After another tedious weekly teleconference our group adjourned and stood up from the table in the conference room.  I was furthest from the door but my normally rapid pace put me in the lead to exit. All at once mid-stride, just as my rearward foot began to move forward, it caught a phone cord that became taut instantly. Consider that a walking stride is a series of balance/off-balance conditions where the walker is constantly catching his/her balance. I had been caught off-balance at the wrong moment in my step.

My recollection of that falling moment brings to mind the droll voice of the bowl of petunias in The Hitchhiker’s Guide to the Galaxy.  Resigned to its fate, its final lament is “Oh no, not again.” I can relate.

Mid-fall my lips came within a hairs breadth of landing face first on an armrest. Luckily I hadn’t shaved that day so I actually had that hairs breadth.  On impact with the carpeted floor my first emotion was one of anger. I had successfully negotiated the cords for nigh on eleven years. But this day it was not to be. This day I would tip like a sack of dirt in front of a room full of colleagues.

After a moment on the floor I spouted an incredulous “Mother F**ker!! followed by an equally enthused “Son of a B*tch!!” Truth be told, it was an utterly sincere cleansing of my dismay. My screens were down and the profanities leapt into the ether. After a few awkward moments I got up and repaired to the solitary confines of my office.

Later I jokingly apologized for my “gravitationally-induced Tourette’s.” I gathered that the unexpected outburst had provided a welcome bit of mirth after a highly technical meeting.

 

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In the course of my forays into chemical sourcing or searching for data, I have begun to notice something about product entries in the online Sigma-Aldrich catalog. I’m finding that since the acquisition of Sigma Aldrich by Merck KGaA, MilliporeSigma as it is now known, many of the compounds that I find listed say the product has been discontinued. Is it just fortuitous, or is it not? Is the catalog collection being trimmed?

Have I been collecting data? Pffft! Of course not, silly. It’s just the subjective experience of having found few if any Aldrich catalog entries labeled as discontinued over the past few decades. Recently I’m landing on the pages of discontinued products. Hmmm.

Over the many years, buying reagents from Aldrich has saved countless chemist-days in lab productivity. In fact, the availability of their huge collection of chemicals has driven the direction of much research out there based simply on the availability of reagents for purchase.

I blame the MBA’s. This has the smell of overly smart weasels marketing people.

A recent paper (free) in Geophysical Research Letters reports the discovery of long anticipated ionospheric disturbances caused by the passing of the moon’s shadow over the earth during an eclipse. The paper, submitted by the MIT’s Haystack Observatory, reports the occurrence of ionospheric bow waves associated with the shadow ground-track of the August, 2017, North American eclipse.  The online source, MIT News, summarized the discovery.

 

I’ve been using a Mettler-Toledo (MT) RC1e reaction calorimeter for about 6 years. Our system came with MT’s iControl software, RTCal, and 2 feed pumps with balances. Overall it has proven its worth for chemical process safety and has helped us understand and adjust the thermal profile of diverse reactions. Like everything else, MT’s RC1e has many strengths and a few weaknesses.

The RC1e’s mechanical side seems reasonably robust. Our instrument sits in a walk-in fume hood resting on a low lab benchtop supported by an excess of cinder blocks- it is a heavy beast. During installation we discovered that the unit would not achieve stable calibration with the hood sash down. The control box mounted on the instrument didn’t work properly on installation. After a trip to the repair shop, the box was returned as functional but without finding the fault.

Recently we had a mixing valve fail in the heat transfer plumbing, resulting in down time. Diagnosis of this was unsuccessful over the email and phone, necessitating a service call. Parts may not be inventoried in the US and consequently must come from Switzerland. Expect Swiss prices and less than snappy delivery. Hey, it’s been my experience.

A chiller unit is required for RC1 operation and can add 15-30k$ to the setup cost. Users will have to contend with the loss of floor/hood space in the lab for the chiller and RC1. Chillers can take many hours to get down to the set temperature. Given that RC1 experiments can also be lengthy, plan accordingly. Our (brand new Neslab 80) chiller requires nearly 2 and 1/2 hours to get from +20 C to -20 C, which is the upper chiller temperature we use, depending on the reaction chemistry. For reactions that are on the sporty side, we’ll drop the chiller to – 50 C.  This is near the  minimum temperature for the water-based chilling fluid we use. Early on I opted for an aqueous lithium formate solution with a very low freezing point. It’s a little spendy, but a pool of it on the floor cannot warm up to become combustible and an ESD ignition hazard. Also, it is odorless.

The chiller required the wiring-in of a dedicated single-phase 240 VAC circuit. With the chiller using single-phase and the RC1e using 3-phase 240 VAC, it is important to assure that one cannot inadvertently connect into the wrong power circuit (idiot proofing). The chiller plug design should already prevent this. It is critical that the electrician is alert to this and does NOT jury-rig the plugs to use the same style of connectors because he has only one style in the parts bin.

Some comments on the collection and interpretation of RC1 thermograms.

  • It is critical that those who request RC1 experiments understand the limitations of the instrument. For instance, we use a 2 Liter reaction vessel with a 400 mL minimum fill volume. Refluxing is not allowed owing to the huge thermal noise input from the reflux return stream. Special equipment is said to be available for reflux.
  • Experiments must be carefully designed to elicit results that can answer questions about feed rates and energy accumulation.
  • Like many instruments, the RC1 needs a dedicated keeper and contact person for inside and outside communication. A maintenance logbook should be kept next to the instrument if for no other reason than to pass along learnings from previous issues.
  • If thermokinetic measurement is part of your organization’s development SOP, someone on staff should be reasonably familiar with chemical thermodynamics. That can be a chemical engineer, as may often be the case.
  • The users of thermal data are likely to need help with interpretation of the results. Be prepared to offer advice on interpreting the data, taking care not to over-interpret. If you don’t know, say so. It is easier to claw back “I don’t know” than “yeah, go ahead and do that …”.
  • Do not be anxious to singlehandedly bear the weight of responsibility for safety. Safety is a group responsibility.
  • Be curious. How do the insights and learnings from the data translate into best practices? What changes, if any, can the process chemists make to nudge the process for better safety and yields? A credible specialist in RC can make comments or ask questions that lead to better discussions on thermal hazards. Be a fly in the ointment.
  • Never forget that a reaction calorimeter is a blunt instrument for the understanding of a reaction. An RC1 thermogram is a composite of overlapping solution-phase phenomena. Interpretation of results can be greatly refined by pulling timely aliquots for NMR, GC/MS, or HPLC analysis.
  • A database should be constructed to collect and immortalize learnings from all safety work and RC1 learnings fall into that group.

There is the question of who collects and presents the data. An engineer or a chemist? Engineering thermodynamics is a big part of a chemical engineer’s education and skill set. As a plus, an engineer can take thermal data and apply it to scale-up design for safety and sizing of equipment and utilities. You know, the engineering part.

Do not be anxious to singlehandedly bear the weight of responsibility for safety. Alpha males- are you listening??  Safety is a group responsibility that should originate from a healthy group dynamic.

There’s a good argument for a chemist to conduct RC experiments as well. A trained synthesis chemist is qualified to conduct chemical reactions within their organization. That includes sourcing raw materials, handling them, running the reaction, and safely cleaning up the equipment afterwards. But interpreting RC1 data has a large physical chemistry component. In my experience, run of the mill inorganic/organic synthesis people may have seen PChem as an obstacle rather than a focus in their college education. Their skill set is in instrumental analysis like NMR and chromatography, mechanisms, and reaction chemistry. I would recommend having a PhD chemist with a focus on thermo in a leadership role when calorimetry is a key part of a busy process safety environment.

Safety data can be collected and archived all day long. The crucial and often tricky part is how to develop best practices from the data. I would offer that this is inherently a cross-disciplinary problem. Calorimetric data from reaction chemistry can be collected readily, especially with the diverse and excellent instrumentation available today. Adiabatic temperature rise, ΔTad, can be determined by a chemist, but it’s the engineers who understand how the equipment may respond to a given heat release. A smooth and efficient technology transfer from lab to plant happens when good communication skills are used. Yes, SOP’s must be in place for consistency and safety. But the positive effect of individuals who have good social skills and are prone to volunteering information cannot be underestimated.

 

An automated Windows update disrupted my life today. It swooped in overnight like a winged wraith, did its dark deeds, and flapped quietly back to the dank hole from whence it came. My RC1 data may yet reside unscrambled on the disk drive, but it lies orphaned from the mother iControl application which mockingly professes no recollection of 18 hours of sweet data lovingly produced. The curs in IT can only “tsk, tsk” in their antiseptic way while bobbing pointed heads in faux dismay. Another first-world difficulty uncovered for all to see.

The electronic news world is a colossal hodgepodge of media jumping on anything new and “compelling”. The weekend’s compelling news du jour is Ret. Adm. Mike Mullen‘s comments on the likelihood of nuclear war with North Korea (DPRK). As a retired admiral and chairman of the Joint Chiefs, Mullen is a strategic thinker. These days he is very pessimistic of the US finding a peaceful way forward with the DPRK.

Taken alone, this view could be ignored as an outlier. But against a backdrop of other seemingly credible reports, Mullen’s worry could be taken as another indicator of the tempo of concern within much of DC. Consistent with Mullen’s worry is a lengthy 12/14/17 interview with Senator Lindsey Graham written by Uri Friedman at The Atlantic. Graham is an opinion leader on the matter of the DPRK. The article is well written and I must highly recommend it.

The frothy part of this DPRK boil-up is talk of nuclear conflict. The language that I have heard does not distinguish the various scenarios of how a nuclear war would unfold on the Korean Peninsula. One thing that was made clear by Graham in the Atlantic article is that there could be no limited strike on the DPRK. I assume it means defensively or otherwise. Any attack on the North, nuclear or conventional, would have to result in the complete collapse of the Kim regime.

The US military develops and refines war plans in preparation for any contingency. But, I’m curious how the psychological impact of the use of nuclear weapons will play in the various war cabinets of the world. After all, the nuclear-bomb genie has been kept in the bottle since August, 1945. Will a first use on or by the DPRK lower the threshold for other nuclear states?

A nuclear weapon married to a missile is a highly engineered machine that is at the apex of multiple military technologies. Expertise and a minimum of infrastructure in metallurgy, nuclear physics, chemistry, propellants, and delivery vehicle technology is necessary for accurate execution of a strike. For the DPRK to maximize the punch of its limited nuclear armaments, a strike relying on accurate delivery of a nuclear war shot to a remote or hardened target would require their leadership to gamble on layers of unproven or unrefined technology. The Kim regime may be a political malignancy, but they are not stupid.

Suppose the DPRK is able to strike some important targets with its nukes. Surely some in the North’s command know the consequences to follow. Decapitation of its leadership and annihilation of its war making capacity are a certainty.

For the US, the use of a nuclear war shot on the DPRK is not an inevitable result of physics like the apple that fell on Newton’s head. A release from the US nuclear arsenal is a choice and thus psychological in both application and long term consequence. Would a US nuclear response to a nuclear strike- anywhere-  by the DPRK make sense for the US in the subsequent post-war world?

The last big war, WWII, started conventional and ended nuclear.  Since then, the threat of mutual nuclear conflagration has helped to keep the peace by serving as a deterrence. Mutual Assured Destruction, MAD, is credited, superficially a least, with keeping armed conflict a strictly chemical explosives activity. What happens to the ground under the psychological pedestal supporting MAD when a nation-state uses nuclear weapons thinking it could win a conflict? How would the various national policies on first use change across the world and what do the likely outcomes look like?

There are many issues that follow from conflict with the DPRK. I hope that as much energy is given to the diplomatic scene as the theatre of war.

12/20/17. It has been perhaps 6 weeks since CAS has fixed the snag with downloading ACS publications directly from SciFinder. This was a problem because, prior to the SNAFU, the ACS downloads directly from within the SciFinder account would be billed in our monthly statement. Without this feature, every download from the ACS Publications siute, outside the SciFinder account, would then be a separate line item on our in-house expense report with the required circulation for signatures, and absent the contractual discount. So, without the download/billing feature, it was a bigger paper storm and higher document pricing.

Whatever the problem at CAS was, it took some time to fix. Hopefully careers are back on track and all is well.

10/20/17. We have upgraded to Chemical Abstracts Service’s new SciFinder-n which includes PatentPak. After 2 weeks of fairly heavy use I find myself not completely convinced of the marginal value of this upgraded version. Some comments that come to mind-

  • The upgrade resulted in loss of the ability to download ACS publications directly from CAS. This is a glitch that the good folks at CAS are said to be working on. I have no idea as to the extent of this problem across the user base. Obviously ACS publication documents are downloadable from the publication website. The other possibility comes from the official document service of the ACS, FIZ Autodoc. FIZ can provide ACS documents, but for a sizeable premium above an ACS document download fee straight from CAS.
  • All upgrades, good or not good, require the user to adapt to new features. For some navigation, SciFinder-n seems to require fewer clicks and windows to begin a search. The application opens with a Google-like query box allowing the user to input a CASRN, text string, author names, etc., without clicking to a specific search entry window.
  • I use every visit by our CAS rep to lay out what I perceive as weaknesses of SciFinder. So far, no sign that my input even made it into the rental car as they sped away. One big annoyance has been the absence of Boolean searching.  If it can do Boolean searching, I have not found the right syntax or link to use it. This would be welcome.  If I’m wrong here, please leave a comment.
  • I’ve noticed that when looking at a list of references related to a substance query the ‘hits’ are no longer given listing numbers. When you find an abstract to look at more closely and then click back to the list of abstracts, you do not return to the part of the page you clicked away from. I can live with that, but since the document abstracts (see below) are not in a numbered list (1, 2, 3, … n)  you must scroll back and find where you left off by recognition of the text. So unnecessary.

10/24/17. I spoke with a customer service rep at Chemical Abstracts Service (CAS) today. It seems that CAS is in the throes of a software fiasco. The feature that allows a CAS customer to download a pdf document from an ACS publication is presently offline system-wide. This feature allows an account holder to download a document and have the charge added to the monthly billing statement. This greatly simplifies the transaction.

The rep, who was very apologetic, said that as of today it looked like the problem would be fixed in 2 weeks for those using SciFinder Web. No such luck for SciFinder-n however. Evidently the “n” version was released before the ACS document download package was available for it (!!). Luckily a SciFinder-n user can open up the web version. Funny thing is, I have no recollection that our regional representative divulged any of such details during his sales call. Simple sod that I am, my understanding was that “n” was an upgrade encompassing all of the previous web version features. Not quite, it appears. The rep said that the ACS download feature on “n” wouldn’t be available until next year.

Using both the web and the “n” versions side-by-side I must confess that I prefer the web version in many ways. Perhaps due to familiarity. I wonder what others think.

 

 

How to follow directions-

  1. Look at the person
  2. Say ‘OK’
  3. Do it

How to do anything-

  1. Start at the beginning
  2. Proceed through the middle
  3. Stop when finished

How to save electrical energy-

  1. When leaving an area, Turn Off the Goddamned Lights!

I’ll confess that I am especially peevish about the last instruction.

What instructions do you have to share, dear reader?

 

Recital.

Whereas contemplation of the lawful removal of the 45th President of the United States is a serious matter; and,

Whereas the President of the United States, Donald Trump, has displayed public behavior that can reasonably be characterized as profane, untruthful, misogynistic, and a demonstrated top-level fomenter of many of the base instincts of man; and,

Whereas the President has consistently displayed conduct, both internationally and within US borders, that is unbecoming of the top-level executive and de facto moral representative of the citizens of the United States of America; and,

Whereas the President has with malice and purpose attempted to incite foreign states with disrespect, schoolyard taunts, slander, and in the case of the DPRK, public threats of total annihilation, nuclear or otherwise; and,

Whereas the President has unilateral control over the release of nuclear war shots while, in this capacity, cultivated a mode of operation that is antithetical to US norms and traditions, and is unburdened by knowledge of the hard earned historical precedents relating to our nuclear weapons complex and decades of successful strategy pertaining to nuclear conflict and their enduring effects;

Therefore, be it resolved that the 45th President of the United States should be lawfully removed the from office by the US Congress under the terms of Section 4 of the 25th Amendment to the Constitution of the United States.

Note: This is only one of a great many possible declarations calling for the removal of President Trump. Focus your thoughts. Try writing and publishing your own.

 

Twenty-fifth Amendment to the United States Constitution

Section 1. In case of the removal of the President from office or of his death or resignation, the Vice President shall become President.

Section 2. Whenever there is a vacancy in the office of the Vice President, the President shall nominate a Vice President who shall take office upon confirmation by a majority vote of both Houses of Congress.

Section 3. Whenever the President transmits to the President pro tempore of the Senate and the Speaker of the House of Representatives his written declaration that he is unable to discharge the powers and duties of his office, and until he transmits to them a written declaration to the contrary, such powers and duties shall be discharged by the Vice President as Acting President.

Section 4. Whenever the Vice President and a majority of either the principal officers of the executive departments or of such other body as Congress may by law provide, transmit to the President pro tempore of the Senate and the Speaker of the House of Representatives their written declaration that the President is unable to discharge the powers and duties of his office, the Vice President shall immediately assume the powers and duties of the office as Acting President.

Thereafter, when the President transmits to the President pro tempore of the Senate and the Speaker of the House of Representatives his written declaration that no inability exists, he shall resume the powers and duties of his office unless the Vice President and a majority of either the principal officers of the executive department or of such other body as Congress may by law provide, transmit within four days to the President pro tempore of the Senate and the Speaker of the House of Representatives their written declaration that the President is unable to discharge the powers and duties of his office. Thereupon Congress shall decide the issue, assembling within forty-eight hours for that purpose if not in session. If the Congress, within twenty-one days after receipt of the latter written declaration, or, if Congress is not in session, within twenty-one days after Congress is required to assemble, determines by two-thirds vote of both Houses that the President is unable to discharge the powers and duties of his office, the Vice President shall continue to discharge the same as Acting President; otherwise, the President shall resume the powers and duties of his office.  Source: Wikipedia.

The weighty voices of the GOP evangelical propaganda wing have activated following the awful soaking that Houston received. The wagging fingers of TV evangelists were not far behind to remind us of the looming existential threat.

We’ve witnessed a burlesque of  righteous-sounding preachers leaning in from the video pulpit and warning, solemnly and in no uncertain terms, that hurricane Harvey is only the latest in a series of calamities to befall our nation. Our corrupt society is wallowing in a fetid pit of sin and depravity. The storms were heaven sent they intone, to show Who is actually in charge.

It’s all so very clear to these folks. The root cause of the mass murder at Sandy Hook and hurricanes Katrina, and now Harvey is the grievous sin of omission. For what? For failing to put an end to abortion and gay marriage. They’ve been connecting the dots and these dots lead to perdition. An existential threat is on the move. It’s Old Nick up to no good.

The conservative fear machine has kicked into full ruckus configuration. They deploy their weapons of incitement via their heavy presence on AM radio and cable TV. For elections and in the face of national debate, these evangelical conservatives know that they can dependably frighten just enough people to swerve the Republican hive mind. Who are these pliable voters? I think more than a few of them are people who for one reason or another did not take advantage of the education opportunities decades ago and now find themselves near the terminus of a life of toil.

Conveniently for those right of center, the Democratic Party is comatose and strapped into an iron lung, wheezing away the years in an undisclosed location.

9/10/17, Addendum.  In case I was not clear, it’s my observation that conservative protestant evangelical organizations have become a menace to American civilization. It seems to me that the election of Trump and the support bestowed upon him by conservative Christian groups, many of whom can be found out in the open on his evangelical advisory board, has opened the door to opaque theocratic influence on the large scale conduct of American government.

It’s axiomatic that people have an inherent right to worship as they please. So imagine the nightmare of trying to control what people believe when religion is folded into the curriculum of the public schools. What a tragic misunderstanding of human nature it would be to attempt to impose religious doctrine upon students. Parents would have none of it. But, a private school may have much more flexibility to teach a particular sect of religious belief. Is it  a coincidence that privatizing schools is favored by many religious organizations?

Finally, there is the matter of magisteria. Steven J. Gould wrote about religion and science as being non-overlapping magisteria. A magisterium is defined as a “a domain where one form of teaching holds the appropriate tools for meaningful discourse and resolution”. A magisterium may or may not recognize an external system of laws, facts, or values. Gould maintained that science and religion were non-overlapping magisteria in the sense that the tools of science were of no use in solving religious questions.

The secular world can be thought of that which describes what is human made and of human concern. It can also be thought of as that which is independent of religion. It is not atheistic or better or worse in any way. In chemistry we might say that the secular is orthogonal or perpendicular the religious. A bolt, an integrated circuit, or a tractor would be in the domain of the secular. So would the National Electrical Code, city ordinances, and state and federal law. All of these items are contrivances made by people for purposes living a better or safer life. Added to these items would be mathematics, the sciences and engineering. That which is measureable like the Volt or the kilogram have no defining attribute which traces back to religious definition.

It has been said that the purpose of government is to protect ourselves from each other. I would extend that to include the general domain of the secular. Having secular government means that subjective interpretations of religious matters must be secondary. This is owing to the reality that there are many religious beliefs in the world and the question of whose religion will prevail in an action involving the public will rapidly become intractable due to disparate beliefs. The secular world has elements of logic, measurement and guidelines for evidence or objective observation. All of these examples could be contained within a secular magisterium.

Public schools have long been the institutions where secular matters were introduced and learned. Government at all levels has been steadfastly kept within the secular domain. There was and remains to be a need for government to manage the secular details of a thriving civilization. The religious magisterium has a heavy reliance on beliefs which is a subjective matter subject to interpretation. A democracy requires a goodly amount of objectivity and evidence.

The notion of non-overlapping magisteria raises an interesting question. What if elements in one magisterium want control of elements in another magisterium? To have elements of a subjective domain in control of elements in the objective domain is to introduce chaos in both. Since neither side has the tools to operate in the other we have to conclude that this circumstance makes no sense for either domains.

 

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