Basics in Food Chemistry Water

Chapter II
WATER

Introduction
We all know that water is essential for the sustenance of all forms of life on the planet Earth.
Its enormous usability and utility makes it a wonder liquid. It not only occupies about 70% of our
planet but also constitutes a good component of the living systems like the plants, animals, and the
human body. All the food products contain varying amount of water in their tissues; in many cases to
the extent of more than 90 per cent. Various quality and processing attributes like deterioration,
dehydration, spoilage etc., in raw as well as processed foods, are influenced by the water content.

It is very important to understand the nature and properties of water to relate these with
various processes related to the food quality and its maintenance in food industry. Water activity and
sorption isotherms are two important concepts which help in understanding the role of water in
drying, packaging and preservation etc. The physical, chemical and microbiological quality of water
used in food processing operations should conform to certain standards. Therefore, knowledge of the
quality parameters and standards of water is also very important.

Moisture in foods

1. The most abundant compound and the one which is almost always present in foods is
water.

2. Water is the chemical substance with chemical formula H2O: one molecule of water has
two hydrogen atoms covalently bonded to a single oxygen atom.

3. Occasional a food such as oil will be dry; but even crystallized substances which are
relatively pure, such as sugar and salt, contain small amounts of water absorbed on the
surfaces of the crystals.

4. Cellular material, whether plant or animal contains an abundance of water.

5. In leafy green vegetables there is more than 90 percent water, while even in cooked meat
where some water has been driven off the amount is between 50 and 65%.

The water which is present in foods may be held as

1. As a free liquid in which substances are dissolved & dispersed

2. As hydrates

3. As imbibed water in gels

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Basics in Food Chemistry Water

4. By absorption on the surfaces of solids.

Examples of the first type are found in cytoplasm intracellular fluid and any of the
circulating fluids of tissue.In the second type, hydrates form either when hydrogen bonds are
established between water molecules and ions or molecules which contain oxygen or nitrogen or
when the unshared electrons of the oxygen or nitrogen or when the unshared electrons of the
oxygen are coordinated with an ion starches.Imbibed water may not be different from water held
as a hydrate. Some substances pick up water and swell when they come in contact with water.
The fourth type of water is held on all surfaces exposed to air in which water vapour is present
“Dry” coca holds water and air on the surface of the particles.

Type of Water in Foods

The water content or the moisture content of a food influences its appearance, texture and
flavour. It varies a great deal in different food items. The green leafy vegetables contain more than
90 per cent of water while it may be negligible in oils and fats like ghee, butter, oil etc. Table 1
enlists the water content of some common food materials.

Table 1:Water Content of Some Common Foods

Sr. Products Water (%)

No.
1. Green leaves 95
2. Tomato 95
3. Water melon 93
4. Orange 87
5. Potato 78
6. Banana 75
7. Butter 16
8. Legumes (dry) 9-11
9. Rice, Wheat, Jowar 12 – 13
10. Tur &Mungdal, chawali 10 – 13
11. Groundnut, sesame, 3–8
Mustard
12. Jaggery, sugar 4 – 0.4
13. Butter & Ghee, oil, 19 & 0
vanaspati
14. Apricots, Raisins, dates 15 – 20
15. Leafy vegetables 92
16. Cabbage, spinach 92
17. Tapioca 60
18. Radish 95
19. Cucumber, pumpkin 92 – 96
20. Milk, cows 88

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Basics in Food Chemistry Water

21. Fish 75
22. Eggs 74
23. Poultry, 72
24. Meat, Mutton 70

Water is most abundant substance in plant and animal matter. The water content of
animals and plant varies widely.

Types of water:

Water is as much a part of all, foods as a carbohydrates, fats and proteins. Cellular
material contains a abundance of water. In leafy green there is 90% or more fruits and vegetables
contain plenty of moisture to the extent of 70-80 percent. Water, which is present in foods, may
be held as

1. Free water
2. Bound water
3. Imbibed water
Free wateris present in cells, and in circulating fluids of tissues as in cell sap. It contains
dissolved and dispersed solutes in the cell. It is easily lost by drying the food. The free water is
the bulk water free from any other constituents. It is held in narrow channels between certain
food components due to capillary forces and is held trapped within the spaces in food. It is
surrounded by physical barrier e.g., biological cell that prevents it from escaping. The free water
is actually responsible for the microbial growth and deterioration of food. This form of water is
also called the available water.
The ‘bound water’ refers to water that is physically or chemically bound to other food
components Many compounds like starch, proteins and some salts have water bound to them in
the form of hydrates. The bound waterin foods is held by proteins, polysaccharides and fats in
the living cells. Bound water may also be absorbed on the surfaces of solids in foods. The
removal of bound water from tissues is very difficult. Bound water is resistant to freezing and
chilling.

Another form of water in food is called imbibed water. This water is found in hydrophilic
gums like gelatin which is a type of protein with ability to absorb a large amount of water.
Gelatin forms a jelly like mass on absorbing or imbibing water. Imbibed water is more or less
like the hydrate formation and involves hydrogen bonding. A yet another form of water in food
is adsorbed water. Some solid foods have the ability or tendency to adsorb water on surface.
The powdered forms of the solids adsorb more water because of a larger surface area. Imbibed
water may not be different from water held as a hydrate.Some substances pick up water and
swell when they come in contact with water

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Basics in Food Chemistry Water

Role or functions of water in Food

Low moisture foods e.g., dried or freeze dried foods having a moisture content of 5-15
per cent intermediate moisture foods e.g., cakes and dates with a moisture content of 20-40 per
cent and high moisture foods e.g. fresh fruits and vegetables of greater than 40 per cent of
moisture.

The role of water in food preparation is of great importance.

1. As a cooking medium:-
This is perhaps the most common and important its many uses in cookery. Water has
been universally used as a medium of cooking. The ubiquitous nature of water, its free
availability and its low cost of supply are some of the factors which influence the use of water as
a cooking medium.
Dry foods absorb water and swell before they get cooked. Water acts as a medium of
heat transfer from the surface area to the different parts of the food. Therefore foods which have
moisture content take a longer time than foods with greater moisture content.
2. As a solvent :-
Water is a universal solvent for many food substances. Water not only dissolve flavours, but also
colour pigments in fruits and vegetables like anthocyanins and odours. Thus the solvent action
of water is responsible for the palatability of the food cooked in it.

3. Water absorption :-
Dry foods cooked in water absorb water, expand in volume and increase in weight. Foods
like cereals and pulses when cooked water, gain weight to the extent of 2 – 3 times. Therefore
the nutrients supplied per unit weight are diluted to that extent. Water also functions in food
preparation as a dispersing medium and helps to produce smooth texture. It helps to distribute
particles of materials like starch and protein. When flour is used to thicken liquids, the particles
need to be dispersed throughout the liquid phase as in a starch gel. Dry foods like cereals,
millets, pulses are generally first soaked for a period of time before they are cooked as they take
a longer time to cook than foods with a greater moisture content. This helps to decrease the
cooking time, very often rice, dals and legumes are cooked under pressure to hasten the cooking
process. Water acts as a leavening agent in food preparations. When batters and doughs are
exposed to heat the water present is converted to steam. The steam expands and is response for
the leavening effect.
4. Keeping Quality of Foods :-
The shelf-life or storage period of food is greatly influenced by its moisture content.
Water is essential for the growth of microorganisms. In the presence of enough moisture,
microorganisms multiply. It some of these are harm then they will render the food inedible.
Therefore on the basis of their stability during storage, foods can be
divided into 3 categories.

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Basics in Food Chemistry Water

1. Non-perishable
2. Semi perishable
3. Perishable
1. Non-perishable:-
It may be noted that cereals, dals and legumes with moisture content below 13 percent are
nonperishable if stored in a cool, dry place. It is important to store dry foods like sugar, salt,
coffee powder in very dry containers. For these foods pick up moisture readily from the
atmosphere and may deteriorate.
2. Semi perishable :
Semi perishable foods can be stored for a week to a month at room temperature without
any undesirable change in flavor or texture
Eg: biscuits, roasted chana dal etc.
3. Perishable foods :-
Which have high moisture content can be kept only for a short period. They have to be
stored at refrigeration temperature, if their shelf life is to be perishable.
Eg: milk, paneer, meat, fresh fruits & vegetables.

5. Texture and consistency :-

The amount of moisture present in food stuffs affects its textureconsistency& feel in the
mouth softer foods & liquid foods areswallowed easily, while crisper and drier foods are more
difficult toswallow.
6. Body Needs:-
Water is an essential nutrient next only in importance to oxygen.Deprivation of water even
for a few days can lead to death. An adultman need about 1.0-1.5 litres of water per day, in
addition to themoistures content contained in foods, eaten.
7. Dispersing medium- for nutrients

8. Water acts as leavening agent- dough, heat, steam, expansion.

9. Universal solvent (salt, vitamins, sugar, gases, pigment)

10. Capable of ionizing (H3O+, OH-)

11. Stabilizing the colloids by hydration

12. Necessary for micro-organisms growth

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Basics in Food Chemistry Water

Properties of water
Water exists in three forms: found as solid (ice) below 0°C in liquid form as water
between 0°C and 100°C and as gas above 100°C at the atmospheric pressure. All the three states
exist as part of the hydrological cycle. Water is indispensable and unique in many ways. In its
liquid form, it is considered a universal solvent due to the ease with which many substances
dissolve in it. Its being liquid is striking in contrast to the hydrides of elements close to oxygen in
the periodic table (e.g. NH , H S etc.), which are gases at room temperature. Similarly the
3 2
solidform of water i.e. ice has lower density than its liquid form. It is another unique feature of
water. The lower density of ice helps it to float on the surface of water bodies in cold regions and
thus facilitates in the sustenance of aquatic life during very cold seasons. The gaseous form of
water i.e. water vapour is an essential constituent of atmosphere responsible for the humidity and
a number of phenomena like precipitation (rain) etc. The uniqueness of water can be attributed to
its structure. Let us try to look into it. Water is the most abundant compound on Earth's surface.
In nature, water exists in the liquid, solid, and gaseous states. It is in dynamic equilibrium
between the liquid and gas states at 0 degrees Celsius and 1 atm of pressure. At room
temperature (approximately 25 degrees Celsius), it is a tasteless, odorless, and colorless liquid.
Many substances dissolve in water, and it is commonly referred to as the universal solvent.

Physical properties of water

Systematic name
Alternative names
Molecular formula
Molar mass
Density and phase
Melting point
Boiling point
Specific heat capacity
water
Aqua, dihydrogen monoxide,
hydrogen hydroxide, (more)
HO
2
18.0153 g/mol
0.998 g/cm³ (liquid at 20 °C)
0.92 g/cm³ (solid)
0 °C (273.15 K) (32 °F)
100 °C (373.15 K) (212 °F)
4.184(g·K) (liquid at 20 °C)

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Basics in Food Chemistry Water

1. Melting and boiling points:

Water has high melting and boiling points as compared to the substances of similar
molecular weight. This is attributed to hydrogen bonding that leads to the association of a large
number of water molecules. Though hydrogen bonds are weak, they are present in large number.
Therefore, lot of energy is required to break these leading to increased the melting and boiling
points.

2. Specific heat/Heat capacity:

The heat capacity of a substance is defined as the energy required in changing the
temperature of the substance by 1°C. It is actually a measure of the amount of heat a substance
can store. Liquid water has the largest heat capacity per unit mass of all substances. It is due to
slow hydrogen bond breaking. It implies that high energy consumption would be required for
processing the food containing water. However, the high heat capacity is advantageous for
humans in buffering the rapid temperature changes with alterations in the environment.

3. Heat of fusion, Latent heat vapourisation and Heat of sublimation:

Water has high heat of fusion, vapourisation and sublimation. Heat of fusion is defined as
the energy required in changing 1 g of ice at 0°C to liquid whereas the latent heat of
vapourisationrefers to the heat required to change liquid water to the gaseous state. Similarly,
heat of sublimation is concerned with the sublimation process i.e., direct conversion of solid (ice)
to gas (water vapour). This is done at pressures below 4.58 mm Hg and forms the basis of freeze
drying.

4. Density:

The liquid water has a hexagonal lattice structure. When the temperature of liquid water at
room temperature is lowered, its density increases like that of any other substance and reaches a
o
maximum value of 1.00 at around 4 C. However, on further decreasing the temperature it starts
decreasing. This unusual decrease is due to the organization of water molecules in such a way
that each of the oxygen atoms is surrounded in tetrahedral fashion by four additional oxygen
atoms.

5. Dielectric Constant:
Water has high dielectric constant. Dielectric constant is a measure of the relative effect of
the medium or the force with which two oppositely charged poles attract each other. The high
dielectric constant of water is due to the polarity in the molecule. It enables water to separate
ions of electrolytes by reducing the electrostatic attraction between them.

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Basics in Food Chemistry Water

6. Supercooling:
Another property of water which is important in the preservation and deterioration of food
products is its supercooling. It refers to cooling the pure water to below 0°C down to about -
40°C to -50°C. Supercooling finds application in the storage of food products like fruits and
vegetables and also the prepared products.

Phases of Water
Similar to many other substances, water can take numerous forms. Its liquid phase, the
most common phase of water on Earth, is the form that is generally meant by the word "water."

Solid Phase (Ice)

The solid phase of water is known as ice and commonly takes the structure of hard,
amalgamated crystals, such as ice cubes, or of loosely accumulated granular crystals, such as
snow. Unlike most other substances, water's solid form (ice) is less dense than its liquid form, as
a result of the nature of its hexagonal packing within its crystalline structure. This lattice contains
more space than when the molecules are in the liquid state.

Liquid Phase (Water)

Water is primarily a liquid under standard conditions (25 degrees Celsius and 1 atm of
pressure). This characteristic could not be predicted by its relationship to other, gaseous hydrides
of the oxygenfamily in the periodic table, such as hydrogen sulfide. The elementssurrounding
oxygen in the periodic table – nitrogen, fluorine, phosphorus, sulfur, and chlorine – all combine
with hydrogen to produce gases under standard conditions. Water forms a liquid instead of a gas
because oxygen is more electronegative than the surrounding elements, with the exception of
fluorine. Oxygen attracts electrons much more strongly than does hydrogen, resulting in a partial
positive charge on the hydrogen atoms and a partial negative charge on the oxygen atom. The
presence of such a charge on each of these atoms gives a water molecule a net dipole moment.

Phase diagram of water

Water freezes to form ice, ice thaws to form liquid water, and both water and ice can
transform into the vapor state. Phase diagrams help describe how water changes states depending
on the pressure and temperature.

The three phases of water – liquid, solid, and vapor – are shown in temperature-pressure space.

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Basics in Food Chemistry Water

Note the following key points on a phase diagram:

 The critical point (CP), above which only supercritical fluids exist.
 The triple point (TP), a well-defined coordinate where the curves intersect, at which the
three states of matter (solid, liquid, gas) exist at equilibrium with each other.
 Well-defined boundaries between solid and liquid, solid and gas, and liquid and gas.
During the phase transition between two phases (i.e, along these boundaries), the phases
are in equilibrium with each other.

Structure of water
Water is a tiny bent molecule with the molecular formula H2O, consisting of two light
hydrogen atoms attached to each 16-fold heavier oxygen atom. The molecular formula of water
is H2O. You know that oxygen has six valence electrons and hydrogen has one valence electron.
According to Lewis formulation, in order to complete the octet, oxygen shares one electron each
with the two hydrogen atoms. In the process, the hydrogen atoms also acquire two electrons thus
completing their duplet as shown in Fig..

Water Water is a bent molecule with a bond angle of 104.5° and its shape may be
explained in terms of hybridisation of the valence orbitals of oxygen to give tetrahedrally
oriented sp3 hybridised orbitals. Two of these hybridised orbitals form bonds with hydrogen
atoms by overlapping with their 1s orbitals while the other two accommodate the non-bonding

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Basics in Food Chemistry Water

electron pairs. You would recall that a tetrahedral structure has a bond angle of 109.5o.However,
due to differential interaction between the bonded and non bonded pairs of electrons as shown in
the structure of H2O molecule 5.1(b), the tetrahedral gets slightly distorted and the H-O-H bond
angle becomes 104.5°

The unshared pair of electrons on oxygen atom makes it slightly negative while the two
H atoms become slightly positive. The charge separation in water molecule gives rise to two
dipoles in the molecule. These dipoles are responsible for causing strong interactions with the
other water molecules forming hydrogen bonds as shown in Fig. . It is due to these
intermolecular hydrogen bonds that the water remains in liquid form at room temperature.

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Basics in Food Chemistry Water

Water Activity
However, it has also been observed that various types of food with the same water
content differ significantly in perishability. Thus, it is evident that water content alone is not a
reliable indicator of perishability.

As described in most physical chemistry textbooks, Lewis and Randall rigorously

derived the notion of substance “activity” from the laws of thermodynamics, and Scott pioneered
its application to foods.

Water Activity

In 1952, Scott came to the conclusion that the storage quality of fooddoes not depend on
the water content but on water activity (aw).

Definition:
Water activity is a measure of relative vapor pressure of water molecules in the head
space above a food vs. vapor pressure above pure water.

OR

Water activity is defined as the ratio of the vapour pressure of water in a food item (p) to
the vapour pressure of pure water (pO) at the same temperature.

The tendency of water molecules to escape the food product from liquid to vapor defines the aw

aw = p/pO
= % ERH/100

Where,
ERH = Equilibrium relative humidity
P = Partial vapour pressure
P0 = Saturation vapour pressure
Water activity has scale from 0 (no water) to 1 (pure water).Since water activity is a ratio
of vapour pressures; it has no units. Its value ranges from 0.0 (bone dry) to 1.0 (pure water) but
most food products have awvalue in the range of 0.2 for very dry fruits to 0.99 for moist fresh
foods.

Compiled and Edited by:- Prof (Dr.) R. R. Andhale MIT CFT,MIT ADT University, Pune
Basics in Food Chemistry Water

Table 2: Water Activity of Some Food Products

S. Products Water
No. Activity
1. Highly perishable vegetables, meat, 0.95
fish, milk, bread
2. Cheese, fruit juice 0.91
3. Dry cheese, sponge cakes 0.87
4. Fruit juice concentrates, flour, rice, 0.80
pulses
5. Jam, marmalade 0.75
6. Dried fruits, nuts 0.65
7. Noodles, spaghetti, etc. 0.50

Water activity foods:

Highly perishable foods aw> 0.9

Intermediate moist foods aw = 0.6-0.9

Shelf stable foods aw< 0.6

Moisture Sorption Isotherm

You are now familiar with two important water related terms i.e., water content or the
moisture content and the water activity in the context of foods. These are interrelated; higher
moisture content normally means a larger water activity. The relationship, however, is not linear.
In fact, the variation in aw with an increase in water content generally shows a sigmoid (S-
shaped) curve. Such a curve at a given temperature is called the moisture sorption isotherm.
Definition :
“The relationship between water activity (aw) and moisture content at a given temperature
is called the moisture sorption isotherm”.

These isotherms are obtained by placing completely dry food samples in the atmospheres
of increasing relative humidity at a given temperature and measuring the increase in the weight
of the sample due to absorption of water. The data so obtained is then plotted to get the sorption
isotherm. Thus a sorption isotherm is a plot of the amount of water absorbed (moisture content)
as a function of relative humidity (or water activity). A schematic representation of a sorption
isotherm is given in Fig.
The moisture sorption isotherm of a food is obtained from the equilibrium moisture contents
determined at several water activity levels at constant temperature.

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Basics in Food Chemistry Water

There are three types of isotherm curves;

1. Adsorption (starting from the dry state),
2. Desorption (starting from the wet state) and
3. Working (native state).

Significance of Sorption-Desorption Isotherms

The sorption isotherms drawn for different food products are quite significant in a number of
ways. Some of these are listed below:
1. These provide useful information for processing and packaging the dehydrated food
items.
2. A study of these graphs will be helpful in deciding about the food products that may be
packed together.
3. These help in determining the water content at certain critical a values related to stability
w
and safety of the food items.
4. These can be used in the selection of suitable ingredient to make a safe formulation at
high moisture content.

An isotherm prepared by adsorption will not necessarily be the same as an isotherm

prepared by desorption. This phenomenon of different moisture contents for the same aw is
called moisture sorption hysteresis, and is exhibited by many foods. Eg.Meat(70 % moisture) and
Fruits & Veggies (90-95 % moisture).

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Basics in Food Chemistry Water

Sorption isotherms also explain the level of water binding in a food (i.e. types
of water)
Type I:Tightly “bound” water (monolayer)
 Unavailable/Unfreezable (at -40C)
 Water - ion; water - dipole interactions
Type II: additional water layer (Vicinal water) Monolayer Multilayer
 Slightly more mobility
 Some solvent capacity True
Type III:Watercondensating in capillaries and pores monolayer

(Multilayer  Bulk-phase water)

 More available (like dilute salt solution)
 Can be entrapped in gels
 Supports biological and chemical rections, Freezable

Water Activity Vs Food Stability

Food stability directly related to aw,Influences storage, microbial growth, chemical & enzymatic
Deteriorations, etc.

A. Microbial stability
 Foods with aw > 0.9require refrigeration because of bacteria spoilage
 Exception: Very low pH Foods

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Basics in Food Chemistry Water

 Can control by making intermediate moisture foods (IMF)

 Food with low aw to prevent microbial spoilage at room temp. But which can be eaten
w/o hydration.
 aw = 0.7 - 0.9 (20 -50% water) - achieved by drying or using solutes (sugar, salt), dried
fruits, jelly and jam, pet foods, fruity cakes, dry sausage, marshmallow, bread, country
style hams.
 Minimal processinghowever preferred over IMF
Special problems
 May need mold inhibitor
 Lipid oxidation - may need antioxidant or inert packaging
Important in grains to prevent mold growth & possibly mycotoxin development, the awMust be
below 0.8

B. Chemical stability
 Maillard browning
 Doesn't occur below type II water
 Increases in type II water - water becomes a better solvent while reactants become
more mobile
 Reduced in type III - dilution or water is an inhibitor
 Depends on food product (aw 0.53-0.55 in apple juice vs. 0.93 in anchovy).

 Lipid oxidation
 Low aw, lipid oxidation high - due to instability of hydroperoxides (HP)- unstable
w/o water, no H-bonding
 Slightly more addition of water stabilizes the HP and catalysts
 Above type II water, water promotes the lipid oxidation rate because it helps to
dissolve the catalysts for the reaction.

 Vitamin and pigment stability

 Ascorbic acid very unstable at high aw
 Stability best in dehydrated foods - type II water
 Problem with intermediate to high moisture foods
 Must consider packaging for these foods.

C. Enzyme stability
 Hydration of enzyme
 Diffusion of substrate (solubility)
 Not significant in dehydrated foods
 Little enzyme activity below type II water
 Exceptions: in some cases we get increased activity at decreased a weg. Frozen
foodsLipases (work in a lipid environment)

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Basics in Food Chemistry Water

Applications of measurement of aw in food stuffs:

By measuring and controlling the water activity of foodstuffs, it is possible to

1. Predict which microorganisms will be potential sources of spoilage and infection,
2. Maintain the chemical stability of foods,
3. Minimize non-enzymatic browning reactions and spontaneous autocatalytic lipid
oxidation reactions,
4. Prolong the activity of enzymes and vitamins in food, and
5. Optimize the physical properties of foods such as texture and shelf life
6. Water activity is an important critical control point for riskanalysis as defined by the
HACCP concept. These regulations and requirements are based onthe current FDA Food
Code efinition of potentially hazardous foods.
7. Potentially hazardous foods are those that require temperature control because they
support the rapid and progressive growth of pathogenic microorganisms.
8. Potentially hazardous food does not include items :
With water activity values of 0.85 or less,
Food with a pH level of 4.6 or less,
Food in unopened hermetically sealed containers, those that maintain commercial sterility
under non-refrigerated storage and distribution, or those in which rapid and progressive
growth of pathogenic microorganisms cannot occur.

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