Water

Importance of Studying Water in Foods

Food Safety
Microorganisms need water to grow

Food Quality
Chemical reactions depend on water content
Physical properties depend on water content

Food Cost

Molecular Structure of Liquid Water

Molecular Interactions & Organization
Oxygen has
strongly positive
nucleus
(pulls electrons)

Tetrahedral
structure of
water

Hydrogen
bonds

Physicochemical
Properties

Strong Attractive Forces (Hydrogen-bonds)

Highly Directional (Tetrahedral)
About 4 Hydrogen-bonds per Molecule
System Organized to Maximize H-bonds

Boiling point, melting

point, density, viscosity,
polarity
Chemical Reactivity

Water: Physicochemical
Properties
Unique Properties of Water:
High boiling
High melting point
High heat of vaporization

Properties related
to strong hydrogenbonding

H2 O

CH4

NH3

MW (g/mol)

18

16

17

m.p. (C)

-183

-78

b.p. (C)

100

-161

-33

HV (kJ/mol)

40.7

8.2

23.4

Types of Water in
Foods
Bulk water

Capillary water

Physically
bound water

Trapped water

Chemically
bound water

Physical States

Gas vapor
Liquid water
Solid ice

MgSO47H2O
Water of crystallization

Water in different environments has different molecular properties and therefore different
physicochemical properties

Phase Behavior:
Ice, Water and Steam

Medium Entropy
Medium interactions

Liquid

Solid
Low Entropy
Strong interactions

Gas
High Entropy
Weak interactions

Water exists in different states (solid, liquid, and gas) depending on temperature and pressure that have
different structural organizations and interactions. The equilibrium behavior of water can be described by
a phase diagram.

Phase Behavior: Ice

Crystallization

Importance of ice formation:

Preservation

Microbial, Chemical, Physical

Quality

Liquid water-to-solid ice transition

Why does it happen?
What factors affect it?

Flavor, Texture, Appearance

Ice Crystallization: Thermodynamics

Melting

Ice

Water

Phase
Transition
(G)

Crystallization
Water

Ice

G > 0
T < Tm
Ice

G < 0
T > Tm
Water

G = 0
T = Tm
Thermodynamics
The thermodynamically favorable physical state of water at a particular temperature and pressure is
governed by the free energies of the states in question (which are determined by molecular interactions and
entropy)
Thermodynamics determines the maximum amount of crystallization that can occur under a particular set
of conditions if the system can come to equilibrium.

Ice Crystallization: Kinetics

Nuclei
Formation

Crystal
Growth

G*

Water

Ice
Transition is thermodynamically
favorable below Tm

Liquid water-to-solid ice transition:

(1) Supercooling - Liquid water can be cooled appreciably below its melting point
before crystallization occurs: T = T - Tm
(2) Nucleation Small clusters of water molecules, called nuclei, need to form
and be stable before crystals can grow
(3) Growth Water molecules join the existing crystal surfaces

Ice Crystallization:
Effect of Kinetics on Ice Crystal
Size
Need to Rapidly Cool
To Particular
Temperature to Avoid
Large Crystals

Nucleation or Growth Rate

Nucleation

Growth

Large ice crystals cause

quality problems, such
as grittiness and
iciness

High viscosity slows

diffusion processes at
very low temperatures

Supercooling (Tmp-T)

Factors Affecting Crystal Size

The size of the crystals formed depends on the relative rates of nucleation and growth.

Faster Nucleation Rate Many nuclei are initially formed that grow slowly, which
results in the formation of many small crystals.

Faster Growth Rate A few nuclei are initially formed that grow quickly, which results
in the formation of few large crystals

Solute-Water Interactions:
Nature, Effects and Importance
Molecular interactions:
Water acts with solutes differently
depending on their molecular
characteristics, e.g., polarity,
charge, shape.
Effects:
Water-solute interactions
determine many of the physical
and chemical properties of foods
Water acts as a solvent for many solutes
A solute is a substance that can be dispersed in a
solvent (in this case water)
The are many different kinds of solutes in foods,
including carbohydrates, proteins, salts, acids,
bases, surfactants

Importance:
Safety
Microbial contamination
Quality
Flavor, Texture, Appearance
Stability
Chemical & Physical

Dissolution: Thermodynamics
Will a solute dissolve or not?

Solute
Solvent

G = H-TS
Dissolution
Phase
Separation

Unmixed

Separate phases

Mixed

Solution

Entropy of Mixing
S > 0 - Always FAVORS MIXING (increases with higher T)

Enthalpy of Mixing
If H < 0 - FAVORS MIXING If solvent-solute bonds are stronger than bonds within separate phases.
If H > 0 - OPPOSES MIXING If solvent-solute bonds are weaker than bonds within separate phases.

Free Energy of Mixing

The overall free energy is made of entropy and enthalpy terms
If G < 0 - FAVORS MIXING
If G > 0 - OPPOSES MIXING

Dissolution in Water: Polar Solutes

Functional Groups: Polar molecules have regions that

have a partial charge, e.g., alcohols (-OH), amines (-NH2),

& thiols (-SH)
Examples: Water, Sugars, Alcohols, Amino acids,
Aldehydes, Ketones
Molecular interactions: The dominant interactions are:
Fundamental: Dipole-dipole
Compound: Hydrogen bonds

Dissolution in Water: Polar Solutes

Sugar

Water

Polar solutes normally have good solubility in water because solutewater interactions are fairly similar in strength to water-water
interactions.
Solubility depends on strength of interactions and solute compatibility
with tetrahedral structure of water
Molecular dimensions
Bond orientations

Dissolution in Water: Polar Solutes

Solubilities & Water activities (aw) of saturated sugar solutions at 25C
Ingredient

Sugars can have

different
solubilities in water
because of different
structures

Solubility (%)

aw

Sucrose

67.4

0.844

Glucose

51.0

0.891

Fructose

80.0

0.634

Lactose

18.7

0.931

Sorbitol

73.0

0.725

Mannitol

18.0

0.977
(Bussiere and Serpelloni, 1985)

Dissolution in Water: Polar Solutes

Water

Sugar molecules vary in

their shape, dimensions &
bond orientations
Sugar

Cavity in Water
Tetrahedral structure
Correct Shape &
Charge Distribution

High Solubility

Correct Shape; Wrong

Charge Distribution

+
+

Low Solubility

Wrong Shape; Correct

Charge Distribution

Low Solubility

Dissolution in Water: Ionic Solutes

Ions:
Sign
Magnitude
Dimensions

Na+

Cl-

Many ionic solutes have good solubility in water

Ions can form strong ion dipole bonds with water
Water close to ion is bound & therefore has different properties than bulk
water

Dissolution in Water: Ionic Solutes

Structure
Breaker

Ion
Ion-ordered
region
Intermediate
disordered region

Structure
Maker

Water-ordered
region

Dissolution in Water: Ionic Solutes

The Hofmeister Series

Low Charge
Density

High Charge
Density

Increase
salting
out

Increase
salting
in

Low Charge
Density

High Charge
Density

Some ions alter water structure more effectively than others due to differences
in their size and charge (which determines their charge density).
Small ions with high charges are most effective since they have the highest
charge density
The interaction of water with ionic solutes alters the functionality of other
ingredients in water, e.g., (NH4)2SO4 is used to precipitate proteins

Periodic Table

Dissolution in Water: Ionic Solutes

Salting Out

Limited
Free water

Protein
Aggregation

Hydrated
Protein

No Salt

Low Salt

High Salt

100
80
Solubility (% )
60
40

20

0
-10

Proteins precipitate at high salt concentrations:

The amount of salt required depends on protein type
and salt type. Some salts are more effective at
strongly binding water than others e.g. (NH4)2SO4.

10

30

50

70

90

Salt Concentration

110 130 150

Dissolution in Water: Non-Polar Solutes

- The Hydrophobic Effect
Water molecules
highly organized in
tetrahedral structure

Non-polar
solute
Magnitude

Most non-polar solutes have poor solubility in water

V. Strong
Origin water molecules form strong hydrogen bonds with each
Weak
other, but only weak VDW bonds with non-polar solutes
V. Weak

Type
Dipole-dipole
VDW
VDW

Hydrophobic Effect:
Transfer of Oil Molecule to Water
Water
Cavity
Formation

Introduce non-polar
molecule into water

Break strong
Hydrogen
bonds
Transfer Oil Molecule
to Water

Gtransfer

Form weak
VDV bonds

Cavity
Formation

Break weak
VDW
bonds

Oil

Overall: Replace strong

hydrogen bonds with weak van
der Waals bonds, which is
thermodynamically unfavorable

Hydrophobic Effect: Origin

Bulk Water
Molecular Interactions:
3-3.5 H-bonds
Entropy: Some disorder
Bound Water
Molecular Interactions:
4 H-bonds
Entropy: Highly ordered

G is positive (unfavorable) overall

Entropy change always unfavorable

Enthalpy change depends on temperature

Change
molecular
interactions and
entropy

Hydrophobic Effect: Origin of Hydrophobic

Interactions
Association of
Non-polar groups
Non-polar
groups

Reduced contact area

between non-polar
groups and water
- Thermodynamically
favorable

Water

G = A
G = Free energy change due to hydrophobic effect (J)
A = Change in the contact area between non-polar groups and water (m 2)
= Interfacial tension (J m-2)

Hydrophobic Effect: Importance

Protein
Conformation

Surface
activity
Adsorption of emulsifiers to oil
droplets and air bubbles

Structure and transitions of globular proteins

Solubility

Binding
Structure
formation

Immiscibility of oil and water

Binding of polar lipids to starch helices
Lipid membranes and surfactant micelles

Dissolution in Water: Influence on Physicochemical

Gas

Properties of Water
Adding a solute to water changes its phase behavior
Freezing point depression

Boiling point elevation

Solution
Water
G = H - TS

In
Solution:

Lower
disorder

Higher
disorder

Greater possible disorder

(entropy) of molecules in
solution, than in pure liquid,
therefore driving force for
solidification or vaporazation
is less
Higher
disorder

Lower
disorder

Dissolution in Water:
Phase behavior of sucrose-water
77%

One phase
(aqueous sucrose solution)

Room temp

Two phase
(sucrose
crystals +
saturated
aqueous
sucrose
solution)

Mass balance:

x = mass fraction of crystals

CT = Total [solute]
CS [solute] in saturated solution
CC = [solute] in crystal (=100%)

The phase behavior of a solute-water mixture can be described by a phase

diagram, which specifies the type of system formed under different conditions,

Dissolution in Water: Influence

of sucrose on ice formation
20% sucrose
solution

Cool
One phase
(aqueous sucrose solution)

Pure ice

50% sucrose
solution

Two phase
(Ice crystals + aqueous
sucrose solution)

The phase behavior of a solute-water mixture can be described by a phase

diagram, which specifies the type of system formed under different conditions,

Use of Sugars as
Cryoprotectants:
Freezing & Thawing

0 wt% sucrose

20 wt% sucrose

Hydrogenated palm oil-in-water emulsions stabilized by WPI (-40

C/40C) sucrose modifies ice crystal formation

Water Activity:
A parameter to characterize influence of water on food stability and properties

Problem:
Water is known to play an important role in determining food properties
However, there is not a good correlation between total water content and
food properties:
Chemical reaction rates
Microbial growth rates
Physical properties
A new parameter was needed to describe waters behavior
Water Activity
UMASS Pilot Plant: 1988-1990
>130 million pounds today
Microbial stability: aw < 0.62
& Moisture migration control

Moisture content versus water activity

Icing: MC= 15%
mwater
MC 100
msample

MC= 40%

Cake: MC= 30%

Will water move from the cake to the icing ?

The answer is
not sure
- because the moisture content does not predict
water movement
Lili He

30

Water Activity:

Thermodynamic Definition

Thermodynamic Definition:

fw
aw 0
fw

pw
0
pw

Ideal Situation (Equilibrium)

T
aw = water activity
fw = fugacity (escaping tendency)
pw = partial vapor pressure (head space concentration)

Problem:
Most foods are not at equilibrium!

Food

P0

Pure Water

Water Activity:

Practical

Definition
Practical Definition:
Real Situation (Non-Equilibrium)
RVP = Relative Vapor Pressure
pw = partial vapor pressure

Food

Po

Pure Water

pw
RVP 0
pw

Water Activity: Raoults Law

How does solute concentration affect water activity?

aw X water

nwater

nwater nsolute

Parameters
Xwater = Mole fraction of water
nwater = Number of moles of water
nsolute= Number of moles of solute

Assumptions
Ideal Mixture All molecular interactions are equal
Solution - Modify by activity coefficient: aw = sXwater
Solute
Solvent

Raoults Law

Water Activity: Moisture Sorption

Isotherm
Moisture Sorption Isotherm

A moisture sorption isotherm provides

information about how water interacts with a

material, and how much available water is present

Water Activity: Moisture Sorption Isotherm

Influence of Solute Molecular Weight

Same mass
More moles

Same mass
Less moles

The above graph shows the relationship between Raoults law approach and the

moisture sorption isotherm approach (i.e. it ignores molecular interaction effects)

The moisture sorption isotherm depends on the molecular weight of the solutes
involved (since there are different moles of solute per 100 g of material)

Water Activity: Moisture Sorption

Isotherm Influence of Molecular Interactions
Moisture Sorption Isotherms

A moisture sorption isotherm is highly dependent on the material

being tested due to differences in the molecular weights of solutes, as

well molecular interactions between water and the solute components.
If it is assumed that the A, B & C have similar molecular weights, then the
water solute interactions would be: A > B > C (since at the same water
content, the water activity is much lower for A, which means the water is
bound more tightly)

Water Activity: Moisture Sorption

Isotherm Shapes

Moisture sorption isotherms can usually be divided into three regions:

I.
Low water activity: Monolayer binding of water to molecular surfaces, e.g.,
potato chips, crackers, cookies
II.
Intermediate water activity: Multilayer binding of water to molecular
surfaces, e.g., breakfast cereals, rice, pasta, hard candy, chewing gum, raisons
III.
High water activity: Free water due to saturation of molecular surfaces, e.g.,
jams and jellies, bread, milk, meat, yogurt, fruits

Water Activity: Moisture Sorption

Moisture Content

Isotherm Hysteresis

Water Activity
A moisture sorption isotherm often depends on

whether water is added to a material (adsorption)

or removed (desorption) leading to hysteresis

Thermodynamics: The two curves should be the same.

Kinetics: Hysteresis occurs due to kinetic phenomenon

such as super saturation, crust formation or capillary

formation

Water Activity: Approaches to controlling

water migration

Water will tend to flow from raisins to

cereal. To prevent:
(i) Change driving force: e.g., add
glycerol to lower aw of raisin.
(ii) Create kinetic energy barrier: e.g.,
coat raisins with a material that prevents
water flow (e.g., fat).

Raisin aw = 0.55
Cereal aw = 0.1

To prevent water-migration:
(i) Thermodynamic approach: Change
driving force by equaling aw. (G 0)
(ii) Kinetic approach: create an
activation energy (energy barrier, G*) to
inhibit movement.

G*

G
Thermodynamically
Favorable State
39

Water Activity:

Influence on Chemical,
Biochemical and Microbial Reaction Rates

Water Activity

The water activity of a food influences many

important kinetic processes in foods:

Chemical Reaction Rates
Microorganism growth
Enzyme Activity

Water Activity: Influence on

Chemical Reaction Rates

Restricted mobility
slower movement

Concentration
closer together

The chemical reactivity of water-soluble reactants

depends on the water activity:

Concentration decreases distance between reactants

High solute concentrations causes restricted molecular

diffusion

Water Activity:
Influence on Physical Properties

Candy Floss

Cookies & Crackers

Cereals

Water activity plays a major role in determining their

physical properties, such as texture (crispiness,
crunchiness)
Elastic Modulus

Potato & Tortilla

Chips

Rubber
y
State
(Soggy)

Glassy
State
(Crispy)

Moisture Gain

Crystalline and Amorphous

Solids: Small Molecules

Crystalline state

Glassy state

Thermodynamically stable
Low molecular mobility
Highly ordered packing
Elastic, strong

Metastable
Low molecular mobility
Disordered packing
Jammed
Highly Brittle

Crystalline and Amorphous

Solids: Polymers

Crystalline state

Glassy state

Low molecular mobility

Highly ordered packing

Elastic, strong

Low molecular mobility

Disordered packing
Jammed
Brittle (Glassy)

Rubbery state

Higher molecular mobility

Disordered packing
Pliable (Rubbery)

Glass-Rubbery Transitions:
Temperature and Water

Heat

Rubbery
state

Water

Glassy
state

Rubbery
state

Water Activity: Glass Transitions

Temperature Increase

Rubbery state
(Soggy)

Glassy
State
(Crispy)
Moisture Gain

Water Activity: Glass Transitions

glassy state

rubbery state

Acids, Bases, & Buffers

Importance of pH in foods
Influences flavor
tartness, sourness
Influences stability and
reactivity
Physical, chemical & microbial
Influences texture & appearance
Aggregation, gelation

Acid-base equilibria:
Water
Actual:
Simplified:

H2O
H2O
[OH ][ H ]
KW '

[
H
O
]
2

H3O+ + OHH+ + OHKW [OH ][ H ]

Dissociation Equilibrium Constant: Kw = 10-14

Acid-base equilibria:
pH
H2O

H+ + OH

pH log 10[ H ]
pH
1
2
3
4
5
6
7
8

[H+]
10-1
10-2
10-3
10-4
10-5
10-6
10-7
10-8

[OH-]
10-13
10-12
10-11
10-10
10-9
10-8
10-7
10-6

[OH-][H+]
10-14
10-14
10-14
10-14
10-14
10-14
10-14
10-14

Acid-base equilibria: Buffers

UCDavis, ChemWiki

Acid:
Actual:

AH

[conjugated acid]1

Simplified:

H2O

A-

[conjugated base]2

[conjugated base]1

AH

H3O+
[conjugated acid]2

A- + H +

What fraction of a weak acid or base dissociates in water?

A strong acid/base fully dissociates (e.g., HCl or NaOH)
A weak acid/base partially dissociates (e.g., -COOH or -NH2)
How does this change the pH of the resulting solution?

Base:
BH+

B + H+

How does charge change with

pH?
HendersonHasselbalch

AH

A- + H+

[ A ][ H ]
[ A ]

K
[H ]

[ AH ] [ AH ]

Property of the
molecule

[A ]
pK pH log 10
[ AH ]
Property of the
solution

Deprotonated form
Protonated form

Information of fraction of molecule

protonated or deprotonated

How does charge change with

pH?
AH
A- + H+
100

AH
80

60

pKa = 5

Charged
Concentration of Species
40

20

5
pH

K H

2.3K a H C

Acid-base equilibria:
Buffers
a

Titration of a weak acid

The buffer capacity (in the alkali

direction) is defined as the number of
moles of OH- that must be added to one
liter of buffer in order to increase the pH
by 1 unit.

pKa = 5

Titration of a strong acid

=1/Slope

A buffer is a weak acid or base that can retard the change in pH when acid or base is
added

Acid-base equilibria:
Buffer Capacity

2.3 C 10 pKa pH

1 10

pKa pH 2

The buffer capacity (in the alkali direction) is defined as the number of moles of OH- that must be added to one
liter of buffer in order to increase the pH by 1 unit.
A buffer works best at pH values close to its pKa value.

Food Acids, Bases & Buffers

Acid

Step

pKa

Organic Acids

Acid

Step

pKa

6.37

10.25

2.12

Inorganic Acids

Acetic

4.75

Citric

3.14

4.77

6.39

7.21

3.03

12.67

4.44

0.85

Lactic

3.08

1.49

Malic

3.40

5.77

5.10

8.22

Propionic

4.87

-3.0

Succinic

4.16

1.92

5.61

Step

pKa

Fumeric

Carbonic

o-Phosphoric

Pyrophosphoric

Sulfuric

Base

Acid-base equilibria: Effect on Functionality

-NH3+

-CO2H

-NH2
Milk Curds

+
+

VDW + Attraction
(Insoluble)

-CO2-

Electrostatic
Repulsion
(Soluble)

Electrostatic
Repulsion
(Soluble)

Protein solubility

Acid-base equilibria: Effect

on Functionality
Native
Proteins

Electron Microscopy

Heat

Filamentous
High WHC
Transparent
Elastic

pH << pI

pH = pI

Particulate
Low WHC
Opaque
Rubbery

WHC = water holding capacity

Protein Gel Type

Acid-base equilibria: Effect on

Functionality
Benzoic acid is only used as a preservative

in acid foods (e.g., fruit juices, pH 2-3)

because it becomes non-ionized at low pH
and can enter the lipid membranes of cells
pKa= 4.2

Antimicrobial Activity

Acid-base equilibria: Effect on

Functionality
Citral is a flavor molecule in many

beverages. Its degradation rate is highly

dependent on pH

Flavor Stability