INTRODUCTION where a* is the thermodynamic activity of water, 7* the

activity coefficient of water, and Xw the total mole fraction

Thermodynamics provides means for predicting and of water in the solution. 7e and T are in oK. Water's
correlating: 1) equilibrium freezitg points of foods; 2) molecular weight is 18.02. AII., is the average latent heat
food's equilibrium liquid water and ice contents as of fusion between Ts and T . The ideal gas law constant R i s
1 1.
functions of temperature during freezing; 3) heat-removal 8.314 kJ (kg mole)- K- The freezing point depression
requirements for freezing; and 4) effects of pressure and (To - T) is the same in K and "C. 7* is difficult to predict
ice crystal size on freezing points. and correlate for foods. Because aqueous solutions contain
At atmospheric pressure, the equilibrium freezing point both solvent water and water, which is bound to solute
of pure water, 76, is 273.L6K (0t or 32"F). To decreases molecules and acts as part of those molecules,t3l
by 0.0074K atm-t as pressure increases.tll Water often has
to be subcooled before the ice crystal nuclei form. Once N* - n* bn"
nucleation occurs, the temperature of the ice-water mix
an - X*": N*+Ns n*-bn"*En" (2)

rises rapidly to 7 and remains there as cooled liquid

converts to ice. When only ice exists, its temperature drops
below Zs and gradually approaches that of the coolant.
4y'1q, water's latent heat of freezing at 7o, is
333.6 kJ kg-1 (143.4 Btu lb-1). C*, liquidwater'sheatcapa-
city, averages 4. I 87 kJ kg-1 K- I or 1.00 Btu lb- 1 o F-1. At
To, Ct, ice's heat capacify, is 2.093kJkg-tK-t or
0.500Btu 16-r op-r. C1 decreases roughly by
0.007kJkg-1K-l per K or 0.00093BtulbllT-1 per T
as ice cools.
FREEZING POINT DEPRESSION
Dissolved solutes depress water's fteezing point. As Fig.
lshows, freezing point depression increases as solute
concentration increases.[2] As water in a solution freezes,
solute concenfration in the remaining solution increases
except when solutes also solidify; and 7, the equilibrium
temperature of the ice-solution mix, decreases as ice
formation continues. If the solution contains a single
solute, cooling-induced ice formation.causes I to drop
until it reaches ZB, the eutectic temperature, where it
remains while the remaining water and the solute solidify.
After both completely solidifu, continued cooling will
cause I to drop further and gradually approach the
temperature of the coolant.
Equilibrium freezing points of aqueous solutions are
governed by the following equationt2]
ln(a*) : ln(7*X*): - t8.024,H"'(To - T)
(1)
RTsT
where X*" is the effective mole fraction of solvent water in
the solution, N*, the moles of solvent water, i.e., unbound
water, N the moles of solute, n* the total mass fraction of
water in the solution, z" the mass fraction of solute in the
solution, the mass of water bound per unit mass of solute,
E : 18.021M,, and M, the solute's molecular weight. Eq. I
with X*,, given by Eq. 2, substituted for a* will be calld
modified Eq. l.
Food solutions usually contain many solutes. Unless a
solute precipitates, the relative weight proportions of the
dissolved solutes do not change during freezing. There-
fore, constant effective E and b can usually be used for
solute mixtures. Very good fits between modified Eq. 1
and experimental freezing point depressions vs. solute
concentration data are obtained for single and mixed
solutes when best-fit values of E and b are used. X*", E,
and b can similarly be determined for moist solid foods
that contain insoluble solids and water sorbed by those
solids in addition to solvent water and solute-bound water.
By using 2(X*. - l)l(X*. * 1), the first term of a series
expansion for ln(X*"), in place of ln(X*") in modified Eq. I
and noting that AHayf (TsT) - LHolTS, one obtains
En" En"
n* - bn" * 0.5En, n* - Bn" t
_t&.o2LHo(To - T)
(3)
'r
RT i
: {
where B (b - 0.58). Applying Eq. 3 when n: n*o,tre
total weight fraction of water in the food prior to freezing, c
and 7: Z, its equilibrium initial freezing point, one
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Thermoilynamics of Food Freezing

obtains

En, _l8.O2AHo(To-T) (4)

-4
nno - Bn" R-
Dividing Eq. 4 by Eq. 3, one obtains
o-6
n* - B:"
n-o-Bn,-!4
(s)
-8 To-T
-10
the equilibrium weight fraction of unfrozen water in the
-12 food at 7. The weight fraction of ice in the food is

-14
,t: Lwo - w -(*o - n*,l!:!)
"'To-T (6)

-16
Dimensionless Eqs. 5 and 6 can be used with temperatures
-18 in K, or oF. The combined weight fraction of solutes
t,
and solids in the food is n. : (1 - n*o).
-20

-22
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 VOLUME CHANGES

Weight Fraction Solutes The respective densities of liquid water and ice are
Ftg. 1 Freezing point vs. solute weight fraction for wine and
1000kgm-3 and 917kgm-3. Therefore as aqueous
juices. (From Ref. 4, p. 137.) solutions freeze, expansion occurs. Freeze-concentrated
solution may exude from spaces between the growing ice
crystals. Gas-filled pores in foods may compact as ice
forms. Therefore, extents of freezing-induced expansion in
porous foods are difficult to predict.

ENTHALPIES
90

80
350 At temperaturesT 1 Ti, enthalpies (heat contents) of foods
undergoing freezing can be obtained by summing up the
70 300 enthalpy contributions of the components involved, i.e.,
(,)
60 ll H : nnH* * n1H1 * nrH, O)
250
50 where 1, H*, Hb and H* are the enthalpy per unit mass for
200 = the food, liquid water, ice, and the combined solids and
40 o- solutes, respectively. The 1/s are measured with respect to
J
150 a reference temperature Ip, usually 233.16K ( - 40'C or
30 -F - 40'D, where each H is zerc. n* at T can be obtained
100 z from modified \. I , n1: flwo - *. If, instead , n* and ni
20 LrJ
are obtained from Eqs. 5 and 6, respectively, the relative
50 error will be at most 0.47o. H*: LHo + C*(I - 7n),
10
h: C{T - In), and I/. : C"(T - Zn). C. is the partial @
'E

0r- J0 heat capacity for the combined solutes and solids in the
-50 -44 -30 -20 -10 0 10 20 food. Using Eqs. 5 and 6, substituting for II", H*, H ns,
T(oC) z*, and ny arld rearranging, one obtains

Fig. 2 Enalpy vs. temperature for lean beef. Sod lines--data H : (T - r*) fc, *(n*o - Bn")LHo!!:-T'1
from Eqs. 6 ad 7. O---+alorimetric data by Reidel.t5]
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L046
The heat capacity of the food in the completely frozen
state is C o (n*o - bn")Ct I bn"C* * n"C". If 1 vs. 7
data obtained by calorimetry are available, C, B, andT,for
use in Eq. 8, can be found by best-fit methods. Above [,
H : (Tt- ril [C,
*
(*o- Bn')A]Iol t Co(T -7)
Zo-In
Cs is the heat capacity of the food in the thawed state. Fig. 2
Iplot for beef.tsl Eqs. 5, 6, 8, and 9 are
depicts an 11 vs.
more accurate than similar equations derived earliertal
where n" was used instead of Bn". The amount of heat
removed per unit mass in cooling a food initially at
temperature Tt ) Ti to subfreezing temperature 12 is
Ht - Hz, where I11 is obtained by substituting T1 for T in
Eq. 9 and I12 by substituting T2 for I in Eq. 8.
Effective Heat Capaci
As freezing of foods takes place over a range of
temperatures, the effective heat capacity C" at T for
T < Ti is obtained by differentiang F,q. 6 with respect to
T. C.: dHldT, yielding
. LHs(n*o -
Le:Lf+6 Bn,)(To - Ti)
Eq. l0 is valid only at 7 below Ti. As T increases, C,
increases and peaks sharply at Ti, a.9., for lean beef it
goes from 2.2AkJkg- rK-l at 233.16K (-40'C)
220.6Ukg- 1K- 1 at Ti,i.e.,272.16K(-1.0b'C). As soon
as Iis above ?], Eq. 10 no longer applies and C, immediately
1 1
drops to Cs, a.g.,3.456 kJ kg- K- for lean beef.
THERMAL CONDUCTIVITY
The respective thermal conductivities of ice and
water at 273.16K are kt:2.25Wm- 1K- 1 and
k* : 0.569Wm- I K- l. Therefore, the thermal conduc-
tivity /c of a foodincreases markedly as it freezes. Thermal
conductivity is a transport property, not a thermodynamic
property. Nevertheless, Eq. 9 correlates /< for foods fairly
well at T < Ti when, as frequently occurs, dendritic (tree-
like) ice crystals form during freezing.
k: kr *(ro - frr) +#1 (1r)
ftq and t are the thermal conductivities of food in the fully
thawed and fully frozen states, respectively. At T > Ti,
Eq. I 1 no longer applies and : h.Bq. 1 1 does not fully
account for increases in /c that occur as 7 decreases, but is
accurate enough for most engineering purposes. Eq. 11 is
not valid for materials that contain dispersed, rounded ice
Thermodynamics of Food Freezing
crystals instead of dendritic crystals. ,t, given by Eq. 11,
and C. from Eq. 10 or.Fl from Eqs. 8 and t have been used
in modeling how 7 varies with time and position during
fre,ezing and thawing.
(e)
DEVIATIONS FROM EOUILBRIUM
During freezing, heat transfers from ice growth sites,
and water diffuses through water-depleted regions to
those sites. In cellular foods, membranes impede such
diffusion. As freezing progresses and solute concen-
tration in the residual solution increases, food solutions
become very viscous. Because of high viscosity, water
diffuses more slowly to ice gowth sites. Solute
concentrations at those sites rise above those in the
rest of the residual fluid; and the temperature falls
below the equilibrium temperature for the current
average bulk solute concentration. Deviations from
equilibrium are greatest when freezing is carried out
rapidly and at I below -2O"C. Therefore, extremely
slow cooling has to be used in calorimetric measnre-
ments intended to determine equilibrium properties of
(10)
freezing foods. Deviations from equilibrium often occur
in industrial freezing processes. Thus, the equations
presented earlier will be somewhat in error for such
processes. As most heat removal and ice formation
occurs just below T and well above - 20oC, the errbr
to involved will be tolerable for most practical purposes.
EFFECTS OF CRYSTAL SIZE
Small crystals possess more surface energy per unit mass
than larger ones. Therefore, equilibrium Z for small ice
crystals are slightly lower than that for larger crystals. The
in I is inversely proportional to ice crystal
depression
diameter. For lpm crystals the depression is roughly
0.1"K, for 10 pm crystals roughly 0.0 1"K, and for 100 pm
crystals roughly 0.001'K. Smaller crystals tend to melt and
larger crystals tend to grow in foods containing ice crystals
of mixed size. This effect, Ostwald ripening, can lead to
graininess in ice cream. Ostwald ripening is used to
produce large, readily separable ice crystals in modern
freeze-concentraon systems. t2I
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REFERENCES ,j
H
1. Hobbs, P.J. Ice Physbs; Oxford University Press: Oxford,
1974;346-364. e
2. Schwartzberg, H.G. Food Freeze Concentration. In Biotech-
nology and Freeze Concentration; IFT Basic Symposium o
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N{a:nr Dnxxen, INc.
270 Mad.ison Avenue, New York, New York ltfll
 Thermddynmics of Food tr.rering lM7

Series, Schwartzberg, H.G., Rao, M.A., Eds.; Marcel 4. Schwartzberg,H.G.EffectiveHeatCapacitiesfortheFreezing

Dekker, Inc.: New York, 1990; 127 -2O2. and Thawing of Foods. J. Food Scr.lyl6,4l,l52-156.
3. Riedel, L. On the hoblem of Bound Water in Meat. 5. Riedel, L. Calorimetric Investigation of the Meat Freezing
Kaltetechnik 1961,13,41-43. Process. Kaltetechnik 1957,9,38-40.

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