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Thermodynamics for Engineers

1) The document discusses the thermodynamic definition of pressure. 2) It considers an isolated system composed of two subsystems initially at different equilibrium states, where motion of the barrier and heat transfer are allowed. The final states will be ones where the subsystems have equalized to a common temperature and pressure. 3) By applying the differential form of the fundamental relation and adding a volume constraint, it is shown that the thermodynamic pressure p is defined as p ≡ T(∂S/∂V)U,Ni , where S is entropy, V is volume, T is temperature, and Ni are mole amounts of constituents.

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90 views6 pages

Thermodynamics for Engineers

1) The document discusses the thermodynamic definition of pressure. 2) It considers an isolated system composed of two subsystems initially at different equilibrium states, where motion of the barrier and heat transfer are allowed. The final states will be ones where the subsystems have equalized to a common temperature and pressure. 3) By applying the differential form of the fundamental relation and adding a volume constraint, it is shown that the thermodynamic pressure p is defined as p ≡ T(∂S/∂V)U,Ni , where S is entropy, V is volume, T is temperature, and Ni are mole amounts of constituents.

Uploaded by

Anonymous G3DRjDMk
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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The Thermodynamic Definition

of Pressure

John W Daily
Mechanical Equilibrium

A B

An isolated system, composed of two subsystems


initially at different equilibrium states. Motion of the
barrier is allowed as is heat transfer. What are the
final states?
Heat Transfer and Friction
• When exploring both pressure we allowed
heat transfer to occur.
• Without heat transfer there is no mechanism
to stop the piston from oscillating back and
forth forever.
• Friction is the mechanism that stops the
motion at equilibrium.
• And friction results in heat transfer.
Mechanical Equilibrium
Differential form of FR:

∂S # ∂S # ∂S # ∂S #
dS = ! dU A + ! dV A + ! dU B + ! dVB
∂U " A ∂V " A ∂U " B ∂V " B

Add volume constraint to energy constraint

V = VA + VB = Constant dV = 0 = dVA + dVB

So that
& ∂S ) ∂S ) # & ∂S ) ∂S ) #
dS = 0 = % ' − ' "dU A + % ' − ' "dVA
$ ∂U ( A ∂U ( B ! $ ∂V ( A ∂V ( B !
Mechanical Equilibrium
The consequence is

∂S # ∂S # ∂S # ∂S #
! = !
∂U " A ∂U " B
and ! = !
∂V " A ∂V " B

∂S #
So what is ∂V ! ?
"U , N i
Mechanical Equilibrium
& Entropy # & Energy # & Force * Length # & Force #
= = =
$% Volume !" $Volume * Temperature ! $ Length 3 * Temperature ! $ Length 2 * Temperature !
% " % " % "

so
p ∂S #
≡ %
T ∂V $U ,Ni

and TA = TB and pA = pB

Now you know what “thermodynamic” pressure is!

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