A New Thermodynamics

www.newthermodynamics.com

By Kent W. Mayhew
Blog: Global Warming Models: Problematic?
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  Global Warming Models:     Also see global warming and lost work 

 

   Problematic Models

 

  The real issue is how much can global warming be attributed to mankind. Remember lost work ultimately means thermal energy flows into our atmosphere from most useful systems that power our lives i.e. car engines, making of electricity (other than hydro) etc even farting by cows. To this author all this may be part of the real issues concerning  global warming has arguably been overlooked. Certainly this author’s lost work defies traditionally entropy as well as the second law, both of which too often  illogically reign supreme when applied to atmospheric thermodynamics.

 

  Then again, perhaps the biggest issue is arguably the restriction of greenhouse to certain gases! Our reality is that all polyatomic gases have the ability to act as a greenhouse gas. This will be discussed in more detail.

 

  Certainly current models claim that the solar input is such that in 1.5 hrs the Sun shines as much energy onto the Earth as humans consumed in a yr (study in 2001) See: “Green house effect & global climate changeas put out by Carnegie Mellon University in 2006. This provides a great for understanding for some of the fundamentals of global warming. However, like most theories, it applies traditional thermodynamics and overlooks the fact that man’s contribution is located at the Earth’s surface, while the Sun’s contribution although significant here on Earth’s, really enters our atmosphere from outer space. And it uses traditional greenhouse considerattions in its model. Accordingly, we shall challenge their model! 

 

  Interestingly a rightful challenge to greenhouse gas global warming models has been presented by Ned Nikolov and Karl Zeller1 who assert that our witnessed temperature is a actually a combination of:

 

1)      Insolation i.e. the solar input

2)      Pressure of our atmosphere i.e. a natural P-T relationship

 

  Nikolov and Zeller1 also rightfully contends that although conceived in the late 19th century, the theories concerning the real impact of greenhouse gases has never really been properly verified in experimental study.  

 

   It should be stated that the natural P-T relationships are not readily explainable in terms of traditional thermodynamics, which is based upon elastic collisions. However, our new understanding that intermolecular collisions are inelastic helps explain natural P-T relations in ways that traditional thermodynamics never could. Specifically, thermal photons are a result of intermolecular inelastic collisions. Hence greater pressure means some combination of the following:

 

1)      An increase to the number of intermolecular collisions, hence an increase to the number of thermal photons generated, as the mean molecular volumes decreases

2)     An increase to the forces experienced per collision when the mean molecular volumes remain constant while the mean molecular kinetic energy increases. This should also increase the amount of thermal energy generated!

  

  Certainly, the above 1) and/or 2) will readily explain why temperatures tend to increase with pressure i.e. witnessed natural P-T relationships.

 

  Greenhouse Gases

 

  Before we continue let us revisit how greenhouse gases are perceived. Basically greenhouse gases are those that readily prevent long wavelength (i.e. infrared) photons from radiating outwards into outer space. The mechanism is that the gas molecules adsorb infrared photons from the Earth’s surface. This results in molecular vibrational energy which is then radially re-emitted as photons in all directions. Hence a large percentage of these adsorbed photons will be re-emitted back towards the Earth.

 

  It should be further stated that molecules tend to emit photons in a spectrum in the form of blackbody radiation whose temperature is associated with that associated with the emitting molecules. Thus molecules whose temperatures are lower than that of original source photons, will tend to emit (re-radiate) longer wavelengths photons than the photons that they adsorbed  i.e. photons from our Sun that are adsorbed by our atmospheric gases tend to be re-emitted by those gases at lower frequencies (higher wavelengths, or if you prefer lower energy). Of course in order to conserve energy this often means that they emit more and lower energy than they adsorb.    

 

  The main accepted greenhouse gases are water vapour (H2O), carbon dioxide ( CO2), nitrous oxide (N2O), methane (CH4), and ozone (O3). All of which readily adsorb and radiate in the infra-red hence seemingly explain the greenhouse gas effect.

 

  What about the diatomic molecules [nitrogen (N2) and oxygen (O2)] , which makes up 90% of our atmosphere (N2:78%)? It is generally accepted that neither nitrogen nor oxygen readily adsorbs infra-red! Yet studies have shown that nitrogen actually adsorbs in the far infra-red spectrum2 while oxygen & nitrogen mixtures experience absorption in the near infra-red3. The point becomes that although we have traditionally (wrongly?) accepted that neither nitrogen nor oxygen contribute to the greenhouse effect, such theorization should be revisited, especially based upon their abundance!

Moreover,  I often ponder the sanity of applying absorption spectra of specific molecules to the overall ability of a mixture of gases to behave as greenhouse gas. This point is strongly exemplified by looking at the heat capacities of air and/or its constituent gases.

 

  Look at the following Table 5.4 taken from my book. Clearly the heat capacity of air is similar to that of diatomic molecules such as oxygen, nitrogen and hydrogen. And this is an exceptional fit to my theoretical equations for such diatomic heat capacities as based upon my recently published improved/newKinetic theory.

 

 

Table 5.4: Accepted isometric ( ) and isobaric ( ) heat capacities and theoretical;   [My Mayhew equation]

and   [My Mayhew equation]

.Note: Accepted science heat capacities were calculated from the engineer values

Substance

 

Accepted Empirical

[J/(mol*K)]

Theoretical

[J/(mol*K)]

Accepted Empirical  [J/(mol*K)]

Theoretical

 [J/(mol*K)]

Hydrogen

H2

2

28.83

29.09

20.52

20.78

Nitrogen

N2

2

29.14

29.09

20.82

20.78

Oxygen

O2

2

29.34

29.09

21.02

20.78

Air

 

 

29.15

 

 

20.08

Carbon Dioxide

CO2

3

37.14

37.39

28.83

29.09

Water vapor

H2O

3

33.58

37.40

25.26

29.09

Methane

CH4

5

35.72

54.0

27.4

45.71

 

  Obviously air, nitrogen and oxygen all clearly adsorb hence radiate thermal energy (infrared) as would be described by kinetic theory, so again ask: Why do their infrared adsorption spectra seeming imply otherwise?  

 

There is an obvious disconnect between a gas molecule’s ability to behave as a greenhouse gas and its absorption spectrum! Specifically, as described by this author’s rewrite of kinetic theory the mean vibrational energy (Ev) of a diatomic gas molecule (n”=2) e.g. nitrogen, is:

  

      Ev=kT            (1)

 

  Certainly diatomic molecules only have one vibrational bond, but still this bond adsorbs and radiates thermal energy/radiation in heat capacity experiments: Again seemingly not in adsorption spectra. Certainly a strange disconnect! There is probably an explanation but the point remains that all polyatomic gases must adsorb and re-radiate thermal photons!

  

  Similarly, for a triatomic gas  (n”=3) e.g. water, where there are two bonds, the mean vibrational energy is:

  

     Ev = 2kT         (2)

 

  And for a 4-atom  molecule (n”=4), with three bonds:

  

      Ev = 3kT             (3)

 

  And for an n” – atom  molecule with n”-1 bonds, the  mean vibrational energy is:

  

    Ev = (n”-1)kT     (4)

 

  Note that the total energy of a gas in a walled container  e.g. experimental apparatus, includes the measured gas’s mean kinetic energy (3kT/2), hence becomes:

   

    Etot = (n”+ 1/2)kT     (5)

 

  Consider that the thermal radiation/energy in the atmosphere’s freespace (volume between  gas molecules) as being the a major constituent of the energy that is continually  absorbed and  re-radiated within our atmosphere. Hence such thermal radiation/energy is both the:

 

1)      Vibrational energy of polyatomic gas molecules within our atmosphere

2)      Thermal energy that flow both  into and out of the Earth’s atmosphere

 

  In order to drive the point home:One would think that if the adsorption spectra clearly defined a gas’s ability to adsorb and radiate surrounding  thermal radiation then, nitrogen, oxygen and even air should have abnormally low specific heats. Since they all have heat capacities that are similar to other diatomic gases, all of which fits our theoretical new values very well then one must ponder what exactly is going on. Remember: Our new kinetic theory fits accepted empirical findings better than they fit traditionally accepted kinetic theory.

 

  Next consider triatomic carbon dioxide with its two vibrational bonds.  As an accepted greenhouse gas it has a strong absorption spectra in the infrared.  Yet CO2 has empirically found heat capacities slightly less than theoretical values! For your information the adsorption/emission spectra of carbon dioxide has three strong narrow peaks at 2.7,4.3 and 15 micrometers. Note: Gary Novak (website) points out that these peaks would only constitute 8% of all of the radiation]


 Interestingly: Five atom methane is accepted as having very strong infra-red adsorption, hence is believed thought to have 8 times the greenhouse capacity of carbon dioxide on a per molecule basis. Seemingly, this is verified by it’s theoretical heat capacity being so much higher than theory predicts. 
Obviously all polyatomic gases adsorb thermal radiation irrelevant of their adsorption spectra! Could it be that the spectra is over and above this?  Perhaps others have insights that I do not.

  

  All that said, then O2 and N2 must also contribute to our atmosphere behaving like a thermal blanket e.g. thermal greenhouse gas effect! Perhaps not as much on a per molecule basis when compared to certain accepted greenhouse gases but on the basis of a totality in the atmosphere, their contribution must have be strong!! Furthermore mixtures of gases may adsorb differently than solitary types of molecules in some experimental apparatus.  Mind you, as a mixture air’s heat capacity is very close to that expected for any diatomic gas.

 

  If the question concerning global warming concerns the mean  temperature near the Earth’s surface, and if the total atmosphere acts as a thermal blanket, then obviously all previous global warming  models are out to lunch. Remember that the atmosphere absorbs and re-radiates both the solar flux into our atmosphere, as well as, any thermal radiation from planet Earth plus mankind’s additional heat as illustrated in Fig 1. (link to Figure 1)

 

   Note one must include the temperature increase as one nears Earth’s surface due to the natural pressure-temperature relationship in any model. Never forget that this only truly becomes relevant when one realizes that the vast majority of intermolecular collisions are inelastic, as discussed in this author’s kinetic theory.  

   

  Never forget that man’s contribution to warming is located on the Earth’s surface, hence must be more significant to global warming as measured here on Earth’s surface!!!

  

  What is the truth?

 

  Now I must state that one may have doubts as to how much damage a moving car or even mankind as a whole does onto the atmosphere. But before any conclusions can be had, we must include all of the atmosphere’s molecules as having the capability to behave as a greenhouse gas in our analysis. Until we do so this author remains very doubtful that man’s contribution to global warming does not include our activities. Note: Every time we disturb the natural dynamics of the atmosphere in any way shape or form, then we are actually heating Earth’s atmosphere. And remember it is Earth’s atmosphere, not our atmosphere!!!

 

  We must keep in mind that when we apply traditional thermodynamics based upon entropy and the second law, we accept that lost work exists but we explain it in terms of an entropy increase within the expanding system. In other words there is a general lack of clarity as to where the lost work goes. One actually may conclude that the work goes into the expanding system or even into the hands of god (something Enrico Fermi once said about lost work of an expanding universe).

 

  By giving clarity to lost work is now done, we now must accept that the work is lost by the expanding system into the surrounding atmosphere. Now that we have irrefutable clarity, one should realize that all this lost work is heating our atmosphere. Okay your one drive to the corner store only put a small amount of lost work [ (PdV)atm] into our atmosphere. But what happens if ten people do I, Or even say a 100 million people do the same thing. No that lost work has the potential to becomes significant, so much so that we must now question to what degree is this associated with climate change.

 

  If one realizes that adding all the motions and lost energy involved in driving a car, then the simple way is to say this. Assume that a car accelerates hence increases its inertia. The inertia increase only considers the energy required to accelerate that car, and that all other energy goes into heating our atmosphere. Heck even the inertia energy is eventually turned into atmospheric heat when one applies the brakes.

 

  So never forget that your car’s motion continually disturbs the air’s equilibrium that being something you may call drag, which reduces a car’s efficiency. I.e. drag is nothing short of the direct heating of our atmosphere via increased intermolecular friction i.e. viscous dissipation. This can be added to all the heat generated by the friction of all the various moving parts both inside of and outside of your car.  

 

  What about Nikolov and Zeller1?

 

  Interestingly: Our new realization that intermolecular collisions are inelastic coincides with Nikolov’s and Zeller’s understanding that a pressure-temperature relation exists in all planetary atmospheres. But just like previous global warming models. Nikolov’s and Zellers theory lacks full proper understanding! Moreover, it addresses expected temperatures in a rather broad context. A context where a few degrees of rapid temperature change is not properly contemplated, i.e. a few unwarranted unwanted degrees created by humanity, which occurred too rapidily for Earth’s environments to adjust.   

 

  Conclusions

 

  All we can say right now is that none of the models make sense. It may very well be the case that we all must downsize; this means our economies, what we do as well as how many of us do what we do! Of course the vast majority of human economy is based upon the suicidal insanity of perpetual continual growth, which allows so many foolish politicians to pass the buck onto future generations. 

 

  Never forget that climate change is not just about greenhouse gases. It concerns  the whole atmosphere and how it prevents thermal energy from radiating from our planet into space, with emphasis being on the dynamics close to Earth’s surface. As for expanding systems i.e. steam engine, herein we continually pump into our atmosphere irreversible lost work , as defined by [Wlost=(PdV)atm] and this generally occurs  rather close to Earth’s surface .

 

  My Apology

 

   I am sorry but I have not calculated this as I certainly will need help. Anyhow right now I am having enough of a problem in finding people who actually give a s**t that we have horrible problems in our understanding of thermodynamics. Until I find a way of knocking common sense into our scientific community, we will never stand a chance of really comprehemding climate change.

 

   So onto you good folk who read this, I hope that you take what I say to heart, I have no children, so I have no real worries about our future. Even so, as I write this blog, I look at my 2.5 yr old 135 lb dog and realize that yes his eye watering farts affect the planet but he will never do the damage that me, and my fellow humans have done and seemingly continue to do. Too often I find myself viewing human intelligence as an oxymoron. Please step up and prove me wrong!!

 

  Thank you for reading what I have to say.

 

1)      Nikolov, Ned and Zeller, Karl, “New Insights on the Physical Nature of the Atmospheric Greenhouse Effect Deduced from an Empirical Temperature Model” Environ Pollutt Climate Change 2017 1,2

2)      Joslin, G.C., Gray C.G, Gburski, Z., “ Far Infrared Adsorption in Nitrogen Gas”, J. Molecu. Phys.  1984, 1

3)      Smith, K.M. and Newnham, D.A. “Near infrared absorption spectroscopy of Oxygen & Nitrogen Gas Mixtures, Chem Phys. Letters Vool 308 1-2 1999 pg 1-6