that Snyder possessed items that could produce an explosion, there was no evidence he planned to mix them or create a destructive device.
Holzapfer argued in return that Snyder had mixed ammonium nitrate prills with aluminum, showing his intent to make a destructive device. He also made nitroglycerin and put it into a device, the one in Snyder’s bedroom that exploded when investigators tried to test it.
Parisi also asked the judge to combine counts 1-4 on reckless disposal of hazardous waste into one count, saying that although hazardous material had been deposited at four locations, there was no evidence that Snyder directed alleged accomplice Tashari El-Sheikh to do so or that Snyder had knowledge of the separate placements.
Holzapfer said that when you ask a second person to dispose of items, it’s a natural conclusion that they might place them in separate locations. Additionally, Snyder asked El-Sheikh to move a particular item from one place to another, Holzapfer said. Holzapfer also noted that there were multiple dumpsters involved at the four locations, and that there was significant risk to the community in both transporting the items to the locations and in leaving them in the dumpsters.
Parisi also argued that the firearms charges, counts 11-17, should be combined into one.
Holzapfer responded that the chargers are for each of the guns that investigators found in Snyder’s apartment.
Judge Reed then took a 10-minute recess to look at the exhibits and review his notes. When he returned, he said there was sufficient evidence to support the charges, such that there is a strong suspicion that the violations occurred and that Snyder committed the offenses. Reed did not change any of the charges. Reed set a “meet and confer” appointment with the attorneys for Oct. 25 and scheduled Snyder to be arraigned on Nov. 1.
A few weeks back, we had a letter to the editor in C&EN that took us to task for using “blast” and “explosion” to describe two industrial incidents. We have more in this week’s issue (which, I might add, is a particularly awesome one in celebration of C&EN’s 90th anniversary). The consensus? The rupture of a nitrogen line is a mechanical explosion, and C&EN used the words appropriately. Here’s what our readers said:
Regarding Richard Rosera’s letter “Choosing the Right Words,” explosion is the correct term (C&EN, Aug. 5, page 4). The definition of the word explosion is the rapid expansion of a gas.
To quote Rosera, the case at hand was “caused by the rupture of a nitrogen line or vessel by overpressure.”
Hood River, Ore.
Recalling my years dealing with hazard evaluation led me to question Rosera’s letter. An explosion is defined as the rapid increase in volume and release of energy in an extreme manner. Or, as Frank T. Bodurtha explains in his book “Industrial Explosion Prevention and Protection,” “an explosion is the result, not the cause, of a rapid expansion of gases. It may occur from physical or mechanical change.”
Thus, the rupture of a nitrogen line or vessel does indeed result in an explosion, as does the rupture of an overfilled tire.
Robert G. Robinson
As a chemistry educator and professional pyrotechnician, I answer myriad questions regarding explosions. If the term explosion is used to refer to “the rupture of a nitrogen line or vessel by overpressure,” it is more specifically a mechanical explosion, but it’s an explosion nonetheless.
The criticism leveled by Rosera is unwarranted. Both the mainstream press and C&EN are correct in addressing the CF Industries accident as an explosion. Although physical failure of materials containment may be due to either chemical or mechanical reasons, the result is still an explosion.
At the time of the original news story, the cause of the explosion at a Williams C. ethylene plant in Geismar, La., was unknown. A July 31 story in the New Orleans Times-Picayune indicates that it was still unknown by that time. I can’t find anything more recent, but the U.S. Chemical Safety & Hazard Investigation Board is investigating it, so we’ll have an answer eventually. The incident killed two workers.
By Michael Torrice
A Los Angeles County Superior Court judge today denied three defense motions that could have dismissed a criminal case against University of California, Los Angeles, chemistry professor Patrick Harran. With the rulings going against the defense, the case moves closer to trial. The judge set the next court date for Oct. 3. Harran could go to trial within 60 days of that date.
Harran faces four felony charges of violating the state labor code. The charges stem from the death of research assistant Sheharbano (Sheri) Sangji after a 2008 fire in Harran’s lab. In November and December, 2012, Judge Lisa B. Lench heard testimony in a preliminary hearing on the case. She ruled in April that there was sufficient evidence to send the case to trial. After the preliminary hearing, the case was sent to Judge George G. Lomeli for trial.
Before today’s hearing, Harran’s attorneys submitted three motions: one asking the judge for a so-called Franks hearing, another called a demurrer, and a third to dismiss the charges based on lack of probable cause. The district attorney’s office replied to each motion, and the defense then responded in writing to those replies.
In court today, the judge started by asking the defense and prosecution to go to chambers to discuss the Franks hearing motion. The hearing is often used to throw out warrants, such as search or arrest warrants, on the grounds that the police or district attorney obtained the warrant using false statements. In this case, the defense argued that Harran deserved such a hearing in part because David Higuera, a senior investigator for the Los Angeles County District Attorney’s Office, allegedly omitted key information from his affidavit for an arrest warrant for Harran.
A Los Angeles County judge today scheduled a hearing for Aug. 26 in the case against University of California, Los Angeles, chemistry professor Patrick Harran. The chemist faces four felony charges of violating the state labor code. The charges stem from the death of research assistant Sheharbano (Sheri) Sangji after a 2008 fire in Harran’s lab.
At the August hearing, the judge will consider arguments on motions that Harran’s attorneys will file before the hearing. In court today, Harran’s attorney, Thomas P. O’Brien, explained that one motion he plans to file is a demurrer motion to dismiss the charges.
O’Brien also said that he plans to ask for a hearing regarding the validity of the original arrest warrant for Harran. Harran’s defense team filed a similar request in July, 2012, that questioned the credibility of a California Division of Occupational Safety & Health investigator who wrote a key report. The defense withdrew that motion when a judge decided to arraign Harran.
I’ll save a full round-up for tomorrow, but I wanted to point to two fatal accidents last week in Louisiana that C&EN is following:
- Explosion at 8:30 AM on Thursday, June 13, in Geismar, La., at an olefins plant that produces ethylene and propylene
- Two people died: Zachary Green, 29, and Scott Thrower, 47; more than 75 others were injured
- The root cause is still being investigated, but the fire was reportedly fed by propylene and propane; pipe corrosion resulted in a propylene leak in December, 2012
- “The investigation will also have to take into account that the facility had racked up 12 straight quarters (three years) of noncompliance with federal Clean Air Act regulations and hadn’t been inspected by OSHA, the Occupational Safety and Health Administration, in a decade.”
- Despite the environmental compliance failings, the Louisiana Department of Environmental Quality had approved a $400 million plant expansion project that would increase ethylene capacity by 50%
- The Chemical Safety Board is investigating
- New Orleans Times-Picayune coverage, company information
- Incident occurred at 6:00 PM on Friday, June 14, in Donaldsonville, La., at an ammonia plant
- One person died: Ronald “Rocky” Morris Jr., 34; seven others were injured
- “The incident involved the rupture of a nitrogen distribution header during the off-loading of nitrogen. There was no fire or chemical release”; the section of the plant involved was shut down for maintenance
- “A worker who didn’t want to give his name said other workers were trying to replace a valve, and the pressure blew. Whoever was standing within a 15 to 20 foot radius, the concussion of that will hurt you really bad.’”
- The complex is the largest nitrogen fertilizer production facility in North America
- OSHA fined the ocmpany $150,000 in 2000 for a blast that killed three and injured eight additional workers
- Company information