To my mind, all of the laws of thermodynamics involve relationships to zero.
The first law of thermodynamics, for instance, states that dU = 0 which means that the energy, U, of the universe is constant, with the caveat that some energy may be in the form of mass, the equivalence of mass and energy being stated in Einstein's famous equation.
The second law of thermodynamics, the one that Congress and many others are trying to repeal, states that dS > 0 for the universe as a whole, where S is the entropy, a thermodynamic function that is expressed on an atomic scale as disorder. Stated differently, it means that as time passes, the world becomes more disorderly, even without the Bush Presidency.
The third law of thermodynamics, the one that pissed off Fritz Haber - one subject of these diaries - for personal reasons, is stated that S = 0 at T = 0, where T is the thermodynamic temperature (on the Kelvin scale) and the zero is absolute zero (-273.15C) for a perfect ordered crystal. There is no such thing, by the way, as a perfect ordered crystal at absolute zero. Although temperatures within a few millionth's of a degree of absolute zero have been reached, it is considered impossible to actually reach absolute zero.
Since the laws of thermodynamics involve so many zeros, it's only fair that there is also zeroth law of thermodynamics, and of course, it involves zeros: Let X be some system that is adiabatically sealed off - meaning no heat gets in or out and let r be some spatial vector totally contained in X, then, after a sufficiently long time, dT/dr = 0.
In other words, in less mathematical terms, the temperature is the same everywhere in a space that is insulated from all other spaces. This is intuitively obvious. A hot coffee cup in a room at "room temperature" will reach room temperature and an ice cube will melt at room temperature.
There are other ways to state the laws of thermodynamics, not all involving zeros, but I like to state them with zeros, because zeros are, in my opinion, aesthetically pleasing in some way.
One can state "NNadir's postulate" in terms of zero. Here is the postulate I express in different ways when I have time: "There are zero ethically satisfying ways to solve the human problem of climate change without the use of nuclear energy." Ethically satisfying is a term that probably would be difficult to state mathematically. One might use the variable P, for human population, and refer to dP, the change in population and then include a bunch of subscripts like W, S, T, and P where the W, S, T and P do not refer to work, entropy, temperature, pressure as in thermodynamics, but instead refer to war, starvation, thirst, and poverty. Then we could write dP = 0 with a set of "P's" with the each of the subscripts. Of course, it does not follow that all changes of P are ethically unsatisfying. I personally think that the value of P should decrease, but only by attrition, with fewer people being born that die from natural causes.
Of course, NNadir's postulate will be true of there are zero ways to solve the problem of human induced climate change with or without nuclear energy, which is very possibly true as well, but we'll leave that alone for a minute, and assume that there is at least one method of addressing climate change. I don't know if this assumption is valid. Maybe it isn't.
We have lots of people attacking the largest, by far, form of climate change gas free energy, even though dangerous fossil fuel waste accumulating in the atmosphere is increasingly fatal around the world. A corollary to NNadir's postulate is that people who attack the world's largest form of climate change free energy couldn't care less about dangerous fossil fuel waste.
Anyway.
This is supposed to be a set of diaries about Fritz Haber and troll rating Fritz Haber. Fritz Haber is the man who discovered how to make ammonia out of nitrogen and hydrogen, thus making industrially produced fertilizers available to the human race. This discovery has made a huge mess on one level, although it is now clear that a large portion of humanity owes its existence to this technology.
I'm trying to quantify how much of humanity, indeed how much of the mass of life on earth, depends on Haber nitrogen.
That's what I do. I count things, or to put it better, try to quantify things, like the number of exajoules produced by different forms of energy, like the number of sources of fixed nitrogen, like the number of times I made love to my future wife in redwood groves in 1985, and the number of times I have been troll rated by people who couldn't care less about dangerous fossil fuels.
Some things are more pleasant to quantitate than others.
While we're counting things, let's count the reasons that Fritz Haber troll rated Walther Nerst, who formulated the famous Nerst equation that relates the value of the reaction quotient (the equilibrium constant at equilibrium) to the electromotive force. Without this equation, it would be difficult to have much sense about making batteries for all those superdelicious solar panels everybody's always blabbing about. One of the things that Fritz Haber troll rated Walther Nerst for was for inventing the third law of thermodynamics, described above. Haber felt that he, having recently made himself an expert on physical chemistry about which he wrote a textbook, should have invented the third law of thermodynamics. It makes no difference that Haber would be awarded the Nobel Prize in Chemistry (1918) for nitrogen fixation before Nerst would win the same prize (1920) for the third law, Haber was jealous. And then there was the whole Clara Immerwahr thing. Dr. Immerwahr, in case you haven't followed this series, or couldn't care less about it, was Fritz Haber's first wife. She was very beautiful and very smart and very ethical and very resentful of the fact that marrying Haber had deprived her of a life in science, converting her from a world class physical chemist into a functional housewife. One of the troll ratings that Nerst got from Haber probably involved the fact that Nerst was best friends with Richard Abegg, who introduced Haber to Immerwahr. The marriage of Immerwahr and Haber didn't go well. She was appalled by Haber's war work which included developing poison gas. She troll rated Haber during the heart of the war by protesting his war work, a protest she made by committing suicide with his military issued gun.
Anyway. Haber did great things.
In the zeroth part of this series I offered some general ideas from popular sources about how much of the world's protein and nucleic acids results from human activity but promised to try to dig up some stuff from the primary scientific literature.
That's not so easy as it turns out, but here are some things I found:
First a few words about nitrogen. It is the common element in the atmosphere and one of the more common elements in the universe, thought to be number 7 after hydrogen, helium, carbon and oxygen, silicon, and iron. The cosmological abundance of the elements (on a logarithmic scale) is given in the graph found by following this link.
The saw tooth pattern observed in this graph after the sixth element (carbon) is a reflection of a curious fact in nuclear physics, elements having even numbers of protons and neutrons tend to be more stable than those having odd numbers. Thus the elements with odd numbers of protons (and odd atomic numbers) are less abundant than those with even atomic numbers. The number of isotopes (examples of the same element having different atomic masses) of elements with odd atomic numbers is 0, 1, or 2. For example, the element technetium, element 43 has zero stable isotopes - all of its isotopes are radioactive. Fluorine, element number 9, feared by the fictional Jack T. Ripper and the real life Ralph Nader, has only one stable isotope with 10 neutrons, F-19. Potassium, element 19, has two stable isotopes, K-39 and K-41, but it is always found on earth with a small amount of naturally occurring but long lived radioactive, K-40. By contrast the elements calcium, element 20, and titanium, element 22, each have 5 stable isotopes. Odd neutron numbers aren't particularly favored either. In fact, all the stable isotopes in the universe with two exceptions have either an even number of protons or an even number of neutrons. The two exceptions are deuterium, an uncommon form of hydrogen that has one neutron and one proton and is stable and the most common isotope of nitrogen, N-14, which has seven protons and seven neutrons.
The reason that this diversion about isotopes is relevant to the discussion of troll rating Fritz Haber is that the existence of nitrogen isotopes proves to be one way to examine the question of what Haber's invention has wrought. It is possible to make estimations about whether nitrogen is naturally fixed by natural processes or industrially fixed. This will help us understand the question I asked in the zeroth installment, "What percentage of the world's protein depends on industrial nitrogen fixation?"
In part zero of this series, I talked about how nitrous oxide is now the third most common greenhouse gas, after the dangerous fossil fuel waste carbon dioxide and methane, which is both a dangerous fossil fuel methane and a product of biological processes involved in agriculture, and various natural and technologically created reservoirs. Readers of that diary and I chatted pleasantly about nitrous oxide "sinks" - ways that this relatively stable gas, also known as "laughing gas," is removed from the atmosphere. I indicated that I believed (from general knowledge) that most nitrous oxide in the nitrogen cycle was removed by irradiation with UV radiation in the upper atmosphere and had, until disturbed by industrial nitrogen fixation, established an equilibrium over billions of years of planetary evolution.
Here now is some literature support for my opinion about the nature of nitrous oxide sinks:
UV photolysis is the dominant stratospheric sink for the long-lived greenhouse gas N2O. This reaction contributes 90% to the total loss due to photolysis and reaction with O(1D)...
...By virtue of reaction (R2), N2O is also the major source of stratospheric NOx and thus contributes to stratospheric ozone destruction.
N2O is produced mainly at the Earth’s surface by microbial nitrification and denitrification processes in soils and water. Due to its long atmospheric lifetime of approximately 120 years,2 the tropospheric distribution of N2O is very homogeneous and bears an interhemispheric gradient and an annual cycle hardly above the detection limit. The globally-averaged tropospheric mixing ratio has increased from a pre-industrial value of about 270 ppb (as measured in ice cores) to presently 317 ppb with a recent annual growth rate of 0.2 to 0.3%...
...Isotopic analyses may provide additional constraints on the N2O budget, as was demonstrated for CH4, CO2 and CO, and efforts have been
made in this direction for N2O.5–8 A prerequisite for this approach is a profound understanding of N2O isotope processing in its stratospheric sink reactions. Photolysis has been dealt with in a number of studies.9–15 In addition, we have recently investigated isotopic fractionations in the reaction of N2O+O(1D).16 In this paper, we focus on a previously neglected aspect of the photolysis sink, namely the temperature-
dependence of isotopic fractionation.
Although enrichments of heavy isotopes in stratospheric N2O were already noticed in 1974,17 measurements in the middle atmosphere were not continued until two decades later.5 In the meantime, laboratory measurements had shown that UV photolysis of N2O could cause isotopic enrichments, but they were restricted only to a wavelength range of stratospherically minor importance (173 to 197 nm)18...
The reference here is Phys. Chem. Chem. Phys., 2002, 4, 4420–4430 and the paper (which is somewhat beyond me) is evoked only to show how careful these types of analysis are.
The original Troll Rating Fritz Haber, Jimmy Kunstler and the Oracle at Snowmass, Part 3 of this series, the fourth installment when you include part 0, I counted on talking about some of the dead people I know, their funerals and the issue of respect. I had a particular design in doing this, which was addressing the smug, supercilious, sanctimonious members of the anti-nuclear industry who come to my diaries and who couldn't care less about dangerous fossil fuel waste, dangerous fossil fuel terrorism, dangerous fossil fuel war, dangerous fossil fuel accidents, dangerous fossil fuel depletion, or dangerous fossil fuel pollution. The members of this set get all worked up in troll rating when I take a mocking tone in reporting dangerous fossil fuel accidents about which they couldn't care less. For instance, when I talked about the 181 Chinese coal miners who were killed a few weeks ago, I got lots of troll rates from people who couldn't care less about Chinese coal miners but who nonetheless felt I was showing disrespect.
If you count things like I do, you should be aware that "Part 3," the fourth part in the series, will now probably be "Part 4," the fifth part of the series that began with a zeroth part. You may have to read all the parts if you want to quantitate or count industrially fixed nitrogen, but, of course, no one is required to read anything I write. I will probably also count exajoules, but I always do that.
Anyway.
We were talking about people who complain about my lack of respect...
We may ask ourselves, of course, if ignoring the existence of a particular group of victims is a form of respect.
I have to listen all the time to lectures about how dangerous uranium mining is supposed to be - and all of the discussions involve events in the 1960's using 1960's technology - from people who couldn't care less about the effects of coal mining. In one of my exercises mocking this "couldn't care less" set, I brought up the matter of Chinese coal mines as unnatural karsts, noting that the world couldn't care less about this topic.
Now, of course, I'm discussing fixed nitrogen, and it turns out that there is recent scientific literature on nitrogen and Chinese karsts, the karsts being very much involved in Chinese ground water and its pollution. Once again the topic involves isotopic tracing "to identify nitrate sources in karst ground water, Guiyang, Southwest
China." The quoted words are from the title of the paper found in Environ. Sci. Technol. 2006, 40, 6928-6933.
Nitrate is possibly the most widespread groundwater contaminant in the world caused by anthropogenic activities, imposing a serious threat to drinking water supplies and promoting eutrophication (1-4). In drinking water, high nitrate concentrations are believed to be a health hazard because it may cause methemeoglobinemia in infants and be responsible for increases in stomach cancer in others (5). Groundwater is a major source of drinking water for a part of the residents of Guiyang, a city with a typical karstic landform in southwestern China. Nitrate, along with SO4 2- and Cl-, pollution of groundwater is an increasingly serious problem with the development of the city (6, 7). According to Lang et al. (7), the higher content of NO3- in groundwater as compared to surface water during the summer and winter seasons indicates that the karstic groundwater system is not capable of denitrification and therefore does not easily recover once contaminated with nitrates...
...The high (del) 15N values of the groundwater in winter might be relative to the typical denitrification trend (40). The anomalously heavy (del) 15N-NO3- value of groundwater and high nitrate concentrations with high Cl- contents observed in the urban area suggest that these wells had a significant contribution of NO3- from an isotopically heavy (del) 15N source, denitrification probably occurred, and there was a serious anthropogenic pollution input into the groundwater systems in urban Guiyang...
...
I have edited this text, substituting the word "del" to substitute for the Greek letter not available to me in this editor.
Unsurprisingly the conclusion is that urban nitrate pollution in this area of China is dominated by sewage effluent, and the suburban contamination is dominated by agricultural run-off. Both of these terms involve Fritz Haber's industrial nitrogen fixation technology, so for our purposes, the distinction is trivial.
The Long Island Sound is subject of another paper, Environ. Sci. Technol. 2006, 40, 6928-6933, talking about nitrate pollution, this from the Quinnipiac and Naugatuck Rivers, which are just chock full of nitrate pollution.
Long Island Sound (LIS) has experienced recurrent summertime hypoxia that has been attributed to excess nitrogen inputs. As a result, a large-scale effort to control nitrogen sources to LIS is underway, within the framework of the total maximum daily load (TMDL) program (28). Current estimates (based on nonisotopic methods) are that almost 75% of the in-basin N loading to LIS is derived from point sources, namely sewage treatment plants (STPs) (28). Other important sources of N to LIS include septic tanks, fertilizer runoff, animal waste, and release from soils. In addition, there has been great interest in recent years in atmospheric deposition of N, both to LIS directly and to its watershed, and questions remain about the importance of this source. We describe here our work in using the dual isotope approach to identify NO3
- sources during both baseflow and stormflow in two urbanized rivers draining to LIS.
The authors are able to establish that the atmospheric contribution of this nitrate pollution is generally less than 10%, but were unable to conclude whether the bulk of the remaining pollution came from septic and sewage treatment or just run-off from Connecticut fertilized lawns and agricultural fields.
In either case, Fritz Haber's work is involved.
There is lots of other work in this area, and the intent here is just to give a flavor, and to point out that fixed nitrogen from the Haber process is a pollution problem of serious proportions. In the atmosphere, fixed nitrogen has implications in ozone chemistry, in greenhouse effects, primarily involved in long lived nitrous oxide, and in acidity.
In the seas and in surface waters, nitrate is a both a serious toxin, mutagen, and algae stimulating agent, the latter having serious implications for ecosystems, basically destroying them by removing all of their oxygen.
The problem shows up in groundwater. (I have a paper, by the way, on the related phosphorous problem and may write a quick diary on that equally interesting subject some day.) We see that the matter is very serious in China, and many other places as well.
It would be fine, of course, to wave our hands and say, "we must stop the Haber process!" However it's not so easy.
There are two books discussing the life of Fritz Haber and the nature of human dependence on nitrogen fixation. One is Vaclav Smil's Enriching the Earth (MIT Press, 2001) which I suspect is very good and answers some of the questions about the proportion of human and other protein on earth that is obtained by industrial nitrogen fixation. The other is Daniel Charles, Mastermind, The Rise and Fall of Fritz Haber... (Harper Collins, 2005) I am reading the latter and don't have immediate access to the former. Charles's book is OK, I guess, although it has the most annoying system of references I have ever seen in a book of this type, so annoying as to be almost useless. Still, there are some interesting stories told, including one that indicates that the main reason for the American-Chinese rapprochement of the Nixon years from the Chinese perspective was to get access to American and European Haber Process plant technology. Without it, the Chinese expected to starve and facing starvation, the Chinese set aside some of their revolutionary approaches to the capitalist west.
This almost about wraps up Part 3, the fourth member of this series that is about counting things. One more thing, though: In my literature searches, I stumbled across a paper in Science (SCIENCE 6 SEPTEMBER 2002 VOL 297 pp 1654-55. "Nitrogenase Reveals its Inner Secrets")
I quote:
Biological nitrogen fixation still contributes about half of the total nitrogen input to global agriculture, the rest principally coming from nitrogenous fertilizer produced chemically from the Haber-Bosch synthesis of ammonia. To produce the hydrogen gas together with the high temperatures and pressures needed for this chemical process, about 1% of the world’s total annual energy supply has to be consumed. In marked contrast, a similar chemical process requiring only atmospheric temperature and pressure is carried out by nitrogen-fixing bacteria, many of which live in symbiotic association with legume plants.
This claim is unreferenced, and does not meet the standard of primary scientific literature, any more than the Biochemistry Textbook - Biochemistry Jeremy Berg, John Tymoczko, and Lubert Stryer, Freeman 2002, page 666 - that claims, also without references, that 25% of the world's protein derives from industrially fixed Haber nitrogen.
Maybe I'll be able to meet a better standard in the future. I don't know.
Still, the claim made in the Science letter about energy is interesting. You hear these panic reports about "peak natural gas" that seem to represent that the minute the dangerous natural gas is gone we are going to run out the fertilizer that fueled the so called "green revolution." Currently the world energy demand, as of 2005, was 488 exajoules, up from 470 exajoules in 2004. If the "1%" figure for nitrogen fixation is true, then world energy demand devoted to nitrogen is about 5 exajoules, roughly the primary energy supplied by non-hydrorenewables, and about 1/6 of the primary energy supplied by nuclear energy. This is about half the energy used by the UK for all purposes, nearly double what Sweden uses, and about a third of all German energy use and about 5% of US use. As of 2005, the world consumption of dangerous natural gas was about 113 exajoules, meaning that if all the Haber nitrogen was fueled by natural gas, it required somewhere between 4 and 5 percent of the world's natural gas.
But the Haber process was not invented to utilize German dangerous natural gas reserves. It was, in fact, invented to exploit German dangerous coal reserves. Thus the "peak gas"/fertilizer fear mongering is somewhat ill informed. We don't need natural gas to fix nitrogen. It's cheaper and more convenient, but not essential. You need hydrogen and air and heat to fix nitrogen. All three are available by a multitude of means.
It is interesting, though, to note that the Russian Gazprom pipeline to Germany is owned by a company that bought the former Chancellor of Germany, the anti-nuke Gerhard Schroeder, and is itself partially owned by BASF. (Gazprom, the majority owner of the pipeline, just passed Microsoft to become the world's largest corporation.) BASF is the same company that commercialized the Haber process, beginning in 1910, four years before the outbreak of the war to end all wars, World War One. In fact the Bosch in Haber-Bosch was a BASF industrial chemical engineer. The fast commercialization of the process enabled Germany, cut off by the British Navy from the Chilean saltpeter (nitrate) mines that fueled the rest of the world's gunpowder factories, to make gunpowder to fight through the four year war that would be, up until that time, the most brutal war in human history.
We will have more to say about that war when we talk some more about Dr. Haber.