Académique Documents
Professionnel Documents
Culture Documents
Food Quality
Chemical reactions depend on water content
Physical properties depend on water content
Food Cost
Tetrahedral
structure of
water
Hydrogen
bonds
Physicochemical
Properties
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.
Quality
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.
Crystal
Growth
G*
Water
Ice
Transition is thermodynamically
favorable below Tm
(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
Growth
Supercooling (Tmp-T)
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.
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
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)
Cavity in Water
Tetrahedral structure
Correct Shape &
Charge Distribution
High Solubility
+
+
Low Solubility
Low Solubility
Na+
Cl-
Ion
Ion-ordered
region
Intermediate
disordered region
Structure
Maker
Water-ordered
region
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
Limited
Free water
Protein
Aggregation
Hydrated
Protein
No Salt
Low Salt
High Salt
100
80
Solubility (% )
60
40
20
0
-10
10
30
50
70
90
Salt Concentration
Non-polar
solute
Magnitude
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
Bulk Water
Molecular Interactions:
3-3.5 H-bonds
Entropy: Some disorder
Bound Water
Molecular Interactions:
4 H-bonds
Entropy: Highly ordered
Change
molecular
interactions and
entropy
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)
Surface
activity
Adsorption of emulsifiers to oil
droplets and air bubbles
Solubility
Binding
Structure
formation
Properties of Water
Adding a solute to water changes its phase behavior
Freezing point depression
Solution
Water
G = H - TS
In
Solution:
Lower
disorder
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:
Cool
One phase
(aqueous sucrose solution)
Pure ice
50% sucrose
solution
Two phase
(Ice crystals + aqueous
sucrose solution)
Use of Sugars as
Cryoprotectants:
Freezing & Thawing
0 wt% sucrose
20 wt% sucrose
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
MC= 40%
30
Water Activity:
Thermodynamic Definition
Thermodynamic Definition:
fw
aw 0
fw
pw
0
pw
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
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
Same mass
More moles
Same mass
Less moles
The above graph shows the relationship between Raoults law approach and the
Isotherm Hysteresis
Water Activity
A moisture sorption isotherm often depends on
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
Restricted mobility
slower movement
Concentration
closer together
diffusion
Water Activity:
Influence on Physical Properties
Candy Floss
Cereals
Rubber
y
State
(Soggy)
Glassy
State
(Crispy)
Moisture Gain
Crystalline state
Glassy state
Thermodynamically stable
Low molecular mobility
Highly ordered packing
Elastic, strong
Metastable
Low molecular mobility
Disordered packing
Jammed
Highly Brittle
Crystalline state
Glassy state
Elastic, strong
Rubbery state
Glass-Rubbery Transitions:
Temperature and Water
Heat
Rubbery
state
Water
Glassy
state
Rubbery
state
Rubbery state
(Soggy)
Glassy
State
(Crispy)
Moisture Gain
glassy state
rubbery state
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
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:
Actual:
AH
[conjugated acid]1
Simplified:
H2O
A-
[conjugated base]2
[conjugated base]1
AH
H3O+
[conjugated acid]2
A- + H +
Base:
BH+
B + H+
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
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
pKa = 5
=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.
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
-CO2H
-NH2
Milk Curds
+
+
VDW + Attraction
(Insoluble)
-CO2-
Electrostatic
Repulsion
(Soluble)
Electrostatic
Repulsion
(Soluble)
Protein solubility
Electron Microscopy
Heat
Filamentous
High WHC
Transparent
Elastic
pH << pI
pH = pI
Particulate
Low WHC
Opaque
Rubbery
Antimicrobial Activity
Flavor Stability