First New Day In The House Of The Rising Sun

The days are getting longer now--can you feel it or is it too soon? Temperature is a lagging indicator so it may be a while before the frigid days pass us by.

The Downside Of Trade Unionism

Walter Reuther (1907-1970)

My dad belonged to a union--albeit a very weak one--The International Typographical Union. Printing technology undermined the ITU.  But he (and we) no doubt enjoyed bargained-for benefits.  I have fond memories of the annual summer "Company Picnic" at Hoyt Park in Madison, which his union partially sponsored.

The history of American unionization is pretty bloody--like the rest of world history. Walter "The Redhead" Reuther started growing Detroit's UAW beginning around 1934 until his death in 1970. For a readable account of him, see William Manchester's "The Glory And The Dream" beginning on p. 388. Men like Reuther were fighting for living standards and basic equity back then. They played offense and they mostly won.

Private sector unions like the UAW grew first and the public sector unions--always lagging in growth--followed. Decisions like Wisconsin's to allow public sector unions to collectively bargain led the way in 1959.

I'm old enough to be grounded by memories of the days when public sector workers were not the best paid workers on the block--we called them "State Workers" in Madison--but they gained steadily. Teachers, professors, clericals, even janitors.

When trade unionism in the private sector began to ebb, it exposed inequalities enjoyed by State employees. Here in California, state employees built a cozy relationship with the California State government which may have peaked but has not subsided. It's not really the fault of individual state employees that they enjoy benefits away and above others--it's a collective thing.

We saw a violent defensive play in Michigan today.  Gone are the days of playing offense in a growing economy. The general public--if they get the facts--will not sympathize like they did in the 1930's. It's just the wrong time of the life cycle.

Can Lithium Help Detroit?

Bolivian Lithium

Back to chemblogging for a bit.  Hmmm, let's see...I left off quite a while ago with lithium, helium, and hydrogen. I'll finish off lithium before moving onto beryllium, the fourth element.

Lithium Pharmacology
Lithium (or more accurately Li⁺) is pharmacologically active and is used to treat bipolar disorder. It's not at all clear to me (nor to Wiki) how this works.  Let's improvise. Here's my armchair analysis:
Observations: (1) In the body, Li⁺ is awash with lots of similar cations, namely, sodium (Na⁺) and potassium (K⁺). Moreover, there's realistically no way that one could swamp the body with so much Li⁺ that it would simply displace Na⁺ and K⁺; moreover, both sodium and potassium are essential and we'd die without them. Better to look for something that Li⁺ does better than Na⁺ and K⁺ do.
(2) Lithium is found in nature as lithium carbonate (in nature, elements tend to be found with other elements for which they have natural affinity). There is also experimental evidence that Li⁺ binds better to carboxylate groups, –CO₂^(-) than do either Na⁺ or K⁺:  ref.  In other words, Li⁺ has a higher affinity for the carboxylate functional group¹ and could displace a greater concentration of Na⁺ and K⁺. The pharmacists already know about this special affinity and Li⁺ is commonly formulated as lithium citrate:

Notice that the citrate has three carboxylate groups. Lithium citrate was once an ingredient in 7-Up, the Uncola, but was removed in 1950. It's important to realize that once in the body, the citrate part is easily chewed up and metabolized, leaving three Li⁺ cations, each in search of a carboxylate. 
(3) Carboxylates are ubiquitous, being the terminal side chain of common amino acids aspartic acid and glutamic acid.
(4) Glutamate is implicated in all kinds of neurochemical functions.

Hypothesis: Li⁺ displaces Na⁺ to such an extent as to affect the role of glutamate. The carboxylate functional groups are intimately involved in how neurotransmissions occur.  Essentially what lithium does is to monkey wrench this somehow. Anyway, it's just food for thought. Prove it wrong. A cursory Google search suggests there is something to this: ref, ref, and ref.

There are other proposed mechanisms of action for lithium and, if interested, check out the Wiki page here.  I love ill-defined chemical mechanisms, especially when an element is involved.  I'll return to this theme when I consider the essential role of boron (element 5, after beryllium) in plants. Meanwhile, I hope a lithium expert finds this blogpost and jumps in to correct me. I will retract the hypothesis.

Lithium Ion Batteries
Lithium ion batteries power lots of everyday electronic gadgets like cellphones, laptops and other electronic gadgets and, hopefully soon, lots of electric cars. Several generations of rechargeable batteries include lead-acid, nickel-cadium, nickel-metal hydride (NMH), lithium, and now lithium ion. By far and away the lithium ion battery is superior--enough to revolutionize the small gadget industry. Why is that?
First, it's very light. Lead-acid (think 12 V car batteries) and NMH batteries (think Prius batteries) are very heavy. Old fashioned carbon-zinc batteries are light but are not rechargable). Weight is very counterproductive deadweight when you're trying to move something around.
Second, lithium has a relatively high redox potential² for conversion of Li⁺ to lithium metal. Early lithium batteries did in fact use lithium metal and lithium ions, however it was quickly realized that the dangers of using lithium metal could not be overcome.  Lithium is a highly electropositive element and would seem well suited for 3 V applications. If you consider that the nominal voltage of common batteries: viz., AA, AAA, C, and D is, 1.5 V you'll realize that a 3.0 V battery would be useful, given that 3 V is commonly acheived by using two 1.5 V batteries in series. (This is why so many devices use two such batteries head to tail).
Lithium’s exceptional light weight is currently wasted in present generation batteries, especially automobile-sized ones: the battery train for the Chevy Volt weighs about 600 lbs. Much of this weight is due to cobalt oxide present. However, next generation breathing batteries intend to do away with the relatively heavy cobalt or iron-based components. I really hope the Volt does well and I suspect it will. Detroit needs a home run like the Toyota Pruis. I think the Volt is especially suited for the urban coastal hipsters. Me? I'll stick with diesel for the time being.

Lithium in Synthetic Organic Chemistry

The wonderful and unique properties of lithium just go on and on. A single inorganic compound, LiAlH₄ or LAH in the parlance, enabled the synthesis of entirely new classes of compounds, including pharmaceuticals. Organolithiums are a class of compounds wherein lithium replaces a hydrogen atom.  They are useful because they allow carbon in a hydrocarbon to behave as a negatively charged anion-a carbanion. Carbon normally engages in chemical reactions as an electrophile, i.e., having a tendency to attract negatively charged coupling partners. An obvious example of this is peptide synthesis in which donor nitrogen meets acceptor carbon.
Alkali metals, Li, Na, potassium, etc. dissolve in liquid ammonia to give intense blue solutions. Liquid ammonia itself is colorless, and so are solutions of Li⁺.  The blue color comes from solvated electrons:
              Na   --------> Na⁺ [e^–]
                        NH₃
The compound is called sodium electride.  You can watch it form here

Worries About Lithium Supplies
Worries about Bolivia becoming the Saudi Arabia of lithium are overblown. First of all, the photos (see above) are deceptive: those miles and miles of white salt flats are not heaps of lithium salt: it’s mainly just dried up sodium chloride. The salts are enriched in lithium carbonates. Unlike fossil fuels, the lithium inside batteries is not destructively consumed. Lithium is not a source of energy: remember that the energy has to put back inside the batteries. We have ample domestic sources for the time being from the brines of Searles Lake, CA and in Nevada.

Last but not least, don't forget the dilithium crystals!
______________________________
¹Functional Group defined
² Redox Potential is term of art and usually refers to chemical element's potential to gain or lose an electron. In lithium, there is a high propensity for the metal to lose one electron and thus obtain the noble gas electronic configuration of helium.