Derivation: Entropy of Vaporisation using Redlich-Kwong EoS

In summary, the conversation is discussing a question about obtaining an equation for entropy of vaporisation using the Redlich-Kwong equation. The solution involves using the known fact that at equilibrium, the free energy of both phases must be the same and writing an equation for change in entropy due to vaporisation. The conversation also addresses the issue of taking the derivative of pressure with respect to temperature and suggests using dU=TdS=PdV for a reversible path. The limits of integration are also discussed, with the lower limit being the liquid phase volume.
  • #1
Tom Hardy
46
1

Homework Statement


For some reason it is not letting me add the image here, here is the link to the question:

http://imgur.com/a/3DLWM

The part I'm stuck on is the last part. Basically, the question is to obtain the following equation for the entropy of vaporisation using the Redlich-Kwong equation:
$$
\Delta S = R\Bigg[ \ln \frac{V_2 -b}{V_1 - b} \Bigg] + \frac{0.5a}{bT^{1.5}}\ln \Bigg[ \frac{V_2(V_1-b)}{V_1(V_2-b)} \Bigg]
$$

Homework Equations


Redlich-Kwong equation:
$$
P = \frac{RT}{V-b} - \frac{a}{T^{0.5}V(V+b)}
$$

The Attempt at a Solution


I think I should start by using the known fact that at equilibrium, the free energy of both phases must be the same. Using Gibbs free energy:
$$
dG = -SdT + VdP \implies -S_1dT + V_1dP = -S_2dT + V_2dP
$$
Therefore, I can write an equation for change in entropy due to vaporisation:
$$
S_1 - S_2 = (V_1 - V_2)\frac{dP}{dT}
$$
However when I simply differentiate the given EoS and multiply by $V_1 - V_2$ I don't get the same result. Clearly, in the answer they have integrated wrt v at some point but I just don't get why or how. Any help will be appreciated, thank you.
 
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  • #2
We can't just take the derivative of P wrt to T since P is also a function of V, unless we would assume V to be constant, which would be unusual for vaporization.

Instead we can write dU=TdS=PdV for a reversible path.
If we assume isothermal vaporization, we get ##T\Delta S=\int PdV##, from which the equation follows.
 
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Likes Greg Bernhardt and Tom Hardy
  • #3
I like Serena said:
We can't just take the derivative of P wrt to T since P is also a function of V, unless we would assume V to be constant, which would be unusual for vaporization.

Instead we can write dU=TdS=PdV for a reversible path.
If we assume isothermal vaporization, we get ##T\Delta S=\int PdV##, from which the equation follows.
Thank you, my only concern is the limits of integration. Seemingly, the lower is limit is the liquid phase volume, but how can we use this with the EoS that is only valid for gases?
 

What is "Derivation: Entropy of Vaporisation using Redlich-Kwong EoS"?

"Derivation: Entropy of Vaporisation using Redlich-Kwong EoS" is a scientific process that involves using the Redlich-Kwong equation of state (EoS) to calculate the entropy of vaporisation for a given substance. This is an important calculation in thermodynamics and is used to understand the behavior of substances at different temperatures and pressures.

Why is the Redlich-Kwong EoS used for this derivation?

The Redlich-Kwong equation of state is a widely used model for predicting the behavior of real gases. It takes into account the attractive and repulsive forces between gas molecules, making it more accurate than simpler equations of state. This makes it a suitable choice for calculating the entropy of vaporisation, which is influenced by these intermolecular forces.

What is the significance of the entropy of vaporisation?

The entropy of vaporisation is a measure of the amount of disorder or randomness in a substance as it changes from a liquid to a gas. It is an important thermodynamic property that helps us understand the behavior of substances during phase changes and can also be used to calculate other properties such as heat capacity and enthalpy.

What are the inputs required for this derivation?

To calculate the entropy of vaporisation using the Redlich-Kwong EoS, you will need to know the temperature, pressure, and molar volume of the substance in both its liquid and vapor phases. These values can often be obtained from experimental data or from other thermodynamic models.

How accurate is this derivation?

The accuracy of this derivation will depend on the accuracy of the inputs used, as well as the limitations of the Redlich-Kwong equation of state. While it is a widely used and reliable model, it may not accurately predict the behavior of all substances. Therefore, it is important to validate the results with experimental data whenever possible.

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