As you may have seen at the end of my last post, I received an objection to the existence of a greenhouse effect on the grounds that it violated the thermodynamics of heat transfer, and if you read what it says it is essentially focused on heat conduction. The reason I am bothering with this post is that it is an opportunity to consider how theories and explanations should be formed. We start by noting that mathematics does not determine what happens; it calculates what happens provided the background premises are correct.
The objection mentioned convection as a complicating feature. Actually, the transfer of heat in the lower atmosphere is largely dependent on the evaporation and condensation of water, and wind transferring the heat from one place to another, and it is these, and ocean currents, that are the problems for the ice caps. Further, as I shall show, heat conduction cannot be relevant to the major cooling of the upper atmosphere. But first, let me show you how complicated heat conduction is. The correct equation for one-dimensional heat conduction is represented by a partial differential equation of the Laplace type, (which I would quote if I knew how to get such an equation into this limited htm formatting) and the simplest form only works as written when the medium is homogenous. Since the atmosphere thins out with height, this clearly needs modification, and for those who know anything about partial differential equations, they become a nightmare once the system becomes anything but absolutely simple. Such equations also apply to convection and evaporative transfer, once corrected for the nightmare of non-homogeneity and motion in three dimensions. Good luck with that!
This form of heat transfer is irrelevant to the so-called greenhouse effect. To show why, I start by considering what heat is, and that is random kinetic energy. The molecules are bouncing around, colliding with each other, and the collisions are elastic, which means energy is conserved, as is momentum. Most of the collisions are glancing, and that means from momentum conservation that we get a range of velocities distributed about an “average”. Heat is transferred because fast moving molecules collide with slower ones, and speed them up. The objection noted heat does not flow from cold to hot spontaneously. That is true because momentum is conserved in collisions. A molecule does not speed up when hit by a slower molecule. That is why that equation has heat going only in one way.
Now, suppose with this mechanism, we get to the top of the atmosphere. What happens then? No more heat can be transferred because there are no molecules to collide with in space. If heat pours in, and nothing goes out, eventually we become infinitely hot. Obviously that does not happen, and the reason becomes obvious when we ask how the heat gets in in the first place. The heat from the sun comes from the effects of solar radiation. Something like 1.36 kW/m^2 comes in on a surface in space at right angles to the line from the sun, but the average is much less on the surface of earth as the angle is at best normal only at noon, and if the sun is overhead. About a quarter of that is directly reflected to space, and that may increase if the cloud cover increases. The important point here is that light is not heat. When it is absorbed, it will direct an electronic transition, but that energy will eventually decay into heat. Initially, however, the material goes to an excited state, but its temperature remains constant, because the energy has not been randomised. Now we see that if energy comes in as radiation, it follows to get an equilibrium, equivalent energy must go out, and as radiation, not heat, because that is the only way it can get out in a vacuum.
The ground continuously sends radiation (mainly infrared) upwards and the intensity is proportional to the fourth power of the temperature. The average temperature is thus determined through radiant energy in equals radiant out. The radiance for a given material, which is described as a grey body radiator, is also dependent on its nature. The radiation occurs because any change of dipole moment leads to electromagnetic radiation, but the dipoles must change between quantised energy states. What that means is they come from motion that can be described in one way or another as a wave, and the waves change to longer wavelengths when they radiate. The reason the waves representing ground states switch to shorter wavelengths is that the heat energy from collisions can excite them, similar in a way to when you pluck a guitar string. Thus the body cools by heat exciting some vibratory states, which collapse by radiation leaving them. (This is similar to the guitar string losing energy by emitting sound, except that the guitar string emits continuous decaying sound; the quantised state lets it go all at once as one photon.)
Such changes are reversible; if the wave has collapsed to a longer wavelength when energy is radiated away, then if a photon of the same frequency is returned, that excites the state. That slows cooling because the next photon emitted from the ground did not need heat to excite it, and hence that same heat remains. The reason there is back radiation is that certain frequencies of infrared radiation leaving the ground get absorbed by molecules in the atmosphere when their molecular vibrational or rotational excited states have a different electric moment from the ground state. Carbon dioxide has two such vibrational states that absorb mildly, and one that does not. Water is a much stronger absorber, and methane has more states available to it. Agriculture offers N2O, which is bad because it is harder to remove than carbon dioxide, and the worst are chlorocarbons and fluorocarbons, because the vibrations have stronger dipole moment changes. Each of these different materials has vibrations at different frequencies, which make them even more problematical as radiation at more frequencies are slowed in their escape to space. The excited states decay and emit photons in random directions, hence only about half of that continues on it way to space, the rest returning to the ground. Of that that goes upwards, it will be absorbed by more molecules, and the same will happen, and of course some coming back from up there with be absorbed at a lower level and half of that will go back up. In detail, there is some rather difficult calculus, but the effect could be described as a field of oscillators.
So the take-away message is the physics are well understood, the effect of the greenhouse gases is it slows the cooling process, so the ground stays warmer than it would if they were not there. Now the good thing about a theory is that it should predict things. Here we can make a prediction. In winter, in the absence of wind, the night should be warmer if there is cloud cover, because water is a strong greenhouse material. Go outside one evening and see.