No heat exchange with the surroundings in an irreversible expansion of an ideal gas?

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    Entropy Thermodynamics
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Discussion Overview

The discussion revolves around the concept of irreversible expansion of an ideal gas, specifically addressing the heat exchange with surroundings and the implications for entropy changes. Participants explore theoretical aspects of thermodynamics, particularly focusing on entropy calculations and assumptions regarding heat exchange in different scenarios.

Discussion Character

  • Technical explanation
  • Conceptual clarification
  • Debate/contested

Main Points Raised

  • One participant presents calculations for the change in entropy during a reversible process and questions the assumptions made for an irreversible expansion, particularly regarding heat exchange with surroundings.
  • Another participant suggests imagining the process occurring in a thermally insulating dewar, implying that no heat exchange occurs with the surroundings.
  • A different participant challenges the assumption of insulation, noting that the first question did not involve such an apparatus, raising concerns about the validity of the heat exchange assumption in the second question.
  • Another participant explains that in the context of question 2, the setup allows for heat exchange through a stopcock, leading to the conclusion that the internal energy change is zero and thus Q=0, which implies no heat is exchanged.

Areas of Agreement / Disagreement

Participants express differing views on whether heat exchange with the surroundings is valid in the context of the irreversible expansion. There is no consensus on the assumptions regarding insulation or heat exchange, indicating ongoing debate.

Contextual Notes

Participants highlight the dependence on specific assumptions about the system setup, such as the presence of insulating apparatus or mechanisms for heat exchange, which remain unresolved.

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Homework Statement
1) Half a mole of an ideal as expands isothermally and reversibly at 298.15K from a volume of 10L to a volume of 20L.

a) What is the change in entropy of the gas?
b) How much work is done on the gas?
c) What is ##q_{surr}##, the heat change of the surroundings?
d) What is the change in the entropy of the surroundings?
e) What is the change in entropy of the system plus surroundings?
Relevant Equations
2) Now consider that the expansion in the preceding question occurs irreversibly by simply opening a stopcock and allowing the gas to rush into an evacuated bulb of 10L volume.

a) What is the change in entropy of the gas?
b) How much work is done on the gas?
c) What is ##q_{surr}##, the heat change of the surroundings?
d) What is the change in the entropy of the surroundings?
e) What is the change in entropy of the system plus surroundings?
My doubts are about the second question above, ie the irreversibly expansion.

For the first question, we have

a)

$$dS=\frac{dq_{rev}}{T}=\frac{nR}{V}dV$$

$$\implies \Delta S=nR\ln{\frac{V_2}{V_1}}=2.88\mathrm{\frac{J}{K}}$$

b)

$$q_{rev}=T\Delta S=298.15\text{K}\cdot 2.88\mathrm{\frac{J}{K}}=859\text{J}$$

c)

$$q_{surr}=-q_{rev}=-859\text{J}$$

d)

$$dS_{surr}=-\frac{dq_{rev}}{T}$$

$$\Delta S_{surr}=-\int\frac{dq_{rev}}{T}=-\Delta S=-2.88\mathrm{\frac{J}{K}}$$

e)

$$\Delta S=0$$

For the second question, which is where I have issues, we have

a)

Though the process now is irreversible, the start and end states seem to be the same and so the change in entropy is the same, namely $\Delta S=0$.

b)

When the gas expands without any external pressure working against it, the work done is zero.

My doubts start at this point, namely, item (c) of question 2.

The book I am reading says

c) No heat is exchanged with the surroundings.

d) The entropy of the surroundings does not change.

e) The entropy of the system plus surroundings increases by 2.88 ##\mathrm{J\cdot K^{-1}}##. Since this is an irreversible process we expect the entropy to increase.

How do we know no heat is exchanged with the surroundings?

If we accept that no heat is exchanged, then of course the entropy of the surroundings does not change.
 
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You can imagine the process to take place in a thermally insulating dewar.
 
@DrDu I can certainly imagine an apparatus used to insulate the system. But I don't see why there is the assumption that there is such an apparatus in the setup of question 2. After all, in question 1 there was no such apparatus.
 
In question 2, it is assumed that the stopcock can exchange heat between the two sections so that the final state of the system is the same as in question 1. The combined system is rigid, so no work is done on the surroundings, and , since the temperature does not change, the change in internal energy of the combined system is zero. So, from the first law of thermodynamics, Q=0.
 

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