Collisional De-Excitation Discussed

Several months ago, I became interested in the Global Warming controversy and in doing so I realized that it wasn't enough to just say I was a "believer" or a "denier".  I realized that I really knew nothing about the science that supports this philosophy mostly because I was putting my faith in the purveyors of mainstream media news to deliver the truth to me. Well, that was silly. Turns out that the whole thing is a massive controversy and it also turns out that people are polarized due to the positioning of the various media themselves. Since media have their own agendas I realized that you can't just leave everything there and move blissfully on. I needed to go deeper.

Because I have a lot of scientific training my research was probably of a different nature than most regular people would take. I questioned the things I was being told based on my own scientific background and searched out others who had published more objective data which addressed the chemistry behind the proclamations of doom. I went back to the books and revisited my original studies on chemistry and thermodynamics, updating myself on knowledge that I'd let slip over the years away. 

I found interpreting the mainstream literature was an extremely difficult task because there is a massive amount of information out there and it is all generally misleading according to which "camp" the authors were in. I had to wade through it all in order to come to my own conclusions and create my own philosophy, which of course will be attacked the moment I express it. Nevertheless, this is my blog and to be honest this blog tries to show that the current theory and description of greenhouse gas based warming of the planet is total bullshit because the science does not support the theory of how GHG's actually perform their magic.  So, here goes:

DEFINITIONS OF ENERGY

The Greenhouse Effect is all about interpreting radiant energy transfer from one object to another.  In order to keep from becoming confused we should spend some time defining what energy is and what forms we see it.  Some references are quoted below to cover the major types of energy climate scientists deal with and how they are measured.

Physics defines Energy by means of the force required to change the state of motion of an object ( eg. voltage ).  The amount of energy delivered per unit of time is defined as power ( eg. amperage ).  Watts are calculated by multiplying voltage times amperage.  In electrical terms then energy would be defined as  watts / second and this is further defined as being a Joule 

So, a Joule is a unit of energy that is equivalent to 1 watt / second. To visualize this, consider a 50 watt light bulb as an artificial Sun - it is delivering 50 joules of light and heat energy to the whole space of the room every second, in total.  

The Sun at full force (ie. at the equator) is defined as delivering  - 1370 joules / sec / m^2. The Sun is also defined to deliver an average 235 joules / sec / m2 to the total earth's surface. 

This energy warms up the Earth by delivering heat energy to it in the form of short wave infrared waves. If this heat is not thrown back to outer space it will continue to warm the Earth ad infinitum and the temperature (how we measure heat energy) would reach unbearable / unliveable limits. The Earth Energy Budget defines the mechanisms by which the Earth gets rid of its daily uptake of heat energy; mechanisms in which Greenhouse Gases (GHG's) supposedly interfere reducing the ability to lose heat from the Earth and supposedly causing the average global temperature to slowly rise.

STATES OF INTERCHANGEABLE ENERGY

Types of energy can be categorised into two broad categories - kinetic energy (the energy of moving objects) and potential energy (energy that is stored). These are the two basic forms of energy. The different types of energy include thermal energy, radiant energy, chemical energy, nuclear energy, electrical energy, motion energy, sound energy, elastic energy and gravitational energy.

Radiant energy is the energy of photon based electromagnetic waves.  It is a form of energy that can travel through space. For example, we receive the heat from the sun, which is located very far from the earth via radiation. The sun's heat is not transmitted through any solid medium, but through a vacuum.

Vibrational energy is the energy in a vibrating system, otherwise at rest; especially that in a molecule due to the vibrations of its atoms.  A molecular vibration occurs when atoms in a molecule are in periodic motion while the molecule as a whole has constant translational and rotational motion. ... A fundamental vibration is excited when one such photon of energy is absorbed by the molecule in its ground state.

Kinetic energy of an object is the energy that it possesses due to its motion. It is defined as the work needed to accelerate a body of a given mass from rest to its stated velocity. Having gained this energy during its acceleration, the body maintains this kinetic energy unless its speed changes.

Heat is the form of energy (calories, joules) that is transferred between two substances at different temperatures. ... Temperature is the measure of hotness or coldness of matter.  Stated another way, temperature is the average kinetic energy per molecule of a substance.

WHAT ARE WE WORRIED ABOUT ANYWAY?

Perhaps to start this conversation we should ask why we even care if there is greenhouse effect occurring in our skies.  There is certainly a lot of hysteria, hand wringing and doom and gloom prophesizing about the fact that it is supposedly at work. But what is it that we are concerned about - exactly?

We are concerned that this process is not allowing enough heat to escape the Earth during the night when its' surface faces the blackness and coldness of outer space. We feel that if we do not remove enough heat from the actual mass of the earth then the land and the oceans will become hotter. We are concerned that the air mass that surrounds us and hovers over our land and water surfaces will also overheat and we will be subjected to extreme weather turbulence with associated tornado and hurricane events, excessive melting of ice packs with subsequent ocean level rise, hot atmospheres with oppressive heat for comfortable living  levels, warmed oceans with consequences, dry lands, droughts, water shortages, crop failure and other extremes because of massive changes to normal and expected circulation and turbulence patterns that form our weather.

Earth achieves heat balance if it removes the heat that entered its mass (land and waters) during the day and it also achieves balance if it doesn't allow the heat it removes from those surfaces to simply remain as a hot air layer hovering over that surface without moving upwards to where it can dispose of its excess heat. 

Heat energy is a real thing - not some abstract concept. It is a measurable, quantifiable substance that can be absorbed, moved around and extracted from our Earth's mass. Think of it as ghost like vapour that can't be seen but is still there and can be captured and shared at the molecular level, where it acts the same as adrenalin on the human body - energizing and increasing action of the materials holding it. 

Removal of heat from the Earth is two stage process. The first step is to take it out of the Earth's "hard mass" of land and water. This is done by various mechanisms involving conduction, convection and radiant transfers. The second stage is to get that extracted heat to pass through our atmosphere(s) and get it away from the Earth's surface to where it can be "cast off" into the blackness of outer space. Achieving this removal and transfer results in an energy in/out balance and maintenance of an even overall Earth average temperature. - Our goal apparently.

The Greenhouse Effect theory says the Earth is not removing that undesirable heat because of a heat "capture and hold" process linked to  gases which trap it coming up from a cooling Earth and then holding it as a blanket of hot air next to the Earth's surface. This blog disputes that assumption.

 

THE GREENHOUSE EFFECT - THE POPULAR THEORY AS IT STANDS TODAY

During the last 100 years we have increased our atmospheric carbon dioxide levels by 115 ppm to a present day level of 415 ppm. This is considered a global problem because carbon dioxide is the major gas involved in a phenomenon called the "greenhouse effect".  CO2 along with other GHG's (N2O, CH3, CFC's, H2O, O3) intercept long wave infrared radiation (the actual amount intercepted is never specified) given off by the Earth at night when the Sun is done for the day with its task of warming up the Earth's land and ocean surfaces. This interception by CO2 of Earth's outgoing IR prevents the extracted heat from passing through to outer space and being dissipated which would then cool the Earth's surface. 

The mechanism behind explaining greenhouse warming begins with  a CO2 molecule that absorbs the long wave IR given off by a warmed Earth (100% absorption because IPCC says C02 is a black body).  This increases its vibrational energy levels within the molecule inducing it to  re-emit a new IR (full strength because it is a black body) wave in all directions, sending it upwards out to space, sideways across to other molecules surrounding it, and most importantly back down to the Earth.  This return of energy back to the Earth (never specified how much returns to Earth) is considered to be  responsible for a long term build up of heat in its mass (disposal of this returned IR by Earth's multiple mechanisms is also never considered) resulting in an eventual increase in the world's average global temperature. 

This is the crux of the theory linking GHG's (predominantly CO2) to global temperature increases that are now affecting all aspects of our weather and living environments. Note again, that IPCC says this scenario happens and in particular that IR exchanges are significant because C02 is a 100% absorber / emitter (a black body). This assumption is critical to giving credence to the greenhouse gas concept. 


 A CRITIQUE OF CARBON DIOXIDE BASED GREENHOUSE EFFECT THEORY.

THE EARTH HEAT BALANCE .


The first image above gives a reasonably good representation of the "big picture" regarding the various mechanisms present in Earth's atmosphere and surface that collectively  remove the heat gained during each day as the Sun beats down from above.  The following three images tell the same story but strongly slant the information  to emphasize the greenhouse gas effect while minimizing other significant "coolers" such as evaporation, hot air convection and unimpeded long wave IR transmission from Earth to space. This is common practice in the literature and is one of the main reasons why it is so difficult for normal people to make informed decisions on the subject. 

Just remember, it is equilibrium that determines the temperature of the atmosphere, which is independent of how the heat gets into the atmosphere. Equilibrium means the temperature builds up until the amount of heat loss into space equals the amount of radiation entering from the sun.

 Net zero buildup or loss of heat in order to maintain balance - how do the images above reflect this statement - look for subtleties that sway your opinions - they are present in all of them.

Concentrating mostly on image #1, it can be seen that much of the Sun's incoming IR radiation (shortwave) is reflected, radiated, and convected by air back to the top of the atmosphere where it is beamed out into outer space.  Extraction from Earth is accomplished by evaporation, air convection and radiant emission. By adding up the numbers we can see that balance is achieved when the sum of each cooling element equals the total of the energy delivered to the Earth. We can see that clouds, ozone, dust, aerosols, and air (N2, O2, CO2, etc.) all share the role of removing heat from the Earth and delivering it upstairs to be cast off into space. All of these are very logical and understandable mechanisms with no "magic" in how they achieve their tasks. 

GHG's however are treated differently, particularly because they are shown to deliver radiant energy back to the Earth rather than away, even though the their numbers are balanced in these charts through inserting IR radiation of other wavelengths not affected by CO2 (somewhat of a conflict, but that's how they chose to draw their image).  The image shows a total 22 units of energy being radiated out to space: 

1).  8 units in the form of wavelengths not absorbed by CO2. 

2). 14 units in the wavelength that is absorbed by CO2 (2.3, 4.6, 14.77 um). 

It also shows IR energy being returned to the ground by the re-emittance of IR from CO2. Total balance would be maintained if the cooling mechanisms dealt with all of this returned energy as well, but the theory states that it doesn't and there is net gain in energy by the Earth, resulting in warmer air and land leading to an increased global temperature. In this case, the GHG value of 14 sent to space would be expected to be  <14  units and the energy balance would no longer be equal, showing net warming of the Earth instead.

"Believers" state that the Earth is not in balance and that the amount being radiated back to space is less than the IR sent out from its surfaces. They blame CO2 predominantly, stating that it is intercepting the IR from earth, raising its own vibrational energy states and then re-radiating that IR in all directions. Some goes to space and some returns to the Earth, where it stays slowing warming the surface. They claim that increased CO2 caused by humans will only increase the process and increase the rate at which the earth warms up, leading to future catastrophe as temperatures rise.

The things that they ignore or simply don't talk about include the following:

1. Each molecule of CO2 is surrounded by 2500 molecules of air (N2, O2). Greenhouse theory states that these gases cannot absorb IR because they do not have the unique chemical structure that CO2 does (ie. they are essentially "neutral") but they DON'T STATE  that they can RECEIVE the energy of excited CO2 by collisions and then hold that energy as kinetic energy as they rise up, shifting it to upper levels where they CAN AND DO radiate it out to space. 

2. They really fail to mention that CO2 can only absorb about 8% of the total IR emitted from the earth in the first place because the wavelengths CO2 absorbs at (2.3, 4.6, 14.77 um) are only a portion of the total IR spectrum emitted (0 to 70 um). 

3. The theory supports re-radiation from CO2 but doesn't emphasize that the amount returned to earth is  diluted because the molecules radiate in all directions, not just downward. How much actually gets back to earth anyway? There is little literature defining this. 

4. They stop talking after the returned IR is absorbed by the Earth, giving the impression that it just stays there warming everything up. But this returned IR is just heat and there are more mechanisms than IR to remove heat from its surface.  Returned IR would be subject to evaporation, convection, unrestricted IR (bandwidth effect) emission as well as repeated CO2 affected IR radiation. How much dilution is that going to cause?

5. There is little mention of the fact that CO2, although heavier than air, does not accumulate at ground level where its absorption would be maximized and a returned IR mechanism could be seen as possible. Instead, turbulence mixes CO2 into the atmosphere and spreads it pretty evenly throughout the mass of the troposphere, right up to the upper limits. CO2 at high levels releasing IR are unlikely to see that IR reach Earth as there is so much air between it and the ground.

6. They don't mention the massive IR absorption power of H2O and the extremely wide bandwidth that it absorbs that IR over, dwarfing the effect that CO2 might have and negating its effect. Water vapour also rises and, in this case, condenses - throwing off massive quantities of heat to space in the process. They call it a greenhouse gas but it isn't because it doesn't re-radiate heat back to earth.

7. They ignore or dismiss the strength of other coolants - Sun intensity variations (input), Clouds (reflection, evaporation), Dust and Aerosols (reflection), Hot air thermals (conduction, convection), unrestricted IR wavelengths, placing all of their emphasis / blame on this one simple questionable reaction.

8. The IPCC assumes that the emissivity of both the Earth and a Carbon Dioxide molecule are 1.0. this means that both are 100% perfect emitters and absorbers of IR radiation (no losses in the exchange). In point of fact the Earth is not a "black body" but rather a "gray body" that has an emissivity value <1.0 as many materials contribute to its overall transmission of IR. More importantly, C02 has an emissivity of .0024 - practically a complete non-absorber and non-emitter of IR radiation at all!  Even so, a whole theory has been promoted that assumes it absorbs and emits IR literally 500 times its actual value to perform these tasks!  This is discussed thoroughly in Blog #2, accessed below.

 This is the essence of the Greenhouse Effect narrative and the basis for the worldwide global warming hysteria. Pressure is on to prevent any further rise in CO2 and even to find ways to reduce it back to the happy days when it was running around 300 ppm. Only then will our world go back to "normal". 

COLLISIONAL DE-EXCITATION - LET'S REWRITE THE THEORY

The first part of the popular modern Greenhouse Gas theory regarding the ability of CO2 to absorb IR from the Earth is probably correct, but definitely NOT the second part involving its ability to radiate significant amounts of that IR heat back to the Earth.  More accurately, we should state that:

 "CO2 (and other GHG's) probably absorb SOME portion of the total IR radiation from the ground (but not all) and we can be quite certain that only an insignificant amount (if any amount at all) of that energy returns to the Earth as IR emitted from excited CO2 molecules".  

The ability of CO2 to absorb long wave infrared heat at the wavelengths 2.3, 4.6, 14.77 microns has been known for decades. This absorption is a characteristic of its unique chemical structure whereby multiple bonds within the molecule receive IR heat and hold it in a higher state of energy as vibrational energy. Then, a dynamic process known as "collisional de-excitation" occurs which removes heat stripped from energized CO2 molecules and convects it to space where it is discarded.

Note that of the three wavelengths that C02 can absorb the 2.3 and 4.6 wavelengths are essentially non significant as these are not emitted by the Sun to any significant degree nor are they in the long wave IR spectrum emitted by the Earth. It is the 14.66 spectrum where all the work is done. 



Heat Loss by Collisional De-Excitation : When a molecule of carbon dioxide gas absorbs a photon of IR radiation of acceptable wavelengths (14.77 microns) the bonds of the molecule begin to stretch and bend as a result of electron shifts within the molecular structure

As carbon dioxide molecules move throughout the troposphere, they frequently collide with nitrogen and oxygen molecules. When these collisions occur, the vibrational energy (stretching and bending of carbon dioxide molecules) is transferred to nitrogen and oxygen molecules. The nitrogen and oxygen molecules gain kinetic energy and move faster resulting in an increase in temperature, causing them to physically rise.  This process, which transfers energy from greenhouse gas molecules to molecules of nitrogen or oxygen gas through collisions, is called collisional de-excitation.

The process of collisional de-excitation is grounded in kinetic molecular theory, a model that has proven to be very useful in explaining the nature of matter, including the behavior of gases. Collisional de-excitation provides a logical explanation for how the energy in a photon of IR radiation can be translated into an increase in temperature, as temperature is understood in terms of the kinetic molecular theory. Understanding atmospheric warming in terms of collisional de-excitation applies the ideas of continuous motion of particles, constant collisions and the relationship between temperature and the kinetic energy of particles-all of which are based upon kinetic molecular theory."

N2 and O2 (>90% of all air molecules) do NOT absorb any IR heat emitted from the ground. An important point to note is that N2 and O2 cannot duplicate GHG's by accepting any of the IR radiation emitted from the Earth, but they can still achieve increased kinetic energy levels by transference from those GHG molecules that in point of fact really accepted that IR on their behalf. Also don't forget that ALL materials are capable of radiating IR heat away from themselves and N2 and O2 are no exception - they just don't absorb it. 

The CO2 molecule's higher state of energy does NOT dissipate through simply re-radiating IR waves out in all directions as is commonly declared but rather it significantly dissipates its newfound energy by coming in contact with the other air molecules that are sharing atmospheric space with it.  Notably, collisions with nitrogen N2 and oxygen O2, (which are present in levels around 2600 molecules / Co2 molecule) cause energized CO2 to pass on that vibrational energy to these predominant air molecules thereby increasing their levels of kinetic energy.  Loss of energy from Co2 takes away the ability for CO2 to radiate anything more because it has been transformed into its original low energy state (ie. collisional de-excitation).

However, before any outbound radiation can takes place from N2 and O2 these air molecules behave as hot air always does - they rise physically as thermals up to the edge of our atmosphere. Then, on the edge of outer space the N2 and O2 exhibit their ability to RADIATE heat sending IR waves into outer space, followed by returning themselves to lower altitudes as de-energized cold air. This action in turn contributes to atmospheric turbulence which encourages sweeping hot air upwards while replacing lower levels with air ready to accept more energy from any newly activated CO2 molecules.

In this description any return of IR to the Earth is insignificant, if it even occurs at all. The shielding effect of 2600 molecules of air simply prevents any IR from getting through the gauntlet so that it can contact the Earth. Yes, it is likely that heat is retained close to Earth for a time and some transference down could presumably occur, but this also would be insignificant as the rising warm air quickly moves heat (and CO2 molecules as well) upward and away and the Earth would quickly dispel of heat through its multiple extraction mechanisms if any should be absorbed. 

Take note also, CO2 atmospheric gas is not found concentrated at ground level like a layer or a greenhouse "roof", but is actually mixed evenly into the air through atmospheric turbulence and is relatively evenly concentrated up to the edge of the upper atmosphere.  Lack of ground concentration means CO2 does not significantly hold heat at ground level, so why is today's theory continuing to claim that it can transfer back any significant amount that would warm the Earth?  It simply can't. It doesn't make sense.

Some sources continue to say that CO2 can radiate IR even after giving up energy to N2 and O2 but this is discounted as being miniscule and radiating to the colder outer space is more likely rather than back into the warmer Earth's surface. There's also that dilution effect at play. One carbon dioxide molecule receives enough radiation to heat 5 molecules of N2 and / or O2. Since each C02 molecule is surrounded by 2600 air molecules waiting for a dose of radiation there isn't much room left for the CO2 to radiate back to Earth as its energy is being stripped away by "hungry" air densely surrounding it.

Why do believers fail to mention collisional kinetic transfer of energy to air followed by eventual emitting IR from the N2 / O2 that dissipates that energy to space? Even if CO2 IR is playing a role in its capture, the energy is always moving upward and outward towards the extremely cold "sink" of outer space and the effect is always to cool the original warm body, the Earth's surface. 

Even if CO2 (and even N2 / O2) did manage to radiate any IR back downwards any amount actually reaching Earth would be insignificant, and would be quickly dispelled by Earth's many mechanisms for exhausting it. Heat just doesn't get in line and wait to be radiated back to waiting CO2 again. It is subject to all the forces of evaporation, convection, unrestricted radiation in wavelengths not absorbed by CO2, and yes, again, an 8% portion of IR intercepted by CO2 that transfers it to air molecules that flush it up to space. There just isn't enough returned and retained to heat the Earth. It's just not that sensitive.

I give you one of the best arguments I've seen regarding the whole C02 warming argument. It is a Quora article that takes great pains to give you the full picture on how C02 functions. Enjoy. 


SO WHAT IS RESPONSIBLE FOR GLOBAL WARMING AND COOLING ANYWAY?

It's in the images above. Sun, clouds, dust, water vapour, hot air as thermals, IR radiation. They all play a role in keeping the temperature of the earth constant acting in accordance with one another and maintaining a type of thermostat control over the planet. The global environment is homeostatic (the phenomenon of maintaining  a state which is basically unchanging in nature). Perhaps we should worry about many other catastrophes we are in the process of creating than obsessing about 408 ppm of inert gas.

cliffdunlop03@gmail.com

ENERGY DEFINED AND MEASUREMENT TERMINOLOGY EXPLAINED

Physics defines energy by means of the force (eg. voltage) and motion (eg amps) required to do work. The amount of energy delivered per unit of time is defined as power ( eg. watts/ sec ). Watts are calculated by multiplying voltage times amperage. In electrical terms then energy would be defined as watts / second and this is further defined internationally as being a Joule.

So again, a Joule is a unit of energy that is equivalent to 1 watt / second. To visualize this, consider a 50 watt light bulb as an artificial Sun - it is delivering 50 joules of (light and heat energy) to the whole space of the room every second, in total. We don't calculate how much energy falls on our walls but with the Sun we must incorporate this variable in our calculations. So, Sun energy is defined as Joules / sec / sq. meter.

The Sun at full force (ie. at the equator) is defined as delivering 1370 joules / sec / m^2. The Sun is also defined to deliver an average 235 joules / sec / m2 to the total earth's surface as it is sphere and receives most of the Sun's energy as incident radiation, not direct.

FOR YOUR INFORMATION - SOME SEARCH INFORMATION.

( Using my conversion tables I find: 1055 joules = 1 BTU. / 4186 joules = 1 KCal. / 1.355 joules = 1 foot lb.)

energy. [ ĕn′ər-jē ] The capacity or power to do work, such as the capacity to move an object (of a given mass) by the application of force. Energy exists in many different forms. Examples of these are: light energy, heat energy, mechanical energy, gravitational energy, electrical energy, sound energy, chemical energy, nuclear or atomic energy and can be transformed from one form to another. There are two main forms of energy, called potential energy and kinetic energy. Potential energy, sometimes symbolized U, is energy stored in a system. The Sun's light energy came from electrons in its atoms lowering energy states, and releasing energy. The energy in the atoms came from the nuclear reactions in the heart of the Sun.

Please note: these images and the discussions surrounding them are easily found on Google. I'm not even going to attempt to make a bibliography because this isn't a scientific paper, it's an opinion piece. If you doubt me go search them out. The exercise is quite revealing.