Chapter 1

Food Material Properties

Theory

Contents
1 Food Material Properties ............................................................................................................................................ 1-2
1.1 Introduction ........................................................................................................................................................... 1-2
1.2 Phases and states ................................................................................................................................................. 1-2
1.3 State diagrams ...................................................................................................................................................... 1-7
1.4 Chemical potential, concentration and activity ...................................................................................... 1-9
1.5 The sorption isotherm: properties of the product ............................................................................. 1-14
FPE20306 Food Process Engineering

1 Food Material Properties

1.1 Introduction
Food products are very complex products. They do not interact with their environment in a simple
way. We therefore need to look more closely at some essential properties. They are critical in the
treatments discussed in the next chapters: drying, dehydration, frying, crystallisation and more.
The first item is to use state diagrams to estimate the states in which different phases in a product may
be. This influences not only the product properties but places also limits to the methods that we have
to prepare them. A state diagram relates the physical state of components, or mixtures of them to their
overall composition.
A sorption isotherm, the second item to discuss, relates the water activity, which is the affinity of a
product to moisture, to its composition. It thus tells us more about the driving forces in the product for
interaction with a (moist or dry) environment.
We will first discuss phases and states of phases, and then come to the composition of state diagrams,
and the difference with phase diagrams.

1.2 Phases and states

In many processes used for the preparation of food products, products change state. This means that
they go from solid to liquid (dissolution, melting), liquid to solid (freezing), or from a liquid into a
vapour and a solid (drying).
Food products are very complex materials, since the main components in a food, proteins,
carbohydrates and fats do not mix. They are therefore dispersed into each other, and the way that they
are dispersed is a major determinant of the quality of the food. Each major component makes up a
phase. Each phase may contain many components; some ingredients may be dispersed or dissolved
into more than one phase: flavours are often dissolved in the aqueous and in the oily phases of a
product. However, macromolecular components such as proteins, high-molecular weight
carbohydrates, such as starch, pectin, pentosans, xylans, etc., do not mix with other high-molecular
weight components.
Examples are
- Mayonnaise: this contains an aqueous and an oil phase, the aqueous phase contains egg yolk and
some vinegar.
- Ice cream: a dispersion of ice crystals, solidified milk fat and air bubbles, in a concentrated
solution of sugar.
- Bread: a complex mixture of a protein phase (the gluten) and a carbohydrate phase (the starch),
which both are the continuous phase surrounding a dispersed gas phase (the pores in the bread).
- Cheese: a continuous phase of casein, interspersed with fat, and which may contain gas bubbles
(the ‘eyes’).
- Valess: a meat analogue made of caseinate, plus a carbohydrate phase made of calcium alginate.
These two phases are mixed such that they resemble a fibrous structure.
- Meat: individual fibres of actin and mysin, bundled in larger bundles, ultimately held together
with a phase of collagen. All proteins form individual phases, they are not mixed.
- Mustard: a dispersion of solid particles in an aqueous phase containing vinegar.
There are three fundamental states: liquid, vapour or gas, and solid; however each of those can be
present in different form.

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 Food Material Properties - Theory

1.2.1 Gases and vapours

A vapour or a gas is the simplest state. Air is ubiquitous, it is in close contact with most of our foods. It
is a mixture of many gases, and indeed any gas mixes with any other gas. Demixing of gases does not
happen under any conditions that are likely to apply to foods. The fact that gases can mix, also gives
rise to the phenomenon that air can take up moisture from a product.
A well-known relation that is useful to have at hand is the ideal gas law, valid for most gases at
moderate pressures, such as air:

𝑝𝑉 = 𝑛𝑅𝑇 1-1

In which 𝑝 is the pressure (Pa or N/m2), 𝑉 is the volume (m3), 𝑛 is the number of mols of the gas, 𝑅 is
the gas constant (8.314 J/(mol·K)), and 𝑇 is the temperature (K). When two gases mix, you may
imagine that the overall gas is made up of two gases, with each their own number of moles (𝑛1 and 𝑛2 )
and therefore each with their own pressure, 𝑝1 and 𝑝2 . These pressures are called partial pressures.
The sum of all the partial pressures is the overall pressure.
Partial pressures in completely dry air
Component Partial pressure (105 Pa)
N2 78.084
O2 20.948
Ar 0.934
CO2 0.0314
CH4 0.0020
Ne 0.001818
He 0.000524
Kr 0.000114
H2 0.000050
N2O 0.000050
Xe 0.0000087
Total pressure 1.000

Gaseous water is usually called a vapour instead of a gas. It is fundamentally the same as a gas, but it
is condensable: it can be at equilibrium with itself in the liquid form. If you lower the temperature or
increase the pressure, moisture vapour will start to condense into water. Oxygen and nitrogen, the
main components of air will not do that, until you cool them down to very low temperatures. Gases
which tend to condense under conditions close to room temperature and pressure are often called
vapours.
Water vapour that is at equilibrium with water, has a certain vapour pressure. If there is only water
vapour present above the water (so, no air), then this vapour pressure is the pressure of the gas above
the water. If there is both vapour and air above the water phase, then part of the gas mixture above the
water will consist of water molecules, next to the air molecules themselves. The total amount of water
molecules in the gas phase per m3 of gas is the same as when there is no air; only there are now more
molecules present.

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5
1.2.10

Sat. water vapour pressure (Pa)

1.105 1 atmosphere
8.104

6.104

4.104

2.104

0
0 20 40 60 80 100
Temperature (deg C)

At 20 0C, the saturated water vapour pressure is equal to 2.3 kPa. This implies that air that is at
equilibrium with water (saturated air), will have a vapour pressure of 2.3 kPa, and if the overall
pressure of the air is 1 bar (=105 Pa), the rest of the partial pressures will sum up to 97.7 kPa (so that
the total is 100 kPa or 1 bar). At 50 0C, the saturated vapour pressure of water has risen to 12.3 kPa,
which means that 12.3% of all molecules in the air are water molecules. At 100 0C, the saturated vapour
pressure is equal to 100 kPa: 100% of the molecules are now water; the air is displaced by the water
vapour, and the liquid boils.
Air that contains less water than the saturated vapour pressure, can take up moisture from a product.
Air that is cooled down will have a lower saturated water vapour pressure, and at some point the actual
water vapour pressure will be higher than the saturated vapour pressure. At that moment, the vapour
will start to condense. This happens for example in the night, when fog forms; or in rising air, in which
clouds form. But it may also happen in air that is cooled in a refrigerator or freezer.
If we would have a product that consists of solids (usually a mixture of many components, but we
consider them here as just ‘the solids’) and water, and we heat it, it would at some point start to boil,
when the water vapour pressure would become 1 bar. This vapour-liquid equilibrium can be shown in
a phase diagram:
200
Vapour +
T (0C) solution
150

Boiling/evaporation
100

Liquid
50
solution

0
0 50 100
Solids (wt%)

Below the curve, the moisture in the product does not boil (even though it may still lose moisture to
air that is not saturated!). At the curve, the product will start to lose moisture. It is not possible for the
product to heat up further: if you do heat it, it will simply lose moisture and the product composition
will shift over the curve to the right. The line shifts slowly upwards, since the product becomes more
and more concentrated, and the boiling of water will take place at slightly higher temperatures. This
is called boiling point elevation.

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 Food Material Properties - Theory

1.2.2 Liquids
Liquids are well known: they are condensed phases that can flow. They have a viscosity (the higher the
viscosity, the more difficult the liquid flows). The viscosity may be constant (a Newtonian liquid), or
dependent on the shear rate (a shear-thinning or thixotropic liquid, or a shear-thickening or dilatant
liquid). Liquid foods, or liquid phases in foods are often solutions and/or mixtures of many
components, and are often the continuous phase for solid particles, or for droplets of another liquid
phase, e.g., oil droplets.
Examples of liquid foods are
- Beverages, such as cola, beer, wine, milk
- Clinical foods for gastric feeding, usually a dispersion or solution of proteins and fats in water; or
clinical food for intravenous feeding, often a mixture of amino acids, glucose and salts
- Energy and sports drinks, often dispersions of proteins in water, together with sugar and salt to
create isotonic conditions

Examples of liquid phases in foods are

- Mayonnaise: both the continuous aqueous phase and the dispersed oily phase are liquid – but
together they form a gel, as discussed below.
- Soup: a more or less concentrated dispersion of solids and some oil, in a solution of salts, amino
acids and peptides.
- The intracellular liquids in vegetables form a dispersed liquid phase in a solid phase formed by the
cell walls. Due to the high pressure (turgor), the fresh product is stiff. As soon as the cell walls
degrade or are punctured, the aqueous phase escapes, the product becomes limp, and the aqueous
phase drains out (the effect is most dramatic with leave vegetables: spinach loses 90% of its
volume in this way).

When the dissolved or dispersed components become concentrated, at some point the rheological
properties start to change qualitatively. At a certain concentration, the dissolved components start to
interact with each other, and a yield stress will form. The liquid now seems a solid at rest, and only
becomes liquid when forced to deform. Typical examples are salad dressings: when at rest the are solid
enough to not allow the sedimentation of the suspended solids in the dressing, but when you start to
pour it, it reacts like a normal liquid.

Salad dressing: particles do not sediment at rest, but you can pour it.

At some point, the yield stress is so strong, that even though you can deform the product, it will
‘bounce’ back, and return, at least partially, to its original shape. This is the behaviour of a visco-elastic
material. Examples are batter, ketchup, peanut butter and cream.

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1.2.3 Gels and rubbers

Gels or rubbers are not fundamentally different from liquids, but they have a much stronger solid
behaviour. One calls a liquid a gel or rubber, when the solid (elastic) properties predominate above
the (viscous) liquid properties.
Gels or rubbers can still be deformed, but generally not endlessly, at some point their structure breaks.
This is in contrast to a liquid which can be deformed without limit; no breakage of the structure will
result.
Not only foods contain gels or rubbers: indeed, the word rubber stems from the behaviour of the cross-
linked latex, that we know as natural rubber – the material that truck tyres are made of 1. Many of the
synthetic resins and polymers, which are used in our daily lives are basically rubbers.
There is no fundamental transition, when going from a liquid to a gel or rubber. In fact, the properties
may change slowly, when adding more and more solids to a product. In other cases, like with proteins,
there may be a point at which the solution become much more solid. This is then called the gelling
point.

Typical gels or rubbers: the elasticity is dominant above the viscous fluidic properties.

1.2.4 Glasses
In systems that have very little water, and in which the temperature is not
too high, the viscosity of a liquid (or gel or rubber) may become higher and
higher (upon cooling or further dehydration). At some point, the viscosity is
so high that for all practical purposes the material becomes solid. Such a
liquid may break as a brittle material – even though in theory it is still a
liquid. The most famous example of this behaviour is glass (a melt of mostly
silicate, which has become a glass). Fundamentally, a glass is still a liquid, but
it flows immeasurably slowly.
Many foods are also glassy, especially when dehydrated. Glassy products
often are crispy in their texture:
- Potato chips have been dehydrated by frying in oil (vide infra), and
are crispy because their starch matrix has become a glass during
cooling.
- The crust of a pizza is crispy because it lost most of its moisture in a
pizza oven2. If you have it delivered, the moisture from the topping

1 Personal cars have tyres made out of isotactic chloroprene, which is a synthetic rubber with much the same
properties as natural rubber, which is made of cross-linked isotactic isoprene. Both are rubbers, which are made
stiffer by dispersing solid soot particles in them.
2 This is the reason that a pizza oven should have a floor of stone. Stone has a very high heat capacity and will be
very hot. The crust is in direct contact with the stone plate, and therefore loses moisture quickly enough. A metal

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percolates into the crust, which then loses its crispiness. The crust of bread is
crispy because it has lost all moisture during baking (though the inner parts of
a bread are a rubber). The same is true for the crust of a French fry.
- A cookie is crispy because its matrix, consisting for a large part of sugar, has
glassified.
- Cruesli is crispy because the cereals are in the glassy state.
All fluids and solutions can become glassy, you just have to cool it down quickly
enough. A concentrated solution of sugar in water at 80 0C, and cooled down
relatively quickly, makes a wonderful glass; this is the material of a lollipop and
many other types of candy. If you cool it down more slowly, and allow for the
crystallization of the sugar, you will end up with a suspension of sugar crystals.

1.2.5 The crystalline state

Crystals are very different from liquids, rubbers or glasses. The latter three states have in common that
there is no long-range ordering of the molecules: they are essentially amorphous states. Crystals are
very ordered: all molecules line up relative to each other, such that (in general) a dense packing is
achieved of those molecules. In many cases, only one type of molecule fits in the crystal packing; in
other cases, the crystal can be a specific ratio of two or more molecules. Lactose, for example,
crystallises at around 90 – 100 0C in crystals containing only lactose; however if you let it crystallise at
lower temperatures, you get crystals of lactose monohydrate: a mixture of one lactose molecule with
one water molecule.
Fats tend to crystallise at around 35 0C; oils typically at lower temperatures. Since most biological oils
are a mixture of many different triglycerides, only part of the oil or fat crystallizes out. Therefore, the
resulting product forms a sort of porous network of crystals that touch each other, while the pores are
filled with the oil that is still fluid.
The most known form of a crystal is the ice crystal. If 200
you freeze a product, you convert (most of) the water
Water vapour +
in the product in ice crystals. The product surrounding 150 sugar solution
those crystals becomes more and more concentrated.
This more concentrated solution has a lower freezing 100
point, a phenomenon that is called freezing point
T (0C)
depression. At low concentration of solids, the water 50
Sugar
Sugar
solution
freezes into ice crystals. However, at high solution
concentration, it may be the solute that crystallizes out. 0
+ sugar
crystals
This is shown for a sugar solution in the phase diagram Ice + solution

at the right. -50

Until about 60 weight% sugar, ice will crystallize out, Ice crystals + sugar crystals
-100
leaving a solution that becomes more and more
concentrated. This proceeds, until the concentration
-150
reached the 60%. At that moment, the sugar also 0 50 100
crystallizes out. At lower temperatures one just has a Sucrose (wt%)
solid mixture of ice and sugar crystals.

1.3 State diagrams

In practice, crystallisation works out differently, due to the glass transition. The establishment of the
equilibrium between ice crystals and sugar solution, or, when starting with a concentrated sugar

plate will not have enough heat capacity, the dough will cool the plate down and the pizza will not be as crispy as
baked on a stone plate.
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FPE20306 Food Process Engineering

solution, between sugar crystals and a sugar solution, takes time; in some cases a lot of time. If you cool
down more quickly, you end up not in the equilibrium state, but in a vitrified state: the glassy state.
The glass transition is not a true transition to another state, but it represents the composition and
temperature at which the viscosity of the solution becomes very high. Therefore, in the system of sugar
and water, it is hardly possible to obtain the state of ice crystals plus sugar crystals, because before
that time the concentrated sugar solution around the crystals has become a glass. If you cool down
further, nothing happens anymore.
We therefore have to modify the phase diagram, to accommodate for this. So, the state diagram is a
modified phase diagram that also shows kinetic limitations, such as the glass transition. The graph
below shows the state diagram of a sugar solution.

200
Vapour +
solution
150

Boiling/evaporation
100
Soln +
T (0C) Liquid crystals
50
solution

-50 Solution
+ ice
crystals
-100
Glass
-150
0 50 100
Solids (wt%)

State diagrams are very convenient to use in the understanding of a process that involves loss or
introduction of moisture and/or change in temperature, such as baking, concentration or drying. One
can easily follow the changes in composition over time, and see how one has to achieve the right
properties. We will use the state diagrams in the understanding of air drying, frying, freeze drying and
crystallization.

1.3.1 The lever rule

One can read out the amount of material that has converted to another phase, using the lever rule. If
you cool down a solution, and cross the crystallisation line, you’ll get crystals in a more concentrated
solution. The deeper you go, the more crystals, and the less liquid you get.

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 Food Material Properties - Theory

wice AB
 0 Liqui
dus
wsolution AC
C A B

This can be read out in the state diagram according to the lines given in the graph above. The product
has cooled down to point A – of course the overall composition has not changed. At point A, the fraction
of the product that has crystallised, is equal to:
𝐴𝐵 1-2
𝑥𝑖𝑐𝑒 =
𝐵𝐶
The lower you get, the longer the line 𝐴𝐵, and the larger 𝑥𝑖𝑐𝑒 will be.

1.4 Chemical potential, concentration and activity

1.4.1 Chemical potential

The concentration of a component (e.g. water) is not the same as the affinity that the matrix has for
that component. For example, a salt solution that contains a significant amount of moisture, may still
draw more moisture from the air, even though the air contains less moisture. Similarly, you can
prepare a syrup waffle, and store it, without having to worry about the transfer of moisture from the
syrup into the waffle – even though the syrup contains more moisture than the waffle. That is because
the syrup has a higher affinity for the moisture than the waffle.
There is equilibrium between two phases, when the so-called chemical potential, 𝜇𝑖 , of all components,
is equal in both phases. Each component therefore has a chemical potential:
phase one phase two 1-3
𝜇𝑖 = 𝜇𝑖 ∀𝑖 in which ∀𝑖 means: for all i
While there is a relation between the chemical potential and the concentration, they are not the same.
The chemical potential depends on the pressure, volume (density), temperature and on the
composition. Therefore, one might write the chemical potential of component i, as having separate
contributions from the different parameters:
𝜇𝑖 = 𝜇𝑖0 (𝑝0 , 𝑇0 ) + Δ𝜇𝑖 (𝑝) + Δ𝜇𝑖 (𝑇) + Δ𝜇𝑖 (𝑥𝑖 ) 1-4

In which 𝜇𝑖0 is the value of the chemical potential at a reference state (which we may choose ourselves,
but for usually 1 bar and 298 K is taken); it is often called the standard chemical potential.

1.4.2 Gases and relative humidity

For a pure gas (one component), the composition part (Δ𝜇𝑖 (𝑥𝑖 )) is one, and we can write the chemical
potential as:
𝑝
𝜇𝑖 = 𝜇𝑖0 (𝑝0 , 𝑇) + 𝑅𝑇 ln ( ) 1-5
𝑝0

For a mixture of gases, we need to specify the chemical potential for each component, and include the
part on the composition, which is:
𝑝 𝑝𝑖
𝜇𝑖 = 𝜇𝑖0 (𝑝0 , 𝑇) + 𝑅𝑇 ln ( ) + 𝑅𝑇 ln ( ) = 𝜇𝑖0 (𝑝, 𝑇) + 𝑅𝑇 ln 𝑥𝑖 1-6
𝑝0 𝑝

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In this, one often takes the pressure part (𝑅𝑇 ln(𝑝/𝑝0 )) in the standard chemical potential (at that
pressure and temperature (𝜇𝑖0 (𝑝, 𝑇)). In this, the molar fraction 𝑥𝑖 is equal to the partial vapour
pressure, divided by the total pressure 𝑝, which is equal to the sum of all partial vapour pressures.

1.4.3 Liquids, activity and activity coefficients

For liquids and solutions, the situation is a bit more complex. Also here, the chemical potential is
defined as
𝜇𝑖 = 𝜇𝑖0 (𝑝0 , 𝑇0 ) + Δ𝜇𝑖 (𝑝) + Δ𝜇𝑖 (𝑇) + Δ𝜇𝑖 (𝑥𝑖 ) = 𝜇𝑖0 (𝑝, 𝑇) + Δ𝜇𝑖 (𝑥𝑖 ) 1-7

We will not look in detail at the pressure and temperature dependent parts of the chemical potential
(in most equilibria during processing, the pressure and temperature is the same in the different
phases) and therefore lump this in the term 𝜇𝑖0 (𝑝, 𝑇). If a specific component is at equilibrium between
two phases, its chemical potential must be the same. So, if water vapour is at equilibrium with pure
water, then both chemical potentials should be the same:
0,𝑔𝑎𝑠 𝑝𝑤,𝑠𝑎𝑡 0,𝑙𝑖𝑞𝑢𝑖𝑑
𝜇𝑤 (𝑝, 𝑇) + 𝑅𝑇 ln ( ) = 𝜇𝑤 (𝑝, 𝑇) 1-8
𝑝
At these conditions, the vapour is saturated with water vapour: if the partial water vapour pressure
would become higher, then the chemical potential of water in the gas phase would become higher, and
it would migrate (condense) into the water. So, this is called the saturated water vapour pressure 𝑝𝑤,𝑠𝑎𝑡 ,
and the ratio 𝑝𝑤 /𝑝𝑤,𝑠𝑎𝑡 is called the relative humidity.
If the water vapour is at equilibrium with a mixture of water and other components, then we should
include a part on the liquid composition.
0,𝑔𝑎𝑠 𝑝𝑤 0,𝑙𝑖𝑞𝑢𝑖𝑑
𝜇𝑤 (𝑝, 𝑇) + 𝑅𝑇 ln ( ) = 𝜇𝑤 (𝑝, 𝑇) + 𝑅𝑇 ln 𝑎𝑤 1-9
𝑝
The quantity 𝑎𝑤 is called the water activity. If the water vapour pressure is equal to the saturated
water vapour pressure, so the relative humidity is 1, then 𝑎𝑤 = 1. If 𝑝𝑤 is lower than 𝑝𝑤,𝑠𝑎𝑡 , then 𝑎𝑤
must be smaller than one.

0,𝑔𝑎𝑠 𝑝𝑤 0,𝑔𝑎𝑠 𝑝𝑤,𝑠𝑎𝑡 𝑝𝑤

𝜇𝑤 (𝑝, 𝑇) + 𝑅𝑇 ln ( ) = 𝜇𝑤 (𝑝, 𝑇) + 𝑅𝑇 ln ( ) + 𝑅𝑇 ln ( )
𝑝 𝑝 𝑝𝑤,𝑠𝑎𝑡 1-10
0,𝑙𝑖𝑞𝑢𝑖𝑑 𝑝𝑤
= 𝜇𝑤 (𝑝, 𝑇) + 𝑅𝑇 ln ( )
𝑝𝑤,𝑠𝑎𝑡
So
𝑝𝑤 𝑝𝑤
𝑅𝑇 ln ( ) = 𝑅𝑇 ln 𝑎𝑤 or = 𝑎𝑤 1-11
𝑝𝑤,𝑠𝑎𝑡 𝑝𝑤,𝑠𝑎𝑡

So, the water activity is equal to the relative humidity of the vapour that is at equilibrium with the
solution (please note that water is only taken as an example; the same would be true for any other
component in a system).
Obviously, the activity is coupled to the composition: a non-saturated water vapour will be at
equilibrium with a solution that is only partly water. However, the relation between the composition
and the activity is quite complex. For so-called ideal solutions, the activity is equal to the molar fraction.
Unfortunately, most food materials are non-ideal. For instance, a salt solution is more hygroscopic than
a sugar solution with the same molar fraction of moisture, and will thus be at equilibrium with a vapour
phase that has a lower water vapour pressure. So, with the same molar fraction, a salt solution will
have a lower water activity than a sugar solution. However, there is still a relation between the activity
and the composition, and therefore, for liquids, we often write for the activity of a component:
𝑎𝑖 = 𝛾𝑖 𝑥𝑖 1-12

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In which 𝛾𝑖 is the activity coefficient. For ideal solutions, the activity coefficient is 1. And by definition,
for pure liquids (𝑥𝑖 = 1), the activity coefficient is 1 as well (because the activity 𝑎𝑤 is 1). For low
concentrations of a component, the activity coefficient 𝛾𝑖 is often constant (though not necessarily 1).
In such a case, Henry’s law applies:
𝑝𝑖
𝛾𝑖 𝑥𝑖 = 𝑜𝑟 𝑝𝑖 = 𝑘𝐻 𝑥𝑖 1-13
𝑝𝑖,𝑠𝑎𝑡
In this, 𝑘𝐻 is Henry’s coefficient, containing both the activity coefficient 𝛾𝑖 , and the saturated vapour
pressure 𝑝𝑖,𝑠𝑎𝑡 . Often, Henry’s law is specified with concentrations (𝑐𝑖,𝑔𝑎𝑠 = 𝑘𝐻 𝑐𝑖,𝑙𝑖𝑞𝑢𝑖𝑑 ), and in that
case, Henry’s constant has a different value. For ideal solutions, the activity coefficient 𝛾𝑖 is 1, and 𝑘𝐻
is equal to the saturated vapour pressure; 𝑝𝑖 = 𝑝𝑖,𝑠𝑎𝑡 𝑥𝑖 . This is called Raoult’s law. For almost pure
liquids (𝑥𝑖 → 1), the activity coefficient always goes to 1, and Raoult’s law is universally valid.
The Henry coefficients depend on the temperature. One may find its value at other temperatures by
using the following relation (note: give T in K), in which some values of the parameter 𝐶 are given in
the table below:

1 1
𝐶( − ) 1-14
𝑘𝐻 = 𝑘𝐻 (𝑇0 )𝑒 𝑇0 𝑇

Henry coefficients for gases dissolving in water (1 bar = 105 Pa):

Gas dissolving 𝑘𝐻 (
𝑏𝑎𝑟∙𝐿
) at 25℃ 𝑘𝐻 (
𝑚𝑜𝑙
) at 25℃ 𝑘𝐻 (𝑏𝑎𝑟) at 25℃ Constant 𝐶 (𝐾) for
𝑚𝑜𝑙 𝑏𝑎𝑟.𝐿 (𝑝𝑖 = 𝑘𝐻 𝑥𝑖 )
in water temperature
(𝑝𝑖 = 𝑘𝐻 𝑐𝑖 ) (𝑝𝑖 = 𝑘𝐻 𝑐𝑖 )
dependence
He
2702.70 3.7 ∙ 10−4 1.50 ∙ 105 230

O2 769.23 1.3 ∙ 10−3 4.27 ∙ 104 1700

N2 1639.34 6.1 ∙ 10−4 9.10 ∙ 104 1300

H2 1282.05 7.8 ∙ 10−4 7.11 ∙ 104 500

CO2 29.41 3.4 ∙ 10−2 1.63 ∙ 103 2400

For more concentrated solutions, finding the activity is not that easy, because 𝛾𝑖 often is not constant
anymore. There are many theories that give estimations of the activity or activity coefficient: the
Wilson and Van Laar methods, the non-random-two-liquids (NRTL) and the UNIFAC method. While
their equations can be a bit daunting, they are not too difficult to use with computers. Their precise
form is out of the scope of this course.
One theory, the Flory-Huggins theory, tells us that for water in a matrix that mostly consists of
(bio)polymers of high molecular weight, such as starch or proteins, the water activity depends on the
volume fraction of water 𝜙𝑤 , according to

𝑙𝑛(𝑎𝑤 ) = 𝑙𝑛(𝜙𝑤 ) + 1 − 𝜙𝑤 + 𝜒(1 − 𝜙𝑤 )2 1-15

In which 𝜒 is a parameter that expresses the interaction between water and the dissolved components.
If the interaction between the matrix and water is the same, then 𝜒 = 0. If the solutes have great affinity
for moisture, then 𝜒 will be negative, and if the solutes do not really like moisture, then it is positive.
For water in starch, 𝜒 is around 0.80; for water in many water soluble proteins such as dairy proteins,
𝜒 is around 0.76; for raw meat it is around 0.86 and for cooked meat 1.2.

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The water activity as predicted by the Flory-Huggins theory for different values of 𝜒. Note that the activity coefficient
is constant when 𝑥𝑤 → 0, and becomes 1 when 𝑥𝑤 → 1.

1.4.4 Solids: gels and rubbers; and crystalline materials, including ice
For solids, one can also define a chemical potential for each component present in the solid. A gel (or
rubber) can be treated similarly to a liquid. In many cases, the water activity is defined in sorption
isotherms, which give the relation between the relative humidity and the amount of moisture in the
solid, that is at equilibrium with that relative humidity. It therefore gives the relation between the
water activity and the concentration of moisture in the solid.
When two phases are at equilibrium, the chemical potential of all components should be equal over
the two phases. If this is not the case, then the difference in chemical potential represents a driving
force for transfer of the component from one phase to the other (from the higher to the lower chemical
potential).
For the crystallization of water upon freezing of a product, one can also define the chemical potential
of ice. If we follow the Flory-Huggins theory (amongst others), one can find that for the crystalline
phase (which is pure water) the following equation is valid:
𝑇𝑚
0
𝜇𝑤,𝑖𝑐𝑒 = 𝜇𝑤 − Δℎ𝑚 (1 − ) 1-16
𝑇𝑚,0
In which Tm is the freezing temperature, 𝑇𝑚,0 is the equilibrium freezing point of pure water, and Δℎ𝑚
is the molar enthalpy of freezing (or melting), in J/mol. Since we already know the chemical potential
of the fluid water surrounding the ice crystal,
0
𝜇𝑤,𝑤𝑎𝑡𝑒𝑟 = 𝜇𝑤 0
+ 𝑅𝑇 𝑙𝑛(𝑎𝑤 ) = 𝜇𝑤 + 𝑅𝑇(𝑙𝑛(𝜙𝑤 ) + 1 − 𝜙𝑤 + 𝜒(1 − 𝜙𝑤 )2) 1-17

And we know that if the ice crystals and the solution are at equilibrium the two chemical potentials
should be the same:
𝑇𝑚
0
𝜇𝑤 + 𝑅𝑇𝑚 (𝑙𝑛(𝜙𝑤 ) + 1 − 𝜙𝑤 + 𝜒(1 − 𝜙𝑤 )2 ) = 𝜇𝑤0
− Δℎ𝑚 (1 − ) 1-18
𝑇𝑚,0
Which gives after rearrangement:
Δℎ𝑚 1 1
𝑙𝑛(𝜙𝑤 ) + 1 − 𝜙𝑤 + 𝜒(1 − 𝜙𝑤 )2 = − ( − ) 1-19
𝑅 𝑇𝑚 𝑇𝑚,0
Which gives a relation between the melting point, and the volume fraction of water in the surrounding
phase. Obviously, if 𝜙𝑤 = 1, then the left hand term is ln 1 + 1 − 1 + 𝜒 ∙ 0 = 0, and the melting
temperature 𝑇𝑚 is equal to 𝑇𝑚,0 .

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 Food Material Properties - Theory

The freezing/melting points predicted according the Flory equation, using the melting enthalpy
for water (334 kJ/kg), and 𝜒 = 0.5. Compare the freezing line in the state diagrams.
One can use exactly the same relation for the crystallization of a product (e.g., sugar), but now with the
crystallization enthalpy of that component. You then get the crystallization line for this solid, as shown
in the state diagrams.

1.4.5 Glasses
There is one phase, that cannot be found in this way. The glassy state is not at equilibrium with its
surroundings, but is simply vitrified. So, the chemical potential of the components in a glass are not the
same as the chemical potentials of the same components in the surrounding phase. Instead, one
generally uses an empirical relation that gives the glass transition temperature as a function of the
glass transition temperatures of the solid matrix, and of water, the so-called Gordon-Taylor equation:
𝑤𝑤 𝑇𝑔,𝑤 + 𝑘(1 − 𝑤𝑤 )𝑇𝑔,𝑠
𝑇𝑔 = 1-20
𝑤𝑤 + 𝑘(1 − 𝑤𝑤 )
In which 𝑇𝑔,𝑤 and 𝑇𝑔,𝑠 are the glass transition temperatures of the two components (water and solids);
and 𝑤𝑤 is the weight fraction of water. The parameter 𝑘 is an empirical factor. The glass transition
temperature of pure water, 𝑇𝑔,𝑤 , is generally assumed to be −135 ℃ or 138 𝐾.

The glass transition as predicted for starch (𝑇𝑔,𝑠 = 165℃) with the Gordon-Taylor equation.

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1.4.6 Conclusion
The thermodynamic potential can be used to predict and describe not only the lines in a state diagram
(with the exception of the glass transition, for which the Gordon-Taylor equation is needed): if the
chemical potentials of each component are the same in both phases, then there is equilibrium.
Equilibrium means that there is no driving force for the components to move from one phase to the
other. Vice versa, if there is a difference in the chemical potential of a component, then there is a driving
force for migration. This driving force is linearly dependent on the difference in chemical potential.
In the next chapter we will see that with this, we can describe how fast matter may go from one phase,
to the other. This is important in any process for making foods; whether you evaporate water, or dry
a food, or whether you dissolve sugar or salt in a product; or extract tea from tea leaves or coffee from
ground coffee, the difference in chemical potential gives the driving force for the transfer.

1.5 The sorption isotherm: properties of the product

The interaction of solid products with the moisture in its surroundings is very important, not only
during production, processing, but also for the properties of the product. The state diagram gives
which state the product will be in, at given moisture content and temperature, but it does not give us
information on the affinity of a product with moisture. For this, the moisture sorption isotherm is
needed. The sorption isotherm is the relation between the amount of moisture in the product, and the
relative humidity of the air that is at equilibrium with the product.
You know that a food that is exposed to dry air will dry. But it will not dry to the same moisture content
as the air. At some point there will be equilibrium between the two phases, even when their moisture
contents are different. This is true for any two phases. You also know that if you contact oil and an
aqueous solution (say, a juice), the water will not distribute over the two phases (oil and water) with
the same moisture content – simply because the oil has a much lower affinity to moisture than the
other phase.
So, the moisture content is not the same as the affinity of a phase or product with for example moisture.
This affinity is expressed with the term activity. If we speak about the affinity of a phase or product for
water, it is the water activity (symbol 𝑎𝑤 ). The water activity is defined to be zero when the product
does not contain any water, and it is 1, when the product is at equilibrium with air (or another gas)
that is saturated with water vapour. So, the water activity of a product is equal to the relative humidity
of air that is at equilibrium with the product.
Since the relative humidity of air is strongly dependent on the temperature, the water activity of a
product is dependent on temperature as well. But it is also strongly dependent on the composition of
the product. Some components have a very strong affinity to water (such as salt); others (such as oil)
have a very low affinity. Many components such as proteins and carbohydrates are in between these
extremes. Basically, the relation between the amount of moisture and the affinity of the product to
water, or its water activity, depends on the temperature and on the composition.
The relation between the amount of moisture in the product, and its water activity, is called the
sorption isotherm, or water vapour sorption isotherm.
Consider a product that does not contain any moisture at all. All hydrophilic groups in the product have
no water molecules surrounding them. As soon as this product is exposed to air that contains just a
very small amount of moisture, it will grasp this moisture to have at least a small amount of moisture
around its most hydrophilic components or groups. At the beginning the product eagerly absorbs a
small amount of moisture, which will not yet increase the water activity that much. This is called
monolayer absorption, and it is related to the first layer of water molecules that will connect to the
most hydrophilic groups of the components in the product. It is shown by the grey sites in the graph.

If you then expose the product to air which is more humid, the product will be a bit slower in taking
up moisture: the most hydrophilic spots have been hydrated, and other, less hydrophilic groups will
slowly become hydrated. But if you then increase the relative humidity of the surrounding air to very

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 Food Material Properties - Theory

high values, the amount of moisture absorbed in the product rises more strongly again. This moisture
remains relatively free (in the graph the black sites), sit in between the protein and carbohydrate
molecules, but the product can absorb more of this. The net result is an S-shaped relation.

aw
It is important to realise that the sorption isotherm does not say anything about the state of the
product. Typically, a product will be glassy (or crystalline) when it has a low moisture content, but
where the glass (or crystalline) region begins can only be found in the state diagram. Also the transition
from a solid product to a flowing (fluid) product cannot be seen from the sorption isotherm. This point
may be related to the glass transition, but in a crystalline product may be somewhere halfway the
crystal melting process: at some point enough fluid material present that the whole concentrated
suspension can start to flow.
There are several equations that describe water vapour sorption in a product: the Freundlich isotherm,
the Guggenheim-Anderson-De Boer (GAB) isotherm, the BET (Brunauer-Emmet-Teller) isotherm, the
Langmuir isotherm, and a recent one, the Flory-Huggins-Free-Volume (FHFV) isotherm.
The Freundlich isotherm is the most simplest and is stated as follows:

1
𝑛 1-21
𝑤𝑤 = 𝑤0 𝑎𝑤

With n the Freundlich constant (dependent on the matrix), and 𝑤0 a constant that indicates the
concentration of moisture, when 𝑎𝑤 = 1. The use of the other ones is however very similar: it is an
equation that gives the relation between the water activity (relative humidity) and the moisture
content in the product.
By far the most used equation for foods is the Guggenheim_Andersen-De Boer (GAB) isotherm; we will
therefore concentrate on using that one:

𝐶𝑘𝑎𝑤
𝑤𝑤 = 𝑤0 1-22
(1 − 𝑘𝑎𝑤 )(1 − 𝑘𝑎𝑤 + 𝐶𝐾𝑎𝑤 )

As it describes behaviour most often found in foods. The parameters 𝑤0 (which is a different 𝑤0 from
that of the Freundlich isotherm), C and k depend on the product.
From the above equations it may be clear that these require calibration for specific products and
conditions (e.g. temperature). These data can be generated by measurement of the moisture content
of a product at a fixed relative humidity. In the past this was very often done by equilibration of a
product in a contained environment with a saturated salt solution. Depending on the chosen salt and
temperature equilibrium is attained at a specific water activity. Subsequently, the moisture content of
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the product is determined by gravimetric analysis. By doing the latter measurement for a series of salt
solutions, the sorption isotherm can be obtained. Because of the long equilibration times, nowadays
an alternative measurement technique is often preferred. A vapour sorption analyser is used for this.
This equipment can expose the product stepwise to air of different relative humidities and measure
the mass increase or decrease of the sample simultaneously. If sufficient time is taken to reach
equilibrium, then also accurate sorption data can be obtained. Below an example of such measurement
is shown.

You will find many scientific publications in literature that lists the parameters for the GAB equation.
However, as examples, some values for the parameters are given here:

Material w0 C K Conditions Reference;

comments
Tomato 16.6 31.4 0.83 30C w0 in g moisture per
100 g dry product.
Corn Bran 7.21 9.8 0.76 25C
Fish flour 5.80 5.1 0.81 25C
Collected by
Potato starch 9.79 20.4 0.75 20C
E.O. Timmermann, J.
Wheat starch 9.89 26.7 0.68 20C Chirife, H.A.Iglesias,
Journal of Food
Wheat 10.24 18.6 0.62 25C Engineering 48
(2001) 19-31
Chicken (cooked) 7.75 18.7 0.86 19.5C
Turkey (cooked)a 9.29 7.41 0.82 22C
a: adsorption
Turkey (cooked)d 6.92 7.50 0.79 22C
d: desorption
Corn flour 10.27 42.4 0.59 25C
Rice 11.0 19.2 0.58 25C

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 Food Material Properties - Theory

Material w0 C K Conditions Reference;

comments
Corn 9.78 18.8 0.633 30C
Wheat gluten 6.38 16.4 0.78 30C
Skim milk 4.27 38.0 0.876 34C
Popcorn 6.744 11.08 0.880 10C M. Maskan et al.,
19993
6.101 15.97 0.856 20C
w0 is on weight%
5.764 7.424 0.850 30C dry basis
*for aw < 0.43
Popcorn coated with 33.25 0.284 0.724 10C M. Maskan et al.,
sugars 19993
28.47 0.276 0.720 20C
w0 is on weight%
24.01 0.254 0.744 30C dry basis
Cracker 0.050 9.012 0.957 20C (S.S. Kim 1998) 4

0.044 5.051 0.974 30C w0 in kg water/kg

solids
0.040 3.378 0.987 40C
Strawberry jam: 37.3
Cookie 0.034 5.866 0.982 20C wt% moisture
0.032 4.204 0.997 30C Thickness of cracker:
3 mm
0.030 2.979 1.010 40C
Thickness of cookie:
Strawberry jam 0.135 75.773 0.990 20C 4 mm
0.080 42.034 1.009 30C Thickness of jam
layer: 2 mm
0.050 25.980 1.031 40C
Cracker + 0.060 67.696 0.972 20C
strawberry jam +
cracker 0.052 38.647 0.976 30C
0.044 20.085 0.981 40C
Cookie + strawberry 0.045 57.978 0.953 20C
jam + cookie
0.038 27.254 0.992 30C
0.034 10.018 1.022 40C
Minced meat −0.054𝑇 1279.3 0.0012 < 40C (I. Lind 1991) 5
𝑒𝑥𝑝 ( − 1.966) 𝑒𝑥𝑝 ( − 0.377)
+ 2254 𝑇 𝑇
T = temperature (K)
4740 > 40C
𝑒𝑥𝑝 (− + 17.9)
𝑇

3 M. Maskan, F. G. (1999). “Water adsorption properties of coated and non-coated popcorns.” J. of Food
Proc. Preservation 23: 499-513.
4 S.S. Kim, S. Y. K., D.W. Kim, S.G. Shin, K.S. Chang (1998). “Moisture sorption characteristics of composite
foods filled with strawberry jam.” Lebensm.-Wiss. u.-Technol. 31: 397-401.
5 I. Lind, C. r. (1991). “Sorption isotherms of mixed minced meat, dough and bread crust.” J. Food Eng. 14:
303-315.
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