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    Clapeyron Equation Derivation

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    subhradeep123
    This document discusses how the equilibrium coexistence temperature between two phases changes with pressure. It derives the Clapeyron equation, which relates the slope of the coexistence curve to the entropy and volume changes between phases. The sign of the volume change determines whether the temperature increases or decreases with increasing pressure.

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    Clapeyron Equation Derivation

    Uploaded by

    subhradeep123
    91 views2 pages
    This document discusses how the equilibrium coexistence temperature between two phases changes with pressure. It derives the Clapeyron equation, which relates the slope of the coexistence curve to the entropy and volume changes between phases. The sign of the volume change determines whether the temperature increases or decreases with increasing pressure.

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    Effect of Pressure on Coexistence Temperature between Phases

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    This document discusses how the equilibrium coexistence temperature between two phases changes with pressure. It derives the Clapeyron equation, which relates the slope of the coexistence curve to the entropy and volume changes between phases. The sign of the volume change determines whether the temperature increases or decreases with increasing pressure.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    91 views2 pages

    Clapeyron Equation Derivation

    Uploaded by

    subhradeep123
    This document discusses how the equilibrium coexistence temperature between two phases changes with pressure. It derives the Clapeyron equation, which relates the slope of the coexistence curve to the entropy and volume changes between phases. The sign of the volume change determines whether the temperature increases or decreases with increasing pressure.

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    Effect of Pressure on Coexistence Temperature between Phases

    We wish to find how much does the equilibrium coexistence temperature between two
    phases, lets say solid (S) and liquid (L), change per unit change in the pressure. We
    restrict our attention to a single component system where phase diagram is expressed as a
    map in the P T space (Figure 1).
    Take two pairs of points labeled 1 10 and 2 20
    which are infinitesimally close to the coexistence curve but on opposite sides of it (in S and L
    field, respectively). Lets denote the properties
    at these two states by (P1 , T1 ) and (P2 , T2 ).
    Also assume that these pairs are located very
    close to each other, i.e., P2 P1 = dP 0.
    10

    20

    L
    2

    Since 1 and
    (similarly 2 and
    too) are infinitesimally close to the same point(s) on the
    coexistence curve, the chemical potentials must
    be equal:

    20
    1
    10

    S (P1 , T1 ) = L (P10 , T10 )


    S

    (P2 , T2 ) = (P20 , T20 )


    Subtraction of Equation 1 from 2 gives

    (1)

    (2)

    Figure 1: Schematic Solid-Liquid Phase


    Diagram of a 1-Component System

    S (P2 , T2 ) S (P1 , T1 ) = L (P20 , T20 ) L (P10 , T10 ).

    (3)

    Please note that since it is a one-component system, the component is not mentioned as a
    subscript of the chemical potential . Also because it is a single component system, in
    i = Gi /N .
    each phase is simply the specific free energy of that phase: i = G
    A change in i brought about by small changes in the independent variables P and T is
    given by:
    di = v i dP si dT
    (4)
    where v i and si are specific (say, molar) volume and entropy of the ith phase.
    Since the pairs of points are infinitesimally close (dP 0), the molar volume and entropy
    are assumed to be constant in each phase within the range of interest. So using Equation 4
    in Equation 3 and rearranging terms we get
    (sS sL )dT = (v S v L )dP

    (5)

    The quantity within the parentheses in the left hand side is the entropy change on freezing:
    sf = lf /Te , where lf is the molar latent heat of solidification and Te is the equilibrium
    solid-liquid coexistence temperature at a given P and T . This gives us the Clapeyron
    Equation for the slope of co-existence curve:

    dT
    dP

    vf
    lf

    =
    e

    Te vf
    lf

    (6)

    This can be integrated to give


    Te(2)

    Te(1)

    

    
    P (2) P (1) .

    (7)

    Whether the transformation temperature increases or decreases with increasing pressure


    depends on the sign of vf . Figure 2 shows the P-T phase diagrams for lead (FCC) and
    silicon (DC). Solid lead is denser than its liquid phase, whereas reverse is true for silicon.
    The opposite effect of pressure on the melting temperature for these elements is easily seen
    from these diagrams.

    (a)

    (b)

    Figure 2: P-T Phase Diagrams of (a) Pb and (b) Si. From Glicksman.

    References
    [1] H. B. Callen, Thermodynamics and An Introduction to Thermostatistics, 2nd Ed., 1985,
    pp. 228-231.
    [2] M. E. Glicksman, Principles of Solidification, 2011, p. 35.

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