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

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SUMMARY

The discussion centers on calculating the latent heat at a new point on the coexistence curve during a solid-liquid phase transition. The problem involves a point at temperature ##T_0## and pressure ##P_0##, with a nearby point at ##P_0+p## and ##T_0+t##. Key equations include the latent heat formula ##l=T_{\text{transition}}(s_{\text{liq.}}-s_{\text{sol.}})## and the total differential of entropy ##ds=-\alpha v dP+c_p dT##. The solution approach involves using a Taylor expansion to express the latent heat in terms of temperature and entropy, ultimately confirming the results through the general equation for differential change in enthalpy.

PREREQUISITES
  • Understanding of phase transitions and the coexistence curve.
  • Familiarity with thermodynamic properties such as entropy, heat capacity, and volume.
  • Knowledge of the Clapeyron equation and its application in phase equilibrium.
  • Proficiency in calculus, particularly in performing Taylor expansions and total differentials.
NEXT STEPS
  • Study the derivation of the Clapeyron equation for vapor-liquid equilibrium.
  • Learn about the relationship between latent heat and entropy changes in phase transitions.
  • Explore advanced thermodynamic concepts such as Maxwell relations and their applications.
  • Investigate the implications of the coefficients ##\alpha## and ##\kappa_T## in phase transition calculations.
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Students and professionals in thermodynamics, particularly those focusing on phase transitions, latent heat calculations, and enthalpy changes in materials science and physical chemistry.

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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