Category Archives: Science

Solar Warming

Here is an interesting analysis of solar min/max data. I can’t vouch for the kind of analysis that was performed. But it is interesting to see. The effects of variations in the solar flux on global temperatures seems to be neglected in discussions I run into. Among other things, these folks suggest that a lesser known 66 year solar cycle may come into play.

One commentor in a previous post suggested that we are approaching the end of the current interglacial period. He said that recent interglacial periods were characterized by polar cap melting followed by entry into the glacial side of the cycle.

Even if the solar output was constant, the interplay of the ocean heat reservoir with the atmosphere, greenhouse gases, vulcanism, asteroids, and the earth’s albedo is complex enough.  Heap on top of that the subtle thermal modulation by the sun and you have a really complex problem.

Global warming could reduce to an equation where one of the components of the sum derives from anthropogenic greenhouse emissions. 

I keep having this thought that Al Gore is eventually going to have a long talk with Tipper about returning the medal to Sweden.

NIH Manditory Open Access

According to C&EN, the NIH has issued a rule that publications resulting from NIH funded research be submitted to PubMed Central for posting.  Naturally, organizations with copyright interest in published research is  less than enthused by this ruling.

What has happened over the last century is that a sizeable publishing industry has grown up around the publication of periodicals specializing in scientific research.  In exchange for release of copyrights, authors get free or nominally priced access to publishing and distribution of their work. For their part, publishers tap into a continuous stream of refreshed content that is virtually free of charge. 

Counterbalancing the low cost of content are the sad facts of subscriptions.  Many (most) journals suffer from low distribution numbers, so the zero cost of content helps to keep overhead down, but publishing and distribution costs cannot benefit from the economy of scale.

The special interests seem to be sitting in watchful waiting, but they have raised the issue of copyright. Their concern is that they are being forced to distribute their property by the strong arm of NIH without the chance for reimbursement.  This could resolve to a property rights battle and as such, I can’t imagine that the NIH would prevail in the courts.

Gaussling’s 7th Epistle to the Bohemians.

In private moments, when I’m not thinking about some chemistry-related train of thought, I often wander to the intellectual bog of religion.  Especially on Sunday, when friends and family are sitting in church and I’m elsewhere.

I try not to write about it too often. It takes a lot of psychic energy to defend an unpopular point of view in public.  I awaken every day with just so many kcals of enthusiasm and am increasingly unwilling to spend it extravagantly in arguments about religion.

One of the surefire ways to rile people into a vein-bursting, mouth-foaming frenzy in this country is to criticize a particular religion or the religious enterprise in general. This sensitivity relates to the nature of the concept of Sacred.  There are several variations on the definition of the word sacred, but the concept in common usage seems to include “to set apart for veneration” or “worthy of respect”.  A corollary is that sacred concepts are to be treated devotionally and are not to be subjected to scrutiny.

Sacred or not, we are starting to see some open analysis of Christian doctrine and are beginning to ask reasonable questions as to the accuracy or validity of the doctrine guiding the religious right. Consider the following analysis from Terri Murray posted at the Yurica Report-

If liberals are more sympathetic to secular humanism than to Christian doctrine it is because Christian Scripture is ambivalent in its view of human nature, and second, because Christian doctrine has over-emphasized Paul’s pessimistic construction of human nature. The latter makes nonsense of moral responsibility, because it posits a deterministic model of human nature that is inconsistent with human experience, moral exhortation and human reason. Jesus’ system of morality, which most liberals greatly admire, conflicts with the misanthropy expressed in Pauline doctrine. Jesus’ ethical teachings are more consistent with the values of enlightenment humanism than with biblical theocracy, which Jesus spent his rabbinical career assailing.

‘Christianity’ is an abstract concept badly in need of analysis and definition. The authoritarian Christian right have assumed, with little argument, that Pauline doctrine is more essential to ‘Christianity’ than the teachings and traditions about Jesus, where they conflict. And conflict they do.

To outline how and where Pauline doctrine is incompatible with the “American worldview” it is important to clarify my terms first. For the purposes of this essay a ‘Christian worldview’ is defined as the Pauline doctrine of salvation, according to which all of humankind are rendered ‘sinners’ by virtue of the past transgressions of our progenitors Adam and Eve, or by virtue of an intrinsic defect in human nature. This same Pauline doctrine also makes it a matter of Christian orthodoxy that Jesus’ sacrificial death on our behalf atoned for man’s sin and offered each of us redeeming salvation by means of the profession of the Christian faith and obedience to its rules. ‘Christianity’ in this context does not refer to the teachings of Jesus of Nazareth but to the Pauline teachings about the significance of his death and resurrection for the salvation of mankind.

As Murray suggests, the strident orthodoxy of the protestant religious right in America is based in large part on a particular slant of interpretation on the life and times of Jesus of Nazareth. But rather than anchoring doctrine to his words and deeds, the American evangelical focus is on the special effects of the supernatural transition to the spirit world- part of what Murray calls the Pauline Doctrine. 

I have always been quite uneasy with many aspects of the Christian doctrine.  While I have been able to extract useful concepts by partitioning the doctrine into a) moral philosophy with historical details, b) crime and punishment, and c) an iron age form of cosmology, I have always been uneasy with the necessity of an anthropomorphic deity.  In other words, does the existence of a supernatural being actually solve the problem of how the universe works? Does God use physics, or did he have a backstage pass to do as he pleased?

What makes the universe a workable place is the fact that not everything is possible. There are boundary conditions. Objects and events in the universe exist within constraints. Not everything can happen.  God must have known this and in fact, had to have been the installer of this attribute. As Einstein would have asked, did he have any choice in the the way the universe was constructed?

In the Christian tradition, God lets loose with an occasional miracle. We know by inspection that God uses physics in the everyday conduct of things, but when “miracles” happen, are they quantifiable? Is it possible to have one miracle be twice as big as another? If you divide the number of miracles by the volume in which they occur, you come up with a miracle density. What is the average miracle density of the universe? Is God restricted by the rule that you can’t divide a number by zero?  Hmmm. Maybe He relies on this fact?

Why do we consent to adherence to an ancient religion that is constructed on iron age notions of social order, justice, and the supernatural when we have a modern understanding of democracy, history, and physics that suggests an altogether different organization to the universe?

Religious adherents will guffaw and correct my comments with an assertion that our human concepts of God are too inadequate to subject the diety to such simple analysis. Well, God holds us to standards relating to faith, love, and sin that are assumed to be within our understanding- our sins certainly get the dieties attention. Our mortal souls hang by a thread, based on our thoughts and actions relating to our knowledge of His divine plan. Why would the rest of it be so incomprehensible? Why the disconnect?

Today, the blowtorch of religious conservatism on the public stage has abated temorarily while adherents re-group. No doubt, they will be organized for the upcoming general election in the fall of 2008. I think this time around they need to be questioned a little more closely as to the basis of their doctrines.

Descriptive Inorganic Chemistry

Now that I am doing a fair amount of inorganic synthesis and preparation of metal coordination complexes, I look back to my undergraduate education and wish that it had been somewhat different.

In my undergrad time in the early 80’s, inorganic texts were heavy in theoretical concepts- molecular spectroscopy, ligand field theory, and group theory. It made for a tidy textbook package and coursework was constructed around it.  I cannot speak for other institutions, but in my experience the inorganic curriculum is (was) somewhat leaner in course options than is organic or biochemistry. In particular, the inorganic lab experience was somewhat less endowed with resources than the more popular biochemistry lab.

In graduate school, our graduate level inorganic coursework was even more theoretical than was the undergrad coursework. Obviously, there is a good argument for this and I am not actually complaining about it. But I will say that, in my experience, descriptive inorganic chemistry in the lecture section was sacrificed by the professors apparent preference for the elegance and tidiness of theoretical inorganic chemistry.

To his credit, my undergrad inorganic professor did try to give us the best lab experience possible. We had a vacuum line and did have the chance to use it. We did a prepn of AlI3 a tube furnace. We prepared Cu2(OAc)4 and a few other complexes.  He was also a glass blower  and did his best to teach us a bit about glass.

But in the end, the department was much more highly invested in organic and biochemistry. I was enchanted by synthetic organic chemistry and continued down that track.

With the benefit of hindsight, I now see that the curriculum that I was channeled through was too lean with respect to the rest of the periodic table.  Decriptive and  preparative inorganic chemistry was wedged in only by virtue of the strength of the professors interests and personality. Theoretical inorganic chemistry does not require expensive laboratory facilities.

So, I have come out to speak in favor of more descriptive inorganic chemistry in the curriculum.  More reaction chemistry. More preparation of materials in the lab. More characterization of or reaction products. More experience with setting up reactions and isolations.  More experience with hazardous materials!!

The notion that laboratory experiences for chemistry majors must be constrained by the need for Green consideration is nonsense.

I believe that microscale equipment for chemistry majors should be banned. Students should minimally prepare a few grams of materials so that they can be handled for subsequent purification and characterization. Forcing inexperienced students to prepare a spatula tip of product is unfair and needlessly harsh.

The idea that constraining a junior or senior to preparing less than 100 mg of product in a reaction is somehow green and worthy of merit is absolutely ridiculous. This is chemistry lab, not church camp.  The savings in environmental insult is minimal. There are much bigger fish to fry than this anyway. 

I suspect that equipment expenses and waste costs for university chemistry departments are drivers in what is chosen for the lab experience. If indeed efforts are being thrown on better instrumental experiences rather than better preparatory experiences, then I would say that we are missing the point. Given the creeping featurism in computer controlled instrumentation, I would suggest that monies be spent on better synthetic experiences than on the latest hyphenated instrument. 

Perhaps someone could comment on this.

Farewell to Arthur C. Clark

I’m saddened by the recent passage of the science and science fiction (SF) writer Arthur C. Clark. I blundered into the SF works of Clark, Asimov, and a few others as a high school sophomore. Freshly relocated from the midwest in 1971, I fell into a social group that was largely scientifically and technically oriented. We shunned hippies, pot, and cigarettes in favor of electronics, SF, chess, and physics.  We were juvenile scientists and engineers.

I have always enjoyed the narrative style of Clark. He was able to write thought provoking SF with dialog that was comfortable yet focused. He could manage plot development with technical subjects without collapse into a pedantic or evangelical tone.

What I am left with from my years of reading SF is a particular world view.  My vision of the future is greatly shaped by numerous SF stories written over the last 75 years. It is an egalitarian world where people have reasoned their way around nuclear self-immolation. A world where the quest for knowledge is prized and where the extinguishment of pain and suffering is sought by all. Greed has been abandoned as a way of life.  People spend the bulk of their lives seeking pleasure and understanding, not just the next meal.

But, it’s just science fiction.

Herr Doktor Professor

According to the March 10, 2008 issue of C&EN, a number of US PhD scientists working at Max Planck are facing charges for illegal use of the title “Dr.” According to the article, the title Dr is reserved for graduates of EU universities. From C&EN-

According to German criminal law, the title “Dr.” is reserved only for individuals who received a doctoral degree from a European Union institution, explains Erik Kraatz, a criminal lawyer at the Free University, Berlin. Kraatz notes that the law also prohibits masquerading as a police officer, medical doctor, or professor.

Indeed, to legally use the title “Dr.” in Germany, foreign-trained scientists must request permission from their local German state government. With this state-level consent, they can use the title “Dr.” anywhere in the country. But without the state’s permission to use the title, a scientist breaks two laws: the state law requiring approval to use the “Dr.” title and the federal impersonation law, Kraatz says.

Breaking the state law is punishable with a fine akin to that associated with a traffic ticket. However, breaking the federal law is punishable by a larger fine or up to one year in jail, Kraatz adds.

This is a very hard-core, nanny-state policy to apply to an honorific. Golly. To avoid trouble with Interpol, I’ll make sure to change my business cards and my email lest I be mistaken for a physician wannabe.  Heavens.  We don’t want that. \;-)

Hopefully someone in the German legislature will propose a reform for this ridiculous law.

Green Innovation Lag

It is not unusual for a long time to elapse between an initial customer inquiry and when commercial quantities of product are loaded on the truck and driven out the gate. I have seen it happen over 1 to 10 years, with 3 years being quite common. The chemical industry is not like the semiconductor business. The paradigm shift period seems much longer. In fact, any given chemical processing technology can last for a large part of a career or more. The last big chemical paradigm shift I have noticed is high throughput experimentation (HTE).  Maybe others have a more recent example.

Green chemistry is considered by many to be a new frontier of opportunity. To its detriment, many of us are unsure of what green chemistry really is and how to implement it in manufacturing. Realistically, for green chemistry to find wide acceptance, it needs to turn a profit or offer some kind of concrete advantage. Pollution avoidance is too abstract. For any new method or technology, there must be a payoff.

It seems simple. Reduce VOC emissions by using aqueous solvent compositions. Increase atom efficiency in transformations. Minimize persistant pollutants, organic or metal. Increase space yields, reduce consumables.  Green chemistry is not so easily demonstrated to the public and it may not be in the public domain. Your green technology may be proprietary, so the ballyhoo factor will collapse to zero. The processor may have to labor down the green path in silence.   

A process changeover to a green process may require many people in several companies to align to the change like compass needles to the north pole. A chemical process change must offer some kind of improvement that, by consensus, is meritorious. There is a good chance that the change will require notification of the customer and possibly even their permission. Customers often want a price concession when there is a process change so they can capture some of the value, so this may mean reduced sales volume and profits for the processor.

The customer may require that the proposed process change will be cause for a new validation of their customers product, in which case, the final user will also have to perform a validation.   In all likelihood, you are proposing a green change to a process that previously offered no problem to the downstream users.

Obviously, the time for green process implementation is at the very beginning of process development. The development chemist must have an existing toolbag of techniques, transformations, and reagents to choose from to go forward with implementation. The best way to get to this point is with curriculum change at the university level. Chemists need to have green chemistry awareness from the beginning of their training. Converting souls when they are already within industry is the hard way to do it.

Microscale labs in the undergrad experience maybe green for the university, but it is hard to see how it translates to the implementation of green technology in industry. The green revolution must come from textbooks that use green transformations in chemistry and engineering coursework. It must come from professors who weave it into their lectures and provide examples of such transformations and practices in the lab experience.

Chemists and engineers from such backgrounds must move into industry and become group leaders and managers. Only at this point will green chemistry become “normal” and expected.

Shermer’s “Mind of the Market”

Google has been posting a series of interesting talks by contemporary authors. This talk is by Michael Shermer, author of Mind of the Market, and editor of the popular magazine Skeptic. It is a lengthy 53 minute video, but I would highly recommend it. I think Shermer has a good grasp on the anthropology of our present world.

This is off-topic, but useful. This link gives a bunch of really good hints on how to save money for your start-up company.

Incident Attenuation in Chemical Plant Design

If you work in a location that handles or processes hazardous materials, eventually you have to come to grips with the matter of risk and accidents. It is possible to design procedures that prevent certain kinds of accidents and casualties.  It is possible to install devices and automated contrivances that can eliminate specific failures and the resulting cascade of multistage calamities that might follow.

Over time and with plenty of thought, a chemical plant can be fool-proofed to a large extent. But in the end, residual margins of safety depend on the man-machine interface. People have to undergo recurrent training and certain staff must be assigned to specialize in safety.

All devices have a failure rate. The rate may be small or large. A device may fail safely or not. Most chemical plants are, to a large extent, hand built. They are fabricated by skilled tradesmen who connect pre-fabricated parts to one-of-a-kind assemblies built on-site. In this way, expertise is captured from the plant designers, contractors, and the manufacturers of the installed equipment.  In the end though, it is up to the designers to assure that there is compatibility and some margin of overdesign in the finished facility.

While it is possible to assemble a facility from the very best equipment, the fascinating question of design for the attenuation of accident propagation is not often discussed, at least openly.  Accidents can usually be reduced to a few characteristic phases. They are initiation, propagation, and termination. 

An incident begins with an initiating event. Some release of hazardous energy is presented to the surroundings that may begin a propagation of undesired events. Events can propagate in series or parallel chains.  Hazardous energy can be electrical, chemical, or mechanical. The initiation is the tipping of a domino as a triggering event that causes the release of other hazardous conditions to ensue. Eventually, the propagation of the hazardous energy release is suppressed, extinguished, or simply exhausted in the termination phase.

One of the best ways of learning about the phenomenon of accidents is reading about them. A website worth visiting is the US Chemical and Hazard Investigation Board. It is useful for chemists and engineers to study the anlyses of the CSB and gain useful insight into the dynamics of chemical plant accidents.

It is possible to configure a chemical plant in such a manner as to attenuate the propagation of hazardous energy during an incident. In general, a large distance between reservoirs of potential energy is the easiest solution. Explosives manufacturers have known this for a long time. One well known German manufacturer of energetic materials has a manufacturing site spread over a large rural area and has built in bunkers with berms and trees to attenuate the propagation of shockwaves and allow flying fragments to land safely in an uninhabited area.  Fortunately, not many manufacturers have processes and products requiring this kind of design consideration.

Situations of “ordinary” risk magnitude do require some thought, however. Consider the storage of drums of flammable materials. Most companies that handle palletized drums of flammable liquids meet the minimal fire and insurance codes for the handling of these materials.

But consider this. What if a forklift driver spears a drum of solvent with his lift, and then in a panic, backs up and pulls the fork out of the drum resulting in a spill? At this point, policy and regulations are irrelevant. The only question is this-  Where does the liquid and the potential fire go?

Indoor storage of flammable materials requires fire suppression. Fire suppression is not the same as fire extinguishment. It is about knocking down the fire to a manageable level for emergency egress, to suppress the spread of the fire, and for firefighters to make some kind of attempt to extinguish the blaze. This is routine firefighter stuff.

What is less than routine, however, is the issue of BLEVE’s. I have written on this phenomenon previously.  Fire suppression is one thing, but BLEVE’s – Boiling Liquid Expanding Vapor Explosions- are quite another matter to deal with.

This is where a well designed facility with passive architectural features to attenuate the spread of hazardous energy can be helpful. An indoor BLEVE is virtually assured to accelerate the pace of a disaster.  So, in the planning phase of a plant, it is important to consider how energy release during an accident may propagate.  Drummed flammable liquids should be isolated from work areas and egress paths. This is pretty obvious to initial designers, but not necessarily years down the road during an expansion.

Consideration should be given to the anticipated direction in which energy is released. Where possible, energy should be released away from populated areas and away from major capital equipment. A fire in a materials storage area shouldn’t lead to an extended plant shutdown due to damaged process equipment. Segregation is key to plant safety and business viability.

Smoke is a potential killer and there are architectural tricks that can add provide slightly greater safety margins. Ceilings designed to collect and channel smoke out of the space could reduce the likelihood of suffocation of stranded workers and suppress the chances of a flashover. Smoke curtains properly placed can channel smoke away from hallways and the resulting spread.

Another concern is the fate of spilled flammable liquids in a storage area. Where should the spill go? Should the spill be concentrated in a small space or channeled to another space where a fire can burn with lower negative consequence? Nobody likes to pay for an overengineered warehouse, but fire resistant partitions in a solvent storage area can go a long way toward the isolation of a fire and attenuation of a larger scale calamity.

One major plant accident I am familiar with has a number of attributes that other operators would do well to consider.  A 750 gallon reactor explosion resulted in the complete fragmentation of the vessel.  A few pieces ejected from the hole in the roof were found lodged in the walls of neighboring structures off-site.  Fortunately, this reactor was in an enclosed space with no other reactors or stored hazardous materials. In one way, this accident was isolated due to passive attributes. However, the building space was interconnected to other spaces by a series of adjacent rooms and hallways. While fragmentation and fire damage were contained due to the happy fortune of isolation, the shockwave was able to follow all of the connected and enclosed pathways.  The connected pathways were a convenience to the workers, but this feature channeled a pressure wave throughout the entire facility, lifting the roof enough to damage large -remote- sections of it as well as badly damaging overhead doors and windows throughout the facility.

Take home lessons? 1) Leave open space walkways between production and storage buildings and the rest of the facility. Collateral damage is likely to be suppressed with this cheap, passive feature. 2) isolate and dedicate certain vessels to hazardous operations. 3) Store hazardous materials well away from processing areas. Storage and processing have their own hazards and a disaster in one area should not be allowed to propagate to the other.

The matter of flammable solvent storage and accident attenuation is only partially solved with enclosed flammable materials lockers. It seems to me that some research should be done to advance the level of best practices in this area.

Lunar Eclipse 2008

The eclipsed moon finally made itself visible only minutes from totality this evening. Through the gauzy haze the lopsided apparition loomed in the eastern sky. We pointed the 18 ” telescope at it, but with its narrow field of view we could only gaze at part of the moon at a time. With the haze and the low contrast, only washed out moonscape was visible. An eclipsed moon is best witnessed with the naked eye or from binoculars.

We found Mars and Saturn in open patches of the sky. Saturn was sharper than I’ve seen it in while. The rings and planet in sharp relief against the black velvet background. Titan and a few other moons were to be seen as well. 

A line of visitors queue around the dome and down the stairs to see the planets and M42, the Great Nebula of Orion.  We’re lucky this evening. The clouds parted and the wondrous sky was made visible.