Phase (matter)

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In the physical sciences, a phase is a region of material that is chemically uniform, physically distinct, and (often) mechanically separable. In a system consisting of ice and water in a glass jar, the ice cubes are one phase, the water is a second phase, and the humid air is a third phase over the ice and water. The glass of the jar is another separate phase. (See state of matter § Glass.)

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More precisely, a phase is a region of space (a thermodynamic system), throughout which all physical properties of a material are essentially uniform. [1] [2] :86 [3] :3 Examples of physical properties include density, index of refraction, magnetization and chemical composition.

The term phase is sometimes used as a synonym for state of matter, but there can be several immiscible phases of the same state of matter (as where oil and water separate into distinct phases, both in the liquid state). It is also sometimes used to refer to the equilibrium states shown on a phase diagram, described in terms of state variables such as pressure and temperature and demarcated by phase boundaries. (Phase boundaries relate to changes in the organization of matter, including for example a subtle change within the solid state from one crystal structure to another, as well as state-changes such as between solid and liquid.) These two usages are not commensurate with the formal definition given above and the intended meaning must be determined in part from the context in which the term is used.

A small piece of rapidly melting argon ice shows the transition from solid to liquid. Argon ice 1.jpg
A small piece of rapidly melting argon ice shows the transition from solid to liquid.

Types of phases

Iron-carbon phase diagram, showing the conditions necessary to form different phases Iron carbon phase diagram.svg
Iron-carbon phase diagram, showing the conditions necessary to form different phases

Distinct phases may be described as different states of matter such as gas, liquid, solid, plasma or Bose–Einstein condensate. Useful mesophases between solid and liquid form other states of matter.

Distinct phases may also exist within a given state of matter. As shown in the diagram for iron alloys, several phases exist for both the solid and liquid states. Phases may also be differentiated based on solubility as in polar (hydrophilic) or non-polar (hydrophobic). A mixture of water (a polar liquid) and oil (a non-polar liquid) will spontaneously separate into two phases. Water has a very low solubility (is insoluble) in oil, and oil has a low solubility in water. Solubility is the maximum amount of a solute that can dissolve in a solvent before the solute ceases to dissolve and remains in a separate phase. A mixture can separate into more than two liquid phases and the concept of phase separation extends to solids, i.e., solids can form solid solutions or crystallize into distinct crystal phases. Metal pairs that are mutually soluble can form alloys, whereas metal pairs that are mutually insoluble cannot.

As many as eight immiscible liquid phases have been observed. [lower-alpha 1] Mutually immiscible liquid phases are formed from water (aqueous phase), hydrophobic organic solvents, perfluorocarbons (fluorous phase), silicones, several different metals, and also from molten phosphorus. Not all organic solvents are completely miscible, e.g. a mixture of ethylene glycol and toluene may separate into two distinct organic phases. [lower-alpha 2]

Phases do not need to macroscopically separate spontaneously. Emulsions and colloids are examples of immiscible phase pair combinations that do not physically separate.

Phase equilibrium

Left to equilibration, many compositions will form a uniform single phase, but depending on the temperature and pressure even a single substance may separate into two or more distinct phases. Within each phase, the properties are uniform but between the two phases properties differ.

Water in a closed jar with an air space over it forms a two-phase system. Most of the water is in the liquid phase, where it is held by the mutual attraction of water molecules. Even at equilibrium molecules are constantly in motion and, once in a while, a molecule in the liquid phase gains enough kinetic energy to break away from the liquid phase and enter the gas phase. Likewise, every once in a while a vapor molecule collides with the liquid surface and condenses into the liquid. At equilibrium, evaporation and condensation processes exactly balance and there is no net change in the volume of either phase.

At room temperature and pressure, the water jar reaches equilibrium when the air over the water has a humidity of about 3%. This percentage increases as the temperature goes up. At 100 °C and atmospheric pressure, equilibrium is not reached until the air is 100% water. If the liquid is heated a little over 100 °C, the transition from liquid to gas will occur not only at the surface but throughout the liquid volume: the water boils.

Number of phases

A typical phase diagram for a single-component material, exhibiting solid, liquid and gaseous phases. The solid green line shows the usual shape of the liquid-solid phase line. The dotted green line shows the anomalous behavior of water when the pressure increases. The triple point and the critical point are shown as red dots. Phase-diag2.svg
A typical phase diagram for a single-component material, exhibiting solid, liquid and gaseous phases. The solid green line shows the usual shape of the liquid–solid phase line. The dotted green line shows the anomalous behavior of water when the pressure increases. The triple point and the critical point are shown as red dots.

For a given composition, only certain phases are possible at a given temperature and pressure. The number and type of phases that will form is hard to predict and is usually determined by experiment. The results of such experiments can be plotted in phase diagrams.

The phase diagram shown here is for a single component system. In this simple system, phases that are possible, depend only on pressure and temperature. The markings show points where two or more phases can co-exist in equilibrium. At temperatures and pressures away from the markings, there will be only one phase at equilibrium.

In the diagram, the blue line marking the boundary between liquid and gas does not continue indefinitely, but terminates at a point called the critical point. As the temperature and pressure approach the critical point, the properties of the liquid and gas become progressively more similar. At the critical point, the liquid and gas become indistinguishable. Above the critical point, there are no longer separate liquid and gas phases: there is only a generic fluid phase referred to as a supercritical fluid. In water, the critical point occurs at around 647 K (374 °C or 705 °F) and 22.064 MPa.

An unusual feature of the water phase diagram is that the solid–liquid phase line (illustrated by the dotted green line) has a negative slope. For most substances, the slope is positive as exemplified by the dark green line. This unusual feature of water is related to ice having a lower density than liquid water. Increasing the pressure drives the water into the higher density phase, which causes melting.

Another interesting though not unusual feature of the phase diagram is the point where the solid–liquid phase line meets the liquid–gas phase line. The intersection is referred to as the triple point. At the triple point, all three phases can coexist.

Experimentally, phase lines are relatively easy to map due to the interdependence of temperature and pressure that develops when multiple phases form. Gibbs' phase rule suggests that different phases are completely determined by these variables. Consider a test apparatus consisting of a closed and well-insulated cylinder equipped with a piston. By controlling the temperature and the pressure, the system can be brought to any point on the phase diagram. From a point in the solid stability region (left side of the diagram), increasing the temperature of the system would bring it into the region where a liquid or a gas is the equilibrium phase (depending on the pressure). If the piston is slowly lowered, the system will trace a curve of increasing temperature and pressure within the gas region of the phase diagram. At the point where gas begins to condense to liquid, the direction of the temperature and pressure curve will abruptly change to trace along the phase line until all of the water has condensed.

Interfacial phenomena

Between two phases in equilibrium there is a narrow region where the properties are not that of either phase. Although this region may be very thin, it can have significant and easily observable effects, such as causing a liquid to exhibit surface tension. In mixtures, some components may preferentially move toward the interface. In terms of modeling, describing, or understanding the behavior of a particular system, it may be efficacious to treat the interfacial region as a separate phase.

Crystal phases

A single material may have several distinct solid states capable of forming separate phases. Water is a well-known example of such a material. For example, water ice is ordinarily found in the hexagonal form ice Ih, but can also exist as the cubic ice Ic, the rhombohedral ice II, and many other forms. Polymorphism is the ability of a solid to exist in more than one crystal form. For pure chemical elements, polymorphism is known as allotropy. For example, diamond, graphite, and fullerenes are different allotropes of carbon.

Phase transitions

When a substance undergoes a phase transition (changes from one state of matter to another) it usually either takes up or releases energy. For example, when water evaporates, the increase in kinetic energy as the evaporating molecules escape the attractive forces of the liquid is reflected in a decrease in temperature. The energy required to induce the phase transition is taken from the internal thermal energy of the water, which cools the liquid to a lower temperature; hence evaporation is useful for cooling. See Enthalpy of vaporization. The reverse process, condensation, releases heat. The heat energy, or enthalpy, associated with a solid to liquid transition is the enthalpy of fusion and that associated with a solid to gas transition is the enthalpy of sublimation.

Phases out of equilibrium

While phases of matter are traditionally defined for systems in thermal equilibrium, work on quantum many-body localized (MBL) systems has provided a framework for defining phases out of equilibrium. MBL phases never reach thermal equilibrium, and can allow for new forms of order disallowed in equilibrium via a phenomenon known as localization protected quantum order. The transitions between different MBL phases and between MBL and thermalizing phases are novel dynamical phase transitions whose properties are active areas of research.

Notes

  1. One such system is, from the top: mineral oil, silicone oil, water, aniline, perfluoro(dimethylcyclohexane), white phosphorus, gallium, and mercury. The system remains indefinitely separated at 45 °C, where gallium and phosphorus are in the molten state. From Reichardt, C. (2006). Solvents and Solvent Effects in Organic Chemistry. Wiley-VCH. pp. 9–10. ISBN   978-3-527-60567-5.
  2. This phenomenon can be used to help with catalyst recycling in Heck vinylation. See Bhanage, B.M.; et al. (1998). "Comparison of activity and selectivity of various metal-TPPTS complex catalysts in ethylene glycol — toluene biphasic Heck vinylation reactions of iodobenzene". Tetrahedron Letters . 39 (51): 9509–9512. doi:10.1016/S0040-4039(98)02225-4.

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<span class="mw-page-title-main">Evaporation</span> Type of vaporization of a liquid that occurs from its surface; surface phenomenon

Evaporation is a type of vaporization that occurs on the surface of a liquid as it changes into the gas phase. A high concentration of the evaporating substance in the surrounding gas significantly slows down evaporation, such as when humidity affects rate of evaporation of water. When the molecules of the liquid collide, they transfer energy to each other based on how they collide. When a molecule near the surface absorbs enough energy to overcome the vapor pressure, it will escape and enter the surrounding air as a gas. When evaporation occurs, the energy removed from the vaporized liquid will reduce the temperature of the liquid, resulting in evaporative cooling.

<span class="mw-page-title-main">Solution (chemistry)</span> Homogeneous mixture of a solute and a solvent

In chemistry, a solution is a special type of homogeneous mixture composed of two or more substances. In such a mixture, a solute is a substance dissolved in another substance, known as a solvent. If the attractive forces between the solvent and solute particles are greater than the attractive forces holding the solute particles together, the solvent particles pull the solute particles apart and surround them. These surrounded solute particles then move away from the solid solute and out into the solution. The mixing process of a solution happens at a scale where the effects of chemical polarity are involved, resulting in interactions that are specific to solvation. The solution usually has the state of the solvent when the solvent is the larger fraction of the mixture, as is commonly the case. One important parameter of a solution is the concentration, which is a measure of the amount of solute in a given amount of solution or solvent. The term "aqueous solution" is used when one of the solvents is water.

<span class="mw-page-title-main">Triple point</span> Thermodynamic point where three matter phases exist

In thermodynamics, the triple point of a substance is the temperature and pressure at which the three phases of that substance coexist in thermodynamic equilibrium. It is that temperature and pressure at which the sublimation, fusion, and vaporisation curves meet. For example, the triple point of mercury occurs at a temperature of −38.8 °C (−37.8 °F) and a pressure of 0.165 mPa.

<span class="mw-page-title-main">State of matter</span> Distinct forms that matter take on

In physics, a state of matter is one of the distinct forms in which matter can exist. Four states of matter are observable in everyday life: solid, liquid, gas, and plasma. Many intermediate states are known to exist, such as liquid crystal, and some states only exist under extreme conditions, such as Bose–Einstein condensates and Fermionic condensates, neutron-degenerate matter, and quark–gluon plasma. For a list of exotic states of matter, see the article List of states of matter.

<span class="mw-page-title-main">Enthalpy of vaporization</span> Energy to convert a liquid substance to a gas at a given pressure

In thermodynamics, the enthalpy of vaporization, also known as the (latent) heat of vaporization or heat of evaporation, is the amount of energy (enthalpy) that must be added to a liquid substance to transform a quantity of that substance into a gas. The enthalpy of vaporization is a function of the pressure and temperature at which the transformation takes place.

<span class="mw-page-title-main">Vapor pressure</span> Pressure exerted by a vapor in thermodynamic equilibrium

Vapor pressure or equilibrium vapor pressure is the pressure exerted by a vapor in thermodynamic equilibrium with its condensed phases at a given temperature in a closed system. The equilibrium vapor pressure is an indication of a liquid's thermodynamic tendency to evaporate. It relates to the balance of particles escaping from the liquid in equilibrium with those in a coexisting vapor phase. A substance with a high vapor pressure at normal temperatures is often referred to as volatile. The pressure exhibited by vapor present above a liquid surface is known as vapor pressure. As the temperature of a liquid increases, the attractive interactions between liquid molecules become less significant in comparison to the entropy of those molecules in the gas phase, increasing the vapor pressure. Thus, liquids with strong intermolecular interactions are likely to have smaller vapor pressures, with the reverse true for weaker interactions.

<span class="mw-page-title-main">Condensation</span> Condensation is the change of state of matter from a gas phase into a liquid phase.

Condensation is the change of the state of matter from the gas phase into the liquid phase, and is the reverse of vaporization. The word most often refers to the water cycle. It can also be defined as the change in the state of water vapor to liquid water when in contact with a liquid or solid surface or cloud condensation nuclei within the atmosphere. When the transition happens from the gaseous phase into the solid phase directly, the change is called deposition.

<span class="mw-page-title-main">Phase diagram</span> Chart used to show conditions at which physical phases of a substance occur

A phase diagram in physical chemistry, engineering, mineralogy, and materials science is a type of chart used to show conditions at which thermodynamically distinct phases occur and coexist at equilibrium.

<span class="mw-page-title-main">Solubility</span> Capacity of a substance to dissolve in a solvent in a homogeneous way

In chemistry, solubility is the ability of a substance, the solute, to form a solution with another substance, the solvent. Insolubility is the opposite property, the inability of the solute to form such a solution.

In physical chemistry, supersaturation occurs with a solution when the concentration of a solute exceeds the concentration specified by the value of solubility at equilibrium. Most commonly the term is applied to a solution of a solid in a liquid, but it can also be applied to liquids and gases dissolved in a liquid. A supersaturated solution is in a metastable state; it may return to equilibrium by separation of the excess of solute from the solution, by dilution of the solution by adding solvent, or by increasing the solubility of the solute in the solvent.

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<span class="mw-page-title-main">Sublimation (phase transition)</span> Transition of a substance directly from the solid to the gas state

Sublimation is the transition of a substance directly from the solid to the gas state, without passing through the liquid state. The verb form of sublimation is sublime, or less preferably, sublimate. Sublimate also refers to the product obtained by sublimation. The point at which sublimation occurs rapidly is called critical sublimation point, or simply sublimation point. Notable examples include sublimation of dry ice at room temperature and atmospheric pressure, and that of solid iodine with heating.

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<span class="mw-page-title-main">Crystallization</span> Process by which a solid with a highly organized atomic or molecular structure forms

Crystallization is the process by which solid forms, where the atoms or molecules are highly organized into a structure known as a crystal. Some ways by which crystals form are precipitating from a solution, freezing, or more rarely deposition directly from a gas. Attributes of the resulting crystal depend largely on factors such as temperature, air pressure, and in the case of liquid crystals, time of fluid evaporation.

This glossary of chemistry terms is a list of terms and definitions relevant to chemistry, including chemical laws, diagrams and formulae, laboratory tools, glassware, and equipment. Chemistry is a physical science concerned with the composition, structure, and properties of matter, as well as the changes it undergoes during chemical reactions; it features an extensive vocabulary and a significant amount of jargon.

<span class="mw-page-title-main">Liquid</span> State of matter

A liquid is a nearly incompressible fluid that conforms to the shape of its container but retains a nearly constant volume independent of pressure. It is one of the four fundamental states of matter, and is the only state with a definite volume but no fixed shape.

<span class="mw-page-title-main">Enthalpy of fusion</span> Enthalpy change when a substance melts

In thermodynamics, the enthalpy of fusion of a substance, also known as (latent) heat of fusion, is the change in its enthalpy resulting from providing energy, typically heat, to a specific quantity of the substance to change its state from a solid to a liquid, at constant pressure.

References

  1. Modell, Michael; Robert C. Reid (1974). Thermodynamics and Its Applications . Englewood Cliffs, NJ: Prentice-Hall. ISBN   978-0-13-914861-3.
  2. Enrico Fermi (2012). Thermodynamics. Courier Corporation. ISBN   978-0-486-13485-7.
  3. Clement John Adkins (1983). Equilibrium Thermodynamics. Cambridge University Press. ISBN   978-0-521-27456-2.