Tuesday, August 4, 2015

Why the Pauli Exclusion Principle of quantum mechanics forbids CO2 photons from warming the Earth surface

This post contains excerpts from "Principles of Modern Chemistry, 7th Edition" and will be a reference text for comments here and elsewhere regarding the physics and physical chemistry of the atmosphere, the gravito-thermal greenhouse effect, the laws of thermodynamics, entropy, enthalpy, and other related topics.

First up, a common misconception in the climate debate is that radiation from a cold body (e.g. the -18C atmosphere) can warm a hot body (e.g. the +15C Earth surface) just because the cold body does indeed send very-low-energy photons to the hot body. Heat transfer (not radiation) from cold to hot is forbidden by the 2nd Law of Thermodynamics on a macro basis, and by the Pauli Exclusion Principle of fundamental quantum theory on an atomic and molecular basis. 

If a lower-quantum-energy photon is "absorbed" by the completely saturated low-energy microstates (eg vibrational, translational, rotational, chemical bonds) & molecular or atomic orbitals of a higher-energy body, the hot body must simultaneously eject a photon of the exact same wavelength/frequency/energy as that absorbed, due to the Pauli Exclusion Principle of fundamental quantum theory. Thus there is no change whatsoever in the energy content/temperature of the hotter body due to "absorbing" a low-energy photon from the colder source with simultaneous emission of an identical photon of the exact same wavelength/frequency/energy (some instead refer to this as "reflection" of the lower-energy photon). This explains the 2nd Law of Thermodynamics on a quantum basis, thus why low frequency/energy photons from a cold emitter cannot warm a warmer blackbody at a higher frequency/temperature/energy. 

Since the emitting temperature of ~15um photons from atmospheric CO2 is -80C by Wein's & Planck's Laws (also explained in the reference below), these photons cannot possibly be thermalized/increase the energy or temperature of the much warmer Earth surface at +15C. 

In the reference below, the Pauli exclusion principle is discussed on pages 215, 224, 230, 254, 268, and others. The Pauli exclusion principle prohibits more than 2 electrons from being in the same atomic or molecular orbital simultaneously. In the hot body, photons from a colder emitting source will not be able to join the higher-energy orbitals in the hot body both because they contain insufficient quantum energy, and those orbitals are already saturated with a maximum of 2 higher-quantum-energy electrons. 

In the (simplified) Bohr theory, the energy well is very steep and any incoming photon at a lower-quantum-energy level than that of the target will not "catch and stick" on the sides of the energy well as illustrated in the figures below (from an earlier 4th edition of the Principles of Modern Chemistry, p. 540), thus, such lower-quantum-energy photons are not thermalized and cannot increase the energy/heat content/temperature of the hotter body.  




Also in the reference below (beginning on page 236), microstates of molecules, for instance chemical bond energies and molecular orbitals are also subject to discrete quantum energy levels. A molecular orbital or chemical bond can only have a 1-2 electron wave functions at a time, analogous to the Pauli Exclusion Principle for atoms. A photon must contain sufficient quantum energy to increase such electrons to the next higher quantum energy level in order to be thermalized/increase the energy of the hotter body. 

 
PDF available here

17 comments:

  1. I agree that the hotter body cannot be warmed by the colder body but can the colder body reduce the rate of cooling of the hotter body ?

    Suppose the hotter body cools a fraction by emission of a photon (presumably of higher energy due to the higher temperature), would it not then be able to successfully receive and retain one or more low energy photons from the colder body?

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    1. Yes the colder body can reduce the rate of cooling by the hotter body, by replacing a low-energy photon emitted from the hot body of the same energy. Reducing the rate of cooling does not equal warming. GHGs only delay IR photons on their way from surface to space by a few milliseconds, and any such slight "heat trapping" of a few millisecond delay is reversed at night.

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    2. The whole CAGW is based on the reduced rate of cooling, which means mornings won't be so cold and the following day will be warmer. It is not based on cold air directly warming already warm ground.

      If somebody says a blanket "warms" it means it reduces cooling to a cold environment. As a matter of fact, a blanket can keep you cool to some extent as well, because it reduces thermal transfer rather than warms.

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    3. Sorry MS, I think you are wrong here and Stephen is right. If the sun provides a constant rate of energy input, for instance a constant flux of say 1000 W/m2 (remember that W is J/s so it is a rate). If earth can only emit 900 W/m2 then the earth will gain 100 W/m2, i.e. 100 J/s per square meter, which is a net increase in energy and heat so the temperature will rise. However when the temperature increases so does the flux of black (or grey) body radiation until you find a new radiative equilibrium position, although now at a higher temperature.

      You don’t have to invoke any arguments from thermodynamics to explain this. The only thing the green-house gases do is that they slow down the rate of emission and hence they don’t break any thermodynamic laws.

      This emphasizes that you cannot understand the radiative greenhouse theory, as formulated by Arrhenius, using thermodynamic reasoning because it is a kinetic effect, i.e. depends on the rate of processes. Arrhenius was a brilliant chemist and worked mainly on kinetics of chemical reactions, which is why one of the most important equations describing the rate of such processes is named after him. But he also realized that kinetics can control other dynamic processes as well. Maybe some people had/have a hard time understanding his theory because they were/are stuck in only using thermodynamic principles, and those principles have indeed contributed immensely to science and society. But they can’t be applied to or explain everything.

      Best wishes
      /Martin

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    4. Martin, the Earth/atmosphere are effectively a blackbody and emit exactly the same energy as received from the Sun. The temperature of the Earth seen from space is 255K, which is exactly the same as the 255K equilibrium temperature with the Sun. There is no "heat trapping" by GHGs, which actually help to enhance heat loss via accelerated convection & and increased radiative surface area to space. All the gravito-thermal GHE does is redistribute the heat energy closer to the surface and less in the upper troposphere.

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    5. MS,
      I agree that the rate of energy-loss by black-body radiation from earth, as observed from space and corresponding to 255K, is the same as the energy gained by insolation. This has to be the same with or without an atmosphere to keep energy balance, right? But that doesn’t prevent the surface from being hotter than 255K if there are GHGs in the atmosphere that can slow down the rate of the emission that goes out into space to a corresponding degree, which is what I explained above. So you have not contradicted in any way what I wrote.

      I guess we also can agree that most of the energy that comes from the sun goes into heating the surface and that this is the largest source of heat energy on earth, right? How can you then argue that gravity, or convection or whatever, redistributes heat from the cold top atmosphere to the hot surface? (your last sentence above). That must violate the laws of thermodynamics if anything does.

      Furthermore, for a planet without GHGs in the atmosphere the planetäs surface is the only place from which long-wave heat radiation can be emitted and hence the surface would have to be 255K to radiate the same amount of energy that is coming in from the sun. The same as if there was no atmosphere. But with the gravitothermal GHE of the atmosphere the planet would actually be hotter and radiate more energy than what is coming in. This would violate the first law of thermodynamics, at least for an atmosphere in hydrostatic equilibrium.

      However, gravity could generate heat if the atmosphere would be continuously contracting, i.e. not hydrostatic equilibrium. This is the Kelvin-Helmholtz contraction mechanism and is what astronomers and physicists are using to explain how stars can get hot enough for fusion to start. But contraction of the atmosphere is necessary not to violate any thermodynamic laws. Earth’s atmosphere must be way too thin to sustain 33K by contraction for a long time, and we are all assuming hydrostatic equilibrium for the atmosphere, right?

      I imagine that you somehow think that this heating by contraction could be made continuous by energy from the outside or convection. But if you use energy from the sun to expand the atmosphere again then that solar energy is not used to heat the planet and you would have to subtract that from the incoming flux that heats the planet. You can’t have both heat and increased potential energy. When the atmosphere then again contracts the same amount of energy that was used in the expansion is released as heat so no net increase is possible. This is the essence of gravity being a conservative force. Convection is driven by energy from the sun so the same applies there.

      And finally, if your theory would be correct why havn’t anyone, including all the great scientist you claim support it, invented a perpetual heat engine by just filling a tall a column with mercury, that should generate even more gravitothermal energy due to the higher density? Maybe it’s because the theory is incorrect.

      Best wishes
      /Martin

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    6. Martin,

      The gravito-thermal GHE does not create any energy. Please take a look at Carnot's book, available online, which uses our atmosphere as his model of a heat engine and development of his heat engine theories of adiabatic compression and expansion.

      Here's Maxwell's explanation in his own words:

      http://hockeyschtick.blogspot.com/2014/05/maxwell-established-that-gravity.html

      and I used the same barometric relations (the Poisson relation and ideal gas law) in formulating the HS 'greenhouse equation' which exactly reproduces the US Standard Atmosphere

      Please also see the posts on a Boltzmann distribution which explains how gravity creates the temperature gradient, without or without GHGs and without one single radiative calculation.

      http://hockeyschtick.blogspot.com/search?q=boltzmann+distribution

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  2. In a situation where there is continuing insolation and the hotter body has reached its S-B temperature it may be that the loss of a higher energy photon is immediately replaced by a new photon from the radiating source so that the hotter body still cannot accept a low energy photon from the colder object.

    Perhaps the colder body can only reduce the rate of cooling of the hotter body when insolation stops?

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  3. "In the hot body, those low-energy molecular and atomic orbitals are already completely saturated with 2 electrons (of opposite spin)..."

    Why? I would have thought this to be the case in a cold body. In a hot one, I'd expect low energy levels to be vacated by electrons moving to higher orbitals. Am I missing something?

    I suspect, what you mean here is low energy transitions that occur at the top of the energy well, not low energy levels, the ones at its bottom.

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    1. You're right, I'm going to rewrite the last sentence. Incoming low-frequency-energy photons have insuffient quantum energy E=hv to raise the higher E level in the hot body and thus are "reflected" or "absorbed" & immediately re-emitted from the hot body with no gain in energy of the hot body.

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    2. Post now revised with Pauli exclusion principle applied to the higher-orbital-electrons and the Bohr "energy well" concept of saturation applied to the lower-orbitals all the way to the ground state.

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    3. I also need to add to the post that in the case of the 15um wavelength band from CO2, which is the only CO2 band relevant to the climate debate, all of the absorption & emission in that band is from the vibrational microstates in the double bonds between the C and O atoms. Double bonds are just shared electrons between atoms which are in molecular orbitals. Bonds/molecular orbitals are also governed by quantum mechanics and the Pauli Exclusion Principle, thus limited to a maximum of 1-2 electrons/energy states at any point in time.

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  4. Most of the alarmists and the luke-warmers have retreated to the position that more CO2 will warm the planet by reducing the rate at which the planet can shed heat built up from day time isolation. But they never offer any numbers on that. Will it "keep the surface warmer" by 33C? 1C? 2C? What? And, for how long?

    It is my understanding that H2O in the atmosphere keeps the high temperature lower than it would otherwise be (desert vs. tropics) during the day and that H2O keeps the night time temperatures warmer. This all leads to a more narrow temperature band in the wet tropics compared to the dry deserts.

    Am I on the right track here?

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    1. Reducing the rate of *cooling* does not equal warming, much less 33C of warming/increased energy/temperature/frequency as claimed by the Arrhenius radiative GHE.

      In reality, the troposphere temperature gradient of 85C from the tropopause to surface is entirely created by the gravito-thermal "greenhouse effect" of Maxwell/Clausius/Carnot/Feynman/US Std Atmosphere/Chilingar/HS 'greenhouse en/International Std Atmosphere/ etc etc., not the Arrhenius GHE which has confused the cause with the effect.

      H2O has a much higher heat capacity than air, and heat capacity is inversely related to temperature change, thus temperature change in humid areas is much much less than temperature change in arid areas. In addition, H2O greatly cools the planet by negative lapse rate feedback & clouds, which reduce solar insolation by 30%.

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  5. Very nice article indeed. I like it. This conforms very well to my simple bicycle wheel analogy. That is, imagine a molecule as a spinning bicycle wheel (freely suspended), the spin rate represents the energetic state of that molecule, and could also be viewed in relation to its temperature. If I slap my hand along the tire of the wheel at a higher energy than the current state of the wheel, then the spin of the wheel speeds up (higher energy, higher temperature), but if I slap the tire with the same force as the wheel, the spin stays the same, no matter how many times I slap it, the energetic state of the wheel does not change. If I slap the wheel with lesser force, the wheel will slow slightly (less energy, cooler) and a little of that energy is transferred back to my hand.

    What you describe here in quantum terms is precisely this behavior, and is also why "heat" cannot "pile". It doesn't matter how many times I slap the wheel, if the force is equal to the spin rate of the wheel, there is no net energy transfer at all, and the system remains the same. Just like adding 80F to 80F doesn't give you a temperature greater than 80F, no matter how many time you add them together (like adding coffee to your cup). Similarly, taking a cup of coffee at 120F and removing half of that coffee does not reduce the temperature of the coffee that remains in the cup. It is still 120F, and the excess coffee is still 120F ... just like you cannot "pile" heat, you cannot "divide" heat either. As I have explained so many times, "heat" is not a thing, "heat" is a result, a result of the energetic state of the molecules themselves. As such, one cannot actually move "heat" around, one can only transfer the energy around, and "heat" is the result of the energetic state remaining for each molecule.

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    1. That's right, all the gravito-thermal "GHE" does is redistribute the heat energy in the troposphere, producing the +33C "GHE" from the 255K ERL located at the center of mass at ~5.5km to the surface at 288K, AND the negative -35C anti-greenhouse effect from the 255K ERL to the 220K tropopause. There is no creation of heat or energy and the 1st law is conserved. The Arrhenius radiative GHE violates both the 1st and 2nd Laws.

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  6. Please see my comment today at Climate, Etc. once again debunking the anti-astrophysics and anti-HS troll named "ristvan" yet again, both in regard to his lies about the Volokin paper above and the Pauli Exclusion Principle, etc. as well:

    http://judithcurry.com/2015/09/04/week-in-review-science-edition-20/#comment-729691

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