How to Calculate Latent Heat at a New Point on the Coexistence Curve?

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Homework Help Overview

The discussion revolves around calculating the latent heat of vaporization at a new point on the coexistence curve during a solid-liquid phase transition. The original poster presents a scenario involving specific pressure and temperature changes near a known coexistence point.

Discussion Character

  • Exploratory, Mathematical reasoning, Assumption checking

Approaches and Questions Raised

  • The original poster attempts to express the entropies of the liquid and solid phases as functions of various thermodynamic properties. They explore the use of total differentials and Taylor expansions to relate latent heat to temperature and entropy changes.
  • Some participants suggest referencing the Clapeyron equation and its derivation for vapor-liquid equilibrium, noting parallels to the solid-liquid transition.
  • Others mention the use of a general equation for the differential change in enthalpy and confirm the results obtained by the original poster.

Discussion Status

The discussion includes various approaches to the problem, with some participants confirming the original poster's findings while others explore different derivations. There is no explicit consensus, but productive dialogue is evident as participants share insights and methods.

Contextual Notes

Participants are navigating the complexities of thermodynamic relationships and the implications of various properties like entropy, pressure, and temperature on latent heat calculations. There is an acknowledgment of the limitations of certain equations in this context.

fluidistic
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Homework Statement


I'm stuck in the following problem: In a particular solid-liquid phase transition the point ##T_0##, ##P_0## lies on the coexistence curve. The latent heat of vaporization at this point is ##l_0##. A nearby point on the existence curve has pressure ##P_0+p## and temperature ##T_0+t##; the local slope of the coexistence curve in the P-T plane is p/t. Assuming ##v##, ##c_p##, ##\alpha## and ##\kappa _T## to be known in each phase in the vicinty of the states of interest, find the latent heat at the point ##P_0+p##, ##T_0+t##.


Homework Equations


##l=T_{\text{transition}}(s_{\text{liq.}}-s_{\text{sol.}})##. (1)
##c_p=\left ( \frac{\partial s}{\partial T} \right ) _P##
##\alpha = \frac{1}{v} \left ( \frac{\partial v}{\partial T} \right ) _P##
##\kappa _T =-\frac{1}{v} \left ( \frac{\partial v}{\partial P} \right )##

The Attempt at a Solution


So I want to use equation (1). My idea is to expression the entropies of the liquid and solid phase as functions of alpha, kappa, etc.
So I've thought of s as a function of P and T to start with. I then took the total differential of s to reach ##ds=-\alpha v dP+c_p dT##. I've tried to make appear ##\kappa _T## without any success.
That's basically where I've been stuck for the last days, almost a week now. My friend told me to make a Taylor's expansion for the latent heat, so I've written down ##l(T) \approx l(T_0)+ l'(T_0)(T-T_0)## though I don't think that's correct since the latent heat depends on both the temperature and entropy; not the temperature alone.
So I'm looking for getting the ##\Delta s##. I've ran out of ideas, any tip is welcome.
 
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Check out the derivation of the Clapeyron equation for vapor-liquid equilibrium. The derivation for going from solid to liquid should parallel this.
 
I've solved the problem via a Taylor's expansion, the derivation up to the solution is rather lengthy in latex. This differs quite a lot from the 2 derivations given in wikipedia of the Clausius-Clapeyron's relation.
So I'll write final answer that I got:
l(T_0+t)\approx l_0 + \frac{tl_0}{T_0}+t(c_P^{\text{liq}}-c_P^{\text{sol.}})-T_0p(\alpha ^{\text{liq.}}v ^{\text{liq.}}-\alpha ^{\text{sol.}}v ^{\text{sol.}})
. I've found no dependence on ##\kappa _T##.
 
fluidistic said:
I've solved the problem via a Taylor's expansion, the derivation up to the solution is rather lengthy in latex. This differs quite a lot from the 2 derivations given in wikipedia of the Clausius-Clapeyron's relation.
So I'll write final answer that I got:
l(T_0+t)\approx l_0 + \frac{tl_0}{T_0}+t(c_P^{\text{liq}}-c_P^{\text{sol.}})-T_0p(\alpha ^{\text{liq.}}v ^{\text{liq.}}-\alpha ^{\text{sol.}}v ^{\text{sol.}})
. I've found no dependence on ##\kappa _T##.

You're right. The Clapeyron equation is not the way to go. I've solved this problem starting with general equation for the differential change in enthalpy dH=C_pdT+V(1-Tα)dP in conjunction with the Clapeyron equation, and have confirmed your result. Very nice job.
 
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