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    SVE Notes

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    billu
    This pdf covers the fundamental concepts of solid vapour equilibrium.

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    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd

    SVE Notes

    Uploaded by

    billu
    8 views2 pages
    This pdf covers the fundamental concepts of solid vapour equilibrium.

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    SVE-Notes

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    This pdf covers the fundamental concepts of solid vapour equilibrium.

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

    SVE Notes

    Uploaded by

    billu
    This pdf covers the fundamental concepts of solid vapour equilibrium.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    of 2

    9.

    3 Solid-Vapour Equilibrium
    This section deals with the solubility of solids in gases. The solubility of gases in solids is
    usually negligible. Therefore, the solid phase may be considered as pure; all non-ideality in
    the system therefore, derives from that of the gas phase. In the following analysis we, thus,
    consider that a pure solid phase (1) co-exists in equilibrium with a vapour-phase mixture of
    the gas (or solvent, 2) and the solute (i.e., 1). The phase equilibria relation for the component
    1 may be written as:
    f1S  fˆ1V ..(9.78)

    A relation of the form of eqn. 6.119 used for pure liquid phase fugacity calculation may be
    employed to compute the fugacity of a pure solid at the temperature T and pressure P of the
    system.
    Vi l ( P  Pi sat )
    f i (T , P)  isat Pi sat exp[ ] ..(6.119)
    RT
    For a pure solid the corresponding equation is:
    V1S  P  P1sat  
    S sat sat
    f1  P  1 1 exp   ..(9.79)
     RT 

    Here V1S is the molar volume of the solid, and P1sat is the vapour-phase saturation pressure for
    the solid solute at the given temperature. Now for the vapour phase fugacity of the solute on
    has:
    fˆ1V  y1ˆ1 P ..(9.80)

    Thus using eqns. 9.78 – 9.80 one obtains:


    V1S  P  P1sat  
    1
    sat sat
    P  1 exp    y1ˆ1P ..(9.81)
     RT 

    The above equation may be written in a compressed form as follows:


     P sat 
    y1   1  E ..(9.82)
     P 
    Where,

    1sat V1S  P  P1sat  


    E exp   ..(9.83)
    ˆ1  RT 

    The term E is called the enhancement factor. The vapour pressure P1sat of solids is typically

    very low (~ 10 -5 – 10 -3 bar), hence 1sat  1.0. Further if the system pressure is also low or as

    1
    P  P1sat , ˆ1  1. Thus, on inspecting eqn. 9.82, it is evident that under such a condition

    E  1. The corresponding solubility y1 is termed the ideal solubility. At high pressures (with

    P  P1sat ) , the exponential Poynting factor tends to be greater than one, and the values of ˆ1

    are lower than unity. As a result, the factor E typically is higher than one. The enhancement
    factor, therefore, provides a measure of the degree to which pressure augments the solubility
    of the solid in the gas phase. Fig. 9.6 shows a comparison of experimental values of solubility
    of solid carbon dioxide in air at 1430K with ideal and corrected solubilities using the virial
    EOS. As expected the ideal solubility departs significantly from the actual solubility at high
    pressures.

    Example: A certain solid A has a vapour pressure of 0.01 bar at 3000K. Compute its
    solubility at the same temperature in a gas B at a pressure of 1.0bar. The molar volume of the
    solid is 125cc/mol. We start with the following equation:
    VAS  P  PAsat  
    PAsat Asat exp    y AˆA P
     RT 

    Since PAsat  102 bar ,  Asat  1.0

    Further as the total system pressure is 1.0bar, it follows that


    ˆA  1.0

    Thus the solubility of the solid at the system pressure is given by:
     VAS  P  PAsat  
    sat
    yA  ( P A / P) exp  
     RT 

    Substituting all relevant data the solubility is:


    y A  1.05 x102.

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