Phase (matter)

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In the physical sciences, a phase is a set of states of a macroscopic physical system that have relatively uniform chemical composition and physical properties (i.e. density, crystal structure, index of refraction, and so forth).

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Phases and states of matter

Phases are sometimes confused with states of matter, but there are significant differences. States of matter refers to the differences between gases, liquids and solids, etc. If there are two regions in a chemical system that are in different states of matter, then they must be different phases. However, the reverse is not true -- a system can have multiple phases which are in equilibrium with each other and also in the same state of matter. For example, diamond and graphite are both solids but they are different phases, even though their composition may be identical. A system with oil and water at room temperature will be two different phases of differing composition, but both will be the liquid state of matter. This difference is especially important when considering the Gibbs' phase rule, which governs the number of allowed phases.

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General definition of phases

In general, two different states of a system are in different phases if there is an abrupt change in their physical properties while transforming from one state to the other. Conversely, two states are in the same phase if they can be transformed into one another without any abrupt changes. There are, however, exceptions to this statement -- for example the liquid-gas critical point discussed below in the Phase Diagrams section.

An important point is that different types of phases are associated with different physical qualities. When discussing the solid, liquid, and gaseous phases, we talked about rigidity and compressibility, and the effects of varying the pressure and volume, because those are the relevant properties that distinguish a solid, a liquid, and a gas. On the other hand, when discussing paramagnetism and ferromagnetism, we look at the magnetization, because that is what distinguishes the ferromagnetic phase from the paramagnetic phase. Several more examples of phases will be given in the following section.

In more technical language, a phase is a region in the parameter space of thermodynamic variables in which the free energy is analytic. As long as the free energy is analytic, all thermodynamic properties (such as entropy, heat capacity, magnetization, and compressibility) will be well-behaved, because they can be expressed in terms of the free energy and its derivatives. For example, the entropy is the first derivative of the free energy with temperature.

When a system goes from one phase to another, there will generally be a stage where the free energy is non-analytic. This is a phase transition. Due to this non-analyticity, the free energies on either side of the transition are two different functions, so one or more thermodynamic properties will behave very differently after the transition. The property most commonly examined in this context is the heat capacity. During a transition, the heat capacity may become infinite, jump abruptly to a different value, or exhibit a "kink" or discontinuity in its derivative. See also differential scanning calorimetry.

Possible graphs of heat capacity (C) against temperature (T) at a phase transition
Possible graphs of heat capacity (C) against temperature (T) at a phase transition

In this section, we will present several systems that exhibit phase phenomena.

In many materials, there are actually a variety of solid phases, each corresponding to a unique crystal structure. These varying crystal phases of the same substance are called "allotropes" if intramolecular bonding changes or "polymorphs" if only intermolecular bonding changes. For instance, there are at least nine different polymorphs of ice that manifest under different temperature and pressure conditions. To take another example, diamond and graphite are allotropes of carbon. Graphite is composed of layers of hexagonally arranged carbon atoms, in which each carbon atom is strongly bound to three neighboring atoms in the same layer and is weakly bound to atoms in the neighboring layers. By contrast, in diamond each carbon atom is strongly bound to four neighboring carbon atoms in a diamond cubic array, with tetrahedral bonding. The unique crystal structures of graphite and diamond are responsible for the vastly different properties of these two materials.

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Two dimensional phases

Phases can also exist in two dimensions. The boundaries between two different three-dimensional phases, the surfaces of materials, and the grain boundaries between different crystallographic orientations of a single material can also show distinct phases. For example, surface reconstructions on metal and semiconductor surfaces are two dimensional phases.

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Phase diagrams

Main article: Phase diagram

The different phases of a system may be represented using a phase diagram. The axes of the diagrams are the relevant thermodynamic variables. For simple mechanical systems, we generally use the pressure and temperature.

A phase diagram for a typical material exhibiting solid, liquid and gaseous phases
A phase diagram for a typical material exhibiting solid, liquid and gaseous phases

The markings on the phase diagram show the points where the free energy is non-analytic. The open spaces, where the free energy is analytic, correspond to the phases. The phases are separated by lines of non-analyticity, where phase transitions occur, which are called phase boundaries.

In the diagram, the phase boundary between liquid and gas does not continue indefinitely. Instead, it terminates at a point on the phase diagram called the critical point. At temperatures and pressure above the critical point, the physical property differences that differentiate the liquid phase from the gas phase become less defined. This reflects the fact that, at extremely high temperatures and pressures, the liquid and gaseous phases become indistinguishable. In water, the critical point occurs at around 647 K (374 °C or 705 °F) and 22.064 MPa.

The existence of the liquid-gas critical point reveals a slight ambiguity in our above definitions. When going from the liquid to the gaseous phase, one usually crosses the phase boundary, but it is possible to choose a path that never crosses the boundary by going to the right of the critical point. Thus, phases can sometimes blend continuously into each other. This new phase which has some properties that are similar to a liquid and some properties that are similar to a gas is called a supercritical fluid. We should note, however, that this does not always happen. For example, it is impossible for the solid-liquid phase boundary to end in a critical point in the same way as the liquid-gas boundary, because the solid and liquid phases have different symmetry.

An interesting thing to note is that the solid-liquid phase boundary in the phase diagram of most substances, such as the one shown above, has a positive slope. This is due to the solid phase having a higher density than the liquid, so that increasing the pressure increases the melting temperature. However, in the phase diagram for water the solid-liquid phase boundary has a negative slope. This reflects the fact that ice has a lower density than water, which is an unusual property for a material.

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Phase separation

Phase separation is transformation of a homogenous system in two (or more) phases and commonly encountered in many branches of science and technology. One example is the crystallization of a solid from a solution.

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Metastable phases

Sometimes a substance or mixture can be heated, compressed, etc., beyond the point at which it would normally exhibit a phase change, but without actually triggering the change. Examples include supercooling, superheating, and supersaturation.

Usually each polymorph of a given substance is only stable over a specific range of conditions. For example, diamond is the stable form of carbon at extremely high pressures while graphite is the stable form at normal atmospheric pressures. Regardless, diamonds appear stable at normal temperatures and pressures, but, in fact, are very slowly converting to graphite. Heat increases the rate of this transformation, but at normal temperatures the diamond is practically stable.

Another important example of metastable polymorphs occurs in the processing of steel. Steels are often subjected to a variety of thermal treatments designed to produce various combinations of stable and metastable iron phases. In this way the steel properties, such as hardness and strength can be adjusted by controlling the relative amounts and crystal sizes of the various phases that form.

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Phase equilibrium

The distribution of kinetic energy among molecules is not uniform, and it changes randomly. This means that at, say, the surface of a liquid, there may be an individual molecule with enough kinetic energy to jump into the gas phase. Likewise, individual gas molecules may have low enough kinetic energy to join other molecules in the liquid phase. This phenomenon means that at any given temperature and pressure, multiple phases may co-exist.

For example, under standard conditions for temperature and pressure, a bowl of liquid water in dry air will evaporate until the partial pressure of gaseous water equals the vapor pressure of water. At this point, the rate of molecules leaving and entering the liquid phase becomes the same (due to the increased number of gaseous water molecules available to re-condense). The fact that liquid molecules with above-average kinetic energy have been removed from the bowl results in evaporative cooling. Similar processes may occur on other types of phase boundaries.

Gibbs' phase rule relates the number of possible phases, variables such as temperature and pressure, and whether or not an equilibrium will be reached.

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Emergence and universality

Phases are emergent phenomena produced by the self-organization of a macroscopic number of particles. Typical samples of matter, for example, contain around 1023 particles (of the order of Avogadro's number). In systems that are too small -- even, say, a thousand atoms -- the distinction between phases disappears, since the appearance of non-analyticity in the free energy requires a huge, formally infinite, number of particles to be present.

One might ask why real systems exhibit phases, since they are not actually infinite. The reason is that real systems contain thermodynamic fluctuations. When a system is far from a phase transition, these fluctuations are unimportant, but as it approaches a phase transition, the fluctuations begin to grow in size (i.e. spatial extent). At the ideal transition point, their size would be infinite, but before that can happen the fluctuations will have become as large as the system itself. In this regime, "finite-size" effects come into play, and we are unable to accurately predict the behavior of the system. Thus, phases in a real system are only well-defined away from phase transitions, and how far away it needs to be is dependent on the size of the system.

There is a corollary to the emergent nature of phase phenomena, known as the principle of universality. The properties of phases are largely independent of the underlying microscopic physics, so that the same types of phases arise in a wide variety of systems. This is a familiar fact of life. We know, for example, that the property that defines a solid -- resistance to deformation -- is exhibited by materials as diverse as iron, ice, and Silly Putty. The only differences are matters of scale. Iron may resist deformation more strongly than Silly Putty, but both maintain their shape if the applied forces are not too strong.

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External links

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See also

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