It was announced that a US company will be supplying critical components for Electric Vehicle (EV) batteries to Panasonic. Redwood Materials, Inc., is set to supply EV battery cathode components from its facility in Kansas City. Redwood Materials was founded to close the battery recycle loop by JB Straubel. Straubel was a co-founder and former CTO of Tesla.
A lithium-ion battery doesn’t just rely on lithium. Other substances work together with lithium and the whole composition will vary between manufacturers. The Wikipedia entry for lithium-ion batteries lists the Panasonic cathode material as LiNiCoAlO2. Panasonic works in cooperation with Tesla to supply batteries using Lithium Nickel Cobalt Aluminum Oxide cathode batteries. As alluded to above, Redwood will be supplying cathodes made of recycled battery materials.
The lithium battery electrolyte is almost always contains a lithium salt such as LiPF6, lithium hexafluorophosphate, in a non-aqueous organic carbonate electrolyte like ethylene or propylene carbonate. These two carbonates function as high boiling, polar aprotic dispersants. The substances are cyclic carbonate ester compounds and have a high dielectric constant. The high dielectric constant means that the molecules are polar enough to coordinate Li+ ions to aid in electrolyte mobilization of the Li salt. The electrolyte may also contain a solvent like diethyl carbonate to decrease viscosity and lower the melting point. The PF6 anion is a large, charge diffuse, weakly coordinating anion that helps keep the lithium cation mobilized and loosely bound in the polar aprotic carbonate solution. This anion is inert enough and lends solubility in organic solvents making it useful for many applications. Ammonium salts with PF6 anion are often used as ionic liquids. Weakly coordinating anions are used to allow the corresponding cation to be partially unsolvated and therefore more available for reaction chemistry.
Both in producing power and in recharge, when electrons are being passed around between chemical species and changing oxidation states, it means that chemical changes are occurring. When chemical changes (reactions) are happening, it means that heat is being absorbed or evolved. In the emission of heat, the amount of heat energy per second (power) produced can be large or small. It is critical that the temperature of the battery not exceed the boiling point of the lowest boiling component which may be the carbonate dispersant, as in ethylene carbonate (bp 243 C) or viscosity modifier like diethyl carbonate (bp 126 C). A liquid phase internal to the battery flashing to vapor can overpressure the casing and rupture the battery. A liquid changing into a vapor phase wants to increase its volume by from ~650 to 900 times or beyond. To make matters worse, a chemical reaction generally doubles its rate with every 10 degrees C of temperature rise. Runaway reactions generate runaway heat production.
Lithium batteries have flammable components such as ethylene carbonate (flash point 150 C) and diethyl carbonate (flash point 33 C) that could be discharged and ignited if the battery bursts open, possibly leading to ignition of the surroundings, be it in your pants pocket or in the cargo hold of a passenger aircraft.
From my self-appointed, presumptuous and totally bogus position as temporary apologist for the State of Colorado, I wish to convey our deepest regrets for the reelection of Rep. Lauren Boebert (R-CO) to the US House of Representatives. She very nearly lost. You may be asking yourself how it is that this newly blue state produced such a mouthy, unwholesome pistol-packin’ troll. My answer would be that it is impossible to account for the stupid voting decisions some people make.
So, here we go again. We will be treated to another term of the despicable duo of Reps Marjorie Taylor Green and Lauren Boebert skipping their merry way down the MAGA trail.
This is where I would have liked to paste a funny cartoon. I can’t because they’re all copywritten.
So, what’s the deal with Colorado politics? It used to be pretty darned conservative. That’s easy to answer. There is now a large liberal to centrist urban population. Comparing us to California, though, is fightin’ words. No Coloradoan tolerates such a put-down. And then there is Texas …
And now some geopolitical scribblings. Going west from the Kansas border to the east and across to the western border with Utah, the north/south running Rocky Mountains abruptly jut skyward in the middle of the state, sharply marking the western edge of the Great Plains of the United States. Along this westward direction from Kansas, you’ll drive through the eastern plains and halfway across the state until you encounter the mountains. The eastern plains are sparsely populated and comprised of semi-arid land. There is dryland farming and a good bit of center-pivot irrigation, but it is in no way the richest farmland around.
The rural parts of the state are reliably Republican to a large extent. The several counties making up suburban Denver generally dominate the politics of the state, which is presently Democratic. Colorado Springs, though, could be called the buckle of the state bible belt. It is the center of Christian nationalism around these parts.
Coloradoans generalize regions of the state in terms of the eastern slope and the western slope. This refers to which side of the continental divide you are talking about. There are certain real differences between the two. But, both sides do favor the ridiculous Wal-Mart Broncos. The southern part of the state is largely forgotten about. New Mexico could pull a land grab and invade southern Colorado but no one would notice for at least a week.
Continuing westward from the eastern plains, we encounter the Front Range Urban Corridor where a large fraction of the state’s population is found. This region sits along the eastern slope foothills and reaches from Fort Collins in the north to Pueblo in the south along Interstate 25. The political distribution ranges from centrist/liberal from Denver northward and conservative in Colorado Springs. I just don’t know what the hell happens in Pueblo.
I think it is fair to say that the rural parts of the state, which is most of the state in land area, trends to Republican sentiment. Despite the geographical advantage of land area, most of the population lives in the urban corridor which trends from centrist to more liberal politics.
From about the continental divide westward is the western slope. This part of the state is reliably Republican for the most part. The Republican trend includes the southern part of the state as well. Boebert’s District 3 covers the L-shaped west and south 1/4th of the state. It is approximately half of the land area of the state. Given the conservative nature of the district, it is surprising that her race was so close. But, you know, maybe folks have actually been payin’ attention to her terrible behavior. Will it temper this behavior? Seems doubtful.
Post script.
I am shocked but not surprised by the mass killing at the LGBTQ club in Colorado Springs the other day. Th’ Springs is a hub of prickly white nationalist evangelical Christians whose bizarre eschatology parks them always near the end of times. What a weird way to live.
This article amounts to a plea to analytical chemists, supervisors, and organizations who use perchloric acid to make the effort to understand its reaction chemistry, as an acid or salt, and the peculiarities of the numerous mixtures used in analytical sample digestion. If your organization uses standard methods of digestion via one of the many acid mixtures and temperatures, it behooves your organization to have at least one individual on site who understands a bit more than just the procedure. If there is an incident of some kind involving perchloric acid, be it a spill, splash, or worse, having a grasp of the real hazard presented before you is useful. It is possible to underreact or overreact to any given incident scenario.
I am not an analyst. My interest is to understand reactive chemical hazards and devise means for preventing the transition from hazard to danger. Whether someone uses perchloric acid or not makes no difference to me. I have no investment in perchloric acid. However, I’m greatly interested in users being informed.
Comments on Safety Training
Safety training is commonly executed as a result of company policy where documentation of satisfactory completion is collected and filed. For lab chemists this includes training sessions on chemical storage, fire safety, fire extinguisher training, hazardous waste practices and regulations, storm water regulations, company safety and health SOP training, building evacuation, general lab safety, and perhaps basic first aid.
Often safety training sessions are canned professional video presentations or a corporate home brew of PowerPoint slide shows followed by some Q&A and a quiz. It is what I refer to as infotainment. Attendees may watch a video with dramatized incidents while the voiceover describes what should have happened. This approach is not without merit or some success, but this passive approach may not be of lasting value. Furthermore, it is a very sketchy assumption that such passive training will result in proper decision making in an off-normal circumstance where hazard may transition to danger.
The military has solved this problem long ago by mastering the art of the drill. They realize that if you need people to respond in a particular way rapidly, they have to be trained and drilled. In times of peace, the military has the opportunity to train and drill to maintain operational readiness. This is one way to address the difficult problem of low probability, high consequence scenarios. Industry as a whole, however, may not inclined to offer a lot of free time to dedicate to training. Man-hours in drills subtract from productivity. In my opinion, much of industrial management suffers from a lack of imagination in this matter. Safety training and drills are cost overhead. But, what you lack in training hours may be made up for by effective mentoring.
We live in the age of OSHA regulations. Of importance to the process industry is Process Safety Management or PSM. The mission of OSHA is copied and pasted below.
The Wikipedia link below gives an excellent summary of OSHA regulations relating to the chemical process industry. PSM in 29 CFR §1910.119 titled Process safety management of highly hazardous chemicals, is a regulatory framework covering all aspects of safety management and threshold quantities (Appendix A) of highly hazardous materials. Whether your facility is operating at the PSM scale of operation or not, employers have a duty to assure a safe operating environment for their employees. In my view, PSM regulations frame a safety mindset and diligence that is useful outside of PSM reach. Given that a debilitating injury, fatality, explosion or major fire will bring the unblinking eye of regulators and possible litigation, sensible practices found in 29 CFR §1910.119 that are woven into your chemical safety SOPs are in the direction of goodness. Again, this is my view and should not be construed as legal advice. Your chemical safety plan is your responsibility alone.
Finally, a word to lab managers and supervisors. I cannot point to a ancient stone or a law of nature that commands that leaders be effective instructors and mentors. But I can throw an idea on the table which is that as a senior employee in a supervisory role, you have a moral obligation to your charges to make sure that they practice their art with diligence and in a safe manner. The best way I know of is to train staff thoroughly in lab operations and have high expectations of your staff. Management by wandering around can be very effective in maintaining discipline and keeping tabs on your shop. Besides, you should be walking around and asking questions anyway.
HClO4 – The Meat and Potatoes
There is much to know about the chemistry of perchloric acid digestion beyond it’s renowned acidity and explosive potential. Appreciating the corrosivity and close adherence to standard laboratory techniques are necessary but not always enough. One such circumstance begging for informed action is method development. In researching this topic I was a little surprised to find that many important details are buried in the primary literature. Worse, a few key references are downright difficult to obtain. By important details, I mean whatever information might help define the safe operating window for a given digestion, or, better put, under what circumstances might a digestion procedure transition from hazardous to dangerous.
The major supplier of perchloric acid and perchlorate salts in the USA is GFS Chemicals in Powell, OH. The founder of this company, G. Frederick Smith was, and remains posthumously through his writings, a top authority on the properties of this acid and numerous perchlorate salts as the result of his many decades of research. Laboratory quantities of perchloric acid can be had from GFS and the usual group of research chemical suppliers.
It is easy to find MSDS data and exemplar laboratory safety guides on your browser detailing sensible storage and use policy. Several found in google-space stand out in my opinion as comprehensive perchloric acid safety documents and SOP’s; UC Berkeley; Boston University; MIT; Harvard; British Columbia Code for Mines to name a few. Again, this is my opinion- form your own. If your perchloric acid “policy” is limited to an MSDS document and perhaps a few safety statements found in a procedure, then I would urge someone in your organization to take it upon themselves to dig in a little deeper. Generate SOPs for all aspects of the perchloric acid life cycle in your facility.
There are many accounts of incidents with perchloric acid that should convince even the most refractory skeptic of the potential for a violent release of energy. There is a perchloric acid incident that stands out as an example of the dangers of a chemical ignorance. It happened February 20, 1947, when a large and violent explosion killed 17 people and led the city of Los Angeles to specifically bar the use of perchloric acid (1) through numerous sections of it’s zoning code.
The most common laboratory use of perchloric acid is in the analytical digestion of samples containing a matrix of organic matter, sludge, tissue, biomass or organic chemicals. There are a great many lab procedures to be found by an internet search including Chemical Abstracts (CAS), the AOAC Official Methods of Analysis manual, and ASTM relating to HClO4. Numerous policy and prudent practices documents can be downloaded from well established institutions that outline some very sensible policies regarding the storage, use, and disposal of HClO4. One particularly good source for sample digestion methods across the periodic table is from Inorganic Ventures. Kudos to Dr. Paul Gaines and this company for the quality of their products and their willingness to share their expertise in trace element analysis.
A search of Chemical Abstracts will turn up many research papers giving digestion procedures in the experimental section. However, it is not often made clear how the workers came upon their particular digestion conditions other than from a reference in an earlier procedure. This is because these papers are about the use and not about the chemistry of digestion. Most of the procedure writers will have done their diligence and provide warning about hazards. What may be omitted within papers that use the HClO4 procedure are the boundaries of safe operation and how the reactivity may vary with concentration and temperature.
For greater detail one must look elsewhere and well back into the 20th century. Much useful information on HClO4 and its salts is to be found in papers from the 1930’s thru the 1970’s. Because of their energetic properties, the propellant and explosives folks usually expand on energetic materials including perchlorates, and yes, they go into some great and admirable detail (2). However these sources tend to be thermochemical in nature and perhaps not a lot of immediate help to a bench chemist.
Unlike many other reagents in the laboratory, perchloric acid can have a downside with immediate negative safety consequences. In particular, if one is aiming to develop a digestion procedure for a new type of sample, say, something with a mixed organic/inorganic matrix or certain heteroatoms compounds with nitrogen or sulfur, it behooves the chemist to take a serious interest in rooting out information about the safe operating boundaries of perchloric acid and what kinds of materials may be problematic. A perchloric acid MSDS will inform you of potential safety hazards, hazard classifications, etc., but a well researched and validated procedure can go far towards keeping you out of trouble. I would recommend that at least one person at your organization be more thoroughly educated in the chemistry of perchloric acid digestion, or wet ashing as it is called. Unlike some other strong acids, contact with organics may have immediate explosive consequences. And by explosive I mean violent, deafening, shrapnel-blasting detonations. Hazardous contact can include contact of hot concentrated acid on paper, on sample material, or even contact of perchloric acid vapor on a gloved hand passing through fumes.
There are some particularly comprehensive and broadly informative publications covering perchloric acid chemistry. A more recent work by John Long (3) of GFS is particularly insightful in regard to drawing a line between perchlorate salts and perchloric acid. The 1960 publication Perchlorates: Their properties, manufacture, and uses by J.C. Schumacher (4) contains an informative chapter (Ch 11) on perchloric acid safety. Perhaps the most useful reference is a book available from GFS (5) or Amazon titled Perchloric Acid and Perchlorates, by A.A. Schilt. The 2nd edition in particular contains a great many useful references.
On heating at ambient pressure, aqueous perchloric acid will concentrate by distillation to a constant boiling azeotrope of 72.5 % HClO4 and water. At this composition its number of waters of hydration is slightly greater than two. In the climb from ca 160 °C to a bp of 203 °C at 1 atm, the 72.5 % acid will transition from being “just” a hot super acid to a super acid and a potent oxidizer.
In the gas phase, this acid can decompose via a radical pathway leading to the evolution of Cl2, O2, H2O either abruptly or after an time interval (6). Note that when something quite hot abruptly decomposes to a greater number of moles of gaseous products, there can be plenty of potential for destructive pressure effects.
For the uninitiated, HClO4 is a “super” mineral acid capable of complete dissociation in aqueous concentrations up to about 4 molar (7). The dissociated form in water is H3O+ ClO4-, or oxonium perchlorate. This is normal Brønsted acid behavior in water, but three things set this acid apart from others, even nitric acid: i) due to the extremely weak coordinating ability of the perchlorate anion, the acid proton is extraordinarily mobile and reactive; ii) at room temperature the anhydrous acid will at some point spontaneously explode; and iii) in concentrated aqueous form at elevated temperatures, say > 160 ºC, the acid becomes an increasingly potent oxidizer with temperature.
The perchlorate anion has a central chlorine atom, formally +7, that sits in a tetrahedral array of four O2- anions to make it anionic. On average the negative charge is spread over the surface of the symmetric anion making the negative charge diffuse with the enthalpy of formation unfavorable to close ion pairing. The perchlorate anion is only weakly attracted to a given cation like H3O+ or oligomers and as such, allows the H3O+ (or larger clusters) to reside in a solvent shell unencumbered by tight ion pairing, depending on the nature of the solvent. Perchlorate salts can have very high water solubility and, in the case of magnesium perchlorate, serve as an excellent desiccant. One exception to the high solubility of perchlorates is potassium perchlorate at only 1.5 g per 100 mL H2O at 25 °C.
Perchlorates: A review of their thermal decomposition and combustion, with an appendix on perchloric acid, G.S. Pearson; Rocket Propulsion Establishment; October 1968. http://www.dtic.mil/dtic/tr/fulltext/u2/857556.pdf
In this post I’ll feature a particularly well-done group of videos on precious metals prospecting, milling and smelting. The producer of this content is Jason Gaber at Mount Baker Mining and Metals, MBMM. The website says that Jason is a geophysicist. His company manufactures small-scale industrial grade equipment for the processing of ore. He produces videos that show how things are done in prospecting, mining, and even smelting. His videos give long, lingering views of the milling and smelting processes in operation. I was interested in particular in the process of cupellation, which has always been a bit of a mystery.
Gold ore is dropped into a crusher then pulverized to millimeter-size with a hammer mill. The finely divided ore is then fed onto a shaker table for separation by density with flowing water. The shaker table is a mechanical separation method that allows the isolation of metal fines without chemical processing methods. No cyanide or mercury here. The only waste materials are the pulverized ore tailings.
Editorial comment: To be sure, there is nothing innocent about ore tailings. The large surface area along with the presence of sulfides and water allow air to oxidize the sulfur to strong mineral acid and accelerate the leaching of hazardous metals into streams over the long term. It is very damaging to wildlife and municipalities that draw water from the stream and rivers. Water pollution is a problem all around the American West. Metals are forever.
The smelting videos are interesting for a chemist to watch. Jason uses his knowledge of pyrometallurgy to extract the values and partition impurities away from the target metal. Of course, chemists will recognize this as high temperature inorganic chemistry. Before watching this, I had a poor understanding of the importance of fluxes and slag. Jason quantitatively formulates custom fluxes to fit the problem as he sees it. He uses iron bars for redox processes to change the chemical composition of the melt and give a better partitioning of components.
The goal in smelting is to get a clean separation of the metal value from the ore by partitioning between liquid phases. Lead is often used as a “collector” metal to accumulate reduced metal species as a separate liquid phase on the bottom of the melt. The upper slag phase is a complex mixture of the ore matrix material and contains silicates, aluminates, and a dog’s lunch of other undesirable substances. And. not all metals are miscible or highly soluble in the collector phase, so there is some art in this.
Jason also discusses matte and how to deal with it. Matte is frequently discussed in 19th century works on gold smelting, but this was before atomic theory or sophisticated analytical chemistry. Matte was something to place in a reverberatory furnace and calcine. Sulfides in the matte were converted to oxides and gold residues.
Cupellation is a technique that he uses in the final isolation of gold, silver or PGMs from the collector metal. At the scale of material handling Jason works with, a small cupel and a muffle furnace is all that is necessary for this step. Cupellation for gold isolation was described by Agricola in the 16th century. The lead collector mass selectively oxidizes to the PbO, or litharge, and diffuses into the cupel leaving behind the precious metal. Cupels were formerly made of bone ash or other materials that will not combine with the molten PbO to produce a viscous layer that would prevent seeping of the PbO into the container. This is also how gold was isolated in the old days by the assay office to determine the gold content of ore samples. Today several methods are available to assayers, including x-ray fluorescence.
For your viewing pleasure I have provided a link to a short but interesting video. It shows the disposal of large drums of wartime metallic sodium into a lake in Washington. It has that WWII news reel sound.
“Wartime sodium” in Washington suggests that the Na is from Hanford. Just a guess.
Engineers at the Gas Coalification Institute at Poltroon University in Guapo, AZ, have produced a breakthrough in the coalification of natural gas (CNG). Professor Horst Graben, Director of the GCI, announced a breakthrough in the carbonization of desulfurized natural gas. Graben said that using existing rail infrastructure to transport bulk carbonized natural gas would be more economically feasible than building gas pipelines to remaining coal fired power plants. He went on to say that plants burning this new fuel would not generate water vapor, eliminating a source of corrosion. The conversion from coal to CNG would require minimal modification of equipment.
Graben also disclosed a new process for the capture of CO2 and its direct incorporation into beer and soft drinks. Graben said that CO2-capture breweries and soft drink bottling plants could be built alongside the CNG power plants. The plans call for power plant exhaust to be piped across the fence to the beverage plants for immediate CO2 capture, eliminating the need for storage. Major bottling companies have already expressed interest.
The GCI plans to start up a pilot-scale plant in Confounded, Montana, in the second quarter of 2024. A 100 million metric ton per year plant is currently in the design phase.
It is guaranteed that if you write anything on the internet that is less than high praise for the American 2nd Amendment to the constitution, you will shake the crazy tree and trolls will tumble out all around you. So, here goes.
A dear friend has been piping up on Facebook lately with urgent warnings about many of his ultraconservative beliefs. Today it was a somber warning about the danger of losing the 2nd Amendment. Like many, he truly believes that we are in imminent danger of losing it to some dark and secret government conspiracy. I could offer in the comments that this is highly unlikely, that trying it could lead to a civil war and the demise of our democratic republic. As far as secret conspiracies go, it is worth remembering that three people can keep a secret if two of them are dead.
Commenting would only be ineffective and inflammatory and would result in damaging our lifelong friendship if I crossed swords with him. I don’t want this outcome even though I believe that he has gone off the deep end. I won’t offer criticism to his plainly crazy rantings. Why do I feel the need to comment?
Here is where it all goes nonlinear. To people like my friend, not falling in line with his 2nd Amendment belief is equivalent to giving support for eliminating guns. I have always had a nagging suspicion that there can be such a thing as an unhealthy fascination with weapons and their use. Even though I am not a gun enthusiast, I realize that attempting to remove guns from citizens would be like digging up a badger’s burrow bare handed and trying to yank the angry creature out while avoiding its dangerous gnashing teeth and sharp claws. It would be a fool’s errand and would end in a draw.
My friend’s early fascination with firearms fed his interest in joining the Navy when in his 20’s where he served on a missile frigate. There he learned a valuable trade that would later lead him to a highly technical career in the semiconductor field with much international travel. He chose well and did well. He has a strong moral center based on deeply conservative principles. I’m proud to know him.
While my friend served in the Navy facing actual hostility, I was in college thrashing around studying chemistry. His time was spent honorably defending the country. I spent a year in Air Force ROTC only to realize that I wasn’t military material. He gets to speak about preserving our rights with some authority and I get to speak about organic chemistry, with questionable authority.
In reality, we both get to voice our opinions about our democratic culture but the greater credibility can often go to the military veteran. They put their lives on the line for all of us- a very concrete contribution. My choice of becoming a scientist and contributing to the understanding of the molecular universe is much more abstract and remote. It can be hard for many to see the social benefit of a lifetime of contributing to science. In some ways scholarship is very self-centered and even hedonistic. My contribution seems to have been to help in the safe operation of a chemical plant and to help fellow employees maintain a comfortable living. Seems pretty tame.
It has been my experience that many boys pick up an interest in the martial arts and weapons in middle school. I think there is a legitimate nature or nurture question here but that is for someone else to consider. Middle school is an awkward time of hormones and conflicting behaviors and feelings. The feeling of control over your surroundings with new skills in fighting and weapons is natural and strong. This is an awakening that many boys experience.
After an NRA course in hunter safety as an early teen, I recall walking around a river bottom in the countryside alone with a .22 caliber rifle looking desperately for something to shoot. It was exhilarating. Luckily for the wildlife, no living targets appeared. Just having the gun in my possession made me want to fire it. And therein may be the problem.
It seems to me that the pure exhilaration of handling and shooting a firearm is an irresistible attraction to some people. You know, like sport shooting. There are people who just need to shoot at things. I’ve experienced it. Within the limits of lawful behavior, it’s not wrong to shoot at inorganic things.
The problem arises when people shoot other people as a way to resolve conflict against a background of law and order. The ability to commit violence from a safe distance is a plus with firearms that is lost on no one. Perhaps we should just yield to it and bring back dueling with pistols between consenting parties?
So, here is my conclusion. The US will continue to suffer through individual and mass shootings well into the future. As a society, there will remain a critical mass of people who will oppose any sort of gun control despite the positive counter examples from other countries. Empirical evidence doesn’t matter, only voting does and even that is now in question. The mindless gun violence will subside only when we stop wanting to display our personal power with threats of violence. There must be a large-scale phase change in psychology and some reasonable alterations in the legal environment behind it. Perhaps after a devastating world war Americans, or whoever is left, will decide to lay down their arms and choose non-violence. But I doubt even then it would happen. Violence is a primate thing that is hard wired into our brains.
This is a guest post written by a good friend and colleague who retired as an executive from the specialty chemical industry. He is an author and editor of a popular book on a certain variety of organometallic chemistry. It is an honor for me to post his recollections on this site with his permission.
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The TOXCO Story – Part I
I suppose this story begins during the Cold War. The US had developed a triad of defense capabilities to deter Soviet aggression. We had the Air Force B-52 bombers armed with atomic weapons, the submarine based Trident missiles, and the land based ICBMs–first the liquid fuel Atlas rockets and later the solid fuel Minuteman missiles hidden is silos in North Dakota and elsewhere.
Then came 1989, the destruction of the Berlin Wall, the subsequent collapse of the Soviet Union and, suddenly, the Russians were no longer the dreaded foes whom we once feared. Maybe it was time to “stand down” our hair-trigger defense posture.
Those solid fuel Minuteman rockets were designed to be launched on short notice. Firing them required a significant amount of electricity. This was to come from the electric power grid. But our military, recognizing that this source of power could be compromised in the tense times leading up to a nuclear confrontation, needed a backup. As a result, each missile silo was equipped with a diesel powered electric generator, just in case.
But things could go wrong. The diesel fuel might be contaminated, or sabotaged by Russian saboteurs, or any of a number of other problems. So, in an overabundance of precaution, the military insisted on a “backup to the backup”. And what could be better or more reliable as a source of electricity, than a battery. To be sure, these would have to be BIG batteries, bigger and more powerful than any produced thus far, but they would be certain.
And so, the Defense Department commissioned the production of the world’s largest and most powerful batteries. These were based on lithium-thionyl chloride chemistry[1]. Each primary cell contained sheets of elemental lithium, surrounded by gallons of thionyl chloride, a reactive liquid which on contact with water produces a mixture of sulfuric acid and hydrochloric acid—really nasty stuff. These primary cells were each about the size of a coffin and it took three, ganged together to generate the power needed to initiate a missile launch. The government contracted for thousands of them and Union Carbide supplied them.
Apparently, at some point, there was a fatal incident involving a 10,000 amp Minuteman battery being drained and replaced[2] and this contributed to a decision in the early-mid 1990s to dispose of these hazardous items. The DOD issued a Request for Proposals (RFP) which caught the attention of a group of businessmen and entrepreneurs in southern California.
Operating in Orange County, California, headquartered in Anaheim, near Disneyland, were three affiliated companies. Adams Steel was in the ferrous metal recycling business-old washing machines, refrigerators, scrapped cars. Before you scrap a car, you remove the lead-acid battery and the catalytic converter. The battery, containing lead metal, lead salts and sulfuric acid is a hazardous waste and its disposal is regulated by the EPA. The catalytic converter contains precious metals such as platinum, rhodium and iridium. These two items (batteries and catalytic converters) were handled by Kinsbursky Brothers. Non-ferrous metals (common ones such as copper and aluminum and non-common ones like tantalum and gallium from electronic devices) were processed by Alpert & Alpert. The companies had worked together for a number of years.
Principals at Adams Steel and Kinsbursky decided to form a joint venture to bid on the lithium battery disposal opportunity. They created TOXCO for this purpose. It was headed by Terry Adams (the youngest sibling in the Adams family) and Steve Kinsbursky. And they won the bid. The government would pay TOXCO millions of dollars to dispose of these batteries that the government had paid millions of dollars to manufacture some years earlier. Your tax dollars at work.
So, how do you dispose of a lithium-thionyl chloride cell weighing hundreds of pound and filled with dangerous and explosive ingredients? Well, if you are a mechanical engineer, trained at USC (as Terry Adams was), you take a mechanical engineering approach the problem. You have to neutralize the thionyl chloride and the lithium by reaction with water. And reactions take place more slowly (and more safely) at lower temperatures. So, the answer is to chill the cell in liquid nitrogen down to 77°K, put it in a large container filled with water and chop it apart with big mechanical knives (like you chop an automobile into small pieces for scrap). This actually works. Provided you’re certain that the cells have been fully discharged first. But don’t take the military’s word for it. If you do, there may be an embarrassing incident, as there was in 2000, during the disposal process.[3]
Next question. Where do you do this disposal? The TOXCO team discovered that there was an underused industrial site in Trail, British Columbia, on the Canadian side of the Idaho border. It had been part of the Cominco Smelter operations and was one of the most heavily polluted sites in North America[4]. What better place to site a hazardous battery disposal plant? If something went wrong, who would notice?
And so, TOXCO went into business, disposing of lithium batteries, successfully (except for a few incidents like the one incident alluded to above).
One of the by-products of this process was a stream of aqueous lithium salts. These had value and could be recovered and that put TOXCO into the lithium chemicals business. But that’s part II of this story.
The TOXCO Story – Part II (the Lithchem Story)
This story also begins in the Cold War. Even as the atomic bomb (the uranium and the plutonium fission bomb) was being engineered into reality at Los Alamos in the mid 1940s, plans were being made for the next generation weapon—a fusion bomb.
The first H-bomb, based on the concept of fusing light nuclei, was tested at Eniwetok in the South Pacific in 1953. Improvements in the initial “clunky” design quickly followed. One way to boost the power of the explosion was to surround the core of the bomb with a layer of lithium deuteride, LiD. Lithium is, well, the element lithium, atomic number 3 in the Periodic Chart. And deuterium is the name for “heavy hydrogen”, an atom of hydrogen, atomic number 1, but also containing an uncharged neutron[5]. Provided that the lithium used was of atomic weight 6, the fusion of the lithium(6) and the deuterium(2) would produce two nuclei of helium(4), plus lots of energy.
This would only work if you used lithium-6. Unfortunately, the lithium available to us on this planet in mineral form, deposited around the globe, is a mixture of lithium-6 and lithium-7 (the same element, but with one extra neutron). And God, in His infinite wisdom, chose to endow the earth with mostly lithium-7. Of the naturally occurring deposits of lithium, 93% is lithium-7.
So, if you need to use just Li-6, you have to separate it out from the more abundant, naturally occurring Li-7. And the US government proceeded to do just that. Starting in the 1950s, they processed millions of pounds of lithium containing minerals to extract the less abundant isotope that was required for its military purpose. For every hundred pounds of lithium salt they processed, they got, at most, 6 pounds of lithium-6 salt[6].
And what do you do with the “leftover” 94+ pounds. Well, you can’t just turn it back into the lithium chemicals marketplace. For one thing, it’s “depleted” lithium (missing its naturally occurring share of Li-6.) This would be easily noticed by someone using the lithium for routine chemical purposes. The extent of “depletion”, that is, of extraction of the Li-6 would be measureable, and that information was a secret[7]. Moreover, if the quantity of depleted Li were ever realized, that number could be used to infer the number of LiD containing bombs, and that too was a secret.
So, for more than five decades, for more than half a century, the US government simply stockpiled the “by-product” depleted lithium in a warehouse, in the form of the simple salt, lithium hydroxide monohydrate, LiOH•H2O. Millions of pounds of it. Packaged in poly lined, 55 gallon fiber drums.
In later years, the cardboard drums began to deteriorate. Some of them were damaged during handling and relocation. Sometime in the 1980s the decision was made to repack the inventory in bright yellow steel “overpack” drums.
Now comes the early 1990s. The Cold War is over. Our nuclear secrets, at least those from the 1950s, are far less precious. And the Clinton administration is looking through Fibber McGee’s closet[8] to see what can be disposed of, and maybe generate a revenue stream for the government in the process.
What they discover is 100,000,000 pounds of “depleted” lithium hydroxide monohydrate, with a potential market value approaching $1 per pound. And so, it goes out for bids.
The terms of the sealed bid auction were that the final sale would be split 70-30 between the highest bidder (who would get 70% of the inventory) and the second highest bidder (who would get 30%, but at the high bid price).
This was a perfect set up. At that time there were only two lithium companies operating in the US who could handle this quantity of inventory—Lithium Corporation of America[9] and Foote Mineral Company[10]. And both of them knew that there was no incentive for overbidding since even the loser would get 30% of the supply.
And that’s where Lithchem appeared on the scene. The TOXCO team was already in the “recovered lithium” business. All they had to do was bid one penny more per pound than the other two majors and they would be awarded the lion’s share of the inventory. They incorporated Lithchem for that purpose. I’m told that LCA and Foote each bid the same number, somewhere in the 20+ cents per pound range, and Lithchem bid one cent more. As a result, Lithchem became the proud owner of 70,000,000 pounds of depleted lithium hydroxide monohydrate.
Now what? The principal use of LiOH is in the manufacture of high performance lithium greases, used in heavy industrial applications-heavy trucks, railroads, etc. Much of the market for lithium greases is in the third world and quality is less of a concern than price.
Still, to be sold on the open market, the LiOH from the government stockpile had to meet certain specifications. Some of the yellow drums contained beautiful white crystalline powder. Others contained dead cats and cigarette butts. It was “government quality” inventory.
One condition of the bid was that the winning bidder had to remove the inventory from its location in a government warehouse (in southeast Ohio[11]) within 12 months of the successful bid. I had the occasion to visit that warehouse, before the stock was removed and it was a memorable sight.
If you recall the final scene in the movie “Raiders of the Lost Ark”, the Ark of the Covenant is being stored in a gigantic government warehouse, filled floor to ceiling with identical gray boxes. A warehouse stretching far into the next county. Now replace those gray boxes with yellow overpack drums, stacked 6 or 8 high, stretching far into the next county. That’s what it was like. That’s what 70,000,000 pounds of LiOH hydrate looked like.
[1] The lithium – thionyl chloride primary cell has a high voltage (3.5 V) and a high current density.
[2]Battery Hazards and Accident Prevention, By S.C. Levy, P. Bro
[3] In November 2009 a fire broke out at the Trail BC facility in a storage shed containing lithium batteries slated for disposal. It was their sixth fire in fifteen years. Prior to that, a major fire in 1995 destroyed 40,000 kg of batteries at the facility. Three fires occurred in 2000, including one caused by some lithium batteries. This was during the summer when negotiations were underway between Toxco and Atochem for the acquisition of the Ozark business. http://www.cbc.ca/news/canada/british-columbia/trail-battery-recycling-fire-leaves-questions-1.805780
[5] Elements with the same atomic number but different weights are called isotopes. Heavy hydrogen (with an atomic weight 2) is an isotope of hydrogen (atomic number 1). Another example is carbon-14, useful for radiocarbon dating. It’s a heavier version of the more common version of carbon, C-12.
[6] Actually less than 6 pounds. The extraction process was less than perfectly efficient. The actual yield of Li-6 was a closely guarded national secret.
[7] In depleted lithium (with the Li-6 removed), the relative abundance of lithium-6 can be reduced to as little as 20 percent of its normal value, giving the measured atomic mass ranging from 6.94 Da to 7.00 Da.
Reuters: Tesla announced that they will begin mass producing the Cybertruck, their ugly monstrosity of a pickup, by the end of 2023. Oh joy. Maybe with any luck it will go the way of the Edsel. I condemn the vehicle solely on the basis of styling. It looks like something from a 1970’s low budget made for TV SciFi movie.
DW News: That fetid little pouch mouse leader of North Korea fired more than a dozen missiles across the Northern Limit Line in a single day as well as 100 rounds of artillery shells, rattling the nerves of South Korea and Japan. There is speculation that the scurvy little pustule intends to test another nuclear weapon soon. The guy seems anxious for a fight. One day he’ll get it.
Reuters: I just don’t understand Israeli politics. Netanyahu is close to winning a majority of seats in the Knesset in Israel’s 5th election in 4 years. I thought he was shown to be corrupt and thrown out of power.
Reuters: In the trial of the January 6 incident, the Oath Keepers defendant said “I felt it was like a Bastille time in history,” referring to the raid on the Bastille in Paris that led to the French revolution. I don’t think that these guys understand just what “tyrannical” really means. Thinking of the milquetoast Biden as a tyrannical leader seems, well, stupid.
An organization called the Well Done Foundation is working to cap abandoned and orphaned oil and gas wells spread across the country. The organization will adopt a well and get it plugged. This informative video gives an idea of what the foundation does. Forbes magazine has written an informative article on the subject. It would just be redundant to rattle off what is already on the interwebs so have a look at the Forbes article.
Lamentations on Chemistry 
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