Cinética de Muerte

Reaction Kinetics of Thermal Death
page # 1
FScN 8312
MICROBIAL DEATH
KINETICS
page # 2
1. First Order assumptions

a. general equation
dN
= kN
dt
E
A
N
ln = kt = ke R T t
No
plot ln N or log N vs time ---> straight line
pseudo first order with death rate constant k
2.3 * slope = k constant for death from semilog paper
Microbial Death Time Curve
10
6
240
243
250
cfu/gram
10 5
10 4
240F
10 3
243F
250F
10 2
0
Minutes
eg @ 250F k=2.3 min-1
in many cases lag time and non-linear due to
comeup time
page # 3
spore clumping
population distribution
injury and pretreatment
some spores get activated at different temperatures
at long times also non-linear due to inaccuracy
page # 4
b. D value
(1) definition
D = time when N = No/10
Bigelow Model
DRT = time to reduce population to 1/10 of original

population = D
D = DRT = t 0.1
N
0.1N o
ln = ln
= 2.3 kD
No
No
k = 2.3 D
page # 5
read off semilog plot

from prior example D= 1 min @ 250F
D = 3 min @ 240 F
thus D inverse to k value

@ 250F k =2.3 = 2.3/D= 2.3/1 = 2.3
Example values
B. megaterium
C. botulinum
B stearothermophilis
B subtilus
A. niger
D100 = 10 min
D100 = 27 min
D130 = 20 min
D135 = 9 min
D100 = 10-5 min
(2) effect of water activity
page # 6
page # 7
2 . Z value - microbial temperature dependence

plot D value on semilog vs time
similar to shelf life plot - time to 90% reduction
Z Value Plot
DRT-Minutes
10
.1
230
240
250
260
270
280
temperature F
D = Do e bT
ln
for
0.1D1
= 0.1
D1
0.1D1
= ln 0.1 = bTz = bz
D1
z = C = Tz
b = 2.3 / Z = slope Z
define Z as temperature difference for one log difference in D value
Z is not a slope as stated in micro text books = inverse slope
above example Z = 22F= 12.2 C
page # 8
similar to temperature sensitivity or activation energy
z=
T2 T1 250 T
=
D2
D
log
log
D1
D 250
above example
z=
T2 T1 114 102
=
= 12F
D2
10
log
log
D1
1
Z =6.7 C
page # 9
Process times follow same format

eg meat cooking t=7 D for Salmonellae death
Listeria in eggs follows similar pattern
Salmonellae Z = 5.2F = 2.9 C

Effect of medium (Davies J. Food Tech 12:115 (1977)
TC
120
140
160
D water (min)
1000
2.45
0.22
D milk (min)
468
3.02
0.32
Q 10
Z
23.5
7.3C
8.9C
13.2
page # 10
Process time plot for milk pasteurization from FDA vs E. coli death
FDA t140 = 30 min @140F
t 160= 15 sec @ 160F
page # 11
3. Arrhenius relationship
ln k vs 1/T
or ln D vs 1/T
D = Do e
EA
RT
EA 1 1

T 2 T1
D2
R
=e
D1
=e
EA
R
T 2 T 1
T 2 T 1
0.1D1
D2
E T T1
E
= ln
= ln 0.1 = 2.3 = A 2
A
D1
D1
R T2 T1
R
2.3RT12 4.576T12
=
T K
z
EA
EA
ln
z1
T 2
1
Z decreases as EA increases - less F to cause 10 fold change

eg C. botulinum data
z ~ 10C Q10= 10
page # 12
page # 13
EA = 70.6 Kcal/mole @ 120C from equation

= 63.7 Kcal/mole @ 100C from equation
EA = 66.7 Kcal/mole from graph
suggests need to check paper to see how calculated
as can be slightly off
page # 14
4. . Q10 , Z and EA relationship in C

(1) equations
ln Q10
2.3 logQ10 = 10b =
10 * 2.3
= 10b =
z
10 * 2.3
z
Q10 = 10
10
(2) typical values

Salmonellae
Z = 4.5C
Q10 = 167
EA = 113 Kcal/mole
yeast
Z=5 C
Q10=100
EA= 98 Kcal/mole
E. coli
Z = 6.1 C
Q10=43.6
EA= 83.2 Kcal/mole
S. aureus Z = 9 C
Q10 = 13Kcal/mole
EA = 56.4 Kcal/mole
C. bot spores
Z=10C
Q10 = 10
EA = 67 Kcal/mole
page # 15
5. . F value for processing

a. equations for constant temperature
FT = time for process desired for x log cycle reduction

N
N
2.3
2.3
t=
Ft
ln = 2.3 log = kt =
N
N
D
D
o
o
N
F = D log
No
for T = constant
Fo = min at 250F for 12 log cycles reduction

Fo = D250. X 12 = ~ 2.3 minutes for C. botulinum
page # 16
b. variable temperature process T = f(t)
N
ln = kt = k o e
No 0
0
t
E
RT (f (t ))
k t
i i
i =1
sum up time temperature sequence till equals value desired

eg if 12 log cycles desired then = 2.3 * 12 = 27.6
page # 17
c. Area Under Curve Method - kinetic method

(1) measure time-temperature sequence at slowest point
of heating gives T=f(t)
2) then plot value of k for each temperature at given time

increment vs total time elapsed area under curve is sum of integral
(3). continue till reach value desired for area

gives process time
easy to do on computer for continuous
process
page # 18
d. Lethality Method
set fo = 1 for desired process
N
N t 2.3
ln = 2.3 log =
t
No
N o 0 D (f (t ))
t
1
N
log o =
t=
(
(
))
N
D
f
t
0
ti
i = 1 Di
N
set x = log o
N
n
n
ti
t
f =
= i
i = 1 xD i
i = 1 LT i
1
1
=
= lethality rate
xD Lt
page # 19
plot 1/lethal time for given x reduction vs time

or sum up on computer until Fo =1 area under curve
page # 20
6. Canning Calculations
a. Unsteady State Heat transfer for object
2T
T
2T
2T
2
=T =
+
+
2
t
y 2 z 2
x
T Ti
ln T = ln out
= 2t
Tout T r
k
=
C p
a = thermal diffusivity = cm2/hr

r = characteristic thickness
Tout = retort temperature = TR
Ti = initial temperature
T = temperature @ time t
= unaccomplished temperature change
plot ln vs time ---> straight line to predict temperature
at any time
page # 21
b. Temperature plot
ln[Tout
T ] = ln C 2 t
r
fH = F for 1 log cycle
page # 22
d. Balls Formula
B = 0.42t cut + fH [log(JI ) log(g )]

JI = pseudo initial temperature [TR - TJ] after come
up time tcut
g = TR - TS where TS is temperature when cooling
starts obtained from Z and Fo values by trial and
error
time to turn off steam.
page # 23
7 . Quality Loss in Thermal Processing

a. Equations
dN
= kN
dt
Nx
ln
= kt x
No
dA
= kA
dt
A
ln
= kt x
Ao
time is set for microbial death so quality loss depends on

quality rate function and temperature
page # 24
b. Typical values for rate constants and EA in canning

Reference
Other
Gold and Weckel
(1959)
Blanched
Component
Medium
pH
Temp
Range
( F)
Ea
(KcalMole)
Chlorophyll
Pea puree
Nat2
240-280
16.1
14.0 min
do
do
do
do
12.1
13.9 do
D1211
Unblanced
Lenz and Lund
(1974)
Mackinney and
Joslyn (1941)
Chlorophyll
do
Pea puree
Spinach puree
6.5
6.5
175-280
do
22
19
113 min
166 do
Chlorophyll a
Chlorophyll b
Buffered soln
do
--
32-122
--
7.5
do
-9.0
--
Dietrich et al.
(1959)
Chlorophyll
Green beans
Nat2
190-212
12.0
10.1 min
Timerss (1971)
Color
Peas
Asparagus
Green beans
Whole kernel corn
Nat2
do
do
do
175-300
do
do
do
15.0
14.0
15.0
19.5
25.0 min
17.0 do
21.0 do
6.0 do
do
do
22.5
2.3 do
Whole green beans do
do
22.0
4.0 do
Time for
Whole peas
taste panel
to
judge 4.0/
9.0
compared
to
frozen
control.
Hermann (1970)
Chlorophyll a
Chlorophyll b
Maillard reaction
Nonenzymatic
browning
B-1
Spinach
Spinach
Apple juice
Nat2
do
do
212-266
do
100-266
12.5
10.0
27.0
34.1 min
48.3 do
4.52 hr
Apple juice
Pork
do
do
do
? - 250
20.7
19.5
4.75 hr
6.03 hr
Penting et al.
(1960)
Anthocyanin
Grape juice
Nat2
Boysenberry juice do
Strawberry juice
do
68-2250
do
do
28.0
20.0
19.0
17.8 min
102.5 do
110.3 do
Tanchev and
Joncheva (1973)
Cyanidin-3-rutinoside
Citrate buffer
Plum juice
Citrate buffer
Plum juice
170-225
do
do
do
23.7
23.1
26.2
22.1
28.5 min
41.6 do
21.6 do
27.7 do
Peonidin-3-rutinoside
4.5
4.5
4.5
4.5
page # 25
Reference
Temp
Range
pH
Bendix et al. (1951)

Feliciotti and
Essselem (1957)
Mulley et al. (1974)
Gillespy (1962)
Garrett (1956)
Garrett (1956)
Davidek et al.
(1972)
Gupte et al. (1964)
Ramakrishnan and
Francis (1973)
von Elbe et al.
(1974)
Burton (1963)
Williams and Nelson
(1974)
Taira et al. (1966)

Mansfield (1974)
Component
Mole)
220-270
21.2
164 min
D1211
Thiamin
Whole peas
Nat
Thiamin
do
do
do
do
do
Carrot puree
Green bean do
Pea
do
Spinach do
Beef heart do
Beef liver
do
5.9
5.8
6.6
6.5
6.1
6.1
228-300
do
do
do
do
do
27
do
do
do
do
do
158 min
145 do
163 do
134 do
115 do
124 do
do
do
Thiamin
do
do
do
6.2
6.2
6.0
Nat2
do
do
do
250-280
do
do
do
do
29.4
27.5
27.4
120 do
157 do
156.8 min
246.9 do
254.2 do
do
-----
do
20.0
23.0
27.0
d-Pantothenic acid
C
B-12
Folic acid
A
Lamb
do
Pork
do
Phosphate buffer
Pea puree
Beef puree
Peas-in-brine
puree
--------Liquid multi
vitamin prep
do
do
do
Vitamin prep
do
3.2
do
do
do
3.2
do
39-158
do
do
do
30-158
do
26
21
23.1
23.1
16.8
14.6
Inosinic acid
(IMP)
(IMP)
Chlorophyll a
Chlorophyll b
Buffer soln
do
do
Spinach
do
3
4
5
6.5
5.5
140-208
do
do
260-300
260-300
34.0
30.4
28.1
15.5
7.5
------13.0 min
14.7 do
Carotensids
Paprika
Nat2
125-150
34.0
0.038 min
Betanin
do
Browning
do
Buffer
Beet juice
Goats milk
do
5.0
do
6.5-6.6
do
122-212
do
200-250
do
12.5
10.0
27.0
do
19.5 min
46.6 do
1.08 min
0..91 do
Methylmethionine
sulfonium
bromideDMS
Sodium-citrate
buffer
6.0
Sweet corn
6.9
Tomato
4.4
Soybean meal
--Peas
Nat2
Peas
Beets
Whole kernel corn
Broccoli
178-212
do
do
212-260
170-200
210-240
180-210
212-250
212-250
34.8
31.6
27.2
30.0
19.5
19.5
34.0
16.0
13.0
8.4 min
4.5 do
23.2 do
13.1 hr
1.4 min
2.5 do
2.0 do
2.4 do
4.4 do
Squash
Carrots
Green beans
Potato
182-240
176-240
182-240
161-240
25.0
38.0
41.0
27.5
1.5 do
1.4 do
1.0 do
1.2 do
Thiamin
Riboflavin
B-1 - HC1
Lysine
Texture
Overall cook quality
do
do
do
do
do
do
do
Hackler et al.
(1965)
Adams and Yawger
(1961)
Medium
Ea
(Kcal(F)
226.7 do
----1.35 days
4.46 do
1.12 do
1.94 do
1.95 days
12.4 do
Trypsin inhibitor
Soybean milk
---
200-250
18.5
13.3 min
Peroxidase
Whole peas
Nat2
230-280
16.0
3.0 min
Reference
Licciardello et al.
(1967)
Read and Bradshaw

(1966)
Stumbo (1973)
Component
Medium
pH
Temp
Range
(F)
C. botulinum
toxin-type E
Growth
Media
do
6.2
do
do
125-135
26.4
135-140
57.4
1140-145 153.5
3.8 min
( ) 60C
Milk
6.4-6.6
210-260
25.9
9.4 min
Variety
do
>4.5
220- ?
do
64-82
53-82
Staphylococcus
enterotoxin B
C. botulinum spores
(type A and B)
B. stearothermophilus
D-value at 121C.
Indicates natural pH of the system.
page # 26
Ea
(KcalMole)
D1211
0.1-0.2 min
4.0-5.0 min
page # 27
c. HTST processing effect
Example calculation for N/No = 10-7 or 7 log cycle destruction

k death B. stearothermophilis = 0.7 min-1 @ 125C
k thiamine = 0.014 min-1 at 102C
for each temperature calculate time for 7 D destruction
plug into quality equation for calculation of A/Ao
see plot next page
% Thiamine
TC 1000/T spores kD min-1
t for 7 D
100
110
120
130
140
150
2.681
2.611
2.545
2.481
2.421
2.364
0.002
0.017
0.16
1.3
9.6
62
8050
947
100
12.4
1.7
0.26
Amount loss
100
100
99.5
74.5
34
11
example calculation plot
page # 28
page # 29
8. Canned Food Storage

a. Modes of deterioration
microbial - only if > 40C
oxidation - little oxygen left
enzymes - should be inactivated
chemical - major reaction especially with container wall
texture - basically during processing
b. Shelf life test considerations
(1). MCCP - 2 weeks @ 80F
(2). FSIS test - 95F 2F
(a) 10 days
(b) 20 days high fat or > 3 lbs
(c) pH meat/sauce different - 30 days
c. temperature abuse conditions
1 year
70F
6 months 100F
3 months 120F
page # 30
d. nutrient loss during storage

CANNED FOODS
Maximum Storage Temperatures F
for canned foods to assure not more than 10% loss of vitamin C, B1 ,
carotene, or riboflavin
(adapted from Feaster, 1960; Cecil and Woodroof, 1963)
__________
Ascorbic acid
(Vitamin C)
Thiamine
Carotene
(Vitamin B1) (Vitamin A pres
) (Vitamin B )
Riboflavin
Canned
product
12 mo 18 mo 24 mo
12 mo
18 mo
24 mo
12 mo 18 mo 24 mo
12 mo 18 mo
76
74
68
65
60
58
>32
45
--38
70
32
62
72
54
58
--45
-57
--50
60
45
32
57
45
32
---
---
---
57
50
74
60
45
>32
---
---
---
---
---
65
---
---
---
---
---
---
80+
80+
80+
---
71
60
50
64
58
53
75
66
58
70
---
---
---
56
47
41
---
---
---
---
60
45
32
---
---
---
---
---
---
---
65
50
40
84
80
76
70
40
32
---
74
66
52
62
56
50
72
58
45
55
---
---
---
---
---
---
80+
80+
80+
68
54
32
80
80
80
---
---
---
---
---
68
60
52
63
57
49
46
41
38
63
46
68
60
45
70
60
50
24 mo
Apricots
Asparagus
45
Beans, green
45
Beans, lima
32
Carrots
--Corn, sweet
48
Frankfurters
and beans
--Grapefruit
segments
--Peaches
--Peas
45
Plums
Pineapple
slices
--Spinach
32
Tomatoes
a
b
c
d
e
f
10% loss in 17 months - no temperature effect

20% loss in 12 months, 15% in 24 months, no temperature effect
No loss
10% loss - no time or temperature effect
8% loss in 12 months, 13% in 24 months, no temperature effect
20% loss, no time or temperature effect
40
--55
------50
f
page # 31
e. Nutrient loss problems

(1). field variability
(2). choice of index of deterioration
(3). overpack and storage
(4) variation depending on level and test
page # 32
D. Problem Set
1. (10 points) In a Study of the heat inactivation of Staphylococcal enterotoxin A
(Denny et al., J. Food Sci. 37:762, 1966), the procedure used was to grow the
organisms on special culture plates, isolate the endotoxin by dialysis and then use
TDT tubes for the heat inactivation studies. The heated extract was then injected into
each of five cats, a positive test, i.e., presence of toxin, being taken if one of the cats
reacted violently to the injection. The following data were obtained. Times are minutes
of heating at the given temperature. Initial toxin concentration was the same in all
cases.
-+ means at least one of five cats reacted (presence in all cases)
- means no reaction (i.e., all toxin destroyed)
(a) Prepare a graph that shows safe processing time as a function of temperature.
(b) What is the activation energy for heat inactivation of the staph enterotoxin?
State all assumptions that must be made in you analysis of the data.
Temperature F
Times min.
Cat reaction
210
95
80
60
+
30
+
220
60
50
40
30
+
230
50
40
30
20
+
240
40
30
20
15
+
10
+
8
+
250
12
11
10
9
+
page # 33
2. (5 points) The following data (JFS 42:1224; 1977) have been found for the time to
reach 50 ug/g patulin on corn by Penicillium patulin M59 @ 75%RH.
51 days @ 5C
29 days @12 C
12.6 days @ 25C
(a) Write a general expression for the production of patulin as a function of time
(what order would you expect).
(b) What is the apparent activation energy for its production?
(c) The LD50 (lethal dose for a 50% chance of death) for mice is 40 mg/Kg body
weight. Mature wild mice eat about 6 g corn a day in their diet and weigh about 100 g.
How long would the corn have to sit at 22C to give a 50% probability of death, if the
corn gets contaminated with the mold? Assume that the mold immediately begins
growing at zero time and that the initial level is at least a factor of ten times under the
detection limit of 0.l ug/g food. The mouse in this problem eats the corn only once and
at the time when the patulin reaches a concentration that is 50% lethal to the mouse.
POOR MOUSE!

Cinética de Muerte

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Reaction Kinetics of Thermal Death

Reaction Kinetics of Thermal Death

1. First Order assumptions

Reaction Kinetics of Thermal Death

Reaction Kinetics of Thermal Death

DRT = time to reduce population to 1/10 of original

Reaction Kinetics of Thermal Death

read off semilog plot

thus D inverse to k value

Reaction Kinetics of Thermal Death

(2) effect of water activity

Reaction Kinetics of Thermal Death

2 . Z value - microbial temperature dependence

Reaction Kinetics of Thermal Death

similar to temperature sensitivity or activation energy

Reaction Kinetics of Thermal Death

Process times follow same format

Salmonellae Z = 5.2F = 2.9 C

Reaction Kinetics of Thermal Death

t 160= 15 sec @ 160F

Reaction Kinetics of Thermal Death

Z decreases as EA increases - less F to cause 10 fold change

Reaction Kinetics of Thermal Death

Reaction Kinetics of Thermal Death

EA = 70.6 Kcal/mole @ 120C from equation

Reaction Kinetics of Thermal Death

4. . Q10 , Z and EA relationship in C

(2) typical values

Reaction Kinetics of Thermal Death

5. . F value for processing

FT = time for process desired for x log cycle reduction

Fo = min at 250F for 12 log cycles reduction

Reaction Kinetics of Thermal Death

b. variable temperature process T = f(t)

sum up time temperature sequence till equals value desired

Reaction Kinetics of Thermal Death

c. Area Under Curve Method - kinetic method

2) then plot value of k for each temperature at given time

(3). continue till reach value desired for area

Reaction Kinetics of Thermal Death

Reaction Kinetics of Thermal Death

plot 1/lethal time for given x reduction vs time

Reaction Kinetics of Thermal Death

a = thermal diffusivity = cm2/hr

Reaction Kinetics of Thermal Death

fH = F for 1 log cycle

Reaction Kinetics of Thermal Death

B = 0.42t cut + fH [log(JI ) log(g )]

Reaction Kinetics of Thermal Death

7 . Quality Loss in Thermal Processing

time is set for microbial death so quality loss depends on

Reaction Kinetics of Thermal Death

b. Typical values for rate constants and EA in canning

Whole green beans do

Reaction Kinetics of Thermal Death

Bendix et al. (1951)

Mulley et al. (1974)

Taira et al. (1966)

Reaction Kinetics of Thermal Death

Read and Bradshaw

Reaction Kinetics of Thermal Death

c. HTST processing effect

Example calculation for N/No = 10-7 or 7 log cycle destruction

Reaction Kinetics of Thermal Death