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    Activity

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    Andrés Ortiz
    The document discusses methods for estimating activity coefficients, which measure the non-ideality of mixing in solutions. It describes two common group contribution methods: the UNIFAC model, which calculates activity coefficients based on contributions from functional groups; and using Hansen solubility parameters, which are based on cohesive energy densities. Both methods allow approximating activity coefficients in complex mixtures where direct measurement is impractical.

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    Activity

    Uploaded by

    Andrés Ortiz
    63 views25 pages
    The document discusses methods for estimating activity coefficients, which measure the non-ideality of mixing in solutions. It describes two common group contribution methods: the UNIFAC model, which calculates activity coefficients based on contributions from functional groups; and using Hansen solubility parameters, which are based on cohesive energy densities. Both methods allow approximating activity coefficients in complex mixtures where direct measurement is impractical.

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    UNIFAC

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    The document discusses methods for estimating activity coefficients, which measure the non-ideality of mixing in solutions. It describes two common group contribution methods: the UNIFAC model, which calculates activity coefficients based on contributions from functional groups; and using Hansen solubility parameters, which are based on cohesive energy densities. Both methods allow approximating activity coefficients in complex mixtures where direct measurement is impractical.

    Copyright:

    © All Rights Reserved
    Download as PPT, PDF, TXT or read online from Scribd
    Download as ppt, pdf, or txt
    63 views25 pages

    Activity

    Uploaded by

    Andrés Ortiz
    The document discusses methods for estimating activity coefficients, which measure the non-ideality of mixing in solutions. It describes two common group contribution methods: the UNIFAC model, which calculates activity coefficients based on contributions from functional groups; and using Hansen solubility parameters, which are based on cohesive energy densities. Both methods allow approximating activity coefficients in complex mixtures where direct measurement is impractical.

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    Activity Coefficient Estimation

    Methods

    Bharat Chandramouli
    February 5, 2002
    Activity Coefficient
    The activity coefficient is a measure of
    the non-ideality of mixing
    Gs RT ln x w RT ln w





    Gmix ideal Gse nonideal

    Two components, Enthalpic and


    Entropic
    Estimation/Measurement
    Activity coefficients in single
    component/simple mixtures easy to
    measure
    1
    sat
    x sat
    Activity coefficients in water or octanol
    can be calculated from solubility given
    sufficiently sensitive methods
    Need for estimation
    What about complex mixtures?
    What about dynamic systems with
    changing compositions?
    It becomes more practical to use
    estimation methods to approximate in
    these cases
    Estimation Methods
    Group contribution methods are most
    common because they have predictive
    ability
    There are two group contribution
    methods commonly used for iom
    calculation from solubility parameters
    UNIFAC calculation
    UNIFAC the UNIversal Functional
    group Activity Coefficient model
    The activity coefficient is calculated
    from two components
    ln ln
    i i C
    ln
    i R

    Combinational Residual (interactions)


    (V, SA) (Experiment Fit)
    UNIFAC
    The group contribution components consist of
    volume contributor -Rk
    surface area contribution -Qk
    interaction parameter between functional groups
    Amk
    To calculate interactions, similar sub-groups
    are assigned to groups and interactions are
    between these groups
    Calculate activity coefficients by summing all
    contributions and interactions
    UNIFAC-Simple example
    Ethanol CH3-CH2-OH

    Main Group. Subgroup Rk (vol) Qk (SA) Amk

    CH3 CH3 CH3 (1) 0.9011 0.848 0, 0

    CH2 CH2 CH2 (2) 0.6744 0.540 0, 0

    OH OH OH (2) 1.000 1.200 986.5, 156.4


    UNIFAC Methods
    Interaction parameters are fit from
    experimental data
    This work is still ongoing and many
    parameters still not available
    Hansen Solubility Parameter
    This method calculates activity
    coefficients from the solubility
    parameter
    Theory of cohesive energy developed
    by Hildebrand for dispersive systems
    and extended by Hansen for polar and
    hydrogen bonding
    Hansen Activity Coefficient
    The activity coefficient is given by
    i i i ,om i ,om
    ln om ( V / RT ) A d

    Cohesive energy density


    Molar Volume Size effect term

    Enthalpy Entropy
    The Size Effect Term
    i,omd is a measure of the effect of
    differing sizes of i and om on their
    entropy of mixing
    This was derived by Flory and Huggins
    using statistical thermodynamics
    For an infinitely dilute solution
    i ,om i i
    d ln( V /V ) 1 V /V
    Cohesive Energy (Ecoh)
    Closely linked to the heat of evaporation
    It is a measure of a the ability of a liquid
    molecule to stay together
    i i i i
    Ecoh Ed ( ispersive) E p( olar ) Eh( ydrogen)
    Theory of cohesive energy developed by
    Hildebrand for dispersive systems and
    extended by Hansen for polar and hydrogen
    bonding
    Solubility parameter
    Solubility parameters are measures of
    cohesive energy
    1/ 2 i 1/ 2
    ( e coh ) ( Ecoh / V )
    solubility parameter cohesive energy
    coh. energy density
    Calculating solubility
    parameters
    Hansen and others compiled molar
    attraction constants for functional
    groups, which are additive contributions
    to the solubility parameter
    d Fd ,k / iV
    i

    p ( Fp2,k )1/ 2 / iV
    i

    h ( Eh , k / V )
    i i 1/ 2
    Attraction Constants (F)
    The product of V was found to vary
    linearly across homologous series
    Additivity of structural sub-groups
    F = V values compiled for dispersion
    and polar components of
    Hansen later compiled additive
    contributions to Eh
    Multi-component Mixtures
    How are om parameters calculated?
    Parameters weighted using component
    mole fraction and molar volume to get
    average om
    om
    d ( i x Fd ,k ) /Vom
    om
    p [( x
    i 2 1/ 2
    F p ,k )] /Vom
    om
    h [ ( i x Eh ,k ) /Vom ]1/ 2
    Cohesive Energy Density
    i,omA can be derived as
    om i 2 i om i 2 i om i 2
    ( d d ) b( p p ) b( h h )
    i b is a weighting factor based on
    dispersive forces, has been tabulated
    for a variety of compounds
    ib corrects for the fact that polar and H
    bonding forces are localized
    Activity Coefficient
    Putting the two components together
    ln iom =

    i om i 2 i om i 2 i om i 2
    V [( d d ) b( p p ) b( h h ) ]/ RT
    +

    ln( i V / om V ) 1 i V / om V
    Calculation
    First, calculate group contributions for
    each component in the mixture
    Calculate om parameters by weighting
    with mole fraction and molar volume
    Calculate parameters for compound of
    interest
    Calculate activity coefficient
    Hansen or UNIFAC?
    UNIFAC more powerful interaction
    UNIFAC not universalmissing parameters
    Hansen has certain inconsistencies as certain
    parameters have to be culled from different
    sources. Very sensitive to parameter choice
    ib not widely available for many compounds,

    so estimation may be difficult


    Where do you use this?
    1. Water solubility estimation
    1
    x wsat
    wsat
    2. Solvent-Water partitioning (Kow)
    1 1 1
    K sw sat
    C w (1, L ) s Vs
    Gas/Particle Partitioning
    gas
    Thermodynamic Equilibrium?

    Kp
    Cgas particle C part

    Temperature particle Compound


    Humidity Particle type

    What happens when a semivolatile organic


    (SOC) encounters a particle??
    Partitioning Modes
    Mode of SOC-particle interaction depends on
    the particle
    Adsorption Solid particle, no organic liquid layer
    (dust, inorganic salts)
    Absorption Particle either liquid, or has substantial
    liquid layer (combustion particles, secondary
    organic aerosol)
    SOCs such as PAHs, and alkanes primarily
    partition to organic or carbonaceous aerosols
    rather than to mineral-based aerosols
    Predictive Partitioning models
    Pankow (1994) for absorptive
    partitioning
    7.501RTf om
    Kp 9 i 0
    10 MWom om p L
    fom- fraction extractable organic matter
    i - activity coefficient of SOC in om
    om

    MWom - molecular weight of om

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