Monday, 11 December 2017

thermodynamics - Why is dE=CVdT for an ideal gas, even when the process is not constant volume?




I have come across the following derivation for the "equation of an adiabat for an ideal gas" in many textbooks. The following steps are referenced from a separate question:



  1. dE=dQ+dW

  2. dW=−pdV

  3. dQ=0

  4. dE=CVdT

  5. therefore CVdT=−pdV


All the symbols have the usual meaning.(The derivation then proceeds to use the eqn. of state arriving at PVγ=const.)



Problem



  1. I don't understand the use of eqn. 4 in step 5. In an adiabatic process both P and V can vary so, then how can one use a quantity that requires V to be constant?



Answer



For an ideal gas any process


ΔU=CvΔT


so even though it is not a constant volume process it still applies.


I can give you a proof if you need it.


Here is the proof. Actually it is not a proof, but shows that it is true for the examples of an isobaric and adiabatic process. You can do the same for an isothermal or any other process.



For a constant pressure process:


ΔU=QW

ΔU=CpΔTPΔV
For one mole of an ideal gas PΔV=RΔT
Therefore ΔU=CpΔTRΔT


For an ideal gas,


R=CpCv


Therefore, ΔU=CpΔT(CpCv)ΔT

ΔU=CvΔT


For an adiabatic process (Q=0): ΔU=W

ΔU=RΔT1k
For an ideal gas k=CpCv
and again R=CpCv
Therefore ΔU=(CpCv)ΔT1Cp/Cv
ΔU=CVΔT


So you might ask, what is the proof that for an ideal gas CpCv=R. It is based on the definitions of the specific heats and enthalpy, combined with the ideal gas law.


Specific heat definitions, ideal gas (they are actually partial derivatives holding P and V constant, respectively): Cp=dHdT

Cv=dUdT
Definition of enthalpy (H) H=U+PV
For one mole of an ideal gas, ideal gas law PV=RT
Therefore H=U+RT


Taking the derivative of the last equation with respect to temperature: dHdT=dUdT+R

Substituting the specific heat definitions into the last equation, we get CpCv=R


Finally, as J. Murray points out, this only applies to an ideal gas.



Hope this helps.


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