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A grim message from Chairperson Vanessa Allen Sutherland of the US Chemical Safety Board reads-

“The U.S. Chemical Safety Board (CSB) is disappointed to see the President’s budget proposal to eliminate the agency.  The CSB is an independent agency whose sole mission is to investigate accidents in the chemical industry and to make recommendations to prevent future accidents and improve safety.  For over 20 years, the CSB has conducted hundreds of investigations of high consequence chemical incidents, such as the Deepwater Horizon and West Fertilizer disasters.  Our investigations and recommendations have had an enormous effect on improving public safety.   Our recommendations have resulted in banned natural gas blows in Connecticut, an improved fire code in New York City, and increased public safety at oil and gas sites across the State of Mississippi.  The CSB has been able to accomplish all of this with a small and limited budget.  The American public is safer today as a result of the work of the dedicated and professional staff of the CSB.  As this process moves forward, we hope that the important mission of this agency will be preserved. ”     -posted 3/20/17

I want to voice my support generally for this elite group of accident investigators. As a chemical safety professional myself I am disappointed to see the CSB regarded low enough by the President’s budget writers to warrant being in the proposal for elimination. The job of the CSB is to investigate the cause(s) of chemical, petrochemical, or other facilities that handle materials having the potential to produce serious accidents. Having done accident investigations myself, albeit at much reduced scale from a petrochemical refinery, I appreciate what a difficult job this is and the great value of the disseminating findings to the industry.

The value of any given CSB report is the story of how an accident is initiated, how it propagates, and how it may couple with diverse systems. As a crucial part of the report is a detailed dissection of the relevant operational systems and human/machine interfaces and how they may have coupled to the event. It is educational and very useful for the safety community to learn how unfamiliar failure modes initiate and how knock-on effects may steer the accident in directions that are difficult to predict.

Planning for process safety involves input from the fields of chemistry, engineering and operations. Importantly, it requires imagination because planning safe operations is about predicting the future. Shutting down CSB investigations will deprive the engineering and safety community of a valuable resource detailing subtle or non-obvious ways in which complex systems can fail.

Recall the Apollo 1 fire or the Challenger explosion and how inquiry into those events lead to better appreciation of failure modes and the layers of protection that can be put in place to prevent the failure. If this kind of investigation is kept confidential, the advance of safe system design will stagnate.

This post has been updated. Th’ Gaussling, 6/4/16.

If you work with chemicals at the level of chemist in a production environment, chances are at some time in your career you’ll be called upon to help decide when a material is too hazardous to use in manufacture. It can be in regard to raw materials or as the final product. Your organization may have protocols or institutional policies or memories relating to certain classes of substances. Some companies, for instance, will not use diethyl ether in its processes. Others may require hydrocarbon solvents *absolutely* free of BTX. Some companies are so fastidious about worker exposure that the faintest whiff of solvent constitutes a breach. One world class company I know requires R&D chemists to include a process hazard analysis, review, and an inspection for all R&D reactions performed in the hood.  Whatever the company, most have fashioned some kind of boundary as to what is permissible to have on site and what isn’t.

Large chemical companies tend to have large EH&S departments with well established SOP’s and protocols with regard to personal protective equipment (PPE) and the measurement of occupational exposure to substances. Larger companies may have an OSHA attorney on retainer and staff members specializing in regulatory compliance.

One might suppose that smaller chemical companies may not have the depth of hazardous material experience that the larger companies have for many reasons. Smaller companies may have smaller capital equipment and a smaller staff. But smaller companies may have a greater organizational freedom which can lead to a great variety of projects. A great variety of projects often means that a great variety of materials are used on site. As such, a smaller company might very well have considerable expertise in a wide variety of chemical substances and, consequently, a wide variety of hazards.

While a smaller chemical company may have considerable expertise in handling its hazardous materials, it may be lacking in infrastructure for administrative controls and regulatory compliance. A wise CEO watches this aspect as closely as the actual operations.

Whether large or small, eventually a company has to draw the line on what hazards it will bring on site. The chemist has some very sober responsibility in this regard. Through the normal ordeal of process development, the diligent synthesis chemist will find the optimum path from raw material to product. All synthesis consists of the exploitation and management of reactivity. But there is always the “deal with the devil”. In exchange for a useful transformation, properly reactive precursors must be prepared and combined. A mishap with a 1-5 liter reaction on the bench top is messy and possibly an immediate threat to the chemist. But that same reaction in a 50 gallon or 5000 gallon pot can turn into the wrath of God if it runs away. The chemists judgment is the first layer of protection in this regard. All process chemists have to develop judgment with respect to what reagents, solvents, and conditions are feasible. Economics and safety come into play.

A runaway reaction poses several kinds of threats to people, equipment, and the viability of the company. There is the immediate thermokinetic threat stemming from the PV=nRT, meaning that energy can be dumped into PV work leading to the high speed disassembly of your equipment. A prompt release of heat and molecules kicked into the gas phase may or may not be controllable. Especially if the runaway leads to non-condensable gases. A runaway has a mechanical component in addition to the chemical action.

An runaway may cause the reactor contents to be abruptly discharged. Several questions should be answered ahead of time. Where do you want the contents to go and what are you going to do with it once it is there? Catchpots and emergency relief systems are common and resources should be invested there.

A question that the wary chemist must ask is this: What if a cloud of my highly useful though reactive compound gets discharged into the air or onto the ground? Do the benefits of this reagent outweigh the downside costs? Even if a release is not the result of a thermokinetic disaster like a runaway, explosion, or fire, a simple release of some materials may be consequential enough to require the evacuation of a neighborhood. Once your materials have left the site in the form of a cloud or a liquid spill and you make the call to the fire department, you have lost control of the incident. Even if nobody gets hurt or exposed, the ensuing “regulatory compliance explosion” may knock you down.

A chemical process incident can have mechanical consequences, chemical release issues, and the matter of fire. Substances that are pyrophoric have automatic ignition problems that may be surprisingly easy to deal with, especially if they are liquid. Liquid transfer systems can be inerted easily and pyrophoric liquids can be transferred airlessly and safely. Pyrophoric solids are another matter. There  are few generalizations I can make about pyrophoric solids. Inert solids pose enough handling issues without having the added complication of air/water sensitivity. All I can say about pyrophoric solids- waste or finished product- is that you will need solids handling equipment, a big supply of LN2 and procedures for passivating hot filter cakes. Production glove boxes and Aurora filters are particularly useful. Also required is a space on the plant site where you can open up a container and let the contents burn if needed. If air gets into a container of pyrophoric solids, it’ll begin to get hot. That is when you need to have an open spot where it can smolder or ignite harmlessly and not bring the facility down. Crowded industrial parks are a bad place for such material handling.

When designing a chemical handling space, it is important to think about what happens in a fire. Flammable liquids are under the constant influence of gravity and will run to the low point on a floor. The question you must to ask beforehand is this: Where do I want the burning liquid to go? There are good choices and poor choices. Preferably a stream of burning or flammable liquid should run away from evacuation pathways and exits as well as anywhere other hazardous materials or combustibles may be contained. To some extent this is moot because indoor spaces should be covered by a fire suppression system. But outdoor spaces may be problematic in regard to crowding of a tank farm and drums and cylinders.

Burning pools of organic liquids radiate considerable energy per sq ft per sec (power in Watts). The temperature of nearby objects will rise rapidly to the flash point and the ceiling spaces will accumulate smoke and hot gas. Drums and cylinders filled with flammable liquids or gases will eventually overpressure and release their contents adding to the mayhem. The release can be in the form of a BLEVE or a flood of flammable liquid leading to a widespread pool fire.

There are resoures available to quantitate the risks of such releases. The American Institute of Chemical Engineers (AIChE) is well organized and provides much literature on the topic of chemical plant safety. In particular I am thinking of Dow’s Chemical Exposure Index Guide, 1994, 1st Edition, AIChE, ISBN 0-8169-0647-5.  This handbook takes the reader through calculations aimed at estimating the risk and likelihood of chemical releases.

Also available is Dow’s Fire & Explosion Index and Hazard Classification Guide, 1994, Seventh Edition, AIChE, ISBN 978-0-8169-0623-9.  This handbook supports the use of a quantitative risk analysis chart for the use of a risk and hazard index for generating numbers associated with process activities for cost/benefit analysis. It is well worth the addition to your library

Such flammable liquid scenarios can begin many ways.  Forklift and maintenance operations are particularly rich in opportunity for a fire. The physical location of flammable liquid storage must be well thought out. Ideally a warehouse fire should not be allowed to spread to capital equipment locations. This helps to keep workers out of harms way and contains the magnitude of the financial disaster as well.  Since most chemical plants seem to grow organically over time, unfortunate choices are usually made in regard to incident propagation.

One type of propagation incident can be ameliorated through the clever use of architecture. I am aware of one tragic incident where an explosion occurred in a processing space of a facility that had grown over the years by the addition of contiguous manufacturing and warehouse spaces. A rabbit’s warren of interconnected rooms and hallways accumulated over time. At the moment of the reactor explosion, the room and adjacent spaces were badly damaged by the blast overpressure as you’d expect. However, since the building was interconnected the overpressure propagated throughout many other distant spaces and delivered considerable structural damage to the facility. Overhead doors were bent outwards and windows and man doors blown out. Extensive damage may have been avoided by the simple expedient of providing open air walkways to separated buildings rather than enclosed hallways between adjoining areas. Of course, the benefit of this depends on the who, what, where, when, and how, but eliminating pathways for a blast wave is a cheap and easy way to start.

When is a substance just too hazardous? This is fundamentally a business or policy decision. Ultimately, it is the responsibility of the organizational leadership to draw the line on the risks that are deemed acceptable. It is the ethical responsibility of those knowledgeable and experienced with the proposed chemistries to combine information with pragmatics to provide persuasive feedback to the decision makers in charge.

There are plants that routinely manufacture nitroglycerine, phosgene, chlorine, phosphine and HCN. Workers spend their careers in these places.  Most risks can be abated by properly engineered processing and packaging. It really comes down to personal choice. Is that ammonium perchlorate plant that just offered me a job operated safely? These reactive and/or energetic materials all have properties that lead to demand for their use. Somebody is going to supply that demand. We chemists have to look inward and then act with our eyes wide open and our heads on a swivel. Myself? I wouldn’t work in a nitroglycerine factory, but I’m glad that someone does.’

[Added 6/4/16 by Th’ Gaussling] I happened to go back to this post and in doing so read a comment by “Bob”, which you can see in the comment section below. Here is a copy

“I actually believe that as a society should keep the safety rules relaxed a bit in academia. Academia, for better or worse, is our national chemical research institution”

So underpaid grad students, postdocs and staff working at  a univeristy are less human, and less deserving of safety than their for profit brethren?

That’s diabolical Mr. Gaussling. Pure evil incarnate. For whose gain do you sacrifice their lives?

I want to address this now better than I did back then. To Bob I say this: Everyone has a right to a safe workplace. Academic institutions as well as industrial operations must use best practices in regard to worker safety. This is axiomatic. Plainly I did not articulate my contention as well as I could have. I will do so now.

We have to assume that junior chemists are likely grow to be senior chemists in an organization. The role of a senior chemist in industry for example, may be quite varied through her/his career. A senior chemist who has stayed in the technical environment will almost unavoidably have been confronted with a large variety of questions in regard to circumstances and outcomes relating to hazardous materials and tricky reactions. Moreover, a senior chemist is likely to have been promoted to a level that also involves supervision, the drafting of SOPs, work instructions, MSDS documents, emergency planning, laboratory design, etc.

In my view, a senior chemist as described above has an ethical and moral responsibility to coworkers, plant operators, material handlers, and customers to oversee chemical safety. A chemist at any level has a responsibility to make known to all involved what dangerous circumstance might arise with any given chemical operation. Either in relation to the hazardous properties of substances that may be released in mishandling, or in regard to hazardous processing conditions that can lead to danger.

I’ve used the word hazard(ous) and the word danger(ous). We need some clarity on this. If you Google the words and stop with the dictionary definitions you will be left with the shallow notion that they are synonyms. If you dig deeper, say at the website of the Canadian Centre for Occupational Health and Safety (OSH), you will find a definition of “hazard” that I find particularly useful. To wit:

A hazard is any source of potential damage, harm or adverse health effects on something or someone under certain conditions at work. [italics mine]

The same fuzziness in definition exists for the word danger(ous) as well. A definition I prefer is below:

A dangerous occurrence is an unplanned and undesired occurrence (incident) which has the potential to cause injury and which may or may not cause damage to property, equipment or the environment. [italics mine]

This definition is borrowed from the University College Cork, Ireland (UCC). I believe this is a good definition and it readily sits apart from the definition of hazard above.

The key difference is that a hazard is any source of potential of damage … under certain conditions.. whereas danger is a condition brought on by an unplanned or undesired occurrence. Next, lets consider these terms in the context of chemistry.

On the shelf in the fire cabinet is a glass bottle of phosphorus oxychloride, properly sealed and segregated. As the POCl3 sits on the shelf in the cabinet, I would argue that it is only hazardous. If, however, you pick up the bottle and in walking to the fume hood drop it causing it to break and spill the contents in the open, you’ve caused a dangerous situation. It’s an imminent threat to health and safety.

Conversely, let’s say that you carried the bottle to the hood, used it, then returned it to storage without incident. In the reaction the POCl3 is consumed and in the workup the residual acid chloride is quenched by water. Congratulations! You have taken a hazardous material, used it safely, passivated the actives during workup, and eliminated at least the acute hazard relating to POCl3.

In the first situation, a hazardous material was mishandled and became dangerous. In the second situation, the hazardous material was handled properly, consumed, and residuals passivated. In this case a hazardous material was used safely and to positive effect.

Seem trivial? Well, it’s not. This difference in meaning leads to a confusion that is especially acute among the non-chemist population. But my point leads to the question of how students are taught to use hazardous materials.

I spoke of relaxing safety requirements in academia. An example of such a thing might be the use of diethyl ether. This useful solvent is banned outright in some chemical manufacturing operations across the country owing to the flammability. Even in their R&D labs. This is corporate policy handed down by those responsible for risk management, not scientists. In some industrial labs, woe is he who has an unexpected occurrence like a boil-over or a spill.

I believe that Et2O should remain in academic research labs for both the research value and for the development of valuable lab experience by students and postdocs.

You learn to handle hazardous materials by having the opportunity to handle hazardous materials.

Ether is only a simple example of what I’m trying to communicate. In order for chemists to graduate as experienced scientists with working familiarity in the properties of substances, they must have experience handling and using a large variety of substances, many of which may be substantially hazardous. And by hazardous I mean much more than just toxic. A substance may have a reactive hazard aspect that is a large part of it’s utility.  To safely handle substances that pose a reactive hazard, a chemist needs to have experience in using it. And killing it. The chemist must try to gauge the level of reactivity and modify the use of the substance to use it safely. If you’ve made or used a Grignard reagent you know what I mean. Expertise in laboratory chemistry only comes through direct experience.

Hazardous reactive materials do useful things under reasonable conditions. Non-hazardous, unreactive materials find great utility in road and bridge construction.

If we regulate out all of the risk by eliminating hazardous materials in academic chemistry, what kind of scientists and future captains of industry are we producing? What we can do is to put layers of administrative and engineering protection in the space where the hazardous transitions to the dangerous.  Academic laboratory safety is promoted by close supervision by experienced people. Limits on the amount of flammables in a lab space, proper syringe use, safe quenching of reactive residues, proper use of pressurized equipment, and a basic assessment of reactive hazards present in an experiment will go a long way to improving academic lab safety. Experienced people usually have a trail of mistakes and mishaps behind them. If we corporatize the academic research experience to a zero risk condition, we may kill the goose that lays the golden egg.

 

The US Chemical Safety Board has approved and released the final report on the Macondo /Deepwater Horizon  blowout and explosion of 4/20/10 in the Gulf of Mexico. The report is in two volumes and does include an animation of the sequence of events. I have found the CSB animations to be particularly helpful in understanding the key features revealed by their investigations.

The CSB recently released their final report on the ammonium nitrate fire and explosion in West, Texas on 4/17/13. A few months after the release of the final report the ATF announced a reward of up to $50,000 for information leading to the arrest of person or persons responsible for the industrial fire and explosion that killed 15 people.

If the forensic aspects of industrial accidents is of interest to you, I’d recommend having a look at the CSB website. Knowledge of various initiation and propagation modes in past industrial accidents is useful for those of us trying to prevent initiating events on our own sites.

I have spent some time researching basic magnesium chemistry. Not anything synthetic but more safety and thermochemically related. I am not able to give a lot of particulars motivating the study, but I can say that one should consider that nitrogen over activated magnesium may not be as innocent as you think. While lithium is widely known to react with nitrogen gas to form a passivating nitride layer, the reaction of dinitrogen with magnesium is rarely encountered.

Activated magnesium residues from a Grignard or other magnesium metallation reaction may self-heat to incandescence under a nitrogen atmosphere in the right circumstances. Activated residues left isolated on the reactor wall or other features in a nitrogen blanketed reactor during an aqueous quenching procedure may self-heat to incandescence. In the presence of reactive gas-phase components like water vapor in nitrogen, activated metals can self-heat over an induction period of minutes to hours or longer.

Many metals, including magnesium and aluminum, can be rendered kinetically stable to air or humidity by the formation of a protective oxide layer. Once heated to some onset temperature by a low activation reaction, penetration of the protective layer by reactive gas composition can occur, leading to an exothermic reaction.

Performing a “kill reaction” or a quench of a reactive metal at the bench or at scale is always problematic and requires the skill and close attention of the process chemists and operators. I guess what I’d like to pass on is that nitrogen is not an innocent spectator in the presence of finely divided, activated magnesium. Humid nitrogen can support a combustion reaction to produce nitrided magnesium once preheated to an onset temperature.

If you mean to kill any reactive residues, it is important to apply the quenching agent in such a manner that the heat generated can be readily absorbed in the quenching medium itself. A good example of a quenching agent is water. Often a reactive must be killed slowly due to gas generation or some particular. Adding a quenching agent to a solution or slurry by slow feed or titration may be your best bet. If you have another vessel available, a feed to a chilled quenching agent will also work.  Dribs and drabs of water on a neat reactive material will lead to hotspots that may be incendive.

Ran into an interesting recommendation on fighting a lithium fire in Joshi, D.K., et al, Organic Process Research & Development, 2005, 9, 997-1002.

In addition to the usual admonitions on the handling of a reactive metal like Li, they warned that water, sand, carbon dioxide, dry chemical, or halon should not be used. Rather, they suggest dry graphite or lithium chloride instead.  This seems quite reasonable to me, having reacted both silica and CO2 with magnesium powder in chemical demonstrations in a previous life. If Mg will reduce SiO2 and CO2, then hot/burning lithium ought to be reactive as well.

A similar recommendation is given in Furr, A.K. CRC Handbook of Laboratory Safety, 5th Edition, p. 299, ISBN 0-8493-2523-4.

We will soon have a new HEL Phi-TEC Adiabatic Reaction Calorimeter up and running. Hopefully this will help solve some nagging questions I have about the thermal stability of certain compounds. Time to maximum rate (TMR) is a useful parameter and ARC testing helps to find this value.

I have spent  a good deal of time with the Mettler-Toledo RC1 and have found it to be very useful in process development. There is a tendency for chemists to design exothermic reactions to start at low temperature and at perhaps some point raise the temperature to take the reaction to completion. The RC1 will indicate accumulation of energy in a vessel following a charge. By varying the temperature of the reaction mass and modulating the dosing rate it is possible to find a reaction temperature and feed rate that affords a steady state (or manageable, at least) output of power with minimal energy accumulation.

With the reactions I have been studying it has become apparent that sometimes a preference for low temperature (-30 C to 0 C) by the chemist may in fact be based on habit rather than need.

Naturally, the thermal picture is not the entirety of the problem. Product stability in the reaction mass and residence time at temperature play a role in how the process is configured. But a reaction calorimeter can help find threshold temperatures below which the reaction substantially shuts down.

The RC1 measures heat of reaction in Joules and power in Watts. After some time on the instrument one comes to view a reaction mass as a power generator or an absorber. Power is reported in Watts and is indicated by the magnitude of the deflection of the power curve from baseline.  Joules of energy are calculated from the area under the power curve.

The instrument has a calibration routine where it determines the Cp of the vessel contents. If you have the reaction mass, heat of reaction, and Cp, you can calculate the adiabatic temperature rise for a given dose of reactant. This is an extremely useful element in sketching out the safe operating parameter space of a reaction.

Safety is a political concept. Safety has no basis in physics. It is an artifact of anthropology. It is a fuzzy construct defined by a magnitude of “likelihood” and type of consequence individuals and organizations are willing to absorb to obtain a particular outcome.  But when you sit down in a meeting with thermokinetic data and solid interpretation, all of the stakeholders in a plant can brainstorm and home in on a fairly rational and agreed upon process profile. This is politics at its finest- data driven and substantially rational.

It is time that someone questions the use of the phrase “meth lab”. Just as a cook would object to the phrase “meth kitchen”,  those of us who spend our careers in the laboratory should push back on the use of the word “lab” in this manner.  The use of this word confers the notion that a workspace is fitted for chemical handling activity and is operated by someone who knows what they are doing. Dubbing a meth operation as laboratory surrenders too much credit to the operator. These people are moonshiners skulking around on the periphery of society.

A meth lab is not a lab. It is the workshop of a criminal enterprise where unscrupulous people manufacture a dangerous substance. Its sole purpose is to profit from the uncontrollable neurological train wreck of methamphetamine addiction. This is not laboratory work. It’s just crime.

Of late I have been concerned with R&D information and various homebrew means of storing it and retrieving it. Institutionalizing R&D results into easily accessed knowledge can roll into a real hairball if you’re not careful. More on that another time.

My adventures with CHETAH 9.0 have caused me to look deeply into SMILES strings and what utility might be found there. This lead me to rediscover ChemSpider and the many services it provides for free to the user.

Consider the following: if you generate a SMILES structure of acetylsalicylic acid, say, from Chemdraw, O=C(O)C1=C(OC(C)=O)C=CC=C1, and use this character string as a search term in ChemSpider, it will take you to the entry for aspirin. What you get is a treasure trove of information on this substance. Go to ChemSpider, cut and paste the above SMILES string into the search box, and let her rip. I’m not your Momma. Just try it.

The breadth of references is encyclopedic.  But the truly amazing part is found when you scroll to the end of the page. There is a drop down window for SimBioSys LASSO. ChemSpider is working to provide LASSO data on its large database of compounds.  LASSO generates a structure and grinds it through a neural net processor module and produces a score between zero and one. The closer the score is to 1.00, the greater the surface conformity or compatibility of the ligand to a target receptor site.  As you would expect, there is a high score associated with aspirin and the COX-1 receptor. From what I can tell, the software is self-learning in some fashion.

The uses are many. Substances can be screened for drug-like attributes within the 40 receptor types provided.  I would like to hear from someone who might have something to say about the use of LASSO for the estimation of possible toxic effects of substances that have not been biologically tested. I fully realize the hazards of this, but perhaps LASSO scores might help flag particular substances for closer examination by testing.

The matter of medical x-radiation dosing is surfacing again. I wrote a post about this in 2009.

Let’s get to the core of the matter. Physicians need to take charge of this since only they have any real control. It’s a pretty goddamned simple concept. Doc’s who are calling for x-ray’s need to begin recording calculated dosing from this hazardous energy. If it is too troublesome for them, then the x-ray techs should record the information.

CT scanning seems to be problematic. There is no business incentive to hold back on CT use in for-profit settings. I suppose that documentation would only reveal the extent and magnitude of x-ray use. It would be fodder for malpractice law firms.

I can just see the billboards- Have you or a loved one ever gotten a tan from x-rays? If you have, call Dooleysquat, Schwartz and Schmuck for a free consultation. Do it Now!

Here is a link to a US Chemical Safety Board video summarizing several recent lab accidents.  If you have never visited or heard of the CSB, here is a link to their web site. Have a look around.

This link is to the case CSB case Study of the Texas Tech explosion with nickel hydrazine perchlorate. It has a nice illustration of the Swiss Cheese Model of safety. This model was devised by British Psychologist James T. Reason at the University of Manchester in 1990.

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