CHAPTER

Reaction Kinetics
4
4.1 Introduction
Foods are highly reactive systems. Chemical reactions occur constantly between
the component substances of foods, and between foods and their surroundings
(air, packaging materials, equipment surfaces, etc.). Fresh fruits and
vegetables undergo rapid post-harvest biochemical changes. Post-mortem reac-
tions deeply affect the characteristics of meat and fish. Numerous types of chemi-
cal and biochemical reactions occur during food processing and storage. The
systematic study of reactions in foods is the subject matter of food chemistry and
food biochemistry. However, the rate at which these reactions take place is of
utmost interest to the food process engineer (Earle and Earle, 2003; Toledo, 2007;
Villota and Hawkes, 1992). The following are some of the most important appli-
cations of reaction kinetics in food engineering:
Calculation of thermal processing for the destruction of microorganisms and
for the inactivation of enzymes.
Optimization of thermal processes with respect to quality.
Optimization of processes with respect to cost.
Prediction of the shelf life of foods as a function of storage conditions.
Calculation of refrigeration load in the storage of respiring agricultural
produce
Development of time-temperature integrators.
Reactions in food processing may be classified into two groups (Toledo,
2007):
1. Desirable or induced reactions. These are reactions that are intentionally
induced by the process in order to produce a desirable transformation in the
food. The pyrolysis of carbohydrates during coffee roasting, the hydrolysis of
collagen when meat is cooked, the conversion of lactose to lactic acid by
fermentation in the production of yogurt, and the hydrogenation of oils to
produce solid fats are examples of intentionally induced reactions.
2. Undesirable reactions. These are chemical or biochemical reactions that occur
during processing or storage and result in undesirable effects on food quality.
Maillard-type browning in lemon juice, onset of rancidity as a result of lipid

Food Process Engineering and Technology. DOI: http://dx.doi.org/10.1016/B978-0-12-415923-5.00004-6

2013 Elsevier Inc. All rights reserved.
127
128 CHAPTER 4 Reaction Kinetics

oxidation in nuts and crackers, and spoilage reactions induced by

microorganisms are examples of this group of reactions.
This classification is, obviously, imperfect. The same reaction may be desir-
able in one case and undesirable in another. In the production of wine, alcoholic
fermentation is induced; in tomato juice, the same reaction is considered spoilage.
Enzymatic browning is essential for the development of color in tea; in potatoes
and apples, it is a defect. Very often, the characterization of a reaction as desir-
able or undesirable is a matter of degree. Proteolysis in some cheeses is essential
for the development of flavor. Too much of it is spoilage.
Another way to classify reactions in food is based on the distinction between
enzyme-catalyzed (enzymatic) and non-enzymatic reactions. Very often, non-
enzymatic reactions are called chemical reactions while reactions where enzymes
or cells are involved are distinguished as biochemical reactions.

4.2 Basic concepts

4.2.1 Elementary and non-elementary reactions
Elementary reactions are well-defined reactions resulting from a single collision
between two (and rarely three) molecules or ions. The neutralization of OH2 with
H1 is an elementary reaction. Non-elementary reactions consist of a series of ele-
mentary reactions. Although the kinetics of each elementary reaction in the series
affects the rate of the total change, non-elementary reactions are often treated as a
black box, where only the rate of disappearance of the reactants entering the
box or the rate of formation of the final products is considered. We shall refer
to non-elementary reactions as overall reactions. The thermal inactivation of
microorganisms or the formation of dark pigments in the Maillard reaction are
non-elementary reactions. The rate of Maillard browning is usually expressed as
the rate of colorimetric darkening or the rate of formation of an intermediate mol-
ecule such as hydroxymethyl furfural (HMF). Most reactions of interest in food
processing are of the overall type.

4.2.2 Reaction order

Consider an elementary chemical reaction between the molecules A and B, result-
ing in the formation of the molecules E and F, according to Eq. (4.1):
k
aA 1 bB - eE 1 fF (4.1)
The rate of a reaction is defined as the rate at which the number of molecules
of the reacting species increases or decreases with time. In constant-volume pro-
cesses, the number of molecules may be replaced by concentration. According to
the law of mass action, the rate of any reaction at a given time is proportional to
 4.2 Basic concepts 129

the concentrations of the reacting substances, raised to a power equal to the num-
ber of molecules participating in the reaction. The proportionality constant is
called the rate constant and is designated by the symbol k. Thus, the rate of the
reaction shown in Eq. (4.1), in terms of the disappearance of the species A, is:

dCA
2 5 kCA a CB b (4.2)
dt
where C represents the concentration of the different chemical species.
Theoretically, reverse reactions occur simultaneously with each reaction.
Assume that the rate constant of the reverse reaction shown in Eq. (4.3) is k0 :
k0
eE 1 fF - aA 1 bB (4.3)
The rate of disappearance of A for the complete reversible reaction is then:
dCA
2 5 kCA a CB b 2 k0 CE e 2 CF f (4.4)
dt
In the case of the reactions of interest in food processing, the rate constant of
the reverse reaction is very often negligible. Furthermore, the concentration of
one of the reactants is usually much higher than that of the other and therefore
not affected considerably by the reaction  for example, the concentration of
water in hydrolysis, which is often (but not always) carried out with water in
large excess. Then, the reaction may be written as a pseudo-monomolecular non-
reversible process and Eq. (4.4) becomes:
dCA
2 5 kCA n (4.5)
dt
The exponent n in Eq. (4.5) is called the reaction order. In elementary reac-
tions it is usually equal to the number of molecules of the reactant participating
in the reaction (molecularity, e.g., n 5 a in the example given, with respect to the
disappearance of A). In non-elementary reactions, such as the thermal inactivation
of microorganisms, the reaction order is simply an experimental value with no
meaning whatsoever as to the molecularity or mechanism of the reaction.

Zero-order kinetics
If n 5 0, the rate of the reaction becomes equal to the rate constant k, independent
of the concentration of the reactants:
dCA
2 5k (4.6)
dt
The SI units of k, for zero-order reactions, are mol  s21. Assuming constant k
(constant temperature, pH, etc.), integration between t 5 0 and t 5 t gives:
CA 5 CA0 2 kt (4.7)
130 CHAPTER 4 Reaction Kinetics

C = Concentration

t
FIGURE 4.1
Graphical representation of zero-order kinetics.

The concentration of A decreases linearly with time (Figure 4.1). The slope of
the C vs t line is 2 k. Zero-order food reactions are not very common. Zero-order
kinetics has been reported in some cases of non-enzymatic browning, carameliza-
tion and lipid oxidation (Bimbenet et al., 2002). Zero-order behavior for the accu-
mulation of HMF (hydroxymethyl furfural, a key intermediate in non-enzymatic
browning) was reported by Burdurlu et al. (2005).

First-order kinetics
With n 5 1, Eq. (4.5) becomes:
dCA
2 5 k CA (4.8)
dt
The SI units of k for first-order reactions are s21. Assuming constant k as
before, integration gives:
CA
ln 5 2 kt (4.9)
CA0
The logarithm of CA decreases linearly with time (Figure 4.2). According to
Eq. (4.9) reactant A cannot be totally depleted. A useful notion in first-order
kinetics is that of half life, t1/2. The half life of A in this reaction is the time
required for the quantity of A to be reduced to half its original value. It follows
that:
ln2
t1=2 5 (4.10)
k
First-order kinetics is approximated by many phenomena of interest in food
processing. Thermal destruction of microorganisms is treated as a first-order
 4.2 Basic concepts 131

C = Concentration

ln C/C0
k

t
FIGURE 4.2
Graphical representation of first-order kinetics.

reaction. Non-enzymatic browning of citrus juice concentrates has been reported

to follow first-order kinetics (Berk and Mannheim, 1986). First-order kinetics was
confirmed for Vitamin C loss in orange juice concentrate during storage
(Burdurlu et al., 2005). Mathematical methods for the determination of the rate
constants of consecutive first-order reactions were developed and tested by
Erdogdu and Sahmurat (2007).
In many cases, the concentration of the reactant studied (e.g., reactant A)
is high and the reaction rate is relatively slow. In this case, after a short
time, the concentration of A is still very high and not very different from its
original value. The initial rate of reaction is nearly constant, as in a zero-
order reaction. This may be the reason for the contradictory publications in
the literature, where the same reaction is reported as zero order in some and
first order in others.

EXAMPLE 4.1
The average retention of ascorbic acid in concentrated orange juice, after 8 weeks of stor-
age at 28 C, was reported to be 68% (Burdurlu et al., 2005). Assuming first-order kinet-
ics, calculate the rate constant of ascorbic acid loss at 28 C.
Solution
For first-order kinetics, Eq. (4.9) applies:
CA
ln 5 2 kt
CA0
1 C 1 100 2 68
k 5 2 ln 52 ln 5 0:02 day21
t C0 837 100
132 CHAPTER 4 Reaction Kinetics

4.2.3 Effect of temperature on reaction kinetics

All chemical reactions are accelerated when the temperature is increased. The
relationship between the reaction rate constant k and the temperature is described
in Eq. (4.11):
2E
k 5 A exp (4.11)
RT
where:
A 5 a constant, named the pre-exponential factor; its units are the same as
those of the rate constant k, which in turn depend on the order of the reaction
R 5 universal gas constant 5 8.314 kJ  K21  kmol21
T 5 absolute temperature, K
E 5 activation energy, kJ  kmol21.
Equation (4.11) is known as the Arrhenius equation after the Swedish chemist
Svante August Arrhenius (18891927, Nobel Prize in Chemistry, 1903). A graph-
ical representation of the Arrhenius equation is shown in Figure 4.3.
The activation energy actually represents the sensitivity of the reaction rate to
changes in temperature. If k1 and k2 are the rate constants at temperatures T1 and
T2, respectively, then:
k2 ET2 2 T1
ln 5 (4.12)
k1 RT1 T2
Arrhenius Law is extensively used for the prediction of quality loss as a func-
tion of temperature (e.g., Labuza and Riboh, 1982).
Another way of representing the sensitivity of a reaction to a change in tem-
perature is the factor known as Q10 or the temperature quotient. Q10 is the ratio
of the rate constant of a reaction to that of the same reaction at a temperature

E/R
ln k

T= Absolute temperature

1/T
FIGURE 4.3
Graphical representation of the Arrhenius Law.
 4.2 Basic concepts 133

lower by 10 C. Applying this definition to Eq. (4.12), we obtain the relationship
between the activation energy and the temperature quotient:
10 E 10E
ln Q10 5 D (4.13)
RT1 T1 1 10 RT12

Typical ranges of E and Q10 for different types of reactions are given in
Chapter 17, Table 17.1.
In elementary reactions, the energy of activation has a physical meaning and
is related to the reaction mechanism at the molecular level. In overall reactions of
interest in food processing, the Arrhenius equation is simply an empirical approxi-
mation and E is an experimental parameter of that equation with no theoretical
significance.
One of the applications of the Arrhenius model in food process engineering is
the accelerated storage test. Investigation of the changes in food during normal
storage may require a long time. The changes can be accelerated, however, by
using a higher temperature for test storage. If the system is known to obey the
Arrhenius Law and if the activation energy is known, the rate of change at the
normal storage temperature can be calculated from the accelerated rate (Mizrahi
et al., 1970; Labuza and Riboh, 1982).

EXAMPLE 4.2
It has been reported that the rate of an enzymatic reaction is increased by a factor of 3.2
if the reaction is carried out at 45 C (318 K) instead of 37 C (310 K). Calculate the
energy of activation and the Q10 value.
Solution
Apply Eq. (4.12):
k2 ET2 2 T1 E318 2 310 E
ln 5 . ln3:2 5 1:163 5 5
k1 RT1 T2 8:314 3 318 3 310 102 450
E 5 102 450 3 1:163 5 119 150 kJ  kg21  mol21
The Q10 value is calculated using Eq. (4.13):
10 E 10 3 119 150
ln Q10 5 5 5 1:4446 . Q10 5 4:24
RT1 T1 1 10 8:314 3 310 3 320

EXAMPLE 4.3
Pasteurized grapefruit juice is aseptically packaged in multi-layer containers and stored
under refrigeration. The ascorbic content of the juice at time of packaging is 55 mg per
100 g. The nutritional information on the label specifies an ascorbic acid content of
40 mg per 100 g. What should be the maximum temperature of storage (assumed
134 CHAPTER 4 Reaction Kinetics

constant) be, if the product has to comply with the specification on the label after 180
days of storage?
Ascorbic acid loss in grapefruit juice follows first-order kinetics with a rate constant of
0.006 day21 at 20 C. The activation energy of the reaction is 70 000 kJ/kmol.
Solution
First we calculate the rate constant at the storage temperature, using Eq. (4.9):
C 40
ln 5 2 kt . ln 5 2 k 3 180 . k 5 0:00177 day21
C0 55
Next, we calculate the storage temperature T, using the Arrhenius law, substituting in
the equation the values of k at 20 C (293 K), k at the (unknown) storage temperature, and
the energy of activation.
k2 ET2 2 T1 0:00177 70000T 2 293
ln 5 ln 5 5 2 1:221
k1 RT1 T2 0:006 8:314 3 293 3 T
T 5 281 K 5 8 C

4.3 Kinetics of biological processes

4.3.1 Enzyme-catalyzed reactions
The rate of enzymatic reactions depends on a number of conditions, such as the
concentration of the enzyme and the substrate, the temperature, pH, ionic
strength, etc.
If the substrate is present in large excess, the rate of an enzymatic reaction is
proportional to the concentration of the enzyme. This is the basis for the quantita-
tive definition and determination of enzyme activity.
The effect of substrate concentration is more complex. The velocity of an
enzymatic reaction, in terms of the rate of product formation is given by the well-
known MichaelisMenten equation:
s
v 5 vmax (4.14)
Km 1 s
where:
v 5 velocity of the reaction (rate of product formation)
vmax 5 a maximum value to which v tends asymptotically as the substrate
concentration increases
Km 5 a parameter of the reaction, known as the MichaelisMenten Constant.
The effect of substrate concentration on the rate of a hypothetical enzymatic
reaction, according to the MichaelisMenten model is shown in Figure 4.4.
The rate of enzymatic reactions is strongly affected by the temperature. As the
temperature is increased, the reaction rate increases up to a maximum value (at
 4.3 Kinetics of biological processes 135

v
vmax

vmax

Km s

FIGURE 4.4
The MichaelisMenten plot.
Activity

TOpt T

FIGURE 4.5
Effect of temperature on enzyme activity.

the optimal temperature) and then decreases (Figure 4.5). This behavior is not in
contradiction with the Arrhenius model. The bell-shaped ratetemperature curve
is the consequence of the simultaneous occurrence of two contradicting processes,
namely the enzymatic reaction itself and the thermal inactivation of the enzyme,
both enhanced by higher temperature.
The effect of pH on the rate of enzymatic reactions also follows a bell-shaped
curve, with maximum activity at the optimal pH. Control of enzymatic activity by
adjusting the pH is a frequently applied practice in food processing.

4.3.2 Growth of microorganisms

The term growth of microorganisms may be interpreted either as the increase in
the number of living cells or as the increase in biomass. In this discussion, we
shall study the kinetics of microbial growth with reference to the number of cells
and not to their mass.
136 CHAPTER 4 Reaction Kinetics

log N
A B C D

Time
FIGURE 4.6
Schematic representation of microbial growth curve: A, lag phase; B, log phase; C,
stationary phase; D, decline phase.

The classical curve of microbial growth (number of living cells N versus time,
Figure 4.6) shows four phases (Loncin and Merson, 1979):
1. Lag phase. Initially, there is no growth. The cells may use food to increase in
mass but not in number.
2. Log (logarithmic, exponential) phase. The number of living cells increases
with time exponentially.
3. Stationary phase. The number of living cells remains nearly constant in time.
This phase is usually explained as one during which the rate of new cell
generation is equal to the rate of death.
4. Decline. The number of living cells decline with time, usually in an
exponential manner.
The rate of microbial growth follows a pattern known as the Monod kinet-
ics, after the French biologist Jacques Lucien Monod (19101976, Nobel Prize
in Physiology and Medicine, 1965). Since growth occurs as the result of division
of a living cell into two, it may be assumed that the rate of growth at any moment
will be proportional to the number of living cells at that moment:
dN
5 N (4.15)
dt
Equation (4.15) actually represents first-order kinetics. The rate constant is
called the specific growth rate. One of the interesting features of is its depen-
dence on substrate concentration. The relationship between and substrate con-
centration is very similar to the MichaelisMenten equation:
S
5 max (4.16)
KS 1 S
where max is a maximum value to which the specific growth rate tends asymptot-
ically as the availability of substrate increases.
 4.4 Residence time and residence time distribution 137

Cell death occurs simultaneously with cell generation. Assuming that cell
death also follows first-order kinetics with a rate constant kd, the actual increase
in the number of living cells can be written as follows:
dN
5 rate of generation 2 rate of death 5 N 2 kd N (4.17)
dt
During the log phase, the substrate is abundant, is almost at its maximum
and the rate of death is relatively negligible (assuming that the temperature, pH,
water activity and other conditions are favorable to growth).
The growth rate of microorganisms is strongly temperature-dependent. Just
like the rate constant of enzymatic reactions, it increases with increasing tempera-
ture up to a maximum, then declines rapidly. At a certain temperature it becomes
negative  i.e., the number of living cells decreases with time. The minimum,
optimum and maximum temperatures for microbial growth depend on the micro-
organism species (see Chapters 17 and 18).

4.4 Residence time and residence time distribution

4.4.1 Reactors in food processing
Residence time (RT) and residence time distribution (RTD) are notions that serve
to describe, primarily, the length of time during which the food or portions of it
have been subjected to a certain treatment (Bimbenet et al., 2002). For conve-
nience, this is defined as the length of time during which the food has resided
in a reactor. In chemical process engineering, the term reactor often means a
specialized device (generally a vessel with accessories) used to carry out a con-
trolled reaction. In this section, however, any portion of the physical process sys-
tem where reactions occur will be considered a reactor. By this definition, a
fermentor, an oven, an extruder, a drying tunnel, an oak barrel used for aging
wine, or a box of cookies are reactors.
In a batch reactor, the notion of residence time is trivial. It is simply the
duration of the batch cycle, and it is the same for every portion of material in the
batch. In contrast, residence time analysis in continuous operations must take into
consideration the physical characteristics of the reactor and the operation condi-
tions. Most reactors are too complex for accurate analysis. Therefore, reactors are
typified according to a number of idealized models (Figure 4.7). The following
are some of these models.
1. The plug flow reactor (PFR). In this type of reactor, the material flows as a
block (plug). Each part of the fluid has the same velocity. There is no mixing
within the fluid. Consequently, the residence time is equal for every portion of
the fluid. The residence time distribution (see below) is flat.
2. The laminar flow reactor (LFR). The fluid moves through the reactor (usually
a tubular reactor) in laminar flow, i.e., in parallel layers. The layers do not
138 CHAPTER 4 Reaction Kinetics

Plug flow (tubular) CSTR

FIGURE 4.7
Two ideal reactor models.

E(t)

t Time

t + dt
FIGURE 4.8
Residence time distribution, E(t) function.

move at the same velocity, but there is no mixing between the layers (see
Chapter 2, Section 2.2.2). Residence time is not uniform.
3. The continuous stirred tank reactor (CSTR). Physically, this type of reactor
corresponds to a perfectly agitated vessel with continuous feeding and
discharge. As a result of perfect mixing, the composition and all other
conditions at a given moment are uniform at all points within the reactor. The
composition of the fluid discharged is identical to that of the fluid bulk in the
reactor at the same moment.

4.4.2 Residence time distribution

Residence time distribution (RTD) is treated with the help of classical statistical
functions and parameters.
The RDT function E(t), known as the frequency density function, describes the
probability of a given particle or portion spending a time t in the reactor. A hypo-
thetical curve representing the E(t) function versus t is shown in Figure 4.8. In
this figure, the area of the shaded strip gives the mass fraction of the fluid that
has spent a time between t and t 1 t in the reactor.
 4.4 Residence time and residence time distribution 139

F(t)

Time
FIGURE 4.9
Residence time distribution, F(t) function.

Another useful RDT function is F(t), known as the cumulative distribution

function. It represents the mass fraction of the fluid that has spent a time t or less
in the reactor. A hypothetical curve corresponding to F(t) is shown in Figure 4.9.
The mean residence time tm is:
N
tm 5 t:Et:dt (4.18)
0

Ideally (i.e., with no diffusion, dispersion and no volume change), the mean
residence time is equal to the mean travel time through the reactor (space time),
:

V
tm  5 (4.19)
Q

where V 5 active volume (capacity) of the reactor, m3, and Q 5 volumetric rate
of throughput, m3  s21.
One of the procedures for the experimental determination of the RDT
functions is the method of pulse injection, described schematically in
Figure 4.10.
At time t 5 0, a small quantity of a tracer is rapidly injected into the reactor
with the feed. The concentration of the tracer is measured at the reactor exit as
a function of time. Denoting the exit concentration of the tracer as C, we
obtain:
Ct
Et 5 N (4.20)
0 Ct dt

E(t) and F(t) curves for a plug-flow reactor and a CSTR are shown in
Figures 4.11 and 4.12, respectively.
140 CHAPTER 4 Reaction Kinetics

Pulse Plug flow

C

CSTR

Time
FIGURE 4.10
Reaction of a plug-flow reactor and a CSTR to a pulse injection.

E(t)

Time
FIGURE 4.11
E(t) curve for CSTR.

F(t)

Time
FIGURE 4.12
F{t} curve for CSTR.
 References 141

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