There is absolutely no way that so-called greenhouse gas emissions can cause warming or generate heat.
It is a fiction that is spread by such august bodies as the IPCC, and promulgated by news channels like the BBC and CNN and is even taught to unsuspecting children in schools.
Far from greenhouse gas emissions generating heat, precisely the opposite is true.
What is the principal greenhouse gas? It is water vapor, which constitutes 90% of all greenhouse gases.
How is it generated? Answer: As the infrared radiation from the Sun strikes the surface of the oceans, liquid saltwater is turned into a gas, water vapor, by evaporation. Evaporation is cooling, not warming – every simpleton knows that.
This gas, this water vapor, then rises up by convection and condenses into clouds. Clouds are also cooling as they scatter the incoming solar infrared radiation. Then rain, snow or sleet falls from these clouds.
What is a common observation, most remarkably in summer? The temperature drops, as the atmosphere cools rapidly.
So here we see that the principle greenhouse gas leads to cooling all around. It is hardly surprising that we do not hear calls for emissions of water vapor to be culled.
What is even more remarkable is that the saltwater of the oceans is turned into freshwater to fill our reservoirs, lakes, rivers, and streams, which in turn find their way out to the sea.
This is the miracle of the water cycle – truly the miracle of water into wine, of saltwater into fresh.
The transport of perishable foodstuffs depends upon refrigeration, whether by lorry, by aircraft or most importantly by container ships at sea.
What is the principal refrigerant? It is carbon dioxide, that most maligned of all the greenhouse gases. Far from warming the planet as we are supposed to believe, that clear, colorless gas is not only a coolant but also a fire retardant and a refrigerant.
Ah! say some physicists, sagely nodding their heads, but carbon dioxide absorbs infrared. In layman’s language that means it ‘warms up’.
But then everything under the Sun absorbs infrared and warms up except three things. The two principle gases of the atmosphere, nitrogen, and oxygen, are transparent to infrared, whether incoming or outgoing, so they do not warm from the infrared.
What is the third item, if one can call it an item? It is a vacuum, it is nothing, one cannot warm ‘anything’ since there is nothing to get warm.
It is absolute folly to dismiss the water cycle, it is even greater folly to forget or misunderstand the carbon cycle.
Carbon dioxide is food for green plants on land and sea. We cannot live without oxygen and green plants and ocean plankton need carbon dioxide as food, from which oxygen is produced as a by-product.
To treat carbon dioxide as a pollutant is one of the biggest mistakes mankind could make and has made these past 30 or more years.
Indeed, all the bad air in cities could be solved by encouraging green spaces, by the planting of more trees. We all need to be green, truly green, not hysterical and politically green, which is another animal altogether.
Great Nature already has the systems in place to produce freshwater from seawater, the water cycle. Great Nature already has the systems in place to produce fresh air from foul air – the carbon cycle.
So we do not need to “save the planet” since the planet knows better than any climate charlatan how to save itself.
Anthony,
Thank you for all of this…I enjoyed it…helped me sleep. But it brings back a bunch of college classes. I was reading an article here and there lately that had a line in it, maybe not verbatim, but that 97% of the Co2 in the atmosphere is naturally occurring, the other 3% is human causal. Do any of those ring a bell or is there a definitive proclamation on this? I’m sure it was a cross-linked article after clicking around…cannot find it…maddening.
The Function of Man Made Climate Change lining the pockets of Trail Lawyers,Al Gore,Leonardo DiCaprio,Laurie David and the various Eco- Groups
The NASA claim that the surface emits 398.2 W/m2 includes only 40.1 W/m2 emitted directly to space. The remaining 358.1 W/m2 that NASA claims is absorbed by the atmosphere implies that the atmosphere is at a temperature of 0 K! This could not be more wrong. On the other hand, a back radiation of 340.3 W/m2 implies that the effective temperature of the radiating atmosphere to the surface is 278.3 K. In the U.S. Standard Atmosphere of 1976, this is an altitude of about 1500 m. So the atmosphere absorbs radiation as though it were cold space and it emits radiation back to the surface as though it has a temperature of 278.3 K. The implied mean free paths for the longwave infra-red radiation which can be absorbed and emitted by infra-red active or greenhouse gases are completely incompatible!
What is more, the atmosphere is generally cooler than the surface, so it radiates only to still cooler parts of the atmosphere or to space. Cooler parts of the atmosphere are usually at higher altitudes, so there is a strong preference for radiated energy from the atmosphere to be transported to higher altitudes. Such transport to lower altitudes as does occur requires a temperature inversion in air layers.
In any case, it is very clear that the net effect of surface radiation absorbed by the atmosphere, back-radiation, any errors in the solar radiation absorbed by the surface, or power lost as thermals, or power used to evaporate water, or the neglect of other heating or cooling mechanisms, amounts to a net cooling effect of 94.9 W/m2 . This does not leave much room for a warming of the surface attributable to back-radiation from greenhouse gases!
In fact, we need more cooling effects to explain the surface temperature being as low as it is. A big part of that is surface longwave radiation absorbed by the atmosphere, but I believe another part of that is other cooling mechanisms due to infra-red active gases (greenhouse gases) and underestimation of the cooling by water evaporation and thermals.
Infra-red active gases (water vapor, carbon dioxide) have a higher heat capacity than do nitrogen and oxygen molecules. Consequently, they can remove more energy from the surface upon collisions with it and add to the heat loss of the surface due to rising thermals. In addition, they make minor contributions to the transfer of heat upward through the atmosphere by radiating infra-red from warmer air layers to the usually cooler air layers just above them. Since that transport of energy is at the speed of light, this effect transfers energy faster than a rising thermal and acts as a cooling mechanism.
The advocates of catastrophic man-made global warming pose the problem of our average surface temperature as one of explaining why it is as high as it is. The real problem is explaining why it is as low as it is. This is the sad state of NASA and generally of the entire set of alarmist man-made global warming advocates understanding of the climate. For this poor service, NASA now spends more than half of its budget on climate change, with the emphasis heavily on catastrophic man-made global warming. ~ Charles R. Anderson, Ph.D., Materials Physicist.
If I may, do nitrogen and oxygen “absorb” more heat from exposure to Infrared Radiation (IR) than carbon dioxide and water?
Two-atom molecules like nitrogen and oxygen are bound together too tightly to be capable of vibrating when exposed to IR and by doing so absorb that energy, so nitrogen and oxygen, the main gasses in the atmosphere that together make up over 99% of the atmosphere, ABSORB virtually NO IR or heat up due to that IR exposure.
Three atom molecules like carbon dioxide and water ARE able to vibrate and absorb this radiant heat energy in the form of kinetic energy and then pass that kinetic energy to other adjacent molecules of greenhouse gasses, but as the article explains, …”the principal greenhouse gas is WATER VAPOR, which constitutes 90% of all greenhouse gases. As the infrared radiation from the Sun strikes the surface of the oceans, liquid saltwater is turned into a gas, water vapor, by evaporation. Evaporation is cooling, not warming – every simpleton knows that.”
The Climate Change movement fixates on the <1% of the atmosphere that can be heated by radiant transfer instead of the 99% and more that is heated by direct contact with the earth’s surface and then by convection, thus, every molecule of atmospheric gas gets heated mainly by conductive transfer.
Independent British climate researcher, Geraint Hughes, has developed a controlled experiment to prove CO2 is innocent of climate change.
For those who haven’t yet seen Geraint’s impressive initial experiment, which successfully demonstrated that CO2 does not induce the non-existent “back radiant heating,” take a few minutes to view the Youtube video here:
Below are two photographs demonstrating the effects of an exposed light filament where exposed to a vacuum (left) and in a pure CO2 environment (right). As can be seen, the filament exposed only to CO2 is dimmer and cooler, showing that CO2 causes COOLING, not heating, of the air around it.
https://i0.wp.com/principia-scientific.org/wp-content/uploads/2019/08/bulb-2.jpg?resize=550%2C345&ssl=1
Okay to quibble about the specific properties of the atmospheric gases, but the point is well made here that water vaport is the greenhouse gas that keeps the planet habitable and carbon dioxide is the trace gas which assures that life can have food.
Can’t quite agree about nitrogen and oxygen being transparent and therefore unable to absorb infrared. Both gases absorb heat (which is infrared). We get cool and warm winds. Glass is transparent but infrared passes through it. The greenhouses get hot because a lot of the infrared cannot get out as it is refracted by the glass. Only infrared incident at an angle 90 degrees or close, escapes
Glass passes visible light but is opaque to IR… IR does not generally pass through glass unless it’s specifically manufactured to do so.
N2 and O2 are homonuclear diatomic molecules with no net magnetic dipole, therefore they are unable to effectively absorb (or emit) IR radiation. Even if they could absorb IR, IR photons do not carry sufficient momentum to cause translational mode energy increase, that energy flows to rotational mode quantum states and vibrational mode quantum states.
Think about it this way… we all know the air warms up during the daytime. Conduction of energy when air contacts the planet’s surface is the major reason air warms up.
Yet the major constituents of the atmosphere (N2 and O2) are homonuclear diatomics and thus cannot radiate energy to cool down. They constitute 99% of the atmosphere. How does that 99% cool down?
The only way our planet can shed energy is via radiative emission to space.
Convection moves energy around in the atmosphere, but it cannot shed energy to space. Conduction depends upon thermal contact with other matter and since space is essentially a vacuum, conduction cannot shed energy to space… this leaves only radiative emission.
But N2 and O2 cannot radiatively emit because, being homonuclear diatomic molecules, they have no net magnetic dipole.
Thus, common sense dictates that the thermal energy of the 99% of the atmosphere which cannot radiatively emit must be transferred to the so-called ‘greenhouse gases’ (CO2 being a lesser contributor in the lower atmosphere and the largest contributor in the upper atmosphere, water vapor being the main contributor in the lower atmosphere) which can radiatively emit and thus shed that energy to space.
So, far from being ‘greenhouse gases’ which ‘trap heat’ in the atmosphere, those radiative gases actually shed energy from the atmosphere to space. They are coolants.
The chance of any N2 or O2 molecule colliding with water vapor is ~3% on average in the troposphere, and for CO2 it’s only ~0.041%. Logic dictates that as atmospheric concentration of CO2 increases, the likelihood of N2 or O2 colliding with it also increases, and thus increases the chance that N2 or O2 can transfer its translational and / or vibrational mode energy to the vibrational mode energy of CO2, which can then shed that energy to space via radiative emission.
Here’s what we need to hit the climate alarmists with when they start bleating that CO2 is going to cause the planet to catastrophically warm.
The climate scientists, the UN IPCC and various US government-funded agencies claim that CO2 will cause catastrophic global warming, and the only remedy is to radically alter our economic system and our way of life.
They claim this occurs via the following mechanism: CO2 absorbs 14.98352 µm radiation, becomes vibrationally excited in the CO2{v21(1)} vibrational mode quantum state, then collides with another atmospheric molecule, whereupon that vibrational mode energy flows to translational mode energy of the other atmospheric molecule. Since we sense translational mode (kinetic) energy as temperature, this process purportedly raises atmospheric temperature. The climate catastrophists claim that CO2 is capable of causing catastrophic warming.
But what if they’re only telling the public half the story as means of pushing a narrative to achieve an end they otherwise would be unable to achieve? It turns out, that is exactly what they’ve done… and I can prove it.
I’m not talking about the “glaciers are growing”, “it’s cold outside”, “take a look at this chart” subjective type of ‘proof’ usually proffered in attempting to counter the climate alarmist claims… I’m talking about diving right down to the quantum level and utilizing particle physics to prove that the mechanism upon which the climate catastrophists hinge their entire multi-billion dollar per year scam does not and cannot occur… if an energetic process (catastrophic atmospheric warming) cannot occur at the quantum level, it most certainly cannot occur macroscopically.
The half of the story the public has been told, that CO2 causes warming, is a narrow and intentionally misconstrued truth hiding two much wider lies.
The truth is that CO2 can indeed cause warming via the mechanism described above… up to ~288 K and at low altitude. Above ~288 K and at low altitude, CO2 is a net atmospheric coolant. Above the tropopause, CO2 is a net atmospheric coolant at any temperature because collisional processes happen less often there due to low atmospheric density, so radiative processes dominate.
One wider lie that’s hiding behind that narrow and misconstrued truth is that the world must de-industrialize, get rid of capitalism and change our way of life… the climate change issue has been hijacked by socialists using it as a vehicle to push for a world-wide totalitarian government. They’ve openly admitted this.
Another wider lie that’s hiding behind that narrow and misconstrued truth is that we must richly fund the climate ‘scientists’ who are pushing the scam, and we must move to so-called ‘green’ power… hundreds of billions of dollars per year are being flushed down the Catastrophic Anthropogenic Global Warming (CAGW) toilet based upon this lie.
The full story: In an atmosphere sufficiently dense such that collisional energy transfer can significantly occur, all radiative molecules play the part of atmospheric coolants at and above the temperature at which the combined translational mode energy of two colliding molecules exceeds the lowest vibrational mode quantum state energy of the radiative molecule. Below this temperature, they act to warm the atmosphere via the mechanism the climate alarmists claim happens all the time, but if that warming mechanism occurs below the tropopause, the net result is an increase of Convective Available Potential Energy (CAPE), which increases convection, which is a net cooling process.
In other words: Below ~288 K, CO2 does indeed cause warming via the mechanism described above. But above ~288 K, the translational mode energy of two colliding molecules is sufficient to begin significantly vibrationally exciting CO2, increasing the time duration during which CO2 is vibrationally excited and therefore the probability that the CO2 will radiatively emit. The conversion of translational mode to vibrational mode energy is, by definition, a cooling process. The emission of the resultant radiation to space is, by definition, a cooling process.
As CO2 concentration increases, the population of CO2 molecules able to become vibrationally excited increases, thus increasing the number of CO2 molecules able to radiatively emit, thus increasing photon flux, thus increasing energy emission to space.
As temperature increases, the population of vibrationally excited CO2 molecules increases, thus increasing the number of CO2 molecules able to radiatively emit, thus increasing photon flux, thus increasing energy emission to space.
This is why I state in the data below that CO2 becomes a net atmospheric coolant at approximately 288 K… the exact solution is near to impossible to calculate, given the nearly infinite number of angles of molecular collision, the equilibrium distribution of molecular speed, and the fact that atmospheric molecular composition varies spatially and temporally with altitude and water vapor concentration variations.
The data below utilizes particle physics first principles to nullify the CAGW hypothesis at the quantum level, leaving the climate catastrophists with absolutely no wiggle room… no matter how many pictures of sick polar bears they put up, no matter how many flawed computer models they cite, no matter how many graphs with cherry-picked date ranges and manipulated data they present… if a process (catastrophic atmospheric warming) cannot occur at the quantum level, it most certainly cannot occur macroscopically.
The data below destroys the underlying premise of CAGW (Catastrophic Anthropogenic Global Warming), and thereby destroys the underpinnings of their multi-billion dollar per year scam.
The data below peals the death knell for CAGW. You’re welcome.
In dealing with solely translational mode energy and neglecting vibrational mode and rotational mode energy for the moment, the Equipartition Theorem states that molecules in thermal equilibrium have the same average energy associated with each of three independent degrees of freedom, equal to:
3/2 kT per molecule, where k = Boltzmann’s Constant
3/2 RT per mole, where R = gas constant
Thus the Equipartition Theorem equation:
KE_avg = 3/2 kT
serves well in the definition of kinetic energy (which we sense as temperature).
It does not do as well at defining the specific heat of polyatomic gases, simply because it does not take into account the increase of internal molecular energy via vibrational mode and rotational mode excitation. Energy imparted to the molecue via either photon absorption or collisional energetic exchange can excite those vibrational mode or rotational mode quantum states, increasing the total molecular energy E_tot, but not affecting temperature at all. Since we’re only looking at translational mode energy at the moment (and not specific heat); and internal molecular energy is not accounted for in measuring temperature (which is a measure of translational mode energy only), this long-known and well-proven equation fits our purpose.
Our thermometers are an instantaneous average of molecular kinetic energy. If they could respond fast enough to register every single molecule impinging upon the thermometer probe, we’d see temperature wildly jumping up and down, with a distribution equal to the Maxwell-Boltzmann Speed Distribution Function. In other words, at any given measured temperature, some molecules will be moving faster (higher temperature) and some slower (lower temperature), with an equilibrium distribution (Planckian) curve.
The Equipartition Theorem states that in Local Thermodynamic Equilibrium conditions all molecules, regardless of molecular weight, will have the same kinetic energy and therefore the same temperature. For higher atomic mass molecules, they’ll be moving slower; for lower atomic mass molecules, they’ll be moving faster; but their kinetic (translational mode) energy will all be the same at the same temperature.
Therefore, utilizing the equation above, at a temperature of 288 K, the average thermal energy of a molecule is 0.03722663337910374 eV. Again, this is the average… there is actually an equilibrium distribution of energies and thereby molecular speeds.
For CO2, with a molecular weight of 44.0095 amu, at 288 K the molecule will have:
Most Probable Speed {(2kT/m)^1/2} = 329.8802984961799 m/s
Mean Speed {(8kT/pm)^1/2} = 372.23005645833854 m/s
Effective (rms) Speed {(3kT/m)^1/2} = 404.0195258297897 m/s
For N2, with a molecular weight of 28.014 amu, at 288 K the molecule will have:
Most Probable Speed {(2kT/m)^1/2} = 413.46812435139907 m/s
Mean Speed {(8kT/pm)^1/2} = 466.5488177761755 m/s
Effective (rms) speed {(3kT/m)^1/2} = 506.3929647832758 m/s
But if those molecules are at the exact same temperature, they’ll have exactly the same translational mode energy.
This energy at exactly 288 K is equivalent to the energy of a 33.3050 µm photon.
If two molecules collide, their translational energy is cumulative, dependent upon angle of collision. In mathematically describing the kinematics of a binary molecular collision, one can consider the relative motion of the molecules in a spatially-fixed 6N-dimensional phase space frame of reference (lab frame) which consists of 3N spatial components and 3N velocity components, to avoid the vagaries of interpreting energy transfer considered from other reference frames.
Simplistically, for a head-on collision between only two molecules, this is described by the equation:
KE = (1/2 mv^2) [molecule 1] + (1/2 mv^2) [molecule 2]
The Maxwell-Boltzmann Speed Distribution Function, taking into account 3N spatial components and 3N velocity components:
https://i.imgur.com/0ZVflnN.png
You may surmise, “But at 288 K, the combined kinetic energy of two molecules in a head-on collision isn’t sufficient to excite CO2’s lowest vibrational mode quantum state! It requires the energy equivalent to a 14.98352 µm photon to vibrationally excite CO2, and the combined translational mode energy of two molecules colliding head-on at 288 K is only equivalent to the energy of a 16.6525 µm photon!”
True, but you’ve not taken into account some mitigating factors…
1) We’re not talking about just translational mode energy, we’re talking about E_tot, the total molecular energy, including translational mode, rotational mode, vibrational mode and electronic mode. At 288 K, nearly all CO2 molecules will be excited in the rotational mode quantum state, increasing CO2’s E_tot. The higher a molecule’s E_tot, the less total energy necessary to excite any of its other modes.
2) Further, the Boltzmann Factor shows that at 288 K, ~10.26671% of N2 molecules are in the N2{v1(1)} vibrationally excited state.
N2{v1(1)} (stretch) mode at 2345 cm-1 (4.26439 µm), correcting for anharmonicity, centrifugal distortion and vibro-rotational interaction
1 cm-1 = 11.9624 J mol-1
2345 cm-1 = 2345 * 11.9624 / 1000 = 28.051828 kJ mol-1
The Boltzmann factor at 288 K has the value 1 / (2805.1828 / 288R) = 0.10266710 which means that 10.26671% of N2 molecules are in the N2{v1(1)} vibrationally excited state.
Given that CO2 constitutes 0.041% of the atmosphere (410 ppm), and N2 constitutes 78.08% of the atmosphere (780800 ppm), this means that 80162.3936 ppm of N2 is vibrationally excited via t-v (translational-vibrational) processes at 288 K. You’ll note this equates to 195 times more vibrationally excited N2 molecules than all CO2 molecules (vibrationally excited or not).
Thus energy will flow from the higher-energy (and higher concentration) N2{v1(1)} molecules to vibrationally ground-state CO2{v20(0)} molecules, exciting the CO2 to its {v3(1)} vibrational mode, whereupon it can drop to its {v1(1)} or {v20(2)} vibrational modes by emission of 9.4 µm or 10.4 µm radiation (wavelength dependent upon isotopic composition of the CO2 molecules).
The energy flow from translational modes of molecules to N2 vibrational mode quantum states, then to CO2 vibrational mode quantum states, then to radiation constitutes a cooling process.
3) The Maxwell-Boltzmann Speed Distribution Function gives a wide translational mode equilibrium distribution. In order for CO2 to be vibrationally excited, it requires the energy equivalent to a 14.98352 µm photon, equating to a CO2 speed of 425.92936688660114 m/s or an N2 speed of 533.8549080851558 m/s.
Remember I wrote above:
For CO2, with a molecular weight of 44.0095 amu, at 288 K the molecule will have:
Most Probable Speed {(2kT/m)^1/2} = 329.8802984961799 m/s
Mean Speed {(8kT/pm)^1/2} = 372.23005645833854 m/s
Effective (rms) Speed {(3kT/m)^1/2} = 404.0195258297897 m/s
For N2, with a molecular weight of 28.014 amu, at 288 K the molecule will have:
Most Probable Speed {(2kT/m)^1/2} = 413.46812435139907 m/s
Mean Speed {(8kT/pm)^1/2} = 466.5488177761755 m/s
Effective (rms) speed {(3kT/m)^1/2} = 506.3929647832758 m/s
For CO2, the Boltzmann Factor probability of one of its molecules being at a speed of 425.92936688660114 m/s; and for N2, the Boltzmann Factor probability of one of its molecules being at a speed of 533.8549080851558 m/s is 0.8461 at 288 K. In other words, for every 100 molecules which are at the Most Probable Speed, another ~84 molecules will be at the speed necessary to vibrationally excite CO2.
Thus at ~288 K and higher temperature, the translational mode energy of atmospheric molecules begins to significantly vibrationally excite CO2, increasing the time duration during which CO2 is vibrationally excited and therefore the probability that the CO2 will radiatively emit. The conversion of translational mode to vibrational mode energy is, by definition, a cooling process. The emission of the resultant radiation to space is, by definition, a cooling process.
As CO2 concentration increases, the population of CO2 molecules able to become vibrationally excited increases, thus increasing the number of CO2 molecules able to radiatively emit, thus increasing photon flux, thus increasing energy emission to space.
As temperature increases, the population of vibrationally excited CO2 molecules increases, thus increasing the number of CO2 molecules able to radiatively emit, thus increasing photon flux, thus increasing energy emission to space.
This is why I state that CO2 becomes a net atmospheric coolant at approximately 288 K… the exact solution is near to impossible to calculate, given the nearly infinite number of angles of molecular collision, the equilibrium distribution of molecular speed, and the fact that atmospheric molecular composition varies spatially and temporally with altitude and water vapor concentration variations.
https://i.imgur.com/v8adCi2.png
Particle physics first principles disprove the CAGW hypothesis. Catastrophic Anthropogenic Global Warming is a physical impossibility.
In an atmosphere sufficiently dense such that collisional energy transfer can significantly occur, all radiative molecules play the part of atmospheric coolants at and above the temperature at which the combined translational mode energy of two colliding molecules exceeds the lowest vibrational mode quantum state energy of the radiative molecule. Below this temperature, they act to warm the atmosphere via the mechanism the climate alarmists claim happens all the time, but if that warming mechanism occurs below the tropopause, the net result is an increase of Convective Available Potential Energy, which increases convection, which is a net cooling process.
Thanks for that. I will be sending this post to many CAGW alarmists. It has always bugged me that many people will accept the water cycle as a coolant of the earth, yet still believe that CO2 “traps heat” and back-radiates it causing CAGW.
I’ve got a much-simplified version (see below). I’ve been drop-kicking climate kooks over at CFACT so hard that they’re now marking my comments as spam and are too scared to respond to me for fear that I’ll humiliate them again… I seem to have this strange effect upon the climate kooks… they start out full of bluster, but within a few days, they all cower from me.
They don’t realize that their marking my comments as spam just gives me the opportunity to simplify and clarify the message until even their diminished mental capacities can grasp it. I’ve red-pilled one of them.
All radiative molecules are dual-role molecules… they can act to warm the atmosphere at atmospheric temperatures below their ‘transition temperature’, or cool the atmosphere at atmospheric temperatures above their ‘transition temperature’.
The ‘transition temperature’ of any given molecular species is dependent upon the differential between:
1) the combined translational mode energy of two colliding molecules,
-and-
2) the lowest vibrational mode quantum state energy of the radiative molecule.
When 2) > 1), energy flows from vibrational mode to translational mode, which is a warming process.
When 1) > 2), energy flows from translational mode to vibrational mode, which is a cooling process.
The atmosphere obeys the fundamental physical laws, after all.
In order for CO2 to be vibrationally excited to its lowest vibrational mode quantum state, it requires the energy equivalent to a 14.98352 µm photon, equating to a CO2 speed of 425.92936688660114 m/s or an N2 speed of 533.8549080851558 m/s.
We can use either of those speeds in the Maxwell-Boltzmann Speed Distribution Function, as long as we also use the equivalent atomic mass of that particular molecule… the Equipartition Theorem dictates that at any given exact monotonic temperature, all molecules regardless of molecular weight will have the same kinetic energy.
In order to ascertain the total population of vibrationally excited CO2 at 288 K (the average, not the exact monotonic temperature), we can use the Maxwell-Boltzmann Speed Distribution Function, setting the minimum speed to that speed which equates to the translational mode energy sufficient to vibrationally excite CO2’s lowest vibrational mode quantum state, and setting the maximum speed to some arbitrarily high number to encompass all molecules above the minimum speed necessary to vibrationally excite CO2 (1650 m/s). The result is on the left-hand side of the graphic below.
Just to show that our math is correct, we’ll also do the same for N2, on the right-hand side of the graphic below.
https://i.imgur.com/tgmPPle.png
As the graphic shows, at 288 K, 34.27% of the entire atmosphere has sufficient translational mode energy to vibrationally excite CO2{v20(0)} to CO2{v21(1)}.
Below are the energetic pathways describing the process detailed above:
X (at ~288K+) + CO2{v20(0)} (at ~288K+) –> X + CO2{v21(1)} –> CO2{v20(0)} + 667.4 cm-1
X (at ~288.1K+) + CO2{v21(1)} (at ~288.1K+) –> X + CO2{v22(2)} –> CO2{v21(1)} + 667.8 cm–1 –> CO2{v20(0)} + 667.4 cm-1
X (at ~288.2K+) + CO2{v22(2)} (at ~288.2K+) –> X + CO2{v23(3)} –> CO2{v22(2)} + 668.10 cm–1 –> CO2{v21(1)} + 667.8 cm–1 –> CO2{v20(0)} + 667.4 cm-1
The conversion of translational mode energy (which we sense as temperature) to vibrational mode energy is, by definition, a cooling process.
The emission of the resultant radiation to space is, by definition, a cooling process.
An increased atmospheric CO2 concentration will increase the likelihood of atmospheric molecular collision with CO2, thereby increasing the likelihood of CO2 radiatively emitting, thereby increasing the radiative cooling effect.
Therefore, CAGW is a physical impossibility by the above interactions alone.
But there are other interactions, notably the interaction by which N2 becomes vibrationally excited via translational-vibrational (t-v) processes, and transfers its vibrational mode energy to the vibrational mode energy of CO2:
X (at ~288K+) + N2{v1(0)} (at ~288K+) –> X + N2{v1(1)} –> N2{v1(1)} + CO2{v20(0)} –> N2{v1(0)} + CO2{v3(1)} –> CO2{v1(1)} + 961.54 cm-1
X (at ~288K+) + N2{v1(0)} (at ~288K+) –> X + N2{v1(1)} –> N2{v1(1)} + CO2{v20(0)} –> N2{v1(0)} + CO2{v3(1)} –> CO2{v20(2)} + 1063.83 cm-1
We can use the Boltzmann Factor to determine the vibrationally excited population of N2 due to translational-vibrational (t-v) collisional processes.
N2{v1(1)} (stretch) mode at 2345 cm-1 (4.26439 µm), correcting for anharmonicity, centrifugal distortion and vibro-rotational interaction
1 cm-1 = 11.9624 J mol-1
2345 cm-1 = 2345 * 11.9624 / 1000 = 28.051828 kJ mol-1
The Boltzmann factor at 288 K has the value 1 / (2805.1828 / 288R) = 0.10266710 which means that 10.26671% of N2 molecules are in the N2{v1(1)} excited state due to translational-vibrational (t-v) processes.
Given that CO2 constitutes 0.041% of the atmosphere (410 ppm), and N2 constitutes 78.08% of the atmosphere (780800 ppm), this means that 4.1984 ppm of CO2 is excited to its {v3} mode quantum state via collisional translational-to-vibrational (t-v) processes, whereas 80162.3936 ppm of N2 is excited via the same (t-v) processes. This is a ratio of 1 vibrationally excited CO2 to 19093 vibrationally excited N2. You’ll note this is 10.028 times higher than the total CO2:N2 ratio of 1:1904, and 195 times more vibrationally excited N2 molecules than all CO2 molecules (vibrationally excited or not). Thus energy will flow from the higher-energy and higher-concentration vibrationally-excited N2 to vibrationally ground-state CO2.
The conversion of translational mode energy (which we sense as temperature) to vibrational mode energy of N2 is by definition, a cooling process.
The transfer of that N2 vibrational mode energy to vibrational mode energy of CO2, then that energy being emitted to space as radiation is, by definition, a cooling process. The resultant radiation from the last two energetic pathways is in the Infrared Atmospheric Window, thus any upwelling radiation has a nearly unfettered path out to space.
An increased atmospheric CO2 concentration will increase the likelihood of vibrationally-excited N2 colliding with CO2, thereby increasing the likelihood of CO2 radiatively emitting, thereby increasing the radiative cooling effect.
At 288 K, fully 34.27% of the atmosphere is vibrationally exciting CO2 via t-v collisional processes; and on top of that, 10.26671% of N2 molecules are vibrationally exciting higher vibrational mode quantum states of CO2.
Five energetic pathways which show that CAGW (Catastrophic Anthropogenic Global Warming due to CO2) is a physical impossibility.
If a process (catastrophic atmospheric warming due to CO2) cannot occur at the quantum level, it most certainly cannot occur macroscopically.
You are surely correct to say that the air gets hot. Since it is transparent to near and far infrared, the question is how. Surely the answer is Conduction. The Sun warms the Earth and the Oceans, and they in turn warm the atmosphere from the bottom up. Also Greenhouses trap air ( not Heat) and the temperature of the air inside varies with the time of day and night.