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    4. Phase Equilibria in Pure Substances: dG α β G = n µ µ dn α β T P dG dn dG dG µ

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    STARCH CELLULOSE IS A PHARMACEUTICAL INACTIVE INGREDIENT ADDED TO ACTIVES AS A BINDER. THIS BINDS MOLECULES TOGETHER TO FORM GRANULE WHICH WILL UNDERGO COMPRESION TO FORM MEDICINES

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    4. Phase Equilibria in Pure Substances: dG α β G = n µ µ dn α β T P dG dn dG dG µ

    Uploaded by

    Kaaya Godfrey
    22 views8 pages
    STARCH CELLULOSE IS A PHARMACEUTICAL INACTIVE INGREDIENT ADDED TO ACTIVES AS A BINDER. THIS BINDS MOLECULES TOGETHER TO FORM GRANULE WHICH WILL UNDERGO COMPRESION TO FORM MEDICINES

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    PC1Chap4

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    STARCH CELLULOSE IS A PHARMACEUTICAL INACTIVE INGREDIENT ADDED TO ACTIVES AS A BINDER. THIS BINDS MOLECULES TOGETHER TO FORM GRANULE WHICH WILL UNDERGO COMPRESION TO FORM MEDICINES

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    4. Phase Equilibria in Pure Substances: dG α β G = n µ µ dn α β T P dG dn dG dG µ

    Uploaded by

    Kaaya Godfrey
    STARCH CELLULOSE IS A PHARMACEUTICAL INACTIVE INGREDIENT ADDED TO ACTIVES AS A BINDER. THIS BINDS MOLECULES TOGETHER TO FORM GRANULE WHICH WILL UNDERGO COMPRESION TO FORM MEDICINES

    Copyright:

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    of 8

    4.

    Phase Equilibria in Pure Substances


    phase: uniform throughout in chemical composition
    and physical state
    Second Law =dG
    T,P
    0
    equilibrium if and only if dG
    T,P
    =0
    consider a system with two phases, say and :
    G =n

    +n

    assume an amount dn goes from phase to phase


    at constant T and P:
    dG
    T,P
    =

    (dn) +

    dn
    dG
    T,P
    =(

    )dn
    dG
    T,P
    <0 if

    >

    spontaneous transport of matter from regions of high


    chemical potential to regions of low chemical poten-
    tial
    PChem I 4.1
    phase with the lowest chemical potential (Gibbs
    free energy) is stable
    chemical potential of a sample is uniform, if the
    sample is at equilibrium, regardless of how many
    phases are present
    _

    T
    _
    P
    =S
    phase coexistence: dG
    T,P
    =0

    (T, P) =

    (T, P)
    PChem I 4.2
    =T =T(P) or P =P(T)
    phase coexistence line or phase boundary in T-P-
    plane
    phase diagrams
    [Figure: typical phase diagram for a PVT system, Fig. 4.1]
    [Figure: phase diagram for water, Fig. 4.5]
    [Figure: phase diagram for carbon dioxide, Fig. 4.4]
    [Figure: phase diagram for helium-4, Fig. 4.7]
    derive equation for phase boundary
    move along phase boundary line from one equlibrium
    point a = (T, P(T)) to another equilibrium point b =
    (T +dT, (P +dP)(T +dT))
    [Figure: phase boundary, Fig. 4.12]

    +d

    +d

    =d

    along P =P(T)
    d=SdT +V dP
    P =P(T) : S

    dT +V

    dP =S

    dT +V

    dP
    PChem I 4.3
    (S

    )dT =(V

    )dP
    P =P(T) :
    dP
    dT
    =
    S

    =
    S
    V
    Clapeyron equation
    S
    trs
    =
    H
    trs
    T
    trs
    dP
    dT

    P=P(T)
    =
    H
    TV
    solid-liquid boundary
    = solid, = liquid
    dP
    dT
    =
    H
    fus
    TV
    fus
    H
    fus
    >0,

    V
    fus

    typically small
    V
    fus
    usually >0 (not true for water)
    =
    dP
    dT
    typically large, usually positive
    PChem I 4.4
    if H
    fus
    =const and V
    fus
    =const, then
    P
    2
    =P
    1
    +
    H
    fus
    V
    fus
    ln
    _
    T
    2
    T
    1
    _
    note: (T
    1
    , P
    1
    ) and (T
    2
    , P
    2
    ) are both points on the phase
    boundary
    T
    2
    T
    1
    =
    T
    1
    +T
    2
    T
    1
    T
    1
    =1+
    T
    2
    T
    1
    T
    1
    ln(1+x) =x +. . . for |x| 1
    P
    2
    P
    1
    +
    H
    fus
    T
    1
    V
    fus

    _
    T
    2
    T
    1
    _
    for

    T
    2
    T
    1

    T
    1
    1
    solid-gas or liquid-gas boundary
    = solid or liquid, = gas
    H =H
    sub
    or =H
    vap
    , V =V
    sub
    or =V
    vap
    dP
    dT
    =
    H
    TV
    PChem I 4.5
    V =V (g)V (s/l ) V (g) =RT/P (treating the gas as
    ideal)
    dP
    dT
    =
    H
    T
    RT
    P
    =
    H P
    RT
    2
    1
    P
    dP
    dT
    =
    H
    RT
    2
    d lnP
    dT
    =
    H
    RT
    2
    Clausius-Clapeyron equation
    if H =const, then
    _
    2
    1
    d lnP =
    H
    R
    _
    2
    1
    1
    T
    2
    dT
    lnP
    2
    lnP
    1
    =
    H
    R
    _

    1
    T
    2
    +
    1
    T
    1
    _
    ln
    _
    P
    2
    P
    1
    _
    =
    H
    R
    _
    1
    T
    2

    1
    T
    1
    _
    P
    2
    =P
    1
    exp
    _

    H
    R
    _
    1
    T
    2

    1
    T
    1
    _
    _
    vapor pressure
    PChem I 4.6
    Troutons rule: S
    vap
    85J K
    1
    mol
    1
    =H
    vap
    T
    boil
    85J K
    1
    mol
    1
    (Troutons rule does not hold for compounds with H-
    bonding)

    l
    (T, P) =
    g
    (T, P) P
    l g
    =P(T)

    s
    (T, P) =
    l
    (T, P) P
    sl
    =P(T)
    _
    intersect in
    one point
    (T
    3
    , P
    3
    ) :
    s
    =
    l
    =
    g
    triple point, material property
    Ehrenfest classication:
    _

    P
    _
    T

    P
    _
    T
    =V

    =V =0
    _

    T
    _
    P

    T
    _
    P
    =S

    +S

    =S =
    H
    T
    =0
    rst derivatives of or G are discontinuous: rst-
    order transition
    C
    P
    =
    _
    H
    T
    _
    P
    =T
    _
    S
    T
    _
    P
    =T
    _

    2
    G
    T
    2
    _
    P
    =
    PChem I 4.7
    H is discontinuous at transition, derivative does not
    exist: C
    P
    =
    dq =C
    P
    dT, phase transition: dq =0, dT =0 =C
    P
    =

    second-order transitions:
    rst derivatives of are continuous, V =0 and S =
    0, and second derivatives are discontinuos, C
    P
    =0
    such transitions are rare
    [Figure: Ehrenfest classication, Fig. 4.16]
    more common:
    V =0, S =0, C
    P
    logarithmically: critical point
    critical point = second-order transition
    [Figure: C
    P
    for critical point, Fig. 4.17]
    PChem I 4.8

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