Water has some amazing properties.

Rain drops falling on still water

New Clue In The Mystery Of Glassy Water
Water has some amazing properties. It is the only natural substance found in all three states -- solid, liquid and gas -- within the range of natural Earth temperatures. Its solid form is less dense than its liquid form, which is why ice floats. It can absorb a great deal of heat without getting hot, has very high surface tension (helping it move through roots and capillaries -- vital to maintaining life on Earth) and is virtually incompressible.

A less commonly known distinction of water, but one of great interest to physical chemists, is its odd behavior at its transition to the glassy phase. The "glassy state" is a sub-state of matter -- glassy water and ice, for example, are chemically identical and have the same state (solid), but have a different structure. Put another way, ice is crystalline, whereas glass is, well, chunky. As water makes the transition to its glassy state, it behaves very oddly, a fact that has baffled scientists.

Arizona State University Regents Professor C. Austen Angell has found a vital clue that helps explain water's bizarre behavior at the glass transition and, along the way, gained important insights into phases of liquid water as well. His research is published in the Feb. 1, 2008 issue of the journal Science.

"We know a lot about glasses that form from ordinary silicates, sugars and metals," Angell says. "They're making golf clubs out of glassy metals these days. But how important is the glassy state of water" And what can it tell us about ordinary water, which is such an anomalous liquid?"

Most glassy forms of matter experience a gradual increase in heat capacity -- the amount of energy it takes to heat a sample by one degree Kelvin -- until a key transition point is reached. At that point (called the "glass temperature"), these materials suddenly up-jump to a new, 100 percent higher, heat capacity zone and change from a solid to very viscous liquid phase -- as if a solid brick of cold honey were heated and suddenly became a sticky liquid again. This occurs even in solutions in which water is the chief component.

In pure water, however, something quite different happens. As cold, glassy water is heated, its heat capacity barely changes until about 136 K (-215 F), where it begins to increase slightly. Then, abruptly at 150 K (-190 F), it crystallizes and stops being glassy. Approached from the other direction, supercooling water produces a similarly odd effect: Heat capacity remains constant as the water cools until around 250 K (-10 F), when it begins to increase very rapidly with decreasing temperature.

Angell wanted to know what was transpiring in the "no man's land" between 150 and 250 K (-190 and -10 F). Where, he wondered, was the "real" glass transition for glassy water?

He solved the problem by looking at the behavior of both supercooled water and "nanoconfined" glassy ice. Nanoconfined water is water that has been squeezed into pores with a diameter of about 20 angstroms, or 20 hundred-millionths of a meter (roughly five times the scale of atoms and chemical bonds). Using the behavior of water in these states and combining it with a hypothetical behavior of bulk water deduced using the laws of thermodynamics, he was able to bracket the possible heat capacity of water in the "no man's land" and come up with a novel cooperative transition to explain the substance's odd behavior.

"Water's heat capacity suddenly goes crazy near this transition and, before we can see what is happening, it crystallizes," Angell says. "One trick for finding out what is going on in there is to put the water in a confinement -- to make it nanoscopic so that it forgets how to crystallize. We see the same behavior but with no data gap."

According to Angell, water does not behave like the usual glass formers and therefore lacks the characteristic heat-capacity jump (glass transition) to the glassy phase; instead, because of its unusual hydrogen bond network, it behaves as if it is in a crystalline phase, making what is known as an "order-disorder transition." This sucks out all of the heat capacity at temperatures around 220 K and explains why the glass transition in water (near 136 K) is so undramatic compared to other substances.

It also gave Angell an idea for a new scenario to explain the odd behavior of supercooled water, one that is compatible with observed behavior but does not require a critical point.

"I wanted to find the answer to the puzzle of what was happening in 'no man's land,'" Angell says. "And so I worked up from the glassy state and nanoconfinement."

"In the end, we say, 'Well that that's not what bulk water would do -- that's been thrust upon it by making it so tiny,'" he explains. "But nevertheless it's an important part of the picture and it supports the conclusion that we've got a different sort of thermodynamics in water than we have in any of these other molecular glass-forming liquids."

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Weird Water: Discovery Challenges Long-held Beliefs About Water's Special Properties


Water has some amazing properties. It is the only natural substance found in all three states -- solid, liquid and gas -- within the range of natural Earth temperatures. Its solid form is less dense than its liquid form, which is why ice floats. It can absorb a great deal of heat without getting hot, has very high surface tension (helping it move through roots and capillaries -- vital to maintaining life on Earth) and is virtually incompressible.
The simple fact that water expands when it freezes -- an effect known to anyone whose plumbing has burst in winter -- is just the beginning of a long list of special characteristics. (Most liquids contract when they freeze.)

That is why chemical engineer Pablo Debenedetti and collaborators at three other institutions were surprised to find a highly simplified model molecule that behaves in much the same way as water, a discovery that upends long-held beliefs about what makes water so special.

"The conventional wisdom is that water is unique," said Debenedetti, the Class of 1950 Professor in Engineering and Applied Science. "And here we have a very simple model that displays behaviors that are very hard to get in anything but water. It forces you to rethink what is unique about water."

While their water imitator is hypothetical -- it was created with computer software that is commonly used for simulating interactions between molecules -- the researchers' discovery may ultimately have implications for industrial or pharmaceutical research. "I would be very interested to see if experimentalists could create colloids (small particles suspended in liquid) that exhibit the water-like properties we observed in our simulations," Debenedetti said. Such laboratory creations might be useful in controlling the self-assembly of complex biomolecules or detergents and other surfactants. .

More fundamentally, the research raises questions about why oil and water don't mix, because the simulated molecule repels oil as water does, but without the delicate interactions between hydrogen and oxygen that are thought to give water much of its special behavior.

The discovery builds on an earlier advance by the same researchers. It had previously been shown that simple molecules can show some water-like features. In 2006, the collaborators published a paper showing that they could induce water-like peculiarities by adjusting the distance at which pairs of particles start to repel each other. Like water, their simulated substance expanded when cooled and became more slippery when pressurized. That finding led them to investigate more closely. They decided to look at how their simulated molecule acts as a solvent -- that is, how it behaves when other materials are dissolved into it -- because water's behavior as a solvent is also unique.

In their current paper, they simulated the introduction of oily materials into their imitator and showed that it had the same oil-water repulsion as real water across a range of temperatures. They also simulated dissolving oily polymers into their substance and, again, found water-like behavior. In particular, the polymers swelled not only when the "water" was heated, but also when it was super-cooled, which is one defining characteristic of real water. Proteins with oily interiors also behave in this way.

In real water, these special behaviors are thought to arise from water's structure -- two hydrogen atoms attached to an oxygen atom. The arrangement of electrical charges causes water molecules to twist and stick to each other in complex ways.

To create their simulation, the researchers ignored these complexities. They specified just two properties: the distance at which two converging particles start to repel each other and the distance at which they actually collide like billiard balls. Their particles could be made of anything -- plastic beads, for example -- and so long as the ratio between these two distances was correct (7:4), then they would display many of the same characteristics as water.

"This model is so simple it is almost a caricature," Debenedetti said. "And yet it has these very special properties. To show that you can have oil-water repulsion without hydrogen bonds is quite interesting."

Debenedetti noted that their particles differ from water in key aspects. When it freezes, for example, the crystals do not look anything like ice. For that reason, the research should not be viewed as leading toward a "water substitute."

As a next step, Debenedetti said he would like to see if experimentalists could create particles that have the same simple specifications as their model and see if their behavior matches the computer simulation.

The researchers published their findings Dec. 12 in the Proceedings of the National Academy of Sciences. The team also included lead author Sergey V. Buldyrev of Yeshiva University, Pradeep Kumar and H. Eugene Stanley of Boston University, and Peter J. Rossky of the University of Texas. The research was funded by the National Science Foundation through a grant shared by Debenedetti, Rossky and Stanley.