Clausius Clapeyron PDF

Derivation from state postulate Edit
Using the state postulate, take the specific entropy {\displaystyle s}s for a homogeneous
substance to be a function of specific volume {\displaystyle v}v and temperature {\displaystyle
T}T.[3]:508
{\displaystyle \mathrm {d} s=\left({\frac {\partial s}{\partial v}}\right)_{T}\,\mathrm {d} v+\left({\frac

{\partial s}{\partial T}}\right)_{v}\,\mathrm {d} T.}{\displaystyle \mathrm {d} s=\left({\frac {\partial
s}{\partial v}}\right)_{T}\,\mathrm {d} v+\left({\frac {\partial s}{\partial T}}\right)_{v}\,\mathrm {d} T.}
The Clausius–Clapeyron relation characterizes behavior of a closed system during a phase
change, during which temperature and pressure are constant by definition. Therefore,[3]:508
{\displaystyle \mathrm {d} s=\left({\frac {\partial s}{\partial v}}\right)_{T}\,\mathrm {d}

v.}{\displaystyle \mathrm {d} s=\left({\frac {\partial s}{\partial v}}\right)_{T}\,\mathrm {d} v.}
Using the appropriate Maxwell relation gives[3]:508
{\displaystyle \mathrm {d} s=\left({\frac {\partial P}{\partial T}}\right)_{v}\,\mathrm {d}

v}{\displaystyle \mathrm {d} s=\left({\frac {\partial P}{\partial T}}\right)_{v}\,\mathrm {d} v}
where {\displaystyle P}P is the pressure. Since pressure and temperature are constant, by
definition the derivative of pressure with respect to temperature does not change.[4][5]:57, 62 &
671 Therefore, the partial derivative of specific entropy may be changed into a total derivative
{\displaystyle \mathrm {d} s={\frac {\mathrm {d} P}{\mathrm {d} T}}\,\mathrm {d} v}{\displaystyle
\mathrm {d} s={\frac {\mathrm {d} P}{\mathrm {d} T}}\,\mathrm {d} v}
and the total derivative of pressure with respect to temperature may be factored out when
integrating from an initial phase {\displaystyle \alpha }\alpha to a final phase {\displaystyle \beta
}\beta ,[3]:508 to obtain
{\displaystyle {\frac {\mathrm {d} P}{\mathrm {d} T}}={\frac {\Delta s}{\Delta v}}}{\displaystyle
{\frac {\mathrm {d} P}{\mathrm {d} T}}={\frac {\Delta s}{\Delta v}}}
where {\displaystyle \Delta s\equiv s_{\beta }-s_{\alpha }}{\displaystyle \Delta s\equiv s_{\beta
}-s_{\alpha }} and {\displaystyle \Delta v\equiv v_{\beta }-v_{\alpha }}\Delta v\equiv
v_{\beta}-v_{\alpha} are respectively the change in specific entropy and specific volume. Given
that a phase change is an internally reversible process, and that our system is closed, the first
law of thermodynamics holds
{\displaystyle \mathrm {d} u=\delta q+\delta w=T\;\mathrm {d} s-P\;\mathrm {d} v}{\displaystyle
\mathrm {d} u=\delta q+\delta w=T\;\mathrm {d} s-P\;\mathrm {d} v}
where {\displaystyle u}u is the internal energy of the system. Given constant pressure and
temperature (during a phase change) and the definition of specific enthalpy {\displaystyle h}h,
we obtain
{\displaystyle \mathrm {d} h=T\;\mathrm {d} s+v\;\mathrm {d} P}{\displaystyle \mathrm {d}
h=T\;\mathrm {d} s+v\;\mathrm {d} P}
{\displaystyle \mathrm {d} h=T\;\mathrm {d} s}{\displaystyle \mathrm {d} h=T\;\mathrm {d} s}
{\displaystyle \mathrm {d} s={\frac {\mathrm {d} h}{T}}}{\mathrm {d}}s={\frac {{\mathrm
{d}}h}{T}}
Given constant pressure and temperature (during a phase change), we obtain[3]:508
{\displaystyle \Delta s={\frac {\Delta h}{T}}}\Delta s={\frac {\Delta h}{T}}

Substituting the definition of specific latent heat {\displaystyle L=\Delta h}L=\Delta h gives
{\displaystyle \Delta s={\frac {L}{T}}}\Delta s={\frac {L}{T}}

Substituting this result into the pressure derivative given above ({\displaystyle \mathrm {d}
P/\mathrm {d} T=\mathrm {\Delta s} /\mathrm {\Delta v} }{\mathrm {d}}P/{\mathrm
{d}}T={\mathrm {\Delta s}}/{\mathrm {\Delta v}}), we obtain[3]:508[6]
{\displaystyle {\frac {\mathrm {d} P}{\mathrm {d} T}}={\frac {L}{T\,\Delta v}}.}{\displaystyle {\frac
{\mathrm {d} P}{\mathrm {d} T}}={\frac {L}{T\,\Delta v}}.}
This result (also known as the Clapeyron equation) equates the slope of the tangent to the
coexistence curve {\displaystyle \mathrm {d} P/\mathrm {d} T}\mathrm {d} P/\mathrm {d} T, at
any given point on the curve, to the function {\displaystyle L/(T\,\Delta v)}{\displaystyle
L/(T\,\Delta v)} of the specific latent heat {\displaystyle L}L, the temperature {\displaystyle T}T,
and the change in specific volume {\displaystyle \Delta v}\Delta v.

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Derivation from state postulate Edit

{\displaystyle \mathrm {d} s=\left({\frac {\partial s}{\partial v}}\right)_{T}\,\mathrm {d} v+\left({\frac

{\displaystyle \mathrm {d} s=\left({\frac {\partial s}{\partial v}}\right)_{T}\,\mathrm {d}

{\displaystyle \mathrm {d} s=\left({\frac {\partial P}{\partial T}}\right)_{v}\,\mathrm {d}

{\displaystyle \Delta s={\frac {\Delta h}{T}}}\Delta s={\frac {\Delta h}{T}}

{\displaystyle \Delta s={\frac {L}{T}}}\Delta s={\frac {L}{T}}

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