From the archives: Chemists move wall with hydrogen peroxide explosion
Feb22

From the archives: Chemists move wall with hydrogen peroxide explosion

More from my trip into the archives earlier this week. From Nov. 20, 1978: Explosive peroxides SIR: We would like to alert persons to possible hazards involved with the rather common laboratory procedure of dissolving electrophoresis polyacrylamide gels with hydrogen peroxide, in order to measure radioactive species by scintillation counting. Recently a very violent explosion occurred in one of our laboratories which caused complete destruction of a hood and moved a cinder-block wall located 30 feet from the blast. Kick-out panels and glass were blown out of the laboratory and chemicals on shelves in the adjacent laboratory were knocked to the floor. Fortunately the blast occurred when the labs were vacant, or otherwise severe injury or loss of life would certainly have occurred to personnel. The blast apparently occurred due to the formation of explosive peroxides formed from the solubilization of polyacrylamide gels and subsequent counting procedures. The procedure used was basically the following: Polyacrylamide gels (1 cm2) were dissolved with the addition of 0.6 ml of 30% H202, and the resulting solution was added to a scintillation cocktail consisting of a 1:1 mixture of toluene and 2-ethoxyethanol along with scintillation fluors. After the samples were counted for 14C, the contents of all scintillation vials were pooled and concentrated over low heat on a hot plate in the hood. Eventually the radiological safety officer was to dispose of the material. Material had been accumulating in the hood for three to four weeks. Addition of hydrogen peroxide to the polyacrylamide gels could result in the formation of peracids azo- or nitro-compounds. This mixture was then added to the toluene-ethoxyethanol cocktail, and hydrogen peroxide not used in solubilization of the gel could form explosive adducts with the ether. Tests of a commercial cocktail mixture showed that peroxides were present even before the hydrogen peroxide was added. The procedure used for dissolving the gels is used by many laboratories and had been used for three years in our labs without incidence. We recommend that either alternate methods be used to solubilize the gels or that the peroxides be immediately destroyed after scintillation counting. –Dennis W. Darnall, Professor of Chemistry, New Mexico State University, Las Cruces And a response, from May 21, 1979: SIR: This is in response to Prof. D. W. Darnall’s chemical safety letter on “Explosive peroxides” in C&EN, Nov 22, 1978, page 47. It is by no means necessary to invoke the formation of an organic peroxide to understand the explosion described by Darnall. Mixtures containing strong hydrogen peroxide and soluble organic matter have been known to be explosive for many years. See, for example, E. S. Shanley and F....

Read More
From the archives: Chemists lose hands from peroxide explosions
Feb21

From the archives: Chemists lose hands from peroxide explosions

Regarding the inadvertent synthesis of TATP at the University of Bristol, someone commented at “In The Pipeline”: I recall a C&EN story from the early 1980s about a group at K (Kansas or Kentucky?) preparing a batch of 100% H2O2. It exploded during purification and blew off a corner of the building. I vaguely recall a picture of the lab walls completely blown out. I believe they (Kansas? Kentucky?) shut down their chemistry program after that incident before restoring it after a couple of years. I dug into our archives to see if I could find the incident in question. I haven’t been able to find it, but I did dig up some other interesting stories: From July 21, 1952: Chemist Loses Hand in Performic Acid Explosion Five milliliters of performic acid exploded recently at Laval University, Quebec, Canada, tearing off the right hand of a graduate student and smashing all glassware in a radius of 2 to 3 feet. Numerous glass slivers were driven into his skin and into one of his eyes. According to information from the student, A. Weingartshofer-Olmos, and Paul A. Giguere, professor of physical chemistry at Laval, a small receiving flask containing the 5 ml of approximately 90% performic acid was being removed from the still when it detonated for no apparent reason. The acid had been prepared by the addition of 25 grams of 99% hydrogen peroxide to 20 grams of 99% formic acid in the presence of 6.5 grams of concentrated sulfuric acid as catalyst. After two hours for reaching equilibrium, the mixture was distilled under reduced pressure (5 to 10 mm Hg) at 30° to 35° C. This preparation had been performed several times before in the same manner without any mishap. The material was known to be dangerous and adequate precautions were taken. All glassware was thoroughly cleaned in fuming sulfuric acid. The distillation apparatus was entirely assembled through ground glass joints and no lubricant of any sort was used. The still was connected to a dry-ice trap, manometer, and vacuum pump through a length of Tygon tubing. Only 5 to 10 milliliters of the acid was prepared at a time. As nothing unusual had happened while the material was heated for distillation and as the distillate was kept at —10° to — 15° C , the operator felt that the danger period was over. He removed his face shield, pushed aside the two safety screens, and reached for the receiving flask. As he was about to touch the discharge tube to collect a pendant drop, the flask exploded. Like all peroxides and ozonides, performic acid is unstable, since it...

Read More
How a student unintentionally made an explosive at U Bristol
Feb15

How a student unintentionally made an explosive at U Bristol

Last week, the Safety Zone reported that a University of Bristol student had unintentionally made approximately 40 g of triacetone triperoxide (TATP), prompting building evacuations and a controlled detonation by an explosives team. Here’s a statement about the incident, prepared by Timothy C. Gallagher, a chemistry professor and dean of the Faculty of Science, and Nicholas C. Norman, head of the school of chemistry. On 3 February 2017, a graduate student in the School of Chemistry at the University of Bristol was carrying out a literature procedure to oxidise an aldehyde to the carboxylic acid using aqueous acidified chlorite. The experiment was carried out on a 5 mmol scale (just under 1g of aldehyde) and risk assessments identifying all hazards had been undertaken and signed off by both student and supervisor. The reaction solvent was acetone (50 mL). Part of the procedure involved adding a quantity of 30% hydrogen peroxide (H2O2) solution to remove some of the by-products of the reaction, whose presence was (apparently) associated with a yellow colour (possibly including chlorine dioxide). The literature indicated that H2O2 be added until this yellow colour had disappeared, which should have required about 1 mL of peroxide solution. The student, focusing on the yellow colour, which did not completely disappear, continued to add hydrogen peroxide solution until about 50 mL had been added. During workup to remove the solvent, the student realised that the solvent volume was not decreasing and that the liquid was becoming viscous, and so likely contained far more “product” than was expected. GCMS analysis indicated the presence of triacetone triperoxide (TATP), and it was estimated that this could amount to 30-40g if all the excess H2O2 had reacted with the acetone solvent. At that point, the graduate student immediately alerted the supervisor, who escalated this to the Head of School. A series of decisions were made and actions taken that resulted in the disposal of the suspected TATP by means of a controlled explosion carried out by the emergency services. Nobody was injured and no damage was done in the lab. Although the TATP presented an explosion hazard, the risk of explosion was considered minor due to all material remaining in solution; TATP is far more sensitive to detonation as a solid. Immediate disposal was warranted, however, due to the risk of precipitation/crystallisation of a solid material. There are lessons to be learned from what happened and some messages. First, the student was concerned with adding hydrogen peroxide to remove the yellow colour (due, at least in part, to chlorine dioxide, which is itself a hazardous material), but overlooked the much greater hazard of adding a...

Read More
Color-blindness as a lab safety concern?
Feb08

Color-blindness as a lab safety concern?

This week’s C&EN includes a Newscripts column about new eyeglasses for color-blind people that enhance color perception. I was struck by these comments by a materials science graduate student who tried the glasses: “Primary colors seemed more their color,” [Patrick] Stanley reports of his time wearing the glasses. “Labels and boxes caught my attention more—and I guess the point of a hazardous label is to catch my attention.” He also could tell the difference between red and green LEDs and felt more adept at color-matching tasks such as tracing gas lines and reading graphs. “I found myself being quicker in making color assertions,” he says. I’d never considered before whether color-blindness might be a lab safety concern. What do you think? Are there labs in which eyeglasses such as these might be helpful to ensure safety? (Combined with appropriate safety glasses or goggles, of...

Read More
Student unintentionally makes explosive at University of Bristol
Feb07

Student unintentionally makes explosive at University of Bristol

A University of Bristol graduate student inadvertently synthesized approximately 40 g of triacetone triperoxide (TATP) on Friday, prompting building evacuations and a controlled detonation by an explosives team, chemistry professor and Faculty of Science dean Timothy C. Gallagher has confirmed to C&EN. No one was injured in the incident. The TATP was in solution and not isolated as a solid. When the student realized what had happened, the student handled the situation very responsibly, Gallagher says. Further response by the department, university, and emergency personnel “went like clockwork,” Gallagher adds. Gallagher says that he is “absolutely convinced” that the preparation of TATP was unintentional rather than deliberate or with malicious intent. Gallagher and others at the university are working to understand exactly how the student came to make the explosive, especially in such quantity. Once that is done, Gallagher plans to share more details and all lessons learned with the chemistry community. “It’s the right thing to do,” he says. Chemist commentary: Chemjobber, Reddit Local news coverage: Epigram (student newspaper), Bristol Post,...

Read More
Safety correction in JACS
Feb02

Safety correction in JACS

A few weeks ago, “Kenrod” left this comment on my post about the new safety policy for ACS journals: So check out the Experimental in the Supporting Information of this Communication in the very first JACS issue of 2017: J. Am. Chem. Soc., 2017, 139 (1), 19; http://pubs.acs.org/doi/full/10.1021/jacs.6b09889 The first two procedures describe the prepn of trinitroaniline (TNA) and triaminotrinitrobenzene (TATB). Both are known explosives. No hazard warnings whatsoever, not even a peep. The paper was reviewed and published before the new policy went into effect. Nevertheless, I contacted JACS editor Peter Stang to ask him about it–in particular, how he’d like to see these sort of safety hazards addressed in JACS in the future. Stang first noted that he did not handle this particular paper, because it was authored some of his colleagues at the University of Utah. That acknowledged, “Clearly safety is an absolutely critical issue, and it’s also a very complex issue,” he said. He pointed to one source of complexity as quantity, because there may be different safety concerns depending on whether you’re making a few milligrams, a few grams, or several kilograms of a particular compound. Another source of complexity is that toxicity is difficult to determine when a brand new compound is synthesized. “To do toxicity tests on every new compound made is not feasible,” Stang said. However, when there are known safety issues, such as in the above paper, “we will require authors to provide a warning, even if they don’t know the full details or extent of toxicity, explosiveness, or other properties,” Stang said. And to that end, JACS has now issued a correction to the paper that adds this to the materials and experimental methods sections of the supporting information: Warning: 2,4,6-Trinitroaniline (TNA) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) are very sensitive and highly explosive. They should be handled with extreme...

Read More
Civil suit filed against University of Hawaii for lab explosion
Jan25

Civil suit filed against University of Hawaii for lab explosion

From my story in C&EN last week: An injured postdoctoral researcher and her spouse have filed a civil suit against the University of Hawaii (UH) and others involved for a 2016 explosion in which the researcher lost one of her arms. At the time of the incident, postdoc Thea Ekins-Coward was preparing a gas mixture of 55% hydrogen, 38% oxygen, and 7% carbon dioxide to feed to bacteria to produce biofuels, according to a report issued by the University of California Center for Laboratory Safety (UCCLS). The center was hired by UH to investigate the incident. The gases were combined in an ungrounded 49-L steel tank designed for compressed air, not for hazardous gases. UCCLS concluded that a static discharge most likely caused the explosion. Ekins-Coward lost her right lower arm and elbow and suffered corneal abrasions, facial burns, and loss of high frequency hearing from nerve damage to her ears, according to a civil complaint filed with a Hawaii court on Jan. 9. Ekins-Coward worked for the Hawaii Natural Energy Institute. The defendants named in the suit are UH; Jian Yu, the principal investigator of the lab in which Ekins-Coward worked; and Richard E. Rocheleau, director of the institute. From the suit itself: Defendants, and each of them, had a duty to train, warn and provide proper equipment to Thea Ekins-Coward, and to follow all applicable safety codes, standards, and regulations for the laboratory and for the type of experiments being conducted in the laboratory. Defendants, and each of them, negligently, grossly negligently, carelessly and recklessly breached their duty by providing unsafe and improper equipment, by failing to provide adequate training, by failing to follow safety codes, standards and regulations in laboratory safety, by directing THEA EKINS-COWARD to undertake experiments that were inherently and unnecessarily unsafe, by failing to make reasonable inspection of the equipment, and by failing to warn of any inadequacy of the equipment or the possible dangerous condition. These are the specific claims: Personal injury Negligence Gross negligence Failure to warn Dangerous condition of public property Negligent infliction of emotional distress Intentional infliction of emotional distress Loss of consortium The court filing says that “plaintiffs pray that judgment be entered against defendants jointly and severally for reasonable expenses of injury, special and general damages, pre-judgment and postjudgment interest, costs, attorneys’ fees and such other relief as the Court deems just,” but doesn’t give a specific amount of...

Read More
Equipment supplier, engineer fined for death at Texas A&M University at Qatar
Dec27

Equipment supplier, engineer fined for death at Texas A&M University at Qatar

A Qatar court has determined sentences for a supplier of petroleum engineering equipment and one of its employees for a 2014 explosion that killed Texas A&M University in Qatar lab technician Hassan Kamal Hussein, Doha News reports. The court fined the company approximately $5,500 and the employee $2,700. “both guilty parties were ordered to pay [$54,900] to Hussein’s family members in blood money,” the Doha News story says. The company is identified as “Interventions,” which might be Intervention Rentals. Hussein was working with equipment to produce gasoline from natural gas, and a natural gas leak likely led to the explosion. The company and employee were charged with involuntary manslaughter, according to an earlier Doha News story. Hussein was survived by a wife and four children, who were between ages six and 12 when he died, Doha News...

Read More