Global Warming: Does CO2 Heat The Atmosphere? No ….

Original post here: http://wattsupwiththat.com/2010/08/05/co2-heats-the-atmosphere-a-counter-view/

CO2 heats the atmosphere…a counter view

A guest post on Watts Up What With That by : Tom Vonk (Tom is a physicist and long time poster at many climate blogs.

The simplistic view of CO2 heat trapping

If you search for “greenhouse effect” in Google and get 1 cent for statements like…

“CO2 absorbs the outgoing infrared energy and warms the atmosphere” – or – “CO2 traps part of the infrared radiation between ground and the upper part of the atmosphere”

…you will be millionaire .

Even Internet sites that are said to have a good scientific level like “Science of doom” publish statements similar to those quoted above . These statements are all wrong yet happen so often that I submitted this guest post to Anthony to clear this issue once for all.

In the case that somebody asks why there is no peer reviewed paper about this issue , it is because everything what follows is textbook material . We will use results from statistical thermodynamics and quantum mechanics that have been known for some 100 years or more . More specifically the statement that we will prove is :

A volume of gas in Local Thermodynamic Equilibrium (LTE) cannot be heated by CO2.

There are 3 concepts that we will introduce below and that are necessary to the understanding .

  1. The Local Thermodynamic Equilibrium (LTE)

This concept plays a central part so some words of definition . First what LTE is not . LTE is not Thermodynamic Equilibrium (TE) , it is a much weaker assumption . LTE requires only that the equilibrium exists in some neighborhood of every point . For example the temperature may vary with time and space within a volume so that this volume is not in a Thermodynamic Equilibrium . However if there is an equilibrium within every small subvolume of this volume , we will have LTE .

Intuitively the notion of LTE is linked to the speed with which the particles move and to their density . If the particle stays long enough in a small volume to interact with other particles in this small volume , for example by collisions , then the particle will equilibrate with others . If it doesn’t stay long enough then it can’t equilibrate with others and there is no LTE .

There are 2 reasons why the importance of LTE is paramount .

First is that a temperature cannot be defined for a volume which is not in LTE . That is easy to understand . The temperature is an average energy of a small volume in equilibrium . Since there is no equilibrium in any small volume if we have not LTE , the temperature cannot be defined in this case.

Second is that the energy distribution in a volume in LTE follows known laws and can be computed .

The energy equipartition law

Kinetic energy is present in several forms . A monoatomic gas has only the translational kinetic energy , the well known ½.m.V² . A polyatomic gas can also vibrate and rotate and therefore has in addition to the translational kinetic energy also the vibrational and the rotational kinetic energy . When we want to specify the total kinetic energy of a molecule , we need to account for all 3 forms of it .

Thus the immediate question we ask is : “If we add energy to a molecule , what will it do ? Increase its velocity ? Increase its vibration ? Increase its rotation ? Some mixture of all 3 ?”

The answer is given by the energy equipartition law . It says : “In LTE the energy is shared equally among its different forms .

As we have seen that the temperature is an average energy ,and that it is defined only under LTE conditions , it is possible to link the average kinetic energy <E> to the temperature . For instance in a monoatomic gas like Helium we have <E>= 3/2.k.T . The factor 3/2 comes because there are 3 translational degrees of freedom (3 space dimensions) and it can be reformulated by saying that the kinetic energy per translational degree of freedom is ½.k.T . From there can be derived ideal gas laws , specific heat capacities and much more . For polyatomic molecules exhibiting vibration and rotation the calculations are more complicated . The important point in this statistical law is that if we add some energy to a great number of molecules , this energy will be shared equally among their translational , rotational and vibrational degrees of freedom .

Quantum mechanical interactions of molecules with infrared radiation

Everything that happens in the interaction between a molecule and the infrared radiation is governed by quantum mechanics . Therefore the processes cannot be understood without at least the basics of the QM theory .

The most important point is that only the vibration and rotation modes of a molecule can interact with the infrared radiation . In addition this interaction will take place only if the molecule presents a non zero dipolar momentum . As a non zero dipolar momentum implies some asymmetry in the distribution of the electrical charges , it is specially important in non symmetric molecules . For instance the nitrogen N-N molecule is symmetrical and has no permanent dipolar momentum .

O=C=O is also symmetrical and has no permanent dipolar momentum . C=O is non symmetrical and has a permanent dipolar momentum . However to interact with IR it is not necessary that the dipolar momentum be permanent . While O=C=O has no permanent dipolar momentum , it has vibrational modes where an asymmetry appears and it is those modes that will absorb and emit IR . Also nitrogen N-N colliding with another molecule will be deformed and acquire a transient dipolar momentum which will allow it to absorb and emit IR .

In the picture left you see the 4 possible vibration modes of CO2 . The first one is symmetrical and therefore displays no dipolar momentum and doesn’t interact with IR . The second and the third look similar and have a dipolar momentum . It is these both that represent the famous 15µ band . The fourth is highly asymmetrical and also has a dipolar momentum .

What does interaction between a vibration mode and IR mean ?

The vibrational energies are quantified , that means that they can only take some discrete values . In the picture above is shown what happens when a molecule meets a photon whose energy (h.ν or ђ.ω) is exactly equal to the difference between 2 energy levels E2-E1 . The molecule absorbs the photon and “jumps up” from E1 to E2 . Of course the opposite process exists too – a molecule in the energy level E2 can “jump down” from E2 to E1 and emit a photon of energy E2-E1 .

But that is not everything that happens . What also happens are collisions and during collisions all following processes are possible .

  • Translation-translation interaction . This is your usual billiard ball collision .
  • Translation-vibration interaction . Here energy is exchanged between the vibration modes and the translation modes .
  • Translation-rotation interaction . Here energy is is exchanged between the rotation modes and the translation modes .
  • Rotation-vibration interaction … etc .

In the matter that concerns us here , namely a mixture of CO2 and N2 under infrared radiation only 2 processes are important : translation-translation and translation-vibration . We will therefore neglect all other processes without loosing generality .

The proof of our statement

The translation-translation process (sphere collision) has been well understood since more than 100 years . It can be studied by semi-classical statistical mechanics and the result is that the velocities of molecules (translational kinetic energy) within a volume of gas in equilibrium are distributed according to the Maxwell-Boltzmann distribution . As this distribution is invariant for a constant temperature , there are no net energy transfers and we do not need to further analyze this process .

The 2 processes of interest are the following :

CO2 + γ → CO2* (1)

This reads “a CO2 molecule absorbs an infrared photon γ and goes to a vibrationally excited state CO2*

CO2* + N2 → CO2 + N2⁺ (2)

This reads “a vibrationally excited CO2 molecule CO2* collides with an N2 molecule and relaxes to a lower vibrational energy state CO2 while the N2 molecule increases its velocity to N2⁺ “. We use a different symbol * and ⁺ for the excited states to differentiate the energy modes – vibrational (*) for CO2 and translational (⁺) for N2 . In other words , there is transfer between vibrational and translational degrees of freedom in the process (2) . This process in non equilibrium conditions is sometimes called thermalization .

The microscopical process (2) is described by time symmetrical equations . All mechanical and electromagnetical interactions are governed by equations invariant under time reversal . This is not true for electroweak interactions but they play no role in the process (2) .

Again in simple words , it means that if the process (2) happens then the time symmetrical process , namely CO2 + N2⁺ → CO2* + N2 , happens too . Indeed this time reversed process where fast (e.g hot) N2 molecules slow down and excite vibrationally CO2 molecules is what makes an N2/CO2 laser work. Therefore the right way to write the process (2) is the following .

CO2* + N2 ↔ CO2 + N2⁺ (3)

Where the use of the double arrow ↔ instad of the simple arrow → is telling us that this process goes in both directions . Now the most important question is “What are the rates of the → and the ← processes ?

The LTE conditions with the energy equipartition law give immediately the answer : “These rates are exactly equal .” This means that for every collision where a vibrationally excited CO2* transfers energy to N2 , there is a collision where N2⁺ transfers the same energy to CO2 and excites it vibrationally . There is no net energy transfer from CO2 to N2 through the vibration-translation interaction .

As we have seen that CO2 cannot transfer energy to N2 through the translation-translation process either , there is no net energy transfer (e.g “heating”) from CO2 to N2 what proves our statement .

This has an interesting corollary for the process (1) , IR absorption by CO2 molecules . We know that in equilibrium the distribution of the vibrational quantum states (e.g how many molecules are in a state with energy Ei) is invariant and depends only on temperature . For example only about 5 % of CO2 molecules are in a vibrationally excited state at room temperatures , 95 % are in the ground state .

Therefore in order to maintain the number of vibrationally excited molecules constant , every time a CO2 molecule absorbs an infrared photon and excites vibrationally , it is necessary that another CO2 molecule relaxes by going to a lower energy state . As we have seen above that this relaxation cannot happen through collisions with N2 because no net energy transfer is permitted , only the process (1) is available . Indeed the right way to write the process (1) is also :

CO2 + γ ↔ CO2* (1)

Where the use of the double arrow shows that the absorption process (→) happens at the same time as the emission process (←) . Because the number of excited molecules in a small volume in LTE must stay constant , follows that both processes emission/absorption must balance . In other words CO2 which absorbs strongly the 15µ IR , will emit strongly almost exactly as much 15 µ radiation as it absorbs . This is independent of the CO2 concentrations and of the intensity of IR radiation .

For those who prefer experimental proofs to theoretical arguments , here is a simple experiment demonstrating the above statements . Let us consider a hollow sphere at 15°C filled with air . You install an IR detector on the surface of the cavity . This is equivalent to the atmosphere during the night . The cavity will emit IR according to a black body law . Some frequencies of this BB radiation will be absorbed by the vibration modes of the CO2 molecules present in the air . What you will observe is :

  • The detector shows that the cavity absorbs the same power on 15µ as it emits
  • The temperature of the air stays at 15°C and more specifically the N2 and O2 do not heat

These observations demonstrate as expected that CO2 emits the same power as it absorbs and that there is no net energy transfer between the vibrational modes of CO2 and the translational modes of N2 and O2 . If you double the CO2 concentration or make the temperature vary , the observations stay identical showing that the conclusions we made are independent of temperatures and CO2 concentrations .

Conclusion and caveats

The main point is that every time you hear or read that “CO2 heats the atmosphere” , that “energy is trapped by CO2” , that “energy is stored by green house gases” and similar statements , you may be sure that this source is not to be trusted for information about radiation questions .

Caveat 1

The statement we proved cannot be interpreted as “CO2 has no impact on the dynamics of the Earth-atmosphere system” . What we have proven is that the CO2 cannot heat the atmosphere in the bulk but the whole system cannot be reduced to the bulk of the atmosphere . Indeed there are 2 interfaces – the void on one side and the surface of the Earth on the other side . Neither the former nor the latter is in LTE and the arguments we used are not valid . The dynamics of the system are governed by the lapse rate which is “anchored” to the ground and whose variations are dependent not only on convection , latent heat changes and conduction but also radiative transfer . The concentrations of CO2 (and H2O) play a role in this dynamics but it is not the purpose of this post to examine these much more complex and not well understood aspects .

Caveat 2

You will sometimes read or hear that “the CO2 has not the time to emit IR because the relaxation time is much longer than the mean time between collisions .” We know now that this conclusion is clearly wrong but looks like common sense if one accepts the premises which are true . Where is the problem ?

Well as the collisions are dominating , the CO2 will indeed often relax by a collision process . But with the same token it will also often excite by a collision process . And both processes will happen with an equal rate in LTE as we have seen . As for the emission , we are talking typically about 10ⁿ molecules with n of the order of 20 . Even if the average emission time is longer than the time between collisions , there is still a huge number of excited molecules who had not the opportunity to relax collisionally and who will emit . Not surprisingly this is also what experience shows .

http://wattsupwiththat.com/2010/08/05/co2-heats-the-atmosphere-a-counter-view/

Global Warming: Climate Gate – Mann’s Hockey Stick Findings Refuted – Irrelevant To Accurate Warming Predictions – Annals of Applied Statistics

From:

Watts Up With That? –  New paper makes a hockey “sticky wicket” of Mann et al 98/99/08

Sticky Wicket – phrase, meaning: “A difficult situation”.

http://wattsupwiththat.com/2010/08/17/breaking-new-paper-makes-a-hockey-sticky-wicket-of-mann-et-al-99/

Now, there’s a new look to the familiar “hockey stick”.

The “infamous Hockey Stick” below:

Multiproxy reconstruction of Northern Hemisphere surface temperature variations over the past millennium (blue), along with 50-year average (black), a measure of the statistical uncertainty associated with the reconstruction (gray), and instrumental surface temperature data for the last 150 years (red), based on the work by Mann et al. (1999). This figure has sometimes been referred to as the hockey stick. Source: IPCC (2001).

McShane and Wyner re-examine and replot the data below …

Backcast from Bayesian Model of Section 5. CRU Northern Hemisphere annual mean land temperature is given by the thin black line and a smoothed version is given by the thick black line. The forecast is given by the thin red line and a smoothed version is given by the thick red line. The model is fit on 1850-1998 AD and backcasts 998-1849 AD. The cyan region indicates uncertainty due to t, the green region indicates uncertainty due to β, and the gray region indicates total uncertainty.

“Not only are the results stunning, but the paper is highly readable, written in a sensible style that most laymen can absorb, even if they don’t understand some of the finer points of bayesian and loess filters, or principal components. Not only that, this paper is a confirmation of McIntyre and McKitrick’s work, with a strong nod to Wegman. I highly recommend reading this and distributing this story widely.”

http://wattsupwiththat.com/2010/08/17/breaking-new-paper-makes-a-hockey-sticky-wicket-of-mann-et-al-99/

The original paper submitted by McShane and Wyner to Annals of Applied Statistics here: A Statistical Analysis of Multiple Temperature Proxies: Are Reconstructions of Surface Temperatures Over the Last 1000 Years Reliable?

EXCERPT:

On the one hand, we conclude unequivocally that the evidence for a ”long-handled” hockey stick (where the shaft of the hockey stick extends to the year 1000 AD) is lacking in the data … Consequently, the long flat handle of the hockey stick is best understood to be a feature of regression and less a reflection of our knowledge of the truth… Climate scientists have greatly underestimated the uncertainty of proxy based reconstructions and hence have been overconfident in their models…  

Global Warming: IPCC Global Warming Model Used To Predict Temp Changes Overstates Warming By 60% – American Meteorological Society

Abstract

The observed increase in global mean surface temperature (GMST) over the industrial era is less than 40% of that expected from observed increases in long-lived greenhouse gases together with the best-estimate equilibrium climate sensitivity given by the 2007 Assessment Report of the Intergovernmental Panel on Climate Change (IPCC). Possible reasons for this warming discrepancy are systematically examined here. The warming discrepancy is found to be due mainly to some combination of two factors: the IPCC best estimate of climate sensitivity being too high and/or the greenhouse gas forcing being partially offset by forcing by increased concentrations of atmospheric aerosols; the increase in global heat content due to thermal disequilibrium accounts for less than 25% of the discrepancy, and cooling by natural temperature variation can account for only about 15%. Current uncertainty in climate sensitivity is shown to preclude determining the amount of future fossil fuel CO2 emissions that would be compatible with any chosen maximum allowable increase in GMST; even the sign of such allowable future emissions is unconstrained. Resolving this situation, by empirical determination of the earth’s climate sensitivity from the historical record over the industrial period or through use of climate models whose accuracy is evaluated by their performance over this period, is shown to require substantial reduction in the uncertainty of aerosol forcing over this period.

Why Hasn’t Earth Warmed as Much as Expected?

 

Stephen E. Schwartz Brookhaven National Laboratory, Upton, New York

Robert J. Charlson University of Washington, Seattle, Washington

Ralph A. Kahn NASA Goddard Space Flight Center, Greenbelt, Maryland

John A. Ogren NOAA/Earth System Research Laboratory, Boulder, Colorado

Henning Rodhe Department of Meteorology, Stockholm University, Stockholm, Sweden

http://journals.ametsoc.org/doi/abs/10.1175/2009JCLI3461.1

The full PDF of the  paper can be viewed here: http://journals.ametsoc.org/doi/pdf/10.1175/2009JCLI3461.1

2009 Obama Administration Honored BP “outstanding safety and pollution prevention performance “

MMS Industry Awards Program

 
2009 Safety Award for Excellence Finalists and Winners

These awards recognize outstanding safety and pollution prevention performance by the offshore oil and gas industry in four categories.

MMS announced the winners at the Offshore Technology Conference luncheon on May 7, 2009, in Houston, Texas.

The finalists and winners for 2009 in each of the 4 categories are listed below:

2009 Safety Award for Excellence Finalists    Production Contractors:

bullet John Whiteford, President, accepting for Baker Energy
bullet Michael Crosby, Vice President, accepting for C&D Production Specialist Company
bullet Hank Danos, President and CEO, accepting for Danos & Curole Marine Contractors *Winner*

    Drilling Contractors:

bullet Larry Dickerson, President and CEO, accepting for Diamond Offshore Drilling Inc.
bullet John Knowlton, General Manager, accepting for ENSCO International Inc.
bullet Tommy Travis, Vice President and Division Manager, accepting for Noble Drilling Corporation *Winner*
bullet Keelan Adamson, Division Manager, accepting for Transocean

    Moderate Activity Operators:

bullet Steve Maley, Operations Manager, accepting for Badger Oil Corporation
bullet Mike Kelly, Vice President, accepting for BHP Billiton Petroleum
bullet Keith Karwile, Vice President, accepting for Hunt Petroleum Corporation
bullet Michael Radabaugh, Vice-President, accepting for Noble Energy, Inc. *Winner*

    High Activity Operators:

  • Darrel Hollek, Vice President, accepting for Anadarko Petroleum Corporation
  • Richard Morrison, VP of GoM SPU Production, accepting for BP Corporation North America, Inc
  • Tony Vaughn, Senior Vice President, Gulf Division, accepting for Devon Energy Production Company
  • Randy Cleveland, U.S. Production Manager, accepting for Exxon Mobil Corporation

http://www.mms.gov/awards/2009SAFEFinalists.htm

Gulf Oil Crisis – Sanctimonious Congressional Hearings – Obama Administration Awarded BP & Transocean 2009 Safety Award For Excellence

To: President Obama & The  U.S. Congress – Please explain this –   

MMS Industry Awards Program

 These awards recognize outstanding safety and pollution prevention performance by the offshore oil and gas industry in four categories.MMS announced the winners at the Offshore Technology Conference luncheon on May 7, 2009, in Houston, Texas.The finalists and winners for 2009 in each of the 4 categories are listed below:2009 Safety Award for Excellence Finalists   

Production Contractors:

  John Whiteford, President, accepting for Baker Energy
  Michael Crosby, Vice President, accepting for C&D Production Specialist Company
  Hank Danos, President and CEO, accepting for Danos & Curole Marine Contractors

    Drilling Contractors:

  Larry Dickerson, President and CEO, accepting for Diamond Offshore Drilling Inc.
  John Knowlton, General Manager, accepting for ENSCO International Inc.
  Tommy Travis, Vice President and Division Manager, accepting for Noble Drilling Corporation
  Keelan Adamson, Division Manager, accepting for Transocean

    Moderate Activity Operators:

  Steve Maley, Operations Manager, accepting for Badger Oil Corporation
  Mike Kelly, Vice President, accepting for BHP Billiton Petroleum
  Keith Karwile, Vice President, accepting for Hunt Petroleum Corporation
  Michael Radabaugh, Vice-President, accepting for Noble Energy, Inc.

    High Activity Operators:

  • Darrel Hollek, Vice President, accepting for Anadarko Petroleum Corporation
  • Richard Morrison, VP of GoM SPU Production, accepting for BP Corporation North America, Inc.
  • Exxon Mobil Corporation Tony Vaughn
  • Randy Cleveland, U.S. Production Manager, accepting for

 http://www.mms.gov/awards/2009SAFEFinalists.htm

The Congress people are so sanctimonious:

Congressman Dingell is asking about “centralizers” and can’t even read his staffers notes. The ‘BIG” controversy here – Haliburton suggested that 21 “centralizers be used and only 6 “centralizers” were used. Who the hell cares? We don’t know if “centralizers had anything to do with the incident yet. They probably had nothing to do with this incident.

Asking about centralizers now is like asking an Airline President if the Hijackers of 911 were given the proper number of frequent flyer miles. The only difference is that we all know what frequent flyer miles are and most people won’t know what the heck “centralizers” are. “Centralizers” are “rings” placed along the outside of “pipe casing” to hold the casing in the center of the “well hole”. They are intended to help create a “uniform sheath of cement outside the pipe casing”. There is no information to suggest that there was anything wrong with the “cement sheath” around the pipe casing. The importance of using 6 instead of 24 “centralizers” – at present, appears to be none, however, he good Congressman can let the innuendo cast a negative light …. I’ve researched this and 1/3 of all oil wells don’t use any “centralizers” at all – centralizers are really a carryover from the 1920’s and the “oil drilling” of a much earlier day when different materials were used in the industry.

This hearing is ridiculous …. DAY 57 and we don’t know why this happened but the Congressman keep asking … so this happened because you are greedy, because you cut corners … Truthfully, the Congressman has no idea why or how this actually happened. Come November we can ask the politicians where the hell they were before it happened and where were you for the first 2 months afterward it happened.

Why didn’t anyone in Congress come to the assistance of Governor Jindal, Governor Perry and Governor Riley when they were screaming for help. How dare these Congress people sit in this silly ass committee meeting asking their politically motivated questions while the Jones Act is still preventing thousands of skimmer vessels from reaching our coast where they could provide assistance, waiving the Jones Act so we can get thousands of booms and additional assistance from dredging vessels to build more berms ……….

Oh My Gosh – A Congressperson with a memo saying “it was a nightmare well”.

How damning! Say, I can’t imagine that I am the only one to have used the term “nightmare” without it being a “Federal Offense”. When my kids were young, they could be “nightmares”, however, I never meant to imply I thought that my kids would become serial killers. Gee, some nights the drive home is a “nightmare”. As I’ve been single for some time now, I’ve learned that returning to the dating scene can be a “real nightmare”. On any given morning my hair can be “a  nightmare” too. I wonder, are there any congress people who understand the concept of a “bad hair day”. Gee I hope I don’t have to testify before Congress.

Now a Congress person is onto “cement bond logs”! Oh my gosh! – Lets reserve judgment – there is no evidence of improper cement or that improper cementing caused this incident. This may be significant or it may not – I’ll reserve judgment until I know if there were any irregularities in the cement and if irregularities in the cement played a role in this event.

Now there is a Congressman pointing to a highlighted memo, which states, “which will take 10 hours to install and I don’t like that”. I am deeply troubled that a member of Congress would take this effort to misrepresent the contents of a memo. The “upset” refers to a belief that a “contractor” was “overbilling” BP for services rendered, not that BP was trying to cut costs at the expense of safety. Anyone who has had a brake job done on their auto will understand this. When you entrust your vehicle to a “service mechanic” to have your brakes overhauled, you might resent the cost, however, you are willing to pay the prevailing rate in anticipation of having a “proper” job done. If the prevailing “rate” for the brake job includes “5 hours of labor” to complete the job, you expect the invoice to reflect as much. If, however, your mechanic submits an invoice for twice the number of hours, or “10 hours of labor” for a 5 hour job – you had better never relay an email that says “10 hours and I don’t like that”.        

Unseemly and sanctimonious.

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