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    Pure Substances: Vapor-Liquid Critical Point

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    Nihad S Zain
    A critical point occurs under conditions where no phase boundaries exist, such as a specific temperature and pressure. There are vapor-liquid and liquid-liquid critical points. A vapor-liquid critical point is the point where the liquid and gas phases converge into a single supercritical fluid phase with no distinction between them. This occurs at a critical temperature and pressure, above which increases in pressure do not form a liquid phase. A liquid-liquid critical point occurs at the limit of the two-phase region on a phase diagram, where an infinitesimal change in variables like temperature or pressure leads to separation into two liquid phases.

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    Pure Substances: Vapor-Liquid Critical Point

    Uploaded by

    Nihad S Zain
    134 views3 pages
    A critical point occurs under conditions where no phase boundaries exist, such as a specific temperature and pressure. There are vapor-liquid and liquid-liquid critical points. A vapor-liquid critical point is the point where the liquid and gas phases converge into a single supercritical fluid phase with no distinction between them. This occurs at a critical temperature and pressure, above which increases in pressure do not form a liquid phase. A liquid-liquid critical point occurs at the limit of the two-phase region on a phase diagram, where an infinitesimal change in variables like temperature or pressure leads to separation into two liquid phases.

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    Critical Point

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    Critical Point

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    A critical point occurs under conditions where no phase boundaries exist, such as a specific temperature and pressure. There are vapor-liquid and liquid-liquid critical points. A vapor-liquid critical point is the point where the liquid and gas phases converge into a single supercritical fluid phase with no distinction between them. This occurs at a critical temperature and pressure, above which increases in pressure do not form a liquid phase. A liquid-liquid critical point occurs at the limit of the two-phase region on a phase diagram, where an infinitesimal change in variables like temperature or pressure leads to separation into two liquid phases.

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    © All Rights Reserved
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    134 views3 pages

    Pure Substances: Vapor-Liquid Critical Point

    Uploaded by

    Nihad S Zain
    A critical point occurs under conditions where no phase boundaries exist, such as a specific temperature and pressure. There are vapor-liquid and liquid-liquid critical points. A vapor-liquid critical point is the point where the liquid and gas phases converge into a single supercritical fluid phase with no distinction between them. This occurs at a critical temperature and pressure, above which increases in pressure do not form a liquid phase. A liquid-liquid critical point occurs at the limit of the two-phase region on a phase diagram, where an infinitesimal change in variables like temperature or pressure leads to separation into two liquid phases.

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    © All Rights Reserved
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    Critical point

    A critical point, also known as a critical state, occurs under conditions (such as specific values of
    temperature, pressure or composition) at which no phase boundaries exist.
    There are multiple types of critical points, including vaporliquid critical points and liquidliquid
    critical points.

    Pure substances: vaporliquid critical point


    The term "critical point" is sometimes used to specifically denote the vaporliquid critical point of a
    material, above which distinct liquid and gas phases do not exist.

    As shown in the phase diagram, this is the point at which the phase boundary between liquid and gas
    terminates. In water, the critical point occurs at around 647 K (374 C) and 22.064 MPa (218 atm).
    As the substance approaches critical temperature, the properties of its gas and liquid phases
    converge, resulting in only one phase at the critical point: a homogeneous supercritical fluid.
    The heat of vaporization (or enthalpy of vaporization - the energy required to transform a given
    quantity of a substance from a liquid into a gas at a given pressure) is zero at and beyond this critical
    point, and so no distinction exists between the two phases.
    The heat of vaporization diminishes with increasing temperature and it vanishes completely at the
    critical temperature (Tr=1) because above the critical temperature the liquid and vapor phases no
    longer co-exist. (The reduced temperature Tr of a fluid is its actual temperature, divided by its critical
    temperature).

    On the PT diagram, the point at which critical temperature and critical pressure meet is called the
    critical point of the substance. Above the critical temperature, a liquid cannot be formed by an
    increase in pressure, even though a solid may be formed under sufficient pressure. The critical
    pressure is the vapor pressure at the critical temperature. The critical molar volume is the volume of
    one mole of material at the critical temperature and pressure.
    Critical properties vary from material to material, and for many pure substances are readily available
    in the literature. Nonetheless, obtaining critical properties for mixtures is more challenging.
    Mathematical definition
    For pure substances, there is an inflection point in the critical isotherm (constant temperature line) on
    a pV diagram. This means that at the critical point:

    That is, the first and second partial derivatives of the pressure p with respect to the volume V are
    both zero, with the partial derivatives evaluated at constant temperature T.
    Sometimes a set of reduced properties is defined in terms of the critical properties, i.e.:

    where Tr is the reduced temperature, pr is the reduced pressure, Vr is the reduced volume, and R is
    the universal gas constant.

    Mixtures: liquidliquid critical point


    The liquidliquid critical point of a solution, which occurs at the critical solution temperature, occurs
    at the limit of the two-phase region of the phase diagram. In other words, it is the point at which an
    infinitesimal change in some thermodynamic variable (such as temperature or pressure) will lead to
    separation of the mixture into two distinct liquid phases, as shown in the polymersolvent phase
    diagram to the right. Two types of liquidliquid critical points are the upper critical solution
    temperature (UCST), which is the hottest point at which cooling will induce phase separation, and
    the lower critical solution temperature, which is the coldest point at which heating will induce phase
    separation.

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