be projected to other conditions. In addition, some reactions,
A plot of In k or k on a semilog plot
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.
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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