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    2022-1 physical chemistry 1 chapter 8-수업자료

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    1. The relative stability of solid, liquid, and gas phases at given conditions is determined by their Gibbs free energy. The phase with the lowest Gibbs free energy is the most stable. 2. Pressure-temperature phase diagrams graphically depict the conditions under which solid, liquid, and gas phases coexist in equilibrium. They include coexistence curves showing phase transition boundaries and triple points where three phases meet. 3. The phase rule relates the number of phases in equilibrium to the degrees of freedom in temperature and pressure that can be varied independently. For a single substance, there are three degrees of freedom minus the number of phases.

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    2022-1 physical chemistry 1 chapter 8-수업자료

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    1. The relative stability of solid, liquid, and gas phases at given conditions is determined by their Gibbs free energy. The phase with the lowest Gibbs free energy is the most stable. 2. Pressure-temperature phase diagrams graphically depict the conditions under which solid, liquid, and gas phases coexist in equilibrium. They include coexistence curves showing phase transition boundaries and triple points where three phases meet. 3. The phase rule relates the number of phases in equilibrium to the degrees of freedom in temperature and pressure that can be varied independently. For a single substance, there are three degrees of freedom minus the number of phases.

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    1. The relative stability of solid, liquid, and gas phases at given conditions is determined by their Gibbs free energy. The phase with the lowest Gibbs free energy is the most stable. 2. Pressure-temperature phase diagrams graphically depict the conditions under which solid, liquid, and gas phases coexist in equilibrium. They include coexistence curves showing phase transition boundaries and triple points where three phases meet. 3. The phase rule relates the number of phases in equilibrium to the degrees of freedom in temperature and pressure that can be varied independently. For a single substance, there are three degrees of freedom minus the number of phases.

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    6 views10 pages

    2022-1 physical chemistry 1 chapter 8-수업자료

    Uploaded by

    강정우
    1. The relative stability of solid, liquid, and gas phases at given conditions is determined by their Gibbs free energy. The phase with the lowest Gibbs free energy is the most stable. 2. Pressure-temperature phase diagrams graphically depict the conditions under which solid, liquid, and gas phases coexist in equilibrium. They include coexistence curves showing phase transition boundaries and triple points where three phases meet. 3. The phase rule relates the number of phases in equilibrium to the degrees of freedom in temperature and pressure that can be varied independently. For a single substance, there are three degrees of freedom minus the number of phases.

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    of 10

    Chapter 8

    Phase Diagrams and the Relative Stability


    of Solid, Liquids, and Gases
    Which phase is most stable at given conditions ?
    1. What determines the relative stability of the solid, liquid,
    and gas phases?
    phase : form of matter that is uniform with respect to chemical
    composition and the state of aggregation on both microscopic and
    macroscopic length scales
    ex) a mixture of ice and water, iron oxide, helium......
    𝜕𝐺 𝜕 𝑛𝐺𝑚
    For pure substance, 𝜇 = ( ) 𝑇,𝑃 = ( ) 𝑇,𝑃 = 𝐺𝑚
    𝜕𝑛 𝜕𝑛

    P and T change,
    [ Sm and Vm > 0 ]

    [ ΔS = Δ Htransition / T ]
    [Figure 1]
    if P is changed at constant T,
    Vmgas >> Vmliquid > Vmsolid

    Vmliquid > Vmsolid Vmliquid < Vmsolid


    → freezing point elevation → freezing point depression

    For CO2, solid → gas transition is energetically favorable (Figure 3a)


    triple point → all three phases coexist in equilibrium (Figure 3b)
    2. The pressure-temperature phase diagram
    water

    - coexistence curve (slope of solid-liquid)


    - standard (normal) phase transition temperature
    - vapor pressure
    boiling : vapour pressure of a liquid is equal to the external pressure

    supercritical fluid : same density between liquid


    and vapour (no surface)
    Pc and Tc : disappearance of the interface

    triple point, T3
    3. The phase rule
    coexistence of two phase, α and β →
    : only one of T and P is needed to describe the system

    coexistence of three phase, α, β, and γ →


    : only one combination of T and P

    phase rule : number of degrees of freedom to the number of phases in


    a system at equilibrium

    F=C -P+2
    (F : variance, C : # of components (substance),
    P : # of phases at equilibrium)

    component (substance):
    chemically independent constituent of a system
    For pure substance, F = 3 - P
    4. The P-V and P-V-T phase diagrams
    P-V diagram

    P-V-T diagram
    Clapeyron equation

    dμ(α) = dμ(β)
    -Sm(α)dT + Vm(α)dp = -Sm(β)dT + Vm(β)dp
    {Vm(β) - Vm(α)} dp = {Sm(β) - Sm(α)} dT

    solid-liquid boundary

    (ΔtrsS = ΔfusH / T)

    𝑝 ∆𝑓𝑢𝑠 𝐻 𝑇 𝑑𝑇 ∆𝑓𝑢𝑠 𝐻 𝑇
    ∗
    න 𝑑𝑝 = න 𝑝=𝑝 + 𝑙𝑛 ∗
    𝑝∗ ∆𝑓𝑢𝑠 𝑉 𝑇∗ 𝑇 ∆𝑓𝑢𝑠 𝑉 𝑇

    ∆𝑓𝑢𝑠 𝐻
    steep & 𝑝= 𝑝∗ + ∗ (𝑇 − 𝑇 ∗ )
    positive slope 𝑇 ∆𝑓𝑢𝑠 𝑉
    liquid - vapour boundary
    𝑑𝑝 ∆𝑣𝑎𝑝 𝐻 𝑑𝑝 ∆𝑣𝑎𝑝 𝐻 (Δ V = V (g))
    = = vap m
    𝑑𝑇 𝑇∆𝑣𝑎𝑝 𝑉 𝑑𝑇 𝑇(𝑅𝑇/𝑝)
    𝑑 ln 𝑝 ∆𝑣𝑎𝑝 𝐻
    =
    𝑑𝑇 𝑅𝑇 2
    𝑝 ∆𝑣𝑎𝑝 𝐻 𝑇 𝑑𝑇 ∆𝑣𝑎𝑝 𝐻 1 1
    න 𝑑 ln 𝑝 = න 2=− − ∗
    less steep & 𝑝∗ 𝑅 𝑇∗ 𝑇 𝑅 𝑇 𝑇
    positive slope Δ𝑣𝑎𝑝 𝐻 1 1
    𝑝=𝑝 𝑒∗ −𝜒 𝜒= − ∗
    𝑅 𝑇 𝑇
    solid - vapour boundary
    8. Surface tension
    in the absence of a gravitational field
    → a liquid droplet will assume a spherical shape

    work for the creation of additional surface area at constant T and V


    [ A : Helmholtz energy, γ : surface tension, σ : unit element of area ]

    the area :
    the force : [work : 8πγr dr]
    at equilibrium :

    bubble 1 + bubble 2 :

    “coarsening” or “Ostwald ripening”

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