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    Topic 14 - Vaporization

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    1. The equilibrium condition for two phases at constant temperature and pressure is that their specific Gibbs free energies must be equal. 2. On a pressure-temperature diagram, the phase boundary between two phases is a line representing the fixed pressure where the phases can coexist at equilibrium. 3. At a triple point, three phases of a substance (e.g. ice, water, and water vapor) can coexist in equilibrium at a unique temperature and pressure, defining a standard point for thermometry.

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    Topic 14 - Vaporization

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    1. The equilibrium condition for two phases at constant temperature and pressure is that their specific Gibbs free energies must be equal. 2. On a pressure-temperature diagram, the phase boundary between two phases is a line representing the fixed pressure where the phases can coexist at equilibrium. 3. At a triple point, three phases of a substance (e.g. ice, water, and water vapor) can coexist in equilibrium at a unique temperature and pressure, defining a standard point for thermometry.

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    1. The equilibrium condition for two phases at constant temperature and pressure is that their specific Gibbs free energies must be equal. 2. On a pressure-temperature diagram, the phase boundary between two phases is a line representing the fixed pressure where the phases can coexist at equilibrium. 3. At a triple point, three phases of a substance (e.g. ice, water, and water vapor) can coexist in equilibrium at a unique temperature and pressure, defining a standard point for thermometry.

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    74 views4 pages

    Topic 14 - Vaporization

    Uploaded by

    iitdviv
    1. The equilibrium condition for two phases at constant temperature and pressure is that their specific Gibbs free energies must be equal. 2. On a pressure-temperature diagram, the phase boundary between two phases is a line representing the fixed pressure where the phases can coexist at equilibrium. 3. At a triple point, three phases of a substance (e.g. ice, water, and water vapor) can coexist in equilibrium at a unique temperature and pressure, defining a standard point for thermometry.

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    School of Physics and Astronomy

    Junior Honours Thermodynamics

    GJA 2015-2016

    Lecture TOPIC 14 (Finn: 9.1, 9.2, 9.3)


    Synopsis: Phases: the PV T surface and the equilibrium condition for two phases.

    Equation of state for water, given any two of P, V, T gives us the third, and the associated phase(s).

    The equilibrium condition for two phases at fixed temperature and pressure
    In thermal equilibrium, P and T are constant throughout the system, so G must be at a minimum.
    Consider a system of two coexisting phases in equilibrium with specific (i.e. per unit mass) Gibbs free
    energy g1 and g2 and the masses M1 and M2 : the total Gibbs free energy for the system is G = g1 M1 + g2 M2 .
    During a phase transition, the proportions of the two phases change, but T and P do not.
    Conservation of mass: dM1 + dM2 = 0,
    combined with dG = g1 dM1 + g2 dM2 = V dP SdT = 0 (for T and P fixed) gives
    g1 = g2
    Conclusion: when two component phases of a system coexist at constant temperature and pressure, their specific
    Gibbs functions are equal. If g for one phase is lower than the other then only the phase with the lower g is
    present. Under a given external temperature, coexistence is only possible a one fixed external pressure.
    The phase boundary is a line on P-T diagram
    With fixed volume boundaries, equilibrium still requires P and T to be the same in each phase, and g1 = g2 . So
    the pressure is defined as above, however the volume constraint V = v1 M1 + v2 M2 can be met by adjusting the
    amounts of the two phases.
    There is an area of phase coexistence on a V-T diagram (and on P-V)
    1. Phase diagram The projection of the equation of state surface on to the PT is called a phase diagram
    because it shows which phase is stable for given T,P, and the phase boundaries between pairs of phases.
    2. Fixed volume
    The projection on to the TV plane also shows the boundaries, but this time the coexistence at fixed
    volume at the phase transitions is directly evident. Projection onto the PV plane may even allow two
    solutions (e.g. water at ambient pressure has a density maximum, so there may be two temperatures at
    which P,V are the same. In this unusual case, specifying two conjugate variables P and V is not enough
    to determine the state of the system.
    3. Conjugate variables and positive quantities
    P,V are conjugate (appear together in free energy expressions), if P/V > 0 free energy can be spontaneously reduced by volume collapse, implying the system is not in equilibrium. So negative thermal
    expansion is allowed, but negative bulk modulus is not. The TS equivalent of this statement (positive
    heat capacity) is another statement of the Second Law.
    4. Triple point
    Ice, water and water vapour coexist at a unique temperature and pressure at the triple point. Useful for
    defining a standard temperature point for thermometry.
    5. Sublimation
    It is the change of phase directly from solid-to-vapour. This happens for dry ice, which is solid CO2 ,
    under ambient pressure; the heat absorbed by the solid dry ice causes it to change directly into vapour
    without passing via a liquid phase. The same occurs for ice, but at reduced pressure. Equally liquid CO2
    can be formed at room temperature, but only at very high pressure.
    6. Critical point
    Point at which the liquid-vapour transition vanishes. Dense gas is indistinguishable from liquid, it is
    usually called a fluid.
    7. Phase transitions
    Melting and boiling should be familiar. The stable phase is always the one with the lowest free energy
    (Helmholtz or Gibbs, depending on boundary conditions).
    2

    The Helmholtz function as an indicator of equilibrium in fixed volume

    An isotherm on a plot of F vs V typically comprises


    multiple sections, one for each phase.

    Isotherms

    Helmholtz = UTS

    The key property of the Helmholtz function F=U-TS is


    that it has a minimum value for a system in equilibrium
    at constant T and V . This makes it ideally suited to
    treating a mixture of two phases of a single substance,
    such as ice and water. The equilibrium condition becomes
    dF = PdV SdT = 0

    Solid
    Liquid

    Volume
    F may be minimised by a mixture of phases. These can be linked by a common tangent, the slope of
    which is the phase transition pressure.
    
    
    F
    = P(T )
    V T
    The phases have different specific volumes, so relative amounts of the two phases must give the externally
    specified volume V = N1 v1 + N2 v2 ; where N1 and N2 are the number of moles of each phase, which can
    change spontateously subject to dN1 = dN2 and v1 , v2 the molar volumes. This is sometimes known
    as the lever rule. Note that the Helmholtz free energies f1 and f2 are not equal at equilibrium, and the
    pressure and temperature remain constant as the two phase mixture is compressed, provided it remains
    at equilibrium.
    Isotherms of a Van der Waals fluid
    The Van der Waals, equation of state yields more interesting isotherms than for an Ideal gas. The equation
    can be rewritten in the form:
    Pv3 (Pb + RT )v2 + av ab = 0
    where v = V /n, n being the number of moles of molecules in the sample.
    In general, for given a and b (ie a given gas) for each P, T there can be three possible values of v. The
    three roots of the equation coincide for a unique set of values of P, v and T defining a critical point,
    a
    8a
    with coordinates (Pc = 27b
    2 , vc = 3b, RTc = 27b ).
    The Van der Waals equation can be rewritten with a and b replaced with Pc , Tc , vc
    For T > Tc , the equation has only one root.
    At the Boyle temperature TB = a/(Rb) = 27Tc /8, d(PV )/dP)T is zero . At higher T volume
    exclusion effects (b) are important, and PV increases with pressure. At lower T bonding effects
    (a) are important, and PV decreases with pressure. Most real gases have Tb 2.75Tc
    Considering a virial equation of state for gases, TOPIC 12,
    Pv
    = 1 + B2
    RT

     
     2
    1
    1
    + B3
    + ...
    v
    v

    a
    Bi are all functions of T , and at the Boyle Temperature B2 = b RT
    = 0.

    Liquid-vapour transition for the Van der Waals equation of state


    Van der Waals equation can conveniently be written in terms of reduced parameters V /Vc , T /Tc , P/Pc
    where Pc , Tc ,Vc are the values of P, T,V at the critical point (Not to be confused with the triple point):
    
    
    3  V
    T
    P/Pc +
    3

    1
    = 8
    VdWs Eqn of state
    2
    (V /Vc )
    Vc
    Tc
    a
    8a
    with
    Vc = 3b, Pc =
    , Tc =
    2
    27b
    27Rb
    This equation gives a mechanically unstable solution (ie negative compressibility, (dP/dV )T > 0) for
    T < Tc over a range of molar (specific) volumes. This range becomes larger as the temperature is lowered
    further. The fluid therefore must break up into two phases with different densities which in equilibrium
    (same P, T) must have equal Gibbs Free energies. Since the boundary condition is fixed total volume, the
    system minimises its Helmholtz free energy.
    This leads to the construction shown in the second figure, in which a horizontal line is drawn connecting
    the denser phase (liquid) at the left and less dense phase (vapour) on the right. The real isotherm moves
    along this line. The position of the line is such as to enclose equal areas between it and the isotherm
    traced by the Van der Waals equation of state. Remembering that both lines refer to the same isotherm
    the equal area construction ensures that:
    The change in Gibbs
    free energy between the two points at its end is zero. ( g/ P)T = v therefore
    R
    gl gv = g = T const vdP = 0 performing the integral along the VdW isotherm.
    If we construct a heat engine running round the closed cycle moving along the horizontal line from
    liquid to vapour and back along the hypothetical VdW isotherm or vice-versa no work can be done
    according to the second law, since there is no difference in temperature.

    Phase and the PV T surface


    Real substances have similar PV T surfaces to the van der Waals fluid, with a critical point and critical
    isotherm. However, because the van der Waals substance is by construction homogeneous it cannot show
    the phase transitions to solid crystalline phases.
    A real substance compressed slowly at constant temperature might pass through a succession of equilibrium states abcdef including a vapour-to-liquid transition (bc), following the easy compression of the
    vapour. The denser liquid is less compressible but may be transform into successive solid phases. Triple
    points occur where three phases coexist at a temperature TT P . For the case of a liquid-solid-gas triple
    point for T < TT P no liquid phase is formed; the solid transforms directly to vapour (sublimation).

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