Technology of Preservation by

Freezing

COLD PRESERVATION:
Q10 =(K10+T) / KT
10 oC lowering of temperature makes shelf life almost
double.
Chill storage: 0 to 5 oC, only psychrotrophs can grow
relatively slowly. e.g. generation time for pseudomonas
available in fish is 6-8 hours at 5 oC compared to 26 hr at 0
o
C.
As the temperature is lowered the plasma membrane of the
organism undergoes phase transition from liquid crystalline
to the gel in which transportation of solutes is extremely
difficult.
Mesophiles can grow at chilling temperature but not
necessarily killed. Certain psychrotropes
such
as
pseudomonas do grow and cause food poisoning.
2

Large pieces of meat are often packed in plastic bags or

sprayed with various moisture resistant coatings. Eggs are
coated with edible oil which seals the minute pores in egg
shells. Beefs ageing at 90% R.H. for several weeks at 2 oC
is treated with UV rays.
FREEZING: The most popular method and brought
conveniences at homes. Food material begin to freeze in
decreases. Perishable foods are stored at -18oC or below.

Freezing preservation

Effective for retaining color, flavor and nutritive

value and moderately effective for retention of
texture.
In freezing process temperature of product is
reduced to -18 0C or bellow and crystallization
of the part of water and some of solutes takes
place.
Supercooled or under cooled temperature of
water is lowered below its freezing point without
any occurrence of crystallization and HENCE
NO IMPAIRMENT of food quality. So, changes
during freezing is attributable to water-ice
transformation not to reduction in temperature.
4

 Water ice transformation leads to crystall-

formation of a systematically organised solid

phase from solution (solute and water) or melt
(ice and water).
Crystallization- nucleation - association of
molecules into tiny ordered particle of size
sufficient to survive and serve as the site for the
growth of crystal.

Initial freezing point - temperature at which

a tiny crystal of ice can exist in equilibrium
with the liquid phase.
5

 Two types of nucleation: homogeneous

and heterogeneous or catalytic occurs in
food materials which involves formation of
nuclei adjacent to suspended foreign
particles, surface films or on the walls of
containers necessitates some super coolingtemperature is lowered to some critical value,
nucleation begins and further decrease in
temperature results in abrupt increase in
nucleation rate.

 Crystal growthit occurs just bellow the melting point

temperature. At temperatures near the melting
point, water molecules add to existing nuclei in
presence to form new nuclei. CRYSTALIZATION
RATE is governed by heat and mass transfer
rates. Water molecules must move from the
liquid phase to a stable site on the crystal
surface, and solute molecules must diffuse away
from the crystal. Ice crystal growth rate is not
limited by water molecules except during the
final stage of freezing.
small solutes can migrate short distances and
eventually are concentrated among growing ice
7
crystals.

Rate of
Nucleation
0 o
o

Temperature (oC)
Initial Supercooling
Rate of ht removal

-50o

Rate of Crystal
growth
0 o
o

-50o

Temperature (oC)
Initial Supercooling
Rate of ht removal

Suspended matter or cellular components are

unable to migrate and ice crystals either form
around them or push them aside. Hence in
foods (high moisture), rate of ice crystal growth
is generally not limited by mass transfer
process, except during the late stage of
freezing when temperature is low, viscosity is
high and unfrozen water is low.
Hence, heat transfer limits the rate of
crystallization because of large latent heat of
crystallization of water. Growth rate is increased
greatly with increase of heat removal.
10

 Slow freezing: 1 0 C to 10 0 C/h

Commercial freezing: 10 0 C to 50 0 C/h
Ultra rapid freezing: above 100 0 C/h
During freezing of tissues, water from the solution is
transferred into ice crystals of a variable but rather
high degree of purity. Non aqueous constituents are
therefore concentrated in a diminished quantity of
unfrozen water. Unfrozen phase changes significantly
in pH, titratable acidity, ionic strength, viscosity,
freezing point, surface and interfacial tensions etc. O 2
and CO2 may be expelled out from solution,
macromolecules are forced closer together, water
structure and water solute interactions may be
drastically altered.
11

Slow
freezing

Rapid
freezing
12

Volume changes
Composition
Solutes or suspended matter substitution
effect reduce the fraction of water in system.
intracellular air spaces common in plant
tissue can probably accommodate growing
crystals and thereby minimize changes in the
exterior dimensions.
Fraction of water that fails to freeze bound or
supercooled water does not contribute to
expansion during freezing. Kind & amt. of solutes
13
influence amt. of bound water & tendency for SC

 Temperature range under study Observed

changes in volume is a function of temp re change.
Cooling of the food prior to freezing (conc n)
Ice formation (expansion)
Cooling of ice crystals (concentration)
Solute crystallization (concentration)

Cooling of solute crystals present in

eutectics (concentration)
Crystallization and cooling of non solutes
such as fat (concentration)
14

Major point Ice crystals are relatively pure even

when they originate from a complex system.
Proper to assign an expansion value approx 9%
to the qnty of water that freezes. Volume changes
is not uniform through out the food because
most other constituents contract as the temp is
lowered leading to localised areas of expansion
(ice crystals) and localised areas of concentration
likelihood of stresses and possibility of
mechanical damage more likely in plant tissues
with its rigid structure and poorly aligned cells
than in muscle with its pliable consistency and
parallel arrangement of cells (fibers).
15

Effect of initial concentration on the decrease in

volume and the increase in Molality of the
Unfrozen Phase
Unfrozen
(1 liter)

S
S

Frozen
(1 liter)

S S S
S
S S S
S
S S S S
SS SS

SSSS
S
S

ice
Ice

Conc in unfr
5 s per liter
Conc in unfr ph of fr sl 30 s per liter
Increase in conc by fr
6X
Volume of unfr ph aft fr 1/6 liter
Amount of ice formed
5/6 liter

15 s per liter
30 s per liter
2X
liter
16
liter

Eutectic point or Eutectic temperature

As the freeze concentration process
progresses solutes reach or exceed their
respective saturation concentrations and
simultaneous crystallization of ice and solute
becomes possible. The temperature at which
a crystallized solute can exist in equilibrium
with ice and the unfrozen phase is known as
the eutectic point or eutectic temperature of
the solute.
NaCl: -21.130C sucrose: -140C
glucose: -50C
Na2CO3 -2.10C
17

Time Temperature Plots

A-S represents removal of
sensible heat with no water
icetransformation. S is super
cooling. Following on set at A
S, the released heat of
crystallization causes the
temperature to rise promptly
to the apparent initial freezing T
point, B. initial freezing point
is a function of number of
dissolved particles in solution.
B-C, a major portion of water
is crystallized. Since heat of
solidification generated from
ice formation is the major
heat source to be removed

B
S

Time

18

during the freezing and since only solute

concentration in the unfrozen phase is
increased to a moderate level (slight depression
of freezing point), B-C exists as a long plateau
with a negative slope. During the early stages of
freezing, water separates as pure or nearly pure
ice crystals. During the late stages of part B-C
and the entire C-D, eutectic mixtures and other
types of complex solids of largely unknown
structures and composition may form. These
portions are especially complex in tissues
because growing ice crystals exist in and/or
among cells, thereby competing with
19

each other for space and for diminishing supply

freezable water. Beyond point C, each successive
gram of ice formed is responsible for a substantial and
successively larger increase in molality of the unfrozen
phase (lower freezing point). Besides, removal of a
given amount of heat energy can effect a much
greater reduction of sample temperatures during the
portion C-D than B-C because the sample at point C
contains much less freezable water than it had initially.
Unless the temperature is well below the samples
final eutectic point, the sample usually contains some
freezable water even after cooling to the point D. From
the other curves, it is clear that increased rates of heat
removal causes the various stages of cooling and
20

freezing becomes less distinct. At very great

rates of heat removal they become
indistinguishable.

21

freezing becomes less distinct. At very great

rates of heat removal they become
indistinguishable.
Freezing point depression: the temperature at
which the first ice crystals can appear when
cooling is carried out under equilibrium
conditions.

22

 Denaturation: an alteration to protein in which

intermolecular cross linking takes place that
permanently changes the physical and chemical
properties of the protein.
Drip: the expressible fluid from fish flesh. The volume
of drip increases denaturation.
Fatty fish: mackerel herring etc. contain a
considerable quantity of stored lipids. Haddock and
cod fish are non fatty or lean fish.
Freezer burn: describes the area of a frozen product
in which the ice has sublimated leaving the product
dehydrated, porous and spongy. The phenomenon
can affect the entire surface and penetrate deeply
into the product.
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 Tempering: raising the temperature of the

frozen fish or product between -5 0c and -100c
to permit mechanical processes, such as
slicing.
Glazing: it is carried out by quickly immersing
the frozen fish in very cold water immediately
after freezing which produces a protective
shell of ice.

24

Freezing process:
Prefreezing treatments
Freezing
Frozen storage

Each phase is
important
to
produce
food
products
of
maxm quality

Thawing
Fruits and vegetables treatments:- Quality of
fruits and vegetables following the freezing
process depends greatly on:
variety chosen,
growing conditions, and
stage of maturity at harvest
25
mature for fruits and immature for vegetables

o Washing, grading, sorting, cutting, and proper

packaging are some of the obvious operations.
o Keeping them aside some means must be
employed to control enzyme activity.
o Else undesirable changes in flavour, colour,
texture, and nutritive value will occur during
frozen storage.
o control of enzyme activity is generally achieved
by blanching exposing to hot air or water.
o Enzyme catalysed (polyphenoloxidases)
oxidative browning light coloured fruits deep
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colouration not by heating changes desirable

Organoleptic properties of fruits. Chemical

additives inhibit enzymes alter enzyme
substrates limits entrance of oxygen. SO 2,
sulphites, sulfurous acid, citric acid, malic acid
etc. inhibit activity of polyphenoloxidases or
reacts with substrate.
Ascorbic acid costly, effective agent for
controlling enzymatic browning also a valuable
nutrient inhibits browning by maintaining
polyphenolic substances to a reduced and
colourless state. ).3% AA in sugar syrup required
for complete effectiveness. Lower conc 0.1% is
27
frequently used.

Sucrose or sugar syrups added to fruits prior

to freezing accomplishes several purposes :
to contribute sweetness
to retain volatile aromas
To decrease amt of water frozen at any given
subfreezing temp
to lessen enzynatic browning by acting as a
barier to the entrance of oxygen.
Cut fruits must be protected immersion in a
dilute sol of NaCl (1-3%) is a method often used.
28
PPO are inhibited by chloride ions.

Else immerse the fruit in 0.25% NaHSO 3 for 45

sec followed by 5 min dip in 0.2% K2HPO4 (pH
8.8).
Prior to freezing overly soft fruits is firmed to
some extent by brief immersion in a sol
containing Ca2+ - divalent calcium ions form
crosslinks between negatively charged polymers
of pectic substances.

29

Fish:- Quality of frozen-thawed-cooked fish

Species
composition especially fat content
size
how and where caught
elapsed time in the live state betwn harvest & fr.
the state of rigor when frozen
quality when frozen
details of the freezing process

30

Major problems during freeze processing of fish

Oxidative deterioration
Dehydration
Toughening
loss of juiciness
excessive thaw exudate or drip
microorganism
autolysis
To minimize contraction and lessen increase31 in

desirable that rigor mortis is completed at a low

non freezing temperature prior to freezing.
Freezing during rigor is undesirable. State of rigor
at the time of freezing is less important with
whole fish than it is with fillets and smaller pieces.
Hence, freezing promptly after the catch or
harvest (prerigor) is recommended for whole fish.
Undesirable oxidative changes may be minimized
eliminating O2 (vacuum or flushing with inert
gases) or providing a barrier to the entrance of O 2
such as protective coating
32
avoiding contamination with oxidative catalysts

 adding antioxidants.
Avoiding irradiation including light.
Using very low storage temperature or short
storage time.
Avoid dehydration by: applying a suitable protective coating to the
fish. Generally by ice glaze, gelatinous coating,
or conventional package.
Reduce Drip loss or thaw exudate by
controlling the rate and extent of glycolysis prior
33
to freezing.

 applying suitable chemicals (polyphosphates)

following recommended practices for freezing,
frozen storage, and thawing.
Water fr. to ice
(%)
0
10
20
30
40
60
80

Temp

Water fr. to ice

C
-2.5
-2.7
-3.1
-3.5
-4.2
-6.8
-14.8
o

(%)
5
15
25
35
50
70
90

Temp
C
-2.6
-2.9
-3.3
-3.9
-5.2
-9.5
34
-30
o

Storage life of frozen foods at 18 oC

Products with storage lives of 3 mths or less
Mammalian meats, Bakery products etc.
Products with storage lives of 3 to 6 mths
Mammalian meats, poultry, etc.
Products with storage lives of 6 to 12 mths Veg.
Fish, mammalian meats, poultry, bakery products
Products with storage lives of 12 mths or more
Fruits (sugared), vegetables, mammalian meats,
fish, eggs,bakery products etc.
35

 Freezers
Primary freezers: product is in contact with
refrigerant in the form of a cryogenic gas or
liquid or solid.
Merits very much suitable for small and thin
product, very small ice crystals, insignificant
dehydration, color, flavor, structural changes,
drip loss on thawing.
Demerits- may induce considerable thermal
stresses, large product may display severe
cracking due to extremely uneven cooling at
the surface and interior.
36

 Secondary freezers: plate freezers refrigerant

removes heat by circulation within the plates those are
in contact with the product.
Merit- different refrigerants are used to cool air which
can be used.
Demerits- irregular shaped product are very difficult to
freeze, time of freezing is very high, larger ice crystal
are formed.
Tertiary freezing: air blast freezers which is in turn
circulated over the product.
Merit- varied and irregular shaped product can be
frozen, wide variety of shapes, sizes are available.
Demerit- freezer burn, drip loss etc.
Individual Quick Freezing (IQF)
37

 Cryomicroscopy:
microscopical observations of chemical and
biological systems during cooling. Molish discovered
with ice/salt freeze mixture now a days computer
controlled at 0.01 to 1000c per min cooling rate is
available.
Temperature of ice nucleation in tissue
Size shape and location of ice crystals around and
within cells or tissues
Rate and mechanism of propagation of ice crystalliz n
Mechanical effects of extracellular ice crystals on cells
Volumetric response of cells during freezing
Morphological alterations occurring during freezing
Effects of cooling rate, chemical additives and other
38
factors.

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