An Interesting Chemical Radical Species: The Carbon Dioxide Anion.

One of the holy grails of environmental chemistry - and tremendous progress has been made - is the electrochemical reduction of carbon dioxide.

A necessary intermediate in this reduction is the interesting radical carbon dioxide anion, ^.CO₂^-. Believe it or not, despite its ionic and radical nature, this ion can be remarkably stable. In matrices of solid KBr, the radical can be observed spectroscopically (ESR) to have a half-life on the order of years.

In most matrices however, the radical is predictably unstable, and disproportionates into CO gas and the CO₃^-2 anion.

Other possible fates include the formation of oxalic acid, which is merely a radical "chain terminating" step. Formally CO is the anhydride of formic acid, and unsurprisingly, another product that can form in the presence of water is formic acid. Intermolecular reactions can also yield glycolic acid.

Again, the holy grail is to make this ion electrolytically.

However the anion can also be made radiolytically. A relatively old paper on the subject is published in the journal Radiat. Phys. Chem. Vol. 37, No. 2, pp. 363-365, 1991, Int. J. Radiat. Appl. lnstrura., Part C, by the Mexican and Brazilian scientists, GUADALUPE ALBARRAN, l KENNETH E. COLLINS 2 and C. H. COLLINS.

Here is the abstract: http://www.sciencedirect.com/science?_ob=ArticleURL&_udi=B6X4F-46YKP7T-1N&_user=10&_coverDate=12%2F31%2F1991&_alid=1013155069&_rdoc=1&_fmt=high&_orig=search&_cdi=7325&_sort=r&_docanchor=&view=c&_ct=4&_acct=C000050221&_version=1&_urlVersion=0&_userid=10&md5=7aab1cbc33a54878e588df2157332339">International Journal of Radiation Applications and Instrumentation. Part C. Radiation Physics and Chemistry Volume 37, Issue 2, 1991, Pages 363-365

Their approach to the chemistry of this ion was really interesting. The ion was produced by self-irradiation of Ca¹⁴CO₃.

For these experiments, the authors used about 1 mg of Ca¹⁴CO₃, which has, roughly, 6 X 10¹⁸ atoms in it. Yields of ¹⁴C formic acid, oxalic acid, glycolic acid, acetic acid, and glyoxalic acid were all on the order of magnitude of 10¹⁵ to 10¹⁷ atoms.

These are significant yields, especially given the relatively long half-life (5730 years) (and correspondingly low specific activity) and relatively low energy (0.156 MeV) of nuclear decay.

The absorbed doses were on the order of MGy.

Esoteric, maybe, but interesting.

In any case, it might not be too much to say that this anion, the ^.CO₂^- anion, may well prove to be of key technological import should humanity have much of a shot of surviving climate change on any reasonable scale.

what does this all mean?

Before one starts thinking of perpetual motion machines, which violate the second law of thermodynamics, almost certainly an inviolable law, this requires an energy input. Thus such use would be an energy storage scheme, and not an energy production scheme.

(This point is often overlooked by people engaging in hydrogen hype.)

So, by use of this mechanism, it can be used to make electricity or something akin to gasoline?

DME, dimethyl ether.

I am referring to chemical systems that are biomimetics, much as an aircraft are biomimetics of insects and birds.

could easily result in electrochemical reduction of carbon dioxide.

Last time I looked, it took over 3 billion years of engineering to produce organisms that do this, more or less.

I hear lots and lots and lots and lots and lots and lots and lots and lots of stuff about how these "engineered" photosynthetic organisms are going to save our cars, as cars are essential to life, but last I looked, people were still using oil for this purpose, even in Iowa.

The mechanism by which these highly engineered organisms do this does not, however, involve the carbon dioxide anionic radical, but instead involves a hydride transfer to a phosphorylated form of carbon dioxide.

Naturally evolved systems are "efficient" in the sense that just about everything eventually gets recycled into something else. They are also "efficient" in the sense of using protein catalysis to operate at low temperatures (as compared to human industrial processes).

Biological systems are not really very efficient in the more classical thermodynamic sense of low energy loss.

designed to do better.

I don't think we can design a bird that will be more efficient or fly higher than a jet plane.

Chemical approaches, possibly equilibrium driven are, I think superior.

Natural systems exceed our systems in many ways, but definitely not all ways. For example, I don't think natural systems are especially good "role models" for industrial-scale chemistry.

I think living systems have a pretty good record of accomplishing sustainability, mostly through diversity.

Living systems are however, ill suited to transport a bunch of bourgeois brats around from place to place (mostly for no good reason) at high speeds.

Philosophically, I think that all industrial systems should have more or less a biologic model inasmuch as in that there are few bits of matter that can be considered waste, with the possible exception of dangerous coal, dangerous oil, and dangerous natural gas formations that have been deliberately disturbed in the last century or so.

That said, as a practical matter, the situation is quite different, since we are in a hell of a fix with more than six billion people on the planet.

Somehow or another, even though I'm an atheist, I have more or less accepted the Christian postulate that individual human life has merit and can and should be treated as sacred. Thus I would like to prevent wholesale unrestrained death and the rapid decline in the human life span.

But there is no point in being ethereal. Ethereal thinking doesn't accomplish very much, I have finally come to understand, hopefully not too late.

Less and less is there any nobility underlying my ideas. I am much angrier and much more cynical than I have ever been.

In the real case, I have come to understand ideas that will fix carbon dioxide from dilute solutions using the cleanest energy available in a waste minimized way but have decided to do it for somewhat pedestrian and selfish reasons that can no longer be measured in strictly ethical terms. That's a fancy and belabored way of saying I regard the IP as property, my property. It seems outrageous that one needs to appeal to obviously immoral purposes, like sustaining the car CULTure, to generate interest, but that seems to be the case. It's why I won't say everything that could be said about this system.

:shrug:

One of the fun things about this anion is that it is, unlike carbon dioxide itself, non-linear in structure. It bends. This accouts for its activity.

If water was linear, like carbon dioxide, its boiling temperature would be a a couple of 100 C lower than it is.

drive its equilibrium towards solution!

including (but not limited to) air and I've been working on them for some time.

I would tell you about them, but then I'd have to kill you.