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For a reversible process, it is assumed that the external pressure $P_{ext}$ is infinitesimally different from internal pressure $P_{int}$.

So in reversible process, I can have $~P_{int}=P(V,T)~$ but also $~V=V(P_{int},T)~$.

Then what is the obvious reason/advantage for defining $~\delta W=-P(V,T)dV~$ instead of just define $~\delta W=-V(P,T)dP~?~$
it seems that I can always convert one to the other

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    $\begingroup$ If the volume is constant, what kind of work have been done? Work is force times displacement, and changing the volume is a form of displacement. How does change in pressure with constant volume do work? $\endgroup$ Commented Feb 5, 2022 at 15:28
  • $\begingroup$ @OfekGillon that is what I am confused about, if we can just "define" work to be the change in pressure with constant volume (displacement times force), calculation can still be carried, so what is the reason for insisting on defining force over displacement? $\endgroup$
    – P'bD_KU7B2
    Commented Feb 5, 2022 at 15:42
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    $\begingroup$ Fdx is what we define as work, and xdF is not.. $\endgroup$ Commented Feb 5, 2022 at 17:34
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    $\begingroup$ You realize that PdV is the same as Fdx, right? $\endgroup$ Commented Feb 5, 2022 at 17:49
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    $\begingroup$ Essentially a duplicate of physics.stackexchange.com/q/382726/2451 $\endgroup$
    – Qmechanic
    Commented Feb 5, 2022 at 19:01

3 Answers 3

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Every system is defined by a variety of extensive variables: entropy, volume, mass, charge, surface area, magnetization, etc. The internal energy $U$ is a function of these variables—$U=U(S,V,N, Q,A,M,\dots)$—and we seek to know how $U$ changes when the variables change:

$$dU=\left(\frac{\partial U}{\partial S}\right)_{V,N,Q,A,M\dots}dS+ \left(\frac{\partial U}{\partial V}\right)_{S,N,Q,A,M\dots}dV+ \left(\frac{\partial U}{\partial N}\right)_{S,V,Q,A,M\dots}dN+\cdots.$$

We happen to call one of these coefficients, $\left(\frac{\partial U}{\partial V}\right)_{S,N,Q,A,M\dots}$, the negative pressure $-P$. We can increase the energy of a system for positive values of $-P\,dV$. That’s why the parameters are ordered the way they are.

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in reversible process, why define $\delta W=-PdV$ instead of $\delta W=-VdP$?

You need to differentiate between work done in a closed system and an open system.

For a closed system, where there is no flow of mass into or out of the system, work is referred to as "boundary work". This is the work only associated with expanding or contracting the boundaries of the system, i.e., changing the volume of the system. The often used example is the expansion or compression of a gas in a cylinder fitted with a movable piston. For a closed system, where expansion work is considered positive,

$$\delta W=PdV$$

It applies to an irreversible as well as a reversible process. For the irreversible process, $P$ is the external pressure.

For an open system, where work is required to push or pull mass into and out of the system because of pressure differences at the boundary, work is then called flow work and

$$\delta W=VdP$$

Hope this helps.

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  • $\begingroup$ Thank you for the answer. What I am wondering is, in the reversible case, assume I am doing measurements on $P$ and $V$ during an expanding process, I can plot P-V diagram, or V-P diagram. If I assign the area under V-P diagram (VdP) instead of P-V (PdV), it gives the information about the reversible process just as good as the P-V diagram. So why can't I assign the name "Work" to the area under V-P diagram (and then further define the internal energy to be $U=Q+VdP$), but rather choose the area of P-V diagram? $\endgroup$
    – P'bD_KU7B2
    Commented Feb 5, 2022 at 16:21
  • $\begingroup$ @rookie Consider a reversible isobaric (constant pressure) expansion process. The area under the PV diagram (expansion work) is $P\Delta V$. The area under the VP diagram is zero. $\endgroup$
    – Bob D
    Commented Feb 5, 2022 at 17:10
  • $\begingroup$ But if I choose the define "Work" as VdP, then I can just say in this case, the "Work" done is zero. What I am thinking is if I have two variables, $W_1=VdP$ and $W_2=PdV$, then in a reversible process, there should be a bijective mapping from $W_1$ to $W_2$, where the $W_1=0$ represents a different value in $W_2$, which represents the reversible isobaric work. $\endgroup$
    – P'bD_KU7B2
    Commented Feb 5, 2022 at 17:24
  • $\begingroup$ "But if I choose the define "Work" as VdP, then I can just say in this case, the "Work" done is zero." How can you arbitrarily dismiss the expansion work so that the system expands without using any energy. I really don't understand what you are trying to do here. But that's OK. It's probably just me. $\endgroup$
    – Bob D
    Commented Feb 5, 2022 at 17:36
  • $\begingroup$ I am not dismissing the work PdV in this case, what I am trying to say is if there is a function $F(VdP)=PdV$, then $F(0)$ is the isobaric work that you are talking about, in this case, I can redefine "Work" to be VdP instead of PdV $\endgroup$
    – P'bD_KU7B2
    Commented Feb 5, 2022 at 17:43
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Maybe I misunderstand your question, but pdV-work follows naturally from the definition of work $W$ from classical mechanics (in one dimension): $$ dW = F dx = pA dx = p dV $$ where $p$ is pressure, $A$ is the cross sectional area, $F$ is the applied force, $dx$ is the displacement, and $dV(=Adx)$ is the displaced volume.

Furthermore, the thermodynamic identity takes the form $$ dU = TdS - pdV $$ for internal energy. If you formulate the thermodynamic identity in terms of enthalpy you obtain $$ dH = TdS + V dp. $$ So the two terms ($pdV$ and $Vdp$) are related through the Legendre transformation, and their use depends on which potential is relevant to the problem at hand.

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