Two approaches to calculating entropy differ by factor of two. Why?

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    Entropy Thermodynamics
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Discussion Overview

The discussion revolves around two different approaches to calculating the change in entropy during a thermalization process between two samples at different temperatures. Participants explore the implications of their calculations and the reasons for discrepancies in the results obtained from each approach.

Discussion Character

  • Technical explanation
  • Debate/contested
  • Mathematical reasoning

Main Points Raised

  • Post 1 presents two methods for calculating the change in entropy, concluding that the first method yields a result approximately double that of the second method.
  • Post 1 asserts that the first method uses fixed temperatures in the integrals, which may lead to an incorrect result.
  • Post 2 challenges the validity of the first method, suggesting that the temperatures T1 and T2 change during the thermalization process, implying that the integrals should account for varying temperatures.
  • Post 3 inquires about the possibility of substituting for ##\frac{1}{T}## in the first approach instead of substituting for ##dU##.
  • Post 4 suggests a relationship between internal energy and temperature, indicating that T can be expressed as ##T=U/C_V##.

Areas of Agreement / Disagreement

Participants express disagreement regarding the appropriateness of the first method, with some suggesting that the assumptions made about temperature are flawed. The discussion remains unresolved as to which approach is more valid.

Contextual Notes

There is a lack of consensus on how to properly account for the changing temperatures during the thermalization process, and the implications of this on the calculations of entropy are not fully resolved.

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Homework Statement
A sample of monoatomic ideal gas (##n=1.00\text{mol}##) at ##T_1=300\text{K}## is allowed to thermalize with a second sample of the same ideal gas (##n=1.00\text{mol}##) at ##T_2=350\text{K}##.
Relevant Equations
What is the change in entropy for this process?

Recall that for a monoatomic ideal gas ##C_V=\frac{3}{2}R##.
Here is how I did this problem

Let's call the two samples sample 1 and sample 2.

The change in entropy for sample 1 is

$$\Delta S_1=\int dS_1=\int_{U_1}^{U_1+\Delta U}\frac{1}{T_1}dU\tag{1}$$

$$=\frac{1}{T_1}\Delta U\tag{2}$$

Similarly, ##\Delta S_2=-\frac{1}{T_2}\Delta U##.

Note that I used the fact that ##U## is extensive and conserved so

$$U_1+\Delta U_1+U_2+\Delta U_2=U_1+U_2$$

$$\implies \Delta U_1=-\Delta U_2=\Delta U$$

The entropy change of the system is then

$$\Delta S=\Delta U \left (\frac{1}{T_1}-\frac{1}{T_2}\right )\geq 0\tag{3}$$

$$=\Delta U\left ( \frac{1}{300}-\frac{1}{350}\right )\tag{4}$$

$$\implies \Delta U\geq 0\tag{5}$$

Note that in (1) the integral is defined in such a way that the internal energy of sample 1 is increasing by ##\Delta U## which we've now shown is nonnegative.

Thus, energy (heat in this process) flows from sample 2 to sample 1.

We need to find what ##\Delta U## is.

$$dU=dQ=C_VdT=\frac{3}{2}RdT$$

$$\Delta U=\frac{3}{2}R(T-T_1)=-\frac{3}{2}R(T-T_2)$$

$$\implies T=\frac{T_1+T_2}{2}=325\text{K}$$

where ##T## is the equilibrium temperature of the system.

Thus,

$$\Delta U=\frac{3}{2}R\cdot 25$$

and

$$\Delta S=\Delta U\left (\frac{1}{T_1}-\frac{1}{T_2}\right )$$

$$=\frac{3}{2}R\cdot 25\cdot\left (\frac{1}{300}-\frac{1}{350}\right )$$

$$=0.1484$$

Now, this result seems to be incorrect, and more precisely it seems to be about double the correct result which is 0.0740.

Here is another approach.

The change in entropy for an adiabatic process is

$$\Delta S = \int dS=\int_{T_i}^{T_f} \frac{1}{T} C_VdT$$

$$=C_V\ln{\left (\frac{T_f}{T_i}\right )}$$

$$=\frac{3}{2}R\ln{\left (\frac{T_f}{T_i}\right )}$$

Thus

$$\Delta S_{\text{tot}}=\Delta S_1+\Delta S_2$$

$$=\frac{3}{2}R\left ( \ln{\left ( \frac{325}{300} \right )}+\ln{\left ( \frac{325}{350} \right )} \right )$$

$$=0.0740$$

What is wrong with the first approach?
 
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Temperatures T1 and T2 will change during thermalization. Hence eq. 1 and 2 are wrong as you have used fixed T1 and T2 in the integrals instead of the varying temperatures.
 
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Got it. Is there a way to substitute for ##\frac{1}{T}## in (1) instead of subbing in for ##dU##?
 
As U= C_vT, T=U/C_V.
 

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