I am a little confused, from the first law of thermodynamics (energy conservation)
ΔE=δQ−δW
If the amount of work done is a volume expansion of a gas in, say a piston cylinder instrument at constant pressure,
ΔE=δQ−pdv
Here p is the constant pressure and dv is the change in (specific) volume.
So, when do I take into account
δW=d(pv)=pdv+vdp
I am assuming that for cases of boundary work, at constant pressure, the vdp term is zero.
So under what conditions should I consider the vdp term?
Answer
PdV is boundary work. VdP is isentropic shaft work in pumps (as you have identified above), gas turbines, etc. Now you must realize that even in a pump or turbine the mechanism of work is still Pdv, i.e., the gas pushing on the blade out of its way. But, then there is work required to maintain the flow in and out of the device/control volume, which requires flow work PV so the net reversible work from a steady-flow device turns out to be shaft vdP.
Why flow work PV? To push a packet of fluid with volume V forward into a device you have to do work against the pressure of the fluid already in the device, i.e., overcome the back force of that fluid. This implies the work you do in pushing your new packet of length L and cross-section area A into the device is: ∫Fdx=∫L0PAdx=PV
Now consider the device (e.g., turbine to be a control volume). The energy of the fluid going in is its internal energy and the work invested into the fluid to enter the device: Uentry+PentryVentry=Hentry. Similarly for exit from the device. The net change across the device is ΔH. For a differential device (or across a small change) this is dH. The work output from the shaft of then device is the δW=dH.
Now if the device is isentropic, i.e., adiabatic-reversible. The Gibbs equation provides: dH=TdS+VdP=VdPδW=dH=VdP(isentropicdS=0)
Therefore VdP is isentropic shaft work from a flowing device.
Important points: 1) Both internal energy and enthalpy are state variables, therefore can be measured for a system static or flowing. This is why sometimes there is a tendency to use U and H incorrectly. The true purpose of H is to capture the work required to push/maintain a flow against a back pressure, i.e., it incorporates the PV part. Therefore when you write an energy balance with flows coming in and out, the energy crossing boundary is not just U but H and this distinction must be kept in mind.
2) VdP is isentropic steady-flow shaft work. The isentropic is key here.
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