U=Cv(dT) and Enthelphy=Cp(dt) for all processes in thermodynamics?

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Discussion Overview

The discussion revolves around the relationships between internal energy (U), heat capacity at constant volume (Cv), enthalpy (H), and heat capacity at constant pressure (Cp) in thermodynamics. Participants explore whether the equations U=Cv(dT) and H=Cp(dt) hold true for all thermodynamic processes, including isochoric and isobaric conditions.

Discussion Character

  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant asks for an explanation of why U=Cv(dT) and H=Cp(dt) apply to all processes in thermodynamics.
  • Another participant explains that in isochoric processes, where volume is constant, dA=0, leading to dU=dQ=Cv*dT.
  • It is noted that enthalpy is defined as W=U+PV, and in isobaric processes, where pressure is constant, dP=0, resulting in dW=dQ=Cp*dT.
  • A further contribution discusses that U and H are state functions, and changes in them can be expressed in terms of two independent variables, with the chain rule applied to derive dU.
  • The participant clarifies that while dU is not always equal to Cv(dT), for perfect gases, the term (\frac{\partial U}{\partial V})_T is zero, thus dU=Cv(dT) holds for all processes involving perfect gases.
  • There is a discussion on the seeming contradiction of using Cv for processes at constant pressure, with an explanation that U can be computed along any path between initial and final states.

Areas of Agreement / Disagreement

Participants express differing views on the applicability of U=Cv(dT) and H=Cp(dt) across all processes. While some argue these relationships hold for perfect gases, others highlight conditions under which they may not apply universally.

Contextual Notes

The discussion includes assumptions about the behavior of perfect gases and the definitions of state functions, which may not hold for all systems or conditions.

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Can someone explain why U=Cv(dT) and Enthalphy=Cp(dt) for all processes in thermodynamics?
 
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dQ=dU + dA => dU = dQ -dA , in isochoric processes dA = 0 so that dU=dQ(while V=const) =Cv*dT.
Enthalpy W is defined : W = U +PV => dW = dU +PdV +VdP = dU + dA + VdP = dQ + VdP, in isobaric processes dP=0 so dW=dQ (while P=const) =Cp*dT.
 
In thermodynamics you usually study systems with only one kind of work interation, so this means that two independent, intrinsic properties fix the state of the system. Since U and H are functions of state, that means a change in them can be expressed in terms of any two such variables. If we decide to determine U by temperature and volume, then the expression for an infintessimal change in U is, by the chain rule
[tex]dU=(\frac{\partial U} {\partial T})_VdT+(\frac{\partial U} {\partial V})_TdV[/tex]
which, by definition of [itex]c_V[/itex] is
[tex]dU=c_VdT+(\frac{\partial U} {\partial V})_TdV[/tex]
So, dU is not always equal to [itex]c_VdT[/itex]. However, for a perfect gas [tex](\frac{\partial U} {\partial V})_T[/tex] is always equal to zero, so that means that [itex]dU=c_Vdt[/itex] for all processes involving perfect gases. That is probably what you meant. The dH equation is simmilar.

It seems strange at first that you would use the constant volume heat capacity for any process, including one at constant pressure. But this really isn't so strange. Fitrst of all, using [itex]c_P[/itex] would make no sense to find [itex]\Delta U[/itex] because this is defined as [itex](\frac{\partial H} {\partial T})_P[/itex] and notice that dU doesn't even appear there. Secondly, supposing the process is at constant pressure: U is a state function so we can imagine any path between the beginning and end points we want to compute [itex]\Delta U[/itex]. Imagine the gas is first heated at constant volume. [itex]\Delta U[/itex] for this process is clearly [itex]c_V\Delta T[/itex]. Now let the gas expand at constant volume back to its original pressure. [itex]\Delta U[/itex] for this process is [itex](\frac{\partial U} {\partial V})_T \Delta V[/itex]. But [itex](\frac{\partial U} {\partial V})_T[/itex] is zero for a perfect gas, so the total [itex]\Delta U[/itex] is [itex]c_V \Delta T[/itex]
 
wow! thanks! :)
 

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