Category Archives: Chemical Industry

Sanding the Mass Spec

January 19, 2010.  We unpacked our new Agilent GCMS today. It comes with a container of fine alumina abrasive. I’ve never had to maintain one before so this has been an education. It has a triple MSD (mass selective detector) on it for what amounts to a noise cancellation feature. This increases the signal to noise ratio of the output substantially. I never realized that the MSD was off-axis relative to the quadrapole electrodes. The ion beam is steered 90 degrees into the MSD by a 10 kV post that also accelerates the beam.

Oh yes, the abrasive is for polishing the metal surface that sits against the high vacuum seal of the mass analyzer chamber. It struck me as amusing that a mass spec comes with a supply of abrasives. Now it makes sense.

BS, MS, or PhD in Applied Chemical Science

Perhaps one solution to the problem of excess chemistry PhD production by our institutions is to take a step away from the path of pure scholarship into the applied sciences. That is, a chemistry program wherein chemical science is integrated with economics and business.  The goal is to support the industrial part of our civilization with scientifically educated people who desire to apply their knowledge to the industrial arts, i.e., manufacturing, sales, management, and distribution. 

I’m suggesting that chemical education could be split into two streams- scholarship and applied science- because that is where the grads go anyway.  Presently, the scholarly route supplies the entire supply of chemistry graduates.  I think there are several reasons for this. Faculty produce graduates along the manner in which they were schooled. Another reason  for this singular path is the effect of the ACS standardized curriculum.  Most chemistry departments struggle to maintain their ACS certification as a validation stamp for their program .  It also serves as a foil for deans who want to gut the chemistry budget because it is typically very costly.  The ACS program has basic requirements and that is that.

An applied science program would require a modification to the usual faculty profile. Instead of having a faculty of stellar Harvard , MIT, and Stanford graduates, the faculty would have a few from Dow, DuPont, Air Products, etc.

An applied chemical science program could include coursework on the manufacturing processes of petroleum feedstocks from crude oil to BTX, polyolefins, and maybe into some fine chemicals or extractive metallurgy.  It would cover the regulatory environment and give students familiarity with EPA and OSHA regulations as well as those regs governing transportation of hazardous goods. 

At some point there should be coursework in basic accounting, marketing, law, and finance. A business minor would be very useful.  A student should know how to calculate the manufacturing cost of a product based labor & overhead as well as the cost of raw materials.  There are many possibilities here to use real life examples. Y ou never know what will happen to a student once they understand how to get a product to market. The just might want to go do it themselves.

It is not inconceivable that a program along these outlines and with the right faculty could produce graduates who are inclined to do a startup. Once you know something about what is required to get a product out the door, it is natural to begin to dream about doing it yourself. 

American chemistry lacks a culture of strong entrepreneurship among chemists. This is not quite as true for chemical engineers, though. Chemists are afraid to start a company because they have not been exposed to much of the business environment because they are partitioned in the lab. They do not know what the issues are or how to attract resources to get the thing started.

I was on the phone with a professor the other day who has $$ in his eyes. He has a customer who wants x kg of his compound and he thinks that he is going to staff a small production campaign with students in a rental space. He admitted he had no idea of what is required once you have employees doing hazardous activities. He had no idea of what workmans compensation insurance was. 

 His business model was simply a larger version of his research lab. The university would pay his students a stipend and he would have them laboring off campus making some stuff that is too nasty for use on campus.  It is much like gold fever.  Otherwise rational people become greedy and foolish when they think there is a pot of gold at the end of the rainbow.

The over arching goal of an applied science degree program is to produce graduates who have a better understanding of our industrial culture and are prepared to strengthen it by a lifetime of effort in making better things for better living.  The future holds the inevitable confrontation with scarcity. We need a layer of educated industrialists who can help fashion a good life in the US with smarter manufacturing that can accomodate reduced energy and materials consumption.

Words from the Great Gondini

I used to work with a sales consultant who would say smart things now and then. As sales manager, consultants were usually the bane of my existance. Not because they were no good- often they were quite competent- but because they were problematic. Management brought them in because, with its all seeing eye, it believed that we foot soldiers were unable to make certain changes.

So when a consultant arrived we had to bring them up to speed and then watch them slowly fail to make the changes. They nearly always failed. Management was looking for change in the lower eschelons but never considered that change at the top was necessary. Ever. One day we’d hear that so-and-so had moved on to other things.

Working for a corporation is very one-sided unless you are at the very top. Employees are expected to be loyal and hard working no matter how outrageous the working environment and no matter how incompetent the management. Fail to impress management and you’ll face the prospect of job hunting without good references.

But I’ve gotten off track. The Great Gondini (I’ve scrambled the letters in his name) used to say this-

Never work for a company as a chemist if chemistry is not their main activity.

He spent much of his career with IBM and later, Lexmark, involved in magnetic coatings for disk drives, charge transfer agents and other xerography chemicals, and toners. IBM and Lexmark are not chemical companies.

The point my friend was trying to make was that professional isolation within a company has consequences. One consequence is that promotion to upper management is difficult owing to the lack of participation in the management of core projects.  It is understood that there are exceptions.

There are benefits to isolation. You get to be the company wizard. Often management is loath to mess with you because, while they know that you do something important, they aren’t really sure what it is. I experienced this phenomenon when I was a chemist in a dairy lab. It can be quite amusing.

The isolation issue exists even for chemists in chemical companies. Your ascendency to upper level positions is stunted if you have not been involved in the major company projects in a significant way. If you’re running an small lab somewhere in the organization, especially if you’re in a service role, it is hard for management to promote you to VP of Chemistry over that project manager whose successful project went to market on time and on budget.

If you’re not interested in this kind of advancement, then it is a moot point.

Some chemist friends have mentioned to me that I make sweeping generalizations and this is surely true. There are exceptions to all but the most specific statements, eg., x = 3 (wait a minute, doesn’t x = 4 as well !!??).  Generalizing is a rhetorical technique. The view from 50,000 feet is meant to show the overall topography.

Chemists love details and, like a pig in shit, we love to roll around in the data. And for some, no detail is too small to bring the show to a complete halt while they wrestle with details. I’ve seen this many times. This makes it difficult for some chemists to make the transition to other job descriptions. It is a simple fact that we sometimes have to move forward with an incomplete picture.

Who is best served by the chemistry degree pipeline??

Having interviewed numerous bachelors degree job candidates recently, I’m beginning to question some fundamental assumptions about the value of a BA/BS chemistry degree to industry.  Let me say from the outset that I wasn’t interested in hiring an analyst. There are plenty of analysts out there in the market, especially in the temp agencies. I’d been looking for someone to do synthesis. Both organic and inorganic.

Just to be clear, the slot has been filled, so don’t send your resume to me. Sorry.

I had the experience of interviewing a fresh BS chemist from a good- dare I say “elite”- school this week.  He had fulfilled the requirements for graduation and was sitting there at the table beaming at me with great confidence.  This fellow fared poorly on our application chemistry test, but was undeterred.

When asked as to the length and breadth of his organic synthetic experience in school, he admitted that it was limited to that obtained in sophomore organic chemistry.  He did have a trifle of inorganic synthesis experience- he made ferrocene once.  That being said, his interpretation of the NMR spectrum on the test was wrong, his understanding of carbocation stability trends was wrong, and he couldn’t calculate his way out of a paper bag.

This is not so unsual.

So here is what I have observed in the past 6 or 7 years interviewing BS chemists. Precious few of them had any demonstrable interest in organic chemistry or synthesis. It is not because they were lacking ability- they had not had the opportunity to practice the art. They might have been involved in some kind of research in their senior year, but very often it is involved in some highly specialized work with a very narrow scope. OK. That is the nature of research. It’s specialized.  I believe the college chemistry curriculum and the shifting interests of faculty to ultra specialized research are failing students.

I’m glad to hear that students at the local university have experience in operating a tunneling microscope or picosecond  laser equipment. But what about experience in basic synthetic transformations in actual glassware? How about a reduction of an ester or an amide with LAH? What about a catalytic hydrogenation or running a reaction with a Grignard reagent?  Are students limited to the microscale experience? Do chem majors get to handle greater than 100 mg of reagents? Do they learn to handle hazardous materials in a smart way, other than just learning tofear them?

This graduate that I interviewed had experience in some kind of nanoscience, but couldn’t say much at all about basic synthesis. When asked about Grignard reagents, he could not recall having heard of it.  What the hell good did the professor do for this kid?? The kid burned up his senior year doing deep-niche chemistry with skills of questionable transferability. He should have been doing distillations and crystallizations until he could coax pure subtsances out of a mixture that he/she made. That is what an undergrad should be doing.  An undergrad should be refining basic manipulation skills and accumulation experience in running diverse reactions.  Experience is proportional to the number of experiments run.

I have no reason to believe other than undergraduate chemistry education is failing to prepare bachelors students for the practice of the synthetic arts.  It has been my experience- perhaps yours is different- that students with an interest in synthesis go to grad school.  The problem with that is that it immediately doubles the cost of doing synthetic chemistry per unit chemist in society at large.

So, who is best served today in undergraduate education? The students or the institutions? Chemistry departments are faced with rising costs and diminishing funding, especially in public institutions. Faculty do what they know how to do. They promulgate scholarship. That is the comfort zone. And they develop strong opinions about who should join their ranks- people of like mind for the most part.

The pressure to minimize waste streams in undergraduate labs enabled the transition to microscale lab equipment. The development of computer technology has enabled the accumulation and treatment of data by semi-automated data collection tools and spreadsheets. Some of this is good- drudgery for its own sake is dumb. But we are removing students from contact with the very materials they study.  This is not how to accumulate expertise. This is expertise in automation and not automatically in chemistry. 

These graduates move into important roles in industry. Industry, contrary to a popular academic sentiment, isn’t merely a big sack of tedious details. It is a colossal part of our culture. We’re tool users and chemistry is one of the things that tool-using citizens do to improve our lot in life.  The synthetic arts in the USA are somewhat in decline as industry continues to outsource manufacturing and R&D (!!?) to India and China. The USA needs affordable labor to do synthetic chemistry. Continuing to stamp out PhD’s is not the answer. PhD’s are very expensive to have around, and while perhaps they do most of the critical discovery work, the costs are prohibitive. Just look around.

The USA needs a new cultural paradigm. We need a chemistry labor pool that consists of workers of high and medium skill to bring affordable and competitive products to market. Unless we figure this out we are headed for that realm of self-satisfied mediocrity that some of our neighbors across the Atlantic find themselves in. There are many examples of fallen empire around the world and the US is slouching in that direction.

Benchtop ESR Spectrometer, Rare Earths, and Global Politics

A company called Active Spectrum is marketing a benchtop ESR unit called the Micro-ESR that performs electron spin resonance measurements. The site says that the system operates at 3.4 and 9.6 GHz and has sub-micromolar sensitivity.  It’s pretty amazing, really.

I don’t know for a fact but the easy guess is that this ESR instrument and the picoSpin NMR spectrometer are based on some kind of rare earth magnet technology. Both instruments use very small cross section sample space, presumably to accomodate a design scheme to bring magnetic field lines together as closely as possible in the probe giving a useful field strength without a big electromagnet.

A quick patent search fails to turn up patents based on some obvious key words. I’ll have to spend some time looking more intently.

Now that I’ve got you hanging on to the rotating frame, lets tip you over with this.  China’s new policy of restricting rare earth element (REE) export as well as the recent announcement that it would be inposing fairly stiff tariffs means that wonders like these two magnet-based technologies are going to feel a pinch in raw material supply and competition real soon. The aggregate demand picture for REE’s will exceed supply by 2014 or so.  Market purists will nod knowingly and chant their homily on the rational allocation of goods by the market. 

But to what extent is China part of a rational market? China, Inc., really consists of a highly nationalized array of business fronts that are backed to the hilt by the Chinese government by internally favorable regulations on ownership and local sourcing. Don’t forget that Chinese currency is shielded from valuation excursions. 

To a large extent, China is leveraging technology developed in Japan and the west with metal resources highly concentrated within its borders to apply a pincer attack on the market place. China has industrial policy that it is steadfastly acting to strengthen its manufacturing base while the USA has an emphasis on aligning its citizens to be more receptive to consumption.

Wouldn’t it be nice to live in a country that tried harder to make its manufacturing industry more robust rather than the present fascination with finance and the well being of financiers?  Wouldn’t it be nice if westerners transferred a bit less of our magic to countries who will turn it into a stick to beat us over the head with? 

It is going to take a lot more than glib talk about the free market to deal with China and the growing influence of nationalized companies around the world.

New NMR on the Market: Non-Superconducting FT System.

Check out the picoSpin website. This company is coming out with a 45 MHz permanent magnet NMR in 1Q2011 that produces FID’s so the user may collect FT spectra.  The instrument is somewhat larger than a toaster and is sensitive enough for many undergraduate and industrial applications. The customer must provide the computer and data workup software.

The other company out there offering non-superconducting FT systems is Anasazi Instruments. They have been refurbishing the fleet of 60 & 90 MHz CW systems sitting in storage rooms throughout academia into FT instruments.

I am jazzed. I think we might get one. OK. It is low field and low sensitivity. But that is often enough.  For an in-process check very often you’re just looking for one or two diagnostic peaks to collapse or grow to indicate reaction progress. This instrument could fit the bill.

I think many people will agree that the big supercon systems on the market, while well endowed with capability, often provide wildly more capacity than is actually used. A sort of creeping featurism.  This instrument is utterly utilitarian in conception and priced at $20,000.

I think this is a welcome addition to the selection of NMR instruments for the chemical field and I wish them well in their endeavors.

On Thermokinetic Safety

So I’ve been working out a process for the last few days. Among other things the compound is a ketal and it’s synthesis is pretty simple. Ketone and diol brew in a pot of refluxing hydrocarbon and through the magic of equilibration, the water and hydrocarbon vapors condense and phase separate in a Dean-Stark apparatus. The water phase drops to the bottom of a graduated collector and the progress of the reaction is monitored by watching the water volume accumulate. 

This reaction is straight forward enough that I can easily make up the procedure myself. So I calculated a favorite weight percentage for concentration and pitched in the reagents. I chose a few of my favorite acid catalysts as well for a series of trial runs. Everybody knows that these reactions run faster with an acid catalyst. Such mechanisms are used to torment sophomore organic students everywhere.

After satisfactory completion with a few catalysts, I decided to round out my table of data with a run without catalyst. What better way to show the critical nature of the catalyst than to run a blank?

As luck would have it, the reaction ran splendidly without added catalyst. In fact, there was precious little increase in yield over the test interval with added catalyst.  Even better, without the catalyst the color of the reaction mixture was lighter (the substrate is a little sensitive).

So I took the carbonyl reagent and shook it up with some water and plunged a pH probe into it. What I had assumed to be a neutral organic material was quite acidic on contact with water. Hmmm.

A dive into the literature (patents, actually) revealed that the history of the compound most likely involves exposure to HCl from a continuous acid hydrolysis and steam distillation. And the Aldrich bottle did say that ca 1 % water is present. A fact that I neglected in my haste to set up the reaction.

The upshot is that I didn’t anticipate that there was residual acid catalyst in the reagent itself.

This is good to know from the scale-up perspective. An acid catalyst probably won’t be needed and loading procedures and sourcing do not have to be done to use a separate catalyst.  

Now the trick is to determine if it is safe to combine all of the reagents in the reactor or if one needs to be fed in as the reaction proceeds. A run where all of the reagents are in the pot from the start is called a batch run.  A run where one or more reagents are fed into the vessel over the course of the reaction is called a semi-batch run.  The reaction rate is greatest if all of the reagents are present from the start, but it does represent an accumulation of energy in a low phi-factor vessel that could be a runaway hazard. I’ll have to noodle through this issue if this reaction gets scaled up.

Taking into account the phi factor, or the thermal inertia of the system, is one of the crucial details in scale-up. Eventually, you have to make a decision on whether to configure the run as a batch or a semi-batch process. The precautionary principle usually leads to semi-batch unless you can prove that a batch configuration is safe.

Running a process at reflux with a heated jacket relies on the overhead condenser to be the primary thermal safety device. This usually is very effective in knocking down condensable components in the gas phase. A good condenser has a huge effect on the heat balance of a reactor system.

Knocking down condensable components helps to regulate the pressure and temperature of the pot. The transition from liquid to gas phase carries heat away from the reaction mass quite effectively under ordinary conditions.

However, it is possible for a reaction to accelerate to a point where the condenser capacity is inadequate. At such a point the jacket may be filled with heating fluid and a switchover to chiller fluid may take a relatively long time. 

A reactor can behave as an adiabatic system if you pick a time interval that is short enough. So, a reaction mass that exotherms rapidly enough may find itself in an approximately adiabatic containment. In this condition, the reaction mass can accelerate with gusto as pressure and temperature ramp skyward, multiplying the reaction rate. Decomposition reactions kick in and non-condensable gases are evolved that further pressure the system. Hopefully, the rupture disk and vent were properly sized because there is going to be an administrative mess to clean up afterwards.

This scenario is one to be avoided. Reaction calorimetry and ARC testing give results that help tremendously with engineering around a runaway scenario. A parameter of particular interest in the adiabatic Time to Maximum Rate (TMRad).  TMR is extracted from the slope of a linear portion of an Antoine curve determined by ARC. A formula for the line can be substituted with a desired time and a temperature can be calculated.

A particularly useful value to come from this is the temperature affording a 24 hour TMR. Many companies will determine the 24 hr TMR and set a policy to operate at a set temperature margin below the 24 hr TMR temp:  a 60 C margin is not uncommon.

Agricola Christmas

I indulged in the purchase of a book I’ve had my eye on for a while. It is the English translation of De Re Metallica by Georgius Agricola, translated by Herbert Hoover and wife Lou Henry Hoover. This book (or collection of books) was published ca 1550. The English translation came out in 1912, written  by a young mining engineer from Iowa who would eventually become a US president. De Re Metallica is available in newly printed paperback form.

One issue that had stymied previous translators was the fact that Agricola wrote in Latin, a language that had been effectively dead for a thousand years, and Agricola needed vocabulary for situations that were not anticipated while the language was alive. So he invented vocabulary. Somehow the Hoovers were able to noodle  through this.  The translation is heavily footnoted.

Agricola was the first western scholar to document the mining arts as well as considerable geology and mineralogy. While I have not gotten too far with the book, it is apparent that mining technology in the European middle ages was fairly sophisticated by way of the mechanical contrivances used in the operations. Explosives would have been welcome then, but that was not to be for a long time.

They had milling machines, hoists, and sluices. They also performed cupellation, smelting, and calcining. Agricola discusses ore bodies, surveying, milling, property rights, and a host of other practical issues relating to oeprating a mine.

The book was published by a rare book publisher who performs print on demand (POD). There are a number of publishers who do this. Typically the copyright has fallen into the public domain.

Will Academics Ever Teach Industrial Chemistry?

I’ve spent some of my time cheerleading for the profession of chemistry and offering some insights into non-academic career paths that are perhaps less well known.  I’ve tried to offer a positive view on the field, despite the name of the blog, and advance some arguments for why a practitioner of chemistry should be optimistic about the future.

There are some practical difficulties with chemistry as a lifelong field of endeavor relating to the matter of career growth and limitations therein.

Imagine that you are a brightly feathered bird with a very strict diet. Let’s say that you are an exotic bird who feeds on the fruit of a rare tree that grows only on the south facing bank along the headwaters of a minor tributary of a tributary of the Amazon river.  This is the condition many if not most PhD scientists find themselves in.  A company has to limit the number of PhD’s in the organization because they are expensive and can be a little particular about what they do. They are the generators of company technology and IP. It’s hard for a CEO who has come up the ranks through sales and marketing to win an argument with a scientist on matters of technology. That is why you have VP’s of Technology.

Scientists are problem solvers. Some scientists are well suited to industrial activity with a knack for rapid solution of applied science problems. Their work has a beginning, a middle, and an end. Others are, well, eggheads. Some PhD’s couldn’t close the loop on a project if both ends were tied with red yarn to their wrists. They are more interested in the elegance and texture of the system than the punctilious adherence to schedules and timelines.  There is a place for eggheads in industry as well.

I love the science of chemistry. It wraps around the peculiar topography of my consciousness nicely. It satisfies my need to understand the fine material mechanisms of the universe. I crave the next insight into the nuances and subtleties of the material world.  And I’m referring to the fraction of the universe that we can observe- Bright Matter. Dark matter leaves me cold and unmoved. I just don’t care about it at this point.

Realistically, to be in chemistry you need to be in an organization. A chemist without an organization is like a diplomat without a country. The act of obtaining raw materials, processing, and disposing of waste is a tangled mass of regulatory webbing requiring D&B numbers, permits, and money- lots of money. A chemist requires a place to work. At least experimentalists do.

But these issues still do not get to the heart of the question of alternatives to the laboratory. At the heart of the matter, is the question of the dreaded glass ceiling. Chemists have some omissions in their professional education that limit their access to the rarified hights of of industry. I’ve written about this before.

A BA/BS degree in chemistry is a course in science, not industry. The bachelors degree in chemistry is very much oriented to the Three Pillars of Chemistry- Theory, Synthesis, and Analysis. Graduate studies in chemistry are the same.  Chemistry graduates are versed in chemical problem solving because that is what the ACS curriculum demands and what the faculty are able to produce. This is perfectly reasonable.

However, the commercial practice of the chemical arts and sciences requires much more than what the ACS curriculum provides. Industrial chemistry requires managment of material and human resources. It requires the ability to lay out a timeline for multiple, parallel activities and meet deadlines. It requires knowledge of generally accepted business practices in the form of sales, accounting, shipping & receiving.

What are the duties that academia might have to the world outside the cloister? Is the role of academia limited to the continuation and purity of the profession or does it have any obligation to the pragmatics of the outside world? Faculty are always glad (or relieved?) to see their graduates find careers.

Go to the website of any chemistry department and look at the research interests of the faculty. Aside from the faculty who are not research active any longer, it is easy to see in every listing a snapshot of what was considered hot research at the time of hire. Research is a lifelong activity and we all have to pick a specialty to hope to retain some kind of comprehensive expertise.

What you will never (?!) see in a listing of chemistry faculty interests are topics related to industrial issues. Chemistry faculty hires are often chosen for their connection to what are considered cutting edge research topics of the time.  The rationale is that this kind of hiring brings vitality and modernity to the department. It’s perfectly reasonable as long as the hireling can teach the core classes as well. Chemistry faculty hires in the area of industrial science don’t seem to happen. Whether it is because of ignorance of industry or that industrial chemistry is seen as derivative and therefore not cutting edge science I do not know.

How to help students going into industry? Take some business coursework. A minor in business is an easy place to start.

Intro to business
Accounting
Finance
Management
Business Law

What about more industrially related chemistry topics, say, for grad students?   Well, that only works if their advisors are of like mind.  I do not see that happening in my lifetime.

Geology has a subdiscipline called economic geology. It is concerned with the discovery and analysis of economically viable ore bodies as well as the extractive processes involved in the recovery of value.

Perhaps chemistry needs a subdiscipline in the area of operations management. Process economics and engineering are certainly covered in the Chemical Engineering course of study. Why have we partitioned chemists away from this? Again, it is the academic culture that is the driver. If they do not conceive of curricula and hire industrial faculty members, then the thing never begins.

Economic chemistry (Chemeconomics)- covers the economics of chemical manufacturing and the global chemicals market.  It is a subdivision of industrial engineering.

There are some books out there that attempt to address aspects of this. One on my bookshelf is by Derek Walker, The Management of Chemical Process Development in the Pharmaceutical Industry. While Walker’s book does not delve into economics, it does try to bridge the gap from lab to business issues.

The Illuminating History of Rare Earth Element Technology

Until the invention of the electric lamp, the illumination of living and working space was very much the result of sunlight or of combustion.  Since the development of fire making skills in prehistoric times, the combustion of plant matter, fossil fuels, or animal fat was the only source of lighting available to those who wanted to illuminate the dark spaces in their lives.

From ancient times people had to rely on flames to throw heat and an agreeable yellowish light over reasonable distances. A good deal of technology evolved here and there to optimally capture the heat of combustion to do useful work (stoves, furnaces, and boilers) from readily available fuels.

Lighting technology also evolved to maximally produce illumination from flame.  High energy density fuels that offered a measure of convenience for lamp users evolved as well. Liquid fuels like vegetable oils, various nut oils, whale oil and kerosene could flow to the site of combustion and were in some measure controllable for variable output. The simple wick is just such a “conveyance and metering device” for the control of a lamp flame. Liquid fuels flow along the length of a wick by capillary action to a combustion zone whose size was variable by simple manipulation of the exposed wick surface area.

The first reported claim of the destructive distillation of coal was in 1726 by Dr Stephen Hales in England. Hales records that a substantial quantity of “air” was obtained from the distillation of Newcastle coal. It is possible that condensable components were generated, but Hales did not make arrangements to collect them.  Sixty years earlier an account of a coal mine fire from flammable coal gases (firedamp) highlighted the dangerous association of coal with volatiles. So, flammable “air’ was associated with coal for some time.

By 1826 a few chemists and engineers were examining the use of combustible gases for illumination. The historical record reveals two types of flammable gas that were derived from coal- coal gas and water-gas. Both gases came from the heating of coal, but under different conditions. Coal gas was the result of high temperature treatment of coal in reducing conditions. It is a form of destructive distillation where available volatiles are released.  Depending on the temperature, there was the possibility of pyrolytic cracking of heavies to lights as well.

Water-gas was the result of the contact of steam with red hot coal or coke. The water dissociates into H2 and CO. Water gas is a mixture of hydrogen and carbon monoxide, both of which are combustible. The formation of water-gas is reported to have been discovered by Felice Fontana in 1780.

One of the properties of burning coal gas or water-gas was the notably meager output of light from the flame. Workers like Michael Faraday and others noted that these new coal derived gases provided feeble illumination, but if other carbonaceous materials could be entrained, then a brighter flame could result. It was during the course of investigations on illumination with carburized water-gas that Faraday discovered bicarburet of hydrogen, or benzene.

About this time, an engineer named Donovan also noted that if other carbonaceous materials were to be entrained into water-gas, then the light output was enhanced. So, in 1830, engineer Donovan installed a “carburetted” water-gas lighting system for a short run in Dublin.

Coal gas was first exploited for lighting by the Scottish engineer William Murdoch.  Murdoch began his experiments in 1792 while working for Watt and Boulton in England. By the late 1790’s, Murdoch was commercially producing coal gas lighting systems. His home was the first to be lit with coal gas.

The carburization of water gas eventually became an established industry in America in the second half of the 19th century. The treatment of gases, especially with the discovery of natural gas in Ohio, increased the commercial viability of lighting with gas. Carburization of water gas was aided by the discovery of hydrocarbon cracking to afford light components that could be used for this purpose.

Here is where the subject of this post comes in. Since thorium is frequently associated with rare earth elements (REE)  the connection of REE’s to the issue of illumination begins in the laboratories of Berzelius in about 1825. Berzelius had observed that when thoria and zirconia were heated in non-luminous flames, the metal oxides glowed intensely.  But this was not a new phenomenon. Substances like lime, magnesia, alumina, and zinc oxide were known to produce a similar effect. Goldsworthy Gurney had developed the mechanism of the Limelight a few years before. In the limelight, a hydrogen-oxygen flame played on a piece of lime (calcium oxide) to produce a brilliant white glow.  This effect was soon developed by Drummond to produce a working lamp for surveying.

The work of Berzelius was an important step in the development of enhanced flame illumination. He had extended the range of known incandescent oxides to include those that would eventually form the basis of the incandescent mantle industry.  Thoria (mp 3300 C) and zirconia (mp 2715 C) are refractory metal oxides that retain mechanical integrity at very high temperature. This is a key attribute for commercial feasibility.

Numerous forms of incandescent illumination enhancements were tried in the middle 19th century. Platinum wire had the property of glowing intensely in non-luminous flames. But platinum was not robust enough for extended use and was quite rare and consequently very expensive. By 1885, a PhD chemist named Carl Auer von Welsbach patented an incandescent mantle which was to take the gas light industry to a new level of performance. Welsbach studied under professor Robert Bunsen at the University of Heidelberg.

Welsbach fashioned the incandescent mantle into the form that is familiar to anyone today who has used a Coleman lantern. The original mantle was comprised of a small cellulose nitrate bag that had been impregnated with magnesium oxide, lanthanum oxide, and yttrium oxide in the ratio of 60:20:20.  The mantle gave off a greenish light and was not very popular.

By 1890, Welsbach produced an improved incandescent mantle containing thoria and ceria in a ratio of 99:1. This mantle emitted a much whiter light and was very successful. Many combinations of zirconia, thoria, and REE metal oxides were tried owing to their refractory nature, but the combination of thoria-ceria at the ratio of 99:1 was enduring.

Welsbach made another contribution to the commercialization of REEs. Welsbach had experimented with mischmetal and was interested in its pyrophoric nature. He had determined that a mixture of mischmetal and iron, called ferrocerium, when struck or pulled across a rough surface, afforded sparks. In 1903 Welsbach patented what we now call the flint.  In 1907 he founded Treibacher Chemische Werke GesmbH. Today Treibacher is one of the leading REE suppliers in the world.

See the earlier post on REE’s.

REE’s in Greenland.

REE Bubble?

REE’s in Defense.

REE’s at Duke.