Category Archives: CounterCurrent

It’s Mardi Gras Baby

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As usual, I’m the only person at work wearing Mardi Gras beads today.  The day is bitter sweet. Some of the worst, the most savage, thrashing, hurling hangovers I’ve ever had have been in New Orleans.  My memories are filled with the sights and smells of Bourbon Street and the rowdy throngs standing in the street begging for revelers on the balconies to throw some beads or flash the crowd.

Last year in a blues bar a waitress wearing a Daisy Duke outfit and carring a rack of test tubes came up to me and said … something. Obviously I had “Chump” written all over me. I couldn’t understand what she said because the band was so loud, so through the beer fog I just nodded. Next thing I knew she took my money and grabbed my head and plunged it towards the test tubes planted in various locations in her outfit. I grabbed the tubes with my mouth and tipped back the sweet, flammable contents. There was more, but I won’t elaborate on it further.

After less than a minute, I had consumed unknown alcoholic liquids from dubious test tubes and walked away $30 lighter. I left the bar dazed and confused at what happened, feeling incredibly stupid for having been duped like a common tourista. Oh! The shame and degradation, sort of.

Brain Draino

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The Obama administration famously put restructions on executive pay, capping at US$500k for institutions receiving TARP money. Naturally, there has been some shameless howling from the Masters of the Universe. Who? You know, the geniuses who were instrumental in birthing this finance mess.

There has been some wagging of tongues and tut tutting in regard to the problems of living on $500k per year on the upper East Side of Manhattan. Mathematically, this may in fact be true.  But I would offer that this is the market supplying pushback towards equilibrium. If the swanky life in Manhattan is not feasible on the meager sum of $500k, then the banks need to relocate. Banks should consider the kind of lifestyle an executive could have in Manhattan, Kansas, or Little Rock on $500k. Or York, NE. We got yer swank right here!

I love this description of financiers by David Gillen at the NYT-

Banking executives and recruiters say talented financiers — the driven, hyper-numerate, slightly ruthless ones with a preternatural knack for making money in bull markets and bear — are always in high demand. NY Times, Feb 21, 2009.

It sounds to me like the finance industry needs a therapeutic brain drain or a cerebral colonic.

Transformative Research in Many Ways

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A friend who is presently on sabbatical has started a blog about his academic experiences in primarily undergraduate institutions (PUI). It is called Sabbatical Epistles. He mentions a key phrase that is being batted around; it is Transformative Research. According to the NSF, transformative research is-

research that has the capacity to revolutionize existing fields, create new subfields, cause paradigm shifts, support discovery, and lead to radically new technologies.

The context of the use of this phrase was that research funding at PUI’s will increasingly be put to the merit test of transformative research. As such, research into chemical synthesis at PUI’s is especially at risk of not qualifying for funding. I suppose the concern is that multistep synthesis projects for undergrads requires lots of time and skills that undergrads do not have.

Who is against transformative research? It is like motherhood and apple pie. Everybody wants to fund or be part of this kind of effort. We should always ask that research funds be put towards this end. But there is more to it than just an affirmation of meritocracy.

What I sense is that the golden age of undergraduate research programs may be fading into some darker period of scant interest.  The scientific establishment continues to grow larger with each passing year. And in parallel, major research universities continue to add programs, courses, grad students, faculty, bricks and mortar, and administration based on the allocation of grant money. Big institutions depend on grant money to a large extent. 

As grant money gets tighter, program requirements will increasingly filter the small fish from the big fish. Large institutions have many alumni in influential positions and in the end, the programmatic mind-set of large research institutions in conjunction with the definition of success as understood by administrators of first tier schools will win the day. 

There is a pecking order to this. A kind of snobismus. And undergraduate research is not too high in the pecking order.  In relation to undergraduate research in the area of synthesis, in most schools this is the only opportunity for an undergrad to get some advanced experience in the synthetic arts. If you have tried to hire a synthetic savvy BA/BS, you know they are hard to find. In my experience, most synthetikkers want to go to grad school. They want more.

Just in case anybody is listening, I want to make a pitch for continued and stronger funding of undergraduate research. As a student, it changed the course of my life in terms of growth and development. As a former mentor of undergraduate researchers as a post doc and prof, I can say that nearly all of my students are now either PhD’s or MD’s. They are all contibuting greatly to the benefit of our society in industry, teaching hospitals, and academia. I am proud of them and I’d do it over in a heartbeat.  The pedagogy isn’t in dispute, I suppose. But the method of funding is.

Calamity, Interrupted

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JOC will no longer appear in my mailbox. I decided to let go of this icon of my earlier years. Organic Process Research & Development will “arrive”, but this time I have taken a web subscription for $40/year. In the interest of domestic harmony, the rate of paper accumulation will drop somewhat.   The trouble with this form of access to the literature is that I can’t take a journal to the local taco joint where I lunch on occasion.

The recent subscription, the Journal of Loss Prevention, is quite interesting. Lots of articles on the dynamics of explosions and fires as well as studies on calamaties, disasters, and general industrial mayhem. I can dig it.

Both imagination and knowledge are an important part of chemical process safety. A process safety person should have a solid chemistry background to grasp what is happening in a reactor or piece of equipment. Imagination comes in to play when trying to anticipate failure modes leading to initiation and propagation of incidents.

It isn’t possible to anticipate all possible failure modes in a chemical process. And not every failure leads to an incident or casualty. What is possible is to collect as much information as you can for a group to do a process hazards analysis.

A properly facilitated group can unearth many possible failure modes and root causes. Once identified, an effort to remove initiation sources or uncouple possible propagation pathways can be made. The first and best goal is to eliminate a hazardous condition. Management and engineering controls should always be secondary to elimination of a hazardous condition. 

AIChE is a great source of information for process safety.

Update:  The web subscription is quite agreeable to use.

Dark Spot

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Darkness as Metaphor

Darkness as Metaphor

The photo credit goes to Marc Imhoff, Project Scientist for NASA’s Terra satellite, NASA Goddard Space Flight Center.  Shown at night are Japan and the Korean Penninsula.

Golly, I wonder what yawning chasm of darkness cries out for light? Hint: It is run by a shrimpy Latter Day Stalinist.

Gold Refining with Borax

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According to the GEUS, the Geological Survey Office of Denmark and Greenland, it is possible to concentrate and isolate gold from the ore using borax and charcoal. This method has the immediate benefit of making mercury “redundant” in gold isolation.

Extraction of gold by amalgamation with mercury is a simple means of producing metallic gold in the field.  After contact with gold enriched ore, mercury is evaporated into the air by direct application of a torch flame to the puddle of metal leaving purified gold metal.

It is thought that there are millions of miners who scratch out a subsistance living working a small patch of ground for gold. It’s called small scale mining. In the course of this activity, environmental contamination can accrue to the immediate area as well as the watershed at large. Sadly, the toxicological insult to the miners from exposure to mercury vapor can be severe.

This method is an inexpensive and simple alternative to the mercury process. Perhaps the chemistry community has something to contribute by way of education or improved methods of extraction.

8/25/10  Update.  I have revisited this post and am compelled to comment further.  While I am unable to offer a good chemical explanation for the effect of borax on gold ore, I can say that the use of borax as a flux  for smelting goes back to the 19th century during the American gold rush period.  The process described in the link appears to be a smelting process for enriched ore containing elemental gold, as opposed to sulfide, or sulphuretted ore. The function of a flux is to modify the flow and phase separation properties of host rock so as to partition away from the gold phase or layer.  In other words, a flux modifieds the slag to help the gold to separate cleanly from the rock.

Reactivity and Risk. Gaussling’s 10th Epistle to the Bohemians.

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A chemical plant performing synthesis is a place where the materials in use are purposely selected for certain attributes of instability. Chemical stability refers to the tendancy of a substance to remain unchanged when exposed to some kind of stimulus. That stimulus may be exposure to heat energy, mechanical shock, or a more precise chemical attack on particular functional groups. Unstable substances have a low threshold to change. Stable substances require more stimulus to cause a change in composition.

Substances that are extremely stable are often not very useful in near-ambient temperature chemical synthesis, i.e., saturated hydrocarbons, metal sulfates, silica, etc.  The lack of lower temperature reactivity (say, up to 200 C) can be compensated for by application of high temperatures. Petroleum refineries take full advantage of high temperature reaction chemistry to alter the composition of otherwise stable hydrocarbons.

We choose stable substances for duty as solvents, diluents, carriers, etc., precisely because of their non-changeability or stability. “Inert” solvents allow chemists to bring molecules into solution for selective transformations. Of course, we all know that most solvents have some influence on the course of a transformation, the point is that we can transform solute materials without the fuss of altering the solvent too.

Chemical synthesis requires the manipulation of reactivity (and therefore stability) to perform useful transformations. Without well placed instability on a molecule, there cannot be efficient, directed synthesis. It is the job of the synthesis chemist to apply the knowledge of reactivity.

Because of the inherent instability of reactive and flammable materials, chemical plants must require that certain behaviors, procedures, and knowledge be set into a formal structure. Actions and conditions must give predictable consequences. This structure is comprised of a set of standard- operating procedures, equipment, test methods, and safety requirements.

It seems silly to go to the trouble of detailing the merits of running a safe plant, but it is worth pointing out the layers of requirements on an operating plant. 

  1. Preservation of life, health, and the environment
  2. Compliance with federal, state, and local regulations
  3. To provide for the uninterrupted flow of goods and services in the conduct of business
  4. To qualify for affordable business insurance
  5. To be a good neighbor and stable source of gainful employment for all concerned

A company in the business of manufacture is exposed to many kinds of liability. A chemical manufacturing plant is subject to modes of failure and liability that set it apart somewhat. 

One result of chemical manufacture that sets it apart from other forms of industry is the combination of unknown risk and dread fear. For communities in the vicinity of chemical operations, fear comes from the combination of the unknown as new risks, unknown effects, or delayed effects with the dreaded possibility of catastrophic or fatal consequences, inequitable consequences, involuntary effects, and high risk to future generations (see: Perilous Progress: Managing the Hazards of Technology, Edited by Kates, Hohenemser, and Kasperson, 1985, Westview Press, Boulder, Colorado, p 108. ISBN 0-8133-7025-6).

While the neighbors of a furniture factory may be annoyed by the presence of a nearby woodworking shop, it is unlikely that the neighbors will be stirred into existential dread by its presence. The hazards of a woodworking plant are easy to imagine and therefore, easier to rank into the grand list of life’s dangers.

Chemical and nuclear risk perception score at the extreme ranges of risk perception. Both domains involve an agent of potential harm that is poorly understood by most people. Ionizing radiation is inherently destructive to tissues, but the exact relationship between quality and dose to risk is fuzzy at low level exposure. And because it cannot be sensed directly, fear of it’s presence can induce disturbing excursions of imagination and dread.

Fear of chemicals is widespread in the industrialized world. The downside to chemical operations has been immortalized by numerous well known industrial calamities like Love Canal (Hooker Chemical), Bhopal, numerous dioxin fiascos, PCB’s, or occupational exposure to asbestos or chromium (VI). There are a great many chemical items of commerce that are unavoidably hazardous to health.

Because of the risks associated with toxicity or exposure to hazardous energy from machines, chemicals, radiation, heat, noise, gravity, sharp implements, etc., the many layers of government have established agencies and a regulatory structure to diminish risk exposure to workers specifically and citizens generally.

The purpose of the chemical industry is to produce goods and services for people who want or need the value of it’s output. Like the ad says- “We don’t make the surfboard, we make it better”. Well, making the surfboard better inevitably requires that certain kinds of hazards be unleashed and managed. The expectation that hazardous materials can be eliminated in manufacturing is a fantasy. The manipulation of instability is inherent to chemical transformation. Zeroing out hazards has to come from the demand side of the market.

Martian Swamp Gas

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According to recent reports, space scientists using infrared spectrometers at observatories in Hawaii and Chile have detected low levels of methane in the Martian atmosphere. This finding is consistent with results from as far back as 2003 when several studies reported methane at approximately 45 ppb.  Observers performing the latest work conclude that the observed methane must be of recent origin, given the short half-life of atmospheric methane due to photodegradation. 

The connection of these findings with the possibility of past or present life on Mars has proven irresistable. I’m sure there are group leaders beavering away at mission proposals this very moment based upon these findings.

An explanation that is much less exciting and much more challenging in regard to grant proposals is the abiotic explanation. Here on earth there we have a lesser known and widely overlooked abiotic theory of hydrocarbon origin. Abiotic hydrocarbons are often referred to as primordial and are known to exist in planetary atmospheres elsewhere.

According to John S. Lewis, Physics and Chemistry of the Solar System, 2nd edition, 2004, Elsevier, Inc.,  p. 159, the mole fraction of methane in the atmosphere of Jupiter is 0.001 and for Saturn it is 0.002.  The mole fractions of water are 0.001 and 0.002 respectively. Among heavy atom species, only ammonia, hydrogen sulfide, neon, and argon approach these levels within a factor of 0.5 to 0.1.

Oxygen and carbon are two of the most highly abundant heavy atoms and to see them richly represented as their respective hydrogen compounds isn’t so surprising.

At some point in the formation of the solar system, atomic carbon and atomic hydrogen were cool enough to collide and form molecular methane.  Hydrogen with its larger mole fraction would be expected to dominate bond forming interactions with carbon atoms, forming H-saturated methane.

Given the abundance of methane in the gas giants (and don’t forget the methane atmosphere of Titan)  it is hard to discount that Mars has trapped methane in the vast interstitial spaces of the interior of the planet. Methane is known to form clathrate structures with water, so perhaps the proposed underground reservoir of Martian water is comingled with methane.

I believe we should be exploring Mars. But I am increasingly uncomfortable with this stream of “Entertainment Tonight” titillation coming from NASA in regard to the possibility of life on Mars.  Perhaps our culture isn’t as advanced as we assume. Space exploration has always had a large political prestige component to it. Contractors need new contracts and politicians are always keen to bring funding to their districts.  If it takes our lesser angels to make it work, then so be it.