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    APC - Chapter 5 - Part 1 SP22

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    The document discusses phase diagrams for one-component systems. It defines key terms like phases, components, and degrees of freedom. It describes the phase rule and provides examples of its application. It then discusses the Clapeyron equation and how it relates phase boundaries for solid-liquid and liquid-vapor transitions.

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    APC - Chapter 5 - Part 1 SP22

    Uploaded by

    iB13e
    15 views20 pages
    The document discusses phase diagrams for one-component systems. It defines key terms like phases, components, and degrees of freedom. It describes the phase rule and provides examples of its application. It then discusses the Clapeyron equation and how it relates phase boundaries for solid-liquid and liquid-vapor transitions.

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    APC - Chapter 5- part 1 SP22(1)

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    The document discusses phase diagrams for one-component systems. It defines key terms like phases, components, and degrees of freedom. It describes the phase rule and provides examples of its application. It then discusses the Clapeyron equation and how it relates phase boundaries for solid-liquid and liquid-vapor transitions.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    15 views20 pages

    APC - Chapter 5 - Part 1 SP22

    Uploaded by

    iB13e
    The document discusses phase diagrams for one-component systems. It defines key terms like phases, components, and degrees of freedom. It describes the phase rule and provides examples of its application. It then discusses the Clapeyron equation and how it relates phase boundaries for solid-liquid and liquid-vapor transitions.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
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    of 20

    PHASE DIAGRAMS

    Chapter 5
    (part 1)

    1
    In this chapter, the following topics will be discussed

     Phases, components, and degrees of freedom


     The phase rule
     One component systems
     Two-component systems

    Vapour pressure diagrams


    Temperature-composition diagrams
    Liquid-liquid phase diagrams
    Liquid-solid phase diagrams

    2
    Introduction
    • Thermodynamics of simple mixtures can be applied to
    discuss the physical changes of mixtures when they are
    heated or cooled and when their compositions are
    changed.

    • The phase rule of Gibbs allow us to discuss the phase


    diagrams and determine the phases composition.

    • Phase diagrams can be used to judge whether two


    substances are mutually miscible or not under certain
    conditions of T, P and composition.
    3
    • We will see whether equilibrium can exist over a range of
    conditions or whether a system must be bought to a definite
    pressure, temperature and composition before equilibrium is
    established.

    • Phase diagrams are industrially and commercially important.

    • Semiconductor, ceramics, steel and alloy industries rely heavily


    on phase diagrams to ensure uniformity of a product.

    • Phase diagrams are also the basis for separation procedures in


    the petroleum industry and the formulation of foods and
    cosmetic preparations.
    • Then we can say that phase diagrams are extremely useful for
    chemical engineering.

    4
    Phases, components, and degrees of freedom
    Definitions:
    1. A phase is a state of matter that is uniform, not only in
    composition but also in physical state. The number of
    phase in a system is denoted P.

    – Examples of single phase system


    A pure gas, A gaseous mixture, Two totally miscible liquids,
    A crystal , A solution of sodium chloride , Ice.

    – Examples of two phase system


    A mixture of ice and water.
    An alloy is a mixture of two metals, like Fe + Cu, is a two phase
    system if the metals are immiscible, but a single phase system if
    they are miscible.
    5
    2. A constituent of a system is a chemical species (ion or
    molecule) that is present. A mixture of water and ethanol has
    two constituents. A solution of sodium chloride has three
    constituents: Na+, Cl-, H2O.

    3. A component is a chemically independent constituent of a


    system. The number of components in a system is the
    minimum number of independent species necessary to
    define the composition of all the phases present in the
    system.

    Remark: When no reaction takes place and there are no other


    constraints, the number of components is the equal to the
    number of constituents.

    6
    Phase Rule
    • The number of phases, is denoted P.
    • The number of components, is denoted C.
    • The variance (degree of freedom) of the system, denoted F is
    the number of intensive variables (e.g. p and T) that can be
    changed independently without disturbing the number of
    phases in equilibrium.
    F=C–P+2
    • This is not an empirical rule based upon observations, it can
    be derived from chemical thermodynamics .
    • For a one component system F = 3 – P
    • When only one phase is present, F = 2 and both p and T can
    be varied without changing the number of phases.
    7
    C=c–r
    C: Number of components
    c : Number of constituents
    r : Number of reactions (+ the electrical neutrality reaction in the case of aqueous
    solutions).

    C
    F = C – P + 2 = (c – r) – P +2

    8
    Examples:
    1) Perfect gas : F = 1 – 0 – 1 + 2

    2) Aqueous solution of NaCl:

    Na+ , Cl- , H3O+, OH- and H2O

    c=5,r=2;P=1; 2 intensive parameters (P and T)

    F=5–2–1+2=4
    4 independent intensive parameters can be chosen arbitrarily without changing the
    number of phases present.

    3) Saturated aqueous solution of NaCl:

    Na+ , Cl- , H3O+, OH- ; H2O and NaCl

    c=6,r=3;P=2; 2 intensive parameters (P and T)

    F = 6 – 3 – 2 +2 = 3

    Only 3 independent intensive parameters can be chosen arbitrarily without changing the
    number of phases present.
    9
    • When two phases are present, F = 1 which implies that only
    one variable can be varied independently (p or T). This is
    why at a given temperature a liquid has a characteristic vapor
    pressure.

    • When three phases are present, F = 0 (no independent


    variable, degree of freedom =0). This special case occurs
    only at a definite temperature and pressure it is characteristic
    of the substance.

    10
    One Component Systems
    The location of phase boundaries for monocomponent diagrams P = f(T)
    when two phases are in equilibrium, their chemical potentials must be equal. Therefore, where
    the phases α and β are in equilibrium,
    μ(α; p,T) =μ(β; p,T)
    dμ(α) = dμ(β).

    We know that : μ = Gm <==> dGm = dμ

    dGm=dμ =Vmdp − SmdT

    −Sm(α)dT + Vm(α)dp = −Sm(β)dT + Vm(β)dp

    where Sm(α) and Sm(β) are the molar entropies of the phases and Vm(α) and Vm(β) are their
    molar volumes. Hence

    {Vm(β) − Vm(α)}dp = {Sm(β) − Sm(α)}dT

    which rearranges into the Clapeyron equation:

    11
    The Clapeyron equation is an exact expression for the slope of the tangent to the boundary
    at any point and applies to any phase equilibrium of any pure substance. It implies that
    we can use thermodynamic data to predict the appearance of phase diagrams and to
    understand their form. A more practical application is to the prediction of the response of
    freezing and boiling points to the application of pressure.
    The solid–liquid boundary

    We can obtain the formula for the phase boundary by integrating dp/dT, assuming that ΔfusH
    and ΔfusV change so little with temperature and pressure that they can be treated as constant.
    If the melting temperature is T* when the pressure is p*, and T when the pressure is p, the
    integration required is

    When T is close to T*, the logarithm can be approximated by using:

    Therefore:

    12
    This expression is the equation of a steep straight line when p is plotted against T

    A typical solid–liquid phase boundary slopes steeply upwards. This


    slope implies that, as the pressure is raised, the melting temperature
    rises. Most substances behave in this way.
    13
    The liquid–vapour boundary

    For a gas : ΔvapV ≈ Vm(g). if the gas behaves perfectly, Vm(g) = RT/p. These two
    approximations turn the exact Clapeyron equation into

    which rearranges into the Clausius–Clapeyron equation for the variation of vapour pressure
    with temperature:

    this equation can be integrated as follows:

    14
    where p* is the vapour pressure when the temperature is T* and p the vapour pressure
    when the temperature is T. Therefore, because the integral on the left evaluates to ln(p/p*),
    the two vapour pressures are related by:

    Equation 4.12 is plotted as the liquid–vapour boundary in Fig. 4.17. The line does
    not extend beyond the critical temperature Tc, because above this temperature
    the liquid does not exist.

    A typical liquid–vapour phase boundary.


    The boundary can be regarded as a plot of
    the vapour pressure against the
    temperature.

    15
    The solid–vapour boundary

    The only difference between this case and the last is the replacement of the enthalpy of
    vaporization by the enthalpy of sublimation, ΔsubH.

    Typical one component phase diagram


    plotted from Clapeyron equation

    16
    One Component Systems
    Given below the diagram of pure water (F = 3 - P)

    The phase diagram for water , T3 marks the temperature of the triple
    point, Tb the normal boiling point (p = 1atm), and Tf the normal
    freezing point.
    17
    • When only phase is present F = 2, (p and T can be varied
    independently without changing the number of phases). A
    single phase is represented by an area on a phase diagram.

    • When two phases are in equilibrium F = 1, (p or T can be


    varied independently) the equilibrium of two phases is
    represented by a line in the phase diagram.

    • When three phases are in equilibrium, F= 0 and the system is


    invariant. The equilibrium of three phases is represented by
    a point, the triple point, on a phase diagram.

    • Four phases cannot be in equilibrium in a one-component


    system because F cannot be negative.
    18
    This diagram summarizes the changes that take place when a
    sample is cooled at constant pressure. At a, the sample remains
    entirely gaseous until the temperature reaches b, when liquid
    appears. Two phases are now in equilibrium (Liq/gas).
    Lowering the temperature takes the system to c in the one phase,
    liquid region, the temperature can now be varied around the
    point c. Ice appears at d and two phases are now in equilibrium
    (Solid/Liquid). Then lowering the temperature takes the system
    to e in the one phase solid region.

    19
    • Thermal analysis: a sample is allowed to cool and its
    temperature is monitored. When a phase transition occurs,
    cooling may stop until the phase transition is complete and
    is easily observed on a thermogram.

    20

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