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    Phase Equilibria

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    Gianna Cloe
    1) Phase equilibria describes the equilibrium state between two phases where the rate of mass transfer ceases. 2) The driving force for mass transfer is determined by how far a system is from equilibrium, and accurate determination of the driving force relies on understanding the equilibria between phases. 3) Equilibrium relationships can be shown through tables, equations, or graphs, and most operationally relevant relationships are shown graphically.

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    Phase Equilibria

    Uploaded by

    Gianna Cloe
    176 views21 pages
    1) Phase equilibria describes the equilibrium state between two phases where the rate of mass transfer ceases. 2) The driving force for mass transfer is determined by how far a system is from equilibrium, and accurate determination of the driving force relies on understanding the equilibria between phases. 3) Equilibrium relationships can be shown through tables, equations, or graphs, and most operationally relevant relationships are shown graphically.

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    Phase Equilibria

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    1) Phase equilibria describes the equilibrium state between two phases where the rate of mass transfer ceases. 2) The driving force for mass transfer is determined by how far a system is from equilibrium, and accurate determination of the driving force relies on understanding the equilibria between phases. 3) Equilibrium relationships can be shown through tables, equations, or graphs, and most operationally relevant relationships are shown graphically.

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    Download as pptx, pdf, or txt
    176 views21 pages

    Phase Equilibria

    Uploaded by

    Gianna Cloe
    1) Phase equilibria describes the equilibrium state between two phases where the rate of mass transfer ceases. 2) The driving force for mass transfer is determined by how far a system is from equilibrium, and accurate determination of the driving force relies on understanding the equilibria between phases. 3) Equilibrium relationships can be shown through tables, equations, or graphs, and most operationally relevant relationships are shown graphically.

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    PHASE EQUILIBRIA

    References: Unit Operations of Chemical Engineering by


    McCabe, Smith & Harriott, 7th Ed.
    Principles of Transport Processes & Separation
    Processes by Geankoplis, 1st Ed.

    Prepared by: Ma. Junallie F. Pomperada, ChE, MEngr, PhDTM


    Phase Equilibria
    • Mass transfer ceases when an equilibrium between
    the two phases is reached.

    • The rate of mass transfer is directly proportional to


    the driving force (which is a departure from
    equilibrium condition).

    • To be able to evaluate the rate of mass transfer, the


    driving force has to be accurately determined which
    in turn rely on the equilibria between phases.
    Phase Equilibria
    • In nearly all situations two phases are involved
    except two solid phases.

    • The controlling variables are the intensive properties


    of temperature, pressure and concentration.

    • Equilibrium data can be shown either in the form of


    tables, equations and graphs.

    • For most operations however, the pertinent


    equilibrium relationships are shown graphically.
    BASIS FOR PHASE
    EQUILIBRIUM
    I. Phase Rule

    F = C - P + 2

    where: F - number of degrees of freedom


    C - number of components
    P - number of phases
    Degrees of Freedom or Variance

     number of independent intensive variables –


    temperature, pressure and concentrations – that
    must be fixed to define the equilibrium state of the
    system

     If fewer than F variables are fixed, an infinite


    number of states fits the assumption while if F is
    too many, the system is overspecified.
    Degrees of Freedom or Variance

     for a two-phase system, variance is equal to 2 which


    is also equal to the number of components. If for
    example, pressure is fixed, the liquid-phase
    concentration can be changed independently, then
    the gas-phase composition and temperature (for
    liquid-gas equilibria) can be determined.

    Refer to the text by McCabe for specific examples


    on Gas Absorption , Distillation & Liquid Extraction.
    II. Raoult’s Law

    pA  PA xA
    where: pA – partial pressure of A in the gas phase
    xA – mole fraction of A in the liquid phase
    PA – vapor pressure of pure A

    Note: The Law holds for ideal solutions only


    (system which have substances similar
    to each other)
    III. Henry’s Law

    pA  HxA or y A  H ' xA

    where: pA – partial pressure of A in the gas phase


    xA – mole fraction of A in the liquid phase
    H – Henry’s constant
    H’ = H/P
    P – total pressure
    IV. K factor – Distribution Coefficient

    • ratio of the mole fractions in the yie


    vapor and liquid phases at Ki 
    equilibrium xie

    '
    • If Raoult’s Law and Dalton’s Law Pi
    hold then; Ki 
    P
    IV. K factor – Distribution Coefficient

    • If Raoult’s Law holds then the ratio of the K


    factors and relative volatility of the components
    are the same
    yi
    xi K i Pi '
     ij    '
    yj K j Pj
    xj

    • K factors are strongly temperature-dependent but


    the relative values of K for two components
    change only moderately
    Sample Problem 1

    The partial pressure of CO2 in air is 1.333 x 104


    Pa and the total pressure is 1.1333 x105 Pa. The
    gas phase is in equilibrium with the water
    solution at 303K. What is the value of xA of CO2 in
    equilibrium in the solution?

    Note: Henry’s Law Constant for CO2 @ 303.2K = 0.186 x 104


    Appendix A.3-18 pg 988, Geankoplis
    H (atm/mole fraction) G
    Sample Problem 2

    At 303K the concentration of CO2 in water is 0.90


    x 10-4 kg CO2/kg water. Using Henry’s Law
    constant, what partial pressure of CO2 must be
    kept in the gas to keep the CO2 from vaporizing
    from the aqueous solution?

    G
    PHASE EQUILIBRIA OF
    DIFFERENT PROCESSES
    GAS-LIQUID
    EQUILIBRIA
    A. Absorption
    B. Desorption/Stripping
    C. Distillation
    c.1 differential distillation
    c.2 flash distillation
    c.3 open-steam batch distillation
    c.4 Mc-Cabe Thiele Method
    c.5 Ponchon-Savarit Method
    LIQUID-LIQUID
    EQUILIBRIA
    EXTRACTION
    LIQUID- SOLID
    EQUILIBRIA
    LEACHING
    GAS-SOLID EQUILIBRIA
    ADSORPTION
    -END-

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