The wide range of possible envrionmental factors a food we collect data during a storage period for some mode
some mode of de-
could be exposed to brings . up . several verv important con-
sidw;~tionsin setting up a kinetic study o f f d q u a l i t y lms.
For example, should the food product under study he stored
in a contrhled environmentaichamber in the package typi-
cally used for distribution, or should it be stored sealed off
from light and moisture exchange by putting it in a can or jar?
As an example of the problems inherent in this decision, let
us consider a dehydrated or baked cereal product that would
be distributed in a semipermeable pouch. Using the typical
synthetic polymer material as the package during the kinetic
study will give the shelf life of the foodlpackage system, not
the food itself. This could confound the data if the moisture
gainhoss effects on the rate,of loss of quality cannot be sepa-
rated f r m other environmental factors. For example, one
might store the pruduct in an abuse condition at 40°C and 10mo
R H usinv the tvoiral nanrrhuard hox. In this condition the
product will d r G u t and there will be a possibility of an in-
creased rate of rancidity development. On the other hand,
room temperature data (e.g., 23% 50%RH) might not show
t instead pick UD moisture.
anv ranciditv since the ~ r o d u cwill
and the powihle development of nonenzymatic browning will
he thc limitinr factor. If the food were stored in iars instead.
moisture exchgnge would not occur, and the shelf life of the
food at constant reaction phase conditions (e.a.. constant a,)
woulci br rlrtermined. ohe ever, the jar could ;etain oil-odors
that were developed hut which, if the distribution package
wcrr used, might bass through the parkageur he ahsorbed by
thr r~arkurinrmaterial itself. Thus, storarr in a iar could evrn
lead to a cow& predicted shelf life. such probiems are more
difficult to deal with in practice than in theory. This problem
is eliminated with canned foods since moistu~eexchangedoes
not occur. Moisture loss for frozen foods is more of a problem
in the defrost cycle when package ice forms.
Another consideration arises from the fact that, in the high
abuse temperature studies, secondary chemical reactions that
would occur only slowly at the lower temperatures might now
proceed at significant rates. This, of course, could compromise
the predictive power of the data since a different mode of
deterioration might now become the controlling one. Thus,
one should not decide to test only for one chemical index if
there
~~~-~~
~~ ~~
.
is a notential for multinle reactions to occur. This would
~~~
be true for any dry or semimoist food containing unsaturated
l i ~ i d sreducine
. suears. and protein. For example. dehvdrated
pbtatbes go r&cG hklow '30-32'~ and de;eldp browning
(through NEB) above this temperature (I). In cases such as
this, it would he impossible to extrapolate shelf-life data ac-
curatelv from hieh temperature to low temperature unless the
specific effects on the kinetics of the reactibn are understood.
Finally, we have the question of cycling storage temperatures
versus constant temperature. Foods do not experience con-
stant temperature during distribution. Should we thus study
the kinetics under variable conditions, or can constant tem-
perature conditions he used t o make predictions for variable
conditions? Does the temperature cycling itself cause new
reactions that would introduce errors in identifying the main
factor in deterioration, sometimes called a ''history effect"
(14)?
General Approach to Kinetics of Food Deterioration
Basic Mathematical Approach to the Kinetics
of Deterioration of Food
There once was a chemist from Latta
Who couldn't interpret his data,
So he drew a straight line,
Now everything's fine,
Except for the damnable scatter.
The ahove limmerirk from Leffler and Grunwald (15) con-
cisely states the panicular prohlem facing chemists, especially
those who have studied food deterioration for many years. 1f
350 Journal of Chemical Education
terioration or chemical reaction, how can these data be used
to make projections about longer storage periods or other
storage conditions such as higher or lower temperature.
The first attempts to linearize data (i.e., drawing the
straight line as suggested above) were made when chemists
began to study the mechanisms of various reactions; their
approaches have developed over the years into elaborate or
simple models, depending on the degree of sophistication used
to detect the various reactants and end products.
For example, suppose we have the reaction
AZC (2)
where A is a reactant; C, the product; and kf, the forward rate
constant. If we use more sophisticated analytical tools we
might find out, in fact, that the reaction is really much more
complex, possibly
In this case A reacts with B to form two products, C and D,
which can also hack react with a rate constant of kb. The lower
case letters indicate that more than one molecule of each
.
com~onentis ~articinatine. The standard eauation defining-
the rate of loss of the reactants or gain of any component (e.g.,
see Benson (13)) is
T o solve the above equation,.which predicts the change in
concentration of any component with time, one needs to know
the concentrations-of each component as a function of time.
If this were possible, we would still have only one equation
with six un!&owns (kf, kb, a, b , c, d). Thus the situation is
technically impossible to solve. Most kinetics or physical
chemistry books such as Benson (13), Wallas (16),or Amdur
(17) suggest methods to get around this problem. Basically
one needs to choose conditions such that either the forward
or backward reaction predominates andlor the concentrations
of several species such as B are so high that their change in
concentration with time is negligible. Thus, if kb <<< k f and
[B] is very large, the loss in [A] or gain in either [C] or [Dl is
where k / is the ~ s e u d forward
o rate constant. Obviouslv this
form of the equation ignores the true mechanism of theieac-
tion but is useful from a practical standpoint. as we will
see.
A food system is very complex. Assuming that, for a given
mode of deterioration, the above assumptions hold, one can
simply write for the rate of gain of an undesirable quality
factor [B] or loss of a desirable quality factor [A] the following
equations
loss of quality -
gain of undesirable factor
where k is the pseudo rate constant, n is the order of the re-
action (a curve-fitting parameter), and [A] or [B] are the
quality factors measured (e.g., a sensory value such as a he-
donic score).
The above forms of the equations are used only for curve
fitting of the data (as defined by our Latta chemist) and in fact
may have nothing to do with the true mechanistic steps in the
degradation. For example, this simple form has been found
to apply to the growth or death of microorganisms, a process
which must proceed by a very complex set of steps. The major
caveats in usine these eouations are that the above assumo-
tions must h o l i (i.e., the back reaction is negligible, and the
concentrations of other species are not limiting) and that all
reaction phase condition; (pH, water activity, itemperatwe,
redox potential, concentration of all other species) must re-
main ~ o n s t a n t . ~ a s i c athis
l l ~ means that ihe pseudo rate
constant h is varticular to a given food system.
1for up to 50% loss (if this were as far as one collected data)
one would find it hard to distinguish between zero- and
first-order. The poorer the analytical precision the greater
would he the chance of error in deciding on reaction order
unless the study were carried out far enough. Fortunately,
although food quality loss is slow a t room temperature, many
food products become unacceptable with only a 20-30%
change from the initial value. Thus, it may not &en he nec-
essary to decide on thr reaction order and the simpler zero-
order model could he chosen. It should be noted that in~ Firmre
~~ ~
~~~~~~ - ~~~ -

Labuza (1)has outlined in detail the Hpp~icationof these 1the slope of the line is the zero-order rate constant ho {hie
mathematics to the shelf-life testing of foods based on both in Figure 2, using loglo for the ordinate,
temperature and humidity abuse, and Labuza and Kamman
(18) have reviewed some of the computer solutions for analysis
of shelf-life data. Only a brief review of the critical parameters
can he presented here. What should be made clear is that there Thus to get h l one should multiply the value of the slope by
are two general ways to approach shelf-life testing. The most
common method is to select some single abuse condition such
as high temperature, analyze the product two or three times
during some specified storage period, and then extrapolate
the results to normal storage conditions by using some "fudge
factor," perhapsgained by experience with similar foods. The
..
better annroach is to assume that certain nrinci~lesof
r
chemical kinetics apply with respect to temperatureacceler- 0
ation.. ex..
- . the Arrhenius rrlationshiu. ..and w h r e kinetir de- 6 so-
sign to produce a more accurate prediction. a
Y

Reaction Order > 'O-

k
Fortunately, from a data manipulation standpoint, most 2 60-
3
literature data for change in food quality (based either on 0
some chemical reaction, microbial growth, death, or sensory Y
0
value) follow a zero-order (n = 0) or first-order (n = 1) reac-
tion model. Thus integrating eqns. (7) and (8)gives +
Z
40-
3
0
Zero Order L 30-
loss: [A1 = [Aol - kot (9) 4

gain: [Bl = [Bolt kot (10) 20-

First Order 10-

loss: In[A]/[Aol = -kit
or [A] = [A~le-~l'
(11)
(12) 0
I 1
50
I
m e4 200 250 3bo
gain: In[B]/[Bo]=+kit (13) TIME IN DAYS
01 [B] = [ B ~ ] e + ~ l ' (14) Figure 1. Loss of fwd quality as a function of time showing difference between
r e r p and firstkxder reaction. End of shelf life time (t,) occurs when quality
reaches maximum allowable loss value [A,].
If the data are plotted with quality factor on the y-axis versus
time on the x-axis, the above equations determine that the
reaction is zero-order when a straieht line is produced on linear
coordinates and first-order when a straight line is obtained
on semilon -paver.
. . It is possible to determine other orders if
the mechanism is known and the experimental procedure is
very precise. For example, a plot of 1/[A] or .l/[B] versus time
will give a straight line for a second-order reaction such as the
initial vitamin C loss in milk products or infant formula liquid.
Thus, if the order is known, one can extrapolate to the value
of A, or B, (subscripts denotes value at end of shelf life) on
the appropriate plot from only a few data points. Of course
doing this can result in a large error if there is error in the
values of [A] or [B]. Since a straight line can always be drawn
between two points, as we add more data we increase our
ability to predict both outside as well as inside the range of the
data points.
Thus, in Figure 1,a linear plot of quality versus time for a
loss in quality of a food would allow easy extrapolation to the
end of shelf life (t.) since the zero-order data fit a gwd straight
line. However, the first-order data on the same coordinates *:
would be more difficult to extrapolate because of the curvature 10
80 00 1% 00 110
k
300
of the graph. Plotting the first-order data ss in Figure 2 solves TIME H DAYS
this extrapolation problem since it gives us thedesired straight F i w e 2. Loss of fwd quality factor f a a firstqder reaction pldted on semilog
line. w.End of shelf lifetims (ao c m when qualily reaches maximwmallowable
Interestingly, in looking a t the loss-of-quality data in Figure loss value [A.].

Volume 61 Number 4 April 1984 351

2.3. If the actual natural log, of the value of [A] or [B] is
plotted on linear coordinates, then the slope is kl. One simple
mathematical tool for first-order reactions is to use the time
at which the quality decreases to 50% (tllz), then
-1" 501100 =-t0.623
k l= (16)
t ,I2 t112
An illustration of the use of these eauations and the dif-
ference in zero- versus first-order is shown in Table 1where
the losses are calculated based onlv on a zero time value and
on the point at which there was 50% loss of quality. Thus,
using eqn. (9) for zero order,
[Ao] - [A] = -100 - 50 = -
50 quality unit
ko = - =1
t 50 50 d limits
For a first-order reaction (eqn. (16)) the same data give
Here one should note that the units of k for zero order are
amountltime while that for first order is reciprocal time. One
should not mix these k's or compare them absolutely as they
are different. As seen in Table 1, if the analytical error were
f5% one could not really distinguish between the orders using
data for less than 50% loss.
Statistical Evaluation of Rate of Loss of OUaliW
Many different statistical mathematical approaches can
be used to evaluate the soundness of the amount of quality and
time data and to get an estimate of the error in the prediction
o f t , (13, 19, 20). As noted by Lund (21), "Reporting data
without an indication of error is one of the most common oc-
currences in the scientific literature today.. . investigators
have ignorrd the error assoriatrd with a parameter because
the error is so large that it is meaningless to discuss the mean
valueof the parameter." What Lund says is quite true and is
an indication of the problrm the "l.atta" rhemist would have
with moat food deterioration data. The prohkm exists because
it is not always rronomirally frasihle or physically possible
to rollect enmgh data to satisfy some statistical model. As-
suredly. appliration of statistics is most drsirahle and gives
one thk fekiing that the data are more useful, but those data
without statistics should not be deemed useless. Prior
knowledge of the statistical requirements of a kinetic study
should help in the experimental design. Modern calculators
and computer programs make the calculations easy once the
data are collected.
A review of statistical analysis of food deterioration data
has been made hy Labuza and Kamman (181, Lund (211,
Saguy and Karel (22), Lenz and Lund (23), and Hill and
Griep-er-Block (24),and the reader is referred to these for in-
depth analysis. Hasicall" two approarhes ran he used to get
an twimate of the error in the ratr ronswnt k. which is the key
factor used in making predictions for other conditions.
The first approach is to use some standard method of linear
regression o n quality versus time data, for example the
Table 1. Experlrnental Data Manipulation
Basis:A=IOOatt= Od
A = 50att=50d
Calculated QualityValues
Time (d) Zero Order First Order
352 Journal of Chemical Education
least-squares method or a modified-least-squares method
which is used for loearithmic data (first order) to eliminate
sume of the bias of he log function. In thew a;proaches the
measure of how well the dnta fit a straieht line is r2, the coef-
ficient of determination, where r 2 = 1represents a perfect fit.
It should he noted, however, that the r 2 of two points will al-
ways be l, yet one could he far off in any prediction either
outside or inside that range. The more data points the greater
is the confidence in using the r2 value as a statistical tool. Thii
regression analysis could he used to decide between zero- and
first-order.
- ~ ~ - -~ ~
~ ~ ~ -
The next step then in this approach is to get an estimate of
the error ink from these regression calculations. Basically the
true slope (8) is the measured slope (k) f the confidence
where 8 = true slope of regression line, t,lz = Student t value
a t given degree of confidence desired (e.g., 90,95,99%) at
= n - 2 degrees of freedom, n = number of data points, t =
time for each data point and
S. = standard error of [A] versus time
These euuations illustrate that the more data points, esoe-
cially at longer times which produre prater changes of quality
. the smaller will be S, and the smaller the confidenre
from IAol.
limits on the right.hand side of eqn. (1:). For n = 3 samples,
the deeree of freedom is @ = 3 - 2 = I and thus the t . . . value
~
a t 95%confidenceis large (=12.71). If aminimum of 8 samples
are taken as suggested by Labuza and Kamman (18), then t,/z
= 2.45 which gives a reasonable confidence in k and is still
within practical and economic limits of most experimentation.
Benson (13) has used this analysis to illustrate the effect of
precision on percent error in k (see Table 2). The hetter the
analytical precision and the greater the extent t o which the
reaction is studied the hetter is the estimate of k. If the pre-
cision is only f5% and the reaction is carried out to only 20%,
the error in k is f35%.
A serond approarh, which was suggested by Lund (21) as
wellas being il11atrau.d in kineticstexthx,ks.is t assume that
each data point is an independent experiment with respect
to zero time. This is sometimes called point-by-point analysis.
Thus
Xk i -
f l = havg195%confidence limits = - t./zo
(19)
n 6
where o is the standard deviation of all nk values and each k
is determined using the zero value l&l (or IRol) and the ap-
orooriateeuuations (10-15).'l'his method wndsto reduce the
ial;e of the 95% confidence limits making one feel that the
data are better than they may really be. The value of o comes
from the errors in evaluating quality and decreases as the
~rocedure'snrecision aets hetter, The confidence limits also
decrease as ihe numb& of data points is inrreased (propor-
tional t o n - ' % The choire of using this method versus using
Table 2. Estlrnate of Percent Error In Reactlon Rate Constant, k
~.
Analvtical
~~
Precision -Change in reactant species monitored.-,
(%) 1% 5% 10% 20% 30% 40% 50%
least sauares is a matter of the oersonal oreference of there- Kinetic Approach to Accelerating Shelf-Life Deterioration
searcher and the statistical c o n h a n t . E'igure 3 shows a plot
of some actual data for the browning reaction during storage Introduction
of nonhygroscopic whey powder (25) illustrating thevisualiy In order to accelerate a shelf-life study of food deterioration
good fit to zero-order kinetics, whereas Figure 4 shows the as well as to get data which can he applied over a broader range
poor fit to first-order kinetics for the 35'C data. In using hoth of conditions, as noted, certain chemical laws can be used.
statistical methods as well as a visually drawn line to statis- With foods, however, there are limits to use of accelerated test
tically analyze the data a t 35°C the following would he conditions. Generally three approaches have been taken: (1)
found concentration acceleration, (2) moisture or humidity accel-
Zero Order: (35W eration iinrreased a,), and (3) temperature arreleration.
Regression analysis r2 = 0.994 With concentration accelsratirm Le., increasing the amount
S. = 0.79 of a reactant) other changes in the reactant phase or other
t & = 2.2 @ 95% CL *=9
6 = (0.288 i 0.017) X 10V unitlday
mechanisms may occur such that one could not use the data
t o predict for the normal concentration range. For example,
Point-by-point 6 = (0.305 -L. 0.015) X 10V unitlday with lipid oxidation of dry food products there is no change
Visual k = 0.3 X in rate above 10%oxygen in the headspace (26). Below this
oxygen level other reaction steps begin to predominate and
Thus, if the initial browning value were 0.01 and the product the rate decreases exponentially as 0 2 decreases.
hecame unacceotable at a value of 0.5. then we would find that The second test acceleration is to increase the wapr content
the time requiied to attain this value would he: of a food which in turn increases its water activitv. This is a
Average Minimum Maximum
well-known phenomenon which can he applied dry foods to
and has been studied in deoth for manv deterioration reac-
Regression 170 d 161d 181d tions (27,28). Generally, wkat is found is that betkeen the
Point-by-point 161 153 169
Visual 163 ... .. . moisture content corres~ondineto the monolaver (a, of about
0.2-0.4) and the moistire content at an a, of"arouid 0.60.8
(about 15-30 g H20/100 g solids) a plot of the rate constant
These results show that the standard linear remession (usine or shelf-life time (t.) on a log scale versus a, gives a straight
95% confidence limits) gives us a range for the end of shelf li& line, as in Figure 5. No mathematical model exists for this
that is not verv different from the ranee that the ~oint-hv- although several have been attempted (29).Thus for each food
point method gives. In addition, the visual average value is a t each temverature a different curve will he found, although,
within the limits of hoth statistical methods. This is auite a in general, the slope of the line shows about a two- to threefold
good fit to the data since t h ~I~rowning
. precision is generally increase in rate for evew 0.1 a, unit increase over the normal
less than f 2%. In the same study the results for loss of the 2040°C range. Of importance, however, is the observation
nutririmal quality of the protein (a first-order reaction) were that as the a, is increased certain reactions that do not occur
not as good because of the method orecision rf 1590).althouah at lower a,'s will predominate, thus giving results that cannot
eight sampling times were take; and the experiment was
carried out to 60%loss. For example, plotting the lysine data
a t 35°C gave a visual prediction of 65 days to reach 50%loss.
The linear regression value r 2 was only 0.89, and the time to
50% loss predicted by linear regression had a range of 48-56
d (average of 52 d). In this case, it should he noted that the
eyeball plot gave a shelf-life time outside of the calculated
regression range.

I . m . 3 . n . a . &
-0 O
. 110 180 0 20 40 60 80 100

D% DAYS
Figure 3. Zerwrder plot of extent of browningof nanhygr-plc whey powder F i w e 4. Firstader plot of extent of bmwning of omhygroscopicwhey powder
held at water activity of 0.44 for three temperawes. held at 35% and a water activw of 0.44 (data from Fig. 3.)

Volume 61 Number 4 April 1984 353

be projected to other conditions. In addition, some reactions,
such as lipid oxidation, increase in rate as one decreases the
moisture content below the monolayer due to changes in the
controlline kinetic mechanisms (29).
'~'hegel;bral method toaccelerate ihe riite of deterioratim
of foci1 IS to increase the tenmerature at which thc ~ r o d u r is
i The larger the value of EA,the steeper the slope. Thus, data
stored. Both theoretical andkmpirical models ( I ) have been
used to extrapolate the high temperature data to shelf life at
low temperature. These techniques are also common in the
testing of the shelf life of biologics and other drugs (30-36).
The difference, however, is that with drugs the extrapolations
are generally easy because only one reaction is occurring,
whereas with foods there is always the problem that, at higher
temperatures, the reactions which are the limiting mode of
deterioration may be different from those a t lower tempera-
tures.
Temperature Acceleration for Shelf-Life Testing of a Food:
Arrhenius Model
Studies of the effects of temperature on the increase in
chemical reaction rate was first published in the late 1800's
(37). One of the most accepted models is that of Arrhenius in
which the temperature effect is incorporated into an expo-
nential model of the rate constant in the form
k = hoe-EdRT (20)
where ko = pre-exponential factor, E A = activation energy in
callmole, R = gas constant = 1.987 calloK mole, and T = ah-
solute temperature in OK. The theoretical basis for this
equation can be found in some of the physical chemistry
textbooks mentioned previously. The value of E A (activation
energy) is a measure of the temperature sensitivity of the re-
action.. i.e... how much faster it will ao if the temnerature is
raisrd. Mwt simplr hydrolysis renrtims have a value of 10-20
krnllmole, lipid oxidatiun hy a free radical mechanism has an
E A = 15-25 kcallmole, nonenzymatic bruwning about 20-40
kcallmole. and enzvme and microhiill destruction from 50 to
150 kcal/&ole. ~ h e b a l u eof EAis very specific for each system
and can vary with water activity. Basically, this model suggests
that if a molecule has a total energy E 2 EA,then i t has a po-
tential for reactina which is controlled bv the value of ko.
sometimes called the collision factor. As the temperature in-
creases, k~ and E A theoretically remain constant, but the
fraction of molecules with E 2 E A increases, thus the rate
I -1
0.2 0.4 0.6 0.11 1.0
W01.r AcIIYII~
Figure 5. lilustratiMl of the ettect on increasing water activity (a,) on the shelf
life of a food at three differem temperatures ( T , < <
T2 T3).
354 Journal of Chemical Education
constant k increases. A plot of In k or k on a semilog plot
versus 1IT should yield a straight line, as in Figure 6, since
from studies a t several high temperatures can be used to
project the shelf life a t lower temperature, subject, of course,
to the errors in evaluating k previously discussed. Even though
the r 2 is usually high, if standard linear regression methods
were applied to the typical three-temperature study, the 95%
confidence limits of the slope ( E d R ) , and, thus, the error in
EA, could still be quite high. For the browning data a t the
three temperatures shown earlier, we would find
Visual plot
Linear regression r2 = 0.999
(Ink versus 11T) +
EA = 29.68 11.48 kcallmole
In ko = 47.38 + 18.8
Point-by-paint analysis E A = 30.79 + 1.93kcallmale
*
In ko = 49.24 3.15
From this we see that although the three EA'S are close in
value, the linear regression method produces a very large
confidence level for both E Aand ko. NOwonder this kind of
information is not included in the literature, as Lund has
stated (21). I t has been suggested that one should use the
point-by-point method to get an E, from each individual k
(18,21). As seen above, this gives an E Asimilar to that pro-
duced by linear regression and reduces the confidence interval
significantly. This, in turn, would reduce the error limits on
the value of k projected for a lower temperature. Of course,
the better solution would be to do studies a t several more
temperatures or even at the desired temperature, but this is
usually not possible with foods both because of cost and time.
With drugs and simple chemical solutions, another approach
is to do a study on a sample which is put through a sequence
of continuously increasing temperature in some prescribed
manner (linear or exponential). Many samples are taken over
time, and, with the correct mathematical model, the E Acan
0.
es so 3.1 3.2 3.3 M
I/T * K X 103
Figure 6 . Typical Arrhenius plot of log k versus inverse absolute temperature
showing projection to lower temperature.
he determined (30,38). This is usually not possible for food
shelf-life studies because the temperatures required are
usually too high and the physical size of the sample causes heat
transfer limitations. This also would he almost impossible or
illogical to do with the 200-300 lh of food that might he needed
for a sensory study. It should also be noted that several other
statistical models are available to evaluate the confidence
limits on E A such as a weighted-least-squares (39) and a
nonlinear simplex procedure for least squares (40).
A convenient tool in transforming the Arrhenius plot is to
plot t , rather than k on the y-axis, as shown in Figure la. As
was shown by Lahuza (41 ),this derives simply from mathe-
matical manipulation of the reaction equations and the
Arrhenius relationship for any order. I n addition, since most
food studies are done over a rather narrow temperature range
(20-30°C), a simplification can he made in which log t , is
plotted directly against temperature rather than 1/T. Typical
"shelf-life plots" for over 400 different foods and modes of
deterioration have been made ( I ) .
Instead of the activation enerm concept, manv researchers
in the food lield have used the d;oapprdach for;ernperature
acceleration u,here ihe 0," is ihe derreme in shelf life (increase
in rate) for a 1O0C temperature increase.
In fact, many have assumed the Qlo to he equal to a factor
of 2. However, this is erroneous and would apply only to re-
actions a t a certain temperature and E A value. T h e relation-
ship is derived directly from the Arrhenius equation where
By using O°C as an arbitrary reference temperature the
equation for the shelf-life plot may he written
t8 = t,ere-b(~-~mr)
= toe-br (23)
where b =slope in ADC,T = "C, t,.f = shelf life a t reference
temperature T,.f, and to = shelf life a t 0°C.
109
Shelf
L~fe
109
Shelf
Life
Figure 7.A, hansfwmed Anhenius plat of lag of shelf-lifeversus inverse tem-
Peralm. 6, a psedPtransformationof log of shelf life versus temperature for
narrow temperature ranges.
Then, substituting into eqn. (23) for shelf life a t T and T +
1O0C,we get
and
where T is in OK.
Thus, the Qlo or slope b of the shelf-life plot will depend on
the value of the activation energy. Qlo values range from 1.5
to 2 for sensory quality loss in canned foods, 1.5-3 for rau-
cidity, 6 1 0 for browning reactions, and 20-40 for quality loss
of some frozen fruit and vegetables ( I ).
Limitations of the Arrhenius Model
Based on the above discussions. it can he seen that there
c(1~1~1 he many limitations besides s~atisticalr r n m in using
either the Arrhenius ulut or shelf-life nlot to ~ r e d i c shelf t life
a t some lower tempeiature. ~enerall; the prbhlems exist he-
cause somethinz occurs a t hieher temDeratures which does not
occur a t lower temperatures . . (14). ~ h e s limitations
e include
the following
1) At high temperatures (235°C) phase changes such as melting
of fats might occur. The liquid-phase fat can a d as a reaction
medium or react itself where it would not at the lower temper-
ature.
2) During freezing, reactants are concentrated in the unfrozen
water. This concentration is temperature-dependentand not
accounted for in the typical reaction kinetic approach. The
major effectwould be seen just below the thaw point for frozen
foods.
3) Carbohydrates that might he inan amorphous physical state
at room temDerature and available for chemical reaction could
crystallize out at higher temperatuw and tht~etorenot react.
Thia uwld leml ttn ~ ~ ~ e r p r ~ d ~t.frhelf
c t i o ulife at nwm tpmper-
4) Generally, many reactions are possible in any given fwd to cause
its deterioration. It may he possible that above some tempera-
ture a reaction with a higher En will .
~~
vredominate while below
that temperature a diffe;ent reaction will lead to loss of shelf
life. Thus, studying only one reaction will lead to significant
error in oredictions.
5) The untrr art~\,itv of a dehydrated loud at constant moisture
rmrent incrcares wirh Wrnprrature. Since some reacrron rates
are a, dependent, the acceleration of deterioration at higher
temperature would be larger than predicted solely hy~the
Arrhenius model. This would lead to overprediction of the shelf
life at room temperature. Many models exist for incorporating
moisture change and temperature change (22) but will not be
discussed here.
8 Since the solubility of gas decreases as T increases, oxidation
readions might became oxygen limiting. Several test procedures
for shelf life of oils get around this by using oxygen pressures
of 5&200 psi (26).
Other factors causing difficulties in making accurate predic-
tions could include change in paktitioning between the
aqueous and lipid phase, change in pH, protein conformation
changes, and moisture loss. Thus, there generally is an upper
limit of temperature that can he used f& accelkrating &c-
tious; this temperature is about 40% for canned foods (due
in part to possible thermophilic growth which begins a t 40-
45'C), 35-45°C for dry foods, 7-10°C for refrigerated products
and -5'C for frozen foods. Of importance here is that these
possible changes suggest that more than three temperatures
he used if one wants to find out if there is a shift in the kinetic
mode of deterioration with temperature, i.e., is the Arrhenius
or shelf-life plot truly linear?
Shelf-Llfe Predictions
Introduction
Once data are collected to prepare an Arrhenius or shelf-life
plot, one can then use this information to project the shelf life
Volume 61 Number 4 April 1984 355
a t some other temperature. The question, of course, is "what
temperature?" In fact, in the real world food products go
through rather variable temperature distrihutions (especially
canned and dry goods) and those distributions will each de-
pend on the time of year the product is manufactured, the
physical position of the package (i.e., in the case, in the pallet,
and where the pallet is in the warehouse, truck, rail car, or
shelf) and, of course, the peculiarities of the weather. In fact,
the true shelf life of a particular food package which exits a
food plant is unknown. It can only he "guesstimated" for a
particular temperature or temperature distrihution.
Even if these things were taken into consideration, i t is
possible that temperature fluctuations themselves would
cause a "history" effect in which the rate of deterioration is
a function of the timeltemperature of prior storage. Little is
known about the magnitude of the history effect. Quast and
Karel(42) have found this for rancidity development in potato
chi'pg, and some shelf-life studies of this phenomenon have
been conducted with pasta (43,44,45). In these latter studies,
the question asked was whether one could predict the shelf
life of a product undergoing a knowri temperature fluctuation
if one knew the temperature distrihution and had data at
constant temperatures in the form of a shelf-life plot. I t had
been the prejudice in the food research field that a product
undergoing a reguldr temperature fluctuation, such as a 251
45°C sine wave, deteriorated more rapidly than if stored at
the mean temperature (see Fig. 8) due to some "unknown
mechanism," and thus shelf life studies required this tern:
perature cycling. Most large f o d companies, from the 1950's
through the 1970's, in fact creavd weather rooms which cycled
over various extremes. What was not understood was that the
increased rate could he merely due to the logrithmic in-
creaseldecrease in reaction rate constant due to a temperature
change. Thus, in fact, if the theoretical k were calculated and
compared to an actual k , one'could get a measure of the
magnitude of the "history" effect.
Fluctuating Temperature Kinetic Modeb
Early storage studies of the effects of temperature cycling
were done on food quality loss in frozen foods (46-48) and on
ascorhic acid loss, microbial growth, and enzyme destruction
(4Wi2). These studies used one of two models: (1)a simplistic
- 0
8 (days)
Figure 8. Comparison between rate of quality 10% for a f w d held at constant
temperature of 25.35, and 45% and one undergoinga sine wave temperature
cycle of 25145°C.
356 Journal of Chemical Education
additive model called the Time/Temperature/Tolerance
(TTT) method or (2) a kinetic model based on the earlier
theoretical publications of Hicks (53) and Schwimmer et al.
(54). Neither of these models considered the order of the re-
action, thus implying zero order. Lahnza (41) showed how each
of these models could he derived solely from the kinetics
presented earlier and developed the equations for hothfirst-
and zero-order reactions.
The hasic tenet of any model is knowledge of the tempera-
ture distrihution as a functiun of rime whirh is inserted into
either a zero- or first-order reaction equation in differential
form where
The rate constant for each order takes the form
Zero
Rate = k = ([A01 - [%I)
(27)
First
Inserting into eqn. (26) and solving for a single temperature
(Ti), i.e., k is constant then for a given time t
Zero
First
For zero order, the ratio of the time a t some given temperature
(t) to the total time the product could last if i t were always at
that temperature (t.) gives the fraction of shelf life consumed
(f,,) since it is equal to [An] - [A], the amount of the mea-
sured quality which has been used up, divided by [Ao] - [&I,
the amount of that aualitv which could he used up. However,
for first order, sinceit involves a log function, the ratio is not
the fraction of shelf life consumed as was erroneously assumed
in the early research. In these studies, i t was assumed that a
distrihution could he divided into a set of constant tempera-
ture regions, and then the fraction consumed was summed up
for each time period.
The early work presented no hard data comparing theory to
actual results, and no statistics or estimates of the errors were
included in the studies. This T T T method became the ac-
cepted practice in the frozen food field, perhaps because of its
simplicity. I t should he noted that, perhaps fortuitously,
frozen foods were used which generally follow zero-order-loss
kinetics and unacceptahility occurs with only a 20-30s change
in some related chemical index (I).
A group at the University of Georgia followed up on the
T T T studies by applying a more elegant model to ascorbic
acid loss, microhial death, and heat denaturation of enzymes.
This work demonstrated that the reaction was faster for a sine
or square wave temperature periodicity than at the time av-
erage temperature; however, they found errors of from 10 to
60% in comparing theoretical rates to actual loss rates. This
was attributed partially to analytical error and in part to a
possible change in Qlo with temperature (they did not use E d .
The main errors, however, arose from the use of a zero-order
mathematical model for first-order reactions. In addition, heat
transfer limitations were not taken into account when rapid
cycling of temperature was done.
The food kinetics group at the University of Minnesota has
 Table 3. Results of Universitv of Minnesota Shelf-Life Studies
Actual Rate Predicted Rate
F w d Product Reference Condition Constant Constant

W g o s c o p i c whey P o d r
Nonenzymatic browning
(25) square wave 25/4S°C
a. = 0.44 *
0.019 0.0004 ODld 0.015 ODId
6-DNP lysine loss a, = 0.44 0.018 f 0.001 d-' 0.026 d-'
Relative nuhitianal valve a, = 0.44 0.0123 f 0.0004 d-' 0.0155 d-'
Nonhyqoscopic Whey P O W (25)
Nonenzymatic browning a. = 0.44 0.0069 f 0.0002 ODld 0.0076 OD/d
a. = 0.44 0.0189 f 0.004 dC' 0.0223 d-'
6DNP lysine
Relative nuiritionai value a,= 0.44 0.0116 *
0.001 d-' 0.0153 d-'
pasta
Thiamin (43 square wave 25145'C
a, = 0.44 0.0012 f 0.0002 d-' 0.0016 d-'
a. = 0.54 0.0019 f 0.0003 d-' 0.0023 d-'
a, = 0.65 0.0028 f 0.0002 d-' 0.0037 d-'
Thiamin ( 45) sine wave 25145°C
a, = 0.49 0.0016 f 0.0003 d-' 0.0013 d-'
Lysine Iwslprotein quality 144) square wave 35/55-C
a. = 0.44 0.033 f 0.006 wk-' 0.022 wk-'
a. = 0.65 0.063 f 0.012 wk-' 0.063 wk-'
Browning Square wave 35155°C
a, = 0.44 2.69 f 0.7 ODldl100g 2.15
a. = 0.65 4.00 f 0.8 O D / d / 1 0 0 g 2.93
a-ONP lysine loss* I55) sine wave 25145'C
a, = 0.49 0.0104 wk-' 0.0073 wk-'
Relative nutritional value 0.0118 f 0.0013 wk-' 0.0093 f 0.0013 wk-'
potato chips 15s) sine wave 25145%
peroxide iormatlon a,= 0.11 0.115 f 0.006 PVW 0.1 19 f 0.002 PVld

conducted studies of quality loss for a series of different food
oroducts stored for uo to one vear under square wave and sine
wave temperature distributions. Integrated mathematical
models based on the Arrhenius eauation were used and the
equations were corrected for reaction order. In addition, sta-
tistics were applied to some of the results of these studies
where enough data were available. The actual measured k was
compared to the predicted k based on constant temperature
studies from a t least three temperatures.
Using eqn. (26) as the basis, the group developed the fol-
lowing equations for the theoretical rate constants.
Square waue
Sine waue
Spike w o w
In some cases, the actual rate was faster than the predicted
rate indicating a positive-historyeffect while in other cases the
opposite was true. These studies illustrated that, although one
may be able to develop elegant mathematical models based
on kinetics and may use elegant statistical models to get
straight line ~ l o t sthe
, errors involved in analysis plus the
possi%le changes in mechanism with changingtemperature
may preclude one from accurately predicting the quality loss
of a food undergoing a temperature distribution. This does
not mean we should not utilize kinetic principles nor apply
statistics, rather these results indicate the need for better
analytical tools and better experimental design, including
more temnerature measures and samoline times. and the need
toexamiie the Arrhenius plot (or s h h k to determine
if a chanee in kinetics occurs with temoerature. As our "Latta
chemist"may have found, sometimesone should not draw a
straight line.
Acknowledgment
This project was supported in part by the University of
Minnesota Agricultural Experiment Station Grant No. 18-78
and NSF Grant No. 7910370.

where k ~ is, the rate constant a t the mean temperature of the

cycle (T, = (T,,,,,, + T1~~~.)12), Z = (Tm+ lO)I(T, + ad in
OK, 2' = (T, +
10)l(T, - no) in O K , a. = amplitude magni-
tude =, ,T( - Tol ,J/2, and b = slope of shelf life plot from
eqn. (25). Thus, for a reaction undergoing cycling for some
given condition, one can use eqns. (10)-(15) by substituting
in them one of the above rate constants (k,, k.i.., ksd fork.
If the cycling pattern is not regular, then eqn. (26) should be
used, and the quality loss summed up for each timeltemper-
ature segment as in the T T T method.
Table 3 is a summary of the kinetic studies done a t the
Universitv of Minnesota. A wide variety of reactions were
studied mid both sine wave and square wa;e rycling were used.
The differenct between the predicted and actual reaction rare
constant ranged from as small as 3.5% for lipid oxidation to
as high as 30-44% for lysine loss in pasta and whey powder.
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