Critical opalescence

Last updated
Left-to-right sequence of heating a mass of ethane in a constant volume. In the center panel, critical opalescence is seen. CriticalPointMeasurementEthane.jpg
Left-to-right sequence of heating a mass of ethane in a constant volume. In the center panel, critical opalescence is seen.

In physics, critical opalescence refers to the dramatic increase in scattering of light in the region of a continuous, or second-order, phase transition. Near the critical point, the properties of the liquid and gas phases become indistinguishable. The resulting density fluctuations are on such a large scale that they scatter visible light, giving the substance a cloudy or opalescent look. This phenomenon is an indicator of critical phenomena in fluids and can be observed in various materials under the right conditions.

Contents

History

Originally reported by French physicist Charles Cagniard de la Tour in 1823 in mixtures of alcohol and water, its importance was recognised by Irish chemist Thomas Andrews in 1869 following his experiments on the liquid-gas transition in carbon dioxide; many other examples have been discovered since. In 1908 the Polish physicist Marian Smoluchowski became the first to ascribe the phenomenon of critical opalescence to large density fluctuations. In 1910 Albert Einstein showed that the link between critical opalescence and Rayleigh scattering is quantitative. [1]

Examples

Binary fluid mixtures

The phenomenon is most commonly demonstrated in binary fluid mixtures, such as methanol and cyclohexane. As the critical point is approached, the sizes of the gas and liquid region begin to fluctuate over increasingly large length scales (the correlation length of the liquid diverges). As the density fluctuations become of a size comparable to the wavelength of light, the light is scattered and causes the normally transparent liquid to appear cloudy. Tellingly, the opalescence does not diminish as one gets closer to the critical point, where the largest fluctuations can reach even centimetre proportions, confirming the physical relevance of smaller fluctuations.

Approaching the critical point from the opposite direction, in case of liquid-gas transition, the gas phase may contain drops of liquid as mist and spray, and the boiling liquid phase bubbles of gas phase as foam. Far from the critical point the gravity causes liquid drops and gas bubbles to rapidly settle towards the interface and surface tension causes drops and bubbles to rapidly merge to larger ones, which settle even faster. But as critical point is approached, the density difference between liquid and vapour diminishes and so does the surface tension. These effects will slow down settling of drops and bubbles and their merger, such that boiling liquid forms increasingly refractory to settling and fine mist and foam around the interface.

In case of liquid-liquid critical point, again the liquids of limited solubility precipitate out as emulsions which far from critical point on the immiscible side readily settle to interface. As critical point is approached, density difference decreases along with the interfacial surface tension, so that precipitation takes place as increasingly fine and refractory to settling emulsion.

Since liquid-gas critical point occurs at pressures over 30 bar for all substances except some cryogenic gases, demonstrating it requires a transparent vessel safe under over 30 bar, while liquid-liquid critical point for many systems can be demonstrated at ambient pressure and modest temperatures.

Other examples

Ferromagnetic material has large fluctuations of magnetic domains near the Curie point. And since neutron scattering is affected by magnetic moments of atoms, this creates critical opalescence. Specifically, if a beam of neutrons is fired at a ferromagnetic material, then as it approaches the Curie point, it would start scattering the neutrons as if it is turning opaque to neutrons. [2]

Related Research Articles

<span class="mw-page-title-main">Condensed matter physics</span> Branch of physics

Condensed matter physics is the field of physics that deals with the macroscopic and microscopic physical properties of matter, especially the solid and liquid phases, that arise from electromagnetic forces between atoms and electrons. More generally, the subject deals with condensed phases of matter: systems of many constituents with strong interactions among them. More exotic condensed phases include the superconducting phase exhibited by certain materials at extremely low cryogenic temperatures, the ferromagnetic and antiferromagnetic phases of spins on crystal lattices of atoms, the Bose–Einstein condensates found in ultracold atomic systems, and liquid crystals. Condensed matter physicists seek to understand the behavior of these phases by experiments to measure various material properties, and by applying the physical laws of quantum mechanics, electromagnetism, statistical mechanics, and other physics theories to develop mathematical models and predict the properties of extremely large groups of atoms.

An emulsion is a mixture of two or more liquids that are normally immiscible owing to liquid-liquid phase separation. Emulsions are part of a more general class of two-phase systems of matter called colloids. Although the terms colloid and emulsion are sometimes used interchangeably, emulsion should be used when both phases, dispersed and continuous, are liquids. In an emulsion, one liquid is dispersed in the other. Examples of emulsions include vinaigrettes, homogenized milk, liquid biomolecular condensates, and some cutting fluids for metal working.

<span class="mw-page-title-main">Phase (matter)</span> Region of uniform physical properties

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 a different material, in its own separate phase.

<span class="mw-page-title-main">State of matter</span> Forms, such as solid, liquid and gas, which matter can take

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.

<span class="mw-page-title-main">Boiling</span> Rapid phase transition from liquid to gas or vapour

Boiling or ebullition is the rapid phase transition from liquid to gas or vapour; the reverse of boiling is condensation. Boiling occurs when a liquid is heated to its boiling point, so that the vapour pressure of the liquid is equal to the pressure exerted on the liquid by the surrounding atmosphere. Boiling and evaporation are the two main forms of liquid vapourization.

<span class="mw-page-title-main">Phase transition</span> Physical process of transition between basic states of matter

In physics, chemistry, and other related fields like biology, a phase transition is the physical process of transition between one state of a medium and another. Commonly the term is used to refer to changes among the basic states of matter: solid, liquid, and gas, and in rare cases, plasma. A phase of a thermodynamic system and the states of matter have uniform physical properties. During a phase transition of a given medium, certain properties of the medium change as a result of the change of external conditions, such as temperature or pressure. This can be a discontinuous change; for example, a liquid may become gas upon heating to its boiling point, resulting in an abrupt change in volume. The identification of the external conditions at which a transformation occurs defines the phase transition point.

<span class="mw-page-title-main">Surface tension</span> Tendency of a liquid surface to shrink to reduce surface area

Surface tension is the tendency of liquid surfaces at rest to shrink into the minimum surface area possible. Surface tension is what allows objects with a higher density than water such as razor blades and insects to float on a water surface without becoming even partly submerged.

<span class="mw-page-title-main">Curie temperature</span> Temperature above which magnetic properties change

In physics and materials science, the Curie temperature (TC), or Curie point, is the temperature above which certain materials lose their permanent magnetic properties, which can (in most cases) be replaced by induced magnetism. The Curie temperature is named after Pierre Curie, who showed that magnetism is lost at a critical temperature.

<span class="mw-page-title-main">Foam</span> Form of matter

Foams are two-phase material systems where a gas is disbursed in a second, non-gaseous material, specifically, in which gas cells are enclosed by a distinct liquid or solid material. The foam "may contain more or less liquid [or solid] according to circumstances", although in the case of gas-liquid foams, the gas occupies most of the volume. The word derives from the medieval German and otherwise obsolete veim, in reference to the "frothy head forming in the glass once the beer has been freshly poured".

<span class="mw-page-title-main">Suspension (chemistry)</span> Heterogeneous mixture of solid particles dispersed in a medium

In chemistry, a suspension is a heterogeneous mixture of a fluid that contains solid particles sufficiently large for sedimentation. The particles may be visible to the naked eye, usually must be larger than one micrometer, and will eventually settle, although the mixture is only classified as a suspension when and while the particles have not settled out.

In physics, critical phenomena is the collective name associated with the physics of critical points. Most of them stem from the divergence of the correlation length, but also the dynamics slows down. Critical phenomena include scaling relations among different quantities, power-law divergences of some quantities described by critical exponents, universality, fractal behaviour, and ergodicity breaking. Critical phenomena take place in second order phase transitions, although not exclusively.

<span class="mw-page-title-main">Two-phase flow</span> Flow of gas and liquid in the same conduit

In fluid mechanics, two-phase flow is a flow of gas and liquid — a particular example of multiphase flow. Two-phase flow can occur in various forms, such as flows transitioning from pure liquid to vapor as a result of external heating, separated flows, and dispersed two-phase flows where one phase is present in the form of particles, droplets, or bubbles in a continuous carrier phase.

<span class="mw-page-title-main">Magnon</span> Spin 1 quasiparticle; quantum of a spin wave

A magnon is a quasiparticle, a collective excitation of the spin structure of an electron in a crystal lattice. In the equivalent wave picture of quantum mechanics, a magnon can be viewed as a quantized spin wave. Magnons carry a fixed amount of energy and lattice momentum, and are spin-1, indicating they obey boson behavior.

Complex fluids are mixtures that have a coexistence between two phases: solid–liquid, solid–gas (granular), liquid–gas (foams) or liquid–liquid (emulsions). They exhibit unusual mechanical responses to applied stress or strain due to the geometrical constraints that the phase coexistence imposes. The mechanical response includes transitions between solid-like and fluid-like behavior as well as fluctuations. Their mechanical properties can be attributed to characteristics such as high disorder, caging, and clustering on multiple length scales.

<span class="mw-page-title-main">Critical point (thermodynamics)</span> Temperature and pressure point where phase boundaries disappear

In thermodynamics, a critical point is the end point of a phase equilibrium curve. One example is the liquid–vapor critical point, the end point of the pressure–temperature curve that designates conditions under which a liquid and its vapor can coexist. At higher temperatures, the gas comes into a supercritical phase, and so cannot be liquefied by pressure alone. At the critical point, defined by a critical temperatureTc and a critical pressurepc, phase boundaries vanish. Other examples include the liquid–liquid critical points in mixtures, and the ferromagnet–paramagnet transition in the absence of an external magnetic field.

<span class="mw-page-title-main">Fluidized bed</span> Physical phenomenon

A fluidized bed is a physical phenomenon that occurs when a solid particulate substance is under the right conditions so that it behaves like a fluid. The usual way to achieve a fluidized bed is to pump pressurized fluid into the particles. The resulting medium then has many properties and characteristics of normal fluids, such as the ability to free-flow under gravity, or to be pumped using fluid technologies.

<span class="mw-page-title-main">Ouzo effect</span> Phenomenon observed in drink mixing

The ouzo effect, also known as the louche effect and spontaneous emulsification, is the phenomenon of formation of a milky oil-in-water emulsion when water is added to ouzo and other anise-flavored liqueurs and spirits, such as pastis, rakı, arak, sambuca and absinthe. Such emulsions occur with only minimal mixing and are highly stable.

Macroemulsions are dispersed liquid-liquid, thermodynamically unstable systems with particle sizes ranging from 1 to 100 μm, which, most often, do not form spontaneously. Macroemulsions scatter light effectively and therefore appear milky, because their droplets are greater than a wavelength of light. They are part of a larger family of emulsions along with miniemulsions. As with all emulsions, one phase serves as the dispersing agent. It is often called the continuous or outer phase. The remaining phase(s) are disperse or inner phase(s), because the liquid droplets are finely distributed amongst the larger continuous phase droplets. This type of emulsion is thermodynamically unstable, but can be stabilized for a period of time with applications of kinetic energy. Surfactants are used to reduce the interfacial tension between the two phases, and induce macroemulsion stability for a useful amount of time. Emulsions can be stabilized otherwise with polymers, solid particles or proteins.

In thermodynamics, explosive boiling or phase explosion is a method whereby a superheated metastable liquid undergoes an explosive liquid-vapor phase transition into a stable two-phase state because of a massive homogeneous nucleation of vapor bubbles. This concept was pioneered by M. M. Martynyuk in 1976 and then later advanced by Fucke and Seydel.

References

  1. Einstein, A. (January 1910). "Theorie der Opaleszenz von homogenen Flüssigkeiten und Flüssigkeitsgemischen in der Nähe des kritischen Zustandes". Annalen der Physik. 338 (16): 1275–1298. doi:10.1002/andp.19103381612. ISSN   0003-3804.
  2. Van Hove, Léon (1954-09-15). "Time-Dependent Correlations between Spins and Neutron Scattering in Ferromagnetic Crystals". Physical Review. 95 (6): 1374–1384. doi:10.1103/PhysRev.95.1374.

More-detailed experimental demonstrations of critical opalescence may be found at