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Phase separation

physical science Maturity 9-11 Next article →

Phase separation is a physical process where a single, uniform mixture splits into two distinct parts. This phenomenon is known as the creation of different phases from a homogeneous mixture.

Phase separation janus particles
Phase separation janus particles

One common example is liquid-liquid equilibrium, which occurs between two liquids that do not mix, or are immiscible. You might see this when oil and water are combined. While some phase separations result in layers under gravity, others create colloids. Colloids are mixtures where tiny droplets remain suspended in a liquid. Understanding this process helps scientists study how matter organizes itself at different scales.

Olive oil with Balsamic Vinegar
Olive oil with Balsamic Vinegar

The underlying mechanism of phase separation is governed by Gibbs free energy. This energy determines whether a system will stay mixed or choose to separate. The total Gibbs free energy is composed of two specific parts: enthalpy and entropy. The change in free energy during mixing is the sum of the enthalpy of mixing and the entropy of mixing. In many common solutions, the enthalpy of mixing is zero. These are called ideal mixtures. In these cases, the process is driven primarily by the entropy of mixing.

Entropy is a measure related to the space available for particles to explore. Generally, entropy increases when atoms or molecules have a larger common volume to share. Because a higher entropy usually lowers the Gibbs free energy, mixing is often favored. However, phase separation occurs when the energy balance shifts. If the enthalpy of mixing is positive and the temperature is low, the increase in entropy cannot lower the free energy enough to keep the mixture stable. In rare cases, the entropy of mixing is actually unfavorable, meaning it is negative. This leads to the concept of the lower critical solution temperature (LCST).

Helium phase diagram
Helium phase diagram

Scientists use phase diagrams to map out where these changes happen. These diagrams contain regions called miscibility gaps where phase separation occurs. Within these diagrams, there are two critical boundary curves. The first is the binodal coexistence curve, and the second is the spinodal curve. The state of a mixture depends on its position relative to these lines. On one side of the binodal curve, mixtures are considered absolutely stable. In the area between the binodal and the spinodal curves, mixtures are metastable. A metastable mixture may stay mixed or unmixed until a large disturbance occurs.

Beyond the spinodal curve, the mixture enters a state of absolute instability. If a mixture starts in a mixed state within this region, it will undergo spontaneous phase separation. This specific type of spontaneous separation is called spinodal decomposition. The Cahn–Hilliard equation is used to describe this process. Temperature also plays a vital role through critical temperatures. The upper critical solution temperature (UCST) and the lower critical solution temperature (LCST) are key markers. Above the UCST or below the LCST, components are miscible, meaning they can mix in all proportions.

Helium phase diagram
Helium phase diagram

Some systems are unique because they possess both a UCST and an LCST. The nicotine-water system is a notable example of this complexity. It has an LCST of 61 °C. It also has a UCST of 210 °C, provided the pressure is high enough for liquid water to exist. Because of these two points, nicotine and water are miscible in all proportions below 61 °C. They are also miscible above 210 °C at high pressure. However, in the interval between 61 and 210 °C, they are only partially miscible.

Helium phase diagram
Helium phase diagram

Phase separation can also be observed in gases, particularly at very low temperatures. For example, a mixture of two helium isotopes, helium-3 and helium-4, will separate. This mixture spontaneously divides into regions that are rich in helium-4 and regions that are rich in helium-3. Scientists also observe phase separation in ultracold gas systems, such as a two-component ultracold Fermi gas. In these extreme environments, phase separation can compete with other complex phenomena. These include vortex lattice formation or the exotic Fulde-Ferrell-Larkin-Ovchinnikov phase. This shows how phase separation connects to advanced condensed matter physics.

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File:Phase separation janus particles.svg
Phase separation janus particles.svg
File:Olive oil with Balsamic Vinegar.jpg
Olive oil with Balsamic Vinegar.jpg
File:Helium phase diagram.svg
Helium phase diagram.svg
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