Review and Summary of three Important Atmospheric Physics Papers

by Andy May

Introduction

In 2014, Dr. Michael Connolly and Dr. Ronan Connolly posted three important, non-peer reviewed papers on atmospheric physics on their web site. These papers can be accessed online here. The papers are difficult to understand as they cover several fields of study and are very long. But, they present new data and a novel interpretation of energy flow in the atmosphere that should be seriously considered in the climate change debate.

By studying weather balloon data around the world Connolly and Connolly show that the temperature profile of the atmosphere to the stratosphere can be completely explained using the gas laws, humidity and phase changes. The atmospheric temperature profile does not appear to be influenced, to any measurable extent, by infrared active gases like carbon dioxide.

Figure 1, source Connolly and Connolly.

Figure 1 shows the “U.S. standard atmosphere.” The black curve is the standard atmospheric temperature as a function of altitude (Y axis). There are several key points that are important for this post. First, notice that the temperature decreases with altitude in the troposphere, then goes vertical in the tropopause, then it reverses course and increases in the stratosphere. Since we are discussing weather balloon data in this post, we are only concerned about the curve to about 35 kilometers. This region contains about 99% of the atmospheric mass. We will also be discussing the ozone layer, which is at the very top of our layer of investigation.

They evaluate available weather balloon data in terms of molar density and pressure. They find that, above the boundary layer (roughly the surface to 2 kilometers, the atmospheric layer that contains most of our weather), the trend of molar density and pressure is a line until the tropopause is reached. Above the tropopause it is also a line, but with a steeper slope, see figure 2. In figure 2, pressure increases to the right and altitude decreases to the right. Above the tropopause molar density decreases more rapidly with pressure, this suggests a change in the equation of state for the atmosphere above the tropopause. Region 3, the boundary layer, shows much more variability than the higher regions of the graph. This variability is due to changes in humidity and precipitation.

Multimers

A change in the equation of state in the atmosphere means that it will respond to external forces (“forcings”) differently. For the atmosphere, the equation of state is the ideal gas law, modified to account for factors that affect real gases, but not ideal gases. These include varying specific heat capacity, Van der Waals forces and compressibility effects among others. While the molar density versus pressure plots, like figure 2, strongly suggest that the equation of state has changed above the tropopause it does not tell us exactly what happened. Connolly and Connolly think that oxygen and nitrogen multimers form in and above the tropopause (see figure 3). Multimers are called trimers if they contain three molecules and tetramers if they contain four.

Figure 2, after Connolly and Connolly (2014) paper 1.

Figure 3 (source Connolly and Connolly, 2013)

This suggests that the atmosphere above the tropopause has a lower molar density, at a given pressure, than the tropospheric trend would suggest. The atmospheric composition and humidity above and below the tropopause are nearly identical, so composition is not the cause of this change.

The formation of oxygen and nitrogen multimers is a state change that can be called a phase change. If multimers form in the tropopause, they release the energy of formation to the surroundings. This may increase the temperature of the surroundings. The larger multimers have more degrees of freedom than the diatomic monomers (for example O2) and every additional degree of freedom increases the internal energy of a mole of multimers by ½RT. R is the universal gas constant and T is temperature. This is described in more detail in Connolly and Connolly, paper 2, section 2.2. In their section 2.2, the heat of formation (or enthalpy of formation) of the multimer is designated as ΔH. The molar enthalpy (H) of a gas is defined as,

H = U + PV … (1)

Where U is the internal energy of the gas, P is pressure and V is the volume.

U = ½αRT … (2)

The internal energy of the gas is equal to ½ of the degrees of freedom (α) times the gas constant (8.3145) times temperature (T). Degrees of freedom of a gas are defined here as the number of independent ways a gas can have energy. This includes translation, rotation and vibration. Internal energy is the sum of the energy in all the degrees of freedom of the gas. If ΔH is set to zero for a diatomic monomer, it is 4RT with 34 degrees of freedom (α) for a tetramer, according to table 2 from Connolly and Connolly paper 2. So, the heat of formation of a multimer can be significant and will affect the temperature of the tropopause and stratosphere. The formation of oxygen multimers probably involves the emission of microwave radiation.

In the tropopause, the lapse rate is near zero, this means, according to Connolly and Connolly, that the increase in internal energy, due to multimer conversion, is balanced with the loss of thermal energy converted to potential energy, due to gravity, at this altitude. I realize that thermal energy can be defined in different ways, but here we define it as the internal energy of the gas due to its temperature. As altitude increases and we enter the stratosphere, either more multimers are formed or they get larger and internal energy increases more rapidly than thermal energy is converted into potential energy and the air temperature begins to increase. In the troposphere, there are no multimers and thermal energy is transformed into potential energy as the altitude increases and the air temperature steadily decreases (the “lapse rate”). This causes the slope change shown for region 1 (tropopause and stratosphere), seen in figure 2.

Ozone

Ozone concentration starts to increase with altitude in the stratosphere as well. The classical explanation for the formation of ozone is called the Chapman mechanism and it is illustrated in figure 4. Chapman hypothesized that ultraviolet light (UV) striking oxygen molecules will split them into individual oxygen atoms. He then speculates, that some of these would combine with nearby oxygen molecules and form ozone.

Figure 4 (source Connolly and Connolly, 2013)

There are several problems with the Chapman mechanism. First, it requires a great deal of energy to break a diatomic oxygen molecule’s bonds. Further, if the Chapman mechanism were the only mechanism forming ozone, why would ozone concentrations, in the Northern Hemisphere, be the highest in the Arctic in the spring? The equator (the red line in figure 5) receives the most UV from the sun, yet the ozone concentration there is much less than in the Arctic, the dark blue line in figure 5. Further, one would think that the Arctic and Northern Hemisphere ozone concentration would peak in the summer, yet it peaks in the spring and falls in the summer, and begins to increase in the winter. The Chapman mechanism also has other flaws as documented here.

According to classical theory, the extra energy in the tropopause and stratosphere that reverses the negative lapse rate seen in the troposphere, comes from “ozone heating.” Ozone absorbs UV light from the sun and radiates heat which warms the tropopause and stratosphere. Yet, the tropopause stays in place during Arctic and Antarctic winters when there is no sunlight. Given these contradictions, Connolly and Connolly came up with an alternative mechanism.

Figure 5 (source Connolly and Connolly, 2014, paper 2)

Ozone formed directly from oxygen multimers also requires UV radiation, but it requires much less than is required in the Chapman process. Figure 6 shows the process described in Connolly and Connolly (2014). There a multimer of eight oxygen atoms and four oxygen molecules is transformed into two ozone molecules and one regular oxygen molecule. This process requires sunlight and abundant multimers to work, but less energy. Further, the formation of the multimers, themselves, can occur without sunlight and the formation process releases heat of formation, which helps form the tropopause and warms the stratosphere.

Figure 6 (source Connolly and Connolly, 2013)

Their idea allows ozone to form more easily and with less energy and it provides additional energy during the Arctic and Antarctic winters when there is no sunlight for months. The idea that multimers make ozone easier to form, is only one of the potential impacts of possible multimer formation in the tropopause and stratosphere. Multimer formation may also influence tropospheric weather as discussed in Connolly and Connolly paper 2.

The Weather balloon data

Weather balloons record temperature (T), pressure (P) or sometimes altitude (h), horizontal wind speed and direction, and relative humidity. Relative humidity is converted into absolute humidity using the temperature. There have been one to four launches a day from about 1,000 stations around the world – in some cases since the 1950s or earlier. That is about 13 million datasets containing data from the ground to the mid-stratosphere (~30-35km altitude). A weather balloon launch in Chile is shown in figure 7.


Figure 7 (Weather balloon launch in Chile, source: European Southern Observatory)

Nobody had analyzed the weather balloon data in terms of molar density before, but it is quite straightforward to do. Molar density, D = n/V = P/(RT) (where R=8.314, is the universal gas constant). So, all you need to do is divide the P (Pressure) values by the corresponding T values (multiplied by 8.314). The units of “D” are moles/m3.

From a climate perspective, it is better to view the molar density versus pressure plot in terms of temperature and height as in figure 8. To compute temperature, we first have to compute best fit lines to each region of figure 2 to obtain slopes and intercepts. Connolly and Connolly call the slopes “a” and the intercepts “c,” such that:

D = aP + c … (3)

Therefore, since D = P/(RT) and using the ideal gas law:

… (4)

“R” is still the ideal gas constant equal to 8.3145 J/(mol.K). The coefficients, “a” and “c,” are not constants and vary from place to place. Typical a and c coefficients are shown in table 1. In figure 2, the “humid” phase in table 2 is region 3, the “light” phase is region 2 and the “heavy” phase is region 1 or the tropopause and stratosphere. A spreadsheet for computing temperature from the coefficients, using equation 4, is in the supplementary materials for Connolly and Connolly, paper 1. In table 1, there are two entries for the near Artic Norman Wells site. One is for the ground (g) and other is for the tropopause/stratosphere (u). Near the poles the heavy phase (multimer formation) can occur near the ground.


Table 1, from Connolly and Connolly, paper 1.

Using equation 4 and the coefficients of the best fit lines, like those in table 1, we can estimate temperature (T). This has been done in figure 8. Most of the balloon launch sites can be fit with two or three best fit lines. In figure 8, both are fit with three lines. Lake Charles, Louisiana is sub-tropical and the boundary layer requires a separate fit due to high humidity. Norman Wells, Northwest Territories, Canada requires three because the boundary layer, in winter time, can show a phase change very like the phase change observed in the tropopause. This might be due to the formation of multimers at the surface.

Figure 8, after Connolly and Connolly, paper 1

The boundary layer is defined, in the papers, as where the absolute humidity is greater than one gram of water per kg of air. This is roughly greater than 0.1%. As figure 2 shows, the slope is relatively more variable in this region (region 3). Changes in temperature, humidity and precipitation affect the slope in this region. The boundary layer may not exist in the Arctic and Antarctic in winter, where surface humidity can be very close to zero in cold weather. Yet, slope anomalies exist there as well, sometimes going the other way as seen in the Arctic (figure 8B). These Arctic and Antarctic winter anomalies look suspiciously like the tropopause anomalies.

Connolly and Connolly found that there is a change of state, that might be a phase change, at the top of the troposphere and a similar change occasionally at the surface, in the polar regions, in the winter. After accounting for this apparent phase change, they could describe the atmospheric temperature profiles of all ~13 million weather balloons entirely in terms of the thermodynamic properties of the bulk gases and humidity. For the Earth’s atmosphere, the bulk gases are N2, O2, argon and sometimes H2O. By “thermodynamic properties”, they mean the gas laws, the role of gravity, changes in state (i.e., phase changes), differing heat capacities, etc. Of the four bulk gases, only H2O is infrared-active and the influence H2O has on the atmospheric temperature profile has nothing to do with its infrared activity. Instead, it is related to its phase changes and the fact that it has a higher heat capacity than the other bulk gases.

The temperature fits did not require consideration of the CO2 concentration or any of the other infrared-active (“IR-active”) gases. If the effect of CO2 and other greenhouse gases were as strong as predicted by the climate models, one could reasonably expect that they would affect these temperature profiles.

Most versions of “the greenhouse effect” theory argue that the infrared activity of greenhouse gases (“GHG”) alters the atmospheric temperature profile. In particular, the models suggest that as carbon dioxide is added to the troposphere by man’s emissions, the troposphere should warm. This is supposed to be counteracted by increasing the speed of cooling. Thus, they predict that the troposphere warms and the stratosphere cools due to man’s carbon dioxide emissions changing the atmospheric temperature profile. Therefore, a debate exists over whether there is a “tropospheric hotspot” signature from GHG warming. Some also argue that there must be “stratospheric cooling.” But, the key to these theories is that the IR activity of the GHGs is supposed to in some way alter at least some part of the atmospheric temperature profile. This IR-based effect is the greenhouse effect. But, if the IR activity of the GHGs doesn’t influence atmospheric temperatures, as the Connolly’s found, then there isn’t a greenhouse gas greenhouse effect!

As mentioned above, their analysis of molar density versus pressure reveals a change in slope, probably due to a phase change, that occurs above the troposphere. This phase change can explain most, if not all, of the changes in temperature behavior associated with the tropopause and stratosphere. The tropopause and stratosphere are treated as distinct regions from the troposphere because they have different temperature behaviors than the troposphere. That is, the lapse rate approaches zero in the tropopause and becomes positive in the stratosphere. While this is true, the tropopause and stratosphere share the same molar density vs. pressure slope, intercept, and equation of state.

Multimers and the Ozone Layer

In Connolly and Connolly’s paper 2, they argue that the phase change identified in their paper 1 is due to the formation of oxygen (and possibly nitrogen) multimers, i.e., (O2)n, where n>1. The formation of multimers in the atmosphere is not a new idea and has been studied by Slanina, et al., 2001.

They also noted that if multimers are forming in the tropopause and the stratosphere, there is an alternative mechanism for the formation of ozone, which is much more rapid than the standard Chapman mechanism. That is, ozone (O3) could form directly from the photolysis of oxygen multimers, for example, a trimer (three linked O2 molecules) of oxygen could dissociate into two ozone molecules: (O2)3 + uv light → 2O3.

There is a remarkable correlation between the proposed phase change conditions and ozone concentrations, see figure 9. This is consistent with the Connolly’s mechanism for the formation of ozone, and suggests that the ozone is generated rapidly in situ. Table 2 lists the computed phase change conditions for 12 different regions, separated by latitude, around the world:

Table 2, Source: Connolly and Connolly paper 2

Figure 9, Source: Connolly and Connolly paper 2

Figure 9 shows the monthly variation of the optimal phase change pressure for several of the regions versus ozone formation (from NASA’s Total Ozone Mapping Spectrometer) for the same region. The correspondence between them is clear. It is interesting that the optimal pressure conditions for the phase change vary dramatically from month to month in each latitude band in figure 9 and that the level of ozone also varies dramatically from month to month. This suggests that ozone creation is very fast in the upper atmosphere, something that is consistent with the Connolly’s hypothesis, but not consistent with Chapman’s. It is also not consistent with the hypothesis that chlorofluorocarbons destroy the ozone layer, but that is another story.

Local Thermodynamic Equilibrium

Connolly and Connolly have shown, using the weather balloon data, that the atmosphere from the surface to the lower stratosphere, is in thermodynamic equilibrium. They detected no influence on the temperature profile from infrared active (IR-active) gases, including carbon dioxide. This is at odds with current climate models that assume that the atmosphere is only in local thermodynamic equilibrium as discussed by Pierrehumbert 2011 and others.

Climate models split the atmosphere vertically into many different layers, each a few kilometers thick, then the layers are broken up geographically into grid boxes. Each grid box is assumed to be in local thermodynamic equilibrium (LTE). These boxes are assumed to be thermodynamically isolated. However, within each grid box, the total energy content is assumed to be completely mixed. Because each box is isolated from the surrounding boxes, the rates of IR emission and absorption from the box are a function of:

  • The IR flux passing vertically through the box
  • The current average temperature of the box
  • The concentrations of each of the IR-active gases in the box

Since they are thermodynamically isolated from each other, if a grid box absorbs more (or less) IR radiation than it emits, this will alter the energy content and average temperature of the box. For this reason, a grid box can develop an energetic imbalance relative to the surrounding grid boxes through radiative processes. Therefore, in the models, the presence of “greenhouse gases” (e.g., CO2) alters the underlying atmospheric temperature profiles. But, is this LTE assumption valid? So far, it has simply been assumed to be the case.

What would happen if the grid boxes are not thermodynamically isolated? Well, if one grid box becomes “hotter” or “colder” due to radiative heating/cooling than the surrounding boxes, then energy would flow between the neighboring grid boxes until thermodynamic equilibrium was restored. If the rates of energy flow are fast enough to maintain thermodynamic equilibrium then the radiatively-induced imbalances from the IR-active gases would disappear. Instead, the atmospheric temperature profile would be determined by the thermodynamic properties of the bulk gases. This is what Connolly and Connolly found was happening.

With thermodynamic equilibrium, we would still expect to see, the often observed, up-welling and down-welling IR radiation. We would also still expect the total outgoing IR radiation to remain roughly in balance with absorbed incoming solar radiation, as we currently observe. And, we would expect the IR spectrum to show the peaks and troughs characteristic of the main IR-active gases, i.e., H2O, CO2 and O3. However, Connolly and Connolly found that the IR-activity of these gases does not alter the atmospheric temperature profile.

Pervection

The standard mechanisms for energy transmission within the atmosphere usually considered are radiation, convection (of which there are three types: kinetic, thermal and latent) and conduction. Because air is a poor heat conductor, conduction’s role in atmospheric energy transmission is negligible. That initially would appear to leave just radiation and convection. Both radiation and convection move thermal energy slowly, too slowly to keep the atmosphere in thermodynamic equilibrium. However, we know from thermodynamics that thermal energy can be converted to work and transmitted and then turned back into thermal energy. Thermal energy transfer is not the only method of energy transfer at work in this equilibrium process.

Connolly and Connolly found that there is almost no experimental data on the rates of vertical convection outside of clouds and above the boundary layer. But, from the limited data they have, the rates of vertical convection appear to be too slow to maintain thermodynamic equilibrium from the surface to the stratosphere.

They found an additional energy transmission mechanism which seems to have been neglected, “through-mass” mechanical energy transmission. Unlike convection where the energy is only transported by a moving air mass, this mechanism allows mechanical energy to be transmitted through the air mass without the air itself having to move significantly. This is like conduction, except that conduction involves the transmission of thermal energy, while this mechanism involves the transmission of mechanical energy. To distinguish it from “convection” (which comes from the Latin for “carried with”), they use the term “pervection” (from the Latin for “carried through”). In this process, molecules collide transmitting mechanical energy to one another. An analogy would be a long tube filled with ping-pong balls and the tube is only wide enough for one ball. If a ping-pong ball is forced in one end of the tube, one will immediately be forced out the other end. None of the ping-pong balls move very far, but the energy is quickly transmitted, mechanically, a long distance.

In Connolly and Connolly paper 3, they designed a series of controlled experiments to try to quantify the relative rates of energy transmission of each of these mechanisms in air. Their experiments showed that, at ground level, energy transmission by pervection (aka “work”) is several orders of magnitude faster than conduction, convection or radiation! This then explains why the troposphere and stratosphere are not thermodynamically isolated, as the climate models assume.

Pervection is a mechanical energy transmission mechanism, not a thermal energy transmission mechanism, in common thermodynamic terms it can be considered “work.” Mechanical and thermal energy can be converted to one another as thermodynamics teaches us. So, either energy transmission mechanism can, and will, act to restore thermodynamic equilibrium. This also highlights why it is important to consider multiple types of energy and energy transmission mechanisms.

Conclusions

The three papers by Connolly and Connolly provide new data and analysis that show the IR-active trace gases in the atmosphere have an insignificant effect on the atmosphere’s vertical temperature profile. They show the atmosphere, at least to the lower stratosphere, is in thermodynamic equilibrium which invalidates the local thermodynamic equilibrium assumption used by the global climate models.

Unlike other critiques (Jelbring, 2003, Johnson 2010, O’Sullivan, et al. 2010, Hertzberg, et al. 2017, and Nikolov and Zeller, 2011) of the carbon dioxide climate control knob hypothesis (Lacis, et al., 2010), this analysis explains two lines of evidence often used to justify the carbon dioxide greenhouse effect:

  1. Why is the lapse rate positive (temperature increasing with height) in the stratosphere?
  2. Why do we observe both upward and downward traveling IR radiation in the atmosphere?

The lapse rate, which averages about -6.5°C per kilometer in the troposphere, goes vertical and eventually reverses sign in the tropopause and stratosphere due, at least in part, to the formation of multimers according to Connolly and Connolly. The formation of multimers releases energy, which can account for at least some of the tropopause and stratospheric heating. IR-active atmospheric gases like water vapor and carbon dioxide do radiate IR in all directions and this can be detected, it is just that this radiation does not affect the atmospheric temperature profile significantly according to Connolly and Connolly’s work.

It takes less energy to form ozone directly from oxygen multimers than from splitting diatomic oxygen molecules, although both require UV light. Further, ozone formation does correlate well with the conditions required for multimer formation. Multimer formation does not require sunlight and can occur at night. Also, ozone concentrations in the ozone layer vary rapidly, suggesting ozone is created and destroyed monthly. This is inconsistent with the Chapman process.

The key problem with the conventional idea of IR-active gases, like carbon dioxide, influencing atmospheric temperatures is the concept that the atmosphere is only in local thermodynamic equilibrium. The weather balloon data strongly suggest that the atmosphere is in thermodynamic equilibrium, meaning IR-active gases have little to no influence on atmospheric temperatures. For this to be true a very fast energy transfer mechanism must be at work. Connolly and Connolly suggest that this transfer mechanism is mechanical in nature. Using thermodynamic terminology, the mechanism is “work.” They have proposed a name for the mechanism and call it “pervection.”

Currently, the multimer formation in the tropopause and stratosphere is speculative and requires experimental verification. Likewise, the details of forming ozone from oxygen multimers need to be worked out and documented. Pervection is a proposed name for a relatively obvious form of energy transfer that we observe all the time and has just been overlooked for some reason in climate science. Air is compressible, of course, but it does transmit mechanical energy. BB guns, air compressors and inflatable tires wouldn’t work without this energy transfer process.

So, clearly the Connolly and Connolly ideas need further work, but they have put together a very coherent and detailed hypothesis that deserves serious consideration. It is, at least, as well documented and supported as the conventional carbon dioxide greenhouse theory.

For those that want to read a more detailed summary of the Connolly’s work that includes a description of their laboratory work, I refer them to the Connolly’s summary here and to their three papers, linked at the top of this post.

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313 thoughts on “Review and Summary of three Important Atmospheric Physics Papers

  1. Where I do take issue with these authors is in their use of the term ‘pervection’. In my view convection is perfectly adequate to explain observations when one takes into account the mechanical conversion of KE (heat) to PE (not heat) in ascent and the reverse in descent.

    • Stephen, Convection means carrying the thermal energy with the mass as internal energy. This process, when modeled, is way too slow to allow atmospheric thermal equilibrium for the lower 35 km of the atmosphere. Thus, we get into a verbal definition trap. So, the Connolly’s (quite correctly IMHO) decided to make a new term for the energy transmitted (during convective action to be sure!) but transmitted mechanically. Then they measured the speed and found it was very fast, fast enough to account for thermodynamic equilibrium over the lower 35 km of the atmosphere. I realize that introducing a new term for energy transmission can put off a reader, it put me off for a while. But, once you think about the speed issue, you see why they did it. It is key to seeing how the atmosphere can be in overall thermodynamic equilibrium. If you box yourself in, only considering convection and radiation, you are led to Local Thermodynamic Equilibrium only.

      • Andy,
        For an atmosphere in equilibrium as a whole the downward force of gravity must on average exactly offset the upward pressure gradient force created by heating at the surface beneath that atmosphere. Isolating the lower 35km is not appropriate. There is convective overturning above that height too. When the entire atmosphere is considered one only needs convection, no need for ‘pervection’.
        Convection uses work done against gravity in uplift and work done with gravity in descent to switch internal energy between KE (heat) and PE (not heat) as necessary to maintain equilibrium between the downward force of gravity and the upward pressure gradient force. That is the only mechanical process required.
        That switching process serves to neutralise any radiative imbalances that are internally induced.
        Instead of transmitting energy as proposed by the authors there is a transformation of energy between KE and PE whenever and wherever a change in height occurs.
        Proposing some novel form of energy transmission is unnecessary if one can have a transformation instead.
        Only in failing to note that process of energy transformation does it become necessary to propose some novel form of energy transmission.

      • Convective velocity is analogous to drift velocity of electrons in a conductor..for all real world electrical applications, drift velocity is under c/10 (exception being superconductors ). The electric field is however, just under c.

        Or simply put, pervection velocity is sonic.

      • -Stephen
        I don’t mean to put words in Andy’s mouth ( or the Connolly’s) and I barely understand the hypothesis, but I don’t think they are proposing a “new form” of energy transmission. Just breaking out an aspect of convection that they believe is largely unrecognized and important and therefore identifying it separately.

      • John Harmsworth and Stephen Wilde, John, I think you are closer. It is not like mechanical energy transfer is or was unknown, it just is not included in the climate models. Leaving it out has led to the wrong conclusions about equilibrium. After all, no one has proven that local thermodynamic equilibrium exists. It is just an assumption that has been made because models show that radiative transfer and convection are too slow. They felt the trunk and the leg and missed the elephant. By naming “pervection” the Connolly’s are just trying to get people to notice it.

      • In liquid piping systems, movement of substances such as water or oil in long sections of pipe can involve a very considerable mass and hence momentum. Where and how does this energy manifest itself. Water “hammer” is known to most people, as it can damage piping in homes, even in small water lines across quite short distances. In larger pipelines for oil, water or other liquids it is extremely important that one not attempt to stop flow instantaneously as major damage can occur as a result of the hydrostatic pressures directed at the stoppage point and reverberating back as a shock wave. This damage is a function of the large momentum inherent in the motion of the mass along the entire length of line. It can be very substantial.
        Whereas liquids are incompressible and this type of damage can result, gases are not. However, an equal mass of gas in motion contains an equal quantity of momentum energy. As it slows it will compress and rise in temperature instead of creating hydrostatic pressures. No question that large amounts of heat move around the planet as motion of bodies of air. IMO.

      • It’s all vapor and light condensation that evaporates before the surfaces, excepts what sticks as dew depending on surface temp. Cars have dew, driveways do not.

    • The tendency to isolate grid cells, as if no energy moves sideways is just plain stupid, and is why the CAGW models fail. It’s not ALL radiative physics …. there is a lot of kinetic energy involved as well. … and a lot of that is chaotic.

      • Dr Deanster,

        I think it’s the other way around. Radiation goes in all direction connecting all grid cells to each other at the speed of light.

        The premise here seems to be that the ‘disconnected’ cells happen to absorb more or less photons then they emit and must be rebalanced by collisions which won’t happen between disconnected cells.

        Kirchoff’s law is a bulk property, so it’s not clear that it still applies in the limit as assumed by Pierrehumbert. There also seems to be an over generalization of Equipartition of Energy. It’s generally interpreted as meaning that energy stored in all degrees of freedom will be freely exchanged among the molecules until all degrees of freedom are balanced. While this is true with degrees of freedom related to mass in motion, it’s not necessarily true with state energy which is basically stored as a resonant wave in the electron cloud of a molecule which can only be emitted as a photon or completely exchanged with another molecule that has the same resonances, i,e, another GHG molecule of the same type.

        Radiation physics textbooks generally consider only a homogeneous gas, where as a mode of relaxation, an energized molecule collides with a ground state molecule and after the collision the energized molecule is now in the ground state, while the ground state molecule is now energized. This is a lossless transfer of state energy which if I recall, is related to the formation of Cooper Pairs in superconductors. This relaxation mode combined with Equipartition of Energy suggests that state energy stored as an EM wave must be directly converted into the energy of mass in motion in order to achieve LTE. The problem is that state energy is quantized in relative large chunks of energy, compared to that in the mechanical degrees of freedom and Quantum Mechanics requires that the entire quanta of energy be exchanged or emitted in one event. This doesn’t seem likely to occur since the kinetic energy of a molecule in motion is already about the same as the energy of a photon in the LWIR spectrum emitted by the planet, thus for all intents and purposes, it already satisfies Equipartition of Energy as a bulk property.

        It seems to me that at least in the limit, Kirchoff’s Law and Equipartition of Energy should apply independently to state energy and the energy of mass in motion and combined only as a bulk property.

        I also think that there are 2 different kinds of rotation. One is a physical rotation of the molecule, which is mass in motion and is not quantized and the other is a rotating wave in the electron cloud which is quantized and more closely related to quantum mechanical ‘spin’. This addresses the counter example where rotation modes are suggested as one of the mechanisms which converts between the energy of matter in motion and energy stored as E-fields in motion.

    • I agree Steven, “pervection” is a rather ugly word too close to other words beginning with “perv…”
      Plus as you say, semantically it is redundant.

    • water gas is going to the stratosphere no matter what temperature simply cuz of gravity. not even any need for convection.

    • Kinetic energy is velocity (squared) mass where heat energy is its own property. One can see pervection in the anvil top of mesoscale cumulonimbus clouds. The convective kinetic energy changes the stratopause shape and upsets the order of the stratosphere.

      • The energy in cumulonimbus anvils is from excess kinetic energy originally from the surface pushing up into the stratosphere and being prevented from going even higher by the reverse lapse rate slope caused by ozone absorbing solar energy directly.
        Since further upward movement is constrained the warmer air in the updraft pushes sideways instead and the sideways movement into colder air at the relevant height finally converts the residual excess kinetic energy into potential energy prior to descent in the adjacent descending cell.
        The spreading anvil actually proves my point.
        The thing is that all this is implied by general meteorology but that is a specialised discipline that climatologists seem to have never got to grips with.

      • Thunderstorms distort pressure above and below. The reduced density below plus dynamic pressure (density velocity squared) drops pressure while the dynamic pressure above further distorts the stratopause.

  2. Andy.
    There is so new much in this!
    Talk about settled science…
    Great to see this view of atmospheric physics through the eyes of a Petrophysicist.
    Congratulations.

  3. This makes two papers in a row that have been really interesting. The astronomical cycles papers, and now this one.

    I say get it peer reviewed and get it in the pipeline for the next piece of crap out of the IPCC. …. could make the next piece of crap from the IPCC a little less crappy.

    • Dr. Deanster, I agree. The Connolly’s should pull together a paper and submit it for peer-review. I’ve volunteered to help if they need it. But, it is a pain. I submitted a paper (not on this topic) for peer review over a month ago and they are still looking for reviewers!

      • What better peer-review than publication here? This is honest, ruthless, trans-disciplinary, happens in real-time, with no-holds-barred, and conflicts-of-interest exposed. Formal academic peer-review is shallow, procedural, silo’d, corrupt, terminally politicized, and unwieldy. We can (and do) do better than that, and do it almost all of the time.

    • “I say get it peer reviewed…” I couldn’t agree more. They have had 4 years to do so and no sign yet…

      • David Ball: “I am curious what seaice1 would say if it passes peer-review,…..”

        I will of course respect the paper a whole lot more. I will have confidence that the paper does not contain egregious mistakes and that it reviews the current literature reasonably.

        As it is, the whole idea of oligomers of N2 and O2 held together by van der Waal’s forces seems wrong. The authors even tell us these sort of agglomerates have only been detected under very different conditions or at trace levels. Their hypothesis requires a large proportion of the gases to be in this agglomerated form. I am suspicious of their calculation of heats of formation as it looks more like a calculation of heat capacity. I am suspicious of treating the van der Waals bonds in the same way as covalent bonds for some purposes and for allowing the vibrational modes in these bonds to be degrees of freedom. These may be OK, but I have serious doubts. If it had been peer reviewed I would have confidence that these aspects had been checked at a reasonably high level. That would not mean that I would blindly accept the conclusions, but I could accept that the work had been performed at an acceptable level to be worth considering.

        As it is I would have to research each of these aspects myself. I could probably do it to my satisfaction for these papers, but why should I pick these over 1000’s out there? Just on law of averages most will fail. I cannot review every paper myself, nobody can.

        As it is, the process here is also a form of review. I will have a look at the comments and I may find that the review has found fatal errors, or I may find that there are explanations for my concerns. So the review here is not worthless, but it does not have the same weight as peer review.

      • Seaice1

        “I will have a look at the comments and I may find that the review has found fatal errors, or I may find that there are explanations for my concerns. So the review here is not worthless, but it does not have the same weight as peer review”

        Spoken like a true follower, when someone else does tell you what to think of the paper please let us all know right away, i for one am waiting with great anticipation.

      • I think that is a fair assessment by seaice. It definitely needs some attention from an atmospheric physicist with an open mind to provide a first appraisal and see if it is worthy of greater attention or publishing. Hopefully, this site can help provide some critique and direction, and perhaps a connection to more meaningful analysis. It’s implications are certainly interesting.

      • “I am suspicious of their calculation of heats of formation as it looks more like a calculation of heat capacity.”
        No. From the description above, its simply 1/2 the translational degree of freedom because 4 rather than two molecules ( minus the small increase within) move together provides the heat for the PV work. I’ve yet to read the paper but the real problems is why should they spontaneously form and more as the air thins out?

  4. I suggest considering the movement of charge for the formation of ozone: e + O2 -> O- + O; O- + O2 -> O3 + e. It’s called associative detachment and has huge low energy cross sections which does not require a third body for conservation of momentum.

  5. Andy, thanks for drawing attention to these papers. I thought they would be gamechangers at the time, but the alarmist bandwagon rolled on and took no notice. One small edit: temperatures in the tropopause do not rise with altitude (the graph shows this, but the text is misleading).

  6. By studying weather balloon data around the world Connolly and Connolly show that the temperature profile of the atmosphere to the stratosphere can be completely explained using the gas laws, humidity and phase changes. The atmospheric temperature profile does not appear to be influenced, to any measurable extent, by infrared active gases like carbon dioxide

    Being flippant, who would have thought that!

    Obviously, the source material needs to be studied before meaningfully commenting, but I have for years suggested that people may well be confusing the radiative effect of water vapour with the effect it has by virtue of its latent heat content.

    The reason why deserts (such as the Sahara) cool down so much at night is not because they have clear skies with no DWLWIR being provided by clouds, but because there is little energy entrained in the dry atmosphere. it has little energy to give up so when the sun goes down, the nighttime temperatures cool rapidly, and since the atmosphere contains little energy as soon as the sun gets up, the day time temperatures rapidly warm. Little energy, no inertia.

    Just a few hundred kilometers from the Sahara on the shores of the Mediterranean one sees a completely different temperature profile. One has clear cloudless nights but temperatures remain high well into the early hours of the morning. When the sun gets up the following day, the day time temperatures take time to warm. On the shores of the Mediterranean the air is humid. It contains a lot of energy which needs to dissipate such that it takes time to cool, and since in relative terms it still possesses considerable energy, it is slow to warm the following day when the sun is up. It has a lot of inertia.

    On the shores of the Mediterranean in summer, a cloudy night is usual a cool night, whereas a cloudless night is usually warm.

    • but I have for years suggested that people may well be confusing the radiative effect of water vapour with the effect it has by virtue of its latent heat content.

      Yep, it condenses, and the radiation from condensation light’s up the water vapor cloud in the troposhhere, evaporating water. this cycle becomes a heat pipe, warm surface evaporate water, rises, condenses at the top. It all depends on air temp and water load, and yes pressure would also respond. How much does the atm column collapse under clear skies at night, and then how much does it go up during the day? that is solar storage of energy as water vapor, that is then released only after air temp drops, when rel humidity get over ~60%, whether there are either trimer, or just more water molecules involved in the condense and evaporate cycle, I don’t know. But it is a temperature that is defined by air temp and pressure, and how much water vapor the air is carrying.

      This is what keep the surface warmer than it should be. But it also regulates the impact of the other GHG’s!!!!!!
      It counters them with a nearly equivalent negative feedback. I have been yelling about this since last year. There is almost no impact from co2, this explains it.

      The energy stored in even 1,000′ of atm height, all that energy get radiated in the upper troposphere over night, depending on air temp and pressure, as the OP describes. It’s a heat engine. and that prevents the loss of temps the deserts have at night.

      • I don’t disagree with Richard or Micro. I would only add that conditions must change higher in the atmosphere where water vapour is negligible. We know that all heat eventually leaves the planet. GHG theory is all about how long it takes to escape, and that question is dependent on mechanisms of heat transport from the lower atmosphere to altitude. I don’t know if the Connolly’s are on the right track but it looks a lot more like science than anything I’ve scene from mainstream climate science like the Hockey Stick clowns.

      • As OP mentions, it’s temp/pressure where the water vapor condenses at the top. It’s working just like the heat pipe in your laptop does, minus tubes which constrains the ir from the heat of condensation. That IR, keeps the sure warm. But because it’s reference point is independent on co2, this process takes a 0.85C day time increase for instant, and reduces it to a tenth of a degree or two.

    • richard verney August 22, 2017 at 6:19 am

      The reason why deserts (such as the Sahara) cool down so much at night is not because they have clear skies with no DWLWIR being provided by clouds, but because there is little energy entrained in the dry atmosphere. it has little energy to give up so when the sun goes down, the nighttime temperatures cool rapidly, and since the atmosphere contains little energy as soon as the sun gets up, the day time temperatures rapidly warm.

      Imo it is the other way around. The dry soil in deserts warms up easily and loses energy fast as well.
      Wet soil and oceans warm up and cool much slower.
      The atmosphere close to the ground follows the temperature of the surface closely.
      After sunset with a dry atmosphere the atmospheric window is wide open and the ground loses energy directly to space fast. Higher up the atmosphere doesn’t cool that much.
      This is how Nocturnal Inversions are created.

      Posted on another blog

      Actually I made the claim that given the right conditions (no wind, no clouds, low humidity) the surface cools rapidly overnight, creating a nocturnal inversion, since the atmosphere cools slower than the ground in that case.
      Obviously the surface warms faster during the day (sun shining) the atmosphere warms much slower.
      see http://weather.uwyo.edu/cgi-bin/sounding?region=mideast&TYPE=TEXT%3ALIST&YEAR=2017&MONTH=06&FROM=2812&TO=2812&STNM=40437
      and
      http://weather.uwyo.edu/cgi-bin/sounding?region=mideast&TYPE=TEXT%3ALIST&YEAR=2017&MONTH=06&FROM=2900&TO=2900&STNM=40437
      Two soundings at Ryadh airport. First at 1500lt second at 0300lt.
      Temperatures:
      surface 44,2 31,4
      700hPa 16,8 17,2
      500 hPa -1,7 -0,7
      300 hPa -28,1 -28,5

      • This is how Nocturnal Inversions are created

        These are the formation of a vertical heat pipe that uses water vapor as the working fluid. This process is what limits how far temps fall at night.

  7. Pervection is a mechanical energy transmission mechanism, not a thermal energy transmission mechanism, in common thermodynamic terms it can be considered “work.”

    Are you suggesting that the collisions aren’t so much conducting the energy throughout the atmosphere as they are “lifting” the atmosphere? Or something like that?

    • Yes, in a sense. The Connolly’s liken it to a Newton’s cradle toy. The steel balls in the center don’t move, but they push the far ball way in the air. This is pervection. I used a tube filled with ping pong balls, same thing. Air is compressible to be sure, but not completely, thus inflatable tires work, airplanes can fly, etc. If you excite air molecules, they will strike neighboring molecules and they move. Look at the experimental work that the Connolly’s did in section 3 of their paper 3. That explains it fairly well. see here: http://oprj.net/articles/atmospheric-science/25

      • Conversion of PE to KE in descending air manifests as a rise in temperature as per the Gas Laws because molecules move closer together when air descends and that higher temperature tries to push the molecules further apart but the lower height means that the air above is heavier so that moving apart is constrained and the temperature rise is preserved along the lapse rate slope.
        Conversion of KE to PE in rising air manifests as a fall in temperature as per the Gas Laws because molecules move further apart when air rises but the greater height means that the air above is lighter so that they cannot move closer together and the temperature fall is preserved along the lapse rate slope.
        The authors are reinventing the wheel with the concept of ‘pervection’.
        Convection is not just localised parcels of rising air. At any given moment half the atmosphere is slowly spiralling downwards in high pressure cells and half is spiralling upwards in low pressure cells.
        If anyone thinks that convection is not sufficient then they have a conceptual error somewhere in their analysis.
        The atmosphere as a whole is forever in hydrostatic equilibrium whereby radiative imbalances are neutralised by convective adjustments.

      • I believe there is still an aspect of work in addition to the described convection in that there will be momentum in any moving mass of air. It may not seem like air has a great deal of mass or momentum when looked at on the cubic foot scale but the entire atmosphere is in constant motion. That is massive work being done every second, vertically and horizontally and represents enormous energy.

      • John Harmsworth
        Agreed. Zonal wind speed at 60 degree South are a good example. The mass increased along with speed. The effects of both have profound effects on SH “average” temperature and barrier to vortex entry.

  8. Andy, very interesting, just a few questions that went over my head.

    1) What is/are the ‘bond’ that holds Multimers together?
    2) How can O2 go through a phase change at our atmospheric pressure/temp?
    3) Fig. 6 still shows the breaking of the diatomic oxygen bonds. How is this done with less energy?

    • If it is obvious in the article, just tell me to read it again (and again). Don’t want to waste your time.

    • Duncan, 1) Van der Waals forces
      2) Some lab work shows that, at the temperatures seen in the troposphere, some multimers will form. But, this is an area that needs more work to be sure.
      3) This is another area that needs more laboratory verification, but chemical theory suggests it should work. I’ll ask Ronan and Michael to comment further.

      • Thanks Andy, #3 was my major mental sticking point. Possibly some sort of Isotope exchange?? Anyway beyond my Chemistry 101.

  9. Oxygen and nitrogen telomere formed at low pressure. Wow that is new! Telomer formation according to thermodynamics is favoured at high pressures not low. Therefore there should be evidence in the gas law (pV = nRT) for oxygen, and nitrogen . This would be possible to observe in a ground based lab. Show me this evidence and we can take this seriously. At conditions near the boiling point of certain gases these telomers are believed to form , the most notable case is in hydrogen fluoride gas which telomerises before condensation. This has been shown in laboratories by deviations from the gas law. Now according to the graph oxygen and nitrogen are at temperatures well above their normal boiling points some 80K at 1atm pressure.they are at pressures well below normal atmosphere. Show me real evidence for these telomers and you have Nobel prize material. Congratulations.

    Seriously The only form of attraction detected between Nitrogen molecules are van Der Waal forces which are incredibly weaker than proper bindings. For HF we have hydrogen bonding to form these telomers which are orders of magnitude greater than Van Der Waal forces and are about a tenth of the strength of a proper covalent bond, so we get weak association at high pressure. So everything is wrong for these nitrogen and oxygen telomers

  10. Duncan,
    The gas law deviations for oxygen and nitrogen have been measured and are accounted for by the deviations to the gas law. The van Der Waal forces are much weaker than hydrogen bonding which is much weaker than covalent bonding. We know the effects of van Der Waal and they do not form multimeres/telomers they just give a small deviation to the gas law.

    The idea that multimers form at low pressure rather than high pressure is very novel and against thechemical equilibrium laws. (Dissascosiation constant etc)

  11. …But they present new data and a novel interpretation of energy flow in the atmosphere that should be seriously considered in the climate change debate…

    Does that interpretation exaggerate the warming effect of CO2? If so, it will be gleefully embraced. If not, it will be ignored…

    • Does that interpretation exaggerate the warming effect of CO2? If so, it will be gleefully embraced. If not, it will be ignored…

      It nullifies almost all of it.

  12. Andy, let me try again. As an alternative to multimers, let me suggest associative detachment created by following the electrons moved along magnetic field lines. The reaction proceeds in two steps: O2 + e -> O- + O; O- + O2 -> O3 + e. The cross sections for the second reaction are huge at low energy and don’t require a third body for conservation of momentum. This allows for the ozone differential from the tropics to the poles.

  13. The tetramer of oxygen will be governed by the law p (O8) = K p(O2)^4 where p(O8) is the pressure of the tetramer and p(O2) is the pressure of normal oxygen and ^4 is being raised to the fourth power and K is a constant, from the equation deltaG = -RT ln K, where deltaG is the free energy change of the reaction R is the gas constant and T is the absolute temperature. Please explain how using typical Van der Waals energy for the tetramer at 200K how the compound forms at low pressure but not at high pressure?

    I will be very interested in your result

    • Dave, this is Michael Connolly’s answer: “The relationship between the partial pressures of monomers and multimers is indeed given by deltaG = -RT ln K so the ratio of multimer will come down to the value of deltaG
      In an open system like the atmosphere this depends on a lot of different energy parameters as we explain in equation 17 of paper II. Van der Waal forces is a generic name for a lot of different types of interactions, both Coulombic and magnetic. The oxygen monomer is paramagnetic where as the dimer is diamagnetic larger multimers might also be diamagnetic, but this is conjecture at this point. Given the possible stabilization of diamagnetic multimers and the deltaH values of Table2 it is possible that the concentrations of multimers could be significant as we propose.”

      It is important to realize the Connolly’s have no experimental evidence for the multimers, they are speculative at this point. Their lab work and work with weather balloons establish that pervection is a rapid form of energy transfer and that the atmosphere is in thermodynamic equilibrium to 35 km, but the multimers and the ozone formation are hypotheses that need experimental verification.

      • Serious question, would it not be relatively simple to establish the existence of multimers in the lab? After all, they say that the bonds between the molecules count as vibrational degrees of freedom, so these could easily be detected by spectroscopy.

      • So you cannot explain the fourth power that comes into the standard equation. I.e. by halving the pressure then the pressure of tetramer will go down by (0.5)^2 i.e. 1/16 yet these tetramer appear at low pressure not high. They are therefore in contravention of the equilibrium laws that are obtained fromcombining the deltaG values of the individual species. As I state elsewhere Hydrogen fluoride gas forms multimers at pressures and temperatures approaching the dew point. Your T etramers are behaving completely opposite to these well established multimers and in contradiction to established equilibrium laws.

        In addition Hydrogen fluoride forms extremely strong hydrogen bonds and is highly polar. Oxygen does not contain hydrogen and is not polar so one would expect any intermolecular bonding to be much weaker than in HF. I.e. if you are going to see multimers they will be just above oxygen boiling point and at high pressure not at 200K and at near vacuum conditions.
        For real associations between non polar moleculesvyou will need to go down to less than 10K. I.e. -263°C

  14. “They found an additional energy transmission mechanism which seems to have been neglected, “through-mass” mechanical energy transmission. Unlike convection where the energy is only transported by a moving air mass, this mechanism allows mechanical energy to be transmitted through the air mass without the air itself having to move significantly. This is like conduction, except that conduction involves the transmission of thermal energy, while this mechanism involves the transmission of mechanical energy. To distinguish it from “convection” (which comes from the Latin for “carried with”), they use the term “pervection” (from the Latin for “carried through”).”
    With a similar mechanism, a wave also transports energy in any medium. Also the energy during an El Nino is largely transported in such a way, only there is an up and down welling. There is also transport of the heat without the single water molecule from Sumatra to South America must migrate. The energy is given from molecule to molekule. In conjunction with the higher solar irradiation during an El Nino in the respective area, the positive anomaly is thus created.. Also boiling water gives Energy from molecule to molecule. There is no mechanism, that the water molecule, which heated most at the ground of the pot, rise to the top. In Fact, the molecules come in a circling motion and gives their motion-energie from molecule to molecule. That is the mechanism of boiling water. There is so much to learn in the science of the atmosphere.

    • El Nino’s just releases large amounts of water vapor downwind, and it’s actually trapped in the NH as well for the most part. Then MinT follows dew point temps. Same with ocean cycles.

  15. Please explain why the above curve is exactly (almost, only takes minor adjustments in the scale of temperature/speed to make them identical) the same shape as the speed of sound curve in atmosphere by height?

    Does this change in speed slow down/speed up the transfer of energy through the atmosphere?

      • That is interesting. The speed of sound would vary with the pressure/temperature which varies with the density of the medium at diffing altitudes?

      • At first I thought it was density, however, I then noticed that both density and pressure drop 20 esentially ZERO above 30 kilometers. Also does not explain why the speed follows density in the lower atmosphere and then is inverse to density/pressure from 10 to 30 kilometers and then back the other way again just like temperature. Is it some kind of Quantum Mechanics phenomena?

      • @ Andy May if you are reading this I would appreciate your thoughts on the following post at 1:32

    • Look at the graph on the Wikipedia link. Note that temperature an speed of sound BOTH change in a peculiar fashion with height. Below 30km they change in relation with height/density/pressure UP TO 10 km. Then temperature and the speed of sound vary inversely with height/density/pressure. Thern above 30km, where the pressure and density are essentially 0.0, bothe the speed of sound AND Temperature decrease with height up to 80 km whereupon it then begins decreasing! WHY. WHY? at all heights above 30km the density/pressure as almost the same as outer space, very close to zero. That tells me there is a great distance between molecules. So just what is heating them? Then what is cooling them. and again at the highest height what is heating them again where they are the closest to absolute zero – outer space? Logic says they should continue cooling.

      Is all of this an aberration to the method of determining temperature? From my days in college (50 years ago) I was told that temperature is a crude measurement of the strength of the energy. The average kinetic energy of all the atoms or molecules of that substance. With less atoms per unit area there should be LESS average kinetic energy! My Nuclear Physics training tells me that with FEWER atoms per unit area there are fewer collisions and a much smaller chance of energy transfer by particle capture. Seems to me that no one knows what they are measuring.

      • I really don’t know what is happening. The Connolly’s ideas are one of many possible answers. By the way, sound is a form of pervection, but sound travels slower than the pervection the Connolly’s measured.

      • Temperature is the average Kinetic Energy of the atoms (and/or molecules) in that space. Does not matter how many there are. But temperature loses its meaning (or, usefulness) if there are only a handful per cubic centimeter.

        High temps in the Thermosphere results from absorption of the high-energy UV radiation from the sun by the atoms (O, N, Ar, H) and any molecules (N2, O2, O3, H2O, CO2, ) that have not dissociated already. Of course many are ions (OH-), and there are free electrons floating about as well.

    • Speed of sound is exactly what the Connelleys were describing. Energy traveling faster than the medium.

  16. Temperature as measurement includes all forms energy flowing where you do the measurement. It is the net flow in a point resulting from all work and flowing energy in the surroundings.

    An observed temperature is the sum of all work and heat from points of higher emissive power.
    Temperature, representing emissive power/T⁴, determines all rates of all processes transferring energy in the system. The processes of transfer only exist because there is a heat flow, they determines nothing. That is why a probabilistic energy density analysis based on only heat source power and geometry gives a correct profile with high accuracy. And it includes the force of gravity as thermal resistance with units Nm² instead of Nm. N/m² is exactly equal to W/m². Consider the failure of climate science when you see what temperature that is equal to the thermal resistance of 4g². And that tropopause temperature equals 4/3*g².

    • “N/m² is exactly equal to W/m².”
      Can you explain this?

      There was an article here recently looking at dimensional analysis, which revealed interesting relationships between units.

      N/m2 is pressure, or force per area.
      W/m2 is power per unit area
      Power has dimensions mass x length^2 x time^-3
      Divide this by length^2 (m2) we get mass x time^-3

      Newton has dimensions mass x length x time^-2
      Divide by length^2 we get mass x length^-1 x time ^-2

      We can convert N/m2 to W/m2 by multiplying by length x time^-1, or say m/s, which is speed.

      A diversion perhaps, but how can you say N/m2 is equal to W/m2?

      • Both units are energy applied to a unit of area. Energy is energy I guess but I don’t see this “equivalence” as being very useful rather than seeing it just as a relationship.

      • “Both units are energy applied to a unit of area. ”
        Not really. One is energy per unit area and one is force per unit area. Unless you want to argue that energy and force are the same then that is not true.

  17. “The atmospheric temperature profile does not appear to be influenced, to any measurable extent, by infrared active gases like carbon dioxide.” Everything old is new again. In a review of Callendar’s famous paper on CO2 causing atmospheric temperature changes:

    Sir George Simpson, reply to Callendar, Quarterly Journal of the Royal Meteorological Society, vol. 64, issue 275, pp. 223-240, 1938

    “In the first place he thought it was not sufficiently realized by non-meteorologists who came for the first time to help the Society in its study, that it was impossible to solve the problem of the temperature distribution in the atmosphere by working out the radiation. The atmosphere was not in a state of radiative equilibrium, and it also received heat by transfer from one part to another. In the second place, one had to remember that the temperature distribution in the atmosphere was determined almost entirely by the movement of the air up and down. This forced the atmosphere into a temperature distribution which was quite out of balance with the radiation. One could not, therefore, calculate the effect of changing any one factor in the atmosphere, and he felt that the actual numerical results which Mr. Callendar had obtained could not be used to give a definite indication of the order of magnitude of the effect.”

    • This is one of the issues with our atmosphere; the convective nature, and convection over powers everything.

      Think of a BBQ. The heat starts off as radiative energy from the charcoal, but one cooks the steak by convection not by radiaive energy.

      One can cook a steak 18 inches above a BBQ, but not 18 inches to the side or 18 inches underneath, notwithstanding that if one were to measure the temperature of a BBQ, with say a pyrometer from the side or from the underneath, it would show that the BBQ was equally hot.

      The radiative signal is there when viewed from underneath, but it does not enable work to be done. The work is moved by convection.

      • ” but one cooks the steak by convection not by radiative energy.”
        I cook my bacon under a grill. This is entirely radiative energy. To be honest, I don’t know the amount of energy transmitted to my food on barbecue by convection, but I think comparing it to my grill it is probably mostly radiative rather than convection. I have never seen a barbecue design that allows food to be placed underneath the hot coals. The problem would be that the ash would fall on the food. So my electric grill works by having a very hot element above the food, and my barbecue works by having very hot coals below my food, but both seem to work in the same way.

      • I have an electric oven which radiatively heats from above when on broil. It can also be set on broil with convection which cooks food much faster .

      • @seaice1 August 22, 2017 at 1:38 pm

        ” but one cooks the steak by convection not by radiative energy.”
        I cook my bacon under a grill. This is entirely radiative energy.

        You fail to grasp the point. To cook bacon under a grill one has to be within inches of the grill (often in an enclosed space at that). You cannot cook your bacon say 18 inches underneath the grill, because the radiative energy is over powered by convection. And this planet has a convective atmosphere, and this is the work horse.

      • Hey Richard, maybe your barbecue is different from mine. Others also think it is mainly radiation.
        “Radiation is the transfer of heat by direct exposure to a source of light energy… This is how most charcoal grills cook.”

        “Charcoal grills produce a lot of direct scorching infrared radiation that is converted to heat when it strikes food. Gas and pellet grills produce mostly convection heat.”

        Maybe you are thinking if a gas or pellet grill and I am thinking of a charcoal grill. BBQ suggests charcoal to me.

  18. Am familiar with VanDerWaal forces from a different field, graphene clumping. Am also familiar with dimer/trimer formation in a different foeld, anionic surfactant synthesis, when you want to minimize them in the finished ether precursor and then remove the rest by fractional distillation prior to streckerization. Have not done the math, but my intuition suggests that VanDerWall forces are insuffient to form gas multimers as posited. There just isn’t enough force between ordinary gas molecules in the conditions of the region where posited. A graphene has a very high surface to mass ratio, so the force is appreciable under room temperature conditions.

    • I too am concerned by the weak nature of Van der Waal forces.

      It seems to me that there is a need for some experimentation to back up some of the claims being made

    • They can and have been observed at 5K yes that’s -269°C. If you warm them up they fall apart.so 200K as in the atmosphere is positively scorching. With highly polar molecules with hydrogen the hydrogen bonding can make these multimers a bit more robust. But oxygen and nitrogen do not have hydrogen so we are back to 5K to try and find them

    • I’ve found out why there is so little warming from the increase in co2. And why temps are doing what they are.

      It has nothing to do with Co2, and I’m a multi discipline data/circuit analyst. There are no amount of me editing my work that would meet anyone’s approval, because it’s the end of the ride.

      The OP’s original premise is fundamentally correct, he just missed that the water vapor is doing work(inflating the atm column daily), and the by product of that work keeps the surface following dew point.

  19. Andy,

    You remark, “Further, if the Chapman mechanism were the only mechanism forming ozone, why would ozone concentrations, in the Northern Hemisphere, be the highest in the Arctic in the spring?”

    Both the Artic and Antarctic have anomalous high concentrations of ozone outside the polar vortexes during the Spring, and disappear when the vortexes break up in late-Spring. The explanation appears to be in the Brewer-Dobson circulation being impeded by the vortices. It should be noted that the ozone concentrations are not uniformly distributed (look at any collection of NOAA/NASA ozone ‘depletion’ maps) and probably reflect differences in diurnal ozone generation, winds, and other atmospheric phenomena, particularly in proximity to the vortices.

    • What about particle radiation as a cause for ozone formation? It’s concentrated at the poles.

  20. A very good article, Andy, that makes accessible the Connolly’s views on the atmosphere.

    Their work sounds plausible to somebody as ignorant as myself on these issues, but what really should matter is what the experts think of their proposals. As far as I can tell their work does not contain experiments, but a reinterpretation of the evidence. If they can demonstrate that their reinterpretation is better at explaining the observations, they should not have much problem in getting it published.

    However it bothers me that they need a new term to define a vertical transfer of energy in the atmosphere. Scientists have been studying that subject since the dawn of modern science. We are now living in a time with the highest proportion of scientists in society and the highest number by far, and they work in a very competitive environment. They are very intelligent people always on the look for new important discoveries in their areas of study. It is therefore harder than ever for non scientists to make important contributions to science. Not impossible, but not easy at all.

    I don’t know, but their pervection sounds quite a lot as the vertical gravity waves that transfer momentum and energy from the surface and troposphere upwards. Scientists have been studying them for the past 50 years and have a good understanding of their physics.

    • My take on pervection would be the classic Mexican Wave or watching cars/traffic at sets of traffic lights.

      So, all is calm in a group of molecules (all at the same temp) then one of them (possibly a CO2 molecule) catches a passing package of energy (photon)
      It then, almost instantly ‘jumps’ – it becomes excited or more energetic than its immediate neighbours and gives one of them an almighty jolt.
      In turn it ‘jumps’, bumps its neighbour who then bumps the next then the next.
      Just like at the traffic lights, each car, in turn, waits for the one in front of it to start moving before it does. Or the Mexican Wave.
      Or ripples on a pond when a pebble is thrown in.
      And the pebbles come from, or are, packets of energy ‘captured/trapped by ‘green house gases’

      More you think about it, it is sound propagation.

      Is it directional?
      IOW, would/does/do sound waves preferentially accelerate into lower pressure or lower temperature. i.e. go down or up with any preference.
      Or sideways by preference which is why climate models can’t/don’t handle them

      • If this wave formation with vertical energy transport is still further thought, then the mere upward transport of air with convection as a secondary effect can trigger such a transfer of energy from molecule to molecule. Even after the earthquake in Nepal in 2015, it was proved that the ozone layer has been reacting to the earthquake in an incredibly short time (21 minutes). The question now arises, why did he react. Because of electromagnetic waves, which were triggered by the quake or by the displacement of air masses (also air masses have a mass) by the quake and passing of the kinetic energy from molecule to molecule up into the ozone layer.

    • “As far as I can tell their work does not contain experiments, but a reinterpretation of the evidence.”

      It seems to me an obvious experiment would be to detect these trimers and tetramers in gas samples at realistic atmospheric conditions. This should not be too hard to do.

      They say there is a phase change. That could be experimentally checked.

    • Javier, they have experimentally verified the speed of pervection. They have also shown that the lower atmosphere is in thermodynamic equilibrium. The multimer formation is educated speculation, so is the ozone formation mechanism that they propose.

      • So why do you and the authors prefer this new multimer based explanation as against the ozone formation mechanism which has been demonstrated convincingly for decades via observation ?

      • Do you have references to ozone formation from lab results using the UV proposed mechanism? The experimental test of such a mechanism should be straightforward at the pressures indicated. The vibrational excitation of the resulting ozone should be measurable.

    • This appears one of the problems that besets so much of climate science.

      It is just like Climate Sensitivity (if any at all) to CO2. The signal is just too difficult to measure, since if there is any signal it has yet to raise its ugly head over and above the noise of natural variability in temperature, notwithstanding the use of our best and most sensitive measurement devices, and the inherent error bounds of the equipment and practices used.

      Perhaps one day we will be able to detect it, should it exist.

    • The details are sooo HARD! It’s sooo much easier to declare the science settled and collect a cheque sitting in front of a computer changing all the input parameters except CO2 effect and feedback signs. If we solved this thing we’d have to get real jobs!

    • Steven Mosher, if the effect is that small, then AGW really has little to support it. Which is exactly the point the Connolly’s are making. Interesting point of agreement, I would not have expected you to say that.

    • Your link is bad Steven, but I’ve seen other articles that also admit that the effect of AGW on the vertical temperature profile is very small. You and the Connolly’s are not the only ones. However, what it means is that AGW is not significant – that point is often lost. If the atmosphere is in thermodynamic equilibrium to 35 km, the whole AGW argument falls apart.

      • Andy,
        Not only is his link bad, so is his attitude. Using “skeptard” is insulting and I certainly think even less of him for it. It belies an arrogance that reflects on his lack of humility.

  21. Very interesting Andy. This is a good example why gatekeeping and settled science propaganda is certain to lead away from good science. I’m with Steve McIntyre on his appraisal of most of the CliSci Team =>

    They would be high school science teachers in an earlier generation if they were lucky.

    Can multimers be sampled and maybe kept at their ambient pressure and temperature ? Can one take a sample of air in the laboratory and reduce its temperature and pressure to that above the troposphere and make these molecules?

    I’m not clear how polymerizing oxygen would alter the density of the air. It has to mean that there are more oxygen atomic units per cubic meter and it still acts like an ideal gas. If the oxy ‘mers’ were stronger oxydizers, they may also react with nitrogen. That would increase the density of the air also, and NO2 is only 4% lighter than a trimer of oxygen. Who knows what the effect on chemistry of upper layers that ultraviolet, cosmic rays, ozone, etc etc have.

  22. Well, I started reading the paper, but got stuck early on. It seems that the data they are actually working from is measured pressure and temperature. So they define molar density D = P/RT; the identification of that as density comes from the ideal gas law (which is ideal…).

    So then, in Figs 4/5, they plot D against P. Is the slope of this not just 1/RT? And the “regime changes” just changes in T?

    • Nick, you are not clear. Are you saying that the paper has fundamental problems right at the beginning? I focused on the requirement for a substantial proportion of the atmosphere to exist as “multimers” which seems at first glance to be unlikely, given the energy of the system and the weakness of van der Waal’s forces.

      • seaice
        “Are you saying that the paper has fundamental problems right at the beginning?”
        Yes. There’s just no information there. They have readings of P and T. Using the IGL, you can then calculate density. That’s it. You can’t use the calculated density to tell you more about temperature. Or deviations fro IGL, that might lead to multimers or something. For that you need independent data on density, or some such. This stuff is circular.

    • Nick, the answer you seek is too much for a comment. Read section 3.2 in paper 1. Especially lines 396 to 404. Check figure 8 and the spreadsheet in the supplementary materials. I think that will make it all clear to you.

      • Andy,
        I read it (3.2), but it’s even weirder. We start with measured P and T. Then they fit a line to D=P/RT vs P, and then deduce T from the slope of the line. WUWT?. T was the starting information. Maybe this gives a kind of smoothed version, but it’s very roundabout.

      • Nick, I’m not going to disagree with your maths analysis, I think you are correct. But, I think what the Connolly’s are getting at is that the change in slope at the tropopause suggests a change in the equation of state. The change in temperature gradient also suggests the same thing, but is harder to interpret. The second unusual aspect of the graphs is that the same line works in the stratosphere, temperature plots make it look like the stratosphere is different. I don’t know what causes the equation of state to change, neither do the Connolly’s, but they came up with a falsifiable hypothesis to explain it. If the lab work is done. maybe we will learn something. I will leave it here and, hopefully, the Connolly’s will chip in.

      • Nick, One other point. The change in temperature gradient at the tropopause is the question here. If 1/T is the slope, we still have the question of why the temperature gradient changes, right? The temp gradient changes again in the stratosphere, why does the molar density gradient not change there?

      • Andy,
        “The change in temperature gradient also suggests the same thing, but is harder to interpret.”
        They aren’t adding anything by this device of doing a bit of algebra so that 1/T turns up at the slope of another curve, so they talk about that instead. The change in temperature gradient at the tropopause has been known for a very long time, and has a standard interpretation that few seem to find even problematic, let alone requiring the postulation of otherwise unknown molecular behaviour.

      • Andy and Nick: The problem with this “paper” is fairly easy to spot. Equation 8 of Paper 1 is clearly wrong. I says that atmospheric temperature is a function of P and a bunch of constants. So is equation 7, which says that pressure is a simple function of temperature and some constants.

        The pressure at any altitude is simply the weight of the air above that altitude. It is not a function of temperature. What Connelly is forgetting is that the VOLUME of air at any location expands of contracts to satisfy the ideal gas law GIVEN the local temperature and pressure. And volume, of course, effects density.

        Consult the WIkipedia article on “Scale Height” of the atmosphere. It derives:

        dP/P = -dz/H where H = kT/Mg

        P = P_0 * exp(-z/H)

        For modest changes in z (compared with H), the first two terms of the Taylor expansion give P = P_0*(1 – z/H). H ranges from 8500 m at 290 K to 6000 m at 210 K

        In the troposphere, there is a fairly linear relationship temperature and altitude – the lapse rate and an approximately linear relationship of modest changes in altitude between pressure and altitudeIn an isothermal atmosphere he relationship between pressure and altitude. In that domain, Connelly’s D = aP + c can be adjusted to fit radiosonde data. Once one leaves regions where there isn’t a constant lapse rate, this relationship breaks down – as it should. There is NO linear relationship between D and P – there only appears to be in regions with a constant lapse rate and modest changes in altitude compared with H . (The next term in the Taylor expansion is +(z/H)^2/2. At low altitudes where there is a thermal inversion, there are problems.

        I don’t claim to have thoroughly read and understood the 30 pages of Paper 1. I presume that derivations in the appendix always are always making an unwarranted assumption: that T is constant and V is a function of P. That V is constant so that T is a function of P. Or that change are adiabatic, so that total energy is conserved with altitude.

      • Frank, Equations 7&8 describe an atmosphere in thermodynamic equilibrium. They are not wrong or right necessarily, simply descriptive. If they hold and match measurements, the atmosphere is in thermodynamic equilibrium. 13 million weather balloons, launched over 50 years, say they describe the atmosphere. You make an assumption, without any evidence to support it, that they can’t be correct. If you can find data that supports your assertions, I’ll listen. I doubt there is any however.

    • “Norman Wells, Northwest Territories, Canada requires three [separate fits] because the boundary layer, in winter time, can show a phase change very like the phase change observed in the tropopause. This might be due to the formation of multimers at the surface.”

      The inversion layer is now caused by *the formation of multimers*, instead of that massive heat sink called *the ground*.

  23. Nick, I am almost with you. Is is not a rate of change in temperature that causes the change in the regime.

  24. Andy,

    Thanks for doing this summary of our 3 “Physics of the Earth’s Atmosphere” papers! There’s a lot of material and concepts in the papers, but you’ve done a good job of summarising most of the main points.

    Unfortunately, I’m quite busy this week so I might not have time to answer all the comments. But, I’ve time for a few quick responses to some of the questions above, and I’ll try to set aside more time this time tomorrow.

    1) On pervection
    With regards to “pervection”, for a detailed discussion see Paper 3.

    But, the key point is that pervection is not the same as either convection or conduction, but it has some similarities to both.

    There are several different types of convection: thermal convection (e.g., movement of hot air), latent convection (e.g., movement of water vapour) and kinetic convection (e.g., constant temperature winds). However, in all cases, energy is transported from one region to another by the physical movement of the energetic molecules. The linguistic roots of the term “convection” mean “carried with”. In what we refer to as “pervection”, the molecules themselves do not have to be physically transported for the energy to be transmitted. Instead, the energy is transmitted “through” the molecules, and the molecules remain where they were (on average). To compare and contrast this with convection, we kept the “-vection” (“carried”) suffix, but used the “per-“ (“through”) prefix instead of “con-“ (“with”).

    Conduction is also a “through-mass” energy transmission mechanism. However, it involves the transmission of thermal energy, not mechanical energy.

    For those who are uncomfortable using the term “pervection”, you could use the term “through-mass mechanical energy transmission” instead. That was actually our original term for it, but we felt “pervection” was more succinct.

    Keith J suggested above that it is “sonic”. Sonic (or acoustic) energy transmission is indeed a form of what we refer to as “pervection”, but from our laboratory measurements we find “acoustic pervection” is at least two orders of magnitude slower than the rapid “through-mass mechanical energy transmission” we are finding.

    2) On multimers

    In Paper 1, we identified a previously-overlooked phase change associated with the transition between the troposphere and tropopause/stratosphere. In Paper 1, we avoided speculating on what is actually causing this phase change, and instead focused on describing the phase change itself.

    In Paper 2, we offer the best explanation we have come up with so far, which is the partial multimerization of O2 (and possibly some N2), and a detailed rationale of why we came up with this theory. However, regardless of whether our multimer theory is correct, incorrect or partially correct, the phase change is remarkably clear and consistent once you start looking at the weather balloon data in terms of molar density vs. pressure.

    To illustrate this phase change a bit clearer, here is a video showing the temperature vs pressure (top), molar density vs pressure (middle) and horizontal wind speed vs pressure (bottom) plots for all the weather balloons launched in 2012 from Valentia Observatory (Ireland):

    Notice in the molar density (D) vs pressure plots (middle panels) how the rate of change of D with pressure is linear for the troposphere, and linear for the tropopause/stratosphere, but that the slopes of these lines are different?
    This change in slope corresponds to the phase change we are referring to.

    In Section 2.2 of Paper 2 we provide a detailed justification for our multimer explanation. We spent a long time considering (and discarding) multiple different theories, and that is the only one we’ve come up so far that seems to explain all the data. If anyone has a better explanation for the phase change which also resolves the issues we raised in Section 2.2, we’re open to suggestions. But, if you haven’t read that section yet, I’d recommend reading it first.

    Unfortunately, I have to leave now. So, sorry if I haven’t gotten around to addressing all of your comments. But, I will try and get back for more tomorrow.

    • Mods

      This ought to be elevated to the top of the post as it gives further understanding of some of the important concepts involved.

    • Thanks very much Ronan, this helps a lot. Looking forward to additional comments. Thanks for taking the time, I know you and your father are very busy.

    • You are plotting D= P/RT against P therefore a plot of P against P will give a straight line. With a decreasing temperature then you put a bias on one of the P the one you call Density . By increasing temperature you start reversing the bias and there is a change in direction of the graph, there is no new phase! Gas is a gas they are always miscibile all gases are a single phase. Now you speculate on a multi met. But they form with increasing pre sure not decreasing. Send your paper for peer review and you will get the same comments.

      No multimers, no second phase in a gas. Gas is a gas. It does not form 2 phases. Liquids can gases by definition do not.

      • The Connellys are not talking about phase change nor about chemical enthalpy change (like that of oxygen to ozone) but dimerization (or more) of gases to explain the gross deviation of the Ideal Gas Law. IGL deviations are expected at high pressures and low temperatures (compared to standard temperature and pressure).
        Water vapor is a gas. It has limited miscibility in air. Somehow it makes its way past the stratopause to form noctilucent clouds in the mesosphere if only in hemispherical summer. This implies mesosphere lapse rate changes with season…why?

      • Dave, the slope of the line should be 1/T. Why are there 2 slopes? Why is the tropopause slope the same as the stratosphere slope? The formation of multimers is one possible hypothesis, do you have another? I agree multimers, under these conditions, are speculative. Perhaps “phase change” is an inappropriate phrase. But, certainly the equation of state has changed, no doubt about that. The lines, showing a linear relationship between D and P also show no deviation from equilibrium which we should see if greenhouse gases are having an effect.

  25. Between the 1950’s and 1976 NASA (and it’s predecessor the National Advisory Committee for Aeronautics – NACA) were responsible for establishing the properties of the atmosphere to support US military, rocketry and later the space programs.
    They developed a model of the atmosphere that was consistent with literally millions of data points from measurements on the ground, from aircraft, and high-altitude research balloons. The final model, published in 1976, is called variously the NASA standard Atmosphere and the US Standard Atmosphere. It is essentially identical to the ISO standard atmosphere.
    The model was based on physics and thermodynamics, and is essentially independent of the chemical composition of the atmosphere.
    The most important equation for the troposphere, which includes nearly 95% of the air, is the equation for the Adiabatic Lapse Rate, dT/dh = -g/Cp. This describes how the temperature T of the atmosphere varies with height h above the ground because of the acceleration of gravity g and the heat capacity of the air at constant pressure Cp.
    For the earth Cp is slightly a function of the heat capacities of the separate components of the air, but the heat capacity of carbon dioxide is nearly the same as those of nitrogen and oxygen. The concentration of carbon dioxide has a negligible influence on the heat capacity of air as a whole.
    The only gas that can significantly change the heat capacity of air, depending on its concentration, is water vapor. The adiabatic lapse rate for dry air is a decrease of 9.8 °C/km (5.38 °F per 1,000 ft) (3.0 °C/1,000 ft). The moist adiabatic lapse rate varies strongly with temperature. A typical value is around 5 °C/km, (9 °F/km, 2.7 °F/1,000 ft, 1.5 °C/1,000 ft).
    As one’s altitude increases the temperature decreases at this rate. Conversely, as one’s altitude DECREASES, temperature INCREASES accordingly.
    The reason the atmosphere of Venus is so much warmer than that of earth is not its CO2 concentration but its mass. The atmosphere of Venus weighs about 92 times as much as that of earth, so pressures are correspondingly higher, and the atmosphere is correspondingly thicker. At an altitude on Venus where the pressure is about the same as that of Earth’s atmosphere at sea level, about 50 kilometers(!), the temperature is about 55°C (328°K versus Earth’s average 288°K). Given that the earth is 38% farther from the sun, and correspondingly the sunlight on earth is weaker, this is not unexpected from simple solar irradiance calculations.
    The mythical ‘runaway greenhouse effect’ on Venus is simply a political fiction grown from a pedagogical shortcut created no doubt, to avoid trying to explain the ‘adiabatic lapse rate’ to scientifically untrained minds.

    • If there is a radiant GHE on Venus, it does not work in the same way as the postulated theory for the radiant GHE on Earth.

      At the heart of the radiant GHE theory is that Earth’s atmosphere is largely transparent to the wavelength of incoming solar irradiance but somewhat opaque to the wavelength of outgoing/upwelling LWIR.

      Now Venus is very different in that the Venusian atmosphere is almost completely opaque to the wavelength of incoming solar irradiance. The Russian Venera Mission measured solar irradiance received at the surface of Venus at just 17W/m2.

      • Venus also has sulfuric acid virga. No free water as there is considerable sulfur trioxide gas. This is sulfuric acid anhydride. So it could be said there is oleum controlling the climate of Venus . Compare the physical properties of oleum to water.

    • tadchem August 22, 2017 at 12:58 pm

      The most important equation for the troposphere, which includes nearly 95% of the air, is the equation for the Adiabatic Lapse Rate, dT/dh = -g/Cp. This describes how the temperature T of the atmosphere varies with height h above the ground because of the acceleration of gravity g and the heat capacity of the air at constant pressure Cp.

      The ALR does not describe how the temperature of the atmosphere varies with height, but how the temperature of a RISING or SINKING parcel of air varies with height, assuming the atmosphere surrounding the parcel is in hydrostatic equilibrium and that no heat exchange takes place with the surrounding atmosphere.

  26. “The atmospheric temperature profile does not appear to be influenced, to any measurable extent, by infrared active gases like carbon dioxide.”

    So are people going to stop den*ing this now? This has been accurately shown in mathematical models for years. Another paper further detailing this was just published recently.

    https://www.omicsonline.org/open-access/New-Insights-on-the-Physical-Nature-of-the-Atmospheric-Greenhouse-Effect-Deduced-from-an-Empirical-Planetary-Temperature-Model.pdf

    • This has been dealt with in previous posts. Nikolov (or Volokin) are basically doing a curve fitting exercise.

      • I would not be so quick to dismiss out of hand the point being made in that paper.

        One reason for which is Mars, and what NASA says about terraforming.

        It is generally accepted that despite Mars having some 959,700 ppm of CO2, which, on a physical numerical basis, is an order of magnitude more CO2 molecules than exists in Earth’s atmosphere, Mars has no GHE. The reason put forward is that the Martian atmosphere is not sufficiently dense/it lacks pressure.

        Now that reason (ie., the lack of density/pressure of the atmosphere) is coming close to saying that what keeps a planet warm is not molecules of GHGs, but rather the presence of a thick and dense atmosphere.

        NASA’s proposal for terraforming is to increase the density of the atmosphere and hence the pressure, not to increase CO2 from 959,700 ppm to say 970,000 ppm. Indeed, NASA wants to create a breathable atmosphere which inevitably means that the concentration of CO2 must be reduced down from 959,700 ppm.

        There is yet a lot to learnt and understood.

  27. Ronan said:

    “the molecules themselves do not have to be physically transported for the energy to be transmitted. Instead, the energy is transmitted “through” the molecules, and the molecules remain where they were (on average).”

    Well you can say that for an atmosphere in hydrostatic equilibrium the molecules all stay in the same place ON AVERAGE but that doesn’t mean much. At best it just means that the atmosphere as a whole remains suspended off the surface indefinitely.

    Within the body of an atmosphere there is as much movement up as there is movement down on average so that the whole atmosphere is constantly in motion.

    The amount of Potential Energy (PE) required to raise half the bulk of the atmosphere upwards against gravity is huge and the amount of Kinetic Energy (KE) released when half the bulk atmosphere descends with gravity is likewise huge.

    Anyone who thinks that those two energy transformation processes are not enough to drive observed atmospheric behaviour are simply wrong.

    Energy is not transmitted through stationary molecules. Energy is transformed from heat to form potential energy in uplift and from potential energy to heat in descent.

    Our entire global air circulation including the weather systems and climate zones within the troposphere and the Brewer Dobson circulation in the stratosphere are driven by the constantly varying balance of kinetic and potential energies at any given point in three dimensions within the atmosphere.

    People should read up on Convectively Available Potential Energy (CAPE in meteorology) and think it through.

  28. Ronan said:

    “In Section 2.2 of Paper 2 we provide a detailed justification for our multimer explanation. We spent a long time considering (and discarding) multiple different theories, and that is the only one we’ve come up so far that seems to explain all the data. If anyone has a better explanation for the phase change which also resolves the issues we raised in Section 2.2, ”

    The historical understanding is that it is the presence of ozone in the stratosphere that reacts directly with incoming solar radiation so as to heat up and reverse the lapse rate slope.

    That being the case could Ronan please paraphrase briefly why he needs to invoke phase changes and multimers for those of us who may not have time to read all his papers.

    • Stephen, phase changes and multimers were chosen as the most likely explanation that fit all of the data. Experimental verification is still needed. But, the idea fits what we know, alternative explanations are requested if you have one. Experimental data is very welcome.

      What we do know, is the atmosphere is in thermodynamic equilibrium to 35 km (99% of the atmospheric mass) and energy transmission is fast enough to maintain equilibrium. These facts alone invalidate AGW. The only way AGW can work is if thermal energy can build up at the surface, that is be delayed on its trip to outer space, due to greenhouse gases like CO2. For the AGW hypothesis to be viable, the vertical temperature profile of the atmosphere has to change. If the atmosphere is in equilibrium, AGW is bovine excrement. Sorry, but that is the way it is.

      • In what way does ozone creation in the lower stratosphere fail to fit all the data?

        As regards AGW I agree with you but the answer is readily available in the broader science without invoking ‘pervection’ or ‘multimers’.

      • Red oxygen, the multimer they talk of has been characterised at 100 000 atm pressure in solid oxygen. It cannot exist as a gas, if this is their most l ikeley explanation it does not bode well for the rest of their conclusions.

      • I have pondered the same conundrum. If AGW is defensible, trtropospheric lapse rate should change with increasing carbon dioxide. Because carbon dioxide adds to atmospheric mass and density and because the bulk of convection is water vapor, negative feedbacks cancel any hypothetical forcing.

  29. A plot of density agaist pressure is a plot of pressure divided by temperature against pressure.
    Whilst the temperature is decreasing with pressure a bias will be put on the slope of pressure vs pressure. We then start increasing the temperature with pressure , then the slope of pressure/temperature vs pressure wil now change its slope. There that is a much simpler and better explanation than invoicing a second gas phase!

      • Molar density is proportional to density. The kink in the graph will be exactly in the same position i.e. that where the temperature gradient changes, also please see my post on red oxygen. T etramers only exist at 100 000 atmospheres pressure and oxygen is solid

    • Dave, see my answer to Nick on the same subject. Here:
      https://wattsupwiththat.com/2017/08/22/review-and-summary-of-three-important-atmospheric-physics-papers/comment-page-1/#comment-2588435
      “Nick, I’m not going to disagree with your maths analysis, I think you are correct. But, I think what the Connolly’s are getting at is that the change in slope at the tropopause suggests a change in the equation of state. The change in temperature gradient also suggests the same thing, but is harder to interpret. The second unusual aspect of the graphs is that the same line works in the stratosphere, temperature plots make it look like the stratosphere is different. I don’t know what causes the equation of state to change, neither do the Connolly’s, but they came up with a falsifiable hypothesis to explain it. If the lab work is done. maybe we will learn something. I will leave it here and, hopefully, the Connolly’s will chip in.”

      The same information is in temperature, but that begs the question, why the change in temperature gradient?

      • The temperature gradient changes at the tropopause because of ozone creation when sunlight acts on oxygen at that height and above. At lower levels in the tropopause the primary heating process for our largely non radiative atmosphere is conduction from the heated surface at the base.
        Once one reaches the tropopause, radiative effects involving ozone start to take over. The lower atmospheric density above the tropopause provides less of a shielding effect for the oxygen molecules and so ozone forms more readily and takes over from the effect of conduction at the surface.

  30. What are the effects of H2O vapor and CO2? What are the effects of increasing their concentrations?

    The emission and absorption spectra of H2O vapor and CO2 are well-established from laboratory research, and the upward and downward transmission of LWIR have been measured and are reasonably concordant with Planck’s law. (distribution) and the Stefan-Boltzman law (intensity).

    Is all of that irrelevant?

    • They are bonds much weaker than covalent bonds. The strongest of these are hydrogen bonds where hydrogen bridges between two atoms of oxygen or fluorine, hence hydrogen fluoride does form multimers but only just under conditions where it is just above its boiling point .The next strongest are dipole attraction, but oxygen does not have a permanent dipole. So that is out. We are then left with London forces which are even weaker and are due to intermittent dipole that exist in non polar molecules. So oxygen has the weakest of all of the forces and is postulated to form tetramers at conditions of temperature well above the boiling point and at low pressures. I am afraid that I cannot believe this without direct proof, because chemical equilibrium laws state that they are formed at high pressures not low, and if they ain’t in the gas when at a full atmosphere pressure, they certainly ain’t in it at lover pressures. A tetramer has been obtained with oxygen but at 100 000 atmospheres pressure, which is not 10 miles up in the sky

    • Paul Blase August 22, 2017 at 4:33 pm
      For those of us who aren’t chemists, what are the bonds in a multimer?

      There aren’t really any bonds, were such multimers to form the forces holding them together would be
      van der Waals forces which are the weakest class of intermolecular forces (~1kJ/mole). For these forces
      to be significant the molecules have to be within a molecular diameter of each other. In the stratosphere
      at 220 K and 20 kPa pressure the average molecular separation is about 100 diameters and the molecules
      have a mean velocity of ~380 m/s. There’s no way that such multimers could form under those conditions.
      The idea that somehow the multimers would reduce the energy needed to form ozone is also bogus, the bond dissociation energy of oxygen is about 500 kJ/mole, a few kJ from van der Waals forces are negligible by comparison. Their idea about the degrees of freedom is flawed because it treats the attractions as if they were actual bonds which they are not. The ‘phase change’ they propose is a non-starter under the conditions of the atmosphere.
      The Chapman mechanism does a good job of describing the formation of O3 with a few additional reactions which break down the O3 (such as OH, NO, Cl etc.).

    • They can be detected spectroscopically or from deviations from the gas law. With oxygen T etramers they were detected by Xray crystalography but are only formed at 100 000 atmosphere pressure in the solid phase

  31. The tetramer of oxygen can be formed at 1500000 psi i.e. 100 000 atmosphere pressure. Please look up red oxygen in wiki. These are conditions well off those expected in our atmosphere. Oxygen multimers in our atmospheres do not exist

  32. “Connolly and Connolly found that there is at most no experimental data on the rates of vertical convection outside of clouds and above the boundary layer. But, from the limited data they have, the rates of vertical convection appear to be too slow to maintain thermodynamic equilibrium from the surface to the stratosphere.”

    And this is why ‘thermalization’ of energy absorbed by GHG’s isn’t really happening. The predominate mode for an energized CO2 molecule to return to the ground state is by the emission of a photon and not ‘thermalizing’ that energy into the translational energy of the other gases in the atmosphere.

    • co2isnotevil August 22, 2017 at 6:04 pm
      And this is why ‘thermalization’ of energy absorbed by GHG’s isn’t really happening. The predominate mode for an energized CO2 molecule to return to the ground state is by the emission of a photon and not ‘thermalizing’ that energy into the translational energy of the other gases in the atmosphere

      In the lower troposphere thermalization via collisional deactivation is the predominant mode not re-emission of a photon.

      • Phil,
        Please explain how all the state energy of an energized GHG molecule is converted into the energy of matter in motion in a single event, as required by Quantum Mechanics? Bear in mind that the energy of a typical LWIR photon is about the same as the total kinetic energy of an atmospheric gas molecule in motion.

      • @co2isnotevil

        I am not sure whether you are still following the Consensus of Convenience Article. I have just made a short comment on that post which I set out below for convenience. I do not know the data on the vertical profile of CO2, and not sure where and how this has been measured.

        I consider most GHG’s to be well mixed vertically, except H2O and O3 which have altitude dependent concentrations.

        Are you aware that CO2 is very poorly mixed at low altitudes, and varies greatly locally.

        This is why the IPCC rejects the Beck reanalysis of the 19th and 20th Century Chemical Analyses which showed CO2 at more than 400 ppm in the 1930 and 1940s.

        At low altitude, one can see CO2 varying from around 280 ppm to over 700 ppm.

        CO2 is only a well mixed gas (ie., varying by around +/- 10 ppm) at high altitude. Indeed, this is also one reason why Mauna Loa was chosen.

      • co2isnotevil August 22, 2017 at 9:54 pm
        Phil,
        Please explain how all the state energy of an energized GHG molecule is converted into the energy of matter in motion in a single event, as required by Quantum Mechanics?

        A N2 molecule collides with an CO2 molecule at the excited state of v=1, J=7 and removes sufficient energy to reduce it to v=1, J=6. A subsequent event takes it down to v=1, J=5, there’s no requirement for all the excess energy to be removed in one collision.

        Bear in mind that the energy of a typical LWIR photon is about the same as the total kinetic energy of an atmospheric gas molecule in motion.

        About 96% of the molecules at STP have less kinetic energy than a 15 micron photon.

    • Potential energy is thermalised when it is converted to kinetic energy in descending columns of air. If you reach the conclusion that ghgs are not thermalising energy then that is the only remaining option.
      KE from PE in descending air is the elephant in the room.

      • wildeco2014,

        Energy stored by energized GHG’s is not potential energy, so I don’t see how this argument is relevant.

        Perhaps you are making the same assumption that Perry and Pierrehumbert make which is that Equipartition of Energy holds in the limit as delta space goes to zero.

        It actually can’t go to zero and can only go as far as the size of a single molecule. Obviously Equipartition of Energy can’t hold true for a single molecule. There are 3 degrees of freedom in motion, x, y and z and if each degree of freedom had the same energy, the molecule would stay in the same place and have an effective temperature of absolute zero. Equipartition and even Kirchoff’s Law are bulk properties and do not necessarily hold in the limit.

      • wildeco2014.
        I should have said that if Equipartition held for individual molecules, they would all be going in the same direction instead of random directions relative to x, y and z (or theta and phi if you prefer).

    • Dr Spencer has failed to consider the thermal effect of kinetic energy being recovered from potential energy within descending air masses which comprise half of the bulk atmosphere at any given moment.
      That is the same error as committed by the AGW supporters which is why they need to propose a net surface warming from back radiation to make the energy budget balance.
      In reality, the heat energy required to raise surface temperature above S-B comes from those descending columns of air with the net effect of back radiation being zero due to convective adjustments within the bulk atmosphere neutralising it.
      If it were not so then hydrostatic equilibrium could not be maintained and the atmosphere would be lost.

      • Air rising (thermal) increases potential energy. Since you cannot create energy, it must come somewhere. It comes from heat via solar radiation. Air is heated, it expands (lower density) Surrounding air has higher density. Buoyant force pushes warm air upward. It leaves a lower pressure area near the ground. Surrounding air has higher pressure. It rushes to fill the low pressure area. There’s no thermal effect of descending air. It’s purely pressure differential that moves the air. The only thermal effect is solar radiation. It drives convection. Convective heat transfer is just mixing of warm and cool air at different altitudes driven by solar radiation.

      • Dr. Strangelove August 23, 2017 at 6:31 am

        There’s no thermal effect of descending air.

        Descending air warms according the (D)ALR, just as rising air cools according the ALR’s.
        See eg the Föhn wind or the Chinook wind.

      • The greatest recorded temperature change in 24 hours was caused by Chinook winds on January 15, 1972, in Loma, Montana; the temperature rose from −48 to 9 °C (−54 to 49 °F).[3]

        [3} Andrew H. Horvitz, et al. On September 13, 2002 citing a unanimous recommendation from the National Climate Extremes Committee, The Director of NCDC accepted the Loma, Montana 24-hour temperature change of 103F degrees, making it the new official national record.

        I am sure that you accept that Montana is somewhat away from warm oceans Your explanation does not adequately deal with the point made by Ben Wouters.

      • In reality, the heat energy required to raise surface temperature above S-B comes from those descending columns of air with the net effect of back radiation being zero due to convective adjustments within the bulk atmosphere neutralising it.

        I think it’s actually warmed by IR from condensing water vapor as the air mass descends, that’s what that warm muggy feeling is from at 5am on a clear night hours after the cooling rates slowed. It also has high 90’s% rel humidity, so air temps are pushing against dew points, that means for air temps to drop any lower water vapor has to be condensed out. I think above 65% or so, the amount of water vapor that condenses, but reevaporates becomes significant enough to reduce the net rate of outgoing radiation.

        That’s what the net radiation here is showing, and you can see how it changes the cooling curve when the net drops.

      • richard verney August 23, 2017 at 9:06 am

        I am sure that you accept that Montana is somewhat away from warm oceans Your explanation does not adequately deal with the point made by Ben Wouters.

        I’m amazed at the number of people that believe the ALR’s have anything to say about the temperature profile of the ‘static’ atmosphere.
        I like this graphic of the Föhneffect:

        Nicely shows the warming effect and that rain is a requirement for the Föhneffect to develop.

        I reacted to one of your other posts:
        https://wattsupwiththat.com/2017/08/22/review-and-summary-of-three-important-atmospheric-physics-papers/comment-page-1/#comment-2588370
        Interested in your reaction.

      • Rain is a requirement for the Fohn warming effect because rain is condensation of water vapor in the air. It releases the latent heat that warms the non-condensable gases (nitrogen and oxygen) The heat is not due to decrease in potential energy of air. The decrease in PE is converted to increase in kinetic energy of the wind as it speeds up going down the mountain slope. Going up the mountain slope, kinetic energy decreases as potential energy increases.

        All matter that fall (decrease elevation) accelerates (increase kinetic energy) It’s Newton’s 2nd law F = m a
        F is gravitational force, m is mass of descending air, a is acceleration (increase in velocity)
        This can be written in the form of conservation of potential and kinetic energy
        PE = KE
        m g dh = ½ m (v2^2 – v1^2)
        g dh = (v2^2 – v1^2)/2
        where g is acceleration due to gravity, dh is change in elevation, v1 is initial velocity, v2 is final velocity
        It’s all mechanical energy. No thermal energy involved

      • KE is thermal energy whereas PE is not so any transformation between the two involves a change in thermal energy.
        The heating of dry descending air on the downslope is due to adiabatic heating. The latent heat of condensation released at the top where the water vapour condensed out merely affects the starting temperature prior to the descent.

      • Dr. Strangelove August 23, 2017 at 11:48 pm

        Rain is a requirement for the Fohn warming effect because rain is condensation of water vapor in the air. It releases the latent heat that warms the non-condensable gases (nitrogen and oxygen) The heat is not due to decrease in potential energy of air.

        Seems you’re mixing up things. The rain falls on the upslope part of the flow, when PE is increasing.
        Without rain the upslope air cools according the DALR untill clouds form. Thereafter the SALR is valid.
        Downslope the air warms according SALR until cloudbase, which is at the same height as on the upslope flow.Thereafter warming according the DALR.
        With rain the cloudbase in the downslope flow is much higher, giving a longer warming traject according the DALR, giving the higher temperatures when the air reaches the same height again as were it started.

        Windspeed is not relevant for the process. At the top of the mountain range the windspeed may even be higher due to the venturi effect.

  33. Connolly and Connolly have shown, using the weather balloon data, that the atmosphere from the surface to the lower stratosphere, is in thermodynamic equilibrium.

    Always? That would seem to be true only in circumstances that do not destroy the weather balloons. How about during thunderstorms and other heavy rainfalls, which are common in tropical and temperate regions in some seasons, e.g. summer in the Philippines?

    Is the atmosphere in thermodynamic equilibrium when moist thermals are forming clouds? later, when the rain is falling?

    • Below the top of the boundary layer (approx. 2 km up) precipitation and humidity have a lot of influence and this is seen at the higher pressure end of the plots. Above the top of the boundary layer, where water vapor is less than 0.1% (absolute), the plots are a line.

      • Well sure. A considerable amount of energy transfer occurs from the surface to the cloud condensation layer; how is this accounted for by Connolly and Connolly? How does it change if surface temperature changes?

      • How does it change if surface temperature changes?

        Keeps the ground warm. This is the “GHG” effect. except it’d be better described as the water cycle effect.

        But the “Crow” effect will be fine ;)

  34. Yesterday’s eclipse gives a big insight into the effectiveness of so called GHGs, and the results of that and other eclipses need to be considered carefully..

    GHGs impede the passage of photons of LWIR emitted from the surface finding their way to TOA and thence being radiated to the void of space. They do not prevent that journey. GHGs are not a brick wall creating a barrier that cannot be crossed.

    Thus the issue is a simple one. <b.Does the planet during the hours of darkness have sufficient time to shed all the energy that it received during the day? If there is not sufficient time during the hours of darkness to dissipate the energy received during the day, then temperatures will slowly rise.

    Under the eclipse, temperatures fell by up to 20 deg F, with 10 to 12 degF being typical. The planet was able to dissipate and get rid of a lot of heat in a very short period of time. After all, totality only lasted approx 2 1/2 minutes.

    The experience under the eclipse suggests that GHGs such as CO2 may change the temperature profile of the day, and put back slightly the timing of the coldest period of the 24 hour cycle. It may be that if there was no CO2, the coldest period would be say 02:30 hrs, but with CO2 it is 03:00. Perhaps with more CO2, it will become 03.20 hrs etc. But it would appear that there is no build up of temperature since the planet has sufficient time during the hours of darkness to get rid of all the heat generated during the hours of sunlight.

    Of course further study of eclipses is required since these provide a real opportunity to test the effectiveness of GHGs as operating in the real world condition of Earth’s atmosphere. (not laboratory conditions)

    • Thank you. I was wondering about the temperature change during the eclipse and what that might imply for greenhouse theory, and you’ve supplied an answer.

    • Richard every night the sun goes down offering a chance to measure the response.
      Here is a clear calm sky night

      And overall there is no trapping over night, but Min T does follow dew points

      • Thanks your info.

        It seems to me that leaving aside the issue with station drop out (circa 1970), the temperature today is no warmer than it was in the 1940s. Which I have long been suggesting is the case, if we were only to re-measure the Northern Hemisphere properly (eg., to retro fit the best 150 to 200 sited stations with the same LIG thermometers as each station used in the 1930s/1940s and then observe using the same practice as each individual used in the 1930s/1940s.)

        It is sensible to start the comparison around the 1940s since some 95% of all manmade CO2 emissions date from that time.

        The rise of CO2 from ~300 ppm to ~400 ppm does not appear to have done much.

      • Actually, if people only paid attention to how much the temp dropped during the eclipse, they woukd have to come to the conclusion co2 dies not impact cooling in any significant amount. How can it drop 10F, half a nights cooling in 2:30 minutes? Remember co2 is well mixed, it is everywhere!

      • Temperature starts dropping before totality during an eclipse, but is most pronounced at totality. Only a very narrow band experiences maximum totality. At the edges of the zone of totality, it’s more like 40 seconds, at least in the PNW, where the shadow came ashore.

    • Yep, Yeah! More believer, you can see the same globally after El Nino’s, same effect.
      Water vapor goes away, once the Sun goes down, temps drop like a rock.

  35. Where is the evidence that the stratosphere is full of “multimer?” That formation of ‘multimer’ is exothermic and how much heat is released? “Phase change” is a misnomer. It only applies to solid, liquid and gas of same elements and compounds. Diatomic oxygen to ozone is not a phase change.

    “Pervection is a mechanical energy transmission mechanism, not a thermal energy transmission mechanism, in common thermodynamic terms it can be considered “work.”

    Have they never heard of kinetic molecular theory and the 1st law of thermodynamics? Heat is just the random motion of atoms and molecules. Of course heat and work are interchangeable. That’s the 1st law. If they are familiar with thermodynamics, they don’t have to invent new words.

  36. Dear Dr Stangelove, the multi met they talk is formed at 100 000 atm pressure. This is way off what is in the atmosphere which by definition is about 1 atm pressure at sea level and considerably less at the altitude they claim. The equilibrium law states that p (O2)^4 / p(O8) =Kp thus at lower pressure less will be formed. I.e. T etramers do not exist in the air,

  37. Weather balloons record temperature (T), pressure (P) or sometimes altitude (h), horizontal wind speed and direction, and relative humidity. Relative humidity is converted into absolute humidity using the temperature. There have been one to four launches a day from about 1,000 stations around the world – in some cases since the 1950s or earlier. That is about 13 million datasets containing data from the ground to the mid-stratosphere (~30-35km altitude). A weather balloon launch in Chile is shown in figure 7.

    That got me to wondering: Have they ever been launched in matched pairs, say one inside a vortex of ascending moist hot air over a Kansas (say) region in early summer, and the second in the downwelling (at a lower rate) of cool, dry air between vortexes (or vortices)? Neither place is “in equilibrium”, and the contrast ought to be informative. I mentioned Kansas, but the summertime Equatorial Pacific, or Guam or Diego Garcia Island, the Amazon or Congo River basins — lots of places that experience relatively rapid non-radiative energy flows from surface to mid-troposphere ought to be informative. Too much of this discussion is based on equilibrium approximations whereas the public policy interest relates to the hypothetical (i.e. possibly real) change in the dynamics effected by a change in the CO2 concentration.

    • Too much of this discussion is based on equilibrium approximations whereas the public policy interest relates to the hypothetical (i.e. possibly real) change in the dynamics effected by a change in the CO2 concentration.

      This is part of what I have been explaining.
      Water vapor at night during clear calm sky cooling, controls the end MinT you have in the morning, by altering the cooling rate, BASED on Air Temp vs Dew Point Temp, and how long night is.

      Say an increase in co2 caused this afternoons clear sky MaxT be 2F higher. The cooling rate stays in the high cooling rate until the same required temp is reached, which is at about 65%RH. The 2F warmer just takes say 30 minutes longer to cool to 65%RH. But cooling is nonlinear. Once it reaches that point the cooling rate drops, sometimes as low as 0.5F/hr. that extra 40 minutes, since it happens at the high cooling rate, that is replaced by 40 minutes at the slow, end of night cooling rate.

      This is how you make regulators and amplifiers with transistors.

      So, at 2F increase in afternoon temps, will be about 0.5F, and will be lower as the days get even longer because it just doesn’t cooling any more, the ground has reached equilibrium.
      And since there is not positive feedback, a doubling will start about 1.1C, and will be reduced by 75%-80%.
      As you’ve seen in the plots, it’s all there.

  38. Andy wrote: “There are several problems with the Chapman mechanism. First, it requires a great deal of energy to break a diatomic oxygen molecule’s bonds. Further, if the Chapman mechanism were the only mechanism forming ozone, why would ozone concentrations, in the Northern Hemisphere, be the highest in the Arctic in the spring?”

    The amount of ozone present depends on the rate at which ozone is being generated and the rate at which is is being consumed (decomposed). It is meaningless to discuss changes in ozone concentration due to one of these processes without considering the other.

  39. Hi everyone,

    Sorry I haven’t been available for most of this discussion. I’ll try to address some of the main comments/questions now, but apologies if I don’t get around to answering them all & I’ll try to reply again tomorrow.

    On convection vs. pervection
    There still seems to be some confusion over what we are referring to as “pervection” and why we feel it is distinct from both convection and conduction. So, to summarise:

    Pervection is a through-mass mechanical energy transmission mechanism
    Convection is a with-mass energy transmission mechanism – it can involve the transmission of either thermal/latent energy (“enthalpic convection”) or mechanical energy (“kinetic convection”)
    Conduction is a through-mass thermal energy transmission mechanism
    Radiation is a mass-less energy transmission mechanism (it can operate in a vacuum)
    Acoustic energy transmission is a (very well studied!) form of pervection… but not the only form of pervection.

    In the original draft of Paper 3, we reported our laboratory measurements of the relative transmission rates of these different mechanisms (for our laboratory setup) in terms of maximum velocities, as we thought (perhaps incorrectly!) that this would be a relatively intuitive way of describing the data. We didn’t specifically report the values for acoustic energy transmission as our laboratory setup was intentionally designed to minimise acoustic energy transmission, and we assumed (incorrectly, as it happens!) that this would have been apparent.

    However, we also calculated the relative rates of energy transmission (for our particular laboratory set-up) in terms of power flux, i.e., energy transmission in Watts/metre squared (W/m2). We didn’t include these calculations in the original paper. At some point, we plan on updating the paper with these calculations, but in case anyone is interested, I’ve summarised the results below:
    Conduction = 1.5 x 10^-4 W/m2
    Kinetic convection = 7.5 x 10^-6 W/m2
    Enthalpic convection = 0.14 W/m2
    Radiation = 0.29 W/m2
    Acoustic (acoustic component of pervection) = 1.37 W/m2
    (Non-acoustic) pervection = 2400 ± 80 W/m2

    Some people have wondered why we carried out our experiments using a highly confined and controlled laboratory setup when the atmosphere is, of course, an open system where all of the different energy transmission mechanisms simultaneously occur.
    This was actually the point! Because the atmosphere is an open system and all of these energy transmission mechanisms are in operation, it is very difficult to isolate the energy transmission from each of the different mechanisms. We designed the laboratory set-up so that we could specifically distinguish between each of these energy transmission mechanisms.

    As we discuss in the paper, the specific ratios between the energy transmitted by each of these different mechanisms will vary throughout the atmosphere. But, the two main points of Paper 3 we emphasised were:

    1) Energy transmission by pervection is rapid enough that it should be able to maintain thermodynamic equilibrium over distances of 30-35km at least, i.e., the distance between ground and mid-stratosphere.

    2) In our laboratory set-up at least, energy transmission via (non-acoustic) pervection was several orders of magnitude faster than either conduction, convection or radiation (or acoustic). That is, pervection is an important energy transmission mechanism which needs to be considered when dealing with the atmosphere, and is distinct from the other mechanisms.

    Again, I appreciate that some of you don’t like us coining a new term, “pervection”, to describe this specific energy transmission mechanism. But, as we discuss in Paper 3 in detail, it is distinct from the other mechanisms, and so a different term is required to avoid confusion.

    If you don’t want to use the term pervection, you could say “through-mass mechanical energy transmission” instead.
    To distinguish between acoustic pervection and non-acoustic pervection, you could then say “non-acoustic through-mass mechanical energy transmission”.

    • Hi, Ronan.
      Please could you say why a transformation of energy between PE and KE within a vertically moving mass of air is not sufficient to account for observations without the need to suggest a ‘through-mass mechanical energy transmission mechanism’.
      It seems to me that the former is a well established process whereas the latter is just a speculative suggestion on your part but both are theoretically capable of producing the same outcome.

      • Andy,
        Transformation between KE and PE is a separate mechanism that operates instead of carrying heat energy with the air. It can therefore be an alternative to the concept of pervection. During uplift the heat energy simply disappears into potential energy which is not heat and so the heat does not get carried with the air.

      • Stephen Wilde, OK, put that way, meaning the mass does not have to move the full distance, I think I agree with you in part. I’d be interested in what Ronan or Michael would say. But, that said, if the mass is not moving the full distance and we are just swapping KE for PE or vice-versa, causing an internal energy change, resulting in a temperature change, isn’t that simply through-mass energy transmission via work?

      • Andy, I believe it’s working like a open heat pipe, operating on water vapor, and the stored energy in the atm column as it cools at night. And it slows cooling with irradiation from water vapor condensing (much of which re-evaporates) and releasing 4.21J/g.

      • No, it is WITHIN mass energy TRANSFORMATION via work.
        Since it is adequately described by the Gas Laws and the adiabatic process involved in uplift and descent I don’t see why you need pervection or the through mass concept at all.
        The thing is that at base the authors are right but because they are not meteorolgists they are trying to reinvent the wheel.

      • Micro6500, the process you describe is a working process, but only in the boundary layer where there is sufficient water vapor. Above 2km it doesn’t work.

        Stephen, What you say makes sense. But, the climate models people use do not treat convection that way. They don’t include the work/mechanical component of convection, only the moving mass part. For that reason they underestimate the speed and range of energy transfer and go to local thermodynamic equilibrium (LTE). They haven’t checked or validated LTE, they’ve just assumed it. The Connolly’s did check it and found it doesn’t exist.

      • the process you describe is a working process, but only in the boundary layer where there is sufficient water vapor.

        It’s operating across your light Phase indicated here:

        And it’s effect is the bending of the curve in the bottom heavy phase. And likely the upper heavy phases as well.
        I’ve just spent my effort on the bottom effect of reducing cooling rates under clear night skies.

      • Maybe just the bottom phase, just not completely sure on what all of the specific differences between them are, as well as the height of what I’ve been measuring from the surface.

    • I’d like to hear the details of the experiment and see your thermometer that can measure 7.5 microwatts of heat flow!
      Unless you’re referring to the uniform motion of air, your definition of ‘pervection’ is equivalent to conduction because work (mechanical energy) is equivalent to heat (thermal energy) The mechanical equivalence of heat has been known to Joule since 1850
      work = heat
      W = Q

      The ideal gas law is an expression of the mechanical equivalence of heat
      PV = n R T
      The left side of the equation is equivalent to work
      W = d(PV)
      Where d(PV) is change in pressure and volume of gas
      The right side of the equation is equivalent to net heat flow
      Q = n R dT
      Where dT is change in temperature of gas
      It means gas temperature changes in response to heat flow or work done since W = Q
      This equation has been known to Maxwell since 1865. If after 150 years, somebody claims that W is ‘pervection’ and Q is conduction and W is not equal to Q, that would be strange indeed

      • Dr. Strangelove, What you say is true and it is the point that the Connolly’s are making as well. Their point (and yours I think) is that the climate models do not take the equivalency of work and thermal energy into account. They are just pointing out this obvious fact. But, sometimes “obvious” is only in 20/20 hindsight.

      • “the climate models do not take the equivalency of work and thermal energy into account”

        Correct, they do not. Work with gravity in descent transforms PE into thermal energy and work against gravity in ascent transforms thermal energy into PE.

        The weather that results is a consequence of DIFFERENTIALS in densities caused by different KE/PE imbalances in adjacent air masses.

        That is what gives us the whole caboodle including violent jet streams where the differentials are greatest.

        Study Convectively Available Potential Energy (CAPE) in meteorology.

    • Ronan and others: If one is interested in seeing how gas molecules form multimers and dissociate near their boiling point, there is a wonderful online molecular dynamics simulation of the behavior of gas molecules. The simulation contains a 6-14 Leonard-Jones potential field, simulating the van der Waals force between molecules. To see multimers, use a box with about 100 molecules and the slowest possible time step. Adjust the temperature (faster and slower) until there is no liquid phase, but some molecules cling to each other.

      There are all sorts of other things that can be done with this teaching tool. In particular, one can turn on gravity, see molecules fall to the bottom of the box, heat up and then watch that heat diffuse vertically. The result is a box with a density gradient, but no temperature gradient. In other words, themo-gravity doesn’t operate in this system – at least when more than a handful of molecules are present. With one molecule in a box, thermogravity operates. It doesn’t operate in the troposphere.

  40. Nick Stokes and Dave on plotting P vs. P/RT
    When we first started analysing the weather balloon data, we expected it would be exactly how Nick Stokes and Dave described. We would have expected a plot of molar density (D=P/RT) vs. P to yield a simple linear plot of slope 1/RT. But, instead, the data consistently shows a bi-linear behaviour. We analysed over 13 million weather balloons (taken from over 1,000 stations with some data going back to the 1950s), and this bi-linear phenomenon occurred for all of the balloons.

    I showed this video in my reply yesterday, but in case anyone missed it, here are the plots for one year’s data for the Valentia Observatory station in Ireland. The D vs P plots are shown in the middle panels. For comparison, the top panels show the standard T vs P equivalents:

    In all cases, the circular dots represent the experimental data. The two lines in the middle panels illustrate the change in slope. As Nick pointed out, this slope should in theory be constant (1/RT) for the entire plot. But, as Andy pointed out, it’s not.

    I realise that many in the climate science field argue that if the data doesn’t match the theory, there must be something wrong with the data. However, we’re a bit more old-fashioned, so when we find an apparent conflict between the theory and the data, we try to consider the possibility that the theory might be wrong.

    On our atmospheric temperature profile fits
    In Nick Stokes’ August 22, 2017 at 3:23 pm comment, he criticises our analysis in Section 3.2 of Paper 1.
    For those who haven’t read this section yet, we point out there that, for a given balloon, after obtaining the linear fits for each of the two linear regions, you can then use the slopes and intercepts to estimate the atmospheric temperature profile. When you compare these estimates to the original observations, the fits are remarkably good (in our opinion), i.e., the residuals are very small. Andy has shown some of these plots in his post. We think it is striking that the entire atmospheric temperature profile can be described so well merely in terms of the fitting parameters of two (or sometimes three) straight line fits. To us, this suggests that using D vs. P plots could be a very powerful tool for meteorologists.

    • Ronan,
      Please could you specify why you think that the historically accepted process of ozone creation above the tropopause could not fit the observation that the lapse rate slope changes above the tropopause.

    • Ronan: I haven’t read your work in full, but I suspect I understand why you have obtained unusual results: The atmosphere doesn’t have a fixed volume. A layer of atmosphere at a particular altitude/pressure can have any temperature because its volume/thickness can expand or contract with temperature. We almost alway apply PV = nRT to closed systems and the atmosphere is not closed at the top.

      Furthermore, the temperature profile of the troposphere is dominated by a moist ADIABATIC lapse rate, but the atmosphere in general is NOT adiabatic. The stratosphere is warmer than the tropopause because oxygen and ozone absorbed incoming UV from the sun. Temperature – and therefore volume and density – don’t depend on pressure. Temperature and pressure are two totally independent variables with pressure determined by altitude and temperature BY ENERGY FLOW. In general, temperature can not be expressed as a function of pressure and some other constants, nor pressure expressed as a function of temperature and some other constants. Eqns 7 and 8 in paper #1. They can and do vary independently as the volume of the atmosphere VARIES. P = (n/V)RT. Or P/RT = n/V. Whatever pressure and temperature exist somewhere in the atmosphere, there is a volume – and therefore density appropriate for that combination of pressure and temperature.

    • Do you not get two lines because you have a part of the atmosphere where the temperature decreases with lowering pressure, then at higher altitude, the situation is reversed temperature increases with decreasing pressure. Now Temperature and Pressure are measured directly so a nice plot will show two slopes to the graph of density(and even molar density) against pressure. Try it and come back to me with the result

      • Dave, the answer is yes. The temperature gradient changes, but both temperature gradients (Troposphere and tropopause/stratosphere) fall on lines. The question we are trying to answer is why? We know it is not composition. We know the O3 concentration (very small) starts to change. We know the tropopause and the stratosphere fall on the same line. So, why?

    • Ronin, Andy and others: For an ideal gas, V = nRT/P. This is how we calculate that one mole of any ideal gas occupies 22.4 L at 1 atm and 273K. Rearrange for density: n/V = P/RT. Given a temperature and pressure, the density (moles or molecules per unit volume) depends on both P and T. In the atmosphere, T and P can adopt “any” values, so one can not predict density from P and some constants alone (or T and some constants alone) despite Ronan’s eqns 7 and 8.

      Now, what happens if the gas dimerizes without taking up or releasing any heat. n is cut in half and so is V. If all of the N2 between 10 and 16 km suddenly dimerized or trimerized, it would suddenly be only 3.6 or 2.8 km thick. (3 km and 2 km if the atmosphere were 100% N2). If all of the nitrogen molecules dissociated into nitrogen atoms, the layer would expand to 10.8 km. The pressure wouldn’t change; pressure is due to the weight of the gas above. Raising or lowering the gas above involves work, so the temperature of the gas will change. Real chemical reactions almost certainly would involve uptake or release of heat. The same principles apply to partial changes

      We already know how to do most of these calculations, because the problem has been worked out for water vapor. Water vapor doesn’t dimerize or trimerize, it aggregates into a liquid phase, the ultimate multimer, releasing a lot of heat. Since water vapor only occupies about 1% of the volume of the atmosphere, its aggregation into 1/1000th its original volume doesn’t produce much PV work compared with the release of latent heat (but I suspect that calculation has been done somewhere).

      In much of the troposphere, there is a well defined relationship between T and P, because the temperature in the troposphere is controlled by adiabatic expansion and contraction – producing the adiabatic lapse rate. (PV^gamma = constant). Add water vapor and get a moist adiabatic lapse rate. Consequently convective regions in the tropics and seasonally in the temperate zone all have the same moist potential temperature. Given an altitude (and Ts and humidity), one knows the temperature and pressure. In this region, T and P don’t vary independently and one can express density as a simple function of P and some constants.

      Once temperature is not controlled by an adiabatic process, the relationship observed between P and density in the troposphere no longer applies. Adiabatic expansion should make the stratosphere cooler than the tropopause, but absorption of UV by O2 and O3 changes the temperature away from an adiabatic relationship. Thermal inversions near the surface are also regions were the adiabatic lapse rate frequently breaks down.

      • Good summary Frank. I think this is the thought process that Ronan and Michael went through. Equations 7&8 don’t have to hold above the boundary layer, but they do. Why? And if they do hold, what is the implication for the CO2 greenhouse effect? What causes the change in slope at the tropopause? Why the same equation for the tropopause and the stratosphere?

      • Is it the case that equations 7 and 8 must produce the same result through the entire height of an atmosphere in hydrostatic equilibrium?
        The significance for AGW theory is that if that be the case then the Greenhouse effect is mass and density induced via the mechanical process of work done against gravity in rising columns and work done with gravity in descending columns.
        The greenhouse effect is a result of gases conducting and convecting within a gravitational field and thus not a radiative phenomenon at all.
        The fact is that the atmosphere as a whole is, on average, in equilibrium but no specific component of it ever is due to constant motion.
        Water vapour with its phase changes and being lighter than air simply enhances the ability of convection to neutralise radiative imbalances. Even without water vapour convection would successfully maintain equilibrium but would have to run convective turnover at a faster rate.

      • Frank August 24, 2017 at 2:07 pm

        Frank, most of what you write makes good sense to me (not being a chemist ;-)
        The following does not:

        In much of the troposphere, there is a well defined relationship between T and P, because the temperature in the troposphere is controlled by adiabatic expansion and contraction – producing the adiabatic lapse rate. (PV^gamma = constant). Add water vapor and get a moist adiabatic lapse rate.

        This implies that you believe that much of the troposphere is continuously moving up and/or down.
        Personal experience tells me otherwise.
        Have you data to back this up?

        The atmosphere is anything but adiabatic. Energy is continuously flowing from the solar heated surface through the atmosphere to space. What needs to be described is this energy flow and the resulting temperatures for an atmosphere that is in hydrostatic equilibrium.
        On top of this we have layers that are directly heated by the sun (stratosphere and thermosphere)

      • The entire atmosphere is constantly rising or falling. All areas with lower than average pressure are rising and all areas with higher than average pressure are falling.
        Adjustments in speed deal with radiative imbalances such as those from GHGs.
        Thus GHGs do have an effect on the global air circulation but since the sun and oceans constantly cause huge variations we would never notice any effect from our GHGs.

      • Stephen Wilde August 25, 2017 at 5:14 am

        Even without water vapour convection would successfully maintain equilibrium but would have to run convective turnover at a faster rate.

        Without water vapor there wouldn’t be much convection to speak off. Assuming the same average lapse rate as we have today (~6,5 K/km) the dry adiabatic lapse rate (~9,8 K/km) makes sure that any convection is stopped almost immediately. The WV-less atmosphere would be very stable.

      • Stephen Wilde August 25, 2017 at 11:09 am

        The entire atmosphere is constantly rising or falling. All areas with lower than average pressure are rising and all areas with higher than average pressure are falling.

        It isn’t. The Hadley circulation stretches between Equator and ~30 N/S (half the surface area of planet earth) and consists mostly of air flowing along at its density level.
        The run of the mill low pressure area reaches ~20.000-25.000 feet where the air flows out horizontally.
        High pressure areas start around 20.000 feet and horizontal outflow begins around 5000 feet (subsidence inversion). Air descends with ~150 feet / hour so the adiabatic assumption doesn’t hold for this kind of process times. Enough time for radiation to change the temperature of the air.
        Small scale convection doesn’t reach much above 7000-8000 feet or so.
        So the entire atmosphere is definitely not constantly rising or falling.

      • Ben, that is incorrect. Air never flows perfectly horizontally. It is always spiralling down towards the nearest low pressure cell or upwards towards the nearest high pressure cell.
        There is even convective overturning in the stratosphere.

      • So the entire atmosphere is definitely not constantly rising or falling.

        I’m not sure exactly Stephen’s point, but isn’t the atm a different height between day and night?

      • Ben Wouters: “This implies that you believe that much of the troposphere is continuously moving up and/or down. Personal experience tells me otherwise. Have you data to back this up?”

        Excellent question! How fast do I need to prove the atmosphere is moving up and down? Based on the amount of water vapor in the atmosphere (total column water) and the average rate of precipitation (2.7 mm/day), it is easy to calculate that the average water molecule remains in the atmosphere for 9 days after it evaporates. It is 5 days in the tropics. So air must be carrying water vapor upward on that time scale. Modelers say it takes about two weeks for a typical packet of air to make a round trip from the top of the boundary layer to the tropopause and back, with a lot of up and down due to solar heating in the daytime.

        We see a linear adiabatic lapse rate in much of the atmosphere, which implies – to me – that VERTICAL heat transfer by bulk convection is FASTER than any other mechanism. We also see no fractionation of gas molecules by molecular weight, which implies bulk convection (not thermo-gravity). Calculations show that purely radiative heat transfer should at equilibrium cause temperature to rise linearly with optical density, which would be exponentially as we approach the surface. We don’t observe the exponential, so we know radiation isn’t the dominant mechanism. When that exponential gets too steep, the lapse rate is “unstable” and buoyancy-driven convection spontaneously develops.

        In polar regions, there isn’t as much water vapor in the air (lower optical density) and unstable lapse rates don’t develop. Adiabatic is inappropriate there. The stratosphere absorbs a lot of UV (given its low density and heat capacity). Adiabatic is inappropriate there. Thermal inversions are created near the surface at night by faster radiative cooling of the surface. Adiabatic is inappropriate there.

        On Venus, there is a linear adiabatic lapse rate from the surface to about 70 km. IMO, convection must be responsible. It is the only mechanism consist with observation – an extremely weak form of “proof”. On Earth, we have a lot more supporting evidence.

        For a more sophisticated discussion with data, see: https://scienceofdoom.com/2012/02/12/potential-temperature/

      • Andy wrote: Good summary Frank. I think this is the thought process that Ronan and Michael went through. Equations 7&8 don’t have to hold above the boundary layer, but they do. Why? And if they do hold, what is the implication for the CO2 greenhouse effect? What causes the change in slope at the tropopause? Why the same equation for the tropopause and the stratosphere?

        One set of constants works for soundings above the boundary layer but below the tropopause because T and P are linked by adiabatic expansion/contraction. You need different constants elsewhere.

        The introduction to a properly written science paper lays out the context for the author’s new work. Here is what conventional models for the atmosphere predict and this is what observation shows. Then the authors tell us what their novel contribution is – what part of the conventional model they have CHANGED. Then readers can be sure they understand precisely what is new about their proposal. Amateurs start with their new idea. It isn’t clear what part of the textbook explanation for the atmosphere they understand and accept – and what part they are changing. In my experience, it is rarely rewarding to wade through 50-100 pages of manuscript to find out what textbook knowledge the authors accept and what they are changing. Anyone who hasn’t gone to the trouble to check their work against the textbook and who doesn’t clearly understand both the textbook and what they are doing differently, probably isn’t worth my time.

        All of the gases found in the atmosphere have had their infrared spectrum studied in great detail at a wide variety of temperatures and pressures. If new chemistry was caused by merely temperature or pressure, it would have been observed. Le Chatlier’s principle means that lower pressure should not produce multimers. The warmer regions of the stratosphere are not particularly cold (270 K). It would be stupid to suggest that UV radiation in stratosphere could not produce new chemical species that would be missed by simple laboratory experiments. However, given CFCs and ozone depletion, a lot of sophisticate experiment with UV have been done.

      • Stephen Wilde August 26, 2017 at 7:52 am
        <blockquote Air never flows perfectly horizontally. It is always spiralling down towards the nearest low pressure cell or upwards towards the nearest high pressure cell.
        Take eg jetstreams. Will flow mostly horizontal for (very) long distances.
        The outflow near the surface in a high pressure area follows the surface. Not much change in height there, unless some mountains are in the way.

      • Jet streams undulate up and down as they thread between low and high pressure cells. If closer to a low pressure cell they are higher and if closer to a high pressure cell they drop lower.
        Under a high pressure cell, once the air reaches the surface it starts to flow towards the adjacent area of low pressure. The change from spiralling downwards to spiralling upwards occurs at about 1000 mb which is the average pressure for the globe as a whole.

      • Frank August 26, 2017 at 5:26 am

        We see a linear adiabatic lapse rate in much of the atmosphere, which implies – to me – that VERTICAL heat transfer by bulk convection is FASTER than any other mechanism.

        The DALR is the same for the bulk of the atmosphere: 9,8 K/km. The SALR is not linear.
        My point is that you only can ‘see’ the adiabatic lapse rates when air is moving vertically.
        eg Adiabatic compression in a high pressure area is happening, but the vertical speed is so slow that other energy transfer modes must have an important role.
        After all the atmosphere radiates on average ~200 W/m^2 to space. (240 W/m^2 minus surface radiation trough the atmospheric window.)

      • Ben Wouters wrote: “The DALR is the same for the bulk of the atmosphere: 9,8 K/km. The SALR is not linear. My point is that you only can ‘see’ the adiabatic lapse rates when air is moving vertically.
        eg Adiabatic compression in a high pressure area is happening, but the vertical speed is so slow that other energy transfer modes must have an important role. After all the atmosphere radiates on average ~200 W/m^2 to space. (240 W/m^2 minus surface radiation trough the atmospheric window.)”

        Frank replies: Your criticisms of my oversimplifications are generally accurate and your comments appreciated. The SALR is slightly curved, but in the opposite direction from what would be predicted for an atmosphere in radiative equilibrium. Under radiative equilibrium, temperature rises linearly with optical density, which is exponentially as one approaches the surface. So I still assert that the lapse rate we see in much of the troposphere is the product of convection eliminating lapse rates that are unstable toward buoyancy-driven convection = aka radiative-convective equilibrium. Excerpts from textbook derivations of this physics can be found at the scienceofdoom.com, in particular:

        https://scienceofdoom.com/2010/08/08/vanishing-nets/

        https://images.duckduckgo.com/iu/?u=http%3A%2F%2Fwww.drroyspencer.com%2Fwp-content%2Fuploads%2FManabe-Strickler-1964-fig.4.png&f=1

        The observed lapse rate for various regions of the planet at various seasons can be found on the right side of the page at the link below. In the troposphere, the profiles look fairly linear to me, but I don’t know if they have been simplified. Some atmospheric scientists use this software (MODTRAN) for radiative transfer calculations through our atmosphere. It is an older research tool.

        http://climatemodels.uchicago.edu/modtran/

        At every altitude in the atmosphere at steady state, incoming SWR and outgoing LWR + convected latent and simple heat must be equal. At the surface, this is roughly 160 W/m2 of SWR, 60 W/m2 of net radiation (OLR-DLR) and 80 W/m2 of latent and 20 W/m2 of simple heat. At the TOA, this is 240 W/m2 of both SWR and LWR. (80 W/m2 SWR is absorbed by the atmosphere and clouds on the way to the surface.) The amount of heat being convected upward at any altitude is due to the inadequacy of LWR radiative cooling – at current temperature. At the surface, the shortage is 100 W/m2. By the tropopause, radiative cooling alone is adequate; convection is no longer needed. Pick an altitude where the upward convective (non-radiative) flux is 50 W/m2. To keep steady state at that altitude, radiative cooling via LWR must be 50 W/m2 more than the absorbed upward flux of LWR and absorbed downward flux of SWR.

        I’m going to follow the newer post on the Connelly’s work.

      • @Frank, if my understanding is correct. No one uses MODTRAN right. From reading the instructions you select from typical atmospheric conditions, and the do a surface to space line by line analysis.

        The problem is they need to run that atm through an entire 24 hour solar day, and then figure the profile.

        During the night under clear skies, it stops cooling, and it’s not equilibrium.

    • Ronan writes about his video: “When we first started analysing the weather balloon data, we expected it would be exactly how Nick Stokes and Dave described. We would have expected a plot of molar density (D=P/RT) vs. P to yield a simple linear plot of slope 1/RT. But, instead, the data consistently shows a bi-linear behavior.”

      Unfortunately, 1/RT is not a constant. T varies with altitude. So you should NOT observe a simple straight line. Since T only varies between 200 K and 280 K, 1/RT is approximately constant. So the line looks approximately straight.

  41. My views on the Nikolov & Zeller papers
    Like Anthony, seaice1 & Dr. Strangelove, Roy Spencer and many others who have commented here and elsewhere, I agree that Nikolov & Zeller’s papers don’t warrant their conclusions (or the categorical press releases that accompanied it). I agree that their analysis is consistent with their claim that there is no CO2 greenhouse effect. It is also consistent with our analysis. However, as Roy Spencer and others have repeatedly demonstrated, it is also consistent with there being a greenhouse effect.

    Being consistent with a theory is not a proof of that theory, especially when it is also consistent with conflicting theories!

    As seaice1 points out, their analysis is in many ways simply a curve-fitting exercise. Moreover they only used 5 points for their fitting and there is some subjectivity in the exact values they used for those 5 points.

    Also, as Matthew R Marler points out in his August 22, 2017 at 3:07 pm comment, and as Andy summarises in the post, the upward and downward transmission of IR radiation in the atmosphere with characteristic CO2 and H2O peaks has been repeatedly observed experimentally, yet Nikolov & Zeller offer no explanation for this.

    That said, I do think Nikolov & Zeller’s idea of using observations from other celestial bodies in the Solar System is a good one. It’s just that their analysis is not as conclusive as they claim.

    • Ronan,
      Not only does the Nikolov and Zeller analysis fit multiple observed extraterrestrial atmospheres but it also fits what we would expect to see from an application of the gas laws. Why do you think that is insufficient?
      I have told Ned Nikolov that he is just restating old knowledge from the days before the radiative greenhouse effect came to dominate climate science.

      • Stephen, N&Z’s hypothesis is incomplete and needs to be fleshed out. They need to be able to explain the structure of the atmosphere, especially the troposphere/tropopause/stratosphere portion. They also need to explain the characteristics of the upward and downward radiation spectra. To me, these are the weaknesses in their ideas and also the ideas of the dragon slayers. None of them are saying anything all that wrong, their ideas just are not fully fleshed out. Plus, sometimes they put up strawmen (stuff not said by their opponents, but easy to argue against) and then shoot them down. However, they aren’t the only group that does that – their opponents and the alarmists often do that also.

      • N&Z’s hypothesis

        In my exchanges with N, I take it as he thinks that all takes place below the surface of last emission. My argument with that is if you want surface temp, you have to account for work being done by the atm. Him, “that’s all part of the vapor pressure defined by gravity, and therefore temp”, or something like that.

      • Ned doesn’t try to explain the structure of the atmosphere and doesn’t need to for his basic hypothesis.
        However, I can explain that structure.
        For an atmosphere to be retained long term it must always be successful in balancing the downward force of gravity with the upward pressure gradient force which latter force is caused by kinetic energy at the surface acting on the weight of the gases above.
        If you then get variations in layers caused by different radiative characteristics within each layer then the atmosphere uses convection to return to hydrostatic equilibrium.
        So, the lapse rate from surface to the boundary with space must always average out at the slope set by mass and gravity and distortions in one layer will come to be offset by an equal and opposite distortion in another.
        You will see that Earth’s lapse rate structure forms a sideways ‘W’ shape with temperature declining with height in the troposphere and mesosphere but increasing with height in the stratosphere and thermosphere.
        If one were to average out the slope across all four main layers then the slope must match that determined by mass and gravity for long term hydrostatic equilibrium.
        There is no other solution if an atmosphere is to be retained. Otherwise the atmosphere would either float off into space or fall to the ground depending on the sign of any net imbalance.
        Convection always adjusts to neutralise radiative imbalances.

  42. On our multimerization theory
    As we discuss in Section 2.2 of Paper 2, we agree with Dave’s August 22, 2017 at 6:41am comments that while nitrogen and oxygen dimers are found at very low temperatures and laboratory pressure, these conditions are not comparable to the temperatures and pressures found in the tropopause/stratosphere (although, I don’t know why you refer to them as “telomeres” – aren’t telomeres those bits of DNA at the ends of chromosomes?)

    We also pointed out in the same section that the solid “red oxygen” tetramer (which Dave mentions in a few comments) only occurs at very high temperatures and pressures. So, as Dave says, it is not relevant for the temperatures/pressures of the tropopause/stratosphere.

    Also, while oxygen dimers (a dimer = a multimer of size N=2) have been observed in the atmosphere spectroscopily and have been considered both theoretically and computationally, they are only found in trace amounts. So, we don’t believe oxygen dimers can explain the phase change.
    However, from our quite detailed literature review, we didn’t find any groups that had considered or checked for the possibility for the formation of (non-dimer) multimers occurring under the temperatures/pressures of the tropopause/stratosphere.

    As Dave has pointed out, the phase diagrams for oxygen and nitrogen are fairly well characterized experimentally at both low T/high pressure and high T/high pressure. But, it turns out that the low T/low pressure conditions of the tropopause/stratosphere haven’t been well-studied.

    • Telomer is defined in chemistry as a small polymer. It is also used for the short bits at the end of the DNA molecule in contrast to the long bit of DNA which is a polymer.
      Please see wikionary Telomer -an extremely small polymer one whose degree of polymerization is between 2 and 5.

      It is a standard chemical term why do you not seem to know it?

      • In biology, the feature you mention is actually called a telomere, ie, a region of repetitive nucleotide sequences at each end of a chromosome, which protects them from deterioration or from fusion with neighboring chromosomes. .

        In the case of human chromosome #2, the anti-fusion function failed, allowing two smaller, ancestral, standard great ape chromosomes to fuse into a single larger one, indeed the second biggest of our chromosomes. It’s why we have only 46 chromosomes, while all other great apes have 48. This fusion event is associated with upright walking.

  43. Further research on our multimerization theory since our 2014 papers
    Since those papers in 2014, we have been continuing our research into this phase change as well as into our multimerization theory. We have also been discussing our analysis with several prominent atmospheric physicists and chemists, and their comments have been generally encouraging.

    Some commenters above have wondered if our multimer theory could be tested under laboratory conditions. Yes, indeed, last year we carried out some preliminary experiments to reproduce tropopause/stratosphere temperatures and pressures in the laboratory. The results were suggestive of multimer formation, but the experiments were quite expensive and time consuming, and we don’t think we have collected enough data yet (in our opinion) to publish these findings. We do plan on completing these experiments at a later stage, but bear in mind we’re carrying out all of this research in our spare time and at our own expense!

    Still, in case you’re interested, we carried out a series of 8 experiments in which we evacuated dry air in a glass container to pressures down to about 20,000 Pa (200 mbar) and lowered the temperature using dry ice. We recorded the temperature and pressure of the air continuously throughout each experiment, and from these measurements we could also calculate the molar densities. Below about 200K we found that the molar density started to drop by a few percent, which is what we would expect from multimer formation. We also carried out several experiments using oxygen instead of air and found that the drop in molar density was about 5 times greater. Since air is only about 1/5 oxygen, this suggests that, if our multimer theory is correct, then oxygen is the main gas that is forming multimers.

    We have also been in discussion with several groups about the possibility of analysing these experiments spectroscopically. In particular, we are looking at testing for changes in magnetism (monomeric oxygen is paramagnetic, but it is plausible that multimers could be diamagnetic), as well as testing for microwave emissions.

    [OK, it’s late here now, so that’ll have to do for tonight, but I hope the above comments helped to clarify things]

  44. What would be interesting, is combining this ideal molar density stuff with mass density.

    I don’t know how much balloon data has both both pressure and altitude (GPS) independently, but when you have both, mass density should just be ρ = -dP/dH * 1/G * (r+H)^2/r^2.

    (G being gravitational acceleration, r being earth radius. Both calculated at sea level at the launch site)

    ρ/D then gives you the (ideal) molar mass. Still only as good as the ideal gas assumption etc. and it includes the weight of aerosols… but it would be interesting!

  45. >multimers forming a low pressure and low temperature…

    The key is that the bonds between the molecule making up the multimer are weak.

    Multimers can form at high pressure or high temperature, but they aren’t stable. At high temperature a fast moving molecule will slam into the multimer and break it up. At high pressure, collisions with other molecules happen with greater frequency.

    Having the multimer be stable requires that its internal energy (temperature) be low in relation to the bond strength and that collisions be infrequent and with energy that is low with respect to bond strength.

    And, yes, all this can be confirmed in the laboratory.

    • Yes, At very cold temperatures even oxygen molecules begin to stick together and eventually forma a liquid phase. However, if that happened under atmospheric conditions, those studying molecule spectroscopy (attempting to confirm the major tenants of QM) would have noticed the extra lines in the IR spectrum long ago. In fact, water vapor multimers exist in the lower troposphere and create a phenomena called the water vapor continuum absorption. Climate scientists know about it and take it into account.

      Not all gases follow the ideal gas law perfectly. The is called non-ideal behavior. See Wikipedia – Real Gases. However, nitrogen and oxygen show little deviation from ideal behavior.

      • In addition to your comment on water clusters. WATER bonds with hydrogen bonding which is much stronger than the forces that oxygen is supposed to use.

      • When water molecules “stick together”, we call it hydrogen bonding. When oxygen molecules stick together, we say “van der Waals” forces are involved – transient electric dipole moments sticking together in molecules that don’t have permanent electric dipoles. However hydrogen “bonding” is purely electrostatic attraction too.

  46. The spiecies detected were ions not molecules. Again these are within a mass spectrometer which for examining such exotics would be at 10^-10 of an atmosphere and so and are far removed from atmospheric conditions.as you state the least collision would destroy them and the least vibration would split them up. Again to form clusters you need to have started from a condensed phase or solid or liquid which are not formed in the atmosphere. By your own definition a collision at atmospheric temperatures would have too much energy for the weak London forces to make the molecules cling together.

    • Ion beams are normally produced by irradiating a solid with an election beam, eg Secondary Ion Mass Spectroscopy.a solid already has the molecules in close proximity. In an atmosphere they are isolated so to form then spontaneously would require 4 molecules of near zero energy to collide with each other and have insufficient energy to break up the cluster. Alternatively we have a stepwise formation in which e form O4, then It, then O8. Each one of these collisions must be so weak that they cannot destroy the dimer and then the trimer before forming a tetramer. however the more energetic molecules are the ones that collide the most.

      • Dear Frank, your comment that hydrogen bonding is purely electrostatic cannot account for the bifluoride ion FHF- the hydrogen is exactly in between of the two fluorine atoms.

      • Dave: You are correct about bifluoride, which is a linear species with two equal HF bonds. In all hydrogen bonds to neutral atoms, the X-H bond is much longer and doesn’t show a particular preference for a particular bond angle R-X–H. Hydrogen bonds in the alpha helix are linear, in DNA they are bent at 120 degs. In proteins, all angles up to almost 90 deg are found. There is no sign that a particular hybridization for the accepting atom is present. To the best of my knowledge, all neutral hydrogen “bonds” can be explained as purely electron static interactions, without invoking overlapping orbits or molecular orbitals. Birluoride is different.

    • Gloateus, Mostly because this explanation accounts for the atmospheric structure, especially the tropopause and stratosphere. The gravity/pressure explanations cannot account for these major atmospheric structures. This explanation also allows for the Earth’s radiation spectrum. Some would add the balance between input and output radiation, but IMHO, all the various explanations for the Earth’s surface temperature allow for that.

      What the Connolly’s and the slayers have in common, is both predict atmospheric thermodynamic equilibrium. And, frankly, the largest weakness in the CO2 control knob hypothesis is their local thermodynamic equilibrium assumption. It not only makes no sense, there is no data to support it.

      Greenhouse gases are IR-active, I think we all agree with that. Water vapor dominates boundary layer energy transfer, but not because water vapor is IR active. It is the large heat capacity of water and the latent heat energy carrying/storage capacity that causes it to dominate. The trace gases, like CO2, do absorb and emit IR and help move energy around, but they have little or no net effect on surface temperatures. As many have said before me, it is not a debate about CO2 IR activity, it is a debate about “how much.” Estimates vary from immeasurably small to over 50%. I’m at the low end and so are the Connolly’s.

  47. Two requests have already been made as to how this tetramer runs contrary to the law of mass action. A law that is best derived by a combination of the Gibbs free energy values for the reacting species. For the tetramer formation it is p (O8) = K p (O2)^4.

    The tetramer is proposed to exist at 20 km height at which point the partial pressure of Oxygen is 5% that at sea level. A factor of 20. The concentration of the tetramer should therefore be a factor of 20^4 times that at 20 km height. I.e. there will be 160000 times more of the tetramer in an unit volume at sea level than at 20 km height.

    This does need the temperatures to be similar. A quick check indicates that at 20 km a typical temperature at 20 km height is some -60°C . This is similar to that which occur in the polar winters. It is a temperature that can readily be achieved using solid carbon dioxide coolant in the home and certainly in the most basic laboratories.
    Yet there are no reports of the tetramer existing at these readilly achievable conditions.

    One should ask the question Why?

  48. I would like to thank Andy May for doing this blog post and all the participants for their interesting contributions. I am sorry that due to time constraints I could not contribute to the discussions as they were taking place. However I have read all the contributions and I think the following observations might resolve many of the difficulties, but will also raise more problems (at least they do for me).
    In paper 1 we reported that the slope of molar density (D = P/RT) plotted against pressure (P) is greater in the Tropopause – Stratosphere than in the Troposphere for all 13 million Ratiosondes that we analysed.
    Look at the video for Valencia that Ronan posted earlier in this tread (middle panel).
    This is a head scratcher, because according to the current theories of atmospheric behaviour, it should be the other way round (i.e. the slope should be smaller in the Tropopause-Stratosphere than in the Troposphere). As has been pointed out the slope should be 1/RT.
    In the Troposphere T decreases with pressure. In order to increase the slope in the Tropopause –Stratosphere, T would have to decrease at a greater rate. (The slope is the reciprocal of T i.e. increasing T decreases the slope and decreasing T increases the slope). But the temperature does not decrease at a greater rate in the Tropopause, it stops decreasing all together, and in the Stratosphere it actually increases (See the top panel of the YouTube video Ronan posted).
    The current explanation of the temperature profile in the Tropopause- Stratosphere region is that it is caused by UV heating of this region. But heating this region should decrease the slope of D versus P, which is the exact opposite of what happens. Therefore a different explanation is required.
    In paper 2 we suggest that a phase transformation from monomers to multimers, in the Tropopause – Stratosphere, if it took place, could explain the behaviour. An increase in the average molecular weight of the atmospheric gases in this region, would explain an increase in the slope of D versus P plot.
    But is such a phase transition thermodynamically feasible? If not then another explanation is required, and it may well be that another explanation will be found. However at the moment the only explanation we have come up with is the multimer hypothesis, and this is not without its own difficulties. For a gas phase reaction of the form nX2 (X2)n the value of equilibrium constant (which is determined form the partial pressures of the reactants and products) can be used to calculate the direction of the reaction if the change in Gibbs free energy for the reaction is known.
    For a closed system it is sometimes possible to determine the value of the change in Gibbs free energy by experimentally changing the values of the state variables. However, in an open system this is not the case. In a closed system the change in Gibbs free energy is a trade off between the heat of formation of the products ant the change in heat capacity caused by changes in entropy(S) due to the reaction. However in an open system such as the atmosphere where the value the changes in the various components of Gibbs free energy (i.e. the heats of formation and changes in heat capacity of the reaction) are unknown Gibbs is of no value.
    This is very unsatisfactory, in section 2 of paper 2 we have attempted some heavily caveated work arounds but more experimental work is needed before the multimer hypothesis can be confirmed or rejected.
    With respect to paper 3, in our day job we do a lot of work with heat pumps and heat exchangers and I have been awarded patents for novel designs of the same. For years a lot of our designs did not perform as theory predicted. It was only when we realized that we had had been neglecting through mass mechanical energy transmission in fluids (as had everyone else) and that by taking this into account, that we could reconcile theory and performance. Someone in this tread said that there was no need to invent through mass (non acoustic) mechanical transmission which we call ‘perfection’. Well we did not invent it, nature did that all on its own. All we did was name it , measure it and now use it.

    • I suggested there was no need for the concept of pervection due to the conversion of energy between KE and PE within molecules when they change height.
      To my mind that gets round the apparent problem that convection is not sufficient to transport enough energy from place to place to fit observations. Instead, heat simply disappears to PE when air rises. No need for that heat energy (KE) to be moved to another location, it simply becomes non heat energy (PE).
      Could that also deal with the ‘problem’ involving the sign of the slope change between troposphere and stratosphere?

      • Stephen Wilde August 26, 2017 at 3:56 am

        I suggested there was no need for the concept of pervection due to the conversion of energy between KE and PE within molecules when they change height.

        For the zillionth time: during convection (buoyancy) there is no conversion of KE to PE.
        The eg rising air is PUSHED up by the pressure from the air below it, no internal energy used.
        The lowering of the temperature of the rising air is due to its expansion against the surrounding air while rising.
        No conversion between these two processes.

        If you use an elevator your PE rises, but not by using any of your energy.
        Exact same thing for a rising thermal etc.

    • In reply to Dr Connolly, I refer him to JANAF, where the thermodynamic properties of oxygen molecules can be found at the temperature range he is seeking. It is not the deltaG of the pertinent part of the law of mass action rather than the dependence of its to the partial pressure of Oxygen (2 atoms) to the fourth power whereas the tetramerpressure is to the first power. This brings the result independant of the deltaG that the amount at sea level of the tetramer is 160000 times greater than at 20 km height.

  49. Frank August 27, 2017 at 6:39 pm

    The SALR is slightly curved, but in the opposite direction from what would be predicted for an atmosphere in radiative equilibrium.

    The SALR is curved exactly in the right direction to show the release of latent heat from condensation of diminishing amounts of water vapor as the rising air expands and cools.
    Same for sinking air, the use of energy to evaporate water droplets back into water vapor.
    Not sure what radiative equilibrium has to do with the ALR’s. Only requirement I’m aware of is that the air surrounding the rising or sinking air has to be in hydrostatic equilibrium.

    In polar regions, there isn’t as much water vapor in the air (lower optical density) and unstable lapse rates don’t develop. Adiabatic is inappropriate there.

    In polar regions the ALR’s are just as valid as in the tropics. Only region where I expect the (D)ALR to no longer exist is in the very low density / pressure regions (mesosphere – thermosphere).
    Fine example of the DALR showing up in a polar region are the Katabatic winds.
    https://en.wikipedia.org/wiki/Katabatic_wind
    Cold air racing down the slopes of oa Antarctica, and warming 9,8 K/km w

    • The SALR is curved exactly in the right direction to show the release of latent heat from condensation of diminishing amounts of water vapor as the rising air expands and cools.
      Same for sinking air, the use of energy to evaporate water droplets back into water vapor.
      Not sure what radiative equilibrium has to do with the ALR’s. Only requirement I’m aware of is that the air surrounding the rising or sinking air has to be in hydrostatic equilibrium.

      Like clear calm skies. Look at the bend in the cooling rate, and where it would have intersected had the cooling rate not dropped.

      This is the ghg effect warming the surface, and it’s being regulated by water vapor.

  50. Stephen Wilde August 28, 2017 at 8:44 am

    Jet stream heights do vary:

    Obviously, but individual jetstreams stay at their pressure level.
    In the plot above we see jetstreams at Fl300 and FL360 and they stay at that level.
    No undulating up and down as you stated.

    • But the pressure level itself varies and takes the jet stream with it depending on the position of the jet stream in relation to the adjacent high and low pressure cells.
      For simplicity that chart does not show the undulations in height of the pressure level.

      • Stephen Wilde August 29, 2017 at 3:35 am

        But the pressure level itself varies and takes the jet stream with it depending on the position of the jet stream in relation to the adjacent high and low pressure cells.

        You should consult a chart of geopotential heights to check this, but it is irrelevant since the jetstream stays at the same pressure level, so NO adiabatic expansion or compression.

      • The jets move up and down with the changes in geopotential heights. Basic meteorology. Nothing for me to check.
        The jet streams are CAUSED by differences in adiabatic compression or expansion between high and low pressure cells.

    • No undulating up and down as you stated.

      Oh yes there is. Maybe not on that chart. But the jet stream kinks, those are the north-south paths.
      I know they are there, because they affect my weather regularly.

    • Stephen Wilde August 29, 2017 at 1:09 pm

      The jets move up and down with the changes in geopotential heights. Basic meteorology. Nothing for me to check.

      The jetstreams I know move nicely ALONG lines of equal geopotential height, so very little moving up or down. I’m afraid your version of basic meteorology doesn’t match reality.
      http://www.weatheronline.co.uk/cgi-bin/expertcharts?LANG=en&MENU=0000000000&CONT=namk&MODELL=nam&MODELLTYP=1&BASE=-&VAR=jet3&HH=3&ARCHIV=0&ZOOM=0&PERIOD=&WMO=

      The jet streams are CAUSED by differences in adiabatic compression or expansion between high and low pressure cells.

      And how would that work?

      • Less dense rising air in the low pressure cells abuts more dense falling air in the high pressure cell. Normally. high pressure flows towards low pressure but due to the Earth’s rotation it cannot flow directly and so the moving air is forced into a narrow band flowing between the two rotating air masses. The bigger the density differential the faster the jet. The geopotential heights vary along the track of the jet (as it moves first towards the high pressure cell and then towards the low pressure cell and then back again) which moves up and down with those undulations in geopotential height.
        Stuff I learned decades ago in general meteorology.

      • Stephen Wilde August 30, 2017 at 2:23 am

        Less dense rising air in the low pressure cells abuts more dense falling air in the high pressure cell. Normally. high pressure flows towards low pressure but due to the Earth’s rotation it cannot flow directly and so the moving air is forced into a narrow band flowing between the two rotating air masses.

        https://earth.nullschool.net/#current/wind/isobaric/250hPa/orthographic=0.17,-90.03,401/loc=3.316,-50.474

        Current jetstreams at the 250 hPa level over the SH.
        Do you really believe this all is caused by air rising in a low pressure area and flowing out at maybe 25000 feet? (250 hPa is ~34000 feet)
        These highs and lows are CAUSED by the jetstreams (Rosby waves)

      • Convection first.
        High and low pressure cells second.
        Jet streams running between them third.

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