WATER

WATER'S IMPORTANCE

Solvent

Reactant

Water's involvement in hydrolysis reactions

Product

Most molecules dissolved in water

Water's involvement in condensation reactions

Heat transfer medium

E.g. boiling, steaming, cooling

WATER'S IMPORTANCE

Texture

Juiciness, mouthfeel

Preservation

Highly perishable foods usually have high water activity

Snack foods
Vegetables
Meat

E.g. bread vs. cracker or cereal

Economics

More water added = more $

UNDERSTANDING THE PHYSICAL AND CHEMICAL

PROPERTIES OF WATER IS IMPORTANT IN THE
STUDY OF FOOD AND PROCESSING
3

PHYSICAL & CHEMICAL

PROPERTIES OF WATER

Water has very unique properties not shared by other

similar hydrogen compounds or compounds of similar
weight
Compound

Melting point

Boiling point

H2O

0C

100C

H2S

-83C

-60C

NH3

-78C

-33C

Methanol

-98C

65C

Why? this is explained by the unique structure of H2O

4

STRUCTURE OF WATER

Tetrahedral arrangement
Two free electrons of O
act as H-bond acceptors
while H acts as donor
Highly electronegative O
pulls electrons from H,
making H behave like a
bare proton
Forms a dipole because
of the electronegative O

STRUCTURE OF WATER

Because of the DIPOLE

and TETRAHEDRAL
structure we can get
strong H-bonding
Water capable of bonding
to 4 other water molecules
Unique properties of water
from other hydrides
H-bond NOT a static
phenomenon

T dependent
6

PHASE CHANGES OF WATER

WATER VAPOR

Water is free and devoid of any H-bonds

Large input of energy needed

Large dissipation of same energy needed to make

water lose kinetic energy

an endothermic process

an exothermic process

Waters latent heat of vaporization is unusually

high

to change 1 L from liquid to vapor need 539.4 kcal

LIQUID WATER

Extensively H-bonded
H-bond formation dependent on T

With increasing T get more mobility and increased fluidity

T (C)

Density (kg/m3)

Viscosity (m2/s)

999.9

1.7895

1000.0

1.535

25

997.1

0.884

100

958.4

0.294

ICE

Forms when exactly 4 H-bonds

are formed between water
molecules

The strong H-bonding in ice

forms an orderly hexagonal
crystal lattice

To get this order a lot of energy

needs to be adsorbed by the
environment

6 H2O molecules

Has 4X more thermal

conductivity than water at same
temperature
10

Can go from ICE to GAS

BASIS FOR
FREEZE DRYING
SUBLIMATION

11

PROPERTIES OF ICE

Crystallization

Crystal growth occurs at freezing point

Rate of crystal growth decreases with decreasing temperature

Nucleation - affects ice crystal size.

Slow freezing results in few nucleation sites and large, coarse

crystalsSolutes slow ice crystal growth

Fast freezing results in many nucleation sites and small, fine

crystals
Heterogeneous nucleation

usually caused by a foreign particle, such as salt, protein, fat, etc.

Homogeneous nucleation

very rare, mainly occurs in pure systems

12

PROPERTIES OF ICE

SUPERCOOLING

Water can be cooled to temperatures below its

freezing point without crystallization
When an ice crystal is added to supercooled water,
temperature increases and ice formation occurs

13

PROPERTIES OF ICE
Freezing induced changes
in foods (examples)

Example: Effect of freezing on seafoods

Destabilization of emulsions
Flocculation of proteins
Increased lipid oxidation
Meat toughening
Cellular damage
Loss of water holding capacity

14

WATER SOLUTE INTERACTIONS

Association of water to hydrophilic substances

Bound water - occurs in vicinity of solutes

Water with highly reduced mobility

Water that usually won't freeze even at -40C
Water that is unavailable as a solvent

Trapped water

Water holding capacity

Hydrophilic substances are able to entrap large amounts of
water

Jellies, jams, yogurt, jello, meat

Yogurt - often see loss of water holding as whey is released
at the top of the yogurt

15

WATER SOLUTE INTERACTIONS

Ionic polar solutes

React readily with water and most

are usually soluble in water
Water HYDRATES the ions
Charge interactions due to waters
high DIELECTRIC CONSTANT

Large ions can break water

structure

Can easily neutralize charges due

to its high dipole moment

Have weak electric fields

Small ions can induce more

structure in water

Have strong electric fields

16

WATER SOLUTE INTERACTIONS

Nonionic polar solutes

Weaker than water-ion bonds

Major factor here is H-bonding to the polar site
Example: SUCROSE

4-6 H2O per sucrose

Concentration dependent

>30-40% sucrose all H2O is bound

T dependent solubility

C=O, OH, NH2 can also interact with each other and therefore water
can compete with these groups
H-bond disrupters

urea - disrupts water

Water bridge
17

WATER SOLUTE INTERACTIONS

Nonpolar

Unfavorable interaction with water

Water around non-polar substance
is forced into an ordered state

Water affinity for water high

compared to non-polar compound
Water forms a shell

Tries to minimize contact

Hydrophobic interactions

Caused because water interacts

with other water molecules while
hydrophobic groups interact with
other hydrophobic groups

18

EFFECT OF SOLUTES ON WATER

Boiling point
Vapor pressure is equal to atmospheric
pressure
Strongly influenced by water - solute
interaction

Solutes decrease vapor pressure and

thus increase boiling point

Sucrose +0.52C/mol
NaCl +1.04C/mol

ATMOSPHERIC PRESSURE

VAPOR PRESSURE

19

EFFECT OF SOLUTES ON WATER

1 atm (sea level)

mountains

90C 100C

So does it take longer or

shorter to boil an egg in
Baguio? Why?
20

EFFECT OF SOLUTES ON WATER

Let's go back to our egg,

what would happen if you
added salt?

Raoult's
Law

Recommended that you add salt to water at high altitudes

21

EFFECT OF SOLUTES ON WATER

Freezing point lowering
Freezing point can get extensive
depression via solutes

Eutectic pt - temp.

Alter ability of water to form crystals

due to H-bond disruption
Sucrose -1.86C/mol
NaCl -3.72C/mol
Where all water is frozen - usually
around -50C

In most cases small amounts of

water remains unfrozen (-20C)

These small patches of water can

promote chemical reactions and
damage

22

EFFECT OF SOLUTES ON WATER

What explains all this?

Raoult's law
P = P*/X1
or
P*-P/P*= x/55.5M
P = vapor pressure of solution; P* = vapor pressure pure
solvent; X1 = mole fraction of solute; x = grams solutes in
solution; 55.5M = moles of water per liter

This relationship is not only important for explaining the

concepts of depressing freezing point and elevating boiling
point

Also explains the concept of water activity

23

EFFECT OF SOLUTES ON WATER

Osmotic pressure of solutions
There is a tendency for a system containing water and a
solution separated with a membrane to be at equilibrium
The pressure needed to bring the two solutions at equilibrium
is called OSMOTIC PRESSURE
The more the solution has of dissolved solutes (e.g. salt) the
higher its osmotic pressure
Can use this in food processing and preparation

E.g. Crisping salad items

Increase turgor

24

EFFECT OF SOLUTES ON WATER

Surface tension
Water surface behaves
differently than bulk phase

Like an elastic film

Due to unequal inward force
Resist formation of a new
surface thus forming surface
tension

25

EFFECT OF SOLUTES ON WATER

Water has high surface tension

72.75 dynes/cm (20C)

Because of the high surface tension special

considerations are needed in food processing
To affect it one can:

Increase T (more energy) reduces surface tension

Add solutes

NaCl and sugars increase surface tension

Amphipathic molecules reduce surface tension

26

EFFECT OF SOLUTES ON WATER

Ionization of water

Water can ionize into hydronium (H3O+) and hydroxyl (OH-) ions
Transfer of one proton to the unshared sp3 orbital of another
water molecule

Pure water: Keq = Equilibrium (or ionization) constant

Keq = [H3O]+ [OH][H2O]
[H3O]+ [OH]- = Keq = Kw (Water dissociation constant)
[10-7] [10-7] = [10-14]

27

EFFECT OF SOLUTES ON WATER

Acids and bases in food systems

Acid - proton donor

Base - proton acceptor

CH3COOH + H2O CH3COO- + H3O+

Weak acids and bases

NH3 + H2O NH4+ + OH-

Most foods are weak acids

These constituents are responsible for buffering of food
systems

Some examples

Acetic, citric, lactic, phosphoric, etc.

28

EFFECT OF SOLUTES ON WATER

Acids and bases in food systems

Is there a difference between weak and strong acids?

Strong acids

When placed in solution, 100% ionized

HCl = H+ + ClpH = -log [acid] = -log [H]+

Weak acids

+
HOAC
H
+
OAC
Keqacids
= [H]+form
[OAC]
When placed in solutions weak
an equilibrium
[HOAC]
pKa = -log Ka
29

EFFECT OF SOLUTES ON WATER

Weak acids and bases

One cannot relate pH to concentration for weak acids
and bases because of this equilibrium
One must understand how the acid behaves in solution
Knowing the dissociation constant of the acid is
important to determine the effect on the pH of the
system
The relationship of pH for weak acids and bases relies
on the Henderson - Hasselback equation:
pH = pKa + log [salt]
[acid]
30

EFFECT OF SOLUTES ON WATER

Weak acids

Graphically behave
like the figure when
titrated with a strong
base. The reverse
holds true for weak
bases

What do
we
call this
point?

31

EFFECT OF SOLUTES ON WATER

Buffering

Buffers resist
changes in pH
when acids and
bases are added
Characteristics of a
buffer

Maximum when
pH = pKa or
when [acid] =
[salt]
Rule of thumb:
pH = pKa 1

What is
this point
and its
significanc
e to food
systems?

32

EFFECT OF SOLUTES ON WATER

Examples of natural pH control

Fruits - citric, malic, acetic, etc

Microbial control
Flavoring

Milk pH around 6.5

Controlled by three components

Phosphate, citrate, carbonate

Eggs

Fresh eggs - pH = 7.6

After storage for several weeks - pH = 9-9.7

Due to loss of CO2

Problem - Loss of carbohydrate groups on

proteins. Loss of protein functionality, causing
decreased viscosity and poor foaming
properties

33

EFFECT OF SOLUTES ON WATER

Examples of man made pH control

Food additives - ACIDULANTS

Citric acid - pectin jellies

Yogurt and cottage cheese

Fermentation - glucose or lactose to lactic acid

pH reduction to around 4.6 will cause the gelation
Can add acidulants to imitate dairy yogurts - lactic, citric,
phosphoric, HCl

Cheese

pH must be around 2.9-3.0

Also provides balance between tartness and sweetness

Alkaline salts of phosphoric acid to get good protein dispersion

Thermal process control

pH below 4.5 usually hinders C. botulinum growth

Less severe heat treatment required for these
Acidulants used to lower pH below 4.5 for some fruit and tomato
products
34

EFFECT OF SOLUTES ON WATER

Examples of man made pH control

Acidulants - leavening agents

Used in the baking industry to give rise (release of CO 2) alternative to yeast

When HCO3- becomes acidic (pH < 6), CO2 forms, CO2 not
very soluble so released as a gas

Overall eq:

H+ + HCO3- H2O + CO2

35

EFFECT OF SOLUTES ON WATER

Examples of man made pH control

Leavening systems

Bicarbonate (NaHCO3) - source of HCO3 and CO2

Leavening acids

Drive bicarbonate (HCO3) to CO2

Rate of acid release varies and therefore CO2 release

Phosphate - rapid release of CO2

Sulfate slow release of CO2

Pyrophosphate - can be cleaved by phosphatases

becoming more soluble - used in refrigerated doughs
d-Glucono-lactone - used in refrigerated doughs

36

EFFECT OF SOLUTES ON WATER

Examples of man made pH control

Acidulants - antimicrobials

pH is important for two reasons: 1. Solubility and 2. Activity

Benzoic acid (0.05-0.1%)

The salt is more soluble in aqueous systems

The acid is more active in its antimicrobial efficiency
Found naturally in prunes, cranberries, cinnamon and cloves
Active below pH 4 (active acidic form of the salt)
Highly soluble in the form of sodium salt
Effective - yeasts and bacteria, less for molds
Uses in acid foods - soft drinks, juices, pickles, dressings etc.

Parabens or r-hydroxybenzoate esters (0.05-0.1%)

Broader pH range (active at higher pH)

Mainly use methyl and propyl esters
Uses in baked goods, wines, pickles, jams, syrups, etc.

37

EFFECT OF SOLUTES ON WATER

Acidulants - antimicrobials

Sorbic acid (Na+ and K+ salt forms) (0.02-0.3%)

Proprionic acid (proprionate) Ca2+ salt

Max activity at pH 6.5; active at acid pH values

Most effective for yeast and molds
Inhibit, not inactivate
Uses in cheese, juices, wines, baked goods, etc.
Active up to pH 5
Uses in breads (retards Bacillus) which causes ropiness in breads
Ropiness - thick yellow patches that can be formed into a rope-like
structure making the bread inedible

Acetic acid
Nitrites and Nitrates
Sulfites

38

WATER ACTIVITY

What is meant by water activity?

Water has different levels of binding and thus activity or

availability in a food sample
Simply put, Water activity (aw) helps to explain the
relationship between perishability and moisture content

Greater moisture content faster spoilage (normally)

Why are there some perishable foods at the same moisture
content that don't spoil at the same rate?
There is a correlation found between aw and various different
spoilage and safety patterns

39

WATER ACTIVITY

Water has different levels of binding and thus activity or availability in a food
sample
Food companies and regulatory agencies (e.g. FDA) rely on aw as an indicator
of how fast and in what fashion a food product will deteriorate or become
unsafe, and it also helps them set regulatory levels of aw for different foods

Highly perishable foods aw > 0.9

Intermediate moist foods aw = 0.6-0.9
Shelf stable foods aw < 0.6
40

WATER ACTIVITY

Thermodynamic definition of aw

The tendency of water molecules to escape the food

product from liquid to vapor defines the aw

aw = p/pO=%RH/100

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

Scale is from 0 (no water) to 1 (pure water)

41

WATER ACTIVITY

Sorption isotherms

Help relate moisture content to

aw
Each food has their own
sorption isotherm
It is interesting that when
water is added to a dry
product, the adsorption is not
identical to desorption
Some reasons

Temp. dependent

Metastable local domains

Diffusion barriers
Capillary phenomena
Time dependent equilibrium

42

WATER ACTIVITY

Water sorption of a mixture

A mixture of two different food components with different aw leads to

moisture migration from one food to another which can create
problems
This is one reason why it is important to know the aw of a food
product or ingredient
Examples:

Caramel, marshmallows and mints all similar %moisture but very

different aw

Fudge (aw = 0.65-0.75) covered with caramel (aw = 0.4-0.5) what

happens?
Granola bar with soft chewy matrix (aw = 0.6) and sugar coat (aw = 0.3)?

Hard candy (aw = 0.2-0.35) on a humid day?

43

WATER ACTIVITY

So, knowing the aw of a

food component one can
select the proper
ingredients for a
particular food product
For example, it is
possible to create a multitextured food product if
components are added at
the same aw

44

WATER ACTIVITY

Temperature dependency of the sorption isotherm can

be a major problem and often overlooked

Example:
Crackers that experience a
temperature rise during
transportation
At the same moisture content which
would spoil faster?

45

WATER ACTIVITY

Sorption isotherms also explain the level

of water binding in a food (i.e. types of
water)

Type I: Tightly bound water (monolayer)

Type II: additional water layer (Vicinal

water)

Unavailable/Unfreezable (at -40C)

Water - ion; water - dipole interactions
Slightly more mobility
Some solvent capacity

True monolayer
Monolayer

Type III: Water condensating in

capillaries and pores (multilayer bulkphase water)

More available (like dilute salt solution)

Can be entrapped in gels
Supports biological and chemical rections
Freezable

46

WATER ACTIVITY

Importance of aw in foods

Food stability directly

related to aw

Influences storage,
microbial growth, chemical
& enzymatic deteriorations,
etc.

Vit C loss

47

WATER ACTIVITY
A) Microbial stability
Foods with aw > 0.9 require refrigeration
because of bacteria spoilage

Exception: Very low pH Foods

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)

Minimal processing however preferred over

IMF
Special problems

dried fruits, jelly and jam, pet foods, fruity

cakes, dry sausage, marshmallow, bread,
country style hams

May need mold inhibitor

Lipid oxidation - may need antioxidant or
inert packaging

Important in grains to prevent mold growth

& possibly mycotoxin development

Must be below 0.8

48

OSMOPHILICYEAST

YEAST&MOLDS

aw is a major HURDLE
for microorganisms but
not the only one

BACTERIA

WATER ACTIVITY
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

49

WATER ACTIVITY

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 activity at aw

Frozen foods
Lipases (work in a lipid environment)

50