Heat integral and molar heat capacity?

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Discussion Overview

The discussion revolves around the heat integral and molar heat capacity, specifically addressing the assumptions made regarding the number of moles (n) in the context of constant volume processes. Participants explore the implications of these assumptions on the mathematical treatment of heat capacity and the integration process.

Discussion Character

  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant questions the assumption of constant n in the integral, noting that n is dependent on temperature (T) and suggesting that T should be included in the integral.
  • Another participant clarifies that the equation dQ = nCvdT assumes a closed system, implying that n remains constant during the process.
  • A further response indicates that the assumption of a closed system is a typical definition of heat capacity, not necessarily a result of the second law of thermodynamics.
  • One participant mentions the advanced topic of working with systems at constant chemical potential, suggesting that there are exceptions to the typical assumptions.

Areas of Agreement / Disagreement

Participants express differing views on the implications of assuming n is constant and whether this assumption is universally applicable in discussions of heat capacity. The discussion remains unresolved regarding the treatment of n in the context of varying temperature.

Contextual Notes

Participants highlight the dependence of n on temperature and the implications this has for the integration process, but do not resolve the mathematical steps or assumptions involved.

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dQ = nCvdT if volume is constant.
However, n = pV/RT.
What I don't understand is, why are we thinking n as constant when doing the integral?
I had two problems that involved this on a test I had today. At first I kept it constant and then changed n. But then I thought, wait... isn't there a T in n? then that T should be in the integral.
I understand the point, heat capacity per mole. But mathematically, the T that is in the equation for n should matter, right?
dS = dQ / T, if we substitute dQ in that equation we should get 1 / T2 in the integral also.
I know I'm wrong however, so if someone could tell me what's wrong?
 
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The equation dQ = nCvdT also assumes a closed system (i.e., constant n). Otherwise you could effect a temperature change by simply removing gas molecules at constant volume without heating or cooling the system, and this would violate the equation.
 
That's true... higher temperature with lower amount of moles doesn't sound right. When you say that it assumes a closed system, is that a result of the second law?
Or do we always speak of closed systems when talking about heat capacity?
 
It's not a result of the second law. It's a typical assumption of the definition of heat capacity; that is, we mean

[tex]C_{V,N}=T\left(\frac{\partial S}{\partial T}\right)_{V,N}[/tex]

but we generally just write [itex]C_V[/itex].

(In some esoteric circumstances, we want to work with systems at constant chemical potential rather than constant matter, but that's an advanced topic.)
 

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