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I was told that a canister of compressed air gets cold because of the ideal gas law, you are lowering the pressure and since the density of air is the same, the temperature of the can gets cold. I was trying to see this mathematically and I became confused. Can someone please help me with the intuition.

The ideal gas law equation is $PV=nRT$ where R is $8.314 \frac{J}{mol \cdot K}$ if you convert from moles to kg, you get:

$$ R = 8.314 \frac{J}{mol \cdot K} \times \frac{1 mol}{0.02897 kg} = \frac{287 J }{kg \cdot K} $$

So we can change $nR$ where n is number of moles and $R$ is joules per mole-kelvin to $mR$ where m is mass and $R$ is Joules per kg-kelvin because $nR = \text{ joules } = mR$.

This gives $PV=mRT$

Assuming $m$ is the mass of 1 liter of air, and V is 1, then we have $P=\rho RT$, where $\rho$ is density.

I'm told this equation would explain why the can of air gets cold, since the density of air does not change. But this equation was formed under the assumption of a constant mass of air. In the compressed air example, the mass of air in the can is decreasing, and the volume stays the same. So I don't think we can describe the air can with $P = \rho R T$ I think it must be described with $PV = mRT$, and if the mass goes down, the pressure can go down, and the can does not have to get cold.

Am I correct that the $P=\rho RT$ equation does not hold if the mass inside the can is changing?

I saw another stack answer, Why does the gas get cold when I spray it?, but it is insanely complicated and doesn't mention the ideal gas law. I'm mostly trying to figure out why the ideal gas law does or does not answer the question, I can't begin to understand what they are saying in that other answer.

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    $\begingroup$ Does this answer your question? Why does the gas get cold when I spray it? You mention these answers in your question and I think that they are fairly comprehensive. $\endgroup$
    – Farcher
    Commented Feb 7 at 13:21
  • $\begingroup$ Do you know what an adiabatic process is? $\endgroup$ Commented Feb 7 at 13:34
  • $\begingroup$ I'm not sure what an adiabatic process is, but am I correct as to why the ideal gas law in the density form does not explain it? $\endgroup$
    – Frank
    Commented Feb 7 at 14:04
  • $\begingroup$ @Farcher that answer is kind of too complicated, I'm looking for an answer that explains why the ideal gas equation does or does not explain the situation. I'd like the answer to focus on ideal gas equation. The answer can just say why ideal gas equation is wrong or right. Does that make sense? $\endgroup$
    – Frank
    Commented Feb 7 at 14:07
  • $\begingroup$ $nRT$ is so chemist. Try it with $NkT$, then you have $kT$ as energy times $N$, the number of molecules. idk, I think it's conceptually clearer: number of particles times average energy $\endgroup$
    – JEB
    Commented Feb 7 at 14:27

3 Answers 3

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First to answer one of your questions

Am I correct that the P=ρRT equation does not hold if the mass inside the can is changing?

No, this equation always holds true provided a small change : $V= \frac{M(gas) \cdot n}{\rho}$ so if you replace $V$ in the standard expression of the ideal gas law you'll get $P=\frac{ρRT}{M(gas)}$

You can't insert $M(gas)$ into $R$ because the value of $M(gas)$ depends on the gas.

Now here is the complete answer to your problem :

Emptying a canister filled with compressed gas is the same as extending a piston filled with air. You can consider that a plate is positioned horizontally separating the air in two : above is the air that will exit the canister and under is the air staying within.

Canister emptying. Hope y'all like this magnificent drawing of mine

Simple answer :

Since the plate is moving, when a particle hits it, it will bounce back but with a slower speed : the movement of the plate absorbs the impact. Since temperature is strongly linked to the speed of the particle (more accurately to their energy) the movement of the plate causes a drop in temperature.

More complex answer :

Now that the problem is a bit more formalized let's solve it. First, what you need to see is that the ideal gas law alone is not enough to answer the problem. Indeed once you've let some air out the only parameter which value you know is $V$. You have information neither about $P$ nor $T$. So based on that equation only there are infinitely many solutions.

But here are the necessary equations which you may not have seen yet but are not as hard as they seem :

  1. $U = C_v \cdot T$ where $U$ is the internal energy of the gas (basically the sum of potential and kinetic energy for all particles) and $C_v$ a constant depending on the gas (usually $3/2$).
  2. $\Delta U = W_{received}$ where $W$ is the work received by the gas. This basically says that the difference of energy of the gas between two states is equals to the energy received (here under the form of the work $W$ because no heat transfer)
  3. $\delta W_{emitted} = P\cdot S \cdot dx = P\cdot dV$ where $S$ is the surface of the plate. It says that the work created by a pressure is the product of the force ($P\cdot S$) times the displacement ($dx$).

Using equation 2. between $t$ and $t+dt$ we get : $$\frac{dU}{dt}= \frac{dW_{received}}{dt}=-\frac{dW_{emitted}}{dt}$$

Using 3. we have : $$\frac{dU}{dt}= -P\cdot \frac{dV}{dt}$$

Using the law of ideal gas we get : $$\frac{dU}{dt}= -\frac{nRT}{V} \cdot \frac{dV}{dt}$$

Using 1. we get : $$C_v\frac{dT}{dt}= -\frac{nRT}{V} \cdot \frac{dV}{dt}$$

Rearranging the terms with $K = \frac{C_v}{nR} = \text{constant}$ we find : $$K\frac{1}{T}\frac{dT}{dt} = -\frac{1}{V}\frac{dV}{dt}$$

Finally if we integrate between $A$ and $B$ : $$K \ln{\frac{T_B}{T_A}} = - \ln{\frac{V_B}{V_A}}$$

Since $\ln$ is an increasing function, if there is an increase in $V$, then $T$ must decrease.

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  • $\begingroup$ I really am enjoying your answer. But can you please write a bit more about this. If you consider the molar form of PV=nRT, if the number of moles (n) decreases, pressure will go down for a constant volume (or temperature up). But then if you consider the density form P=ρRT, if moles (n) is going down with constant volume, then I don't see how this equation in this form can be valid anymore. It's not capturing the situation, the decreasing mass or moles is not considered. If moles decreases then this form P=ρRT violates this other form PV=nRT right? Am I crazy? P=ρRT is a bs equation? $\endgroup$
    – Frank
    Commented Feb 7 at 23:24
  • $\begingroup$ So it's just the atoms bouncing off the stream of air that is leaving the can? I'm surprised the effect is this strong that it can make a can so cold. $\endgroup$
    – Frank
    Commented Feb 8 at 11:08
  • $\begingroup$ I'm not exactly sure where your confusion lies but I'll try to answer : when considering $P=ρRT$ if $n$ decreases, then if $V$ is constant and you'll have that $\rho$ decreases too. Thus the pressure will decrease. But honestly I don't think it is a good idea to consider a varying $n$. IMO it is better to separate parts of the gas that are going to evolve differently (here the gas staying inside and the gas exiting the can) and then study them separately. Hence the plate I have introduced above. $\endgroup$ Commented Feb 8 at 16:21
  • $\begingroup$ To simplify, consider particles are just going up and down. Now let's consider a single particle and assume that the plate is moving very slowly from $x=L$ to $x=2L$ during $\Delta t$. We can make the rough approximation that the particle is going to bounce on the plate $N= \frac{\Delta t v_{particle}}{2L}$. Since $v_{particle after bounce} = v{particle before bounce} - v_{plate}$ we find (in a rough approximation) that $v_{particle final} = v_{particle initial} - N\cdot v_{plate}$. Thus we get $v_{final} = v_{initial} \left[ 1 - \frac{\Delta t v_{plate}}{2L} \right]$. End in next comment... $\endgroup$ Commented Feb 8 at 16:58
  • $\begingroup$ Finally we get $v_f = \frac{v_i}{2}$. Since $U=\frac{mv^2}{2}$ we have : $U_i-U_f = \frac{3mv_i^2}{4}$. This is huge !!! Since in this case $\Delta T = \frac{2\Delta U\cdot N_A}{5R}$ we find $\Delta T = 280K$ !!! Of course this result is an overestimate because of the different approximations but the order of magnitude is correct. $\endgroup$ Commented Feb 8 at 17:20
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Answer 1: There is some liquid in the can that starts evaporating when the button is pressed.

Answer 2: It's actually such compressed air can where there actually is compressed ideal gas in the can. The gas does work against the atmospheric pressure. The gas in the can helps the gas inside the nozzle to get out by pushing its back. So it loses energy.

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  • $\begingroup$ In my question, I asked something specific, can you speak to it in your answer? -> "Am I correct that the P=ρRT equation does not hold if the mass inside the can is changing" $\endgroup$
    – Frank
    Commented Feb 7 at 18:52
  • $\begingroup$ @Frank I believe the ideal gas law always applies to a gas that is ideal. You think otherwise? Density of the gas in the can decreases when gas is let out. Density is mass/volume. $\endgroup$
    – stuffu
    Commented Feb 7 at 23:57
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See https://en.wikipedia.org/wiki/Joule%E2%80%93Thomson_effect#Physical_mechanism

There are two factors that can change the temperature of a fluid during an adiabatic expansion: a change in internal energy or the conversion between potential and kinetic internal energy. Temperature is the measure of thermal kinetic energy (energy associated with molecular motion); so a change in temperature indicates a change in thermal kinetic energy. The internal energy is the sum of thermal kinetic energy and thermal potential energy. Thus, even if the internal energy does not change, the temperature can change due to conversion between kinetic and potential energy; this is what happens in a free expansion and typically produces a decrease in temperature as the fluid expands. If work is done on or by the fluid as it expands, then the total internal energy changes. This is what happens in a Joule–Thomson expansion and can produce larger heating or cooling than observed in a free expansion.

The atoms of an ideal gas are hard bouncy particles with no internal structure. If you allow an ideal gas to expand, the atoms have more space in which to bounce around. But their kinetic energy doesn't change. So the temperature doesn't change.

Molecules have bonds. These can be modeled, at least approximately, as balls on spring. When they bounce around, the springs get compressed. Some of the internal energy is potential energy of the bonds. Depending on the molecule, if you let this gas expand, the potential energy can change.

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  • $\begingroup$ Am I correct that the P=ρRT equation does not hold here because the mass inside the can is changing, and P=ρRT only holds if the mass in the container is constant? $\endgroup$
    – Frank
    Commented Feb 7 at 16:37

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