For me, the epitome of stovetop alchemy is making caramel from table sugar. You start with refined sucrose, pure crystalline sweetness, put it in a pan by itself, and turn on the heat. When the sugar rises above 320°F/160°C, the solid crystals begin to melt together into a colorless syrup. Then another 10 or 20 degrees above that, the syrup begins to turn brown, emits a rich, mouth-watering aroma, and adds tart and savory and bitter to its original sweetness.
That's the magic of cooking front and center: from one odorless, colorless, simply sweet molecule, heat creates hundreds of different molecules, some aromatic and some tasty and some colored.
How does heat turn sugar into caramel? Heat is a kind of energy that makes atoms and molecules move faster. In room-temperature table sugar, the sucrose molecules are jittery but standing in place, held still by the forces of attraction to their neighbors. As the sugar heats up in the pan, its molecules get more and more jittery, to the point that their jitters overcome the attractive forces and they can jump from one set of neighbors to another. The solid crystals thus become a free-flowing liquid. Then, as the temperature of the sugar molecules continues to rise, the force of their jittering and jumping becomes stronger than the forces holding their own atoms together. The molecules break apart into fragments, and the fragments slam into each other hard enough to form new molecules.
That's what I've thought for many years, along with most cooks and confectioners and carbohydrate chemists: heat melts sugar, and then begins to break it apart and create the delicious mixture we call caramel.
And we've all been wrong.
It turns out that, strictly speaking, sugar doesn't actually melt. And it can caramelize while it's still solid. So proved chemist Shelly Schmidt and her colleagues at the University of Illinois in studies published last year.
It's dismaying to think that so many could be so wrong for so long about such a basic ingredient and process! But it's also a rare opportunity to rethink the possibilities of the basic. Here's a plateful of possibilities; scroll down for more.
Professor Schmidt's group made their discovery when they tried to nail down the precise melting point of sucrose. The figures reported in the technical literature vary widely, and it wasn't clear why.
The melting point of a substance is the temperature at which it turns from a solid into a liquid while maintaining its chemical identity. When solid ice turns into liquid water, for example, the molecules of H2O move fast enough to escape the attractive forces of their neighbors, but they're still H2O. And it doesn't matter how fast the substance heats up: the melting point is the same. Ice melts at 32°F/0°C. Always.
After careful analysis, Professor Schmidt found that whenever sugar gets hot enough to turn from a solid into a liquid, some of its molecules are also breaking apart. So sucrose doesn't have a true melting point. Instead it has a range of temperatures in which its molecules are energetic enough to shake loose from their neighbors, and a range in which the molecules jitter themselves apart and form new ones. And these two ranges overlap. Whenever sugar gets hot enough to liquefy, it's also breaking down and turning into caramel. But it starts to break down even before it starts to liquefy. And the more that sugar breaks down while it's still solid, the lower the temperature at which it will liquefy.
When we make caramel standing at the stove, we use high heat to liquefy and then brown the sugar in a few minutes, and the liquefying temperature can be upwards of 380°F/190°C. But Professor Schmidt's group found that when they ramped up the heat slowly, over the course of an hour, so that significant chemical breakdown takes place before the solid structure gives way, the sugar liquefied at 290°F/145°C.
I made the caramelized sugars in these photos by putting crystals and cubes in my gas oven at around 250°F/125°C, shielding them with foil above and below to avoid temperature extremes from the cycling heating element, and leaving them there overnight and longer. In the large sugar crystals, which I got in a Chinese market, it's clear that breakdown and caramelization is fastest in the center. That may be because the center is where impurities get concentrated as the crystals are made, and the impurities then kickstart the breakdown process.
Caramel makers have long known that, as is true in most kinds of cooking, the key to caramelization is the combination of cooking temperature and cooking time. But the the temperatures have typically been very high, the times measured in minutes. Now we know that you can caramelize low and very slow and get something different. Sugar breakdown even occurs at ambient storage temperatures, though it takes months for the discoloration and flavor change to become noticeable. For a manufacturer this is undesirable deterioration. But for a cook in search of interesting ingredients, it could be desirable aging.
In a follow-up to her initial scientific reports, Professor Schmidt wrote in Manufacturing Confectioner that
from a practical point of view, caramelization can be thought of as browning of sucrose by applying heat for a length of time. Thus it may be possible to better control the caramelization reaction by identifying the time-temperature conditions that optimize the production of desirable caramel flavors compounds, while minimizing undesirable ones. Confectionery manufacturers and sugar artisans, armed with this new scientific knowledge, may be able to push their craft in unforeseeable directions.
For example: aged sugar, roasted sugar, caramel-center crystals. Let the pushing begin!
Schmidt, S.J. Exploring the sucrose-water state diagram. Manufacturing Confectioner, January 2012, 79-89.
Lee, J. W. et al. Investigation of the heating rate dependency associated with the loss of crystalline structure in sucrose, glucose, and fructose using a thermal analysis approach (Part I). J Agric. Food Chemistry 2011, 59: 684-701.
Lee, J. W. et al. Investigation of thermal decomposition as the kinetic process that causes the loss of crystalline structure in sucrose using a chemical analysis approach (Part II). J. Agric. Food Chemistry 2011, 59: 702-12.
