Dr.

Nguyen Minh Xuan Hong

FOOD CHEMISTRY
210251
Chapter 2.
Water in Food
Dr. NGUYỄN MINH XUÂN HỒNG
Department of Food Biochemistry and Human Nutrition
Faculty of Chemical Engineering and Food Technology
Nong Lam University Ho Chi Minh City
[email protected]
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Water
Outlines
major components of many foods.
Structure and general properties of water occur as an intercellular or extracellular
component in vegetable and animal products
Bound water and water activity
Water activity and food stability occur as a dispersing medium or solvent in a
variety of products,
Moisture sorption isotherms
occur as a dispersed phase in emulsified products
such as butter and margarine.
Water affects structure, appearance, and taste
of foods and their susceptibility to spoilage.
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Water contents of some foods

Food Water content (%)
Structure of water molecules
Meat: Pork (raw), Beef (raw), Chicken (raw),
53-60; 50-70, 74; 65-81 In the water molecules, the H and O atoms are arranged at the angle
Fish
Fruit 80-95 of 104.5 degrees (H-O-H).
Vegetable : banana, peas, avocado 74 - 80
: Carrots, potatoes, broccoli 85 - 90
: Asparagus, beans, cabbage, 90 - 95
cauliflower, lettuce
The bond angle is slightly less than the 109.5 of a perfect tetrahedron
Milk 87 because of crowding by the nonbonding orbitals of the oxygen atom.
Wheat flour 12
The oxygen nucleus attracts electrons more strongly than does the
Bread, white 35 hydrogen nucleus (a proton)  oxygen is more electronegative
Butter and margarine 16  two electric dipoles in the water molecule
Cheese 37  There is an electrostatic attraction between the O atom of one
Honey 20 water molecule and the H of another, called a hydrogen bond.
Shortening 0 5 6

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Water Structure

2 electric
Dipoles

Monomolecular water :
there is no hydrogen bond Water molecules are engaged in
hydrogen bonding. Lifetime of each
hydrogen bond is just 1 to 20
picoseconds (1 ps = 10–12s).
Upon breakage, another hydrogen
bond forms. Each molecule forms
hydrogen bonds with an average of
only 3.4 other molecules.
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SOLID STATE: SOLID WATER Structure of water molecules (cont.)

 Hydrogen bonds between water molecules provide

the cohesive forces that make water a liquid at room
temperature and that favor the extreme ordering of
molecules that is typical of crystalline water (ice).

 Water has a higher melting point, boiling point, and

In ice, each water molecule forms the maximum of four hydrogen bonds, heat of vaporization than most other common
creating a regular crystal lattice. This crystal lattice of ice makes it less solvents. These unusual properties are a consequence
dense than liquid water, and thus ice floats on liquid water. of attractions between adjacent water molecules that
Breaking a sufficient proportion of hydrogen bonds to destabilize the give liquid water great internal cohesion.
crystal lattice of ice requires much thermal energy, which accounts for
the relatively high melting point of water.
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 Water has a higher melting point, boiling point, and

heat of vaporization than most other common solvents.
These unusual properties are a consequence of attractions
between adjacent water molecules that give liquid water
great internal cohesion.
Physical Properties Of Some Hydrides:

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Water-solute interaction
Hydrogen bonds are not unique to water. Water forms hydrogen
bonds with polar solutes.

Common hydrogen bonds in biological systems.

The hydrogen acceptor is usually oxygen or nitrogen; the
hydrogen donor is another electronegative atom.
Hydrogen atoms covalently bonded to carbon atoms do
not participate in hydrogen bonding
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Water is a polar solvent. It readily dissolves most biomolecules, which

are generally charged or polar compounds. Compounds that dissolve
easily in water are hydrophilic. Some Examples of Polar, Nonpolar, and Amphipathic Biomolecules
(shown as ionic forms at pH7)

Nonpolar solvents such as chloroform and benzene are poor

solvents for polar biomolecules but easily dissolve those that
are hydrophobic.
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 As a polar solvent, water readily dissolves most biomolecules,

which are generally charged or polar compounds.

 Water dissolves salts (Ex: NaCl) by hydrating and stabilizing

Na and Cl ions, weakening the electrostatic interactions
between them and thus counteracting their tendency to
associate in a crystalline lattice.

 The same factors apply to charged biomolecules, compounds

with functional groups such as ionized carboxylic acids (-COO-),
protonated amines (NH3+ ), and phosphate esters or anhydrides.
Water readily dissolves such compounds by replacing solute-
solute hydrogen bonds with solute-water hydrogen bonds, thus
screening the electrostatic interactions between solute molecules.

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Sodium chloride : solute

Water - nonpolar compound interaction
Dissolved chloride ion Dissolved sodium ion

 Nonpolar compounds such as benzene and hexane are

hydrophobic. When water is mixed with them, two phases
form. They are unable to undergo energetically favorable
interactions with water molecules, and they interfere with the
hydrogen bonding among water molecules.

hexane benzene

Bound water and free water

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Water - Amphipathic compounds interaction

Water orientation at
hydrophobic surface Amphipathic compounds contain both polar and non
polar regions, such as protein, phospholipids pigments
and some vitamins.

When an amphipathic compound is mixed with water,

the polar, hydrophilic region interacts favorably with
the solvent and tends to dissolve, but the nonpolar,
 Water form a highly ordered cagelike shell hydrophobic region tends to avoid contact with water.
around each nonpolar molecule.
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The nonpolar regions of the molecules cluster together

to present the smallest hydrophobic area to the aqueous
solvent, and the polar regions are arranged to maximize Because exposure of
their interaction with the solvent  micelles. protein nonpolar groups to
water is thermodynamically
unfavorable, association of
hydrophobic groups or
hydrophobic interaction is
occurred.
Hydrophobic interaction
provides a driving force for
protein folding, causing
hydrophobic residues
positions in the interior of
protein molecules.

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Bound water vs. Free water

Bound water: portion of water that is tightly held by solutes
or hydrated compounds (food components)
Free water: portion of water that has no bond with other food
components
Bound water is that which:
◦ is unavailable for the proliferation of microorganism
◦ is unavailable as a solvent and therefore is not considered as a
medium for the diffusion of active agents that produce chemical
reactions
◦ does not freeze at some low temperature (usually –40oC)
◦ is not evaporative
Free water is that which:
◦ available for the proliferation of microorganism
◦ available as a solvent and therefore as a medium for the
diffusion of active agents that produce chemical reactions
◦ is readily freezable
◦ is evaporative

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Bound water Forms of Water in Foods

Definition The ease of water removal from foods depends on how it
 Bound water is the water that remains unfrozen at some prescribed temperature below exists in the food product. The three states of water in food
0 oC, usually -20 oC. products are:

 Bound water is the amount of water in a system that is unavailable as a solvent.  Free water: this water retains its physical properties and
thus acts as the dispersing agent for colloids and the
 Based on protein content, about 8 to 10% of the total water in animal tissue is
solvent for salts.
unavailable for ice formation. Egg white, egg yolk, meat, and fish all contain
approximately 0.4 g of unfreezable water per g of dry protein. Most fruits and  Adsorbed water: this water is held tightly or is occluded
vegetables contain less than 6% unfreezable water. in cell walls or protoplasm and is held tightly to proteins.
 Bound water is the water that bound to the macromolecules through Van der
 Water of hydration: this water is bound chemically, for
Waal’s forces and hydrogen bonds. Bound water lost is solvent power, and it can not
example, lactose monohydrate; also some salts such as
be frozen since the energies of water-molecule bonds are higher than those between the Na2SO4.10H20.
water molecules in ice.
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In food, free water functions as a medium for

chemical reactions.
In food, free water functions as a medium for
microbiological growth

Free water: profoundly influences the susceptibility to spoilage of foods

The storage quality of food does not depend on the

water content, but on the water availability for chemical
reactions and for microbiological growth (Scott, 1952)
 water activity (aw)

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Water activity
 Water activity defined as follows:
a w = P/P 0 = ERH/100 = n a /(n a +n b )
where P = partial vapor pressure of food moisture at temperature T
P0 = saturation vapor pressure of pure water at temperature T
ERH = equilibrium relative humidity at temperature T
na = mole of solvent in the solution
nb = mole of solute in the solution

 Measure water in vapor in equilibrium with water in food.

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 In a container, there is equality between the activity of the food stuff and the  Placed the open air, the activity of the foodstuff equals
partial vapor pressure which is exerts. the relative humidity of the air.
aw = ERH / 100 ERH = equilibrium relative humidity at T.

 relationship between water content and water activity

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Water activity levels

Water activity negatively correlated with
solute and intermolecular interaction.

 For aw < 0.2 ; water strongly interacts with

solutes and not available as solvent, reactant,
for freezing and vaporization.

For aw close to 1; water act as a bulk water,

available for reaction, for freezing and for
vaporization.
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Water activity (cont.)

Water engaged in strong associations is less able to support
degradative activities, such as growth of microorganisms and
hydrolytic chemical reactions, than is weakly associated water.
The term “water activity” (aw) was developed to account for
the intensity with which water associates with various non
aqueous constituents.
Food stability, safety, and other properties can be predicted
more reliably from aw than from water content.
Water activity (aw) correlates well with rates of microbial
growth and many chemical reactions.
Color change of milk powder kept at 40oC for 10 days as a function of water activity

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aw can apply to predict the growth of bacteria, yeasts and molds. Water activity
To prolong shelf life at ambient storage, it is necessary to
control either its acidity level (pH) or the level of aw or a
suitable combination of the two. This can effectively increase Calculation
the product's stability.
Water weight 1 kg contain 55.51 mole of water.
The risk of food poisoning must be considered in low acid
foods (pH > 4.5) with a water activity greater than 0.86.
If sugar added for 1 mole to the solution.
Staphylococcus aureus, a common food poisoning organism, Calculate the water activity of the solution.
can grow down to this relatively low water activity level. Foods
which may support the growth of this bacterium include cheese
and fermented sausages stored above correct refrigeration
aw = 55.51/(1+55.51) = 0.9823
temperatures.
Food can be made safe to store by lowering the water activity to
a point that will not allow dangerous pathogens such as
Clostridium botulinum and Staphylococcus aureus to grow in it.
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How to lower water activity? Factor affect water activity

 Decrease moisture content by drying.

 Freezing to make ice that unavailable for degradation

reactions.

 Increase hydrophilic solutes by addition of water-

soluble substances, such as sugar to jams or salt to
Temperature
pickled preserves. The additive such as salt, glycerol,
sorbitol and sucrose with high water binding capacities aw
(humectants) can be used for decreasing water activity
and thus improving the shelf life of food.

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How to measure the water activity?

 A sample is placed in a small closed chamber at constant temperature, and a
relative humidity sensor is used to measure the ERH of the sample atmosphere
after equilibrium.

 The chill mirror technique: the water vapor in the headspace condenses on
the surface of a mirror that is cooled in a control manner. The dew point is
determined by the temperature at which condensation take place and this
determines the relative humidity of the head space.

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In a chilled mirror dewpoint system, water activity is measured by When the water activity of the sample and the relative humidity of the air
equilibrating the liquid phase water in the sample with the vapor phase are in equilibrium, the measurement of the headspace humidity gives the
water in the headspace of a closed chamber and measuring the relative water activity of the sample.
humidity of the headspace.
A sample is placed in a sample cup which is sealed against a sensor block.
The purpose of the fan is to speed equilibrium and to control the boundary
Inside the sensor block is a fan, a dewpoint sensor, a temperature sensor, layer conductance of the dew point sensor.
and an infrared thermometer.
The dewpoint sensor measures the dewpoint temperature of the air, and the
infrared thermometer measures the sample temperature.

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Moisture sorption isotherm (MSI)

 A plot of water content (expressed as mass of water
per unit mass of dry material) of a food versus aw at
constant temperature.

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 Zone 1: most strongly absorbed and least mobile. This water

associates with accessible polar sites by water-ion or water-dipole
interactions, is unfreezable at -40°C, has no ability to dissolve
solutes, and is not present in sufficient amount to have a plasticizing
effect on the solid. It behaves simply as part of the solid.
 Zone 2: loosely bound water, possibly additional layers bound to the
Zone 1 water.
 Zone 3: bulk water, effectively a dilute solution, easily removed
with minimal impact on food stability. This water is freezable,
available as a solvent, and readily supports the growth of
microorganism.
 The high moisture end of Zone I (boundary of Zones I and II) “BET monolayer”
corresponds to the “BET monolayer” moisture content of the
food. The BET monolayer is the amount of water needed to form a
The BET monolayer is the amount of water needed to form a monolayer
monolayer over accessible, highly polar groups of the dry matter. In
the case of starch, this amounts to one HOH per anhydroglucose. over accessible, highly polar groups of the dry matter.
BET monolayer value of a food provides a good first estimate of the
 BET monolayer value of a food provides a good first estimate of water content providing maximum stability of a dry products.
the water content providing maximum stability of a dry products.
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 The dried foods correspond to the lower part of the sorption isotherms.
This includes water in the monolayer and multilayer category.
 Intermediate
moisture foods
(IMF) have water
activities generally
above 0.6.
 These foods are
largely protected
against microbial • The two main shapes found in food isotherms are sigmoidal and J-shaped.
spoilage.
• Most foods are sigmoidal. Some sugar based foods such as fruits,
confections, coffee extracts show a J-shaped isotherm. Foods contain high
sugar content will absorb relatively small amounts of water at low relative
humidity and large amounts when exposed to high relative humidity.
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A steep slope curve indicates that the material is hygroscopic

(curve A) and a flat curve indicates a product that is not very
sensitive to moisture (curve B).
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MSI is useful for

Model for MSI
 Concentration and dehydration processes, because the There are several models for analyze MSI data Model such as
ease or difficulty of water removal is related to water Brunauer, Emmett, and Teller (BET) and Guggenheim, Anderson,
activity. and DeBoer Model (GAB).
 Formulating food mixtures to avoid moisture transfer The BET equation has been used in many cases to describe the
among the ingredients. sorption behavior of foods.
 Determine the moisture barrier properties needed in a BET model
packaging material.
 Determine what moisture content will curtail growth of
microorganisms of interest
 Predict the chemical and physical stability of food as a
function of water content
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Calculate BET monolayer

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Moisture Sorption isotherms

GAB equation for multilayer

m = measured moisture at water activity = aw

mo = monolayer moisture content (the optimal moisture content for
maximum stability
kb = the GAB multilayer constant
c = the isotherm temperature dependence coeffcient

c=e
Qs/RT

where; Qs = excess enthalpy of sorption

BET plots for dehydrated potato R = gas constant
T = temperature in K
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Different types of resorption isotherms. Temperature 20oc, except for no. 1

which was measured at 40oc.
1.Powered sucrose 4.Pig pancrease extract powder
2.Spray-dried chicory extract 5.Native rice starch
3.Roasted columbian coffee

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Importance of Water Activity

Temperature dependence

Water activity limits for growth of microorganisms in foods and examples of foods
with water activities over the range of various growth limits.
But aw is only one factor controlling growth; in addition, there are several other
Temperature dependence of water sorption of corn starch. Changes in temperature and water factors, such as pH and temperature.
content affect water activity as shown (arrows).

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With the exception of lipid oxidation, all of the rates

decrease at least 100 fold as the zone 2 water is
removed and effectively stop at the monolayer value.
This is because reagents responsible for a reaction
need a solvent to move around in order to encounter
each other and react.

As the solvent is removed the rate decreases and,

as monolayer water is not adequately liquid-like to
act as a solvent, the reaction stops.
Several rates may slightly decrease at high water
activities due to dilution of the reagents.

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Development of microorganisms
 Optimum growth of microorganisms is achieved at 0.92 < aw<0.99. The
microbial stability is therefore very great in products which are dehydrated
(aw=0.2-0.4) or at the intermediate moisture content (aw=0.6-0.8) and in
products where the water activity has been lessened by the addition of salt
or sugar (as in cheese, large sausages, jams).
 The minimum levels of water activity required differ according to the
microorganisms: 0.91 for bacteria, 0.88 for yeasts, and 0.80 for molds.
However, certain species may exhibit lower minimal values of aw for
growth; thus the halophilic bacteria, the xerophilic molds and osmophilic
yeasts develop at aw 0.75, 0.65, and 0.60, respectively.
 For molds, the lower limit is 0.7-0.8 which can be dangerous if mycotoxins
are produced.
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 For lipid oxidation, start from the left of isotherm, the rate of
Enzyme reactions oxidation decrease until the BET monolayer value is attained.
Clearly, overdrying of samples subject to oxidation will result in
less than optimum stability. The first water added to a very dried
 Enzyme activity follows water activity because of the sample is bind hydroperoxides, interfering with their
greater mobility of the reactants at a high level of decomposition and thereby hindering the progress of oxidation.
water content. In addition, this water hydrates metal ions that catalyze
oxidation, apparently reducing their effectiveness.
 Addition of water beyond the boundary of Zones I and II results in
 However, most enzymes are inactive when the water increased rates of oxidation suggested that water added in this
activity falls below 0.85. Such enzymes include region of the isotherm accelerates oxidation by increasing the
amylases, phenol oxidases, and peroxidases. solubility of oxygen and by allowing macromolecules to swell,
thereby exposing more catalytic sites.
 There is an exception in the case of lipases. Lipases At still greater (>0.80) the added water
may remain active at values as low as 0.3 or even 0.1. may retard rates of oxidation, and the
suggested explanation is that dilution
of catalysts reduces the effectiveness.
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Lipid oxidation
Browning reaction
 Maillard browning reaction exhibit maximum rate at
 At aw= 0.2 ; maximum stability is obtained when the single layer
of water molecules hinders the passage of oxygen to the lipids or
intermediate to high activity (aw 0.5-0.7), since the
enters into competition with the oxygen molecules to occupy the mobility of the reactants is optimal in this zone.
absorption sites.
 For aw > 0.5-0.7, the speed
 At 0.2< aw< 0.5; the active peroxides are at a low concentration decreases because this
because a high proportion of them bind water. The antioxidants are
mobile and active while the metallic catalysts are not very active corresponding to a tripling in
because of hydration. water content. The water also
 At aw> 0.5 ; the metallic catalysts diffuse freely towards the sites
restrains the reaction if aw >
of oxidation and the catalysts has greater power than the 0.75, because it inhibits the
antioxidant effect in the water. Consequently, the oxidation speed reactions of internal
up. dehydration affecting the
 At aw> 0.9; at very high levels of activity, oxidation slows down; Amari compounds formed
this is due to the effect of dilution. through Maillard reaction.
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Hysteresis
 Hysteresis represents the difference in aw between the
adsorption (starting from the dry state) and desorption
(starting from the wet state) isotherms.
 Typically, at any given aw, the water content of the
sample will be greater during desorption than during
adsorption.
 MSIs of polymers, glasses of low molecular weight Same water content: aw in desorption < aw in adsorption
compounds, and many foods exhibit hysteresis. → most adsorbed water is free water
 MSIs are highly product specific and the MSI for a given Same water activity: Water content in desorption > Water
product can be changed significantly by the manner in
which the product is prepared, and that these points are of content in adsorption
practical importance. → Rehydrated food cannot as fresh as the raw food
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Hysteresis
 The magnitude of hysteresis, the shape of the curves, and
the inception and termination points of the hysteresis
loop can vary considerably depending on factors such as
nature of the food, the physical changes it undergoes
when water is removed or added, temperature, the rate of
desorption, and the degree of water removal during
desorption.
 Generally, the adsorption isotherms are required for
the observation of hygroscopic products, and the
desorption isotherms are useful for investigation of
the process of drying.

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Desorption isotherm, indicating the course of a drying process, lies slightly

above the adsorption isotherm pertaining to the storage of moisture-
sensitive food.
Sorption isotherm of wheat flour, starch, and gluten
The position of the hysteresis loop changes when adsorption and desorption
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Water migration Water migration

 Water activity equilibrium (thermodynamics) and For example,
rate of diffusion (dynamics of mass transfer) are the  When a crispy cracker of low water activity is put into
two main factors affected moisture migration in a multi contact with cheese, jam or a fruit paste of high water
domain food. activity, it absorbs water and becomes rubbery.
 Multi domain foods with regions formulated to different  Cereals with semi-dried fruits begin to pick up water
and become less crisp at aw > 0.5. The same alteration
water activities cause the whole system to be in a non
occurs in various multi-domain systems such as pizza
equilibrium state. This will result in moisture migration crust with sauce or a baked cone filled with ice cream.
from the higher aw (higher chemical potential) to the
lower aw region and can result in undesirable changes
in the system.

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Water migration (cont.) Water migration (cont.)

 When a dry cracker at an aw of 0.30 is put in a sealed  The final water activity of both the cracker and
chamber with a relative humidity of 75% at 25oC. The the cheese is 0.75 since they were both
initial moisture of the cracker is 3% (w/w) and thus it equilibrated at 75% RH. The aw of the two
gains water at this high humidity. The final moisture systems is the same, although the moisture
after equilibration may be about 15 % (w/w). contents are very different (15% vs 25%).
 In another chamber under the same conditions, a
piece of cheese with an initial aw of 0.95 is placed.  If the cheese and the cracker are put together
Initially, the cheese has a moisture content of 60% in a package. No moisture exchange occurs
(w/w), but it loses moisture, and after equilibration it because they are in thermodynamic
has a moisture content of 25% (w/w). equilibrium.

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Thermodynamic equilibrium
For the system to be thermodynamic equilibrium it is necessary that it should be
under mechanical, chemical and thermal equilibrium. If any one of the above
condition are not fulfilled, the system is said to be in non-equilibrium.
1) Mechanical equilibrium: When there are no unbalanced forces within the system
and between the system and the surrounding, the system is under mechanical
equilibrium. The system is also in mechanical equilibrium when the pressure
throughout the system and between the system and surrounding is same. Whenever
The end!!
some unbalance forces exist within the system, they will get neutralized to attain the
condition of equilibrium. Two systems are in mechanical equilibrium with each other
when their pressures are same.
Any questions???
2) Chemical equilibrium: The system is in chemical equilibrium when there are no
chemical reactions going on within the system or there is no transfer of matter from
one part of the system to other due to diffusion. Two systems are in chemical
equilibrium with each other when their chemical potentials are same.
3) Thermal equilibrium: When the system is in mechanical and chemical equilibrium
and there is no spontaneous change in any of its properties, the system is in thermal
equilibrium. When the temperature of the system is uniform and not changing
throughout the system and also in the surroundings, the system is thermal
equilibrium. Two systems are thermal equilibrium with each other if their
temperatures are same.
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