When a gas freely expands into a vacuum it is not in thermodynamic equilibrium! It is dynamic. Not all of the gas has the same kinetic energy.
Agree.But I believe the "dm" molecules have the same range of energy as their inmates behind.I will justify it later in this post.
Let's start with a chamber of gas under pressure P and temperature T. There is a small hole in the chamber wall controlled by a valve which opens to a large empty chamber (vacuum). Consider an element of gas dm at that hole. When the valve opens, is pushed out. This is because the molecules inside the chamber are pushing it out and there is nothing on the other side pushing back. So this element of gas of volume dV in the chamber blasts out into the vacuum. Then the valve is closed.
OK.Lets proceed assuming the total system is isolated.
But then the gas in the chamber kicked dm out into the vacuum it added additional kinetic energy. When things settle down and reach equilibrium again, dm will have greater energy than before - so its temperature will be greater than T. Where does this energy come from? From the gas in the chamber. The gas in the chamber performed work on dm and increased its energy. So the gas in the chamber must have lost energy. It has cooled to something less than T.
Do not agree.
Let us first consider the "chember" molecules.In equilbm,they were colliding with each other.They had certain mean free path.From Maxwell's velocity and energy distribution we know that maximum of the "chember" molecules have the same velocity/energy range.So,just at the instant the valve is opened,in that time range t_0 to t_0+dt,the distribution has not been changed remarkably,the outgoing 'faster' (called by you) "dm" moleules must have almost the same kinetic energy as that of their inmates.You cannot insist that your "dm" molecules are the ones having high velocity.You must justify.
(The distribution changes with temperature only.Since temp cannot change in that small duration,the distribution will look like the same).
You claimed the "dm" molecules move faster as they were pushed.If this push is arising from collisions,it simply assymetric.Why should the inner molecules collide "dm"s to impart greater KE on them?How do the inmates know when and whom to collide?Remember atleast in the beginning,the KE range is the same,as I showed.If the push is from interactions then the blow to you will be-for ideal gas,no intermoleculer interaction exist.Hence the molecules in the chember cannot push "dm"s.
For the sake of arguement,let me say what I said earlier is wrong.That is the "dm" molecules truly have greater KE and those left at the "chember" have lower KE.Former has higher temp,the latter has lower.So what?What does it prove?You have made two systems different on closing the valve and you cannot say the "chember" gas has done work on itself,because that has been the part of a different system.
Even,if when all the gas is let out, P,v will change, and T will change... I do not see why t will be the same.
But if it propels itself into a dynamic state, it does do work on itself. The total energy content does not change, but the distribution of energy within the gas changes.
If it is in a dynamic state,and if a gas can work on itself in dynamic state,what is the use of talking about this intermediate energy distribtion?Remember, what I asked was a free expanson within a
single enclosure,where we were concerned about the two eqlbm. points,not any intermediate states.But there you said the gas will work on itself and that you took into consideration in 1st law.
If it is in a dynamic state (not in thermodynamic equilibrium) the motion of the molecules is not completely random - ie. the distribution of velocities is not uniform throughout the gas.
Maxwell's distribution shows the distribution of velocities is not uniform throughout the gas even in equilibrium.So,be precise...what you are saying as dynamic state is nothing but a simple non-equilibrium state.
It goes from a random state (thermodynamic equilibrium) to a dynamic state (not completely random) as it is expanding into the vacuum to a random state when things settle down and again reach thermodynamic equilibrium.
OK,I think I am going to like this part...
I thank you very much as you replied...I might have left this forum...I must praise your commitment.