I Paradox: Thermodynamic equilibrium does not exist in gravitational fields

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The discussion revolves around the paradox of thermodynamic equilibrium in a gas within a gravitational field, where an adiabatic temperature gradient suggests that temperature decreases with height. This leads to the conclusion that the upper and lower walls of the box, which are in thermal contact, should have different temperatures, conflicting with the notion of equilibrium where temperatures should be uniform. Participants argue that in thermodynamic equilibrium, the temperature must be constant throughout the system, and any temperature gradient indicates a lack of equilibrium. The conversation also touches on the implications of gravitational effects and the behavior of gas particles, emphasizing that a true equilibrium state would not support spontaneous energy flows. Ultimately, the paradox highlights the complexities of defining equilibrium in systems influenced by gravitational fields.
  • #31
ChatGPT says 71 nm
 
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  • #32
Petr Matas said:
ChatGPT says 71 nm
In other words, each molecule experiences a multitude of collisions and energy transfers per unit time, which translates into significant heat conduction within the gas.
 
  • #33
Chestermiller said:
In other words, each molecule experiences a multitude of collisions and energy transfers per unit time, which translates into significant heat conduction within the gas.
I agree, but I believe that my approach is independent of the assumption about collisions.
 
  • #34
Petr Matas said:
I agree, but I believe that my approach is independent of the assumption about collisions.
I certainly don’t think so. How does your objection even exist if the gas molecules collide with each other?
 
  • #35
Dale said:
I certainly don’t think so. How does your objection even exist if the gas molecules collide with each other?
I think that in the equilibrium, the velocity distribution must be the same whether collisions among the particles occur or not. Let's assume there is a small solid object somewhere in the gas column. Every particle will hit this object from time to time. Even if the particles don't interact with each other, collisions with this object will mediate energy transfer among the particles. I think this allows me to ignore the collisions among the particles in the analysis of the equilibrium state.
 
  • #36
Petr Matas said:
I think that in the equilibrium, the velocity distribution must be the same whether collisions among the particles occur or not.
With the collisions the distribution of the velocity is uniform in direction and Maxwell-Boltzmann in speed. Can you show that is the case without collisions? I am highly skeptical. I think this is the key. Without this proof you do not have thermal equilibrium and therefore don’t have a well defined temperature in the first place.
 
  • #37
Dale said:
With the collisions the distribution of the velocity is uniform in direction and Maxwell-Boltzmann in speed. Can you show that is the case without collisions? I am highly skeptical. I think this is the key. Without this proof you do not have thermal equilibrium and therefore don’t have a well defined temperature in the first place.
How about the energy transfer mediated by the small solid object that I mentioned? Isn't that enough to allow reaching the equilibrium (after very long time, of course)?
 
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  • #38
Petr Matas said:
How about energy transfer mediated by the small solid object that I mentioned? Isn't that enough to allow reaching the equilibrium (after very long time, of course)?
Not that I can see. Can you derive the distribution from that? I don't think that I could.

Also, if you can derive the usual distribution, doesn't that invalidate your whole argument? Isn't your argument predicated on the distribution being different from the standard thermal equilibrium? I don't see how you can have it both ways.
 
  • #39
Petr Matas said:
I agree, but I believe that my approach is independent of the assumption about collisions.
Have you had a course yet in fluid mechanics or Transport Processes?
Petr Matas said:
I think that in the equilibrium, the velocity distribution must be the same whether collisions among the particles occur or not. Let's assume there is a small solid object somewhere in the gas column. Every particle will hit this object from time to time. Even if the particles don't interact with each other, collisions with this object will mediate energy transfer among the particles. I think this allows me to ignore the collisions among the particles in the analysis of the equilibrium state.
unless there is no object present.
 
  • #40
Chestermiller said:
Have you had a course yet in fluid mechanics or Transport Processes?
Unfortunately not. However, I am going to assume the gas is still.

Chestermiller said:
unless there is no object present.
I am going to assume a usual thermal distribution at certain altitude and from there I expect to conclude that it is such everywhere.

Dale said:
Isn't your argument predicated on the distribution being different from the standard thermal equilibrium?
No, the standard thermal distribution is the result that I am expecting to obtain.
 
  • #41
Petr Matas said:
Unfortunately not. However, I am going to assume the gas is still.


I am going to assume a usual thermal distribution at certain altitude and from there I expect to conclude that it is such everywhere.
Like I said, using continuum fluid mechanics and heat transfer would be much simpler.
 
  • #42
Petr Matas said:
ChatGPT says 7
Tell us again how you're not using an AI?
 
  • #43
Petr Matas said:
No, the standard thermal distribution is the result that I am expecting to obtain
I don’t see how. Can you show it?

I also don’t see the point of adding the little block. What does it do that the walls don’t already do besides make the geometry more complicated?
 
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  • #44
Vanadium 50 said:
Tell us again how you're not using an AI?
This was the second time 😉. I prefer leaving tedious but simple work to AI (while checking its answers of course) to save time for tasks which are currently beyond the AI capabilities. I mark the AI answers clearly whenever I use them. Or would you prefer me to conceal the use of AI? Or not use AI at all? What is the point?
 
  • #45
Dale said:
I don’t see how. Can you show it?
I must shut up and calculate.

Dale said:
I also don’t see the point of adding the little block. What does it do that the walls don’t already do besides make the geometry more complicated?
Walls suffice.
 
  • #46
Chestermiller said:
Like I said, using continuum fluid mechanics and heat transfer would be much simpler.
You mean using the law that heat flows from higher to lower temperature? I want to avoid using this law. Actually, I want to prove (using laws of motion) that it is valid even in gas in gravitation without assuming its validity in the first place.
 
  • #47
Petr Matas said:
You mean using the law that heat flows from higher to lower temperature? I want to avoid using this law. Actually, I want to prove (using laws of motion) that it is valid even in gas in gravitation without assuming its validity in the first place.
Good luck.
 
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  • #48
Dale said:
With the collisions the distribution of the velocity is uniform in direction and Maxwell-Boltzmann in speed. Can you show that is the case without collisions? I am highly skeptical. I think this is the key. Without this proof you do not have thermal equilibrium and therefore don’t have a well defined temperature in the first place.
BTW
1 . When the particles are photons, they do not interact each other but only with walls.
2 . I revisited Laudau Statistical Mechanics chapter II section 27 for relativistic region (27.5)
T=constant \ (1-\phi/c^2)
The temperature is higher at points in the body where ##|\phi|## is greater. So the things seem to change in relativity.
 
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  • #49
Theorem:
A gas column in thermodynamic equilibrium in a classical homogeneous gravitational field has the same temperature everywhere.

Proof using the laws of motion:

Let at time 0 a point particle with mass ##m## is located at height 0 and its velocity is ##\mathbf{v}_0 = (v_{\text x 0}, v_{\text y 0}, v_{\text z 0})##. Its total energy is
$$ E = \tfrac{1}{2} m (v_{\text x 0}^2 + v_{\text y 0}^2 + v_{\text z 0}^2). $$
Let us assume the particle moves without collisions. At time ##t## it is at height ##z##, its velocity is ##\mathbf{v} = (v_{\text x 0}, v_{\text y 0}, v_{\text z})## and it has the same total energy
$$ E = \tfrac{1}{2} m (v_{\text x 0}^2 + v_{\text y 0}^2 + v_{\text z}^2) + mgz,
$$ where ##g## is the gravitational acceleration.

Comparison of the two equations yields
$$
v_{\text z 0}^2 = v_{\text z}^2 + 2gz, \tag 1
$$ $$
v_{\text z 0} = \pm \sqrt{v_{\text z}^2 + 2gz}. \tag 2
$$
Differentiation of equation ##(1)## yields
$$ v_{\text z 0} dv_{\text z 0} = v_{\text z} dv_{\text z}. \tag 3 $$
Let ##\rho(z, v_\text z)## is the density of particles at height ##z## with vertical velocity ##v_\text z##.

Consider at time 0 a bunch of particles at height 0 with velocities in range from ##v_{\text z 0}## to ##(v_{\text z 0} + dv_{\text z 0})##; they contribute to ##\rho(0, v_{\text z 0})##. The number of such particles, which cross a unit-area horizontal boundary at this height in unit time, is
$$ dN = \rho(0, v_{\text z 0}) v_{\text z 0} dv_{\text z 0}. \tag 4$$
At time ##t##, the same particles are at height ##z##, their velocities range from ##v_{\text z}## to ##(v_{\text z} + dv_{\text z})## and they contribute to ##\rho(z, v_{\text z})##. The same number of particles will cross a unit-area horizontal boundary at this height.
$$ dN = \rho(z, v_{\text z}) v_{\text z} dv_{\text z}. \tag 5$$
Equations ##(2)##, ##(3)##, ##(4)##, ##(5)## together yield
$$ \rho(z, v_{\text z}) = \rho\left(0, \pm \sqrt{v_{\text z}^2 + 2gz}\right). \tag 6$$
Let the velocity distribution at height 0 is Maxwell–Boltzmann (i.e. thermal) with temperature ##T##. That means the density at that height is
$$ \rho(0, v_{\text z}) = C \exp\left(-\frac{m}{k_\text B T} \cdot \frac{v_{\text z}^2}{2} \right), \tag 7
$$ where ##C## is a constant.

From equations ##(6)## and ##(7)## we get
$$ \begin{align}
\rho(z, v_{\text z}) \nonumber
& = C \exp\left(-\frac{m}{k_\text B T} \cdot \frac{v_{\text z}^2 + 2gz}{2} \right) \nonumber \\
& = \exp\left(-\frac{m}{k_\text B T} \cdot gz \right) \cdot C \exp\left(-\frac{m}{k_\text B T} \cdot \frac{v_{\text z}^2}{2} \right) \nonumber \\
& = \exp\left(-\frac{m}{k_\text B T} \cdot gz \right) \cdot \rho(0, v_{\text z}). \nonumber
\end{align} $$
We can see that the velocity distribution is the same at all heights ##z## (i.e. the temperature is the same everywhere) and the density decreases exponentially with height ##z##. Interaction between the particles cannot change this distribution, because they are already in equilibrium.

End of proof.

This result may be generalized to non-homogeneous classical gravitational fields by replacing ##V(z) = gz## with a generic gravitational potential ##V(x, y, z)##.
 
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  • #50
Petr Matas said:
Differentiation of equation (1) yields
(3)vz0dvz0=vzdvz.
Let ρ(z,vz) is the density of particles at height z with vertical velocity vz.
By differentiation of (1) I got (3)
v_{\text z 0} dv_{\text z 0} = v_{\text z} dv_{\text z}+gdz. \tag 3
Am I wrong ?
 
  • #51
anuttarasammyak said:
By differentiation of (1) I got (3)
v_{\text z 0} dv_{\text z 0} = v_{\text z} dv_{\text z}+gdz. \tag 3
Am I wrong ?
At height 0, let us have a narrow velocity interval from ##v_{\text z 0}## to ##(v_{\text z 0} + dv_{\text z 0})##. The goal is to find what velocity interval at height ##z## it is mapped to. Therefore ##z## is a constant. Any ideas how to express it more clearly?
 
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  • #52
Thanks. So have you conquered your losing-speed intuition by your calculation which tells same velocity distribution but different number density by height ?
 
  • #53
anuttarasammyak said:
Thanks. So have you conquered your losing-speed intuition by your calculation which tells same velocity distribution but different number density by height ?
Exactly.
 
  • #54
Congratulations. Let me understand more. Say a bouncing ball goes up and down between floor and ceiling. By gravity

ball speed near floor > ball speed near ceiling

time duration ball staying in 10cm layer from floor < time duration ball staying in 10cm layer from ceiling

ball number desity in 10cm layer from floor < ball number density in 10cm layer from ceiling

This contradicts the result. Where am I wrong ?
 
  • #55
anuttarasammyak said:
This contradicts the result. Where am I wrong ?
There are many balls.
 
  • #56
Each ball has high probability to be near ceiling and the sum of them, though there is no interaction between, show high number density near floor. Very interesting to me.
 
  • #57
Another observation: Trajectories of individual particles are parabolas. A particle never appears above the top of its parabola.
 
  • #58
Another observation 2: As a bunch of particles rises and loses speed, they come closer together in space, but farther apart in velocity. These opposite effects on density cancel out, which can be seen from equation (6): It is an equality between densities of the same bunch at different heights; all multiplicative factors disappeared.
 
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  • #59
anuttarasammyak said:
Each ball has high probability to be near ceiling and the sum of them, though there is no interaction between, show high number density near floor. Very interesting to me.
Statistical/thermal mechanics explains that maximum entropy state of vertical column gas has throughout same temperature as Maxwell said. Newton Mechanics of bouncing balls seem to have different nature to me where energy conservation is applied individually to the balls not to the whole system and with no concept of entropy.
Anyway it is your thread not mine. If you have no ambiguity I should shut up.
 
  • #60
anuttarasammyak said:
Statistical/thermal mechanics explains that maximum entropy state of vertical column gas has throughout same temperature as Maxwell said. Newton Mechanics of bouncing balls seem to have different nature to me where energy conservation is applied individually to the balls not to the whole system and with no concept of entropy.
Anyway it is your thread not mine. If you have no ambiguity I should shut up.
Analysis using Newton mechanics may be too difficult to apply on large ensembles, but it must give the same results as thermal laws. In our case its application was rather easy and it showed me where exactly my intuition went wrong. This allows me to attain deeper understanding.
 

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