What energy is this? Related to monoatomic ideal gas

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Discussion Overview

The discussion revolves around the internal energy of a monoatomic ideal gas and its relationship to different state equations, particularly focusing on the expressions for internal energy in terms of temperature and other variables. Participants explore the implications of using various equations of state and the conditions under which they apply, as well as the distinctions between internal energy and total energy.

Discussion Character

  • Exploratory
  • Technical explanation
  • Debate/contested

Main Points Raised

  • Some participants assert that for a monoatomic ideal gas, the internal energy can be expressed as ##U=\frac{3nRT}{2}##, while questioning the equivalence of this expression to other forms like ##U(S,V,n)##.
  • Others argue that the fundamental equation ##S(U,V,n)## provides a different perspective on internal energy, suggesting that ##U(S,V,n)## is not simply the internal energy but may represent total energy.
  • There is a discussion about the necessity of multiple state equations to derive the fundamental equation, with some participants suggesting that a single state equation is insufficient.
  • Some participants propose that while ##U(T)## contains less information than ##U(S,V,n)##, they can be considered equivalent under certain conditions, such as when the gas is identified as ideal or Van der Waals.
  • Concerns are raised about the applicability of the internal energy expression for non-ideal gases, indicating that for such gases, internal energy depends on both temperature and volume.
  • One participant mentions that the expression for internal energy in the context of non-ideal gases suggests a relationship to Helmholtz free energy.

Areas of Agreement / Disagreement

Participants express differing views on the equivalence of various expressions for internal energy and the conditions under which they apply. There is no consensus on whether ##U(S,V,n)## can be directly equated to ##U(T)## without additional information.

Contextual Notes

Participants note that the derivation of the fundamental equation requires multiple state equations and that the relationship between internal energy and other forms may vary depending on the type of gas (ideal vs. non-ideal). The discussion highlights the complexity of these relationships and the assumptions involved.

fluidistic
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For a monoatomic ideal gas, if ##c_v## is constant then the internal energy is worth ##U=\frac{3nRT}{2}##. This is a state equation.
From the fundamental equation ##S(U,V,n)= \frac {nS_0}{n_0}+nR \ln \left [ \left ( \frac {U}{U_0} \right ) ^{3/2} \left ( \frac{V}{V_0} \right ) \left ( \frac {n}{n_0} \right ) ^{-5/2} \right ]##, one could get ##U(S,V,n)## which would also be a fundamental equation.
But ##U(S,V,n)## is not equal to ##U(T)=\frac{3nRT}{2}##. In other words, U(S,V,n) is not the internal energy of the gas. Then what is it? The total energy? I thought that the total energy of the gas was the internal energy... I'm confused.
 
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fluidistic said:
For a monoatomic ideal gas, if ##c_v## is constant then the internal energy is worth ##U=\frac{3nRT}{2}##. This is a state equation.
From the fundamental equation ##S(U,V,n)= \frac {nS_0}{n_0}+nR \ln \left [ \left ( \frac {U}{U_0} \right ) ^{3/2} \left ( \frac{V}{V_0} \right ) \left ( \frac {n}{n_0} \right ) ^{-5/2} \right ]##, one could get ##U(S,V,n)## which would also be a fundamental equation.
But ##U(S,V,n)## is not equal to ##U(T)=\frac{3nRT}{2}##. In other words, U(S,V,n) is not the internal energy of the gas. Then what is it? The total energy? I thought that the total energy of the gas was the internal energy... I'm confused.
The equations are equivalent. In differential form:

dU = nCvdT = TdS - PdV + μΔN

Assuming N does not change, and dividing by T:

nCvdT/T = dS - PdV/T = dS - nRdV/V

Integrating from T0 to T:

ΔS = nCvln(T/T0) + nRln(V/V0) = nRln(T/T0)3/2 + nRln(V/V0)

Without the change in n, that is just: ##S(U,V,n)= nR \ln \left [ \left ( \frac {U}{U_0} \right ) ^{3/2} \left ( \frac{V}{V_0} \right ) \right ]## which is what you started with.

AM
 
Last edited:
Andrew Mason said:
The equations are equivalent. In differential form:

dU = nCvdT = TdS - PdV + μΔN

Assuming N does not change, and dividing by T:

nCvdT/T = dS - PdV/T = dS - nRdV/V

Integrating from T0 to T:

ΔS = nCvln(T/T0) + nRln(V/V0) = nRln(T/T0)3/2 + nRln(V/V0)

Without the change in n, that is just: ##S(U,V,n)= nR \ln \left [ \left ( \frac {U}{U_0} \right ) ^{3/2} \left ( \frac{V}{V_0} \right ) \right ]## which is what you started with.

AM
I see yes, but you had to use the other state equation "PV=nRT" to replace P by nRT/V when you integrate with respect to T.
In other words you had to use some extra information to reach the fundamental equation. Because a single state equation is not enough to reach the fundamental equation (you need at least 2, though you could use 3, the other one being the one with mu), they should not be equivalent.
From the fundamental equation you can get any of the 3 state equations without any extra information. But you can't reach the fundamental equation with any of the 3 state equation alone. In that sense the fundamental equation is not equivalent to a single state equation but to at least a set of 2 of them.
So this would mean that U(S,V,n) has more information than U(T). I'm not sure what energy then is U(S,V,n)...
 
fluidistic said:
I see yes, but you had to use the other state equation "PV=nRT" to replace P by nRT/V when you integrate with respect to T.

In other words you had to use some extra information to reach the fundamental equation. Because a single state equation is not enough to reach the fundamental equation (you need at least 2, though you could use 3, the other one being the one with mu), they should not be equivalent.
From the fundamental equation you can get any of the 3 state equations without any extra information. But you can't reach the fundamental equation with any of the 3 state equation alone. In that sense the fundamental equation is not equivalent to a single state equation but to at least a set of 2 of them.
So this would mean that U(S,V,n) has more information than U(T).
You just need to know that that U/U0 = T/T0, which is true only because it is an ideal gas.

dU = nCvdT is true only for an ideal gas. But dU = TdS-PdV is true for any gas.

I'm not sure what energy then is U(S,V,n)...
It is the internal energy of the gas. It is the total kinetic and potential energies of all the gas molecules.

AM
 
Andrew Mason said:
You just need to know that that U/U0 = T/T0, which is true only because it is an ideal gas.

dU = nCvdT is true only for an ideal gas. But dU = TdS-PdV is true for any gas.

It is the internal energy of the gas. It is the total kinetic and potential energies of all the gas molecules.

AM

Ok I think I'm finally understanding it...
If the gas was a Van der Waals gas then I would still get that U(S,V,n) is the internal energy, which would correspond to kinetic+potential energies.
All in all, despite U(T) contains less information than U(S,V,n), if one completes the information according to the system one has (i.e. give the information that the gas is ideal or Van der Waals for instance) then one get that U(T) is in fact equivalent to U(S,V,n) in the sense that they represent the same energy; the total energy of the system.
Thanks for the replies.
 
fluidistic said:
All in all, despite U(T) contains less information than U(S,V,n), if one completes the information according to the system one has (i.e. give the information that the gas is ideal or Van der Waals for instance) then one get that U(T) is in fact equivalent to U(S,V,n) in the sense that they represent the same energy; the total energy of the system.
But for non-ideal gases, such as Van der Waals gases, U is not a function of T alone. U depends on T and V.

AM
 
Andrew Mason said:
But for non-ideal gases, such as Van der Waals gases, U is not a function of T alone. U depends on T and V.

AM

Oh right. In that case U(T,V,n) would be equivalent to U(S,V,n) if I use "an extra" state equation that tells me it's a Van der Waals gas (like the one that relates P to V).
The expression "U(T,V,n)" makes me think of the Helmholtz free energy.
 

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