Physicists Break 150-Year-Old Rule for Phase Behavior – Something Many Considered Impossible

Polymers and Rods

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A five-phase stability with at the top a gas stage with unaligned rods (isotropic stage), then a liquid stage with rods pointing in about the exact same instructions (nematic liquid crystal), consequently a liquid stage with rods depending on various layers (smectic liquid crystal), and 2 strong stages at the bottom. Credit: ICMS animation studio

Eindhoven University of Technology scientists discovered 5 various stages in mixes of 2 compounds.

Frozen water can handle approximately 3 kinds at the exact same time when it melts: liquid, ice, and gas. This concept, which specifies that lots of compounds can happen in approximately 3 stages at the same time, was discussed 150 years earlier by the Gibbs stage guideline. Today, scientists from Eindhoven University of Technology and University Paris-Saclay are defying this classical theory, with evidence of a five-phase stability, something that lots of scholars thought about difficult. This brand-new understanding yields beneficial insights for markets that deal with intricate mixes, such as in the production of mayo, paint, or LCD’s. The scientists have actually released their lead to the journal Physical Review Letters.

The creator of modern thermodynamics and physical chemistry is the American physicist Josiah Willard Gibbs. In the 1870s he obtained the stage guideline, which explains the optimal variety of various stages a compound or mix of compounds can presume at the same time. For pure compounds, the Gibbs Phase Rule forecasts an optimum of 3 stages.

Professor Remco Tuinier, of the Institute for Complex Molecular Systems: “At the time, Einstein called Gibbs’ thermodynamics the only theory he really trusted. If we take water as an example, there is one point, with a specific temperature and pressure, where water occurs as gas, liquid, and ice at the same time. The so-called triple point.” Assistant teacher Mark Vis, from the exact same research study group as Tuinier, includes: “This classic Gibbs phase rule is as solid as a rock and has never been defied.”

Shape matters

According to this stage guideline, the mix studied by the scientists would likewise display an optimum of 3 stages at one particular point at the exact same time. But Tuinier and his associates now reveal that in this mix there is an entire series of scenarios in which 4 stages exist at the exact same time. There is even one point at which there are 5 existing side-by-side stages. Two a lot of, according to Gibbs. At that particular one point, likewise called a five-phase stability, a gas stage, 2 liquid crystal stages, and 2 strong stages with ‘ordinary’ crystals exist at the same time. And that has actually never ever been seen prior to. “This is the first time that the famous Gibbs rule has been broken,” Vis states enthusiastically.

The essence depends on the shape of the particles in the mix. Gibbs did not take this into factor to consider, however the Eindhoven researchers now reveal that it is specifically the particular length and size of the particles that play a significant function. Tuinier: “In addition to the known variables of temperature and pressure, you get two additional variables: the length of the particle in relation to its diameter, and the diameter of the particle in relation to the diameter of other particles in the solution.”

Ranked rods

In their theoretical designs, the scientists dealt with a mix of 2 compounds in a background solvent: rods and polymers. This is likewise called a colloidal system, in which the particles are strong and the medium is liquid. Because the particles cannot inhabit precisely the exact same area, they connect with each other. “This is also called the excluded volume effect; it causes the rods to want to sit together. They are, as it were, pushed towards each other by the polymer chains. In this way, you get a region in the mixture that mainly contains rods, and an area that is rich in polymers,” discusses Tuinier.

He continues: “The rods then sink to the bottom, because they’re usually heavier. That’s the beginning of segregation, creating phases.” The lower part, which primarily includes rods, will ultimately end up being so crowded that the rods will disrupt each other. They then use up a preferential position, so that they are less in each other’s method.

With the rods it appears like a cool plan beside each other. Eventually you get 5 various stages, a gas stage with unaligned rods at the top (an isotropic stage), a liquid stage with rods pointing in about the exact same instructions (nematic liquid crystal), a liquid stage with rods depending on various layers (smectic liquid crystal), and 2 strong stages at the bottom.

Mayonnaise and displays

Vis: “Our research contributes to the fundamental knowledge about this kind of phase transition and helps to understand and predict more precisely when these kinds of transition occur.” And that works in lots of locations. Think of pumping intricate mixes around in commercial reactors, making intricate items like colloidal mixes such as mayo and paint, or ice that forms on automobile windows and black ice on roadways.

Even in liquid crystals in displays, these procedures contribute. “Most industries choose to work with a single-phase system, where there is no segregation. But if the exact transitions are clearly described, then the industry can actually use those different phases instead of avoiding them,” states Vis.


It was basically opportunity that the scientists came to a stability of more than 3 stages. When imitating and setting plate-shaped particles and polymers, PhD trainees Álvaro González García and Vincent Peters from Tuinier’s group saw a four-phase stability. Tuinier: “Álvaro came to me one day and asked me what had gone wrong. Because four phases just couldn’t be right.”

Then the scientists experimented with numerous shapes, such as cubes and likewise rods. Tuinier: “With the rods, most phases turned out to be possible, we even found a five-phase equilibrium. That could also mean that even more complicated equilibria are possible, as long as you search long enough for complex different particle shapes.”

Reference: “Defying the Gibbs Phase Rule: Evidence for an Entropy-Driven Quintuple Point in Colloid-Polymer Mixtures” by V. F. D. Peters, M. Vis, Á. González García, H. H. Wensink and R. Tuinier, 18 September 2020, Physical Review Letters.
DOI: 10.1103/PhysRevLett.125.127803

The research study has actually been performed at Eindhoven University of Technology, at the Department of Chemical Engineering and Chemistry and the Institute for Complex Molecular Systems, and at Paris-Saclay University.