Wednesday, 1 April 2015

thermodynamics - Does PV work violate conservation of energy?



Suppose a container separating two gases via a movable massless piston. If the pressure of gas 1 is higher than that of gas 2, the piston will move. In an infinitesimal volume change, the energy lost by gas 1 will be P1.dV and that gained by gas 2 will be P2.dV. As P1 is higher than P2, where is the extra energy going?


Note: no heat exchange is considered. The only change in energy is caused by work.



Answer



Let the system 1 be one gas, the system 2 be the other gas, and P be the piston. The process is short enough to consider it adiabatic, so the first principle of thermodynamics gives


dEp+dU1+dU2=δWext


where Ep is the mechanical energy of the piston and Wext the work done by the operator. Indeed, dUp=0 since the piston is a rigid body and there is no heat transfer, and dE1=dE2=0 in the first order since the transformation is infinitesimal.


However, the process can be quasi-static, so dEp=0, so we got


dU1+dU2=δWext


Here, you made the following mistake: you said that δWext=0, but this is physically impossible. Indeed, P1P2, so the piston won't evolve smoothly at all if there's no external force applied on it. Thus, if the process is quasi-static, then there is an external force, so


dU1+dU20



But we can also say that the operator doesn't touch the device. Then, δWext=0, however the kinetic energy of the piston have changed during the process, so dEp0, which gives


dU1+dU20


In both cases, at first sight the conservation of energy is violated, however once you've taken the piston into account, there's no problem anymore.


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