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Food Solids

Food Solids

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Published by: fitsnj on Oct 23, 2008
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11/15/2013

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Amorphous and Crystalline Solids and the Properties of Solid Foods
Background

All matter, including food, can exist in different physical states. Some of these states,
such as the crystal (ice), liquid (water), and vapor (steam) states of water (H2O), are truly stable
states that all matter can exist in (these are called thermodynamic phases by chemists). Other
states, such as the hard/dry (glass) and soft/viscous (rubber or melt) states of noodles and pasta
and hard candies, are not true stable states characteristic of all matter but are rather peculiar to
materials such as foods and most plastics that can form non-crystalline (amorphous) solids.

Stable (thermodynamic) phases

Water, like all pure substances, can exist in crystalline solid (s), liquid (l), and vapor
states (v). These states are stable over specific temperature ranges. We can represent this
schematically as follows (Tm is the melting temperature and Tb is the boiling temperature).

H2O(s)
\ue002
H2O(l)
\ue002
H2O(v)
T\ue000 Tm
Tm = 0\ue003C
Tm\ue000 T\ue000 Tb
Tb = 100\ue003C
T\ue001 Tb
The phase transitions connecting these different states of water have characteristic features.
1) The transition occurs at a specific and defined temperature (0\ue003, 100\ue003C).

2) Two phases can co-exist (ice plus water, boiling water plus steam) only at the phase transition temperature. This means, for example, that liquid water in equilibrium with ice is always at exactly 0\ue003C under one atmosphere of pressure, and that boiling water (water in equilibrium with steam) is always at exactly 100\ue003C under one atmosphere pressure.

3) The transition between phases involves a large flow of heat into (ice to water; water
to steam) or out of (water to ice; steam to water) the material.

4) Each transition involves a large change in molecular order: liquids have less
molecular order than crystals; vapors have much less molecular order than liquids. This is
actually the most salient feature of phase transitions. True phase transitions involve a change
in the molecular order of a material.

Glass and Rubber: States of Matter

Some materials, such as sugars, carbohydrates, proteins, and most synthetic polymers
(plastics), do not readily form crystals. In these materials, crystallization is often \u201cfrustrated\u201d by
either the high viscosity of the liquid (sugars) or by entaglements of the polymer that prevent
molecules coming together in the proper orientation to form crystals. In these materials, rapid
cooling does not result in crystallization. As the temperature of these liquids drops below the
melting temperature (Tf), the liquids become more viscous. This gradual increase in viscosity as
the temperature decreases eventually generates a liquid whose viscosity is so high that the liquid
behaves like a soft solid; this soft solid is in a rubbery state. The rubbery state of a solid is
flexible and soft but can support its own weight. As the temperature decreases, however, the
rubber will undergo a distinct transition in which the viscosity will increase dramatically
(perhaps by greater than 1000-fold in a temperature interval of 10-20\ue003C) to form a glassy solid
that is hard and brittle. The temperature (midpoint) of this transition is called the glass transition
temperature Tg. The two states have the following characteristic properties.

Glassy solid: hard and brittle; stable to chemical and physical change; nearly complex
absence of molecular motion (other than vibration); complete absence of macroscopic flow.
Rubbery solid: viscous soft and flexible; unstable to chemical and physical change (albeit
slow); presence of molecular motion; macroscopic flow is slow but occurs. If the material is a
polymer the state is called rubbery; if not, it is called a supercooled liquid.

The glass transition temperature is an important temperature for the material because it
determines many of the physical properties and the chemical stability of the material. For a
plastic, the glass transition temperature will determine whether the plastic is glassy (hard) or
rubbery (soft) under the conditions of normal use (room temperature); an application requiring a
hard, rigid material will need a polymer with a Tg > room temperature, while an application
requiring a soft, flexible material will need a polymer with a Tg < room temperature. For foods,
the Tg is also an appropriate reference temperature for stability. Foods are stable for long periods
of time at T < Tg (years perhaps) and are stable for much shorter periods at T > Tg (hours to
days). Examples include noodles and other pasta products, breakfast cereals, dried soups,
puddings, and other mixes, and corn, potato, and other chips. The Tg also influences the texture
of the food. Glassy foods (those with Tg > temperature of consumption) are crispy and brittle
(potato chips); rubbery foods are soft and flexible (cooked pasta).

The glass transition temperature of foods is very sensitive to the amount of water in the
food. The more moisture, the lower the Tg; the less moisture, the greater the Tg. For this reason,
dry foods are usually glassy at room temperature while moist foods are usually rubbery. The
hydration of dry foods will dramatically lower their Tg; the effect is such that addition of about
20% water (by weight) can lower Tg by over 100\ue003C. This is why potato and corn chips will
become soft and flexible if allowed to absorb moisture from the air (on a humid day), why glassy
breakfast cereals become soft and flexible in milk, and why pasta and noodles become soft and
flexible after boiling in water for 5-10 minutes.

Molecular Order and Molecular Motion

Liquids are both similar to and different from solids. Both are condensed phases: the
molecules in liquids and in solids are in contact with one another (compare a solid or liquid with
a gas or vapor in which the molecules are not in contact). But the phases are obviously different:
liquids can flow while solids cannot. The molecular origins of the differences between liquids
and solids lie in two aspects: molecular order and molecular motion.

Molecular order. Liquids are disordered. The molecules in a liquid, although in contact,

do not exhibit any long range molecular order (they exhibit short range order just due to the fact
that they are in contact and thus, on average, all molecules are the same distance from their
neighbors). Liquids typically become solids by crystallizing. In the crystal, the molecules are
packed into regular three-dimensional arrays; imagine rows of desks arranged in three
dimensions. Each molecule is fixed in space due to specific and exact interactions with its
neighbors. There is long range order: molecules a great distance apart have specific spatial
relationships with one another.

In amorphous solids, either glassy or rubbery, molecules are not in regular arrays; the
solids are not crystalline. Amorphous solids are thus liquid-like in that they have the molecular
order (or, rather, disorder) of a liquid.

Molecular motion. The molecules in a liquid are in rapid motion; liquids can flow

because the molecules can move in space with respect to one another. This type of motion in
space is referred to as translational motion. The molecules in a crystal, however, cannot move in
space; they thus exhibit no translational motion. Molecules can also rotate about their centers of
gravity and they can vibrate if they have two or more atoms (the more atoms in a molecule the
more ways that the molecule can vibrate). Due to the constraints of the regular contacts present
in a crystal, the molecules cannot rotate. They can, however, vibrate in place.

In amorphous glassy solids the molecules move as they do in a crystalline solid: they can
vibrate in place but they cannot rotate and cannot move through space (translate). Amorphous
glassy solids are thus crystal-like in that the molecules in them cannot move by rotation or
translation. At the glass transition temperature the molecules begin to undergo rotational and
translational motion; this is the physical basis for the increase in viscosity and the onset of flow
that occurs at the Tg.

We can thus say clearly and unambiguously that amorphous solids are like liquids in that
their molecules are disordered; and that glassy solids are like crystals in that their molecules
cannot rotate or translate. The ambiguous and complex nature of amorphous solids makes them
truly an unusual state of matter.

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