Change in molar entropy of steam

AI Thread Summary
The discussion focuses on calculating the change in molar entropy of steam when heated from 100 to 120 °C at constant volume, using the equation dS = nCv ln(T1/T0). Participants clarify that the value of Cv for steam is essential for the calculation, with a commonly accepted value being 27.5 J/mol*K. There is confusion regarding the application of the equation and the correct units, leading to different entropy values being calculated. The conversation also touches on the degrees of freedom for steam and how they affect Cv, with suggestions to consider vibrational modes at higher temperatures. Ultimately, the correct approach involves verifying Cv against authoritative sources to ensure accurate calculations.
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Homework Statement


Calculate the change in molar entropy of steam heated from 100 to 120 °C at constant volume in units J/K/mol (assume ideal gas behaviour).

Homework Equations


dS = n Cv ln(T1/T0)
T: absolute temperature

The Attempt at a Solution


100 C = 373.15 K
120 C = 393.15 K

dS = nCvln (393.15 / 373.15) = nCv0.052 J/K/mol

I don't really understand why I wasn't told what the Cv was though...
 
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says said:

Homework Statement


Calculate the change in molar entropy of steam heated from 100 to 120 °C at constant volume in units J/K/mol (assume ideal gas behaviour).

Homework Equations


dS = n Cv ln(T1/T0)
T: absolute temperature


The Attempt at a Solution


100 C = 373.15 K
120 C = 393.15 K

dS = nCvln (393.15 / 373.15) = nCv0.052 J/K/mol

I don't really understand why I wasn't told what the Cv was though...
You could look up the value of ##C_v## for steam.
 
tnich said:
You could look up the value of ##C_v## for steam.
Oh, and check your units. Your equation is dimensionally inconsistent.
 
I've tried two ways to calculate this, but have two different answers..

dS = nCvln(T1/T0)

Cv for steam = 27.5 J / mol*K
n = 1 mole
T0: 373.15 K
T1: 393.15 K

dS = (1 mol)(27.5 J / mol*K)(ln(393.15/373.15))
dS = 1.4358 J/K

This link I found says the units for molar entropy are J/mol*K though so I'm not sure if my answer is correct. https://en.wikipedia.org/wiki/Standard_molar_entropy

Cv = (∂U/∂T)V = ∂/∂T(3NkbT/2)=(3Nkb)/2

dS = (3Nkb)/2)(ln(393.15/373.15))
dS = 1.08*10-24 J/K

units are correct in both - not really sure what I'm missing here...
 
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Ok, I think I know what I did wrong. I was getting my n and N mixed up.

dS = Cv ln(T1/T0)

Cv = (∂U/∂T)V = ∂/∂T (3NkbT/2) = 3Nkb/2 = 3nR/2

Cv,m = molar heat capacity, units J/mol*K

Cv,m = Cv/n = 3nR/2n = 3R/2

Cv,m = 3 (8.3144621) / 2 = 12.47169315 J/mol*K

dS = 12.47169315*ln(393.15/373.15) = 0.651 J/mol*K
 
says said:
Cv = (∂U/∂T)V = ∂/∂T (3NkbT/2) = 3Nkb/2 = 3nR/2
I can't help thinking that you have made a mistake in applying this equation. This would give the same molar specific heat for any substance in any phase.

I believe you had it right before when you said.
says said:
dS = nCvln(T1/T0)

Cv for steam = 27.5 J / mol*K
n = 1 mole
T0: 373.15 K
T1: 393.15 K

dS = (1 mol)(27.5 J / mol*K)(ln(393.15/373.15))
dS = 1.4358 J/K

My comment about the units was meant to point out that molar heat capacity should be
dS = Cvln (393.15 / 373.15) without the n, if Cv is molar heat capacity.
The equation as you stated it, dS = nCvln (393.15 / 373.15) would have units of J/K. You have solved that problem by setting n = 1.
 
I thought the same thing about that equation. I thought that would be how Cv is derived.
 
ΔS = Cvln(393.15/373.15) = change in molar entropy. Units are J/mol*K

Now I just need to find/derive an acceptable Cv
 
  • #10
Cv = (∂U/∂T)V = ∂/∂T (3NkbT/2) = 3Nkb/2 = 3R/2

I think that is correct
 
  • #11
says said:
Cv = (∂U/∂T)V = ∂/∂T (3NkbT/2) = 3Nkb/2 = 3R/2

I think that is correct
This formula is for a monatomic gas. Is steam monatomic?
 
  • #12
says said:
I've tried two ways to calculate this, but have two different answers..

dS = nCvln(T1/T0)

Cv for steam = 27.5 J / mol*K
n = 1 mole
T0: 373.15 K
T1: 393.15 K

dS = (1 mol)(27.5 J / mol*K)(ln(393.15/373.15))
dS = 1.4358 J/K

This link I found says the units for molar entropy are J/mol*K though so I'm not sure if my answer is correct. https://en.wikipedia.org/wiki/Standard_molar_entropy

Cv = (∂U/∂T)V = ∂/∂T(3NkbT/2)=(3Nkb)/2

dS = (3Nkb)/2)(ln(393.15/373.15))
dS = 1.08*10-24 J/K

units are correct in both - not really sure what I'm missing here...
This would be correct only if steam (water vapor) were a monoatomic gas, which (of course) it isn't.
 
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Likes says
  • #13
Thanks, missed that. From what I've read steam is a polyatomic molecule, so instead of (3/2)R it should be (5/2)R
 
  • #14
Sorry, that should be 6/2 as steam has 6 degrees of freedom (ignoring vibrational motion)
 
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  • #15
says said:
Sorry, that should be 6/2 as steam has 6 degrees of freedom (ignoring vibrational motion)
Why would you ignore vibrational motion?
 
  • Like
Likes says
  • #16
Temperature isn't very high, so I thought it would be negligible. If I include it then Cv = 9R/2
 
  • #17
ΔS=(9/2)(R)*ln(393.15/373.15) = 1.953 J/mol*k
 
  • #18
says said:
Temperature isn't very high, so I thought it would be negligible. If I include it then Cv = 9R/2
Before you jump to a conclusion, you might compare your value of specific heat capacity to measured values from authoritative sources. I think you are right to consider the temperature, and to wonder how much a specific mode might be excited at that temperature.
says said:
ΔS=(9/2)(R)*ln(393.15/373.15) = 1.953 J/mol*k
 
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