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Some Interesting Stuff on Deep Eutectics.

We are having a remarkable - and appreciated - cold spell here in the Northeast, may it kill some pine beetle larvae and mosquito eggs.

While it will require putting up some insipid remarks from very stupid and ignorant people - like for instance our very stupid and increasing senile orange so called "President - about the non-reality of "global warming," weather like this, as wonderful as it may be for the ecosystem overall, does inspire some consideration of an environmental consequence which is seldom considered, specifically, the issue of salt flows.

The Fahrenheit scale still in use in a prominent North American and increasingly backward nation is based on two points 0 F and 100 F that were defined incorrectly, the first being the eutectic point of the best known salt, sodium chloride, NaCl, and the latter on the supposed normal homothermic temperature of a human being. On the scale currently used as the "fahrenheit scaled" both are actually wrong. The "normal" body temperature of a human being, with some minor variations is 98.6 F The eutectic point of a sodium chloride/water solution is actually -21.1C which translates to -5.98 F, with a weight % of 23.3% NaCl, as shown in the phase diagram below from a Purdue University Website:

Whatever. I confess that while I do all my thinking about science on the more widely used centigrade scale, and calculations on the thermodynamic Kelvin scale, I still - being one of those awful "baby boomer" people - still think about the weather in fahrenheit, although I wish I didn't.

One of the things that really bugs me - although I hypocritically use it, much as I use the two dangerous fossil fuels I so despise, natural gas and gasoline - is the habit of pouring salt on various forms of pavement. The reason is that I have to wonder where it goes, since salt flows are actually a critical issue environmentally.

This cold weather has caused me to reflect on this issue as did a paper I encountered in the primary scientific literature, this one:

Unconventional Deep Eutectic Solvents: Aqueous Salt Hydrates

This paper is about the use of "deep eutectics" as heat transfer media in closed systems, so it is not necessarily about alternatives in pavement ice melts.

If one accesses the paper, one will find in table 3 a list of eutectic inorganic salts and their eutectic temperatures. Notable is the second most utilized salt for melting ice on pavement, calcium chloride, which has a eutectic point considerably lower than that of the sodium chloride version, specifically -49.8C, which is -57.6 F. I don't think that this is a particularly benign salt either in an environmental sense, but those that are better are often more noxious.

Examples include KOH, sodium hydroxide (the solid form will actually generate heat when exposed to ice or water) which has a eutectic temperature of -65.2C or -84.5 F, and Calcium perchlorate, which has a eutectic point of -74.6C or -102 F.

KOH of course will dissolve flesh (and any other living thing, as well as many non-living things.) Exposed to the atmosphere it rapidly takes up carbon dioxide to form carbonates.

Perchlorates are environmental pollutants associated with the exhaust of some rockets and fireworks; they are oxidants and also interfere with iodine metabolism.

Probably, from my perspective, the least obnoxious alternative would be magnesium acetate, since acetate is readily metabolized and magnesium is a constituent of some fertilizers.

Where metabolism is concerned, probably an interesting set of eutectics are represented by choline/urea systems - choline being a constituent of most living cells, as is urea.

A paper on the physical chemistry of the choline/urea/water system has just been accepted for publication and now appears online:

First Principles Molecular Dynamics Study of a Deep Eutectic Solvent: Choline Chloride/Urea and Its Mixture with Water (J. Phys. Chem B. Just accepted, accessed 12/31/17)

Another, from the wonderful accurate and precise journal Chem. Eng. Data appears here: Molar Enthalpy of Mixing for Choline Chloride/Urea Deep Eutectic Solvent + Water System

While being biological molecules these are less obnoxious on land that inorganic salts, it's pretty clear to me that they would create huge problems in the already intractable and serious problem with the nitrogen cycle, which is responsible for the destruction of huge bodies of water owing to eutrophication, and are involved in the atmospheric accumulation of the climate forcing and ozone destroying gas nitrous oxide, N2O, "laughing gas."

(It's no laughing matter.)

It's time to go to New Year's Parties.

Have the happiest and prosperous New Year, irrespective of the Republican's efforts to limit happiness and prosperity to the most venal, selfish, and useless people on the planet.

May I, composed of Eros and Dust..

...Beleaguered by the same
Negation and despair,
Show an affirming flame.

These are the concluding lines of this poem, "September 1, 1939" by W.H. Auden, is displayed on the wall of the Whitney Museum's exhibition of protest art.

An Incomplete History of Protest:

As the New Year approaches, in yet another dark time, this poem is certainly worth reading.

It begins like this:

I sit in one of the dives
On Fifty-second Street
Uncertain and afraid
As the clever hopes expire
Of a low dishonest decade:
Waves of anger and fear
Circulate over the bright
And darkened lands of the earth...

The full poem, worth reading as this awful year ends in great shame for our country, is here:

September 1, 1939

I wish you a happy and sober New Year. We have a world worth saving.

The Mirror of Life


Henry Koerner (1915-1991), (Austrian, American) Mirror of Life, 1946. Oil on composition board, 36 × 42in. (91.4 × 106.7 cm). Whitney Museum of American Art, New York

Addressing the Flammability of Lithium Batteries Using Polystyrene Ionogels.

My son just finished his first semester, very successfully, in Engineering School; I'm a happy and proud dad.

One of the pleasures of having him home is to watch Air Disasters on the Smithsonian Channel, which is a wonderful show to watch with a budding engineer, particularly a budding materials science engineer, since many aircraft failures turn out to be problems in materials science.

The job of engineers is to make the lives of human beings safer and more sustainable, and one of the most important tasks in this enterprise is failure analysis, which is what "Air Disasters" is all about, failure analysis.

(There is good television, if you look.)

A recent episode, which I had to watch alone, concerned the crash of UPS 6, a cargo plane that crashed in Dubai in 2010 despite a heroic effort by its two crew members to land the plane after it has caught fire spontaneously.

The cause of the fire was determined to be spontaneous combustion of lithium batteries. Lithium batteries, of course, are widely used in computers, cell phones (including the Samsung Galaxy 7), and stupid electric cars, and, as Dubai is an air cargo transportation hub for shipping electrical components, it was hauling a few tons of highly flammable lithium batteries.

It was thus with interest that I came across a paper in the scientific literature which is about research into a means to address this problem - the flammability of lithium batteries is tied to the organic solvents utilized as electrolytes, generally organic carbonates, both symmetric and asymmetric. The paper is here: Syndiotactic Polystyrene-Based Ionogel Membranes for High Temperature Electrochemical Applications (Jana, et al (ACS Appl. Mater. Interfaces, 2017, 9 (36), pp 30933–30942)

Some excerpts from the introduction to the paper:

A new generation of high-temperature materials for energy storage applications is the need of time owing to the rise of usage of high-power electric vehicles, aircraft, and pulsed power systems that require energy storage devices for their functions often at elevated temperatures.(1) Lithium-ion batteries (LIBs) present the most suitable storage technology for electric vehicles (EVs) due to their high energy density and better cycling performance over other battery chemistries.(2)...

...Current LIB technologies show thermal stability up to 50 °C; at higher temperatures, LIBs lead to hazards like thermal runaway, gas evolution, and ultimately fire; the primary responsible factors are the volatile liquids used as the electrolytes.(3) The battery packs of hybrid electric vehicles (HEVs) and electric vehicles (EVs) are cooled to ambient temperature to prevent the hazards.(1, 4) The most common cooling agent is air, while more effective liquid-based cooling systems are incorporated to keep up with the increasing demand of higher power in cars that use big battery packs. It is reported that these liquid coolants can be conductive when hot and can, in turn, cause the short circuit of the cells.(5) In this context, a high temperature Li-ion battery (HT-LIB) that is stable and produces higher power density can potentially reduce or even eliminate the energy requirements to cool the battery packs and to allow an overall simplified vehicle cooling system.(4)

Traditionally, the cathode and the anode of the LIBs are highly researched areas, while the electrolytes and separators receive much less attention.(6, 7) A major source of hazards in LIBs originates from the use of highly volatile organic liquids as the electrolytes.(7-9) The carbonate-based liquids are often limited to usage temperatures below 50 °C due to their high volatility and flammability that often lead to such risks as fire and explosions. Ethylene carbonate (EC), propylene carbonate (PC), and diethyl carbonate (DEC) are the most commonly used carbonate-type liquids used in LIBs.

In general, although there is much pop rhetoric to the contrary by people who consider themselves to be environmentalists without actually appreciating the cold hard facts associated with environmental issues, a battery is not a device that increases energy efficiency. Quite the opposite is true. The second law of thermodynamics, which cannot be repealed, dictates that a battery is a device that always wastes energy. It follows that an electric car is also a device that wastes energy, a matter of high environmental relevance in the case where electricity is generated using dangerous fossil fuels, which overwhelmingly, is how most electricity is generated.

This paper adds another point, which is that cooling batteries - anything that needs to be cooled is dumping energy into the environment where it cannot be recovered - can and often does even waste more energy to run the cooling device.

The authors note that the recall of the Samsung Galaxy 7 smart phone because of the spontaneous outbreak of fires originating in the battery was tied to this issue and give the motivation for the research is to address this very real problem:

...The root causes for battery failure were identified as inadequate volume to accommodate the negative electrode and the defects originating from welding.(11) The associated thermal run-away events causing explosion and fire were the products of high volatility of the organic liquids. This work provides an alternative to alleviate the concerns associated with the use of highly volatile liquids and thermal stability of the polyolefin membranes currently used in fabrication of LIBs...

Their work involves the synthesis and evaluation of a syndiotactic polymer impregnated with the salts of an ionic liquid, and ionic liquid being a low melting salt of one or two stable organic ions.

Here is their description, not a bad one, of the relevant points associated with ionic liquids, which is that they don't really have a vapor pressure - a tendency to evaporate - and they therefore are not generally flammable, except at extremely high temperatures, temperatures not found in batteries that are not on fire:

The ionic liquids have the potential to replace the hazardous carbonate-type liquids in LIBs due to their nonvolatile nature, nonflammability, and high ionic conductivity.(12, 13) Their properties can be tuned using several combinations of cations and anions. In this regard, pyrrolidinium-based ionic liquid, for example, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (PYR14TF2N) is suitable for high temperature applications as it is thermally stable up to 300 °C and provides ionic conductivity greater than 1 × 10–3 S/cm.(14-16) Pyrrolidinium cations offer broad electrochemical window in comparison to imidazolium cations when combined with the same TF2N anions in the IL molecular structure.(17) The presence of such ILs allows the use of anode materials with low electrode potential such as graphite. In this work, the ILs are introduced in LIBs in the form of ionogels where the meso- and macropores of a polymeric gel substrate with porosity greater than 90% are filled with the ILs

The authors go on to describe in considerable detail, the process by which they prepare their new electrolyte and then study it using instruments like DSC (differential scanning calorimetry) and TGA (thermogravimetric analysis) as well as evaluating its chemoelectronic properties as an electrolyte.

They compare the performance of their new material with the commercial product in use in lithium batteries today, a product called Celgard 3501.

Their conclusion:

This paper reported a simple two-step procedure for fabrication of sPS ionogel membrane, which was found to be stable for high temperature electrochemical operation, such in LIBs. The porosity of sPS ionogel membranes was significantly higher than that of Celgard-3501 ionogel membranes, which accounted for high IL to polymer weight ratio in the membranes and produced high room temperature conductivity of 6.33 × 10–4 S/cm. The contact angle data showed better wettability of sPS membrane with IL and EC/DEC electrolytes. The high porosity and better wettability of sPS by the electrolyte resulted in lower impedance for sPS ionogels compared to Celgard-3501 ionogel membranes at 25 and 100 °C. The impedance spectroscopy data indicated low bulk charge transfer resistance of sPS-ionogel attributed to better wettability and electrolyte retention of sPS-IL system. The LSV data show improved performance for sPS ionogel membrane over Celgard ionogel membrane at 25 °C. The sPS ionogel membrane also indicated stable electrochemical window up to 4.8 V at 100 °C. This electrochemical and thermal stability of sPS-ionogel allowed continuous operation of LIB cell at 100 °C.

Current lithium batteries can burst into flame at temperatures in excess of 50 °C.

I am not a big fan of storing energy in batteries, except as absolutely necessary. I think that the enthusiasm for them, particularly as macroscale storage devices is misplaced, and is based on the mistaken belief that so called "renewable energy" is sustainable and practical. It hasn't been; it isn't; and it won't be.

My own ideas about energy storage all involve thermal storage, usually in very high temperature materials like, say, supercritical fluids.

But it is very unlikely the need to utilize batteries, particularly in small personal electric devices will go away in the lifetime of anyone now living. Thus this is important research.

I note with less than concealed disgust that this research and all research like it is under threat because a cadre of short sighted and mindless officials holding our government hostage despise science.

I hope you will have a happy and prosperous New Year, and that the New Year will involve the restoration of sanity if not to the White House where fear and ignorance is highly prized, at least then to Congress, now controlled by awful, stupid and extremely ignorant men.

Work for the election of Democrats in 2018!

Get any great surprise books for Christmas?

It's winter break for my boys - they're off from their colleges - and I loved the surprise gifts, history books, with which they surprised me.

One is The Half Has Never Been Told, about how American wealth and its capitalist economic system was generated and sustained through human slavery; the slaves built this country.

The other is The Spy Who Changed the World It's about the nuclear spy/physicist Karl Fuchs, who fed Manhattan Project and British nuclear secrets to the Soviets.

His punishment for his crime - as I told my boys, and they liked the joke - was that he had to live the rest of his life in East Germany.

Distribution of plutonium, uranium and thorium in the tissues of deceased nuclear weapons workers.

In the cold war era there were a number of accidental - and regrettably a number of deliberate - exposures of human beings to nuclear materials.

Some of this has been covered in Eileen Welsome's excellent book The Plutonium Files.

Wandering around, and correctly filing some files I've collected over the years and never read, I came across a cool paper published a few years back about the distribution of the actinide elements plutonium, uranium and thorium, in nuclear workers who were inadvertently exposed to these elements on the job. The tissues were obtained from those collected from those workers after their deaths. The paper is here: Elemental Bio-imaging of Thorium, Uranium, and Plutonium in Tissues from Occupationally Exposed Former Nuclear Workers (Doble et al Anal. Chem., 2010, 82 (8), pp 3176–3182)

The paper includes a description of each of the nuclear workers' accidents, as well as their age at the times of their deaths as well as the cause of death.

The text describing the cases of three sampled workers is worth repeating:

USTUR Case 0303
Case 0303(21) was employed for 30 years at the Hanford complex. He was involved in several minor plutonium exposures and a major exposure in 1968, when he punctured his protective glove and cut his finger on Pu-contaminated equipment. The wound was heavily contaminated with soluble plutonium. Tissue surrounding the wound was excised and intravenous administration of Ca-DPTA enhanced his urinary excretion of plutonium. He did not work with uranium. The registrant died in 2008 at age 87. A tracheobronchial lymph node (taken at autopsy) was studied here.

USTUR Case 0246
This registrant was employed at the Hanford nuclear materials complex in Washington, USA for 25 years.(22) In 1976, an ion-exchange column containing approximately 100 g of 241Am that he was working on exploded, causing him severe acid burns and cuts to his face and upper body. Intravenous Ca-DPTA treatment was commenced promptly, followed by several years of intravenous Zn-DPTA chelation therapy. The Registrant died in 1987 at 75 years of age, from emphysema. Prior to his accidental 241Am exposure, he had suffered a myocardial infarction and coronary artery disease. A right lung superior lobe (taken at autopsy) was studied here.

USTUR Case 1060
This Registrant worked at the Hanford complex for 40 years, where he was chronically exposed to uranium from 1948 to 1950 while working in the uranium melt plant.(23) The form of the uranium was most likely U3O8. Urinalysis suggested there was a single acute incident of uranium exposure occurring in 1948 in addition to chronic U dietary intake. This registrant was also involved in several plutonium contamination incidents and was potentially exposed to elevated airborne plutonium concentrations on two occasions, but only one urine measurement exceeded the minimum detectable activity (MDA) for plutonium. The registrant died (in 2008) at age 83, of a cerebral infarct due to thrombosis of the left carotid artery. A left parabronchial lymph node (taken at autopsy) was studied here.

Laser ablation mass spectrometry imaging is a remarkable analytical technique that has been utilized and advanced notably by Dr. Richard M. Caprioli at Vanderbilt University's Mass Spectrometry Research Center. The technique usually involves imaging of biomolecules (by advanced, but traditional organic molecule focused mass spectrometry) in tissues taken from diseased and healthy patients and represents a tremendous tool for the elucidation of the molecular biology of human disease. It is known by the acronym MALDI-TOF and related terms.

This paper represents one of the few papers I've seen that utilizing LA-ICP/MS (for Laser Ablation Inductively Coupled Plasma Mass Spectrometry) which measures inorganic atoms, in this case actinides.

Here is an image from the tissue of subject USTUR case 407:

The caption: Figure 1. Photomicrograph (top) and m/z 232, 238, 239, and 240 images (65 μm scan spot) of paratracheal lymph node from USTUR case 0407.

This subject's history is not given in this paper, but googling information about him (or her) I was able to learn that he or she lived 47 years after the exposure and died from a Subarachnoid Hemorrhage.

Here's another image from subject USTUR 0303:

Caption: Figure 4. Photomicrograph (top) and m/z 232 and 238 images (65
μm scan spot) of right tracheobronchial lymph node from USTUR case

Note that the concentrations of these elements are on the order of 100 ng/g (nanograms per gram). Modern mass spectrometry is sufficient these days to measure concentrations of bioactive pharmaceuticals and biomarkers that are 3 orders of magnitude lower, at a level of pg/g (picograms per gram), and a few very advanced accelerator based mass specs even lower than that femtograms/gram.

Many compounds are known to be toxic a pg/g levels.

I wish you happiness and success in the coming year.

Oxygen Isotope Ratios at the Trinity Nuclear Test Site and Laser Fluorination Extraction.

Recently I have been interested in the properties of actinide nitrides - which feature very high melting points - and their use in multiphasic nuclear reactors featuring low melting plutonium/neptunium eutectic liquid fuels, reactors about which I've been musing for some time. It seems to me that these types of reactors could be designed to run, without refueling, for more periods well longer than half a century in a "breed and burn" scenario, where the actinide nitride is UN, uranium nitride consisting of unreacted uranium in used nuclear fuels or depleted uranium, thus eliminating, ultimately, the need for mining anything, oil, gas, coal and, um, uranium for a very long time, for generations.

Nitrogen consists of two natural isotopes, N-14 and N-15 which represent respectively, 99.6% and 0.4% of the content of natural nitrogen. Interestingly Nitrogen-14, the most common isotope by far is, parenthetically, the only stable nuclide in the entire table of nuclides to feature both an odd number of neutrons and an odd number of protons.

In a neutron flux, N-14 undergoes a 14N[n,p]14C reaction during which it is converted into radioactive carbon-14. Carbon-14, as I recently confirmed in a search of the literature, itself has a very low neutron capture cross section which means that it would be extremely useful in actinide carbide fuels which also have extremely high melting points, as well as in known carbide refractories such as silicon carbide, titanium carbide and carbon containing MAX phases. Low capture cross section elements in materials increase neutron efficiency and thus breeding ratios.

(Any attempt to reverse the oxidation of carbon to fight climate change - a formidable engineering task to be sure - will require access to extremely refractory materials to provide high temperatures to produce hydrogen from water thermochemically and carbon monoxide from carbon dioxide, also thermochemically.)

Most of the nuclear scientists whose lectures I have the opportunity to attend are fusion people. They are interested in various cross sections of the light elements, whereas generally, I am not, except as described above, in the case of there presence in fusion fuels. (While their work is fun, none of it will become practical in any time remotely capable of addressing climate change; there are far too many practical issues to address for which they only have a loose approach to addressing.)

I should pay more attention though to the light elements though; their nuclear behavior is important in both fusion and fission systems.

A few years back, in some of my desultory wanderings in the scientific literature, I came across an interesting paper relating to the capture cross sections of light elements. Specifically, the material being tested was "trinitite," the glass material that was first observed after the first nuclear weapons test at the Trinity test site in 1945.

That paper is here: Oxygen Isotope Composition of Trinitite Postdetonation Materials (Koeman et al, Anal. Chem., 2013, 85 (24), pp 11913–11919)

To my personal surprise, they find that the oxygen isotopic ratios at the Trinity test site are not significantly altered, indicating that there was very little neutron capture resulting from the high neutron flux associated with the test, which was, after all, a ground test. The oxygen isotopic ratios were consistent with the natural isotopic fractionation that goes on during the formation of various minerals at the site, which consists of arkosic sands.

(A marker for the neutron flux was the radioisotope 152Eu, which formed from neutron capture in natural 151Europium in the sands. This isotope has a half-life of 13.54 years, and a little more than 2% is still present today at the test site.)

What is also very interesting is the analytical technique that was utilized in determining these oxygen isotope ratios, a beautiful extraction technique called "laser fluorination." This technique is described in the following paper authored by French scientists: IR Laser Extraction Technique Applied to Oxygen Isotope Analysis of Small Biogenic Silica Samples (Alexandre et al Anal. Chem., 2008, 80 (7), pp 2372–2378).

In this technique oxygen is liberated from a sample by oxidation by the powerful oxidant BrF5.

A description from the paper:

Oxygen Extraction Using the IR Laser-Heating Fluorination Technique and δ18O Measurement.

Molecular O2 was extracted from silica in a laser extraction line close to the one described by Sharp.35 A Merchanteck 30 W CO2 IR laser was used. The nickel sample holder was loaded in the sample chamber, prefluorinated with 50 mbar of BrF5 for 1 h and pumped for several hours. In an atmosphere of 100 mbar of BrF5, samples were preheated for 20 s with a 2000 μm diameter laser beam, increasing the power of the laser beam until the particles start moving:  from 0% to 3.6% of the laser full power for fine quartz, 2.2% for diatoms, and 2.6% for phytoliths. The laser emission was stopped after 30 s. Quartz grains and phytoliths were then heated with a 2000 μm diameter laser beam at 30−35% of its full power (11−12 W), starting at the center and slowly moving the laser beam following concentric circles until a bowl of liquid silica formed. Diatom samples were heated with a 2000 μm diameter laser beam, starting at the edge and progressively increasing the laser power from 0% up to 30−35% of its full power (11−12 W), slowly moving the laser beam following concentric circles. For all samples, when a bowl of liquid silica formed, the laser beam was then focused at 1000 μm of diameter until the liquid disappeared. The remaining particles were heated with a focused 200 μm of diameter laser beam. Laser emission was stopped when no more reaction to the laser beam occurred. Some residues remained for the diatom subsamples. They decreased from KYO 40 to KYO 90. These protocols prevented ejecta.

The liberated oxygen was then purified and trapped by adsorption in a microvolume filled with 13X molecular sieve and cooled in liquid nitrogen. The oxygen gas was then heated at 100 °C and directly sent to the sample bellow of the dual-inlet mass spectrometer (ThermoQuest Finnigan Delta Plus).

In order to get a sufficient 34/32 signal (2−3 V), the oxygen from 0.3 mg aliquots was concentrated in the mass spectrometer in an autocooled 800 μL microvolume filled with silica gel and directly connected to the dual-inlet system.

Cool I think, at least if you think a certain way. Analytical inorganic chemistry can be very beautiful.

I wish you a happy and prosperous New Year.

Bill Clinton's book review of Chernow's "Grant."

I have long felt that the Presidency of Ulysses S. Grant, often rated by academic historians as disastrous and failed, needs serious reassessment, which happily is now going on, particularly at a time when we have a "President" who is actually worse than Andrew Johnson, one of the worst Presidents ever, who was impeached but not convicted.

I happen to believe that Ulysses S. Grant was a great President, the second most important President of the 19th century, responsible for one of the most important and necessary changes to the US Constitution, the 15th amendment, which happily was recently responsible for the election of Doug Jones in Alabama.

It is very unlikely that the country would have survived at all without Grant's Presidency; without him the Union victory in the Civil War would have been undone as the country lapsed into continuous guerrilla warfare.

The reassessment of the Grant's Presidency is well underway - the low ranking having been fostered on historians by an odd coalition of overt racist "lost cause" advocates and self described "reformers" - and is being advanced at an increasing pace, something that satisfies me personally very much, as I have long admired President Grant.

I wrote about my admiration of Grant elsewhere a long time ago: US Grant and the Worst President Stuff (2007)

The second President to be impeached but not convicted, and who was actually quite a good President, is of course, Bill Clinton, and interestingly, he has reviewed Ron Chernow's best selling book on the 18th President of the United States.

NY Times Book Review of Cherow's "Grant" by Bill Clinton

Clinton writes:

The Union that Grant had been instrumental in saving as a general was splintering anew even before he took his oath of office. As Chernow writes, “If there were many small things Grant didn’t know about the presidency, he knew one big thing: His main mission was to settle unfinished business from the war by preserving the Union and safeguarding the freed slaves.”

And there was a very real chance Grant, and with him the country, would fail.

For that new mission, Grant needed cabinet members, staff and advisers every bit as masterful as his wartime lieutenants. His choices were notably hit-and-miss, but his very first appointee from a Confederate state proved to be one of his best. Amos T. Akerman of Georgia, Grant’s second attorney general, was “honest and incorruptible” and “devoted to the rule of law.” When Congress created the Department of Justice the same week as his appointment, the attorney general became overnight the head of “an active department with a substantial array of new powers.” Those powers were sorely needed to fight the Klan and what Chernow appropriately calls “the worst outbreak of domestic terrorism in American history.”...

...Chernow shows a fine balance in exposing Grant’s flaws and missteps as president, and the ill-fated turn that Reconstruction took after a promising start, while making it clear that Grant’s contributions after Appomattox were as consequential to the survival of our democracy as any that came before. As Americans continue the struggle to defend justice and equality in our tumultuous and divisive era, we need to know what Grant did when our country’s very existence hung in the balance. If we still believe in forming a more perfect union, his steady and courageous example is more valuable than ever.

I almost agree.


In these times where racists are running wild in the Government, where corruption at a very high level is taking place, where the Government is being bankrupted by wealthy scammers and their collaborators, I think Chernow's book is very important.

I've asked Santa to buy it for me, and will be waiting up all night at the Christmas tree to yank that book out of the fat Elf's sack.

Accumulation of a very potent greenhouse gas has stopped.

Recently I was going through some papers I downloaded on the subject of the gas oxygen difluoride, OF2, which is of interest to me because of some ideas I've had about electrochemical/fluoride volatility approaches to the recovery of valuable materials from used nuclear fuels, specifically the elements ruthenium, rhodium, technetium, molybdenum, plutonium, neptunium and uranium.

To my surprise, one of the papers found by my Google scholar search and collected by me was this one: Identifying the Molecular Origin of Global Warming (Lee, Berra and Francisco, J. Phys. Chem. A, 2009, 113 (45), pp 12694–12699) which, it seemed to me, has nothing to do with nuclear fuel reprocessing or even the chemistry of OF2.

But for some reason, the gas OF2 appears in table 1 the paper with a list of gases with global warming potential, their atmospheric lifetimes, global warming potential, etc.

The atmospheric lifetime of OF2 is not listed, which is not surprising, it should be as close to zero as it can be without actually being zero. OF2 is one of the few molecules known in which a positive charge resides on the extremely electronegative atom oxygen. As such it is one of the most powerful oxidants known; it will rapidly and quantitatively oxidize water: OF2 + H2O -> 2HF + O2.

Possibly it was included because it is a powerful fluorinating agent and thus may be utilized in the production of some of the gases that are utilized to make gases like the perfluoroalkanes and hydrofluoroalkanes (HFCs) that have replaced ozone depleting chloroflouroalkanes (CFCs) banned under the Montreal Protocol in refrigeration systems, HFC's being gases that are not ozone depleting but are nonetheless global warming forcing gases.

Otherwise, almost all of the other gases in the table were familiar to me, varieties of the aforementioned CFC's and HFCs, nitrous oxide, N2O (a potent ozone depleting gas as well as a global warming forcing gas), SF6 which replaced polychlorobiphenyls (PCBs) in electronic equipment as is also used in "green" thermally insulating windows in "environmentally aware" McMansions and office buildings meeting LEED certifications...blah...blah...blah.

In contrast to the situation with oxygen, most bonds to fluorine are extremely stable, notably in the case of carbon fluorine bonds, nitrogen fluorine bonds and sulfur flourine bonds, and as a result these compounds can persist for a very long time and are only destroyed by exposure to high energy radiation, far UV, x-rays and gamma rays.

Then there in table 1 was one gas of which I'd never heard, and about which I knew zero, pentafluorosulfuryltrifluoromethane, SF5CF3.

I asked myself, what the hell is that and why is it there and what the hell do they use that for?

In the table, it is listed as the most potent global warming potential gas, said potential being 22,800 on a scale in which the dangerous fossil fuel waste carbon dioxide is defined as having a value of 1.

As for "what the hell do they use that for?" the answer is, apparently, "nothing." The gas was discovered in atmospheric samples in Antarctica in the year 2000 and reported in the journal Science: A Potent Greenhouse Gas Identified in the Atmosphere: SF5CF3 (Sturges et al Science ol. 289, Issue 5479, pp. 611-613) Since there was no known use for the gas, the authors speculated that the gas was being created in the high field electronic equipment in which SF6 was utilized by reaction with teflon components. (The HTML version of the paper is open sourced, the PDF is not.)

It turns out that the authors were wrong and cheerfully admitted as much: Emissions halted of the potent greenhouse gas SF5CF3 (Sturges et al, Atmos. Chem. Phys., 12, 3653–3658, 2012) This paper is also open sourced as a PDF, but I'll excerpt it anyway.

Immediately following publication of our article, however, an open letter to the publishing journal from the company 3M stated that “one source of this compound is as a by-product of the manufacture of certain 3M fluorochemicals” (Santoro et al., 2000). It transpired that the relevant process was electrochemical fluorination for the production of perfluorooctanyl sulphonate, (PFOS) and other fluorosurfactants, used in the manufacture of foams and stain-resist coatings.

They went on to note that these production operations were to be imminently curtailed in the USA. In a subsequent personal communication, their bottom-up emission estimates were evidently close to the global emission rate that we had deduced from observations. We have updated the time series of atmospheric measurements from our original publication, and find that SF5CF3 has ceased to increase in the atmosphere, whereas the abundance of SF6 has continued to rise unabated. This clearly demonstrates that our original supposition that SF5CF3 originates from the degradation of SF6 was incorrect, and that all evidence now points to 3M being correct in their earlier assertion and that, as they predicted, emissions of this greenhouse gas have subsequently reduced to the point where they are no longer distinguishable by observation from zero.

PFOS is a serious persistent pollutant in its own right with a seriously long lifetime. I have written quite a bit about this compound which is also only degraded by high energy radiation, more or less, although some metabolism into potentially worse pollutants has been observed. PFOS can be pretty much detected in every living thing on the planet, particularly in lipids. 3M sold it until early 2000 in the product Scotch Guard which was very popular for protecting furniture.

(Other very persistent pollutants are also related to furniture as well, the flame retardants known as PBDE's, polybromodiphenyl ethers: These are also being phased out in furniture and clothing. They are also highly stable and only degraded radiochemically.)

To the credit of 3M, once they became aware of the persistence problem they voluntarily stopped making the product, which was a big seller, rather than manufacture ersatz "science" proving it was harmless - the Exxon approach.

They also immediately and voluntarily "'fessed up" about the source of SF5CF3, as noted by authors.

It does seem, happily, that this gas will not be growing in the atmosphere, even if most greenhouse gases will continue to rise unabated because, basically, we just don't care.

Have a happy holiday season.

Have you considered the meaning of the word "worthy?"

One of the great pleasures in life is to read and re-read the works of the great historian David McCulloch, and one of his greatest books of course is John Adams. (The HBO film series based on it is also excellent.)

I was leafing through it this morning and came across this excerpt of a letter from Adams, late into his retirement, to his grandson John Smith and in these awful times bears repeating:

Have you considered the meaning of the word "worthy?" We it well...I had rather you should be a worthy processors of one thousand pounds honestly acquired by your own labor and industry, than of tens of millions by banks and tricks. I should rather you be worthy shoemakers than secretaries of states or treasury acquired by libels in newspapers. I had rather you should be worthy makers of brooms and baskets than unworthy presidents of the United States procured b intrigue, factious slander and corruption.

(cf, David McCulloch, John Adams, Simon and Schluster, 2001 pg 608-609)

The bold is mine, but is actually apropos to the present state of affairs, one of the darkest periods in American history through which I've lived, and I lived a long time.

Franklin Roosevelt had these words, written by his predecessor Adams inscribed on the mantle of the fireplace of the White House"

"May none but Honest and Wise Men ever rule under This Roof."

This has obviously failed to be true, and the White House is actively being defiled by a racist pig who obviously can neither think, read or reflect. If he ever bothered in his sneering ignorance to read these words - he would simply continuing sneering at his country using his well known contempt for humanity and his country.

Both Presidents must be rolling in their graves.

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