LAYOUT

• Water content of foods

• Structure of water molecule
• Water binding / sorption isotherms
• Types of water
• Water activity & reaction rate / keeping
quality
• Significance of water
 WATER CONTENT OF FOODS

D Whole milk, non-fat milk, butter milk 87-91%

A
Dry milk powder 4%
I
R Soft cheese (e.g., Cottage) 55-80%
Y
Semi-soft cheese (e.g. Mozzarella) 45-55%
Semi-hard cheese (e.g., Cheddar) 35-45%
F
O Hard cheese (e.g., Parmesan) <35%
O
Butter 15%
D
S Ice cream 65%
Margarin 15%

Mayonnaise 40%

Fruits >90%

Grains 10-12%

Macaroni 9%

White sugar, hard candy, chocolate 1%

Jellies, Marmalades 35%

 STRUCTURE OF WATER MOLECULE
• Some physical properties of water are exceptional:

Common Melting Boiling Heat of Vaporization *

liquids point °C point °C cal/g
Water 0 100 540
Ethanol -117 78 204
Hexane -98 69 101
Chloroform -63 61 59

(* Heat of vaporization: The number of calories of

heat energy required to convert 1.0 g of a liquid at
its boiling point - at atmospheric pressure into its
gaseous state at the same temperature)
There are strong forces of attraction between
adjacent water molecules, which give liquid water
great internal cohesion.

The heat of vaporization is a direct measure of the

amount of energy required to overcome the
attractive forces between adjacent molecules in a
liquid so that they can escape from each other
and enter the gaseous state.
Why does water show such strong intermolecular
attraction?

Each of its hydrogen atoms shares an electron pair with

the oxygen atom. The geometry of the shared electron
pairs causes the molecule to be v-shaped.

δ δ
H
104.5oC
Unshared O H
δ
electron 0.096 nm
covalent
pairs

δ
bond
(σ bond)
 δ δ
H
104.5oC
O H
δ
δ
Two unshared electron pair of
oxygen atom give it a localized
partial negative charge at the
apex of the V.
The strong electron withdrawing tendency of oxygen
gives the two hydrogen nuclei partial positive charges.
 An
An Electric
Electric Dipole
Dipole
Although the water molecule is electrically neutral,
its partial positive and partial negative charges are
separated, with the result that the molecule is an
electric dipole.
Becauseof
Because ofthe
theseparation
separationofofcharges
chargestwo
twowater
water
moleculescan
molecules canbe beattracted
attractedtotoeach
eachother
otherbyby
electrostaticforces
electrostatic forcesbetween
betweenthe
thepartial
partialnegative
negative
chargeon
charge onthe
theoxygen
oxygenatom
atomofofone
onewater
watermolecule
molecule
andpartial
and partialpositive
positivecharge
chargeononaahydrogen
hydrogenatom
atomofof
theother.
the other.
 δ δ
H
104.5oC
O H
δ
δ

Because of the nearly tetrahedral arrangement of

the electrons about the oxygen atom, each water
molecule theoretically can form hydrogen bonds
with as many as 4 neighboring water molecules.
 H H
O
H H
H H O
H O
H
O
H H
O

9At room temperature, each water molecule

forms hydrogen bonds with an average of 3.4
other water molecules.
9Hydrogen bonds are constantly and
rapidly being broken and reformed in liquid
state.

9In ice, each water molecule is fixed in space and

hydrogen bonds with the maximum of 4 other water
molecules, to yield a regular lattice structure
(Relatively high melting point !)
 An example of polar liquid !
9 Non-polar liquids, like benzene or hexane, show
relatively little tendency to attract each other
electrostatically (much lower heat of vaporization).
Bond Energy
The hydrogen bond 4.5 kcal / mol
Covalent H-O bonds 110 kcal / mol

9Because of their large number, hydrogen bonds

give great internal cohesion on liquid water.
Consequently, liquid water is not viscous but very
fluid.
 WATER BINDING / SORPTION ISOTHERMS
9 The state of water in a food is described by the
relationship between its moisture content and the
relative humidity of air surrounding it. The ratio of these
two figures is called water activity (aw).
9 The relative humidity corresponding to each specific
moisture content of the product is called equilibrium
relative humidity and the following relationship applies;
aw = P / Po = ERH / 100

P: Partial vapor pressure of water in food (at T°C)

Po : saturation vapor pressure of pure water at T
ERH: Equilibrium relative humidity at T
9 At high moisture contents, when the amount of
moisture exceeds that of solids, aw is close or equal to
1.0 . When moisture content is lower than that of
solids, aw is lower than 1.0.

100
90
80
70
60
RH %

50
40
30
20
10
0
0 1 2 3
g moisture/g solid

Water activity value between 0.0 -1.0

• An isotherm is a curve that describes the equilibrium relation of the
amount of water sorbed by the food components and vapor pressure
or relative humidity.

Desorption: Process of drying

Moisture %
Adsorption: take up water

A B C RH %

• Depending on whether water is given off or taken up in approaching

the equilibrium between vapor pressure and moisture content a
desorption or an adsorption isotherm results.
NOTICE ! Desorption isotherm curve is somewhat above the adsorption
isotherm. This phenomenon known as HYSTERESIS
 •The relationship between moisture content and RH
is represented by sorption isotherms.

•Adsorption and desorption processes are not fully

reversible.

• Therefore, a distinction can be made between the

adsorption and desorption isotherms by determining
whether a dry product’s moisture levels are increasing,
or whether the product’s moisture is gradually lowering
to reach equilibrium with its surroundings, implying that
product is being dried.
 Typical curve for foods containing high sugar or
salt contents and having low capillary adsorption.
Such foods are hygroscopic.

M.C %

Quite steep,
indicating
highly
hygroscopic
conditions
RH %
The first part of the curve is quite flat
indicating low hygroscopicity
Three regions of water binding are observed in
sorption isotherm curves;
(A) first part corresponds to the adsorption of a
monomolecular layer of water - TYPE III non-
freezeable
(B) The second flatter part corresponds to the
adsorption of additional layers of water - TYPE II
(C) Third part relates to the condensation of
water in capillaries and pores of the material -
TYPE I (mobile)

Pay attention to BET Value! - Monolayer value

 The reason of hysteresis

% Moisture

A B C RH %
• Capillaries close during drying of food, thus decreasing the
free inner space.
• To fill remaining capillaries of which the geometry differs
strongly in various foods, a higher partial pressure of water
vapour is required than in the case of moisture removal.
• Water condenses in capillaries, and the effect occurs in
region C and B.
; It is assumed that capillaries have narrow
necks and large bodies.

2r

2R
; During adsorption the capillary will not
fill completely until an activity is reached
which corresponds to the large radius R.

2r 2r

2R 2R

; During desorption, the unfilling is

controlled by the smaller radius r , thus
lowering the water activity.
 TYPES OF WATER

Free water in the intergranular spaces & pores of the

material. It retains its usual physical properties and
serves as a dispersing agent for colloidal substances
and as a solvent for the crystallizing compounds.
Adsorbed water on surface of macro molecules
(starches, pectin, cellulose, proteins)
Bound water in combination with various substances
that is as water of hydration.

This classification is somewhat arbitrary. Attempts to

determine quantitatively the amounts of various forms
of water in foods have been unsuccessful + + +
WATER ACTIVITY AND REACTION RATES
or KEEPING QUALITY

The rates of many reactions are influenced by the level

B
of aw. In general decreased aw ; r
• retards the growth of e
a
microorganisms d

• slows enzyme catalyzed reactions m

o
• retards non-enzymatic browning l
In contrast, the rate of lipid autooxidation increases in d
dried food systems.
 Water Activity & Reaction Rates

5 6
1 1 Lipid
Reaction oxidation
2 Non-enzymatic
rate browning
3 Enzymatic
browning
4 Fungi
2 5 Yeasts
3 4
6 Bacteria
0 0.2 0.7 1.0

aw
 Microbial
Microbial Growth
Growth

As aw increases, water becomes more available as a

solvent and medium for reactions. Approximate
lower limits of aw for microbial growth are;

0.91 for bacteria

0.88 for yeasts
0.80 for molds
0.75 for halophilic bacteria
0.60 for osmophilic yeasts
 Non-Enzymatic
Non-Enzymatic Browning
Browning Reactions
Reactions

The increased availability of water

accelerates browning reactions and loss of
nutritional value.

The reaction is at maximum at 0.7 of aw.

However at lower aw the rate of reaction is
slower, due to the absence of solvent/water to
carry the reactants to react each other.
 Enzyme
Enzyme Activity
Activity
Enzyme activity increases gradually as the aw
increases.

Lipid
Lipid Oxidation
Oxidation

Rate of lipid oxidation reaches a maximum at 0.7 aw.

This involves a complex set of reactions.
 INTERMEDIATE MOISTURE FOODS

Foods with aw values between 0.6 and 0.9 (IMF)

Salami 0.82-0.85
Dried Fruits 0.72-0.80
Marmalades 0.82-0.94

Can we decrease water activity?

One of the options to decrease water activity and
thus improve the shelf life of food is to use
additives with high water binding capacities
(Humectants : Polyhydric alcohols, sugars and/or
salt)
 SIGNIFICANCE OF WATER
1. Its properties affect thermal conductivity
and diffusion and several heat and mass
transfer properties.

Many changes may take place, particularly,

during freezing and drying operations to
preserve foods.

WHY ???
Deteriorative changes during heat treatment of
foods are accelerated at high temperatures and
slowed down as moisture is reduced !!!
 2. Biochemical stability of foods is related
to the moisture content of foods.

WHY ???
Water acts as a solvent to interact with other
components and provides a medium for
diffusion and reaction of those components

Cl Cl O
O C C
O O C O
HO C
O N OH + HO N OH +
H O C
HO C
Cl H C Cl H C

CHOH CHOH

CH OH CH OH
2 2

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3. The microbiological deterioration of food is
influenced by the water content of foods.

Grain that contains more

than 14 % water (critical
moisture content) is
susceptible to mould
invasion. Also such grain is
subject to deterioration from
heating, insect damage and
sprouting.
4. The amount of water in food is inversely related to
the amount of dry matter.

The concentration of many

biochemical components is
reported on a dry basis in order to
make a meaningful comparison with
available data or literature values.
E.g. Wheat Protein based on 12 %
moisture content
5. The water content of food is of direct economic
concern to the processor and the consumer.

For some foods moisture

content is regulated through
legal enforcements in order
to protect the consumers.
6. The rate of browning of dehydrated vegetables
and fruits, or oxygen absorption by egg powders
increases with an increase in water content.

Water acts as a carrier of

substances to react with
each other (only in a
certain range of aw
values 0.4-0.75).