Thursday, December 6, 2012

Carbon dioxide: a radiation absorber as well as emitter

The most crucial issue in current AGW debate is of course the greenhouse warming effect of CO2 gas.  Laboratory and satellite spectra show CO2 gas has three main absorption bands at wavelengths of 2.7, 4.3 and 15 µm, respectively.  The 15 µm absorption band absorbs significant amount of thermal radiation emitted from the earth ground surface.  We all know that absorption of radiation waves leads to warming up of an object.  Water vapor and CO2 molecules absorb, N2 and O2 do not.  It thus appears logical and straightforward to label water vapor and CO2 greenhouse gases that warm up the atmosphere.  While the warming effect of absorption has been well addressed, the cooling effect of emission for CO2 has not. 

There are two simple physical laws: one is the absorption law describing how much
energy, I, an object absorbs; the other is the Stefan-Boltzmann law expressing how much energy, J, the same object with surface temperature, T, emits per unit area and unit time.

(1)          I = aI0                                           
(2)          J = ε σT4         
where, α and ε are surface absorptivity and emissivity of the object, σ is the Stefan-Boltzmann constant equal to 5.670373 x 10-8 (W/m2K4), and I0 represents the radiation source.  I is the energy in, and J is the energy out of the object.  If I > J, the object gains heat resulting in warming; if I < J, the object loses heat leading to cooling.  When I = J, the object reaches its radiative equilibrium.  For a given radiation source, I0, there is a corresponding radiative equilibrium temperature, T, for an object.

Absorptivity and emissivity are the intrinsic material properties of an object.  According to the Kirchhoff’s law, an object with absorptivity α = 0 (or α = 1), emissivity of the object must be equal to ε = 0 (or ε = 1).  Visa verse, if α ¹ 0 (or α ¹ 1), there must be ε ¹ 0 (or ε ¹ 1).  Put it in words: an object that absorbs emits, or an object that emits absorbs.  Indeed, absorption and emission are two inseparable equivalent identities of the same physical essence.

An important message from Eqs (1) and (2) is that absorption of heat energy relies on and only on EXTERNAL factor - radiation source, I0, whilst emission is determined by and only by INTERNAL factor - surface temperature, T, of the object. 

Bearing these concepts in mind, we are now ready for a thought experiment:

1) Cover the Earth with literally white cloth so that there is no radiation wave for CO2 molecules to absorb.  The temperature of CO2 molecules shall approach 0 K (-273.15°C).  This is because:
If I0 = 0, there must be I = 0 according to Eq. (1);
But J > 0 because T > 0 according to Eq. (2); therefore CO2 keeps losing heat and dropping its temperature until T = 0.

Figure 1.  What will be the CO2 temperature if the Earth ground surface is covered with literally white cloth.

2) Remove the white cloth to expose CO2 molecules to the earth ground surface radiation, I0, which will raise the temperature of CO2 molecules at lowest altitude from -273.15°C to -78°C (math omitted here) because I0 is not strong enough.  CO2 temperatures at higher altitude would be even lower because of damped intensities of the radiation waves. 

3) Now take heat transfer by molecular collision into account.  One may argue that CO2 will not be frozen to 0 K in 1) or -78°C in 2) because of constant heat transfer due to molecular collisions with neighboring N2 and O2 molecules.  In fact, CO2 will be only slightly cooler or even in the practically same temperature as N2 and O2 depending on how fast heat transfer by molecular collisions as compared with radiative emission. 

When CO2 is warmer than its radiative equilibrium temperature, it emits more heat energy than that it absorbs.  In other words, CO2 emits not only the heat energy gained from absorption, but also the heat energy gained from N2 and O2 by molecular collisions.  A heat transfer route is shown below:
N2 and O2 do not emit heat but pass heat to CO2 by molecular collisions;
CO2 dissipates heat by thermal radiation to space.

With this alternative interpretation, we have a better explanation of the temperature-altitude profile in the thermosphere.  A CO2 molecule is heavier than N2 and O2 due to higher molecular weight; so is water vapour but due to aggregation of molecular clusters.  Neither water vapour nor CO2 reaches the high altitude thermosphere.  Even if there are still residual greenhouse gas molecules in the thermosphere, there would be no effective heat transfer by molecular collisions any more because of extremely low air pressure.  The temperature in the thermosphere is well above 100°C, increases steadily and exceeds 1000°K with increasing altitude.  Without so-called greenhouse gases in the thermosphere, N2 and O2 have no mechanism for heat dissipation.

As long as T > 0, CO2 emits, regardless whether its heat is gained by absorption of radiation or molecular collisions.  The downward radiation waves emitted by CO2 are absorbed by the earth’s ground surface, resulting in a small temperature increase so that the outgoing radiation blocked by CO2 goes to space via other wavelength bands.  CO2 functions as a half-mirror hanging on the sky to the earth’s ground surface.  This theme, however, will be addressed in a separate article. 

* * *

It is true that absorption of radiation waves leads to an object warmer than otherwise.  The key question is: what is the temperature of the GHGs without absorption of radiation waves?  It shall not be difficult to find that we have counted, without knowing, twice or more of the warming effect of CO2 absorption.  This perhaps is the most important underlying conceptual issue that must be resolved to advance climate science. 
(Dr Jinan Cao)

1 comment:

  1. Sir, you state above:
    "The 15 µm absorption band absorbs significant amount of thermal radiation emitted from the earth ground surface."

    I have a great problem understanding this. I have no science background and must read up on the subject via the internet. What I have learnt is that each CO2 molecule is a unique entity in the atmosphere and will acquire, by conduction, the thermal energy of the local atmosphere. Since most of the atmosphere is above the peak radiation temperature of the 15 micron radiation band, CO2 molecules will be TOO WARM to absorb that radiation. CO2 WILL be emitting 15 micron radiation, and it is just possible that a 15 micron photon could be absorbed, but this is not a 'warming' of the molecule if it has just emitted a 15 micron photon. Energy in = energy out = no change.

    I see this same problem with the surface. If the surface is emitting proportional to a temperature of 15C (288K), it will be emitting strongly in the 15 micron band. Again, a molecule on the surface could absorb a 15 micron photon immediately after emitting a similar photon, but the energy level in that molecule will not have changed. Radiation into and out of a solid surface is limited to a half sphere and energy below the surface molecules will be HIGHER than the surface molecule so NO energy is passed into the solid by that 15 micron photon. Thus the surface,already radiating at 15 microns, CANNOT absorb other 15 micron photons or increase its energy level by such events.

    My apologies if this is a bit rambling, I was going to discuss kinetic and internal vibrational energy levels but that would have taken much too long. Basically, I believe CO2 is entirely a cooling agent in the atmosphere (when the sun is not shining, another story effecting the 2.7 and 4.3 micron bands) and it seems I am completely wrong.

    Do you have a link that will help me understand your above statement?
    Richard Henderson
    Wales, UK.