Chemical kinetics

Kinetics and food deterioration

• Objective
– Prediction of change in quality as a function
of time and environmental conditions

See Labuza, T. P. 1984. Application of chemical kinetics to

deterioration of food, J. Chemical Education,61, 348.
Kinetics and food deterioration
• Why is this technique needed?
– Evaluation of new ingredients
– Setting of “use by” dates
– To insure nutritional labeling compliance
Quality change prediction
• To predict quality change you need to
know
– Major modes of quality loss
– Factors controlling initial quality
– Environmental conditions
– Nature of the packaging material
– Chemical kinetics
Common modes of
food deterioration
• Microbial decay
– pH, aw, redox potentials, etc.
• Senesence
– Normal enzymatic reactions in post-harvest
physiology of food stuffs
• Non-enzymatic browning
– aw, pH, temperature, etc.
Common modes of
food deterioration
• Lipid oxidation
– Off flavor
– Loss of solubility and biological value of
proteins
– Bleaching of fat-soluble pigments
(carotenoids)
– Loss of efficacy of fat soluble vitamins (A, D,
E, and K)
Common modes of
food deterioration
• Vitamin loss
– Hydrolysis
– Light
– Heat
– Acid
– Oxidation
• Vitamin C is most labile
Common modes of
food deterioration
• Color changes
– Loss of Mg from chlorophyll

• Enzymatic activity
– PPO
– Pectic enzymes
– Lipase
Common modes of
food deterioration
• Sensory changes
• Physical deterioration
– Decreased solubility of certain constituents
– Mushiness
– Freezing-thawing
– Melting-recrystallization of fat
– Bread staling
General methodology
• Select the major mode of deterioration to
study
• Measure some quality factor related to
this mode
• Apply mathematical models to make
predictions
Selecting what to measure
• In selecting what to measure, consider
– Key labile ingredients
– Characteristics of the packaging material
– How the product will be shipped and stored
Selecting what to measure
– Relative humidity
– Temperature
– Susceptibility to light
– If no chemical test exists, would a sensory
test work?
Kinetics
kf
• aA + bB cC + dD
kr

• kf = rate constant for the forward

reaction
• kr = rate constant for the reverse reaction
• Rate of loss of reactants:
• -dA/dt = -dB/dt
Kinetics
• Rate of gain of products:
• dC/dt = dD/dt
• Further, rate of loss = rate of gain
• -dA/dt =-dB/dt = dC/dt = dD/dt
• Rate of reaction
• rate= (rate constant)Π[reactants]n
Kinetics
• Net rate of loss of A:
• -dA/dt = rate of loss - rate of reformation
• -dA/dt = kf[A]a[B]b - kr[C]c[D]d

Rate of forward Rate of reverse

reaction reaction
Kinetics
– To simplify this equation, select conditions
where the forward or reverse reaction
predominates and/or one of the reactants is
in such large concentration excess that it’s
concentration doesn’t change over time.
Kinetics
• Thus, if kr <<< kf and [B] is large relative
to [A] (so that B is effectively constant)
then
• -dA/dt = kf’[A]a , where kf’ is the pseudo
first order rate constant
• Assume for a given mode of food
deterioration that the previous
assumptions are true, then
Kinetics
• Loss of quality may be expressed as
– -dQ/dt = kn[Q]n
• and gain in undesirable factors may be
– +dUF/dt = kn[UF]n
• In these equations, kn is the pseudo first
order rate constant, and n is the order of
the reaction
Reaction order and integration
• -dQ/dt = kn[Q]n
• For n = 0
• -dQ/dt = k0[Q]0 = k0
• -d[Q] = k0dt
• d[Q] = -k0dt
• ∫d[Q] = -k0∫dt
• [Q] - [Q0] = -k0t
• [Q] = -k0t + [Q0]
Reaction order and integration
• For n = 0, a plot of [Q] vs. time should
yield a straight line
[Q0]

Slope = -k0
Q

time
Reaction order and integration
• For n = 1
• -d[Q]/dt = k1[Q]1
• ∫d[Q]/[Q] = -k1∫dt
• ln[Q] - ln[Q0] = -k1t
• log [Q] = -(k1/2.3) t + log [Q0]
Reaction order and integration
• A plot of log [Q] vs. time should yield a
straight line
Log[Q0]
Slope = -k1/2.3
Log [Q]

time
Half-life (first order)
• From ln[Q] - ln[Q0] = -k1t
• ln([Q]/[Q0]) = -k1t, and
• k1 = {-ln([Q]/[Q0])}/t
• When [Q] has decreased to 1/2 of its
original value, we call this time the half-
life of the reaction.
Half-life (first order)
• Then k1 = {-ln[50/100]}/t 1/2
• t 1/2 = 0.693/k1

• This is a general result for any first order

reaction and we will have occasion to use
this equation in a later problem.
Reaction order and integration
• We won’t do this but integration for n = 2
would indicate that plotting 1/[Q] vs. time
would give a straight line.
Kinetic approach to accelerating
shelf life deterioration
• Concentration acceleration

• Moisture or relative humidity

acceleration

• Temperature acceleration
– This is usually done
The Arrhenius equation
• The Arrhenius equation describes the
effect of temperature on chemical
reaction rate

• k = k0e -E/RT
– where k = rate constant, k0 = pre-
exponential factor, E = activation energy, R
= gas constant (8.3 J/deg K), and T = the
absolute temperature in degrees Kelvin
The Arrhenius equation
• Take the natural logarithm of the
Arrhenius equation
• ln k = -(Ea/R)(1/T) + ln0k
The Arrhenius equation
• Thus we can find k at several higher
temperatures (accelerated shelf life
study) than the one in which we are
interested. Then, plot ln k vs. 1/T to get a
straight line which you can extrapolate to
lower temperatures.
The Arrhenius equation
Plot for an accelerated shelf life
study

ln k

1/T (reciprocal degrees K)

 Case study
Asceptic packaged simulated orange drink product

Simulated
orange drink
product How do I establish my
“use by” date?
Use by: ???????
Treatment 1
• On the label of my asceptic packaged
orange drink product it states that each
serving provides 100% of the DV for
vitamin C. I know that vitamin C is the
most labile constituent of my product,
therefore I can use it as a marker
• DV = 60 mg
Treatment 1
• Number of servings per package = 6
• Total minimum vitamin C needed in
package at time of consumption = 360 mg
• To account for breakdown, I add enough
vitamin C to make the total at
manufacture = 720 mg
• Question: How do I determine my “use
by” date?
Treatment 1
• Answer: Do an accelerated shelf life
study. Measure k at 50, 60, and 70
degrees C (323, 333, and 343oK). Do an
Arrhenius plot.
Treatment 1

343 K
333 K
323 K
ln k

1/T (reciprocal degrees K)

Treatment 1
• Extrapolate to storage temperature, in
this case 25 degrees C (298oK).
Treatment 1

343 K
333 K
323 K
ln k
298 K

1/T (reciprocal degrees K)

Treatment 1
• At 25 C (298 oK), k1 = 3.1 x 10-3 days-1
• My maximum allowable loss occurs when
the [vitamin C] reaches one-half of its
initial level, that is, at the half-life for
vitamin C under these conditions.
Treatment 1
• t 1/2= 0.693/k1=0.693/(3.1 x 10-3)
• t 1/2 = 224 days

• So if my simulated orange drink product

is packaged today then it’s use by date is
November 4, 2005.
Treatment 1

Simulated
orange drink
product

Use by: Nov. 4, 2005

Treatment 2
• Same problem as treatment 1
• We know from our kinetic experiments
that vitamin C degradation is a first
order reaction. Thus,
Treatment 2
• ln [vitamin C] - ln [vitamin C]0 = -k1t
• The vitamin C concentration at
consumption (time = t) must be 60
mg/serving.
Treatment 2
• My accelerated shelf life study tells me that
k1 = 3.1 x 10-3 days-1. Thus,
• ln [60] - ln [vitamin C]0 = (3.1 x 10-3)t
• I will specify a shelf life (or t) of 30 days.
• Then, 4.1 - ln [vitamin C]0 = -0.093
• ln [vitamin C]0 = 4.193
Treatment 2
• [vitamin C]0 = 66 mg/serving
• So the total vitamin C needed per
package for a 30 day shelf life is 396 mg
(storage at 25 degrees C/298oK)