Phase Theory: The Thermodynamics of Heterogeneous Equilibria

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Thermodynamics Simulations Applied to Gas-Solid Materials Fabrication Processes

Issue 27, Previous Article Next Article. From the journal: Physical Chemistry Chemical Physics. Non-equilibrium thermodynamics as a tool to compute temperature at the catalyst surface. You have access to this article. Please wait while we load your content Something went wrong. Try again? Cited by. Back to tab navigation Download options Please wait Article type: Paper. The equilibrium conditions are shown as curves on a curved surface in 3D with areas for solid, liquid, and vapor phases and areas where solid and liquid, solid and vapor, or liquid and vapor coexist in equilibrium.

A line on the surface called a triple line is where solid, liquid and vapor can all coexist in equilibrium. The critical point remains a point on the surface even on a 3D phase diagram. For water, the 3D p — v — T diagram is seen here: [11].


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An orthographic projection of the 3D p — v — T graph showing pressure and temperature as the vertical and horizontal axes collapses the 3D plot into the standard 2D pressure—temperature diagram. When this is done, the solid—vapor, solid—liquid, and liquid—vapor surfaces collapse into three corresponding curved lines meeting at the triple point, which is the collapsed orthographic projection of the triple line.

Other much more complex types of phase diagrams can be constructed, particularly when more than one pure component is present. In that case, concentration becomes an important variable. Phase diagrams with more than two dimensions can be constructed that show the effect of more than two variables on the phase of a substance.


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Phase diagrams can use other variables in addition to or in place of temperature, pressure and composition, for example the strength of an applied electrical or magnetic field, and they can also involve substances that take on more than just three states of matter. One type of phase diagram plots temperature against the relative concentrations of two substances in a binary mixture called a binary phase diagram , as shown at right. Such a mixture can be either a solid solution , eutectic or peritectic , among others.

These two types of mixtures result in very different graphs. Another type of binary phase diagram is a boiling-point diagram for a mixture of two components, i. For two particular volatile components at a certain pressure such as atmospheric pressure , a boiling-point diagram shows what vapor gas compositions are in equilibrium with given liquid compositions depending on temperature. In a typical binary boiling-point diagram, temperature is plotted on a vertical axis and mixture composition on a horizontal axis. A simple example diagram with hypothetical components 1 and 2 in a non- azeotropic mixture is shown at right.

The fact that there are two separate curved lines joining the boiling points of the pure components means that the vapor composition is usually not the same as the liquid composition the vapor is in equilibrium with. See Vapor—liquid equilibrium for more information. In addition to the above-mentioned types of phase diagrams, there are thousands of other possible combinations. Some of the major features of phase diagrams include congruent points, where a solid phase transforms directly into a liquid.

There is also the peritectoid , a point where two solid phases combine into one solid phase during cooling.

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The inverse of this, when one solid phase transforms into two solid phases during cooling, is called the eutectoid. The x-axis of such a diagram represents the concentration variable of the mixture. As the mixtures are typically far from dilute and their density as a function of temperature is usually unknown, the preferred concentration measure is mole fraction.

A volume-based measure like molarity would be inadvisable. Polymorphic and polyamorphic substances have multiple crystal or amorphous phases, which can be graphed in a similar fashion to solid, liquid, and gas phases. Some organic materials pass through intermediate states between solid and liquid; these states are called mesophases. Attention has been directed to mesophases because they enable display devices and have become commercially important through the so-called liquid-crystal technology.

Phase diagrams are used to describe the occurrence of mesophases.

Phase Theory : The Thermodynamics of Heterogeneous Equilibria / H.A.J. Oonk - Details - Trove

From Wikipedia, the free encyclopedia. For the use of this term in mathematics and physics, see phase space. Berlin: Springer. General Chemistry 4th ed. Saunders College Publishing. Prentice Hall.

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Principles of General Chemistry. Creative Commons. Geoffrey General Chemistry. Principles and Modern Applications 8th ed. Physical Chemistry. Heat and Thermodynamics 6th ed. Journal of Chemical Education. Chemistry Education Materials. Water structure and science Site by Martin Chaplin, accessed 2 July Liquid Crystals 2nd ed.

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