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    Ideal Solution and Excess functions-Ch11-IV

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    mominhadi
    This chapter discusses solution thermodynamics and the ideal solution model. Key points include: 1) The ideal solution model defines the chemical potential for a component in a mixture based on its mole fraction rather than partial pressure as in an ideal gas. 2) Partial molar properties for the ideal solution such as volume, entropy, and enthalpy can be expressed in terms of the pure component properties and mole fractions. 3) Excess properties are defined relative to the ideal solution model rather than the ideal gas to account for non-ideal behavior in liquid mixtures. The excess Gibbs energy is important for calculating activity coefficients. 4) Activity coefficients relate the chemical potential of a component in a real solution

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    © All Rights Reserved
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    Ideal Solution and Excess functions-Ch11-IV

    Uploaded by

    mominhadi
    110 views32 pages
    This chapter discusses solution thermodynamics and the ideal solution model. Key points include: 1) The ideal solution model defines the chemical potential for a component in a mixture based on its mole fraction rather than partial pressure as in an ideal gas. 2) Partial molar properties for the ideal solution such as volume, entropy, and enthalpy can be expressed in terms of the pure component properties and mole fractions. 3) Excess properties are defined relative to the ideal solution model rather than the ideal gas to account for non-ideal behavior in liquid mixtures. The excess Gibbs energy is important for calculating activity coefficients. 4) Activity coefficients relate the chemical potential of a component in a real solution

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    Ideal solution and excess functions-Ch11-IV

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    This chapter discusses solution thermodynamics and the ideal solution model. Key points include: 1) The ideal solution model defines the chemical potential for a component in a mixture based on its mole fraction rather than partial pressure as in an ideal gas. 2) Partial molar properties for the ideal solution such as volume, entropy, and enthalpy can be expressed in terms of the pure component properties and mole fractions. 3) Excess properties are defined relative to the ideal solution model rather than the ideal gas to account for non-ideal behavior in liquid mixtures. The excess Gibbs energy is important for calculating activity coefficients. 4) Activity coefficients relate the chemical potential of a component in a real solution

    Copyright:

    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    110 views32 pages

    Ideal Solution and Excess functions-Ch11-IV

    Uploaded by

    mominhadi
    This chapter discusses solution thermodynamics and the ideal solution model. Key points include: 1) The ideal solution model defines the chemical potential for a component in a mixture based on its mole fraction rather than partial pressure as in an ideal gas. 2) Partial molar properties for the ideal solution such as volume, entropy, and enthalpy can be expressed in terms of the pure component properties and mole fractions. 3) Excess properties are defined relative to the ideal solution model rather than the ideal gas to account for non-ideal behavior in liquid mixtures. The excess Gibbs energy is important for calculating activity coefficients. 4) Activity coefficients relate the chemical potential of a component in a real solution

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    © All Rights Reserved
    Download as PPTX, PDF, TXT or read online from Scribd
    Download as pptx, pdf, or txt
    of 32

    Solution thermodynamics

    theory—Part IV
    Chapter 11
    When we deal with mixtures of liquids or
    solids
    • We define the ideal solution model

    • Compare it to the ideal gas mixture, analyze


    its similarities and differences
    i  i (T )  RT ln( yi P)
    ig Component i in a mixture
    of ideal gases

    This eqn. is obtained by combining

    Gi  i (T )  RT ln P
    ig

      Gi (T , P)  RT ln yi
    ig
    i
    ig

    Now we define

      Gi (T , P)  RT ln xi
    id
    i Ideal solution model
    Other thermodynamic properties
    for the ideal solution: partial molar volume

    Gi  Gi (T , P)  RT ln xi
    id

     Gi id
      Gi 
    Vi id
           Vi
     P T , x  P T
    V id
      xiVi   xiVi
    id

    i i
    partial molar entropy in the ideal solution

    Gi  Gi (T , P)  RT ln xi
    id

     Gi id
      Gi 
    S id
           R ln xi  Si  R ln xi
     T  T
    i
     P, x P
    S   xi S
    id
    i
    id
      xi Si  R xi ln xi
    i i i
    partial molar enthalpy in the ideal solution

    Gi  Gi (T , P)  RT ln xi
    id

    H iid  Gi id  TSiid  Gi  RT ln xi  TSi  RT ln xi  H i


    H id   xi H iid   xi H i
    i i
    Chemical potential ideal solution

    i  i (T )  RT ln fˆi
    Chemical potential component i
    in a Real solution

    Gi  i (T )  RT ln f i Chemical potential
    Pure component i

    fˆi
    Subtracting:
    i  Gi  RT ln
    fi
    For the ideal solution ˆf id
    i id
     Gi  RT ln i
    fi
    Lewis-Randall rule

    i  Gi  RT ln xi
    id

    ˆf id
    i id
     Gi  RT ln i
    fi
    ˆf id  x f
    i i i Lewis-Randall rule

    ˆ
    i  i
    id
    (Dividing by Pxi each side of the equation)
    When is the ideal solution valid?
    • Mixtures of molecules of similar size and
    similar chemical nature
    • Mixtures of isomers
    • Adjacent members of homologous series
    Virial EOS applied to mixtures
    BP
    Z 1 
    RT
    B   yi y j Bij
    i j
    How to obtain the cross coefficients
    Bij

    ˆ
    Bij  B  ij B
    0 1

    Bij Pcij
    Bˆ ij 
    Tcij

    Mixing rules for Pcij, Tcij, ij, 11-70 to 11.73



    Fugacity coefficient iˆ
    from virial EOS

    ˆ
    ln 1 
    P
    B11  y2 12 
    2

    RT
     12  2 B12  B11  B22

    For a multicomponent mixture, see eqn. 11.64


    problem
    • For the system methane (1)/ethane (2)/propane (3)
    as a gas, estimate
    fˆ , fˆ , fˆ and ˆ , ˆ , ˆ
    1 2 3 1 2 3

    at T = 100oC, P = 35 bar, y1 =0.21, and y2 =0.43


    Assume that the mixture is an ideal solution
    Obtain reduced pressures, reduced temperatures, and calculate

     Prk 0 1 
    k id
     exp  ( Bkk  Bkk )
     Trk 
    ˆf id   id y P
    k k k
    Results: methane (1) ethane (2) propane (3)

    ˆ1  1.02;ˆ2  0.88;ˆ3  0.78 Virial model

    fˆ1  7.49; fˆ2  13.25; fˆ3  9.76bar


    1  0.98;2  0.88;3  0.76 Ideal solution

    ˆf id  7.18; fˆ id  13.25; fˆ id  9.57bar


    1 2 3
    Now we want to define a new type of
    residual properties
    • Instead of using the ideal gas as the reference,
    we use the ideal solution
    Excess properties

    M  M M
    E id

    The most important excess function is


    the excess Gibbs free energy GE

    Excess entropy can be calculated


    from the derivative of GE wrt T

    Excess volume can be calculated


    from the derivative of GE wrt P

    And we also define partial molar excess properties


    ˆ
    Gi  i (T )  RT ln f i
    Gi  i (T )  RT ln xi f i
    id

    subtracting :

    ˆf
    i  i
    Definition of activity coefficient
    xi f i
    Summary

    Gi  RT ln  i
    E

    G  RT ln 
    R ˆ
    i i
    Summary

      G  RT ln yi
    ig
    i i
    ig

      Gi  RT ln xi
    id
    i

    i  Gi  RT ln  i xi
    Note that:
      G  RT ln yi  i (T )  RT ln yi P
    ig
    i i
    ig

      Gi  RT ln xi  i (T )  RT ln xi f i 
    id
    i

    ˆ
     i (T )  RT ln f i id

    i  Gi  RT ln  i xi  i (T )  RT ln  i xi f i 
     i (T )  RT ln fˆi
    problem
    • The excess Gibbs energy of a binary liquid mixture
    at T and P is given by

    G / RT  (2.6 x1  1.8x2 ) x1 x2
    E

    a) Find expressions for ln 1 and ln 2 at T and P


    Using x2 =1 – x1
    GE/RT= x12 -1.8 x1 +0.8 x13
    Since i comes from

    Gi  RT ln  i
    E

    We can use eqns 11.15 and 11.16

    E
    dG
    G  G  x2
    1
    E E
     RT ln  1
    dx1
    E
    dG
    G  G  x1
    2
    E E
     RT ln  2
    dx1
    then
    E
    dG / RT
     1.8  2 x1  2.4 x1
    2

    dx1

    And we obtain

    ln  1  1.8  2 x1  1.4 x  1.6 x


    2
    1
    3
    1

    ln  2   x  1.6 x
    2
    1
    3
    1
    If we apply the additivity rule and the
    Gibbs-Duhem equation
    E
    G
      xi ln  i
    RT i
    At T and P

     x d ln 
    i
    i i 0
    (b and c) Show that the ln i expressions satisfy
    these equations Note: to apply Gibbs-
    Duhem, divide the equation
    by dx1 first
    Plot the functions and show their
    values
    0
    0 0.2 0.4 0.6 0.8 1

    -0.5
    GE/RT

    -1
    ln 1
    -1.5
    ln 2
    -2 GE/RT
    ln g2
    ln g1
    -2.5

    -3
    x1

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