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 THE DETERMINATION OF KINETIC PARAMETERS

IN HEAT PROCESSING OF BABY FOOD

A thesis presented in partial fulfilment

of the r equir ements for the degr e e of Ph.D.
in Biotechnology at Massey University

Kalaya Taimmanenate

1980

. ","lO_l
 ABSTRACT

Two methods of hea t processing kinetic parameter determination

by s teady-state and unsteady-state heating procedures were studied.
The uns teady-state p rocedure was used for colour and viscosi ty where
large amounts of samp les were required for measurement, and both were
used in considering the destruc tion of ascorbic acid and riboflavin
in a baby food .

To ob tain accurate determination of the kinetic parameters,

standard k and Ea, experimental methods had to be developed to measure
the quality fac tors within narrow limits of accuracy.

Determination of the kinetic parameters by unsteady-state

procedure involved the development of a computer method for the can
temperature distribution calculation, the quality retention calculation,
and finally determinat ion of the emp i rical relationships of the standard
parameters,k and Ea,to the residuals ( differences between experimental
and pred i c ted concentrations) . Temperature distribution in a can was
predic ted by a modified computer p rogram based on an analyt i cal solution
to ob tain a form fi t t ing of the experimental heat penetration curve .
From this, the q uality retention was ca lculated by numerical integration.
The standard k and Ea were roughly estimated from the li terature ei ther
on the studied quali ty or on a similar quality . Then the ranges of
s tandard k :and Ea were assigned in an orthogonal composite design and used
to calculate the retained q uality which then was compared with the experi�
mental result to obtain the absolute residual at each standard k and
Ea . The average residual at each processing temperature was used in
mul tip le linear regression to determine the relationships between the
standard k and Ea, and the residual. By op timising the empirical
equat ion the best values for the standard k and Ea were determined.

The standard k and Ea for ascorbic acid and riboflavin were also
determined by the steady-state procedure. In this, small tubes of the
baby food were heated in a constant temperature , oil bath. Nearly
identical results ob tained for ascorbic acid by both methods indicated
that the method used was feasible and the degradation of ascorb i c acid
 0

wa s best describ ed by a f ir s t order reac t ion . For r ibof lavin ,

d if f eren t r esul t s were found from the two methods but these could b e
expla ined as the result s o f the low d estruct ion rate o f riboflavin on
heat ing , the ana lyt ical error and the change in phys ic al cond it ions
from cans to tube s . So , use of the steady-sta t e kinetic parameters
for qual ity retent ion calculat ion in unsteady-state was conf irmed
exper imentally .

For colour and vi sco sity.changes in process ing , the me thod of

kine tic parame ter de termina tion in uns teady-s tate heat ing procedure
.was used assuming f irs t order kine t i cs .

It was conclud ed in this food syst em for the temperature ranges o f

0
60-1 3 9 c, the kinetic rea c t ion r a t e a t 1 2 9 C and the ac t ivat ion energy
°

and 7 7 -8 5 kJ mol e , 0 . 1 1 - 0 . 2 5 x 1 0
-4 -1 -1 -4 - 1
were 0 . 4 2-0 . 44 x 1 0 s s
and 84 - 1 05 kJ mo le , 1 . 20 x 1 0 and 1 22 kJ mole and 1 . 65 x W
-1 -4 - 1 -1 -4
s
-1 -1
s and 1 5 1 kJ mole for a scorbic acid , riboflav in , col our and visc o s ity
respec t ively .
 ACKNOWLEDGEMENTS

The success of this research was due to the experience and

confidence of my supervisors , Prof essor R . L . Earle and Dr Mary D . Earle ,
whom I shall always b e grateful . Their untiring interes t , patience
and encouragement are deeply appreciated .

This work would not have been possible wi thou t the support of
Chulalongkorn Univers i ty to whom I am indeb ted . This scholarship
would no t have been possible to ob tain wi thou t the help of
Dr Mary D. Earle and the Chemical Technology Depar tment , in
particular , Dr K. Santiyanon t , Dr C . Thanyap i t tayaku l , Mr V . Premyothin
and Dr P . Chi t taporn .

I also wish to express my appreciation to var ious people who

assis ted this res earch in many ways . In part icular I would l ike to
thank :

Dr A . C . Cleland f or his valuable d iscussions and criticisms

and also his willing as s is tance .

Food Technology Research Centre , Department of Food Technology

for f inancing the exper imental work .

Prof essor R . Richards for provid ing the f acil i ties and funding
the computer expenses .

Mr T . Gracie f or his assis tance in experimental work .

Miss S . A . Wilkinson for helpful guidance in s e t ting up s teady- s tate

heat ing experiments .

All tas te panelists for taking part in the preliminary work and
all those in the Facul ty of Food Science and Biotechno logy for making
such a happy working environment .
 Also to my typi s t , Vivienne Mair , for her e f ficiency and patience ,
and Nuch for taking part in the f inal preparat ion .

Finally to my mother , sis ter and brothers for their cont inual
moral support dur ing the s tudy .

Kalaya Taimmanenate
Oct ober , 1 9 80
 CONTENTS

Lis t of Tab les

List o f Figures

1. INTRODUCTION 1

2. LITERATURE REVIEW 3

3
2.1 Introduction
2. 2 Kine tic Theory of the Changes in Food During Hea t Processing 4
2.2. 1 Theory o f kine tic reac t i on rate 4
2.2.2 Temperature dependence of the reac t ion rate 6
2.2.3 Effect of o ther variables on the reaction rate 9
2.3 Quantitative Es timation of the Changes in Food During Heat
Process ing 10
2.3.1 Analysis of concen trat ion 10
2.3.2 Determination of temperature d istribution 10
2.3.2. 1 Determination of thermal lag in steady-s tate
heating 11
--

2.3.2.2 Experimental heat penetration measurement 12

2.3.2.3 Theore tical determina t ion 13
2.3.3 Calcula tion o f kinetic parameters 14
2.4 Changes o f Food During Heat Processing 17
2.4. 1 As corbic acid 18
2.4.2 Ribof lavin 22
2.4.3 Colour 25
2.4.3.1 Browning reac tion 25
2.4.3.2 Pigment / chlorophyll destruc tion 28
2.4.3.3 Total colour change 29
2.4.4 Viscosi ty 32
2.5 Conclusion 33

3. INVESTIGATION OF TESTING METHODS AND DEVELOPMENT OF PROCESS 35

3. 1 Introduction 35
3.2 Inves tigation of Tes ting Me thods 36
3.2. 1 Ascorb ic acid 36
3.2.2 Riboflavin 37
3.2.3 Colour 37
3.2 4 Viscos i ty 38
3.3 Development of Process 38

3.3.1 Preparation of baby foods 38

3. 3. 2 Preprocess ing 40

3 . 3 . 2.1 Thawing 40

3.3 . 2 . 2 Preheat ing 40

3.3.3 Process ing 41

3.3 . 3 . 1 Temp era ture measurement 41

3.3.3.2 Re tor t opera tion 42

3.3.3. 3 Process ing cond i t i ons 42

3.4 Adj us tment of Process 44

3. 4 . 1 Formula tion 44

3.4.2 Preprocess ing cond i tions 46

3.5 Final Process 47

4. TEMPERATURE DISTRIBUTION IN A CAN DURING PROCESSING 51

4.1 Introdu c t ion 51

4.2 Experimental De termina t ion of Temperature D i s tribution 52

4.3 Computer Programs f or Temperature Dis tr ibu t ion Calcula tion 54

4.3 . 1 Analy t ical sqlu t i on method 54

4.3.2 Numerical .finite dif ference me thod 57

4.4 Thermal Property Determinat ion 60

4.5 Comparison be tween Predic ted Temperatures f rom the Two Computer
Pro grams - Analy tical Solu t ion and Numer ical Fini te Difference 63
4.6 Comparison of the Pred i c ted Temperatures from the Analy tical
Solu tion Program and the Exper imen tal Temperatures 68

4.6.1 Comparison of temperatures in the heating phase 68

4 . 6.2 Comparis on of temperatures in the cooling phase 71

4.6 . 3 Comparison of temperatures in the overall process 75

4.7 Mod ification of the Analy tical Solu tion Program 75

4.7.1 The beginning of the cooling s tage 75

4.7 . 2 The later cooling s tage 79

4 . 7. 3 Conclusion 80

4.8 Comparison of the Exper imental Temperatures and the Predic ted
Temperatures from the Mod i f ied Analy tical Solu t ion Program 82

4.9 Conclusion 86
5. DETERMINATION OF KINETIC PARAMETERS BY UNSTEADY-STATE PROCEDURE 88

5. 1 Introduction 88
5.2 Experimental Analysis of Quali ty Retention 88
5.3 Quali ty Re tention Calculat ion 89
5.3. 1 Theory of quali ty retention calculat ion 89
5.3.2 Computer program for quali ty reten t ion calculat ion 92
5.3.3 Size o f time increment and d imens ion increment 93
5.4 Determination of Kine tic Parame ters 95
5.4. 1 The des ign 96
5.4.2 The analysis 96
5.5 Determinat ion o f Kine tic Parameters for Ascorbi c Acid 1 00
5.5.1 Determination of the range of k o and Ea 1 00
1 29 c
5.5.2 A model f or ascorbic acid for d e termination o f kinet i c
parame ters 101
5.6 De termination o f Kine tic Parame ters for Riboflavin 105
5.7 Determination o f Kine tic Parame ters for Colour 1 10
5.8 Determination of Kine tic Parame ters for Viscosi ty 111
5.9 Conclus ion 1 14

6. KINETIC PARAMETER DETERMINATION BY STEADY-STATE PROCEDURE 117

6.1 Introduc tion 117

6.2 Experimentation 117
6.2.1 Sample preparation 1 17
6.2.2 Thermal process ing sys tem 1 18
6.2.3 Determination of ascorb ic acid and riboflavin 1 19
6.3 Des truct ion of Ascorb ic Acid and Riboflavin on Heating 1 19
6.4 Determina tion of the Order of Reaction 121
6.5 Kinetic Parameters Determination 1 26
6.5. 1 Calculat ion of kine tic parame ters for f irs t order
reaction 1 26
6.5.2 Calculat ion of kine tic parame ters for second order
rea c tion 127
6.5.3 Determina tion of kinetic parame ters for as corb ic acid 1 29
6.5.4 De termination o f kinetic parame ters for riboflavin 133
6.6 Comparison of Kinetic Parame ters Determined by S t eady- S tate
and Uns teady- S tate Procedures 1 38
 6.6. 1 As corb ic acid 1 38
6.6.2 Ribo flavin 1 39
6.7 Conclusion 142

7. DISCUSSION 144

7.1 Temperature Pred i c t ion in the Can 1 44

7.2 Use of Steady-State Kine t i cs Data to Pred i c t Quali ty Changes
in Uns teady-Sta te Heat Proces sing 145
7.3 Kine tic Analysis Us ing Uns teady-State Heating Procedure 145
7.4 Kine tic Parame ters for As corb ic Acid, Riboflavin, Colour and
Viscos i ty in Heat Process ing of Baby Food 146
7.5 Applicat ion to Process ing 148

8. CONCLUSION 149

REFERENCES 1 50

APPENDICES

3. 1 Analysis of Ascorbic Acid and Riboflavin 1 75

3.2 Analyt i c al Me thod 1 76
3.3 x, y and Y of Control and Heated Samples 1 80
4.1 Analy t ical Solution Program 181
4.2 Numerical Finite Dif ference Me thod Program 1 86
4.3 Thermal D i f fus ivi ty De termination Results 1 89
4.4 Dis tribution o f Residuals for Determining Ac curacy o f the
Analy ti' c al Solut ion for Calcula ting Temperatures 190
4.5 Mod i fied Analyt i cal Solution Program 193
4.6 Comparison o f Experimental Tempera tures and Predic ted
Temperatures from the Mod i fied Analyt i cal Solut ion Program 199
4.7 Me thod o f Quali ty Re tent ion Calcula tion for Micro-organisms
and As corbic Acid 201
4.8 An Example o f Le thali ty Calculat ion 203
4.9 Dis tribution o f Res iduals for Determining Accuracy o f the
Mod i f ied Analy ti cal Solution P rogram for Calcula t ing
Temperatures 205
5. 1 Analyt ical Results 207
5.2 Quali ty Re ten t i on Calculat i on Prog�am 211
5.3 An Examp le of Kine tic Parame ters Calculation 217
5.4 Est ima t i on of k o f or the Design for Ascorb i c Acid 2 24
1 29 C
5.5 Determination of k o and Ea for Ribof lavin , Colour Y , and
1 29 c
Viscos i ty Using Equivalent Process ing Time 226
6.1 Quali ty Re t ention Calculation Program Based on Second Order
Kine tics 2 30
 LIST OF TABLES

2.1 Reac t ion Ra te Cons tants and Ac t ivat i on Energies for Ascorb ic
Acid 21

2.2 Reac tion Rate Cons tants for Riboflavin 24

2.3 Rea c t ion Rate Cons tants and Ac tivation Energ ies for
Non-Enzymic Browning Reac t ion 27

2.4 Rea c t ion Rate Cons tants and Ac t ivat ion Ene rgies f or
Chlorophyll Des truc tion 30

2.5 Rea c t ion Ra te Cons tants and Activat i'o n Energies for Colour
Change 31

3. 1 Dis tance from the Centre to the Measured Points 43

4.1 Experimental Run Number and Proces s ing Cond i tions 53

4.2 Comparison o f the Calculated Tempera tures a t the Centre o f

the Can 57

4.3 Diffus ivities o f Baby Food a t Variuos Tempera tures 62

4. 4 Comparison o f Temperatures Pred i c ted by the Analy ti cal

Solution and the Numeri cal Fini te Dif f erence Programs 64

5. 1 The Mean Ini t ial and Final Quali ty on Hea t Process ing 90

5.2 E f f e c t o f Size o f Increment on Quali ty Re ten tion Calcula t ion 93

5.3 Level o f the k o and the Ea in the Or thogonal Compos i te

1 29 C
Des ign f or As corbic Acid 103

5.4 Or thogonal Compos i te Des ign f or Ribo flavin 106

5.5 Average Absolu te Res iduals and their Standard Deviations

Resulting f rom Dif ferent Levels of k o and Ea 107
129 C
6.1 Hea ting Temperatures and Times for Steady-State Hea ting
Me thod 1 19

6.2 Concentration o f Ascorbic Acid and Riboflavin Be fore and

Af ter Heating 1 20

6.3 Correlat ion Coe f f i c ien ts of Regres s i on Analysis of

Concentrat ion o f As corb i c Acid and Riboflavin wi th Time o f
Heating 1 23
6.4 Kine tic Reaction Rate Cons tants a t Various Temperatures
for Ascorbic Acid 1�

6.5 Ac tivation Energy , Frequency Factor and Kine tic Reaction Rate
°
at 1 2 9 C for As corb ic Acid 1 30

6.6 Kinetic Reaction Rate Cons tants at Various Temperatures for

Riboflavin 1 34

6.7 Activation Energy , Frequency Fac tor and Kine tic Reaction Rate
° 1 34
at 1 29 C for Ribo f lavin

6.8 Second Order Kine tic Reaction Rate Cons tants a t Various
Temperatures for Riboflavin 1 36

6.9 Ac tivation Energy , Frequency Factor , Kinetic Reaction Rate

° 1 36
at 1 2 9 C for Second Order Kine tics for Riboflavin

6 . 10 Comparison of Ea and k o for Ascorbic Acid Determined

129 c
by Steady- and Uns teady-State Procedures 1 38

6. 11 Comparison o f Ea and k o for Ribo f lavin Determined by

1 29 C
Steady- and Uns teady-State Procedures 1 39

6 . 12 Average Res iduals at Various k o and Ea for Riboflavin

129 c
in Uns teady-State Heating in Can 141
 LIST OF FIGURES

3. 1 Thermocouple Arrrangement in a Can 43

3.2 Time , Tempera ture and Viscos i ty Relationships During

Preprocessing of Baby Food 48

4.1 Comparison of Pred i c ted Temperatures from the Computer

Programs at ( r / a , x / h) of (0 . 0 , 0 . 0) 65

4.2 Comparison o f Predic ted Temperatures from the Computer

Programs a t ( r / a , x / b) of ( 2 / 3 , 2 / 3) 66

4.3 Distribution o f Residuals for Comparison o f the Analy tical

Solution and the Numerical Finite Difference Me thod f or · 67
Run no . 6

4.4 Comparison of Experimental Tempera tures and Predic ted

Temp eratures from the Analytical Soluti on Computer Program for
Run no . 6 69

4.5 Comparison o f Experimental Temperatures and Predic ted

Temp eratures f rom the Analyt ical Soluti on Computer Program for
Run no . 7 70

4.6 Heat Pene tration Curves for Dif ferent Can Contents and Different
Head spaces 73

4. 7 Diagram Showing Different Parts in Heat Processing 76

4.8 Variance versus Thermal Dif fusivity 78

4.9 Comparison o f Experimental Temperatures and Predic ted

Temperatures f rom the Modi fied Analy tical Computer Program for
Run no . 6 83

4 . 10 Comparison o f Experimental Temperatures and Predicted

Temperatures from the Modif ied Analytical Computer Program for
Run no . 7 84
5. 1 Flow Char t for Quali ty Re tention Calculation Program 94

5.2 An Or thogonal Central Composite Design to F i t a Second Order

Response Surface 97
5.3 Firs t Design for Ascorbic Acid with Calculated Average
Abs olute Res iduals and thei r Standard Deviations 102

5.4 Orthogonal Design for Ascorbic Acid with Calculated

Average Res iduals and their Standard Deviations 104

5.5 Second Orthogonal Composite Des ign for Riboflavin with

Average Abs o lute Residuals and their S tandard Deviations 108

5.6 First Orthogonal Composite De sign for Colour,Y,with Average

Abs olute Res iduals and their Standard Deviations 1 10
'
5.7 Second Orthogonal C omposite Design for colour, Y, wi th
Average Absolute Res iduals and their S t andard Deviat ions 1 12

5.8 Firs t Orthogonal Compos i te Design f or Visc osity with Average

Absolute Res iduals and their Standard Deviations 113

5.9 Second Orthogonal Composite Des ign for Viscosity with

Average Absolute Residuals and their Standard Deviat ions 1 15

6. 1 Degradation Rate for Ascorbic Acid in Baby Food on Heating

Described by Firs t Order Kinetics 1 24

6.2 Degradation Rate for Ribo f lavin in Baby Food on Heating

Described by Firs t Order Kinetics 1 25

6.3 Degradation Rate for Rib o flavin in Baby Food on Heating

Described by Second Order Kinetics 125

6.4 Arrhenius Plot for Degradation of Ascorbic Acid and Ribo f lavin
in Baby Food on Heating 131

6.5 Probab i l i ty Plot o f Calculated % Residual for Ascorb i c Acid 132

6.6 Prob ability Plot o f Calculated % Res idual for Riboflavin 1 35

6.7 Arrhenius Plot for Degradation o f Ribof lavin in Baby Food on

Heating Des cribed by Second Order Kinetics 137
 1

1. INTRODUCT ION

Although the heating process has b een known for a long t ime to
affect b oth the nu tritional and the sensory qualitie s of food product s ,
there i s a lack o f quantitative data on the des truc t ion o f nutrients
and on the changes in eating quali t ies by the heating process ( Lund ,
1 9 7 5a , b ; Lund , 1 9 7 7) . Thiamine is the only vitamin which is a t all
well documented ( Farrer , 1 9 55; Felic io t t i and Esselen , 1 9 5 7 ) . There
is some data available for o ther v itamins ( Chi t taporn , 1 9 7 7 ) but they
were determined under restric ted condit ions . Reliable kinetic inf or­
ma tion on o ther quality changes occurring in hea t process ing is
practically non-exis tent .

At the present t ime , the nutr ient value o f a f ood a f t er heat

proce s s ing can only be determined emp irically . Es tablishing the
kinetics of changes in vitamins and f ood qualities during processing
is necessary to provide general relat ionships which can be used for
predict ions of nutr it ional los ses and f ood quality change s .

As corb ic acid , riboflavin , colour and viscos ity were the qual i t ies
s elec ted for this s tudy , the heat process used was can retor t ing
( s ter ilisat ion) and the f ood was homogenised , b ab y f ood made from
strained beef and mixed vegetables . Ascorb ic acid and riboflavin
were chosen as they are impor tant con s t ituents , there was no reliable
informat ion on the kinetic parameters and the analyt ical methods were
s impler than the o ther v itamin as says . Can s terilisat ion was used
b ecause this data would be useful for the des ign of canning processes
and because large samples were required for colour and viscos ity
measurements . Homogenised baby food was used b ecaus e the heat trans f er
into the can was only by conduc tion , the food throughout the can was
homogeneous and it was a m ixed food sys tem of commercial s ignificance .

B e ing heated in a can , the food was subj ec ted to a var iation of
t emperature with t ime and pos it ion in the can . I t was ne cessary f or
the quali ty retention calculat ion to determine the t emperature d is tr i­
bution in the can , and this was ob tained from a computer program based
on uns t eady- s ta t e heat trans fer theory .
 2

A method to determine the kine t ic parame t ers was developed working

from the processing t ime and temperature, and from the ini t ial and f inal
quali t ies, which were measured . This involved a computer program con­
structed for t emperature distribut ion and quality retent ion pred ict ion .

The kinetic parameters for ascorb ic acid and riboflavin were also
determined by a s t eady-state procedure where food was heated in a small
tube i n which ins tantaneous heat ing and cooling could be assumed . These
kine tic parameters were compared wi th the ones ob tained from the uns teady-
s tate procedure to tes t the f easibility and accuracy of the computer
model for the can .
 3

2. LITERATURE REVIEW

2. 1 INTRODUCTION

Canning, as a me thod of food preservation, has its origin in the

work of Nicholas Appert ( 1 750- 1 84 1 ) who was the first to use heat as a
means of preserving food in hermet ically sealed containers . Ini tially
boiling water baths were used as heating me d ium but, somet ime before
1 8 30, the autoc lave was introduced as a means o f cooking canned foods
under pres sure . Fur ther developments in processing equipment came with
the introduct ion of ag itating cookers and cont inuous s terilisers which
helped to reduce processing t ime . The f irs t spiral continuous cooker
was patented in 1 899 . In recent years, there have been the introduc t ion of
hyd ros tatic pressure cookers ( 1 9 36 ) , h igh speed spinning cookers ( 1 9 5 2 ) ,
f lame s terilisation ( 1 957 ) , high velocity air s terilisation ( 19 7 4 ) , and
asep tic canning ( 1 9 38) . Th� aim of all these changes was to shorten
the process ing t ime and so reduce the quali ty changes during the heat
process ing . The value of high temperature short-time s terilisation
lies in exploi t ing the princ iple that h igher temperatures have less
effect on quality in propor tion to the le thal effects than lower temper­
a tures . However, it has been found that the high temperature short
time proces ses are no t always beneficial in retaining the qua l i ty of
canned f ood (Te ixeira et al, 1 9 69 ; Lund, 1 9 7 7 ) .

Al though the canning process was int:;:-oduced i.n 1 800 and there have
been many developments, very lit tle is known on the optimisation of
thermal process ing for maximum quality re tent ion . There is a lack o f
kinetic parame ters showing the rate of quality des truc tion and the e f f e c t
of temperature o n the rate ( Lund, 1 9 7 7 ) .

This chap ter s tudies the quanti tative e s t ima t ion methods of the
changes in food and reviews the l iterature on the kine tics of food
quality changes during heat process ing .
 4

2.2 KINETIC THEORY OF THE CHANGES IN FOOD DURING HEAT PROCE S S ING

There are several types of changes occurring in heat processing -

destruc tion of micro-organisms , enzymes , nu trients and changes in
quali ty fac tors such as flavour , colour , texture . Wi th micro-organisms
and enzymes , the obj e c t ive of the hea t processing generally is inacti­
vat ion , whereas with nutrients and o ther quali ty a t tributes , the obj ec tive
is maximum re tention . There are many fac tors af fecting the ex tent of
these changes . Lund ( 1 9 75a) reviewed the f ac tors affecting the thermal
resistance of micro-organisms . Whi taker ( 1 9 7 2) d iscussed the dependence
of enzyme stab il i ty on many fac tors . Harris. and van Loesecke ( 1960)
reviewed the effect of heat processing on nu trients . O ther chemical
changes - browning reac tion , hydrolysis , oxidation-reduct ion reac t ions
also occ�r and these may change food qual i t ies e . g . colour and f lavour
changed by the browning react ion ( Tannenbaum , 1 9 76b) . To follow the
effect of heat on the food components including micro - organisms , two
types o f informa tion are needed ; ( 1 ) the kine tic reaction rate o f
destruc t ion and ( 2 ) the dependence o f the rate constant o n temperature .

--

2.2. 1 Theory of Kine tic React ion Rate

According to the law of mass ac tion , the veloci ty of reac tion at

a given temperature is proport ional to the produ c t of concentrations o f
the reac t ing subs tances . The rate o f the disappearance of reactant ,
A, can be

a b
-kc c (2. 1)
A B

where dc /dt is the rate of disappearance of reac tant , A

A
c ,c . c• • are the concentrat ions of reac tant A , B , • . • N
A B N
k is the reac t ion rate constant
t is time .

The order o f the reac tion i s def ined as the sum o f the powers to
wh ich the concentration of all reac tants are raised , this can be a
frac t ional value or an interger .
 5

Consider ing the destruct ion of nutrients or a specified food quality ,

the concentrations of water , oxygen , acid , alkali and reducing sugar are
of ten impor tant , as are the concentra tions of me tal catalys ts and enzymes .
However , the most impor tant fac tor is the concen trat ion of the reac ting
substance c . The destruc tion of nu tr ient or quality , A , at a given
A
temperature is

( 2 . 2)

where c is the concen trat ion of the nu trient or quali ty , A

A
n is the order of the reac tion .

This equat ion can be separated and on integration gives:

-kt where n 1 ( 2 . 3)

(n- 1 ) kt where n # 1
1-n
and c ( 2 . 4)
A

where c is the concentra tion of A at zero time

0
A
C is the concentra tion of A at time t .
A

The order , n , canno t be found explici tly f rom the above equat ions
so a trial-and-error solut ion must be used . Th is is no t d i f f icul t as
diff erent values o f n can be used in the equation to find the order , n ,
which most closely exp lains the experimental results .

I f the react ion o f nu trient or quality A des truct ion is a first

order reac tion , it will be described by equation (2.3). The plot of
the logari thms of the reac tion against time yields a straight line wi th
slope "-k " . So the reac tion rate constant at a given tempera ture can
be de termined .
 6

In a second order reac tion , the destruction of A can be described

as :

kt ( 2 . 5)

That is , the plot of 1 / c agains t time wil l give a straigh t line

A
wi th the slope k and the intercep t 1 / c .
A
0

For zero reac tion rate , the change in concentration of the reac tant
A is no t dependent on the concentra t i on , a p ' l ot of concentration versus
t ime will y ield a straight l ine of slope " -k " as c - c = kt . However ,
A A
usually react ions are o f zero order only a t high concent � ations of reac­
tant . When the concentration is lowered the reac t ion rate becomes con-
centration dependent , tha t is the order o f reac t ion r ises from zero
(Garret� 1 9 59� The order of ascorbi c acid des truct ion was found to
follow a zero order at high ini t ial concentration and then the order
changed to f irst order where concentration of ascorbi c acid was lower .

For micro-organisms , the thermal destruc t ion generally follows

f irst order kinetics , the t ime required for the survivor curve to trans­
verse one log cycle corresponds to a 90% reduction in the number o f
survivors ( Lund , . 1 9 7 5a) . The " decimal redu c tion t ime " o r D value , which
is the t ime required to reduce the popula tion by 90% , can also be used
to charac terize the reac tion rate constant of micro-organism destruct ion .
The relationships.b etween k and D can be expressed as :

2 . 303
D ( 2 . 6)
k

2.2.2 Temperature Dependence of the Reac t ion Ra te

The effect of tempera ture on the react ion rate has long been known
and the temperature - dependent term o f a rate equation can be wri t ten
in many forms accord ing to var ious theories, The f irst quan t i t a t ive
formulat ion of the dependence of react ion rates on temperature was given
by Arrhenius ( 1889) and this is still extensively used as :
 7

-Ea/RT
k Ae ( 2 . 7)

where A is the f requency factor

Ea is the activat ion energy

R is the gas constant
T is an absolute temperatur e .

This equa t ion is found to f i t many of the available experimental

kinetic da ta (Aib a e t a l , 1 9 65 ) . Taking lo.garithms of the above
equat ion gives :

Ea
ln k ln A -­ ( 2 . 8)
RT

The plot o f ln k against 1 /T yields a straight l ine with slope

equal to -Ea/R . The influence of temp erature on k is then expressed
in terms of Ea , a c t ivat ion energy .

For micro-organisms , the thermal dea th t ime (TDT) method f or

descr ib ing the tempera ture dependence of the destruct ion rate was
introduced by Bigelow ( 1 9 2 1 ) . The slope o f the plot of log ( TDT)
against temperature , - 1 / z , is used to charac terize the dependence of
the reac t ion ra te constant on temperature . In 1 9 5 7 , Ball and Olson
pointed out tha t the use of " z " is equivalent to the use of the Q
10
°
concept which is the rate quot ient for a temperature interval of 10 C .
S ince the use o f thermal death t ime was adapted to the decimal reduc­
tion t ime ( S t umbo , 1 9 48a) , the log D ag ainst l inear tempera ture , has
remained as a basis for process calculat ion and is still used to explain
the effect of tempera ture on the dest ruc t ion ra te in term of "z" .

Over wide temperature ranges , Gillespy ( 1 948) as wel l as Pflug and

Esselen ( 1 953) repor ted that the plot of log D against the rec iprocal
o f absolute temp erature was more nearly l inear . This is the form of the
 8

relationship predic ted by the Arrhenius equation . Gillespy ( 1 948) also

pointed out that over small ranges of temperature , the linear plot gave
a good approximation to the Arrhenius plo t . He also gave the relation­
ship between Ea and z as :

at a given temperature , T

z = (2 . 9)

over a range of temperature , T to T

1 2

z = ( 2 . 10)

Aiba et al ( 1 965) dis cussed the types o f relationships between

reac tion rate and temperature , and included Erying ' s theory of
absolute reac tion rate with the Q (or z ) approach and the Arrhenius
10
equation . According to Eyring:

-ilH*fRT ilS*/R
gTe e (2 . 1 1)

where ilH* is the heat of reaction of ac tivation

ilS* is the entropy change of activa tion
g is a factor including Planck ' s and Bol tzmann ' s cons tants
T is absolu te temperature .

The Arrhenius and Eyring theories were f ound to be no t signi­

ficantly dif ferent . (or z )
When used to extrapolate da ta , the Q
10
basis of calculation gave values of D significant ly less than the o ther
theories . The Arrhenius equation also seemed to be applicable over a
broader temperature range . Aiba et a l stated that where an activation energy
-1
was less than 1 2 6 kJ mole , the Arrhenius equation more accurately
described the temperature dependence over a wide temperature range than
the more corrnno nly used TDT·. equa tion . But where an act ivation energy was
-1
higher than 126 kJ mole bo th equations were comparable . Another
advan tage of the Arrhenius equation over the TDT equation was that it
could be extrapolated safely while the " z " equation is known to become
non-linear at high temperatures (Hayakawa , 1 9 7 8 ) .
 9

The TDT equation was f ound to be easier to apply in industry

because of its simplicity (Hayawaka , 1 9 7 8 ) ; the Arrhenius equation
was a more complicated computation . He also s tated that the Ea value
is more s trongly inf luenced by errors in k values than the s lope o f
z.

There have been a number of other variations of the rate o f reac tion
versus temperature e quations . Moore ( 1 95 7 ) discus sed some of these
equations and stated that it was worthwhile making a correction of
ac tivation energy by E = Ea + �RT . Fennema ( 1 9 7 5 ) de scribed the t emper­
a ture dependence of the des truction rate , k � by an exponential func tion
for enzymes and micro-organisms:

k exp (a T ) ( 2 . 1 2)
i,o i

where k. is a value o f k when the absolute t emperature , T , is zero

1,0 i
T is absolute temperature
a. is a cons tant .
1

For a range o f t emperature , equation ( 2 . 1 2) was used for proces s

calculation (Thij s sen e t al , 1 9 7 8 ) .

k. k exp ( a (Ti - Tr) ) ( 2 . 1 3)

1 i , Tr i

where k is - a value o f k. at reference temperature , Tr .

i , Tr 1

These e quations , ( 2 . 1 1 ) and ( 2 . 1 2 ) , are jus t ano ther way o f expressing

the Q concep t .
10

2.2.3 Effect o f Other Variables on the Reaction Rate

Besid es depending on the temp eratur e , the rates o f the reaction are
also af f ec ted by o ther variabl es , namely , pH , wat er ac t ivity , concentration
of oxygen and concentration o f minor components such as t race metals and
enzymes (Labuza , 1 9 7 2 ; Wanninger , 1 9 7 2 ) . Wanninger ( 19 7 2 ) postulated a
mathemat ical model f or the e f f ec t of moisture content on the rate of
r eactio n . Lee e t al ( 1 9 7 7 ) used the l eas t squares technique in e s t ab lishing
 10

an equation showing the effect o f p H and mois ture con tent on the kine tic
reac tion rate of ascorbic acid in tomato juice .

2.3 QUANTITATIVE ESTIMATION OF THE CHANGES IN FOOD DURING HEAT PROCESS ING

The changes in food during heat processing can be expressed quanti­

tatively by kine tic parame ters . To determine these parameters , the
initial concentration of reactant e . g . nu trients , quality fac tors , the
c oncentration of reac tant af ter certain heating time , and the tempera ture
of heating either by measurement or calculation mus t be known .

2.3.1 Analysis of Concen tra tion

As the accuracy of the kine tic parameters determined depends on the

accuracy of the concentration measu rement , reliable analytical t echniques
f or the sys tem under s tudy mus t be used . Any assumptions made should be
verified experimentally (Hill and Grieger-Block , 1 980) . Benson ( 1 960)
has presented a useful table 'vhich summarizes the errors in calculated
rate cons tants caused by analy tical errors for orders of reac tion from
zero to four . Ins pec tion of the table illus trates the dilemma the
kine ticis t faces in planning experiments (Hill and Grieger-Block , 1 980) .

2.3.2 Determination of Temperature Dis tribution

To d e termine the kinetic model f or des truction of food components

during heat processing, two procedures can be used : a s t eady-s tate
procedure where thermal death time cans or tubes are commonly used and
an uns teady-s tate procedure where f ood is heated in any container
(Lenz and Lund, 1 9 80 ) . Theore tically , the heating and cooling to and
from the desired temperature should be instantaneous so tha t no signi­
ficant des truc tion occurs during the coming-up and coming - down period s
bu t this is practically impossible . The problem of thermal lag in the
s t eady-s tate has been tackled in dif feren t ways . In uns teady-s tate
procedure , the temperature o f food in a container ( usually a can)
changes wi th time and position . The temperature dis tribution in the
container at any given process time mus t be determined as the calcu­
la tion of the kine tic parame ters is based on an average re tention con­
centration . To determine the temperature dis tribution , two me thods can
 11

be used - experimental measurement and theoretical predic tion .

2.3.2.1 Determination of Thermal Lag in S teady-State Heating

Firs tly , the thermal lag periods can be ignored if they are small
and considered insignifican t to the processing effect or they can be
reduced by methods such as reducing the sample size (Lys ter , 1 9 7 0 ;
Mul ley e t al , 1 9 7 5 ) , preheating the heating medium (Paulus et al , 1 9 7 8 ;
Saguy e t al , 1 9 7 8a) , and / or using relatively long heating periods
(Eagerman and Rouse , 1 9 7 6 ; Navankasat tusas , 1 9 7 8 ) where the thermal lag
period effect can be considered negligible • .

Procedures for correcting thermal lag have been proposed and fell
into three general categories - graphical method , numerical me thod and
experimental manipulation . Farkas and Goldblith ( 1 9 6 2 ) studying the
kinetics of lipoxidase inactivation using thin walled , melting poin t )
capillary tubes , estimated the thermal lag by extrapolating the first
order reac tion rate o f destruction curve . Saper and Nickerson ( 1 9 6 2 )
and Gup te e t al ( 1 964) also used a graphical method .

By the numerical method , the thermal lag was de termined by two

dif ferent methods. Firs tly, a " z " value or a rate of reaction was
assumed and used for calculating an equivalent time at a specified
temperature ( Sognefest and Benjamin , 1 944 ; Tan and Francis , 1 96 2 ) .
Secondly , iterative procedures were used (Resende e t al , 1 969 ;
Hayakawa e t al , 1 9 7 7 ) . This me thod was based on the assumption that
the rate o f reac tion was firs t order . A " z " value was assumed , equiva­
lent heating times calculated and graphed with the measured quality to
det ermine a new "z" value . I f there was a significant dif ference
be tween the calcula ted and the assumed " z " value , calculation were
repeated using the de termined "z" value .

In the experimental manipulation me thod , the coming-up time is

determined and then ac tual timing s tarted from this period . The method
was used by Felicio t ti and Esselen ( 1 957 ) , Hamm and Lund ( 1 9 7 8 ) .
 12

2.3.2.2 Experimental Heat Pene tra tion Measurement

The measurement of heat penetration in a can was fir s t done by

Presc o t t and Underwood ( 1 8 9 7 ) using a maximum recording thermome ter .
Because the metal mounting tube of the thermome�er , or the s tem of
the thermometer itself , if no mounting tube was used , could conduc t
hea t to the bulb and thus dis tort the temperature record , this me thod
was criticised by Bigelow et al ( 1 920) . The use o f a chemical thermo­
me ter firs t described by Bit ting ( 1 9 1 2 ) was also criticised by Bigelow
et al ( 1 9 20) for the same reason . However a mercury in s teel recording
thermome ter described by Bigelow et al ( 1 9 2�) also had the same heat
conduc tion errors .

The use of thermocouples in cans was fir s t described by Bit ting and
Bit ting ( 1 9 1 7 ) . The thermocouple probe in glass was described and used
extensively by Thompson ( 1 9 1 9 ) and Bigelow et al ( 1 9 20) . In 1 9 2 7 , Ford
and Osborne s tated that a thin wall copper tube used as par t of the
probe c ould probably be subjec ted to greater conduc tion errors in con­
duc tion heated food than the g lass thermome ter . Various improvements
of a mechanical nature have been made on heat pene tration thermocoup le
probes ( Benjamin , 1 9 38 ; Ecklund , 1 9 49 ) . Conduc tion errors had been
shown to be neg ligible excep t for small cans of conduc tion heated produc t ;
the correlation factor for this error has been proposed also by Ball
( 1 9 2 3) and Ecklund ( 1 949 , 1956) . In 1 9 6 5 , Board introduced the me thod
of mounting thermocouples in cans without the use of suppor t . The two
wires pass through diame trically opposed holes in the can walls or
through holes in the can ends and are sealed wi th a heat resis tant epoxy
resin adhesive . This method is probably the leas t suscep tible to con­
duc tion errors .

As the can mus t be fit ted with thermocouples bef ore filling by this
me thod • Board and S tekly ( 1 9 7 8 ) designed a simple new thermocouple
assembly which allowed the hot junc tion to be placed at the desired
measuring point af ter the can was filled and closed .
 13

Sensitive galvanometers have been used t o indicate the potential

produced by the thermocoup le junc tion ( Thompson , 1 9 1 9 ) . Potentiome tric
devices ( zero current at balance) had become to be preferred later on
as the voltage indicated was independent of the resis tance of the lead
wires ( Ecklund , 1 9 4 9 ) . Automatic or manual cold j unc tion compensation
have both been used , as well as ice-f lask reference j unc tions . Various
types of recording po tentiome ter have been introduced and used ( C lifcorn
et al , 1950 ; Hoare and Warrington , 1 9 6 3) .

There are o ther errors in using thermocoup les caused by the break­
down of insulation at a point dis tant from·the j unction or/ and the
breakdown of insulation or earthing of thermocouple leads outside the
can . These breakdowns could cause d ropping in poten tial dif ference by
the current flowing be tween the points o f contact of the wire and
electrotytes which could be food produc ts , cooling water etc . These
effects have been discuss ed by Midd lehurs t e t al ( 19 6 4 ) who demons trated
that very high emf ( up to 4mV) could be genera ted in unfavorable
condition .

Even though the me thods of measurement have been developed f rom

the use of thermome ters to thermocoup les where more points in the can
can be followed by con tinuous recording poten tiome tric devices , there
is a limitation on the number of points that can be followed and on
the time interval of recorded temperat ure . Therefore , a theoretical
determination is needed for calcula ting temperature dis tribution in
the can .

2.3.2.3 Theoretical De termination

A number of a t temp ts to use basic heat transfer theory in the

calcula tion of heat pene tration have been made ( Olson and S chul t z ,
194 2 ; Hicks , 19 5 1 ; Gillespy , 1 9 5 3; Ball and Olson , 1 9 5 7 ; Board e t al ,
1960 ; Charm, 196 1 ; S tumbo , 1 9 6 4 ) . Various forms o f the heat conduc­
tion equations ( Thomp son , 19 19 ; Cars law and Jaeger , 1959) were used
for determining the temperature of food during heating and cooling .
Thompson ( 19 1 9 ) gave the fundamental equation describing heat pene tra­
tion in uniform conduc tion heating finite cylinders and used these
formulae to calculate values of thermal dif fusivity from various
 14

experimental heating curves . For prac tical purposes , simplifications

were made in the equation by neglec ting terms which were impor tan t only
at the beginning of heating . The predic tion of the cooling curve was
not as satisfac tory as predic tion of the heating curve . Hicks ( 19 5 1 )
proposed the method of predic tion of heating and cooling curves based
on the heat trans fer equa tions (Cars law and Jaege r , 1959) using only
the firs t term in the series for the heating phase and a number of
terms in series for cooling phase . Gillespy ( 1 9 5 3 ) had also out lined
a me thod of calculation for centre temperature in conduc tion heating
can based on the fundamental heat conduc tion equa tion of Carslaw and
Jaeger and Duhamel ' s theorem . Comp lex heating and cooling cycles could
be calculated .

As the technology of the computer has been improved and become

more advanced , computer programs have been writ ten and used for
calculating the temperature dis tribution in the cans during conduc tion
heating based on the heat trans fer equations (Carslaw and Jaeger , 1 9 59 )
by many workers (Hawakawa and Bal l , 1969 ; Flambert and Deltour , 1 9 7 2 b ;
Lenz and Lund , 1 9 7 7a) . The finite dif ference method has been also used
for solving the h eat transfer equations using the computer program by
Teixeira e t al ( 19 6 9 ) and Flambert and Del tour ( 19 7 2b) . The later
technique could also be app lied where the thermal proper ties of the
foods were changed with temperature .

2.3.3 Calculation of Kine tic Parame ters

In a s t eady-s tate procedure , the raw data of concentration of the

desired fac tor versus heating conditions ( tempera ture and time) c an be
analysed by various methods reviewed by Hill and Grieger-Block ( 1 980) .
The data a t each temperature are compared to a mode l of the kinetics
( zero- , firs t- , or s econd-order model) ; a rate cons tan t can be calcu­
lated for that heating temperature when the data suf ficient ly match the
model (Lenz and Lund , 1980) . Then the temperature dependence of the
rate can be determined .
 15

In an uns teady-s tate procedure , the calculation o f kine tics is

based on mass average predic tion . This me thod firs t ly developed for
estimating mass average s terilizing values . Gillespy ( 19 5 1 ) used only
the firs t term in the series of analytical formulae for heat conduc tion
in a cylinder in es timating the temperature dis tribution and developing
parame tric tables for determining mass average s terilizing values .
S t umbo ( 1 9 5 3 ) developed a mathematical procedure to evaluate the capacity
o f a heat process to reduce the number o f bac teria in a con tainer o f
food by considering the heat treatments received by a l l points through­
out the container rather than that received at any one poin t . Ball and
Olson ( 19 5 7 ) developed a similar me thod based on S tumbo ' s original
work , which they applied to the evaluation of thiamine re tentions in
c onduc tion-heated food s . Hicks ( 195 1 ) used the fundamental heat c on­
duction equation , exponential integral func tions and graphical integra­
tions to evalua te survival probabilities for the whole container . He
introduced the very useful concep t o f an equivalent volume , which , when
mul tiplied by the residual number of spores p er unit volume , at the
centre point would give the to tal number of viable spores to be expec ted
in the c ontainer . In 1 9 5 2 , he had also reviewed the similarity and the
imp lication o f the me thods of Stumbo ( 1948a , 1 949a) , Gillespy ( 19 5 1 )
and Hicks ( 19 5 1 ) .

Hayakawa and Timbers ( 19 6 7 ) observed that S tumbo ' s formula did no t

give reliable answers when it was applied to the z and D values o f organ­
o lep tic or nutritional fac tors which are considerably greater than those
.

o f micro-organisms . In 1 9 7 1 , Jen e t al removed this limitation by

deriving another formula which also does not require comp licated calcu­
lations for evaluating mass average s terilizing values . This formula
is based on and similar to S tumbo ( 19 5 3) . Hayakawa ( 19 6 9 ) used dimen­
sional analysis and f ound that six dimensionless groups , which are not
included in both S tumbo and Jen ' s formula , are required for the unique
mathematical es timation of a mass average s terilizing values . The
reliability of the f ormula derived by Jen e t al should be inves tigated
in the future, s tated Hayakawa ( 1 9 7 7 ) . He also derived new tables o f
dimensionless groups for calculating the lethality o r quali ty reten tion
of p rocessed foods . In 1 9 7 7 , Downes and Hayakawa deve loped the table
based on a new parame ter , Ks , developed by Hayakawa using the combina-
.tion of the major theore tical advances of S tumbo ( 1 9 7 3) , Jen e t a l
 16

( 19 7 1 ) and Hayakawa ( 19 70) for mass average s terilizing value calcu­

lation .

Recent advances in computer technology have als o led to computer­

ization o f ther�l process calculations . Mans on and Zahradnik ' s ( 19 6 7 )
program was based on S tumbo ' s method . Hayakawa and Timbers ( 19 6 7 )
calculated the mass average s terilizing value o f a thermal process based
on a fir s t term approximation o f the Fourier-Bessel series for heat
conduction in a finite cy linder . Hayakawa ( 19 6 9 ) applied his me thod
to the evaluation of thiamine retention . Teixeira et al ( 1969 ) deve­
loped a numerical s olution of a finite difference approximation app lied
to both lethality and thiamine retention calculation . Flambert and
Del tour ( 19 72a) used the same method as Teixeira ( 19 6 7 ) with 10 incre­
ments on the radius and on the half heigh t and 0 . 1 2 5 minute time incre­
ments with the firs t order reac tion rate as D and z and calculated the
mean temperature and the mean residual concentration of the entire
process . Manson e t al ( 19 70 ) used the s ame me thod as Teixeira app lied
to a rectangular can of solid food . Sasseen ' s program ( 19 6 9 ) is for
es timating s terilizing values by Ball ' s me thod ( 19 2 3) . Lenz and Lund
( 19 7 7 ) proposed a Lethality - Fourier number me thod for process eval­
uation , which is also used for predic ting the quality re tention , based
on the theore tical heat trans fer equa tion of the analytical method in
combination with the kinetic reac tion rate cons tants , k and Ea . This
method was shown to be as accurate as o ther available me thods for
pre�icting the mass average re tention o f thermally vulnerable components
in conduc tion he�ting of a food . Thijss en et al ( 19 78) proposed a short­
cut me thod for the calcula tion o f s terili sation conditions yielding
op timum q ua lity retention for conduc tion- type heating based on the use
o f the computer in analyzing the temperature dis tribution in the can
and the overall quality retention .
 17

2.4 CHANGES OF FOOD DURING HEAT PROCES S ING

There are a number of s tudies on the change of nutrients during

heat process ing reviewed in Bender ( 1 966) , Cain ( 1 967 ) , Schroeder
( 19 7 1 ) , Harri s and Karmas ( 1 9 7 3 ) , Pries t ley ( 1 9 7 9 ) . Unfor tunately ,
the majori ty o f the data is the result o f end point analysis , that is ,
the measurement o f concentration at the beginning and a t the conclusion
o f a g iven process or s torage period . These data were generally no t
subjec ted to kine t ic analys is . However , Lund ( 19 7 5 ) and Chi t taporn
( 19 7 7 ) have reviewed the kine tic parame ters for various nutrients by
ei ther collection or calculation of the exi£ting data . Lund ( 19 7 5 )
had also inc luded s ome kine tic parame ters for enzyma tic ina c t ivation ,
chlorophyll destruc t ion , browning reaction , colour , texture and f lavour .
Inspec tion o f Lund ' s table shows tha t only one determination of " k "
and "Ea" was found for bo th ascorbic acid and ribof lavin . Thi amine
was the only vitamin that seemed to be well charac teri zed . Although
there were a number of "k" and "Ea" reported for chlorophyll des truc t ion
and browning reac t ion , only one "k" and "Ea" was reported for colour .
However , there are a number o f s tudies on the kine t ics o f the nutri tional
and qua l i ty changes of food dur ing processing af ter 1 9 7 5 - Hamn and
Lund ( 19 7 8) on pantothenic acid , Navankasat tusas ( 19 78) on vitamin B6 ,
Saguy e t al ( 19 78a) on betanin and be talamic acid , Chen and Cooper ( 19 79 )
and Paine-Wilson and Chen ( 19 79 ) on folacin , Slater e t a l ( 19 79 ) on
vi tamin A and Wid icus e t al ( 1 9 80) on a- tocophero l . There were , also ,
a number of s tud ies on ascorbic acid , but mos t of them were on dehydrated
foods . The kine t i c reac tion rate and the ac t ivat ion energy were found
to be in a wide range ( sec tion 2 . 3 . 1 ) . For r iboflavin , the kine tic
s tudies were mos t ly on the pho todegradat ion . Only one s t udy,of Ohlsson
( 19 80 ) ,was found for the changes in s ensory qua l i ty on heating .

Therefore , because of the lack of kine t i c d a t a , ascorbic acid and

r ibof lavin were chosen in this s tudy . Colour and viscosi ty were the
two sensory quali ties chosen as f lavour analys is involved subje c t ive
measurement which was d i f f icult to measure accurately . The details o f
the kine tic s tudies o n thes e chosen qua l i t ies were reviewed .
 18

2.4. 1 Ascorbic Acid

Ascorbic acid i s known as one o f the mos t heat labile vitamins

as reviewed up to 1 960 by Harris and Von Loesecke and thereaf ter by
Lang in 1 9 7 0 and de Rit ter in 1 9 7 6 . The destruction of ascorbic acid
in food can fol low either an aerobic oxidat ion react ion o r an anaerobic
pathway (Tannenbaum , 1 9 7 6a) . Both of these react ions have common inter­
med iates and are hardly d i s t inguishable . The specific pathways and the
degradat ion rate are determined by factors such as oxidation-reduct ion
po tential o f the system , temperature , oxygen , pH , mois ture content ,
trace metals especially copper and iron , enzymes , sugar concentration
and amino acid . (Joslyn , 1 949a , b ; Kurata and S akurai , 1 9 6 7a , b , c ;
Bauernfeind and Pinkert , 1 9 7 0 ; Huelin e t al , 1 9 7 1 ) . Iron was found to
be effective to a lesser extent than copper (Bauernfeind and Pinkert ,
1 9 7 0) . Khan and Mar tell ( 1 9 6 7 ) found tha t in the pH range o f 2-5 , the
des truct ion of ascorbic acid increased with increas ing pH and the
decompos i t ion rate was s trongly accelerated by temperature . The rate of
ascorbic acid destruct ion was found to reach a maximum at the pH near
to pKa ( Lee et al , 1 9 7 7 ) . I t was also found that alcohol and sugar might
be e i ther pro- or an ti-oxidant depend ing on their concentra tion and on
the presence of natural subs tances in food such as anthocyanin or o ther
phenolic compound . Huelin ( 1 9 5 3 ) studying the anaerobic decompo s i t ion
of ascorbic acid found that the destruct ion rate was accelerated by
both sucrose and - fructose .

Mo is ture content and wa ter activity are impor tant factors espe cially
in dried produc ts and they were extensively s tudied ( Gooding , 1 9 6 2 ;
Karel and Nickerson , 1 964 ; Jensen , 1 9 6 7 ; Voj novich and Pfeifer , 1 9 7 0 ;
Lee and Labuza , 1 9 7 5 ; Kirk et al , 1 9 7 7 ; Reimer and Karel , 1 9 7 7 ; Dennison
and Kirk , 1 9 7 8 ; Laing et al , 1 9 7 8 ; and Papanicolaou and Sauvageot , 1 9 7 9 ) .
The des truct ion rate was found to increase with increase in to tal moisture
content and water a c t ivity . This was explained as the result o f dilut ion
of the aqueous phase causing a decrease in viscosi ty which led to increase
in mobility (Lee and Labuza , 1 9 7 5 ) . The a c t ivation energy was found to
increase with mo is ture content (Jensen , 1 9 6 7 ; Voj novich and Pfeifer ,
1 9 70) , but Lee and Labuza ( 1 9 7 5 ) found that there was no effect o f water
act ivity on the a c t ivat ion energy . The reason for this var iat ion was
stated to be unknown by Kirk et al ( 1 9 7 7 ) .
 19

Oxygen or air , as shown by Clifcorn ( 1948) , Mapson ( 1 9 5 6 ) , Bender

( 19 58a) and Chiches ter ( 1 9 7 3) , did effect the des truc tion rate of
ascorbic acid in canned foods . The effect of oxygen on the rate of
ascorbic acid des truc tion in liquid foods was also repor ted ( Joslyn
and Miller , 1 9 49a , b ; Bayes , 1950 ; Khan and Mar tell , 1 96 7 ; Ford et a l ,
1969 ) . In a dehyd rated food system, Kirk et al ( 1 9 7 7 ) found tha t the
rate of ascorbic acid des truc tion was drama tically increased with the
presence of oxygen , as did Dennison and Kirk ( 1 9 7 8 ) .

The anaerobic mechanism o f ascorbic acid des truction in a canned

food was repor ted by Huelin ( 1 9 5 3) and Huelin e t al ( t9 6 7 ) . In 1 9 7 8 ,
Reimer and Karel found that as corbic acid des truc tion in dehydra ted
tomato j uice was largely an anaerobic reac tion . Papanicolaou and
Sauvageo t ( 1 9 79 ) als o found that vi tamin C des truc tion differed j us t
a little be tween samp les o f free ze-dried orange j uice s t ored under
vacuum , nitrogen or air . Therefore , it is likely that bo th aerobic
and anaerobic mechanisms could be involved depending on o ther factors
such as pH and compositional fac tors .

In heat processing , especially , in the canning proces s , the re ten­

tion of ascorbic acid has been s tudied by many workers on various food
products ( Guerrant et a l , 1 94 7 ; Lamb et al , 1 94 7 ; Wagner e t . al , 1 94 7 ;
Cameron et a l , 1 94 9 ; Wa t t and Merrill , 1 9 6 3 ; Marchesini et al , 1 9 7 5 ;
Lee e. c al , 1 9 7 6 ) . The percentage o f as corbic acid re tention varied with
types of prod uc ts as the processing conditions were dif feren t , the reten­
tion was found to vary from 26-90% . Unfor tunately the kine tic parame ters
canno t be determined as the data available were inadequate . The orders
reported in the li tera ture of the des truc tion reac tion of ascorbic acid
were conflic ting . I t was reported as ei ther zero , firs t or pseudo-
firs t order reac tion ( Barron et a l , 1 9 36 ; Pe terson and Wal ton , 1 9 4 3 ;
Weissberger and Thomas , 1 943) . Aerobic destruction o f ascorbic acid was
confirmed to fo llow firs t order kinetics ( Freed e t al , 1949 ; Joslyn
and Miller , 1 949a) . Anaerobic des truction of ascorbic acid was also
found to follow firs t order reac tion kine tics (Huelin , 1 9 5 3 ) . In heating
processes , the des truc tion of as corbic acid was found to be des cribed
by fir s t order kine tics (Paulus et al , 1 9 7 8 ; Saguy et al , 19 7 8b ; Lathrop
and Leung , 1980 ) . The fir s t order kine tics was also found on the
s torage of food produc ts - Voj novich and Pfeifer ( 19 70) in wheat f lour ,
corn s oya milk , infant cereal ; Lee e t al ( 1 9 7 7 ) , Nagy and Smoot ( 19 7 7 )
 20

and Davidek et al ( 1 9 74 ) in frui t juices ; Lee and Labuza ( 19 7 5 ) , Kirk

et al ( 1 9 7 7 ) , Reimer and Karel ( 1 9 7 7 ) and Denni son and Kirk ( 1 9 7 8 ) in
intermed iate mois ture food . The data presented by Sistrunk and Cash ( 1 9 7 0 ) ,
Clydesdale et al ( 1 9 7 1 ) and Abrams ( 1 9 7 5 ) on the effect of heat on the
as corbic acid of food were ana lysed by this author and it was found that
mos t of them could be treated as a first order react ion .

On the other hand , Garre t t ( 1 956) s tudy ing the s tabi l i ty of ascorbic
acid in a pharmaceu t ical preparat ion concluded that ascorbic acid has
an initial pseudo-zero order reac tion which subsequent ly become pseudo­
f i r s t order reac tion . The deviation from f irs t order rate o f reac tion
of ascorbic acid was also f ound by Joslyn and Miller ( 1 949a) . S ingh
et al ( 1 9 7 6 ) found tha t under limited supp ly of oxygen , the degradation
of as corbic acid in infant formulae could be described as a second order
reac tion whereas Laing et al ( 1 9 7 8 ) concluded that the degradation ra te
of as corbic acid in intermed iate mois ture food followed a zero order
reac tion .

Lin and Agalloco ( 1 9 7 9 ) reviewed the effect of temperature , pH and

oxygen on the des truc t ion kine tics of ascorbic acid and s ta ted that the
order of react ion depended on bo th oxygen and initial concentration .

The react ion rate and the activation energy of ascorbic acid
des truc t ion , e i ther collec ted or calcula ted from the l iterature , are shown
in Table 2 . 1 . Assuming that the des truc t ion rate of ascorbic acid in
various foods was a f ir s t order reac tion , Chi t taporn ( 1 9 7 7 ) had pred ic ted
the reac t ion rate and the ac tiva tion energy us ing all data available
-4 - 1
before 1 9 7 7 and found that the react ion rate was 2 . 33 x 10 s at
0 -1
1 29 C and the activat ion energy was 88 . 2 kJ mole Subsequent t o 19 7 7 ,
•

more recent results have continued to show a wide variation , from 1 4 to

-1
1 7 2 kJ mole •
 21
TABLE . 2 . 1 Reaction Rate Constants and Ac tiva tion Energies for Ascorb ic Acid

Ac t iv a t i on
Reac t i o n R a t e Energ�
Re ference Produc t 1
1Q 4 S - 1
Cond i t ions
k X kJ mole _1
( k c a l mole )

° 108 ( 2 5 . 7 ) *
ilrenne r et al, Canned food H i �h t " 2l p e r a t u r e s torage 0 . 000 1 8 , 37 . 8 C
1948 2 1- 3 7 . 8 C , pH 4 . 35
°
Lamb e t al, 1951 Canned tomato j ui c e and S torage . . 2 1 -37 . 8°C 0 . 00022 , 37 . 8 C 8 1 ( 19 . 3 ) *
toma to pas t l.'

°
Hue l i n , 1953 Ascorb i c a c i d i n c i t r a te­ tempe r a t u r e 30 - 100 C , °
phosphate pH 2.2 0 . 00383, 100 °C 78( 1 8 . 6 ) *
b u f f e r s o l u t ion pH 6.0 0 . 0 3 167 , 100 C 96 ( 2 2 . 9 ) *

1956 ° 97(23 . 1)
Garret t , Liquid - mu l t ivi tamin f rom f i r s t order p l o t 0 . 00289 , 70 C
f rom pseudo-zero order
p lot - 9 6 ( 2 2 . 8)

Jensen , 1967 Seaweed Mo i s t ure 1 1 . 1 gH 0/ 100 g

2 - 32( 7 . 7)
s o l id
Mo i s t ure 1 7 . 6 gH 0 / 100 g
2 55 ( 1 3 . 1 )
solid -

Moi s t ure 33 . 3 gH 0 / 100 g

s o l id
2 - 1 27 ( 30 . 3)
°
Vojnovich and Flour tempe ra ture 26 - 4 5 C , °
P f e i fer , 1 9 70 wa t e r a c t i v i ty 0 . 65 0 . 00228 , 45 C 9 4 ( 22 . 3)
°
wa t e r a c t i v i ty 0 . 55 0 . 00022 , 45 C 6 7 ( 1 6 . 0)
°
water ac t i v i ty 0 . 25 0 . 00005 , 45 C 46 ( 1 1 . 0 )
°
B l aug and Ascorb ic acid in buffer temperature 60 - 85 C, °
Haj ra twa l a , 1972 s o l u t ion ( aerob i c o x i d a t ion) pH 5.6 0 . 0 1 500 , 85 C 76 ( 1 8 . 0 )

Labuza , 1972 General review - 37 - 1 89 ( 8 . 8- 4 5 . 0 )

° 59 ( 14 . 1 )
Davidek et al, Orange d r ink L-dchydroasco r b i c a c i d , 0 . 06 700 , 30 C
°
1974 . 4 - 30 C
° -
Ah rams 9 1975 Frozen Brussc l sprouts cook i ng temperature range 0 . 4 2 7 7 8-0 . 47083 , 100 C
°
Lee and Labuza , I n t e rmed i a t e moi s t ure model tempe ra ture 23 - 45 C ,
1975 food wa t e r a c t i v i ty 0 . 23 -0 . 84 - 70 - 95 ( 16 . 7-22 . 6 )
F l a umenbaum e t al C i t rus , s t rawb e r ry , toma t o 0 . 20000-0 . 88000 -
1977 j ui c e and paprika puree

°
0 . 5 -0 . 65
Kirk et al, 1977 For t i f i e d dehyd rated mode l temperature 10 - 37 C , °
sys tem wa ter a c t i v i t y 0 . 00 1 14 - 0 . 0 1822, 37 C 34 - 8 1 ( 8 . 0- 19 . 2)
Mul t i v i t am i n model sys tem temperature 10 - 37 C ,
°
wa t e r a c t i v i t y 0 . 1 - 0 . 6 5 0 . 00 1 14-0 . 009 8 1 , 3 7 C 48 - 84 ( 1 1 . 5 - 20 . 0 )
°
Lee e t al, 1977 Canned tomato j ui ce temperature 0 - 37 . 8 C , °
pH 4 . 06 0 . 00028 , 37 . 8 C 1 4 ( 3 . 3)
° 29 ( 6 . 9 )
·pH 6 . 90 0 . 00025 , 37 . 8 C
0
Nagy and Smoo t , Canned s i ng l e s t rength temperature 2 1 . 1 -4 8 . 9 C - 1 1 2 ( 26 . 7 )
0 - 53( 1 2 . 7 )
1977 orange j ui c e tempe ra ture 4 . 4- 2 1 . 1 C
°
Dennison and Dehydrated mod e l f ood system temperature range 10 - 37 C °
K i rk , 1978 wa t e r a c t i v i t y 0 . 10 0 . 00206 , 37 ° C 4 5 ( 10 . 7 )
w a t e r ac t i vi ty 0 . 40 0 . 00839 , 37 °C 6 7 ( 1 6 . 0)
wa t e r a c t i v i ty 0 . 65 0 . 0 1 39 7 , 37 C 77 ( 18 . 3)
°
Laing e t a l , I n terme d i a t e moi s t ure food temperature 6 1 - 105 C ,
1978 sys t em water activity 0 . 69 - 59 ( 14 . 0 ) *
wa t e r ac t iv i t y 0 . 80 - 7 1 ( 1 7 . 0) *
wa t e r a c t i v i t y 0 . 90 - 6 7 ( 16 . 0) •
° ° 30( 7 . 2)
Paulus et a l , S p i nach puree tempe ra ture 105 - 1 30 C 0 . 0768 1 , 1 30 C
1978
° . 103 ( 24 . 6)
Reimer and Kare l , Dehydrated toma to j ui c e water a c t i v i t y 0 . 00 0 . 00056 , 3 7 °C
1978 wa t e r a c t i v i t y 0.75 0 . 00006 , 37 C 68 ( 16 . 2)·
° °
Saguy e t a l , Grape f r u i t j ui c e temperature 60-96 C 0 . 2 1267 - 0 . 50 36 7 , 6 1 C 2 1 - 48(5 . 0 - 1 1 . 3)
1978
° ° 1 7 2 ( 4 1 ;0)
Lathrop and P e a s i n b ri n e i n TDT cans temperature 1 10 - 1 3 2 C 0 . 08333, 1 10 C
Leung . 1980
* C a lc u l a ted f rom t h e d a t a presented i n t h e r e f e rence
** Zero-orde r reac t ion was pred i c ted .
 22

2.4.2 Ribof lavin

Ribof lavin is comparative ly s table to heat but uns table to ligh t ,

especial ly in the visible spec trum (< 500 nm) . The sensi tivi ty to
light increases with temperature and pH (Harris and von Loesecke ,
1960) . I t is s table to oxygen and acid but uns table to alkaline
condition s ( Bender . 1966) .

Leaching is the main cause of riboflavin loss during food pro­

cessing since it is a water soluble vitamin . Re ten tion of 60% to
100% was found af ter blanching (Rein and Hutchings , 1 9 7 1 ; Barratt ,
19 7 3) . The e f fect of cooking on riboflavin re tention of various
kinds of meats were s tudied , 56-98% re ten tion was found by Griswold
et al ( 19 4 7 , 1949 ) , 7 4% re tention was found by Mcintire e t al
( 19 44) , 55-75% re tention was found by Noble ( 1 9 70) , whereas almos t
100% re tention was found by Engler and Bowers ( 19 76 ) . Ang e t al
( 19 75 ) reported that less than 10% loss of ribof lavin was found af ter
°
three hours holding at 8 2 C . Cain ( 19 6 7 ) s ta ted that dehydrated
bee f and sweet potatoes r.e tained all their riboflavin content . For
milk , heat treatment was found to have lit tle effect on riboflavin
(Ford e t al , 1969 ; Rolls and Por ter , 1 9 7 3) . However , los s can be
significan t if milk is exposed to sunlight ( Singh et al , 1 9 7 5 ;
Sat tar et al , 1 9 7 7 ) . The temperature was also found to have
an effect on riboflavin des truc tion rate .

In canning , dif ferent conclusions have been drawn . Hellendorn

et al ( 19 7 1 ) showed that in canned mea t and vege table dishes , s ter­
°
ilisation and s torage at 22 C for five days produced no significant
los ses in riboflavin . While Wat t and Merrill ( 19 6 3) repor ted that
the losses of riboflavin in canned vege tables could be as high as
70% (including loss in preprocessing) ; excep t tomatoes and tomato
juice that seemed to show be t ter riboflavin reten tion which may be
due to their higher acidi ty or higher ascorbic acid or less leaching
during their processing . The loss of 0 -30% c uring canning was also
repor ted by Guerrant e t a l ( 1946 ); Lamb e t al ( 1 9 4 7 ); Wagner e t al ( 1 9 4 7 ) ;
Cain ( 1 96 7 ). Burger and Wal ters ( 19 7 3) reported 6% loss for canned
chopped bee f , 12% loss for canned corned beef and 29% loss for pork
bacon .
 23

So it would appear that ribof lavin losses do occur on processing ,

inc luding canning . These losses , in the case o f we t t reatmen t , are
probably due to a combination of leaching , ligh t and thermal degrad­
ation .

Very l i t t le kine tic work had been done on riboflavin . S ingh

e t al ( 1 9 7 5 ) and Sat tar et al ( 1 9 7 7 ) had studied the l igh t
induced losses of riboflavin and concluded tha t the des truc tion
reaction was definitely first order in nature . Allen and Parks
( 19 7 9 ) also found that the pho todegrada tion of riboflavin in milk
exposed to f luores cent ligh t ( 2690 lux) could be des cribed by f i r s t
order reaction . The d a t a p resen ted b y Ang e t al ( 19 7 5) could no t
be f i t ted to a firs t order reac tion by the present author . Gil lespy
( 19 6 2 ) assumed first order reac tion and determined the activation
energy for ribof lavin des truction as 96 . 6 kJ mole
-1 -1
( 2 3 . 0 kcal mole ) .
Chit taporn ( 19 7 7 ) also assumed firs t order reaction and c alculated
the kine tic reaction rate from the data collec ted f rom the li terature ,
(Table 2 . 2) and found that activation energy determined from the
-1 -1
calculated "k" was 46 . 2 kJ mole ( 1 1 kcal mole ) . Singh e t al
( 19 7 5 ) found that the a c t ivation energy varied f rom 3 3 . 6 - 1 7 2 . 2 kJ
-1 1
mole ( 8- 4 1 kcal mo le- ) in thei r s tudy of milk depending on the
type of container as i t affected the amount of ligh t . From the lates t
data of Salunkhe e t al ( 19 78) and Kramer et al ( 19 7 7 ) , the f i r s t
order reac tion was assumed and the a c t iva tion energy was found to
-1 1
range from 4 3 . 3-6 3 . 4 kJ mole ( 10 . 3 - 1 5 . 1 kcal mole- ) depending on
-1
the f ood s t udied in Salunkhe et al and from 6 . 7-23 . 5 kJ mole
-
( 1 . 6-5 . 6 kcal �ole 1 ) for salisbury and bee f patties wi th the TVP in
Kramer e t al .

The variation in the kine tic reac t ion rate and the a c t ivation
energy reported may be d ue to the type o f food , the ini tial concen­
tration , the me thod of s tudy and the cond i t i ons being s tudied .
However , i t is obvious that the data on the effect o f heat are very
limi ted .
 24

TABLE 2 . 2 Reaction Rate Cons tants for Ribo flavin

4
X
Mois ture k 10
Temp .
Reference Type of Produc t Conten t o
c -1
% s

Singh e t a l , 1 9 7 5 Milk -
1.7 0 . 00 2 16
Singh e t al , 1 9 7 5 Milk - 4.4 0 . 00 2 4 3
Guerrant e t al , 1945 Canned toma to juice -
5.6 0 . 00003
Guerran t e t al , 1945 Canned green lima beans -
5.6 0 . 00003
Guerrant e t al , 1945 Canned whole kerne l· corn -
5.6 0 . 00004
Singh e t al , 19 75 S torage o f milk - 10 . 0 0 . 0 0 306
Guerrant e t al , 1 9 4 5 Canned toma to juice - 29 . 4 0 . 00006
Guerrant e t al , 1 9 4 5 Canned green lima beans - 29 . 4 0 . 00006
Guerrant e t al , 1945 Canned whole kerne l corn - 29 . 4 0 . 00005
Guerrant e t al , 1945 Canned tomato juice -
43 . 3 0 . 000 1 8
Guerran t e t al , 1945 Canned green lima beans - 43 . 3 0 . 00009
Guerrant e t al , 1945 Canned whole kernel corn -
43 . 3 0 . 00009
Greenwood et a l , 1 9 4 4 Canned luncheon pork 55 . 0 99 . 0 0 . 04 7 6 1
--

Cook and Dundaram, 1 9 6 3 Boiled ar tichokes In water 1 00 . 0 0 . 02674

Greenwood e t al , 1 9 44 Canned luncheon pork 55 . 0 1 10 . 0 0 . 0 14 1 1
Greenwood e t al , 1944 Canned luncheon pork 55 . 0 1 18 . 5 0 . 00 742
Greenwood e t al , 1944 Canned luncheon pork 55 . 0 1 26 . 5 0 . 0 2 1 50
Cook and S undaram, 1 9 6 3 Boiled ar tichokes In water 1 2 1 . 0 2 . 380 7 2
Kennedy and Ley , 1 9 7 1 Fish in pressure cooker -
1 2 1 . 0 39 . 30 36 1
 25

2.4.3 Co lour

S inc e the mod el system used in the pr esent study is a mixed ,

complicated na tural food sys tem cons i s t ing of var ious raw mat er ials
and ingred ient s , many r ea c t ions could b e involved but only two main
colour r eac t ions , browning r eact ion and p igment / chloro phyll d estruc t ion ,
were s tud ied and informat ion was collec ted only on these colour chang es .

2.4.3.1 Browning Reac t ion

Browning r eac t ion , which oc curs in fooq dur ing proc essing caused
the colour change to brown or brownish-black , c an be clas s if ied into
two categor ies , enz yma t ic and non-enzymat ic react ion . The enzymat ic
browning reac t ion can occur in food by the act ion o f catal y t ic enz .ymes ,
phenolase or polypheno lase . As this reac t ion involves enzymes which
wou ld be destro yed by heat , so dur ing thermal process ing where the
temperature is rather h igh , only non-enzymat ic browning reac t ion will
play an important rol e in colour changes .

There are thr ee main t ypes o f non - enzymat ic browning reac t ion , the
carbonyl-amino ac id react ion which i s generall y known a s "Maillard"
react ion , the caramel izat ion reac t ion which occur s at rela t ively high
temperature wi th polyhydroxy -carbonyl compound s , and the oxidat ive
reac t ion where ascorb ic acid or polyphenol s are conver t ed to d i- or
polycarbonyl compound s . The d etails o f mechanisms o f these r eac t ions
were rev iewed by many worker s (Hodge , 1 9 53 ; Reynold s , 1 9 63 ; Lea , 1 9 65 ;
Reynolds , 1 96 5 ; Hurst , 1 9 7 2 ; Adrain , 1 9 7 4 ; McWeeny et al , 1 974) .

The intermed iates , p igment s and melano ids formed by the react ions
ar e al t ered by a number of f ac tors . Their compo s i t ion will depend , not
only on the sugar and amino compounds involved but also on ( a ) the
sugar : amino compound rat io ( Schnic kels et al , 1 9 7 6 ; Warmbier , 1 97 6 ;
Warmbier e t al , 1 97 6) , ( b ) the water con t ent , the h igher the water
content , the quicker the rate of browning ( Stad tman et al , 1 94 6 ;
Legault e t al , 1 95 1 ; Pear son e t al , 1 9 62 ; Labuza and Warren , 1 97 6) ,
( c ) the temperature o f the rea c t ion , ( d ) the pH o f the react ion mixture
and its buf f er capac ity (Pear son et al , 1 9 62 ) where the maximum brown
co lour was found to be produced between pH 5 . 6 and 5 . 9 and ( e)
 26

the presence of o ther compound � or ions such as ascorb i c a c i d which

was f ound to have an effect on the browning extent ( Karel and N ickerson ,
1 9 6 4 ; C legg and Mor ton , 1 9 6 5 ; Clegg , 1 9 66) . In mea t , Khayat ( 19 7 8) f ound
that reducing sugar content was an impor tant fac tor in brown colour
development during thermal processing .

T ime and temperature were f ound t o e f f e c t the rate o f browning

rea c tion ( Pokorny et a l , 1 9 7 5 ; Warmb ier et a l , 1 9 76) . Warmb ier e t al
( 1 9 76) s tudied and found that the rate o f p igment formation followed a
zero- order kine t ic reac tion rate af t er an initial shor t indu c t ion period
while the ra te o f glucos e u t ilizat ion and . loss o f availab le lys ine ob eyed
the f i r s t order rea c t ion . Pokorny et a l ( 1 9 75) studied the non-enzymic
b r owning of caul i f lower and found that it f o llowed the kinet ics of a
f irs t order reac t ion a t h igh temperatures and that of a zero order
r eact ion a t lower temperatures . Resnik and Ch irife ( 1 9 79 ) s tudied the
e f f e c t of mo is ture content and temperature on some aspec t s of non­
enzymic browning of dehydra t ed apples , mois ture content ranged f rom
0
nearly zero to 8 3% , and t emperature ranged from 5 5 -8 3 C and concluded
that the rate of increase of on which i s ass oc iated with the presence
282
o f 5-hydroxy -me thyl-furf u ral followed zero react ion kinetics .

The kinetic parameters were collected and are shown in Tab le 2 . 3 .

The ac t ivat ion energies f or the browning react ion found b y various
-1
workers were in the same range , it was f ound to be more than 1 0 5 kJ mole
-1
( 25 . 0 kcal mole ) . However , the variation in 1 1 k 1 1 was high as the
methods of det erminat ion used by various workers were d i f f eren t .
Therefore , the method of determinat ion mus t b e followed in order to
11
used thos e k 11 values with the ac t ivat ion energy .
 27

TABLE 2 . 3 React ion Rate Cons tants and Ac t ivat ion Energies for
Non-Enzymatic Browning Reac t ion

Moisture Ac t ivation
Tempera 5 ure Content React ion R!! f e Energy_ 1
Reference Food Product pH k X 10 4 S kJ mole _
rangs C gH 0/ 100 g 1
2 (kcsl mole )
(dry basis)

S tadtman et a l , Dried apricot - - - - 109 ( 26 . 0)

1946
°
Legaul t e t a l , Unsul f i ted - 20 - 49 5.4 0 . 00 1 3 9 , 49° C 166 ( 39 . 4)
1 947 carrot 6.2 0 . 00 1 7 4 , 49 ° C 163 ( 38 . 7)
8.0 0 . 00255, 49 C · 159 ( 37 . 9 )
°
U ns u l f i ted - 20 - 49 3.5 0 . 00266 , 49 C 1 7 7 ( 4 2 . 2)
Onion °
Uns u l f i ted - 20 -49 5.3 0 . 00020 , 49 C 1 69 ( 40 . 3)
°
whi te potato 7.6 0 . 0005 1 , 49 C 1 6 1 ( 38 . 4)
°
8.9 0 . 00086 , 49 C 1 5 2 { 36 . 2 )

- °
U::�su l f i ted 20 - 49 7.4 0 . 00006, 49 C 1 34 ( 3 1 . 9 )
sweet potato
- °
Legaul t e t a l , Sul f i ted white 20-49 5.3 0 . 000 1 1 , 49 C 172 {41.0)
°
1951 potato 7.6 0 . 00020 , 49 C 1 5 1 ( 36 . 0)
° 1 4 3 { 34 . 0)
9.2 0 . 0002 6 , 49 C

Sul f i ted - 20 - 49 5.4

°
0 . 000 1 1 , 49 C
°
168 (40 . 0)
carrot 6.2 0 . 000 1 2 , 49 °C 1 5 1 (36.0)
8.0 0 . 000 1 3 , 49 C 1 4 7 { 3 5 . 0)
-
-
Sulf i ted - 20 - 49 2. 1 176 (42 . 0)
cabbage 3.5 1 60 ( 38 . 0)
7.1 - 147 { 35 . 0)
°
-
Hendel et a l , Dried potato - 40-80 4.9 0 . 05 1 39 , 80 C 1 55 { 37 . 0)
° { 32 . 0)
1955 9.4 0 . 07 7 7 8 , 80 C 1 34
° ( 28 . 0)
15.0 0 . 10000 , 80 C 1 18
° 105 ( 25 . 0)
33.0 0 . 0566 7 , 80 C
°
1 10 . 0 0 . 027 7 8 , 80 C 105 ( 2 5 . 0)
°
3 70 . 0 0 .01416, 80 C 109 ( 26 . 0)

Bur ton , 1963 Homogenized 6 . 5 - 9 3 . 3- 1 2 1 . 1 - 355 . 40000 ., 1 1 3 ( 2 7 . 0)

goa t ' s milk 6.6 1 2 1 . 1 °C

Non-homogeni zed 6 . 5 - 9 3 . 3 - 1 2 1 . 1 - 4 2 1 . 80000 . 1 1 3 {27 . 0 )

°
goat ' s milk 6.6 121. 1 C

Hermann, 1970 Apple j uice - 37 . 8 - 1 30 - 1 . 42167,

°
1 1 3 ( 2 7 . 0)
121 . 1 C

Hermann , 1970 Apple j uice - 37 . 8- 1 30 - 1 . 34 86 7 . 87 {20. 7)

121 . 1 c

- -
-
Mi z rahi et al Dehydrated - 1 .0 172 (41 .0)
1970 cabbage - - 18.0 1 09 { 26 . 0)

Drilleau and Apple j uice - - 1 18- 1 66

Priou l t , 197 1 (28-39 . 6 ) *

Flink e t al , Milk - - - 2. 77778,

° 197 (47 .0)
1974 100 C , O%RH
4 1 . 667 00 ,
°
1 1 ! . 1 1 100 ,
1 00 C , 1 1%RH 223 ( 5 3 . 0)

1 00 C , 32%RH 1 39 ( 33 . 0)
- -
-
Pokorny et al , Cau l i flower 40 - 50 - 1 44 ( 3 4 . 2)
1975 50 - 80 - 105 (25 . 1 )
Resnik Dehydrated - 55 - 83 0.0 - 1 7 2 {4 1 . 0) *
and C h i r i f e , apple 83.0 - 1 22 ( 29 . 0)*
1979
* 5 - HMF formation
 28

2.4.3.2 Pigment / Chlorophy ll Des truct ion

In foods tha t contain chlorophylls , the change in colour from a

bright green to an olive-green or olive-yellow colour on process ing
has been the concern of food process ors s ince the introdu c t ion o f
thermal process ing . The change is due t o the convers ion o f chlorophylls
to their respe c t ive pheophy tins and further breakdown products such as
pheophorbides and chlorins (Mackinney and Weas t , 1 940 ; Wes t c o t t et al ,
1 95 5 ; G ilp in et al , 1 9 59 ; Gold and Weckel 1 959 and Spencer , 1 9 7 3 ) .
The percen tage of change of chlorophylls to pheophy t ins has b een s tudied
by many workers . Kaur and Manj rekar ( 1 9 7 5 ) found tha t canned sarson­
ka-sag (prepared mus tard green) los t about 50% of the chlorophyll dur ing
process ing . In green peas , Ac zel ( 1 9 7 1 , 1 9 7 3 ) found that chlorophy ll
content was reduced by 1 0- 1 6% dur ing b lanching and then all chlorophyl l
was conver ted t o pheophytin dur ing s terilisation . The degradation of
chlorophyll was f ound to be dependent on time o f process ing ( Sweeny and
Mar t in , 1 958 and Lee et al , 1 974) . Many workers f ound that the extent
o f degrada tion o f chlorophyll depended on pH and heat source ( Sweeney
and Mar tin , 1 9 6 1 ; Buckle and Edward , 1 9 7 0 ; Lee et al , 1 9 74 ) . Lee e t al
( 1 9 7 4 ) also f ound that s t�am had mor e effect on chlorophyll than boiling
water which had more effect than hot air and microwave .

The effect of time and tempera ture on the degradation of chlorophyl l

has been s tudied by many workers . Gold and Weckel ( 19 5 9 ) s tud ied the
convers ion during s ter ilisation of canned green peas and f ound that i t
was pseudo-f irs t order react ion . Eps tein ( 19 5 9 ) , also found that the
loss of green colour of HTST processed peas was pseudo- f i r s t order .
Mckinney and Weas t ( 1 940) s ta ted in their work that the conversion
o f chlorophyll in aqueous acetone and acid solution was a f i r s t order
reac t ion in respect to both acid and chlorophyll content . Sweeney and
Mar tin ( 1 9 5 8 ) found that i t could be described by e i ther a zero order
or first order reaction in hea ted b roccol i . However , Schanderl e t
a l , ( 1 962) , Gup t a et al � ( 1 9 64 ) and Haisman and Clarke ( 1 9 7 5 ) found
that the convers ion of chlorophyll occured only above a threshold
°
temperature of 50-60 C and the convers ion was mos t probab ly a f i r s t
order reac t ion . I n 1 96 4 , Gup te et a l inve s t igated and de termined not
only the kine tics of chlorophyll degradation in sp inach puree but also
 29

the thermodynamic energ ies f or this degradat ion based on a f ir s t

order reac t ion . Hayakawa and Timbers ( 1 9 7 7 ) s tud ied the inf luence
of var ious therma l treatments on the v isual green colour of canned
asparagus , green beans and peas and determined the kine t ic react ion
rate cons tant by assuming that the reac t ion was a f ir s t order . The
kine t ic rea c t ion rate cons tant f or chlorophyll was also s tudied b y
o ther worker s such as Dietr ich et al ( 1 9 7 0 ) f o r green b eans , Lenz
and Lund ( 1 97 4 ) for pea puree and sp inach pure e , Hermann ( 1 9 7 0 ) for
sp inach . Tan and Franc is ( 1 9 6 2 ) who s tud ied the effect of process ing
on the p igments and colour of sp inach pur ee , provided a resu l t ade­
quate for calculat ing the kine tic react ion rate. The value of the
kinet ic parameters determined by var iou s workers are summarized in
Tab le 2 . 4 . The kinet ic reac t ion rate for chlor ophyll a and b var ied
dep ending on the type of f ood , pH, tempera ture rang e . Lund ( 1 9 7 5b )
c oncluded that the var iability o f resu l t s obtained i n d if f erent
laborator ies may be due to the hea t ing technique and the analyt ical
method . He suggested that the ac t iva t ion energy for chlorophyll a
s hould be 4 2- 1 0 5 kJ mole
-1 -1
( 1 0-2 5 kcal mole ) and f or chlorophyll
b , Ea should be l ower because i t appears to be more stab l e .

2.4.3.3 To tal Colour Change

There were some worker s s tudying the total colour changes of

f ood dur ing process ing . Unfor tunately , the data g iven were not
enough f or determining the kine tic parameters . However , the result s
presented by Salunkhe et al ( 1 97 8 ) o n c olour change dur ing s torage
of various f ood were adequate . The scales were r ead from the Hunt er­
Colour and Colour-D if f erence Meter (Mode l D25D2 , Hunter As sociat ion
Laboratory , Inc . Fa ir fax , V . A . ) . The kinet ic parameters were de ter­
mined as suming f ir s t order kine t ic s and are shown in Table 2 . 5 . The
average a c t ivat ion energy f or L , a , b was 63 , 5 6 and 45 kJ mole ,
-1

respec t ively . Higher ac t ivat ion energy o f 1 35 kJ mole

-1
was f ound
f or the d ecrease in greeness of Brus sels s prou ts dur ing s t orage
(Tij skens et a l , 1 97 9 ) .Tlte rate of d ecrease which could probably
-4 - 1 °
be d escr ibed by f ir s t order kine t ics was 0 . 00 1 1 2 x 1 0 s at -4 C .
 30

TABLE 2 . 4 Reaction Rate Cons tants and Ac t ivat ion Energ ies for
Chlorophyll Des truct ion

Activation
Ener gy _
Reac t ion Rate

kl21 . t�l
Tempera ture
Refe rence Food Product pH 1 Remark
o kJ mole _
c 1
X 10 8 ( kcal mole )

Mackinney and Buf fer solu tion ,

Joslyn , 1941 ch lorophyl l a 0-50 32 ( 7 . 5 )
38 ( 9 . 0 )
- -

chlorophy l l b - 0-50 -

Eps tein , 1959 Green peas ;

chlorophyll 11 -
1 2 1 . 1 - 1 48 . 9 -
52 ( 12 . 2) n o lag
chlorophyll b - 12 1 . 1 - 1 48 . 9 -
80 ( 19 . 0 ) correction

Gold and Peas ;

Wecke l , 1 9 59 b lanched - 1 1 5 . 6- 1 3 7 . 8 2 7 . 4 1 700 6 8 ( 16 . 1 )
unblanched -
1 1 5 . 6- 1 3 7 . 8 2 7 . 6 1 700 53 ( 1 2 . 6)

Schanderl In ac i d sol u�ion ;

et al, 1962 chlorophy l l a -
25-55 -
44 ( 10 . 4)
ethyl
chlorophy l l idc a -
25-55 -
44 ( 10 . 4 )
01e thyl -·

ch lorophy l l idc a -
25-55 -
44 ( 10 . 6 )
free
ch lorophy l lide a -
25-55 -
4 5 ( 10 . 8}

Gupte e t a l , Spinach p u ree ;

1964 chlorophy l l a 6.5 1 26 . 7 - 1 48 . 9 -
65 ( 15 . 5)
chlorophy J.l b 5.5 1 26 . 7 - 1 48 . 9 -
3 2 ( 7 . 5)

Die l rich Green beans Natural 8 7 . 8- 100 . 0 3 8 . 00000 50 ( 1 2 . 0)

et a l , 1 9 70

Hermann , 1 9 70 � p lnacl & ;

c h l orophyll a N.:1tura l 100- 1 30 1 1 . 25000 53 ( 1 2 . 5 )
chlorophyl l b Na tural 100- 1 30 7 . 9 5000 4 2 ( 10 . 0 )

Timbe r s , 1971 Peas Natur a l 7 9 . 4- 1 4 8 . 9 38 . 00000 50 ( 1 2 . 0)

Asparagus Na tur:1 l 7 9 . 4 - 1 '· 8 . 9 ,, . 85000 63 ( 1 5 . 0)
Green beanfl Natural 1 9 . 4 - 1 1. 8 . 9 2 5 . 5 8 300 59 ( 1 4 . 0)
Spinach Natural 7 9 . 4- 1 4 8 . 9 1 8 . 28300 63 ( 1 5 . 0)

Lt:nz ond Lun d , Pea puree 6.5 79 . 4- 1 37 . 8 3 . 40000 9 2 ( 2 2 . 0)

1974 Spinach puree 6.5 7 9 . 4- 1 3 7 . 8 2 . 3 1 700 80 ( 1 9 . 0)
 31

TABLE 2 . 5 Rea c t ion Rate Constants and Ac tivat ion Energies for Colour Change

L-scale a-Scale b-Scal e

� _1 � �
Food Products
37 , 8 C 1
k Ea k Ea k Ea _1

��
37 . 8 C 37 . 8 C
1
_

�
kJ mole _ kJ mole _ kJ mole
x 1Q _
1 X 1 X lQ _

1 ( kcal mole ) ( kcal mole ) l ( kcal mole )

6 s 8

Ham and Chicken 0 . 0000 2 105 ( 25 . 1 ) 0 . 00007 - 0 . 00005 86 ( 20 . 4 )

Loaf

Frankfur t e r s 0 . 00004 48 ( fi. 5) 0 . 00006 70 ( 1 6 . 6 ) 0 . 0000 1 23 ( 5 . 4 )

Beef s teak 0 . 00002 54 ( 1 2 . 9 ) 0 . 00003 104 ( 24 . 8) 0 . 0000 1 2 1 ( 5 . 0)

Beef s t ew 0 . 0000 1 51 ( 1 2 . 1 ) 0 . 00003 36 ( 8 . 6 ) 0 . 000 1 2 3 ( 0 . 8)

..

Cheese s p read 0 . 00003 57 ( 1 3 . 6) 0 . 00005 5 1 ( 1 2 . 1) 0 . 00003 3 5 ( 8 . 3)

Pineapple 0 . 00008 67 ( 1 6 , 0 ) 0 . 00024 47 ( 1 1 . 1 ) 0 . 00008 84 ( 1 9 . 9 )

F r u i t cake 0 . 00006 61 ( 1 4 . 4) 0 . 00003 40 ( 9 . 5 ) 0 . 00009 64 ( 1 5 . 2)

Chocolate Brownies 0 . 00003 57 ( 1 3 . 6) O . OOOOit 43 ( 10 . 2) 0 . 00003 40 ( 9 . 6 )

 32

2.4.4 Viscos i ty

As the model sys tem used , baby food , cons is ted of about 4 . 5%
o f various s tarches , whea t , barley and corn f lour and 30% o f potatoes
in composition , the viscos i ty o f the baby food depended on s tarch
gelatini zation .

S tarch granules f rom d i f ferent s ources have d i f ferent s i zes , they

vary be tween 3 and 30 m� wi th respec t to the average s i ze of their
large s t d iame ter for wheat s tarch , corn and barley s tarch and b e tween
1 0 and 1 00 m� for root and tuber s tarch , as . p o tato s tarch . They are
inso lub le in cold wa ter but swell wi th wa ter when heated . The temper­
a ture at which granule swelling occurs varies wi th d i fferent s tarches .
°
The gelatinization temp erature ranges form 59 . 5- 7 7 . 0 C depending on
type of s tarch wi th the lowes t tempera ture for bar ley s tarch and the
highes t for modi f ied potato s tarch .

In terms of vis cos i ty , i t gradually increases wi th the increase

in temperature . When the gelat ion temperature i s reached , the viscos i ty
will rise rap idly due to the resis tance o f the swollen s tarch granules
to d isplacement . A dynamic s i tua tion eventually p revails in which some
of the granules are s ti l l swelling while o thers are s imultaneous ly
d i s in tegrat ing under the inf luence o f continuous heating and s tirring
(Ka t z , 1 9 38) . Maximum viscos i ty is ob tained when the increase in
s truc tural viscos i ty caused by swo llen s tarch aggregates is counter­
balanced by the decrease in viscosi ty result ing from disintegra t ion
and solub i l i zation of the s tarch . As hea ting is continued , the vis cos i ty
decreases gradually due to the breakdown of s tarch s t ructure . The change
of viscos i ty during heating of the s tarch-wa ter suspens ion can b e
followed o n a record ing vis come ter (Anker and Geddes , 1944 ; Kes ler and
Bech tel , 1 9 4 7 ; Cross land and Favor , 1 948 ; Corn S tarch , 1964 ; Knigh t ,
1 9 69 ) . The pat tern of vis cos i ty change varied from one s tarch to
another depending on the chemical proper ty o f the s tarch ( Corn S tarch ,
1964) . S tarch concentration was also found to affect the p a t tern o f
viscos i ty change (Anker and Geddes , 1944) .
 33

Besides , there are o ther factors affecting the viscos i ty change

which are ( 1 ) temperature ( Corn S t arch , 1 964) , ( 2 ) degree o f agitat ion
(Kat z , 1 9 38 ; Corn S t arch , 1 964) , ( 3 ) pH o f s tarch suspens ion ( Co rn
S t arch , 1 964 ; Whist ler and Paschal l , 1 9 6 5 ) and , ( 4 ) presence of
chemicals ( Whistler and Paschall , 1 96 5 ) . Higher temperature , higher
agitation rate , pH higher than 7 and lower than 4 , were found to
accelerate gela t inization and subsequent breakdown during prolonged
heat ing . Some ingredients had a retarding action such as sugar ,
dextrose and corn syrup .

As d is cussed before , prolonged heat in� can cause the change in

viscosity which means a change in texture o f the p roduc t . Luh
et al ( 1 964) s tudied the ef fect o f convent ional canning and UTST
thermal processing on the viscosity change of food products . Unfor­
tunately the data p resented were inadequate for determination of
° °
kine tic parameters . In terms o f cons i s tency , a "z" o f 2 3 C , 29 C
°
and 20 C were found for f ish pudd ing , l iver p as te and vanilla sauce
during thermal process ing ( Ohlsson , 1 9 80) .
These were equivalent
-1
to the approximate activation energies of 1 30 , 1 0 3 , 1 50 kJ mole •

2.5 CONCLUS ION

The changes in food during heat proces s ing and sto rage were
found to be describ ed by either zero , first or second order kine t ics .
Z ero order kine t ics was found only at high concentrations and then i t
tended t o change t o first order kinetics a s the concentrat ion decreased .
Second order kinetics were also found in some react ions . However , mos t
o f the changes in food could b e described b y first order kinetics .

There were a number of factors affecting the rate o f change -

temperature , pH , water ac t ivity , oxygen concentration and concentrat ion
o f m1nor components e . g . cu • The temperature d epend ence o f rate o f
+2
.

change and in par t i cular the des truc tion rate o f nutrients was exten­
s ively s tud ied and for mos t reac tion rates the Ar�henius equation was found
to adequately describ e the temperature dependence .
 34

Two heating procedures , s teady-s tate and uns teady-s tate , can be
used for e s t imation o f the changes in f ood dur ing process ing . Calcu­
lat ion of kinetic parame ters f rom the data ob tained by the s teady-s ta te
me thod is s imple but only small f ood samples can b e used . Uns teady­
s tate procedure , where f ood is heated in a can , gives adequate sample
s i ze for eating qua l i ty determinations but the calcula t ion is complex .

The rates of des truct ion of ascorb ic acid and of changes in colour
( browning reac tion and chlorophyll des truc t ion ) , and in v iscos i ty were
found to be mos tly described by f irs t order kine t ics . For r ibo flav in ,
only the pho todegradat ion rate was des crib�d b y f irs t order kine t ics .
The react ion rates repor ted were found to be in a wide range . The
-1
a c t ivat ion energy of as corb ic acid ranged from 1 4 to 1 7 2 kJ mole .
-1
The range of 34- 1 7 2 kJ mole was repor ted for riboflavin . For browning
rea c t ion , chlorophyll des t ruc tion , to tal colour change and viscos i ty
-1 -1
the range of activation energ ies were 87-223 kJ mole , 3 2- 9 2 kJ mole ,
-1 -1
45-63 kJ mole and 103- 1 50 kJ mole , respec tively .
 35

3. INVESTIGATION OF TESTING METHODS AND

DEVELOPMENT OF PROCESS

3. 1 INTRODUCTION

The aim of the p resen t research was to determine the kine tic
parame ters for the des truct ion o f as corb i c acid and rib o flavin and
for the changes in colour and viscosi ty of foods during hea t ing .
As colour and viscosi ty required large samp le s i ze , the uns teady-
s tate p rocedure o f heating in can had to be used . Ascorb i c acid and
riboflavin were chosen because the analy tical methods were s imp ler than
for o ther vi tamins and the kinetic parame ters could be determined by
ei ther s teady- s tate or uns teady-s tate heat ing procedure . The feasi­
b i l i ty and accuracy o f the computer model deve loped for the uns teady­
s tate procedure ( in c ans ) , therefore , could be tes ted by comparison
of the kinetic parame ters determined for ascorbi c acid and ribof lavin
from these two procedures- s teady and uns teady-s tate • A baby food
made from s trained beef and mixed vege tab les was used in this experi­
mental work .

To determine the kine tic parame ters , the concentration before

and a f ter heating for a spec i f i c time and temperature mus t be known ,
so the analy tical me thods were first s tudied to g ive assays of suffi­
cient accuracy to follow the kinetics .

The p reparation me thod for homogeni zed , s trained baby food was
also inves tiga ted to give standard raw mater ial for all tests . The
raw materials required were determined by s e t t ing the p roduc t charac­
teris tics required . As only one p roduc t compos i ti on was used in the
s tudy , f ro zen s torage of the p repared raw baby food was necessary to
p rovide exac t ly the same raw ma terial for the heating tes ts .

Us ing the uns teady-s tate p rocedure where foods were heated in cans ,
the canning process - the p reprocessing cond i tions , the retort operation ,
the process ing cond i tions - was s tudied to ob tain accurate con trol of
the process .
 36

Then , the preparation me thod , the f inal formulation , the p re­

processine condi tions and the process ing condi tions were f inali zed to
give a heat ing process which could be accura tely controlled and measured .

3.2 INVESTIGATION OF TESTING METHODS

The obj ect of this part of s tudy was to f ind the s imp l e s t me thod ,
using the equipment available , which would give the accuracy requi red .
The method chosen for each qua l i ty character i s t i c will b e discussed
separa�ely in the f ollowing section .

3.2. 1 Ascorb i c Acid

Specialised ins truments such as autoanalyser , microf luorome ter

were no t available , s o a s imp le me thod o f chemical ti tration with 2-6
dichloroindophenol was inves t igated . However , the colour interference
o f the s amp les made it d i f f icult to achieve an accurate resul t . A
calorime tric me thod of Pearson ( 19 76 ) was tried . Thi s me thod i s based
on the oxidation - reduction rea c t ion of ascorbi c acid and the indicator
dye , 2-6 d ichloroindopheno l . The colour change was measured as ab sor­
bance by the Spec t ronic 20 spectropho tome ter a t waveleng th 5 20 nm wi th
the green f i l ter . A s tandard curve was p repared using various concen­
trat ions of as corb ic acid solut ion showing the rel a tionship b e tween the
concentration of as corbi c acid and the s cale of the absorb ance ob tained .
The concentration of as corb ic acid in the samp le was direc t ly calc ula ted
f rom the prepared s tandard curve .

I t was found that this me thod could be used i f the sample s i ze was
small enough to p revent the colour interference . Reproduc ible results
were ob tained where the total ascorb i c acid conten t in the samp le was
-1
more than 0 . 25 mg g (Appendix 3 . 1a) , and the s amp le s i ze was approx-
ima tely 8- 10 g . The details of analy t ical me thod are in Appendix 3 . 2a .
 37

3. 2.2 Riboflavin

The fluorome tr i c me thod (AOAC , 1 9 7 7 ) was found to give dup li cate

-1
results where the concentration was about 20-30 �g g (Appendix 3 . 1b) .
However , i t was found that when measuring the f luorescence the s amp les
had to b e randomi zed as the ins trument read ings were d r i f t ing . Through­
out all s tages of the me thod , prote c t ion o f solution from undue exposure
to ligh t was done by covering all glasswares wi th a luminium f oi l .
The details o f the me thod are in Append ix 3 . 2b .

3.2.3 Colour

I t is d i f ficult to describe quan t i tatively wha t colour is , as what

is ac tually seen is the overall appearance of the food which depends on
more than the colour alone . S uch quali t ies as surface texture , gloss ,
me tallic charac ter is t ics , trans lucency and many more can contribute
significantly to the to tal visual e f f ec t . In this s tudy , an obj ec t ive
me thod was used in order to ob tain s imple quan t i t a t ive data for des­
cribing the ef fect o f hea t on the colour change o f the processed food .

A DU- colour ins trument (Neotec Ins truments , Inc . o f Si lver Spring ,
MD , 1 9 7 1 ) was used . The measurement was read in the C I E sys tem o f
X , Y , and Z as this sys tem has achieved world wide accep tance and hDs
b een used essentially unchanged for many years ( B i l lmeye r , 1 968) .
Furthermore , the CIE chroma t i c i ty diagram i s also available showing
the colour of the sample on a two dimens ional s cale of x and y where
x = X / (X + Y + Z) and y = Y / (X + Y + Z) . That is , for any given colour
in the colour space , it would be partially des cribed by x and y and
then a third number , the tris timulus value Y , mus t be c i ted to comple tely
describe the colour as ligh tness or darkness .

One impor tan t parame ter in measuring the colour o f the sample by
a reflectance method was the thickness o f the s amp le on the glass
window which mus t b e contro lled . A me tal ring o f about 1 cm dep th was
used . I t was p laced on the glass window , the s amp le was f i l led and
the whi te cover was pressed agains t the ring to allow the excess s amp le
to overflow .
 38

3.2.4 Vis cos i ty

Viscosity is a phys ical p roperty which i s related to texture of

food . It was the obj ect o f thi s s tudy to determine the change of the
viscosi ty in processed foods whi ch would relate to a change in the
texture of the f ood . S ince b aby food is a non-Newtonian f luid , i t is
common p ractice to define a so-called apparent viscosi ty by using a
shear rate sele c ted to , fal l within a range o f pract ical interest .
The Brookfield Synchrolectric (LV type) was used .

The viscosi ty o f non-Newtonian f luids depends on the rate of shear

which is governed b y the speed o f rotation and s i ze of s p ind le . There-
fore , the speed o f rotation o f 0 . 5 s - 1 and the spindle diame ter of
0 . 3 cm ( s i ze 4 ) , which had b een found to give an adequate range o f
viscosi ty , were used . I t was also found tha t the time o f shear did
effect the viscosi ty reading . So i t was decided that the reading would
be taken a t 1 minute a f te r s tarting . The temperature of the sample was
0
exactly con trolled a t 25 C as tempera ture affected the viscosi ty .

- ·

3.3 DEVELOPMENT O F PROCESS

The p reparation o f homogeni zed baby food and the canning p rocess
were s tudied .

3 . 3. 1 Preparat ion of Baby Foods

The compos i t ion of the baby food used was based on the canned b eef
and vegetab le baby f ood on the marke t . The app roximate composi t ion was
found to be beef 5% , mixed vege tab les 45% , f lour , corn f lour and barley
flour 4 . 5 % , yeas t extract 0 . 4% , salt 0 . 4% and water 44 . 7% . The concen­
tration o f as corbi c acid �n the exis t ing canned produ c t on the market
was too low to determine s o 2 mg o f ascorb ic acid per lOO g of raw
ma terial mixed was added . The following composi tion was used for this
preliminary experiment .
 39

Beef 5 . 0%
Carrots 14 . 0%
Peas 9 . 0%
Potatoes 22 . 0%
Flour 1 . 2%
Corn f lour 2 . 5%
Bar ley f lour 0 . 8%
Yeas t extrac t 0 . 4%
Salt 0 . 4%
Water 44 . 7%

Bee f was cut and minced through 1 cm , 0 . 4 cm and 0 . 25 cm d iame ter

p la tes o f a Kenwood mincer for 1 , 2 and 2 t imes , respectively , as f ine
divis ion was needed . Vege tables , excep t peas which were fro zen , wer e
washed , peeled , d iced and then b lanched in a s t eam b lancher . A
b lanching time of 5 minutes was suf f i c ient to des troy enzymes and
therefore prevent enzymic browning reactions occurring . All raw ma ter­
ials inc luding the dry ingredients and water were disintegrated under
vacuum of 6 8 . 9 kPa pressure in the JEFFCO wet dis integrator ( s ize 2
-·

Mode l 29 1 DIMOCK MACH INE , Jeffress Bros . Ltd) for 3 minu tes and then
l e f t - under vacuum for ano ther 2 minutes to draw out as much of the
remaining air as pos s ib le . The vacuum d is integration was necessary so
'
as to reduce the s i ze of the food par tic les to a sui tab le s i ze for
the fur ther s teps in process ing . To prevent b locking of the homogen­
iser , the s lurry was s creened through a 1 cm square s creen be fore
pass ing through the homogeniser . The homogeniser used was a "MINOR"
homogeniser type K (APV Manton - Gaulin homogeniser) with two-
s tages where the slurry was forced through a small annulus at a pressure
o f 34500 kPa to create a very high veloci ty which b roke down the
par ticles into minute f orm . The homogeniser was preferred to the colloid
mill as the strained baby f ood ob tained from the la t t er entrapped a lot
o f air bubbles which could possib ly e f f e c t the qua l i ty o f the s tored
b aby food .

The s t ra ined s lurries were packed in SARAN b ags under vacuum and
frozen immediately in a p late freezer . The s lurries were completely
fro zen wi thin 2 hours . SARAN bags were used to p revent air / oxygen
transmiss ion into the bag . Rapid freezing was used to minimize the
p re-hea ting des truc t ion of the s tudied quali ty factors . The fro zen
 40

0
baby food was s tored a t -30 C where the rate of des truct ion of mos t
vi tamins was neglig ible (Fennema , 1 9 7 5 ) .

As the ini tial produc t charac teris tics required for each run were
the same , the raw baby food had to come e i ther from the s ame batch o f
raw material s lurry or the same propor t ion of various batches . However ,
because o f the quan t i ty of product requir ed , i t became obvious that one
s ingle batch could no t be p repared for the whole s t udy . Therefore a
number o f batches were made and equal amounts o f each batch were mixed
for each experiment . S uf f icient ba tches were made to cover the whole
s tudy , wi th an adequa te safety margin .

3.3.2 Preprocessing

3.3.2. 1 Thawing

The raw s t rained baby food s tored in frozen s ta te was thawed p r ior
to fur ther preprocess ing . During thawing , f oods are subj ec ted to
damage by chemical , phys ical and microb ial means al though microb ial
prob lems are negligible in properly hand led food s . High temperatures
are detrimental to the quali ty of foods so mi ld temperature cond i t i ons
should be used in thawing (Fennema , 1 9 75) .

°
Two d i f f erent thawing condi tions were s tudied , a 30 C water bath
°
and a water b a th in a 25 C controlled room . The thawing time was 1
°
hou� in the 30 C wa ter bath and about 2 hours in the water bath held in
°
25 C controlled room . As large amounts o f frozen baby food were thawed ,
°
i t was more d i f f icult to con trol the condi tion o f 30 C as more than one
water bath was required . There fore , for convenience and more accurate
tempera ture control , thawing in the wa ter bath in 25 ° C for 2� hours
was used .

3.3.2.2 Preheating

As the viscos i ty of baby food was related to gelatinization of

s tarch , preh�ating to gelatinize the s tarch was necessary to give a
cons i s tent ini tial viscos i ty . Another purpose for preheat ing was to
allow hot f illing to be used providing a vacuum in the cans .
 41

°
The temperature for p reheating was chosen as 70 C to lie wi thin
°
the general gelatini zation tempe rature range f or s tarch of 59 . 5- 7 7 . 0 C .
The heating was carried out in a steam j acke ted pan . A s team p ressure
in the j acke t of 1 90 kPa was maintained and the product s t irred by
hand . The t ime requi red for heating to 70 C was 7 minutes and
°

this condi t ion was used in all experimen ts .

Af ter p reheat ing , the heated baby food was f i l led into the
prepared cans with the minimum possible headspace being l e f t so as to
minimi ze can to can variations in the temperature responses of the
s amp les .
The f illed cans were vacuum sealed and immersed in a water
° °
bath at 60 C . The time taken to reach a uniform tempera ture o f 60 C
was found to be 80 minutes .

3 . 3. 3 Processing

°
The cans taken f rom the 60 C wa ter bath wer e processed in a
retort under d i f ferent processing condi tions . Temperature measurement
and retort opera t ion were s tudied . Process ing cond i t ions were set
accord ing to the exis ting retor t .

3.3. 3. 1 Temp erature Measurement

S tandard 24 gauge (Uni ted S ta tes s tandard wire gauge) copper /

cons tantan thermocoup les were used and connec ted to a 1 2-point Honeywel l­
Brown recording po tentiome ter operating on a 7 2 second print cycle .
A tens ion me thod o f thermocouple mounting were used . Holes were located a t
diametrically oppos i te s ides of the can and were p ierced through the can
wall wi th a sharp poin t . The copper and cons tan tan wires were separated
and threaded through holes from oppo s i te s ides o f the can . They were
then carefully j oined and soldered . The j unc t ion poin t was made as smal l as
poss ible to give the tempera ture measurement at the exac t point in the
can . The wires and j unction point were held in p os i t ion with adhes ive
tape on the outs ide of the can . Epoxy resin adhesive was applied on
both s ides o f the hole and l e f t overnigh t to comp le te hardening . For
points near the can wall , following suggest ions made by Packer ( 1 9 6 7 ) the
cons tan tan wire wa s always the shorter within . the can .
 42

Ant i-sulphur , lacquered cans of 7 . 4 cm diame ter and 10 . 8 cm

heigh t were used . For each process ing run , a can wi th thermocouples
at f ive d i f ferent points was f illed with preheated baby food and heated
in the retor t . The tempera ture dis tribution through the food during
processing was measured and recorded by the po tentiome ter . The thermo­
coup le arrangement is shown in Figure 3 . 1 and Table 3 . 1 .

3.3.3.2 Re tort Operation

The retort used was a laboratory-scale , hori zontal autoclave

( locally made by Berry Engineering Ltd . , Palmers ton Nor th , New Zealand ) .
I t was equipped wi th two venting valves , s team inle t , s team by-pas s ,
cooling water inle t and drain water outle t , the s team pressure and
temperature were controlled by an automa t i c pnuema t i c sys tem . At the
end of the 2 minutes ven ting period , the drain valve and two vent
valves were c losed . The required retort s team pressure was reached
within a few seconds af ter closing ven ts and the s team tempera ture could
be controlled for the required period . At the end of the holding period ,

-
the retort pressure was reduced slowly over 4 minu tes . This s tep was
necessary and had to be carefully controlled , as the high processing
temperature involved may create very high pressures wi thin the can
of 200-300 kPa (Goldb l i th et al , 1 9 6 1 , p . 854) . If the retort pressure
was released too quickly , distortion or buckling of the can could occur .

Once the retort pressure was reduced to atmospheric , the cooling water
was turned on and the retort was about 75% f i l led . This water level
was maintained by con tinuous flow of cold water . The total cooling
t ime was 40 minutes . The t ime taken to f i l l 7 5 % o f the retor t was abou t
5 minutes .

3.3.3.3 Process ing Condi tions

The sys tem on the retort used was l imi ted to temperatures below
°
1 30 C . In order to ensure satis fac tory control a t all t imes , the maxi­
a
mum retort tempera ture used was 1 29 C .
 43

e2

+ 3 --

e5
- - - - - -
- ......
.......

FIG . 3 . 1 The rmocouple Arrangement in a Can

TABLE 3 . 1 Dis tance from the Centre to the Measured Points

r* h*
Point Number
cm cm

1 0.0 3.6
2 1.2 1.8
3 0.0 0.0
4 0.0 1.8
5 2.5 3.6

* r is a dis tance from the centre of a can in diame tral

d irec tion .
h is a d is tance from the centre of a can in axial d irec t ion .
··,·

44

For a low acid food of pH of 5 . 5-6 . 0 , the F 10 , which is the

121 • 1
· 1 en t proces s lng t lme
° °
equlva • ln mlnu t es a t 1 2 1 . 1 C f or " z " of 1 0 C ,
· · ·

recommended i s in the range of 10 to 1 5 . I t was dec ided t o carry ou t

°
the exper iment at 1 29 C retort temper ature for var ious processing
10
t imes to ob tain the F of 5 . 0 , 9 . 0 , 1 3 . 0 , 1 7 . 0 and 2 1 . 0
121 . 1

Heated samples were taken from the processed cans after cooling
whereas con trol samp les or zero time samples were taken randomly from
°
the cans af ter removal from the 60 C water ba th . Two samp les of b o th
the control and processed samp les from each process ing experiment were
°
s tored overnight in a chiller at 10 C prio� to viscos i ty , colour , pH
and dissolved oxygen measurements . All o ther control and processed
0
s amples were s tored in - 30 C fro zen s torage for vi tamin analys is .
The control and hea ted cans were complete ly thawed in an ambien t tem­
pera ture water bath . Then the can content was totally mixed be fore the
samp les were taken for analysis .

3.4 ADJUSTMENT OF PROCESS

The resul ts from 3 . 3 sugges ted that adj us tment of the process was
neces sary . Experiments were carried out and the resul ts ob tained were
used to determine the f inal process .

3.4. 1 Formulation

The ascorbic acid content in both con trol and heated s amp les was
too low to ob tain accurate resul ts . The sample s i ze required was large
and caused colour interference in the ascorb ic acid dete rminat ion for
the heated samples . The ribof lavin concentration was also too low and
a large sample s i ze was needed caus ing an error from colour interference .
Therefore , i t was decided to add both as corb i c acid and ribof lavin into
the raw p repared baby food so as to reduce samp le s i ze and colour inter­
ference .

Us ing the measured temperature d i s t r ibution a t the centre and a t

0
the farthe s t point at the highes t process ing temperature of 1 29 C and
the longes t p rocess ing time ( F �� 1 . 1 of about 2 1 . 0) wi th the kine t ic
reac t ion data from Chi t taporn ( 1 9 7 7 ) , the average ascorbi c acid retention
at each point es timated from:
 45

c exp (-k�t)
0
exp (-k x 0 . 02)

where c is the f inal concentration af ter one t ime interval � t

1
k i s the reaction rate calculated for various measured temper­
-1
atures (h )
0 . 02 i s the time interval , �t (h ) , over whi ch the temperature i s
assumed cons tan t
c is the ini tial concentration
0
and this can be con tinued for c , c , . . . c for processing t ime o f n�t .
2 3 n

The average as corbic acid retent ion of these two points was 69% .
The necessary as corbic acid to be added to give an accurate reading in
the heated s ample was calculated as 20 mg per 100 g of raw s lurry . The
riboflavin needed was calculated in a s imi lar way as 2 . 5 mg per 100 g
of raw s lurry .

From the colour measurement , all the heated s amp les were darker
than the contro l . As x and y could be calculated from X , Y and Z data
B i l lmeyer ( 19 6 8 ) , it was found that there was a d i fference b e tween x
and y of the control and heated s amp les but the percentage change was the
s ame for a l l heated samp les subj ected to various degrees of heat treat­
men t . Therefore , i t was concluded a t this point that there was a change
in colour during heat treatment but the change in x and y of the hea ted
samp les was the same , only the darknes s (Y) o f the s amp les changed . Only
Y was therefore necessary to measure the change of colour during heat ing .
The results o f calcula ted x and y are shown in Appendix 3 . 3 .

As the colour o f the control samp les was too dark , the comp o s i t i on
of raw material was altered to p roduce a ligh ter colour in the contro l ,
thus p roviding more room for Y to change in the heated s amp les . The
compos i tion of mixed vege tab les which governed the colour of the produc t
as they were the main raw materials , were changed from 1 4% carrots ,
9 % peas , and 2 2% p otatoes to 10% carro ts , 5% peas and 30% po tatoes .
The experiment s were repeated us ing the modi fied compos i t i on fortif i ed
w i th as corbi c acid and ribof lavin . The analysi s o f both vitamins
were found to be satis factory . The co lour of b o th control and heated
s amples were improved as Y ob tained from a new control samp le was
 46

3 1-32 when the former control samp le was 2 3-24 .

Therefore , the f inal formulation was :

Bee f 5 . 0%
Carrots 1 0 . 0%
Peas 5 . 0%
Potatoes 30 . 0%
Flour 1 . 2%
Corn flour 2 . 5%
Barley f lour 0 . 8%
Yeas t extract 0 . 4%
Sal t 0 . 4%
Wa ter 44 . 7%
-1
As corb ic acid 0 . 2 mg g
-1
Riboflavin 2 5 . 0 �g g

3.4.2 Preprocess ing Condi t i ons

The vis cos i ty of the con trol samp les from various experimental runs
were found to vary so that the change of viscos i ty wi th heat process ing
could not be predic ted . As s tarch gelatinization depends on time and
tempera ture of heating , rate of hea t ing , degree of agi tation , pH and
o ther factors , it was d i f f i cult to ob tain the same viscos i ty in the
product unless all the factors involved were precisely controlled .
Agi tation by hand s t irring may have been one o f the importan t factors
causing fluc tuat ion in results in the pre liminary experiment so a
mechanical s t i rrer wi th controlled speed was used ins tead of hand
s tirring for later work .

Also , because o f the comp lexity o f the viscos i ty change o f s tarch

pas te during heating and s t irr ing , i t was decided to control the viscos i ty
of the control sample in each experimental run at about maximum vis cosi ty ,
then any sub sequent reduct ion in viscos ity could be a t t r ibuted t o the
e f f ec t of further heat ing .
 47

The experiments were carr ied out at f ixed s team pressure o f

1 90-200 kPa i n the j acket of the s team j acke ted pan . The volume of
material in the s team j acke ted pan was f ixed so that the rate of
heat ing would be the same for all runs . Samples were taken at various
t imes for viscos i ty measurement . The temperature and time of hea ting
were recorded . From the results , the rates o f heat ing were d if ferent
and could no t be controlled in the exis ting equipment . The v iscos i t ies
of samples a t various times were also d i f ferent b etween exper imental
runs as a result of dif ferent rates of heating . This can be seen in
Figure 3 . 2 .However , the maximum viscos i ty was reached af ter the tem­
°
pera ture of the baby f ood rose h igher than 87 C and af ter a t ime of
heat ing vary ing from 1 0 to 14 minu tes . At this point , i t was believed
that all the s tarches were fully gelatinized . There fore the preheat ing
was designed to achieve this in all samples . The s team pressure was
1 9 0-200 kPa and the f inal temperature of the baby f ood had to be h igher
°
than 87 C . The time of heat ing could be f lexible depend ing on the
amount of baby food to be hea ted . As the ini t ial temperature could
affect the rate of heat ing so the thawed s lurry had to be chi lled for
°
45 minutes at 1 0 C before preheat ing .

3.5 FINAL PROCESS

The f inal formulat ion decided , was :

Beef 5 . 0%
Carrots 1 0 . 0%
Peas 5 . 0%
Pota toes 30 . 0%
F lour 1 . 2%
Corn f lour 2 . 5%
Bar ley f lour 0 . 8%
Yeas t extract 0 . 4%
Salt · 0 . 4%
Wa ter 44 . 7%
-1
Ascorb i c acid 0 . 2 mg g
-1
Ribof lavin 25 . 0 )l g g
 48

20 . 0 1 00
I '- /'
I , .,. .....
/ -----:- -
- - -./ �
-
-
(!)
0.
tJ
80
16 . 0 �(!)
t1
.......

Ill
'a
("")

�
.....

t1
�
(!)
X
12.0 60
:>..
-

·�
-1-J
0
CJl n
0
tJ
-

CJl
..-i
::> 8.0 .. 40

4.0

o.o

0 10 20 30 40 50

Time (min)

F IG . 3 . 2 Time , Temperature and Viscos i ty Relationshi ps During

Preprocess ing of Baby Food

temperature- time relationships for experiment 1

temperature- time relationships for experiment 2

temperature- time relationships for experiment 3

-- - ---- viscosity- t ime relationships for experiment 1

. .. viscosi ty- time relationships for experiment 2

-- - - -tl viscosi ty- t ime relationships for experiment 3

 49

Frozen coarsely minced beef was minced again through the 0 . 25 cm

diameter plate o f a Kenwood mincer twice and put ( about 500 g ) in a
°
plas tic bag before s tor ing at - 1 0 C . Commercial frozen peas , carrot
cubes and potato chips were used to ease the preparat ion s tep . Frozen
minced beef was thawed , mixed wi th all frozen vegetab les and o ther raw
materials and 20 mg of ascorb ic acid and 2 . 5 mg of ribof lavin per 100 g
of slur ry , dis integrated under vacuum of 68 . 9 kPa pressure in a JEFFCO
we t dis integrator for 3 minutes and then lef t under vacuum for ano ther
2 minu tes . This s lurry was screened and passed through a MINOR-homogen­
iser which was operated at 34500 kPa pressure . The prepared s lurry was
vacuum packed in SARAN bags and frozen immed iately in a plate free zer .
The preparat ion of raw s lurry was carried out in 1 6 kg batches provid ing
enough s lurry for all experimental runs . The frozen prepared slurry
° °
was kep t a t -30 C and thawed in a wa ter bath held in a 25 C controlled
room for 2� hours before further process ing . Exac tly 800 g o f thawed
0
s lurry f rom each batch was mixed and chi lled at 1 0 C for 4 5 minutes
g iving exac tly 12 kg for prehea ting .

Preheat ing was carried out in a MERCER s team j acke ted pan (30 cm
- 3
diame ter , maximum capaci ty of 1 2 , 000 cm ) with a Pioneer mixer model
-1
2600 (Premier Colloid Mills Ltd . ) a t high speed o f 50 s and the s team
pressure in the j acke t of 1 90-200 kPa until the temperature of the
°
b aby food reached 87 C . Lacquered cans were then f i lled wi th hot baby
food wi th minimum pos s ib le headspace and immediately vacuum sealed .
°
The cans of baby f ood were then immersed in a 60 C water bath for 80
minutes before processing in the retor t . E igh t control cans were
randomly taken, 2 cans were kep t at amb ient tempera ture for viscos i ty
°
and co lour analysis , the remaining cans were kep t a t - 1 0 C for as corb ic
acid and ribof lavin analysis .

0
The remaining cans taken from the 60 C water bath were process ed
in a retor t . One of the cans was equipped with 5 thermocouple j unct ions
( Figure 3 . 1 ) . The retort was c losed , and the thermocoup le ends were connected
to a 1 2-point Honeywell - Brown recording po tentiome ter . Re tor t operat ion
was exactly the same as described in 3 . 3 . 3 . 2 . The temperature used and
duration of process ing were varied .
 50

After cooling , two o f the heated cans were kep t at amb ient temper­
°
a ture for viscos i ty and colour measurement , and the res t kep t at - 1 0 C .
Viscos i ty and co lour measurement were car ried ou t in the same day .
Frozen control and heated cans for each experimental run were thawed
in the amb ient tempera ture water bath at the same t ime . The can content
was mixed , then the sample was taken for analysis .
 51

4. TEMPERATURE DISTRIBUTION IN A CAN

DURING PROCESS ING

4. 1 INTRODUCTION

A maj or obj ec tive of this s tudy was to es tab lish a calculation

procedure whi ch , g iven the process ing cond i t ions , could be used to
predi c t the extent of process ing o f the various critical components
of the food . Before describing the detai l , it may be helpful to set
out the sequence of this par t of the inves t1gation .

Firs t , in order to have a basis for comparison a careful series

o f experimen tal tes ts were carried out . Because o f the tempera ture
sens i t iv i ty of the reac tion rates , temperatures should be known accur­
°
ately wi thin � 0 . 25 C . And because tempera tures varied wi th pos i t ion , as
wel l as wi th t ime , it was necessary to be ab le to predi c t tempera tures
at all pos i tions within the can . For tes ting purposes , four points
were cons idered suff icient �. I f these could b e f i t ted then the o thers
would presumab ly conform to the geometrical p a t tern .

For pred ic tion two broad approaches were used , one based on an
analy tical solu tion and the o ther using a numer ical f inite d if ference
me thod , to the heat conduc t ion equat ions . Because o f the many calculations
needed , b o th were carried out by compu ter .

Thermal properties of the material were needed for these calcula tions �
and they were es tima ted f rom the experimental results .

The predi c tions f rom the two calculation approaches were compared
wi th the experimental results . In general b o th approaches , when the bes t
thermal d ata were used , gave a very good f i t and thus confidence to the
pred i c tion procedure , except for a cons is tent irregular i ty in the early
s tages of the cooling phase . This was no t fully explained but s ome
suggestions are advanced to account for i t and modifications to the
cooling calculations allow for i ts effects .
 52

These procedures led f inally to a calculat ion me thod whi ch was

sufficiently accurate for the kinetic predi c tions .

4.2 EXPERIMENTAL DETERMINA TION OF TEMPERATURE DISTRIBUTION

The prepared , prehea ted baby food was f il led and sealed i n the
p repared cans as des cribed in Chap ter 3 . Two d i f f erent re tort temper­
° °
atures were used , 1 20 and 1 29 C , and the canned b aby food was processed
for various t imes to get an approxima te microb i ologica l le thali ty number
10
(F ) of 5 , 9 , 1 3 , 1 7 and 21 min . The experimental runs were randomly
121 . 1
performed . The detailed process ing cond i t i ons together wi th the run
number of each experiment performed in this s tudy are shown in Tab le 4 . 1 .

The retort operation was the same as described in sec t ion 3 . 3 . 3 . 2 .

The temperature d i s t r ib u t ion in the can was measured a t various points
by thermocouples connec ted to the Honeywell-Brown recording po ten tiometer
as describ ed in Table 3 . 1 . The recorded temperatures at points 1 , 2 , 3 and
4 are shown in Figures 4 . 9 and 4 . 1 0 .
 53

TABLE 4 . 1 Exper imen tal Run Number and Process ing Condi t ions

Cooling* Approxima te
Ini tial Re tort* Heating** Cooling***
water 10
temper - temper - time t ime F
Run No . temper- 1 21 . 1
ature ature
o o s ature s intended
c c o
c min

7 60 . 0 1 20 . 2 38 1 6 19 . 4 2400 5
4 60 . 0 1 19 . 6 5112 21. 3 2400 13
9 61.0 1 20 . 0 5256 19 . 9 2400 17
2 60 . 3 1 19 . 8 6 1 20 20 . 8 2400 21

6 61.0 1 29 . 1 2952 20 . 8 2400 5

1 58 . 8 1 28 . 7 3384 20 . 6 2400 9
8 60 . 2 1 28 . 6 3456 22 . 0 2400 13
5 61.0 1 29 . 2 3744 20 . 2 2400 17
10 59 . 0 1 29 . 1 38 1 6 20 . 0 2400 21

* Average temperature calculated from the recorded tempera tures

ob tained from each experimental run .

** The interval be tween the t ime when the required re tor t temperature
was reached to the t ime when the cooling water was turned on .

*** The interval be tween the t ime when the cooling water was turned
on to the end of cooling .
 54

4. 3 COMPUTER PROGRAMS FOR TEMPERATURE DISTRIBUTION CALCULATION

Two computer programs based on the analy tical solution and the
numerical f inite dif ference method were s t udied and compared wi th the
experimental measurements ; the programs were wri t ten in FORTRAN IV
language and run on a Burroughs B6 700 computer .

4. 3. 1 Analytical Solut ion Me thod

The content of the can are a f ini te cylinder at an ini t ial

temperature , TI , and wi th thermal d i f fus ivity , a . When the can is
put in a medium at temperature , TA , there is heat trans fer in all
three direc tions . From hea t transfer theory , thi s complex three
dimens ional heat trans fer can be broken down into the r ad ial heat
trans fer and infinite s lab heat trans fer .

I f YC i s the solution for radial heat transfer

YL is the solution for inf ini te s lab heat transfer .

For a short cylinder

T -TA
(YC) (YL) (4. 1)
TI -TA

where T is the temperature of any point at time , t .

From Cars law and Jaeger ( 19 5 9 , p . 199 and p . 100) , where heat
d i f fus ivi ty is cons tant ,

J ( S r / a) ( -S at / a )
2 2
o n n
S J (S )
YC • e ( 4 . 2)
n 1 n

where a is cylinder radius

r is dis tance from the centre in radial direc tion
S is n
th
pos i t ive roo t of J ( S ) = 0
n o
t is t ime
 ------- ----

55

m
4 (- 1 )
�
oo
YL = rr cos
=0 ( 2m+ 1 )

( 4 . 3)

where h is half-heigh t o f the cylinder

x i s the dis tance from the centre in the axial direction .

2
Where a t / a is less than 0 . 0 2 and r / a is not too small , the series
is slow to converge but a shor t term approxima t ion exists ( CARSLAW
and JAEGER , 1 9 5 9 , p . 3 30 ) .

0 0 5
a ·5 ( ) i erfc ( z ) +
( a-r) ( a ta) "
YC = 1- ( erfc z +
0.5 1 .5
r 4 ar

( 4 . 4)

where z is ( a- r)
0 5
2 ( at) ·

2
F or the same reason , _where a t /h is small , equation ( 4 . 5 ) has to
be used ins tead of equation ( 4 . 2) ( CARSLAW and JAEGER , 1 9 5 9 , p . 309) • .

n ( 2n+l ) h-x
YL = 1- (! (-1) erfc ( ) +
n=O 0
2 (a t ) • 5

n ( 2n+1 ) h+x
'fn=O (- 1 ) erfc (
0
)) ( 4 . 5)
Z (at) . 5

In the canning process , temperature dis t ribution in b o th heating

and cooling phases is required . In the heating phas e , the temperature
dis tribut ion can be calculated by

T = (TA-TI ) � ( r , x , t) + TI ( 4 . 6)

where <f> ( r , x , t ) i s 1 - (YC ) (¥'1) at the point ( r , x) at t ime , t

YC is the solution calculated by equation ( 4 . 2 ) o r ( 4 . 4)
YL is the solution calculated by equation ( 4 . 3) or ( 4 . 5 )
T is the temperature at (r , x) at time , t
TA is the retort temperature
TI is the initial temperature
 56

a is the can radius

h is the half of can height
r is a dis tance from the centre of the can in the rad ial
d irec t ion
x is a dis tance from the centre of the can in the axial
direc tion
t is the to tal t ime from the beginning o f the heating phase
pos i t ive roots of J ( 8) = 0 .
th
is the n
0

In the cooling phase , i f the temperature o f the whole can content

at the beginning of cooling is assumed to b� uni form and eq�al to the
retort temperature ( Hicks , 19 5 1 ) , then the temperature distrib u tion
can be calcula ted by

T ( TA-TI ) � ( r , x , t ) + (TC-TA ) � ( r , x , t - t 1 ) + TI (_4 . 7)

where TC is the cooling water temperature

t is the heat ing time .
1

The computer program was cons truc ted based on the above theory ;
equa tions ( 4 . 1 ) to ( 4 . 7 ) were used . For equa t ion ( 4 . 1 ) and ( 4 . 2) , 6
terms in each series were calcula ted as Fleming ( 1 9 7 1 ) s ta ted tha t up
to 3 terms of the series mus t be evaluated . EquatiQn (_ 4 . 4 ). and
( 4 . 5) were used where a t / a was less than 0 . 0 2 ; r / a was more than 0 . 1
2

and at / h was les_s th.:m 0 . 3 ( F lemin g , 1 9 7 1 ) . Where r / a was less than

2

0 . 1 , the value of YC was se t equal to zero . The f low char t of the

computer program and the details of the program are in Appendix 4 . 1 .

The calculated temperatures from the computer program were compared

with the ones calculated by hand calculator based on the proces sing
cond i t ions of run no . 6 for the heating phase to check the accuracy
of the cons truc ted program, and it was found tha t the calculated
temperatures were identical ( Tab le 4 . 2) .
 57

TABLE 4 . 2 Comparison of the Calculated Temperatures at the Centre

of the Can

°
CALCULATED TEMPERATURE C
Time
Fo * Fo *
s c h
Computer Hand Calculator

0 0 0 6 1 . 00 6 1 . 00
360 0 . 0404 0 . 0 1 89 6 1 . 26 6 1 . 26
720 0 . 0807 0 . 0379 66 . 79 66 . 7 8
1 080 0. 1211 0 . 0 5 69 7 7 . 06 77 . os
1 44 0 0. 1615 0 . 07 5 9 87 . 60 87 . 6 1
1 800 0 . 20 1 8 0 . 09 4 8 96 . 75 9 6 . 74
2 1 60 0 . 2422 0 . 1 1 38 1 04 . 1 8 1 04 . 1 7
2 5 20 0 . 2826 0 . 1 3 28 1 1 0 . 03 1 10 . 03
2880 0 . 3 2 29 0 . 1517 1 1 4 . 57 1 1 4 . 56

* Fo is the F ourier number o f the rad ial direct ion which is equal to
c at/a 2 .

Fo is the F ourier number in the axial direct ion which is equal to

h
at/h 2 .

4 . 3. 2 Numerical Finite Dif f erence Me thod

The general heat trans f er equation for uns teady- s tate in a f inite
cylinder is

(4 . 8)

where C is heat capac i ty on a volume tric be.sis

A is thermal conduc tivity which is assumed to be cons tant
 58

Us ing the numerical f inite d i f ference method , equation (4 . 8 )

becomes

i+l i i i
T
m�n
- T
m2n >.
T - 2 T1 + T
m+l �n m2 n m- l , n
( ) +
M
c
fuc ) 2
(
i i i
T - 2 T + T
>. m , n+l m 2 n m 2 n- l
c
( )
2 +
(�r)

i i
T - T
>. 1 m�n+l m , n- 1
c r
( ) (4 . 9 )
2�r

a (A) + a ( B) + a ( C )

where r is (n- l ) �r
X is (m- 1 ) .6x
i
T represents temperature a t time , t
i+l
T represents temperature at time t + �t
a is the thermal diffusivity which is f. / C .

At the centre , where n= l , equation ( 4 . 9 ) was mod if ied by Albasiny

( 1 960) as

lim 1 2
3T
- a T
r-+0 = --
r ar 2
ar

2
>. 3T a T
>. -
r ar 2
ar

aT 2 2
then a T
c
ar
>. - + 2>. �
2 2
a:x: ar
i+l i i i i
T - T T 2 T + T
m2 1 m2 1 m+l z 1 - m 2 1 m- 1z1
so =a ( ) +
�t )
( fuc
2
i
i i
T - 2 T + T
2a (
m2 2 m1 1 m 20 )
( 4 . 10)
2
( �r)
 59

As suming that the temperature at the point below the centre

line is equal to the temperature at the corresponding point above
the l ine , the temperature at the centre (m= 1 , n= 1 ) and the temper­
ature along the height and the rad ius can be calculated by ( 4 . 1 1 ) ,
( 4 . 1 2 ) and ( 4 . 1 3 ) , respectively .

(4 . 1 1 )
6t

i+1 _ i
T T
m, 1 m, 1
( 4 . 1 2)
6t

i+1 i i i
T T T - T
1 •n )
_

1 ,n l,n 2•n
2a ( + a ( B) + a (C ) (4 . 13)
6t 2
( 6x)

The computer program was cons tructed based on the above equations
by assuming the ini tial temperature at all points was equal throughout the
can , while the temperature at the surf ace was equal to the retort temper­
ature during heat ing and equal to the cooling water temperature during
cooling . The details o f the program are in Appendix 4 . 2 .

Us ing this program , the degree of accuracy of tempera ture dis tri­
bution pred i c t ion was dependent on the number of t ime increment s , 6t ,
and dimensional increments , 6r and 6x . The dimensional increments ,
6r and 6x , of less than 0 . 00 8 and 0 . 0 1 0 m and the t ime increments of
7 . 5 seconds should be used (Teixeira , 1 9 7 1 ) . The d imensional increments ,
6r and 6x of 0 . 00 3 7 and 0 . 00 5 4 m and the t ime increment of 6 seconds were
used in this s tudy .
 60

4.4 THERMAL PROPERTY DETERMINATION

To use the two programs to f ind the temperature d i s t r ibution ,

only one thermal property , the thermal dif fus ivity , a i s needed .
This property can be calcula ted from the exper imental tempera ture
data using the analy t ical solut ion of the hea t transfer equation .

The analyt ical solut ion for heat transfer can b e re-expressed as :

2 2
-Fo f3 -Fo TI /4
T - TI c n X
1-Ae Be ( 4 . 14)
TA - TI

J ( 8 r / a)
00 o n
where A is 2
�= 1 f3 J ( f3 )
n 1 n

m
- l:
4 00 (- 1 ) ( 2m+ 1 ) Tr x
B is cos
TI m=O ( 2m+ l ) 2h

If Y is ( T - TI) / (TA - TI) , where T is the centre temperature ,

and only one term in each series is cons idered , equa tion ( 4 . 1 4 )
s imp l i f ies to :

2 2
CtTI
+
af3
1
ln Y cons tant - t ( - - ) ( 4 . 1 5)
2 2
a 4h

From a plot o f ln Y agains t time , t , the s lope of the regress ion

. 2 2 2 2
line on the s t ra1ght part will be equal to - (af3 / a + arr / 4h ) .
1
Knowing S = 2 . 4048 and the d imens ions of the can used , a = 0 . 037 m ,
1
h = 0 . 054 m , the thermal d if fus ivi ty can b e calcula ted a s illus trated
in equation ( 4 . 16 ) .
 61

_
a ( ( 2 . 4048)
2
+
TT
2
) slope
2 2
( 0 . 03 7 ) 4 (0 . 054)

-slope 2 -1
m s (4. 16)
5070 . 4568

This me thod has been used b y other workers (Olson and Jackson ,
194 2 ; Teixeira , 1 9 6 9 ) . The graph plot ted o f ln Y versus t ime is a
stra ight l ine , af ter the ini t ial heat ing lag period , and only one
term in the summat ion i s adequate (Hicks , 1 9 5 1 ) . Therefor e , the above
method should resul t in an accurate thermal. dif fusivity calculation as
long as the tempera ture measurement is accurate .

In the preliminary exper iments , the canned baby food was proces sed
under various tempera tures and the centre temperature was measured wi th
t ime . The thermal d i f fusivity was calcula ted from the s lope ob tained .
The results are shown in Table 4 . 3 . The average thermal d i f fus ivity
-7 2 - 1
was found to b e 1 . 5 7 3 7 x 10 m s with the s tandard deviation o f
-7 2 -1
0 . 06 7 8 x 1 0 m s • This value of " a " was s imilar to d a t a g iven b y
Teixeira ( 1 9 7 5 ) , C rump ton and Treadgill ( 1 9 7 7 ) and Lenz and Lund ( 1 9 7 7a)
for o ther food sys tems . Crump ton and Treadgill ( 1 9 7 7 ) s ta ted in their
s tudy that the retort tempera ture had less effect on thermal d i f fu s ivity
than the phys ical s tate of the ma terial . The above results agreed with
Crump ton and Treadgill ' s s tudy as the deviation of calculated thermal
d if fusivit ies at d i f f erent retort temperatures was less than the dev ia t i on
of calculated thermal dif fus ivi ties of various exper imental runs at the
same retort temperature . Th is may have resul ted from the variation in
the contents f rom can to can , which was s ignif icant in o ther s tudies .
The variat ion of thermal dif fusivity between cans was 6 . 46% (Hurwitcz
and Tischer , 1 9 56) and 10- 1 5% in work carr ied out by Jackson and Olson
( 1 940) . Heterogeneous packs were found to result in even greater varia­
tions ( Esselen , 1 9 5 1 ) . Therefore , it was concluded that i t was valid
to use the average thermal d i f fus ivity for all process ing tempera ture
cond i t ions s t ud ied, as the baby food was homogeneous and the experimental
variation small .
 62

TABLE 4 . 3 Dif fusivi ties of Baby Food at Var ious Temperatures

7 Correlation
Re tort Tempera ture Dif fusivity X 10 Coef f i cient
o 2 -1 R2
c m s

1 28 . 3 1 . 57 1 7 0 . 999
1 . 5359 1 . 000
1 . 6 2 29 0 . 999
1 . 46 7 7 0 . 999
1 . 5465 0 . 999

1 20 . 6 1 . 5456 0 . 999
1 20 . 0 1 . 6 10 1 0 . 999

1 11 . 1 1 . 5564 0 . 998
1 . 7064 0 . 999
-·

Some o f the raw materials were changed in s ta te s o as to save t ime

in p repara t ion ( s ec t ion 3 . 5 ) , frozen p o ta to chips and carrot cubes and
also frozen minced beef were used ins tead of the fre sh ones . The thermal
d i f fusiv i ty of the baby food was redetermined and found to be 1 . 5429
-7 2 - 1 -7 2 -1 0
x 10 m s with the s tandard deviation o f 0 . 0 19 6 x 10 m s a t 1 20 C
-7 2 -1 -7 2 -1
and 1 . 5 2 7 7 x 10 m s wi th the s tandard deviation of 0 . 0 3 1 8 x 1 0 m s
°
at 1 29 C . The dif ference be tween the s e two means was tes ted and found
to be ins ignif i can t . De tails of the measurements and analy s i s are shown
in Appendix 4 . 3 . Therefore , the mean thermal dif f us ivi ty o f 1 . 5 3 5 3
-7 2 - 1 -7 2 - 1
x 10 m s with s tandard deviat ion o f 0 . 026 1 x 1 0 m s was u s e d for
all the proce s s ing cond i tions s tudied .
 63

4.5 COMPARISON BETWEEN PREDICTED TEMPERATURES FROM THE TWO COMPUTER

PROGRAMS - ANALYTICAL SOLUTI ON AND NUMERICAL FINITE DIFFERENCE

The. pred ic ted temperatures from b o th programs based on 3 points

in the can of run no . 6 were almos t identical ( Tab le 4 . 4 ) . The
°
d i f ferences in tempera tures were mos tly about 0 . 1 to 0 . 2 C in both
heat ing and cooling phases . In the heating phase , the predic ted
temperature by the numerical f inite d i f f erence program was h igher
than the predic ted temperature by the analy t ical solution program
while in the cooling phase , the numerical f ini te d i f ference program
gave a lower predic ted temperature . The d i f ference was greater a t
the outside point than the centre of the can in the beginning o f b o th
0
heating and cooling phases . The greates t difference was 0 . 4 C for
°
the centre and 0 . 9 C for the outs ide point in the heating phas e .
Thi s difference could be due to the slower convergence in the heating
phase of the analy tical solut ion . Als o , as the temperature gradients
were h igh a t the beginning , the temperatures o f the can contents changed
rap id ly , thus smaller t ime s teps should have b een used to ob tain more
accurate approximation in the numerical f ini te d i fference program .
I n the cooling phase , the d i f ferences were larger , these could b e due
to the assump tion made in the analy tical solution p rogram tha t the
ini tial temperatures of the can contents were uniform and equal to the
retort tempera ture ; this resul ted in higher pred i c ted tempera ture s .

The d i f f erences in predic ted temperatures by these two programs

based on run no . 6 are also shown in Figure s 4 , l and 4 . 2 for the centre
poin t and the outside point , ( r / a , x / h) o f ( 2 / 3 , 2 / 3 ) . The res iduals
(predic ted temperatures by analytical solution - predi c ted temperatures
by numerical finite d i f f erence me thod) were calculated for b o th the
centre point and the outs ide point . The calculation was d one at 1 . 2
minute intervals , the d i s t r ibution o f res iduals is shown in Figure 4 . 3 .
° °
The mean res idual was 0 . 0 7 C with a s tandard deviation o f 0 . 34 C for
° °
the centre point and 0 . 0 7 C with a s tandard deviation o f 0 . 54 C for
the outs ide point . These d i f f erences were small and could be considered
insi gni f icant . Therefore , to tes t the accuracy of pred i c tions , only
predic ted temperatures from the analy t ical solution p rogram were compared
with the experimental temperatures .
 64

TABLE 4 . 4 Comparison of Tempe ra tu res Pred i cted by the Analyt ical

Solu tion and the Numerical Finite Difference Programs

°
TEMPERATURE C

at r / a = 1 /3 , a t r /a = 2/3 ,
=
a t the centre
x /h = 1 /3 x /h 2/3
T ime Fo FoX
c
s Analy-
Analy- Analy- Fini te
F inite Fini te
t ical tical t ical

Heat ing
0 0 0 6 1 . 00 6 1 . 00 6 1 . 00 6 1 . 00 6 1 . 00 6 1 . 00
72 0 . 0081 0 . 0038 6 1 . 00 6 1 . 00 6 1 . 00 6 1 . 00 6 1 . 74 6 2 . 64
1 44 0 . 0 1 6 2 0 . 00 7 6 6 1 . 00 6 1 . 00 6 1 . 02 6 1 . 09 66 . 76 68 . 1 6
216 0 . 0242 0 . 0 1 1 4 60 . 99 6 1 . 02 6 1 . 29 6 1 . 50 73 . 46 7 4 . 68
288 0 . 0323 0 . 0 1 5 2 6 1 . 05 61 . 13 6 2 . 05 6 2 . 36 7 9 . 86 80 . 7 9
360 0 . 0404 0 . 0 1 89 6 1 . 26 6 1 . 43 63 . 34 63 . 77 85 . 44 86 . 1 4
7 20 0 . 0807 0 . 0379 66 . 7 9 6 7 . 24 74 . 1 1 7 4 . 60 103 . 1 7 103 . 3 5
1080 0 . 1 2 1 1 0 . 0569 77 . 06 7 7 . 44 86 . 04 86 . 38 1 1 1 . 97 1 1 2 . 04
1 440 0 . 1 6 1 5 0 . 0 7 59 87 .60 87 . 88 96 . 1 5 9 6 . 36 1 17 . 13 1 17 . 17
1 800 0 . 2 0 1 8 0 . 0948 96 . 7 5 96 . 93 104 . 09 1 04 . 2 1 1 20 . 48 1 20 . 50
2 1 60 0 . 24 2 2 0 . 1 1 38 1 04 . 1 8 1 04 . 29 1 10 . 16 1 1 0 . 23 1 22 . 7 9 1 22 . 80
2520 0 . 2826 0 . 1 3 28 1 1 0 . 03 1 1 0 . 09 1 14 . 78 1 14 . 81 1 2 4 . 43 1 24 . 43
2880 0 . 3 2 29 0 . 1 5 1 7 1 1 4 . 57 1 1 4 . 60 1 1 8 . 27 1 1 8 . 28 1 25 . 6 1 1 25 . 6 1
2952 0 . 3 3 1 1 0 . 1 554 1 1 5 . 34 1 1 5 . 36 1 1 8 . 86 1 1 8 . 87 1 25 . 8 1 1 25 . 8 1
Cooling
72 0 . 00 8 1 0 . 0038 1 1 6 . 0 7 1 1 6 . 09 1 19 . 41 1 1 9 . 42 1 24 . 82 1 23 . 38
1 44 0 . 0 1 6 2 0 . 00 7 6 1 1 6 . 7 7 1 16 . 78 1 1 9 . 90 1 19 . 81 117.01 1 14 . 78
216 0 . 0 2 4 2 0 . 0 1 1 4 1 1 7 . 44 117 . 41 1 1 9 . 98 1 1 9 . 65 106 . 5 1 104 . 57
288 0 . 0323 0 . 0 1 5 2 1 1 7 . 9 8 1 1 7 . 85 1 1 9 . 23 1 1 8 . 69 9 6 . 49 9 5 . 00
360 0 . 0404 0 . 0 1 89 1 1 8 . 23 1 1 7 . 96 1 17 . 63 1 1 6 . 94 87 . 7 5 86 . 64
7 20 0 . 0807 0 . 0379 1 1 1 . 96 1 1 1 . 24 1 0 2 . 39 1 0 1 . 60 60 . 1 6 59 . 87
1 440 0 . 1 6 1 5 0 . 07 59 8 2 . 22 69 . 83
2 1 60 0 . 24 2 2 0 . 1 1 38 57 . 80 48 . 9 7
 65

1 30

125
u
,....._

'0
Q) 1 15
lo-t
;:I
+J
CO
lo-t
Q)
p,
105
s
Q)
�

95

85

75

65

55

45

35
0 10 20 30 40 50 60 70 80 90

Time (min )

F IG . 4 . 1 C omparison o f Pred icted Temp eratur es from the Computer Programs

at ( r / a , x / h) of (0 . 0 , 0 . 0 )

(------ ) pred ic ted tempera tures from the analyt ical solu t ion
compu ter program
( ---
---) pred ic ted tempera tures from the numerical f inite
d i f f erence me thod program
 66

1 30

125

u
,-....

0
'-"

QJ
115
H
;:::l
CO
.j.J

H
QJ
p_,
105
r:;
QJ
�
95

85

75

65

55

45

35
0 10 20 30 40 so 60 70 . 80 90

Time (min)

FIG . 4 . 2 Comparison of Pred icted Temp eratures from the Corn uter Programs
at ( r / a , x / h) of ( 2 / 3 , 2 / 3 )

( ------ ) pred ic t ed temp eratur es from the ana ly t ical solut ion
program
(--- --- ) pred ic ted temperatures from the numerical f inite
d i f f erence program
 67

..
o
30 a) median 0.01 c
o
mean = 0 . 07 c
o
standard deviation = 0 . 34 c

o...e
r-.

'-"
20
:>-.
()
�
<1)
;::!
0"'
<1)
I-I
�
10

-0 . 7 5 -0 . 55 -0 . 3 5 -0 . 1 5 0 0. 1 5 0 . 35 0. 45

Re s i dual ( °C )

o
,..... b) median -0 . 0 1 c
=
60
o
mean = 0 . 07 c
o
standard deviat ion "" 0 . 54 c

....
o...e
r-.

1-
'-"

:>-.
40
()
�
<1)
;::!
0"'
<1)
I-I
�
20 1-

0 .rT ll _l _l j_

-2 . 25 - 1 . 50 - 1 . 00 -0 . 50 0 0 . 50 1 . 00 1 . 50

Re s i dual (° C )

F IG . 4 . 3 Distribution o f Res iduals for Compar ison of the Analy tical

Solut ion and the Numerical Finite Dif ference Method f or Run no . 6

a) a t the centre point , (r / a , x / h) of ( 0 . 0 , 0 . 0)

b) a t the p oint ( r / a , x / h ) of ( 2 / 3 , 2 / 3)
 68

Theoret ically , in the heat ing phase , the analyt ical solution could
give more accurate prediction than the numerical f inite d i f f erence method
as it was based on the exact heat trans f er for the uniform ini tial tem­
peratures while the numerical f inite d i f f erence was an approx imate pre­
d i c t ion . In the cooling phase , the temperature pred i c ted by the numerical
f inite d i f f erence me thod should b e more accurate as the actual pred icted
temperatures a t the end of the heating phase were used . In the analy t i cal
solut ion , the ini tial temperature of the can contents in the cooling phase
was assumed to be uniformly equal to the retort temperature and this may
resul t in inaccurate pred i c t ion , especially for a short heat ing t ime
process .

The t ime consumed by these two programs was f ound to b e dependent

on the number of points and the t ime increment required . Where only a
f ew points are required in temperature pred iction , the analytical
solut ion method will take less time than the f inite d i f f erence me thod
program . Where a large number of points are required , the f inite
d i f f erence me thod will consume less time and should be used as i t will
b e cheaper .

4.6 COMPARISON OF THE PREDICTED T EMP ERATURES FROM THE ANALYTICAL

SOLUT ION PROGRAM AND THE EXPERIMENTAL TEMPERATURES

The comparison of experimental temperatures and the analytical

solut ion pred ic ted temperatures was d one on 4 points in the can for
the process ing condi t ions of runs no . 6 and no . 7 . The mean value of
-2 2 - 1
the thermal d i f fusiv i ty o f 1 . 5 3 5 3 x 1 0 m s was used for a ll the
processing conditions .

4.6. 1 Comparison of Tempera tures in the Hea ting Phase

As can be seen from Figures 4 . 4 and 4 . 5 , the calculated temper­

a tures were c lose to the measu red temperatures in the heat ing phase .
°
The temperature d if ference was in the range of 0 . 5- 1 . 0 C a t the
°
b eginning where the temperature was lower than 1 00 C , then , it decreased
°
to 0 . 2-0 . 5 C where the hea ting times were longer and tempera tures were
higher .
 69

-
u u
,....._
1)0

«...-
1 30

0
'-' 120
120

"" ""
Q) Q)

;:l ;:l
1 10

-1-J -1-J
1 10

111 111
"" too ""
100

Q)
0.. 0..
Q)
90 90
s s
e-.
QJ Q)
e-. 80

�
80

\
'\
70 70

bO \ 60
\
\
�0 \ 50

40 40

0 10 20 30 40 50 bO 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

Time (min) Time (min)

- .. - -
( a) at r/a 0.0 , x /h 0.0 (b ) at r/a 0.0 x/h 1/3

- 130 - 130
u u
0 0
'-' '-"
120 • 120

"" ""
QJ
1 10
QJ
1 10

-1-J -1-J
;:l ;:l
111 100 111
"" ""
100

QJ QJ
�
0..
s
90
\ §- 90

\ e-.
\ QJ
80
QJ
\
e-. dO
\
\
\
70

\
60 \ 60
\
50 \
\
50

\
•

40 40

0 10 20 30 40 50 60 70 . 80 90 lOO o · 10 20 30 40 so 60 70 80 90 lOO

Time (min) Time (min)

, ;:;
,
(c) at r/a =
1/3 x/h = 1/3 (d ) at r/a 0.0 x/h =
2/3

FIG . 4 . 4 Comparison o f Experimen tal Temperatures and Pred i c ted Temperatures

from the Analy tical Solution Compu ter Program for Run no . 6 (re to rt
°
temperature was 1 29 C )
( ) experimen tal temperatures
(---- ---) pred i c ted temperatures
 70

120 120

,....._ ,....._
u u
0 '7
� '7
1 10 "" 110

:;."
QJ V
"' '7
......

QJ V
f
100 100

::1 f 1
::1
r
,... ,...

f +J
90 90 -

CO
f
CO '1
+J

,...
QJ QJ r;
0. 'I
80

0.
,... 80

E: E: r;
QJ QJ '/
H
70

H
70

60 60
"/

50

40

0 lO 20 30 40 � 60 70 80 90 100 JIO 10 20 30 40 � 60 70 80 90 100 110

Time (min) Time (min)

( a) at r/a = 0 . 0 , x/h = 0 . 0 (b ) at r/a = 0 . 0 , x/h = 1/3

120 120

,....._ ,....._
u u
0 0
1 10 1 10

......

QJ
......
100 lOO

� ::1
,...

+J
90 90

� CO
80
� QJ
80

� 0.
,...

� E:
QJ
'\
70 70

H
'\
'\
60 '0

�
'\
50

\ 40

0 10 20 30 40 � 60 70 80 90 100 110 0 10 20 30 40 � 60 70 80 90 lOO 110

Time (uiin) Time (min)

( c) at r/a = 1 /3 , x/h = 1 / 3 (d) at r /a = 0 . 0 , x/h = 2 / 3

FIG . 4 . 5 Comparison of Exper imental Tempera tures and Predic ted Temperatures
f rom the Analytical Solution Computer Program for Run no . 7 ( re tort
°
temperature was 1 20 C)
( ------- ) experimental temperatures
(--- --- ) predic ted temperatures
 71

The larger di f ference at the beginning of heating could have

resulted f rom the equations used . When time was small , the value o f
� ( r , x , t) in equation ( 4 . 6 ) was zero . Therefore , the predic ted temper­
atures were equal to or nearly equal to the ini tial temperature . The
deviat ion of the predic ted temperatures from the experimen tal temper­
atures could also have been caused by the errors in the thermocoup les .
These errors were firs tly the inaccuracy of p lacing the thermocoup le
j unctions as only one millime tre could e f fect the temperature , and
secondly the c onduction through the thermocouple wires which could be
high at the beginning of heating phase as the temperature d ifference
between outside and the j unction is high . . This conduction also
depended on the thermal diffusivi ty o f the food . There�ore , the cal­
culated temperatures could possib ly be more accurate than the experi­
mental temperatures .

The residual ( i . e . the experimental temperature - the predicted

temp erature) was calculated for the centre point and shown in Appendix
4 . 4 ( a) for runs no . 6 , 7 , 8 and 9 . The dis tribution o f the residuals
was the normal dis tr ibution . The res idual mean var ied f rom run to ·
0
-·

run , from - 1 . 1 to 0 . 4 C , with the res idual s tandard deviation from

° °
+ 0 . 4 to + 0 . 8 C . This s tandard deviation was less than the 1 . 7 C
f ound by Lenz ( 19 7 7 ) which was described as resulting f rom the biolog­
ical variab i li ty of the phys ical cons tants .

4.6.2 Comparison of Temperatures in the Cooling Phase

An irregular phenomenon was found in the cooling phase ( Figures

0
4 . 4 and 4 . 5 ) . The temperature rap idly decreased to 100 + 5 C and
some times held there f or 1-2 minutes , then , gradually decreased again .
This irregular cooling curve was also found by o ther workers (Powers e t
al , 1 9 5 2 ; Board et a l , 1960) Powers e t al ( 19 5 2 ) exp lained in their s tudy
that the rapid cooling occurred because the home- type canning j ars used
c ould vent during proces s ing and a high vacuum could ensue , which , in
turn , led to vigorous boi ling during cooling when the headspace s team
condensed causing rapid cooling of the c ontents . In 1949 Townsend e t al
in their comparative heat pene tration s tudy in j ars and cans , found that
the c ontents of j ars occasionally coo led faster than those of cans
although the later heated fas ter . They attributed the rapid cooling to
 72

the contents being s t irred by "boiling " . Board e t al ( 1960) also

found this rapid cooling phenomenon in cans . The cooling curves
ob tained when the retort pressure was reduced to 608 kPa or less
during cooling showed fas ter cooling than that calculated for the
conduc t ion mechanism and also some of them showed irregular f luc tua-
tions in rate of cool ing . They concluded that the mechanism of
cooling appeared to depend on whe ther cooling was p redominately by
conduc t ion or if it was accelerated by movement of the contents of
the can . Cooling by conduc tion was found in mos t of the cans where
they were cooled under 1 6 20 kPa super imposed pressure . I t was also
s tated that in the more viscous produc ts , swch as baked beans , cream
s tyle corn and solid meat , boi ling with consequent movement of mater-
ials in the can was probably the main cause of non-conductive cooling .
The phenomenon of boiling of the can content when the pressure was
released was also f ound by Hemler et al ( 1952) . The res iduals were
calculated as in 4 . 5 . 1 , the residual d is tribution is shown in Appendix 4 . 4
(b ) for experimental runs no . 6 , 7 , 8 , and 9 . The residual mean and
the residual s tandard deviation were calcula ted by assuming that the
residual d is tribution was a normal distribut ion . The res idual mean
° -
var ied from -0 . 9 to -3 . 3 C with the s tandard deviation varying from
° °
± 2 . 2 to ± 4 . 5 C . The res idual medians were -0 . 6 t o -2 . 7 C . This
0
indicated tha t the predic ted temperatures were 0 . 9 to 3 . 3 C higher
than the exper imental tempera tures . The res idual s tandard deviation
found was higher than those s ta ted by Lenz ( 1 9 7 7 ) and could not be
trea ted as the reault of the b iological variab i l i ty of the phys ical
cons tants . Thes� higher values were due to the irregular cooling
curve f ound in the present experiments .

Experiments were performed with dif ferent materials in the can ,

namely , water , s tarch so lut ion at the same concentration as in the
baby f ood ( 4 . 2%) , vege tab le puree and the homogenised baby food . The
other materials were fi lled into the cans withcut any headspace as
before . The baby food was filled into the cans wi th different head­
spaces - 0 , 0 . 6 , 1 . 3 .and 1 . 9 cm . The heat pene tration curves and the
cooling curves are shown in Figure 4 . 6 . In the can of water , con­
vec tive heat transfer occurred in both heat ing and cooling . S tarch \
solut ion also showed a s imilar hea ting and cooling pat tern except that
it was s lower i n heating and had a break point in the cooling curve
°
at the temperature of 60 C which could be explained by the change in
 73

- -
u u
Ill IH

0
�
120 120
'-'

110 1 10
QJ QJ
1-< 1-<
;:l 100 ;:l
+-1 lOO
+-1
� �
1-< 1-<
QJ 90 90
QJ
0... 0...
s 10
QJ s ao
H QJ
H
70 70

60 60

la la

40
40

30 30
10 20 lO 40 lO 60 70 80 90 100 0 10 20 30 40 lO 60 70 10 90 lOO 110

Time (min) Time (min)

(a) (b)

-
u
125
o
-
120 uo
u
'-'

......
�
110 0
QJ 1 10
1-<
;:l lOO
\�
+-1 QJ 100
;:l
"�
1-<
1-<
�

·�:;
90 +-1
·�'\
QJ 90
�

·;�
0... 1-<
s
0...
\•t\
10 QJ 10
H
QJ
s
t�
,,
70 QJ
\'\�
70
H

\��
\�
60 60

la - la

40 40

30 30
� io 2� 30 40 50 60 70 80 90 100 1 10 120 0 10 20 30 40 50 60 70 80 90 100 1 10

Time (min) Time (min)

(c) (d )

FIG . 4 . 6 Heat Pene tration Curves for Different Can Contents and Different
Head spaces
(a) for wa ter in a can wi thout any headspace ,
(b) for s tarch solution in a can wi thout any headspace ,
( c) for vegetable puree in a can wi thout any headspace ,
(d) for baby f ood in a can with ,

(_ ) no head space
(
-
_ - ) 0 . 6 cm head space
(-_- - ) 1 . 3 cm headspace
(- - - - -) 1 . 9 cm headspace .
 ------

74

the s tate of the s tarch paste . For puree and baby food with no head­
space , s imilar heating and cooling pat terns were found as before ( in
section 4 . 5 ) , wi th the irregular cooling curve phenomenon . Wi th
d i f ferent headspaces , the irregular cooling curve s till occurred .

From the results ob tained , the irregular cooling curve might be

caused by boiling and s team condensation in the can . When the pressure
was released , boiling could have occurred and the temperature in the
can would have decreased rap idly because of loss o f latent hea t due
to evaporat ion of water .When the pressure in the can was red uced to
°
the atmospheric pressure and the temperature was lower than 10 5 C ,
boi ling s topped , s team in the can condensed giving the latent heat
to the sys tem and the temperature was held there for 1-2 min , and
then the can contents were further cooling by the conduc tion heat
trans fer . This phenomenon created two parts in the cooling phase
involving two dif ferent thermal dif fus ivi t ies . Therefore , in the
cooling phas e , the assumpt ion of cons tant thermal diffus ivity was
invalid .

I t migh t be pos s ible to follow this irregular cooling curve by

us ing the numerical f inite dif ference method . However , i t would be
very complicated as the thermal dif fusiv ity canno t be assumed cons tant .
Further exper imental investigat ion was needed in e stimating the extent
of boiling and the change in therma l dif fus ivity where A and C had to
be determined s eparately . But there was no equipment available for
measuring the A and C , therefore , it was no t possible to use this
me thod to follow the irregular cooling curve in this s tudy . However ,
the predic ted temperatures from the analyt ical solution program and
the numerical f ini te di f ference method program were identical ( in
s ec tion 4 . 5 ) so it was cons idered valid to modify the analy tical sol­
ut ion program s o tha t the cooling curve of the predic ted temperatures
f i t ted the cooling curve of the experimental temperatures .
 75

4.6.3 Comparison o f Tempera tures in the Overall Process

The residual dis tribution , the res idual mean and the res idual
s tandard deviation were also calcula ted for the overall process .
The same method as described in sec tion 4 . 5 was used . The res idual
distribution is shown in Appendix 4 . 4 ( c) for run no . 6 , S , 7 and 9 . The
°
residual means for the overall process varied from -0 . 4 to - 1 . 2 C
° As the
wi th s tandard deviation varying from + 2 . 5 to + 3 . 4 C .
s tandard deviat ion found in the heating phase described in sec tion
4 . 6 . 1 was fairly small , this high s tandard deviation was mainly due
to the h igh devia t ion between the predic ted temperatures and the experi­
mental temperatures in the cooling phase des cribed in sec tion 4 . 6 . 2 as
a result of the irregular cooling phenomenon .

Therefore the analyt ical solution program could be used for the
heating phas e but had to be mod ified for the cooling phase .

4.7 MODIFICATION OF THE ANALYTICAL SOLUTION PROGRAM

The two parts of the cooling phase were referred to as the

"beginning of the cooling s tage " and the " later cooling s tage" , where
the beginning of the cooling s tage was def ined as a s tage s tar ting
f rom the t ime when cooling wa ter was turned on to the time when the
0
tempera ture reached 105 C and then the later cooling s tage s tarted at
°
105 C and continued to the end of cooling phase . This is shown in
Figure 4 . 7 .

4.7.1 The Beginning of the Cooling Stage

As higher thermal dif fus ivity used in the cooling phase would
result in lower predic ted temperatures , the thermal d i f fusivi ties of
7 - -7 -7 -7 2 - 1
1 . 5 353 x 1 0 , 2 . 0 x 1 0 , 2 . 2 x 1 0 , 2 . 5 x 1 0 m s were used in
the analyt ical solut ion . The predic ted temperatures were compared
with the experimental temperatures for f ive d ifferent exper imental
runs .
 76

1 20

u
,-....

0 1 10
..._,

Q)
H
;:I
.jJ 1 00
ell
H
Q)
s-
Q)
E:-l
90

Begin- k­
80
ning o f . 1
I the
I
cooling
70
1 1
s tage

�
60
Later cooling s tage

50

0 10 20 30 40 50 60 70 80 90

T ime (min)

FIG . 4 . 7 Diagram Showing Different Par ts in Hea t Process ing

 77

-7 2 -1
The thermal dif fusivi ty o f 2 . 2 x 1 0 m s was found t o give the
bes t approximation at the centre and at ( r / a , x/h) of ( 0 , 1 / 3 ) and
( 1 / 3 , 1 / 3) .
The variances of the predic ted temperatures at the centre ,
-7 -7
us ing var ious thermal d i f fus ivi ties of 1 . 5 353 x 1 0 , 2 . 0 x 10 ,
-7 -7 2 - 1
2 . 2 x 10 , and 2 . 5 x 10 m s , from the experimental temperatures
were de termined us ing 1 . 2 minute intervals . The plot o f variance versus
thermal diffus ivity is shown in Figure 4 . 8 . The thermal dif fusivi ty
-7 2 - 1
Of 2 . 2 X 10 m s was f ound to g1ve m1n imum var i ance . Th us , thi s
· ·

thermal dif fus ivity would give the bes t approximation of temperature
at the centre of the can .

��ere r/a was more than 1 / 3 and x/h was more than 1 / 3 , i t was found
-7 2 - 1
that thermal dif fus ivity of 2 . 2 x 1 0 m s could no t be applied . The
2
lower value o f 1 . 5 3 5 3 x 1 0 -7 m s - 1 gave a bet ter approximat ion in this
area .

The tempera tures a t (r/a , x/h) of ( 0 , 0 ) , ( 1 /9 , 0) and ( 2 /9 , 0 )

were measured experimentally t o determine the extent o f r where x was
-7 2 - 1
equal to 0 at which the thermal d i f fusivity of 2 . 2 x 1 0 m s could be
used . The experimental temperatures were compared with the predic ted
-7
temperatures calculated wi th thermal dif fus ivi ties of 2 . 2 x 1 0 and
-7 2 - 1
1 . 5353 x 10 m s It was f ound that nei ther of these thermal
dif fusivi ties gave well f i t ted predic ted temperatures at ( 1 /9 , 0 . 0 ) , and
-7 2 - 1
( 2 / 9 , 0 . 0) points . The higher thermal diffus ivi ty of 2 . 2 x 1 0 m s
was f ound to result in the lower predic ted temperatures whi le the lower
th erma 1 dif f us 1v� ty of 1 . 5353 x 1 0 -7 m s
2 -1 . t e d t emper-
· ·
gave hi gh er pre d 1c
atures than the experimen tal temperatures . Therefore , the thermal
-7 2 - 1
di ffusivity o f 2 . 2 x 1 0 m s should be used to prevent an overes t imat ion
of microbiological le thali ty fac tor .

-7 2 -1
In conc lus ion , the thermal dif fus ivi ty o f 2 . 2 x 1 0 m s was
used for temperature calculation of all points in the centre area where
r/a and x/h were less than or equal to 1 / 3 . Where r/a and x/h were more
-7 2 - 1
than t / 3 , the thermal d i f f fus ivity o f 1 . 5 35 3 x 1 0 m s was used .
 78

35

;--..
30
N
u
0
'-"

Q)
()
s:: 25
cu
·r-1
1-l
cu
::>

20 \ \

\ \

15
\

10

5
� £1
--

0
-
-7 2 . 5xl0 7
l . OxlO 1 . 5xl0 - 7 2 . 0x10 - 7

Therma l d i ffus ivi t y (m2 s- 1 )

FIG . 4 . 8 Variance versus Thermal D i f fusivi ty ,

(0 0) run no . 6
(G- - ---£1 ) run no . 7
(o c) run no . 8
(G- - -c ) run no . 9
 79

4.7.2 The Later Cooling S tage

0
When the temperature of the food reached 100 ± 5 C , the temperature
was found to decrease much more s lowly . Thus , the computer model had
to be further modified by set ting the temperature at which the smaller
thermal diffusivity would be used . Again the thermal diffusivity in
thi.s s tage and the signi f icant tempera ture for the beginning of this
s tage were determined by trial and error . It was found that the temper-
a -7
ature should be s e t at 105 C with a thermal dif fus ivi ty o f 1 . 3 2 x 1 0
2 -1
m s

Therefore , the computer program was cons truc ted for the early
coo 1 1ng
. s tage us ing th e th erma 1 diff usiv1ty of 2 . 2 x 10
-7 2 - 1
·
m s for
the centre area of r � a / 3 and x � h / 3 , the thermal dif fus ivi ty of
-7 2 - 1
1 . 53 5 3 x 1 0 m s for the outside area where r/a > 1 / 3 and x/h > 1 / 3
and in the later cool ing s tage the. thermal diffus ivity was set at
-7 2 - 1
1 . 32 x 1 0 m s , for every point in the can where the temperature
°
was lower than 1 05 C .

In the centre area , where the thermal dif fusivity used in the
-7 2 - 1
calculat ion was changed from 2 . 2 x 10 m s in the beginning of
- 7 m2 - l
the cooling to 1 . 3 2 x 1 0 s in the later s tages , it was found
-7 2 - 1
that the calculated temperatures us ing 1 . 32 x 10 m s for the first
few minutes were higher than the earlier pred ic ted tempera tures caus ing
f luc tuat ion in the cooling curve and devia tion from the experimental
temperatures . Therefore , further modification o f the computer model
was required . However , in the outs ide region where the thermal
. -7 2 - 1 -7 2 -1
diffusivity changed from 1 . 5 3 5 3 x 1 0 m s to 1 . 3 2 x 1 0 m s ,
the results obtained were reasonable and modif ication was not necessary .

The computer model was fur ther modif ied for the centre area by
assuming tha t the temperature a t every point in this area at the
beginning of the later cooling s tage were uniform and equal to the set
0
temp era tur e of 105 C . The hea t trans fer equations applied in this la ter
cooling stage were s imula ted from the heating phase , TA and TI in equa tion
( 4 . 6 ) were s ub s t i tuted by TC and TLIMIT giving :

T = YCOOL ( TLIMIT - TC) + TC (4 . 1 7 )

 80

where YCOOL is (YC) (YL)

0
TLIMIT is a set temperature whi ch was 105 C in this s tudy
TC is a cooling water temperature .

This equat ion was used to pred ict the temperatures in the later
cooling s tage for all points in the centre area where r/a was less
than or equal to 1 / 3 and x/h was less than or equal to 1 / 3 wi th the
-7 2 - 1
thermal diffusivity of 1 . 3 2 x 1 0 m s

4.7.3 Conc lus ion

A mod i f ied computer program was cons truc ted providing the oppor­
tuni ty to use any three thermal d if fus ivi ties in each par t o f process ing
and to vary the can s i ze , the time and dis tance increment , the process ing
tempera ture and proces s ing t ime , the set temperature .

The temperature d is tribution in the can in the heat ing phase was
-7 2 - 1
calculated by the following equat ions , using "a" o f 1 . 53 5 3 x 1 0 m s

For the heat ing phas e ,

2
where a t / a was less than 0 . 0 2 and r / a was no t less than 0 . 1 :

o 5 0.5
a + ( a-r) (ata) +
YC 1- ( o erfc ( z) ierfc ( z)
.5 1.5
.

r 4 ar

2 2
(9a - 7r - 2ar)at 2
i erfc ( z) ) (a)
l.5 2·5
3 2a r

where r/a was less than 0 . 1 :

YC = 0.0 (b)
 81

/
2
where at/h was less than 0 . 3 :

n ( 2n+1 ) h-x n ( 2n+1 ) h+x )

YL 1- (E (- 1 ) erf c ( )+ E (- 1 ) erf c ( )
_
n-0 0.5 n_
-0 0 5
2 (at) 2 (at) '
(c)

2
where at/a was more than 0 . 0 2 :

J ( 8 r/a) (-8 at/a )

2
2w
o n n
1 8 J (8 )
YC = z..n= e (d)
n 1 n

2
where at/h was more than 0 . 3 :

m 2 2 2
- I:
4 <X' (- 1 ) ( 2m+1 ) nx - ( 2m+1 ) 'IT at/4h
YL = cos ( ) e (e)
'IT m=O ( 2m+1 ) 2h

then :

T (TA-TI) ( 1- (YC) (YL) ) + TI (f)

For the beginning of- the cooling s tage ,

where r/a and x/h we re less than or equal to 1 / 3 :

T = ( TA-TI ) � ( r , x , t) + (TC-TA) � ( r , x , t- t ) + TI (g)

1

where � ( r , x , t) was 1- (YC ) (YL)

YC , YL were calculated from equa tions ( d ) and ( e ) us ing
-7 2 -1
" a" of 1 . 5 3 5 3 x 10 m s
� ( r , x , t- t ) was 1- (YC ) (YL)
1 t-t t- t
was calculate ! f rom equation (a) , (b) or ( d ) us ing
1
(YC)
t- t 2
1
a ins tead of a depend ing on the value of a ( t- t ) /a
2 2 1
(YL ) was calcula ted from equation ( c ) o r ( e ) using a
t-t 2
2
1 ins tead of a depending on the value o f a ( t- t ) /h
2 1
-7 2 - 1
was 2 . 2 x 1 0 m s .
 82

where r/a and x/h were more than 1 / 3 , the tempera tures were
-7 2 - 1
calculated by equation (g) using a o f 1 . 5 35 3 x 1 0 m s
2
•

For the later cooling s tage ,

where r/a and x/h were more than 1 / 3 the temperatures were
-7 2 - 1
calculated by equat ion (g) using a o f 1 . 3 2 x 1 0 m s
2

where r/a and x/h were less than or equal to 1 / 3 :

T YCOOL (TLIMIT-TC) + TC (h)

where YCOOL was (YC ) (YL)

t-t t- t
1 1
(YC) was calculated from equation (a) , (b) or (d) us ing
t-t 1 . 2
a ins tead of a depend ing on the value o f a ( t-t ) /a
3 3 1
(YL)
t- t was calculated from equat ion ( c ) , or (e) using a
1 3
2
ins tead of a depend ing on the value o f a ( t- t ) /h
3 1

The f low char t of this mod i f ied program and the computer program
are shown in Append ix 4 . 5 . The predic ted temperatures were then compared
with the ac tual tempera tures . The details of the comparison are discussed
in the following sect ion .

4.8 COMPARISON OF THE EXPERIMENTAL TEMPERATURES AND THE PREDICTED

TEMPERATURES FROM THE MODIFIED ANALYTICAL SOLUTION PROGRAM

As can be seen in Figures 4 .9 and 4 . 10 for runs no . 6 and 7 , the p redicted

temperatures f rom the modif ied computer program were much closer to the experimen­ ·

tal tempera tu res , especial ly in the beginning of the cooling . However , a larger
d i fference in the la ter part of cooling was found in some experimen ts ,
but the effect of these differences was much l ower than the d ifferences
in the h igher temperatures in terms of microbiological le thality and therefore
could be neglec ted in this s tudy . The comparison o f exper imental and
predicted temperatures are also shown in Appendix 4 . 6 for runs no . 8 and 9 .
 83

- -
u u
130
l JO

� '-"
0
120 120

(!) (!)
� 1 10 � llO
:::l :::l
+.1 +.1
m m 100
lOO
� �
(!) (!)
p. 90 p. 90
e: e:
(!) (!)
� 80 � 80

10 10

60
60

�0
50

40 40

0 10 20 JO 40 so 60 70 80 90 100 l lO
0 10 20 JO 40 so 60 70 80 90 100 1 10

Time ( min) Time (min)

(a) at r/a = 0.0 , x/h = 0.0 (b) at r/a = 0.0 , x/h • 1/3

- llO - lJO
u u
'-' '-'
0 o
120 120

(!) Cl)
· ::J .lj
�
::l
1 10 � 1 10

+.1 +.1
m 1 00 m lOO b
� �
(!) (!)
p. 90 p. 90
e: s
(!) (!)
� 80 � 80

70 10

60 60

�0
so

�0 40

0 10 20 JO 40 so 60 70 80 90 lOO
0 10 20 JO 40 50 60 10 80 90 lOO

Time (min) Time (mi n)

(c) at r/a 1 /3 , x /h 1/3 (d) at r /a 0.0 , x/h 2/3

= = =

FIG . 4 . 9 Comparison of Exper imental Temperatures and Predic ted Temperatures

from the Modi f ied Analy t ical Computer Program for Run no . 6
0
(retort temperature was 1 29 C)
( ) experimental temperatures
(--- ---) predicted temperatures
 84

1 30 130
u u
...... ......

0 120 0
.......
120
.......

QJ QJ 1 10
1-< 110 1-< 7
7

�
::l ::l �
Cll
� �

�
lOO
1-<
Cll lOO

r
1-<

V
QJ QJ 90
0. 90 0.

�
� �

E-<
QJ QJ

�
80

f
E-< 60

f �
'I �
10 70

60 -'/'
60

so

40
10 20 30 40 so 60 10 80 90 100 1 10 0 10 20 30 40 so 60 70 80 90 100 1 10
0

T ime (min) Time ( min)

( a) at r/a = 0.0 , x /h = 0.0 (b ) at r/a = 0.0 , x/h = 1/3

130 ...-.. I)O

u
0
....... 120
u
...... 120

0
....... 1 10 1 10

QJ
1-4 lOO lOO
::l
�
Cll 90 90
1-<
QJ
0. 80 80
�
QJ
E-< 10 10

60 6U

so

40 40
0 10 20 30 40 so 60 70 10 90 lOO 1 10 0 10 20 30 40 SO 60 70 80 90 100 llO

T ime (min) Time (min)

(c) at r/a = 1/3 , x/h = 1/3 (d) at r/a = 0 . 0 , x/h = 2/3

FIG . 4 . 1 0 Comparison of Exper imental Temperatures and Predic ted Temperatures

from the Modi f ied Analytical Solution Computer Program for Run no . 7
0
( retort temperature was 1 20 C)
( ) experimen tal temperatures
(--- ---) pred ic ted temperatures
 85

The lethali ty , F �� 1 • 1 at the points o f (r / a , x / h) o f ( 0 . 0 , 0 . 0 )

and ( 0 . 0 , 1 / 3) for experimental runs no . 6 and 7 was calculated us ing
temperatures data from the experiments and computer program . The
me thod of calcula tion is described and shown in Appendix 4 . 7 . An
examp le o f the cal cula tion and the resul t is shown in Append ix 4 . 8
for the centre point based on the predic ted tempera tures for run
10
no . 6 . The F calculated from the experimental temperature data
��
121• 1
were higher than the F
1.1
calculated by predi c t ed
The d i f f erence between exper imental and calculated F
mperature data .
for micro­
��
121 • 1
organisms for run no . 6 and run no . 7 , were 5 . 44% and 9 . 28% respectively
at ( 0 . 0 , 0 . 0) and 1 . 7 6% and 1 1 . 2 1 % respec t ively a t ( 0 . 0 , 1 / 3) respec t­
ively . The d i f ference in F �� 1 . 1 for ascorb ic acid , us ing the k and
Ea determined by Chi t taporn ( 1 9 7 7 ) , was lower , 4 . 25 and 3 . 58% at ( 0 , 0 ) and
3 . 1 4 and 4 . 43% at ( 0 . 0 , 1 / 3) for runs no . 6 and 7 respec tive ly . In
terms of concentra tion , the final concentration calculated based on
the experimental temperature data was lower than the f inal concentration
calculated based on the pred ic ted temperature data . The percen tage
d i f ference be tween these calculated f inal concentrations ( (x 1 - x 2 ) / x 2
where x is a calcula ted f inal concentration based on pred i c ted temper­
1
a ture data and x is a calcula ted f inal concentration based on experi­
2
mental temperature data ) was 0 . 6 , 0 . 5% for run no . 6 and 0 . 6 , 0 . 8% for
r un no . 7 a t ( 0 . 0 , 0 . 0 ) and ( 0 . 0 , 1 / 3 ) respec t ively . These d i f ferences

were less than the chemical analyt ical errors .

The d i f f erences be tween the predic ted tempera tures ob tained from
the modified computer program and the experimental tempera tures were
less for the point on the axis where r / a was equal to zero than o ther
points where r / a was increas ed . At r / a equal to 1 / 3 , the d i f f erences
were higher , this could be exp lained by the error in placement of the
thermocoup les . Where r / a was equal to 1 / 3 , the equivalent d is tance
from the centre of the can was 1 . 2 33 cm but the placement dis tance
used in the s tudy was 1 . 2 cm . A d ifference of 0 . 033 cm in the experi­
ment could have resulted in the slower hea ting and cooling rates which
were found in the results shown in Figures 4 . 9 (�) and 4 . 10 (c) .
 86

At the change from the first to the second s tage of cooling , the
predic ted temperatures at the outside points rose sligh t ly ( Fi gures
4 . 9 ( d ) and 4 . 10 ( d) ) .
This could b e explained a s a result of changing
-7 2 - 1 -7 2 - 1
the thermal d i f fus ivi ty from 1 . 5 3 5 3 x 10 m s to 1 . 32 x 10 m s •

However , i t was cons idered to be the b e s t approximat ion o f the temper­

ature dis tribution tha t could be made .

The res idual dis tribution for both the overall process and the
cooling phase were determined for each experiment us ing 1 . 2 minute
intervals . The same me thod as des cribed in section 4 . 5 was used . .
The d i s tr ibution is shown in Append ix 4 . 9 a ,b for the overall process
and for the cooling phase for runs no . 6 , 8 , 7 and 9 . The dis tribution
was a normal dis tribution . The res idual means varied for the overall
°
process f rom 0 . 1 to 0 . 7 C wi th the s tandard deviations varying from
° °
1 . 0 to 1 . 9 C and for the cooling phase from 0 . 9 to 1 . 7 C wi th the
0
s tandard deviations varying from 1 . 2 to 2 . 3 C . These res idual s tandard
deviations were lower than those found from the unmodi fied computer
program in sec tion 4 . 6 . 2 .

For the overall process , the res idual s tandard deviation found
was in the range accep ted as the b i ological variab i l i ty by Lenz ( 1 9 7 7 ) .
Therefore , the overall predic ted temperatures by thi s modi f ied
computer mode l were cons idered to g ive the b e s t approxima tion for
temperature dis tribution during process ing .

4.9 CONCLUSION

The computer model was f inally cons truc ted for the temperature
dis tribution c alcula tion in the can of food based on the analytical
solution . Some modi f i cat ion was found to be necessary . The thermal
d i f fusivity could no t be assumed to be cons tant for the whole processing
sys tem because an irregular cooling curve occurred during cool ing .
-7 2 - 1
The average thermal d i ffusivi ty o f 1 . 5 353 x 10 m s was used f or
the heating phas e , and also for the beginning o f cooling where r / a and
-7 2 - 1
x / h were higher than 1 / 3 . The thermal d i f fus iv i ty o f 2 . 2 x 10 m s
was used for the area in the can where r / a and x / h were less than or
equal to 1 / 3 at the beginning o f cool ing . When the temperature was
 87

0
less the�.n 105 C , the second phase of cooling s tar ted and the thermal
The equation was a 1 so
-7 2 - J.
d 1" f f us 1v1 ty o f 1 32 x 10
· · • m s was use d
•

modi f i ed for the area of r / a and x / h less than or equal to 1 / 3 .

The program was wr i t ten providing the oppor tuni ty t o use any process ing
cond i t i ons , can s ize , time and dimens ional increments , thermal d i f fu­
s ivities , s e t tempera ture . Comparison b etween the predic ted temperatures
and the experimental ones was found to be satis fac tory . Therefore , this
model was used for further calculation of qua l i ty re tention in the
determinat ion of kine t i c parameters .

However , i t i s wor thwhile to s tate here tha t this cons truc ted
model can be used only for a s imilar process ing opera tion where the
irregular cooling phenomenon does occur and if the thermal d i f fus ivities
in d i fferent parts o f the process ing are de termined . For the process
opera tion where the can is cooled under pressure and there is no
irregular cooling phenomenon , i t is believed that the un-modif ied
programs cons truc ted in section 4 . 3 ( using the analytical solu tion and
the numerical f ini te d i f f erence method) could be used �g satis fac tory
results .
ft r
 88

5. DETERMINATION OF KINETIC PARAMETERS

BY UNSTEADY-STATE PROCEDUFE

5. 1 INTRODUCTION

The rate o f changes in food during processing can b e exp ressed

e i ther by a f irs t-order rate cons tant (k) or a decimal reduction time
(D) but"k "i s more f requently used for describ ing the changes in nutri ents
and quality fac tors and there fore " k " was used in this s tudy . There
were many factors affect ing " k " ( s e c t ions 2 . 2 . 2 and 2 . 2 . 3) but only
the tempera ture f ac tor was s tudied . The Arrhenius equa t i on was found to
adequately describe the temperature dependence of the rate and thi s was
expressed in terms o f " Ea 1 1 • For purposes of compar ison i t is convenient
to convert rate cons tants to those at a s t andard temperature , in this s tudy
°
chosen as k o as 1 29 C was the maximum temperature involved . The
1 29 C
value of 11 k 11 a t any temperature in the temperature range of this s tudy
0
(60 - 1 29 C) could then be de termined i f 11 Ea 11 was known .

To determine these parame ters , Ea and k o ' the ini tial concen­
1 29 C
trat ion of reac tant e . g . nutrients and quali ty fac tors , and the concentra­
tion of reac tant af ter process ing were measured in the total can contents ,
us ing the uns teady-s tate procedure . The calculation o f the kine tics was
therefore based on mass average pred i c tion for the whole can . The temper­
a ture d is tribution in the can during heating was d e termined using the
modi fied analyt ical solution program and from this the overal l quali ty
retention was determined . Where the kine t i c parame ters were unknown ,
a method for their determination was developed based on trial and error
comparison o f the experimental and the predicted concentrat ions . The
computer program was cons tructed and the kinetic parame ters for ascorbi c
acid , riboflavin , colour and vis cos i ty were determined .

5.2 EXPERIMENTAL ANALYS I S OF QU.A..L ITY RETENTION

The control and heated canned baby food. was sampled from each experi­
mental run described in sect ion 4 . 2 . All the samples were analysed
at least in dup licate by the me thods in Chapter 3 . The results ob tained

from the ana lysis of the central samples represent the ini tial concen­
tration or qua l ity . The f inal concentrati on or quali ty o f each
experimental run was ob tained from the analysis o f the heated samp les .
The mean ini t ial and f inal concentration / qual i ty from each experimental

run , are shown in Tab le 5 . 1 . Details o f the analy tical results are
in Appendix 5 . 1 .

For colour , i t was found that only Y represented the change during
heating as can be seen in Appendix 5 . 1 ( c ) . The loss in ascorbi c acid
ranged from 6 . 0 to 16 . 0% . For riboflavin , the loss was less than
ascorbic acid ranging from 2 to 7% . The change in colour (Y) and
viscos i ty ranged from 1 3 to 2 3% , 10 to 26% , respectively .

5.3 QUALITY RETENTION CALCULATION

The following discuss ion involves the theory of the qua l i ty re tention
calcula tion , the computer program cons tructed and the e f fect o f the s i ze
o f the t ime increment and the d imens ion increment .

5 . 3. 1 Theory o f Qual i ty Retention Calculation

Assuming that the changes in f ood qual i ties such as vitamins and
s ensory qua l i t ie s can be described by f irs t order klne tics , the concen­
tra tion change will be

de
-kc ( 5 . 1)
dt
where c is the concentration
k is the reac tion rate coef f icient
t is the t ime .

After t ime , t , the f inal concentration can b e determined by integra­

t ion of equation ( 5 . 1 ) .

c
n t
= exp (- f kdt ) ( 5 . 2)
c 0
0

For uns teady- s tate heat trans fer , the tempera tures o f the can
contents change wi th t ime and posi t ion . Therefore , the e f f e c t of
tempera ture on k mus t be t aken into accoun t . This relationship can b e
 90

TABLE 5 . 1 The Mean Init ial and Final Quality on Hea t Process ing

RETORT
o 1 29 1 20
TEMPERATURE c

10
F min 5.0 9.0 13.0 17.0 21.0 5.0 13 . 0 17 . 0 21 . 0
1 21 . 1

Run No .
6 1 8 5 10 7 4 9 2
Details

Ascorbic acid
2 -1
x 1 0 , mg g

initial 25 . 68 23 . 89 25 . 29 24 . 82 23 . 29 2 4 . 50 26 . 1 4 2 5 . 9 5 24 . 1 6
f inal 24 . 1 0 2 1 . 84 23 . 04 2 2 . 56 20 . 9 5 2 2 . 46 23 . 83 23 . 60 2 1 . 7 1

1
Ribof lavin , � g g -

ini tial 2 5 . 28 2 5 . 7 0 25 . 40 26 . :.h 26 . 1 5 25 . 4 1 25 . 59 26 . 06 2 5 . 94

f inal 24 . 7 4 2 4 . 6 3 24 . 06 24 . 6 5 2 4 . 46 2 4 . 6 5 24 . 35 2 4 . 64 2 4 . 24
--

Colour , Y

ini t ial 30 . 5 30 . 3 30 . 4 30 . 2 30 . 9 30 . 3 31 .0 30 . 1 30 . 6
f inal 26 . 1 25 . 4 24 . 9 23 . 5 23 . 8 26 . 9 26 . 4 25 . 1 24. 1

Colour , X

ini t ial 30 . 2 30 . 4 29 . 8 29 . 9 30 . 3 29 . 8 31 .0 30 . 3 30 . 2
f inal 26. 3 26 . 1 25 . 0 23 . 9 24 . 2 27 . 2 27 . 4 25 . 6 24 . 5

Colour , Z

ini t ial 8.0 8.2 8.0 7 .9 8.9 8.0 8.6 8.4 8.4
f inal 6.7 6.6 6.4 6. 1 6.5 6.9 7.1 6.7 6.3

Visco s i ty Reading

ini tial 70 . 1 72.4 67 . 4 64 . 3 75.6 66 . 7 62 . 7 60 . 0 65 . 2

f inal 60 . 0 57 . 3 52 . 4 48 . 8 55 . 6 60 . 1 54 . 9 49 . 6 50 . 1
 91

described by equation ( 5 . 3) ( Lund , 1 9 7 5 ) .

-- (- - - )
Ea 1
R T
1
Tr
k ( 5 . 3)

Then equat ion ( 5 . 2 ) can be sub s t i tuted

c
- n
= ( 5 . 4)
c
0

As the tempera tures in the can vary from posi ti on to pos i tion and
also from t ime to time , to calculate the overall qua l i ty re tention af ter
t ime " t " , integra tion of equation ( 5 . 4) over the to tal volume of the
can is necessary .

Therefore , the f inal total concentration can be de termined from

_ Ea .!. _ .!.
c )
o
fvexp (- o ft k
Tr
e
R T Tr
d t ) dv ( 5 . 5)

where is the f ina l to tal concentrat ion

c is the concentrat ion a f ter time n�t where n= 1 , 2 , 3 • . •

n
c i s the ini tial concentration
0
k i s the reac tion ra te cons tant at reference temperature , Tr
Tr
Ea is the a c t ivation energy
T is the average temperature over � t and �v
v is a volume
�t is a time increment
�v is a volume increment
R is the gas cons tant .

As can b e seen , the eq uation ( 5 . 5) is complex and takes a long

time for calculation , especially where d t and dv are very small , so a
computer program was cons truc ted to calculate the qual i ty re tention
0
from equa tion ( 5 . 6 ) , where Tr was 1 29 C and k was k o :
Tr 1 29 C
 92

(5 . 6)

-1
where Ea is the ac t ivat ion energy ( kJ mole )
-1 0
gas
-1
R i s the cons tant and equal t o 0 . 0083 ( kJ mole K )
0
T i s absolute temperature ( K)

5.3.2 Compu ter Program for Quality Re tent ion Calculation

From equa tion ( 5 . 5 ) , the numerical in.tegration technique over

�v and �t could be used in the calculat ion by the computer program .
O ther mathemat ical me thods could also b e used , namely , S impson ' s rule
which was used by Hicks ( 1 9 5 1 ) in his calcula t ion for the cooling phase
and a weighted-res idual technique which was used by Hayakawa ( 1 9 6 9 ) .
However , thes e methods are more comp licated than the graphical inte­
gration method . Therefore , the numerica l integration technique was
used .

-·
From equation ( 5 . 6 ) , assuming that d t and dv are small , s o T can
be regarded as cons tant . The f inal concentration of the v i t amin or
the quality af ter time , �t , of the small volume , �v , can be calculated
from

_ Ea _!. _1_)
( _
R T 402 (5 . 7)
c exp ( -k o e �t) �v
o 1 29 C

where T is the average temperature over the increment volume , �v ,

over the t ime increment , � t .

The computer program was cons truc ted based on equat ion ( 5 . 6) , c
f
which is the f inal concentration in a small volume of �v a t the end
o f t ime , �t, was calculated to then become the initial concentration
in this small volume for the next �t . The calculation was repeated
until the end of the total t ime .
 93

The s i ze o f the small volum e will depend on the d is tance increment

size used and can be calculated by :

�V ( 5 . 8)

where r and r are the rad ii and r

1 2 2

Therefore , the computer program cons tructed in chap ter 4 was

extended for the qua l i ty re tent ion calculation us ing equat ion ( 5 . 6) .
The flow chart o f the extended program use� is shown in Figure 5 . 1 .
The detail of the compu ter program is shown in Append ix 5 . 2 .

5.3.3 Size of Time Increment and Dimension Increment

The computer program was run through the Burroughs B6700 computer
and the resul t ob tained was expressed in terms of f inal concentra t ion
or f inal quality value . D i f ferent s i zes of t ime increments and d imen­
s ion increments were tr ied and the f inal concentrations and the pro­
cessing t ime consumed by th e computer were compared . Using the same
process ing cond it ions , the resul ts ob tained are shown in Tab le 5 . 2 .
The d imension increment was expressed in term o f ( number of increments
on the radius x number of increments in the half-height) .

TABLE 5 . 2 Effect of S i ze of Increment on Qual i ty Re tent ion Calculation

FINAL ASCORBIC AC I� COMPUTER

CONCENTRAT ! �N x 1 0
DIMENS ION TIME INCREMENT
PROCESSING TIME
INCREMENT s
mg g s

5 X 5 72 18 . 07 8 4 . 86
10 X 10 72 17 . 95 2 54 . 00
15 X 15 72 1 7 . 93 56 2 . 00
10 X 10 36 17 . 93 526 . 39
 94

TUU.: • 0.0

N N • (T!Ht:S t CTIII£) /DT

saae u in u..perat\&1'• 41atrlkt1oo

proar-

te-.peratYce diecr11tuC1•
proar-

ln te��perat&&re dieuiltaaUoa
proaraa

Cdcu l o ne
TAVE(J , l ) , TAVER ( J , l ) ,
C(J , I ) , AVl'T(J , I)

FIG . 5 . 1 Flow Char t for Quality Re tention Calculation Program

 95 .

As can be seen , the smaller the increment s i ze , the longer the

processing t ime required by the computer which means that the cos t
of calculation is higher . Cons idering the resul ts ob tained , the
d imension increment of 5 x 5 wi th 7 2 s time increment which required
the leas t t ime resulted in a final concentration which was higher
than the o thers . When either the d imens ion increment of 1 5 x 1 5 wi th
7 2 s t ime increment or the d imens ion increment of 10 x 10 wi th 36 s
t ime increment was used , the time consumed in cal culation was d ouble
the t ime consumed when the d imens ion increment of 1 0 x 1 0 wi th 72 s
t ime increment was used . But the results ob tained were almos t the
s ame , the d i f ference in calcula ted concentration was only 0 . 0 1 -
0 . 0 2 mg / 1 00 g which was about 0 . 1% . Therefore , the increment s i ze
of 1 0 x 10 with 7 2 s time increment were used for the res t of the
s tudy .

5.4 DETERMINATION O F KINETIC PARAMETERS

As the only results that could be de termined from the experiments

were the initial concentr�tion and the f inal concentrat ion o f the
qua l i ty in the baby food heated at a specif ied tempera ture for a
speci fic t ime ( section 5 . 2) , the computer program for the qua l i ty
re tention calculat ion was used to determine the f inal concentration
( sec tion 5 . 3) . Unfor tuna te ly , the qua l i ty retention cannot be predicted
by thi s computer program unless the kine tic parame ters , k o and E a ,
129 c
f o r that qua l i ty are known . Therefore , thes e parame ters , k o and Ea ,
'
1 29 C
had to be as sumed , the f inal concentra.tion calculated and then the
calculated f inal concentration compared wi th the experimental resul t .
This trial and error method was used to determine the k o and Ea
1 29 C
which would give the closes t approximation of the experimentally
determined f inal qua l i ty . However , this method consumed a lot o f
c omputer time . Therefore , in thi s s tudy , k o and E a were sys tema t­
1 29 C
ically tes ted in the calculat ion . The residual whi ch is the d i f f erence
be tween the ac tual c / c 0 and the calculated c / c 0 was calculated for
various l evels of assumed k o and Ea for each experimental run .
1 29 c
The calculated c / c 0 for each processing run was dependent on only
k o and Ea , so the r� s idual was also dependent on only k o and Ea .
1 29 C 1 29 C
Therefore , to de termine the ac tual k o and Ea o f each qua l i ty , the
1 29 C
relationship be tween the res idual and k o and Ea was evaluated using
1 29 C
 96

mul tiple regress ion analysis to ob tain a second order response surface
model and then the res idual was minimi zed by the d i fferentiation o f the
emp irical relationship . The d e tails of the s tudy are d iscussed in the
following sections .

5.4. 1 The Design

To f i t a second order response surface , a t leas t three levels o f

each vari able are required . Or thogonal compos i te des ign was used as
i t involves three levels of each variab le . o and
In thi s s tudy , k
1 29 C
Ea were the two variab les involved . The des ign is shown in Figure 5 . 2 ,
where X1 i s a coded variab le of k o and X2 i s a coded variable of
1 29 C
Ea .

5.4.2 The Analys is

Using the k o and Ea a t various points in the design , the f inal

1 29 c
concentrat ion of the quali ty of each experimental run was calculated
from the qua l i ty re tentio� program . The absolute residual was then
calcula ted for all points in the experimental des ign , the absolute
res idual (Q) was def ined as :

absolute res idual= I (.£. ) - (.£.. )

c exp c cal I
0 0

(c ) exp is c ob tained from measured c and c 0

c c
where
0 0
c c
<-;- ) cal
is ob tained from calculated c and measured c 0
0
c
0
c is the f inal concentrat ion
c is the ini tial concentration .
0

0 0
The residuals were averaged for each temperature ( 1 20 and 1 29 C)
for each value of k o and Ea . From these calculated res iduals , the
1 29 c
quadratic equation was f i t ted by multip le l inear regress ion . Then , the
k o and Ea were d etermined by minimi zing the residual .
1 29 c

The regress ion equation was f i t ted us ing both the average residuals
and the ind ividual res iduals . The resulting equations were s ligh t ly
d i fferent but the minimi zation o f the residual ( Q) gave almos t the same
k o and Ea . This was true for all four qua l i t ies - ascorb i c acid ,
1 29 C
 . 97

2 • 6*

1 • 1* • 3*

0 8* • 5* • 9*

-1 • 2*

7*
-2

-2 -1 0 1 2

Xl

FIG . 5 . 2 An Orthogonal Central Composite Des ign to Fi t a Second

Order Response Surface
 98

ribof lavin , colour (Y) and viscos i ty as shown b e low .

For ascorbic acid :

2
the regress ion equa tion (R = 83 . 1%) resul t ing from using average
absolute res idual at each process temperature was :

1 0 . 0 1225 0 . 00484X 1X2 1

2
Q = - 0 . 00400X1 + 0 . 00 1 5 1X2 + 0 . 00435X1
(5.9)

2
the regress ion equation ( R 56 . 1 % ) r€sulting from us ing ind ividual
absolute r e s idual s :

Q 1 0 . 0 1 1 83 - 0 . 00392X1 + 0 . 00 1 45X2 + 0 . 00444X1 - 0 . 004 7 5X 1X 2 1

2

( 5 . 10)

minimi zation o f Q gave the k o and Ea from equat ion ( 5 . 9 ) o f

1 �t c
-4 - 1
0 . 4 3 5 2 X 10 S and 80 . 7 k J mole and from equa tion ( 5 . 10) of
-4 - 1 1
0 . 4348 X 10 S and 80 . 9 kJ mole .
-

For ribof lavin :

2
the regress ion equa tion (R 9 2 . 3% ) result ing f rom using
average absolute res iduals was :

I 0 . 00 7 7p - 0 . 003 7 5X 1X2 1
2
Q + 0 . 00 1 4 8X 1 - 0 . 00 1 1 2X2 + 0 . 00 524X1
(5. 1 1)

2
the regression equation (R 6 1 . 3% ) resulting from using individual
absolute res iduals was :

Q = 1 0 . 00 79 5 + 0 . 00 1 50X 1 - 0 . 00 1 06X2 + 0 . 005 20X1

2
- 0 . 00358X 1X2 1
( 5 . 1 2)

minimization o f Q gave the k o and Ea from equation ( 5 . 1 1 ) o f

1�t c
-4 - 1
0 . 236 1 X 1 0 S and 7 9 . 0 kJ mole and from equation ( 5 . 1 2) o f
-4 - 1 -1
0 . 2363 X 10 S and 7 8 . 9 kJ mol e .
. •..

99

For colour , Y :

2
the regression equation (R = 88 . 5%) resulting f rom us ing average
absolute res iduals was :

1 0 . 02592 + 0 . 0 1 5 79X1 - 0 . 0 1 2 26X2 + 0 . 0 1 1 04X 1 - 0 . 0 1 4 1 6X 1X2 1

2
Q
( 5 . 1 3)

2
the regress ion equat ion (R = 80 . 6% ) resulting f rom us ing individual
abs olute residuals was :

j 0 . 0 264 1 + 0 . 0 1 6 1 5X 1 - 0 . 0 1 209X2 + 0 . 0 1 106X1 0 . 0 1 360X 1X2 j

2
Q
( 5 . 14)

minimi zat ion o f Q gave the k o and Ea from equati on ( 5 . 1 3 ) o f

1 29 C
-4 - 1 -1
1 . 2403 x 10 s and 1 22 . 1 kJ mole and f rom equa tion ( 5 . 1 4 ) of
-4 - 1 -1
1 . 2333 x 1 0 s and 1 2 1 . 7 kJ mole •

For vis cos i ty :

2
the regress ion equation (R = 6 4 . 4% ) resul ting from using average
res iduals was :

Q j 0 . 0 2020 - 0 . 00766X2 + 0 . 0 1 282X1

2
+ 0 . 005 30X2
2
- 0 . 0 1464X 1X2 j
( 5 . 15)
2
the regress �on equation (R 49 . 1%) resulting from us ing individual
absolute res iduals was :

j 0 . 0 1963 - 0 . 00686X2 + 0 . 0 1 3 1 3X 1 - 0 . 0 1 4 45X 1X2 j

2 2
Q + 0 . 005 09X2
(5 . 16)
minimi zation o f Q gave the k o and Ea from equation ( 5 . 1 5 ) o f
1 29 c
-4 - 1 -1
1 . 7 2 4 x 10 s and 1 5 5 . 4 k J mole and from equation ( 5 . 1 6 ) of
-4 - 1
1 . 74 2 x 1 0 and 1 5 6 . 5 kJ mole .

There fore , only the average ab s o lute res iduals were used in the

ana lysis . An example of the comp le te me thod of determinat ion of res iduals ,
determina tion o f emp i rical equat ions by mul tiple regression , the decoding
of the regres sion equation , the minimi zation of res idual and , then

NASSEY UNIVERSITY
Ll RARY
 . :
:-.;·,

100

determination of k o and Ea is shown in Append ix 5 . 3 . The program

1 29 c
for contour plots and an examp le of a contour plot are also shown in
Appendix 5 . 3 .

5.5 DETERMINATION OF KINETIC PARAMETERS FOR ASCORBIC ACID

5.5. 1 De termina tion of the Range of k o and Ea

1 29 C

Us ing the k o and Ea repor ted by Chi t taporn ( 1 9 7 7 ) of 2 . 33

1 29 C
-4 - 1 -1
x 10 s and 84 . 2 kJ mole , the calculated f inal concentration o f
ascorb ic a c i d based o n the process ing cond i tions o f run no . 6 was
-2 -1 -2 -1
1 7 . 95 x 1 0 mg g which was much lower than the 24 . 16 x 1 0 mg g
determined from the experiment . To increase the calculated concentra­
tion , the k o and / or the Ea would have to be changed . From the
1 29 C
li terature review , i t appeared that the Ea was in the righ t range but
i t was necessary to d e t ermine the possible range for the k o .
1 29 c

Rough e s t imat ion of the possible k

o .o f ascorb ic acid was carried
1 29 c
out by averaging the measured tempera tures a t all 5 points o f run no . 6 .
0
Us ing the approximate average tempera ture of 1 10 C , the k o was
1 29 C
-4 - 1
calculated as 0 . 4 1 1 5 x 1 0 s (Appendix 5 . 4) . Then this k o was
1 29 C
used to calculate the f inal concentra tion from the c omputer program
based on the process ing condi tions of runs no . 6 and 10 . The equivalent
0
processing t imes at 1 29 C were calculated from the predic ted concentra-
-4 - 1
tions and k o of 0 . 4 1 1 5 x 10 s and then plo t ted agains t the
1 29 C
- -1
measured ln ( c / c ) . The new k o o f 0 . 56 4 1 x 1 0 4 s was ob tained
� 1 29 c
from the s lope of the l ines . Thi s gave the pos s ible range for k o
1 29 C
for use in the sys tema tic calculation o f k o and Ea by use of the
1 29 C
experimental des ign .

-4 -4 - 1
These two k o (0 . 4 1 15 x 1 0 and 0 . 564 1 x 1 0 s ) were used
1 29 c
in the des ign as the coded variab le X1 at levels o f - 1 and + 1 , as the
ac tual k o was l ikely to fall in this range . Then the highes t and
129 C
lowes t levels o f k o ( +2 and -2) were calculated f rom thes e two
1 29 C
k o to ob tain an or thogonal des ign which should cover the possib le
1 29 C
range of k o for ascorb i c acid .
1 29 C
 101

°
Therefore , the kinetic reaction rate at 1 29 C a t each level was
cod ed by :

-4
k o - 0 . 48 7 8 x 10
1 29 C
X1 =
-4
0 . 07 6 3 X 10

-1
The activa tion energies of 63 and 83 kJ mole were used as X2
of respec tively - 1 and +1

Ea - 7 3
X2
10

The absolute res iduals were calculated f o r points , 1 , 2 , 3 , 4 , 5 , 6 and 8

( Figure 5 . 2) . o and Ea a t each poin t are shown in Figure 5 . 3
The k
1 29 C
with the average absolute residual and the standard dev ia tion shown in the
bracket . I t was f ound that the Ea levels used were too low as the
absolute res idual was lowered where the Ea was increased ( point 5 and 6 )
-4 - 1 .
whereas the k o of 0 . 56 4 1 x 1 0 s gave the h ighes t absolute residual
1 29 c
ind icating that the ac tua � k o of ascorbic acid would be in the lower
_ 1 29 c
range of k o rather than in the h igher rang e .
1 29 c

Therefore the levels of the ko and Ea were recons idered . Mos t

1 29 C
of the previous results ob tained were used to minimize the compu tation
cos t .

5.5.2 A Model for Ascorbic Acid f or Determinat ion o f Kine t ic Parame ters

The f inal orthogonal design for ascorb ic acid is shown in Tab le 5 . 3 .

Us ing the k o and Ea a t various points in the des ign , the absolute
1 29 C
res iduals were determined and are shown in F igure 5 . 4 . From these calcu­
lated res iduals , a quadratic model was f i t ted by mul tiple linear
regres s ion . The coef f i cient terms of h igher than 80% s ignificance were
taken into the f inal model .

2
The regress ion equat ion ( R = 83 . 1 % ) resul t ing from using average
absolute res idual at each process tempera ture was :
 102

0 . 009
93 • 6*
(0 . 0 07)

0.011 0 . 02 2
� •
"""'

I •
83 1* 3*
Q)
�
( 0 . 008)
( 0 . 02 3 )
0
s
......,
�
-
0 . 0 18 0 . 0 19
ctl
�
73 • 8* • 5*
• 9*

(0 . 0 1 7 ) ( 0 . 0 16 )

0 . 042
0 . 0 15
63
• 2* • 4*

( 0 . 009 ) ( 0 . 039)

53 • 7*

o . 3 35 2 0 . 4 1 15 0 . 4878 0 . 564 1 0 . 6404

FIG . 5 . 3 Firs t Des ign for Ascorb ic Acid wi th Calculated Average

Abso lute Res iduals and their S tandard Deviations
 1 03

TABLE 5 . 3 Level o f the k o and the Ea in the Orthogonal Compo s i te

1 29 C
Des ign for Ascorbic Acid

k ° Ea
Point X1* 1 29 C X2 *
-1 -1
s kJ mole

-4
1 -1 0 . 3352 X 10 +1 93
-4
2 -1 0 . 3352 X 10 -1 73
-4
3 +1 0 . 4878 X 10 +1 93
-4
4 +1 0 . 4878 X 10 -1 73
-4
5 0 0 . 4 1 15 X 10 0 83
-4
X
-·

6 0 0 . 4 1 15 10 2 103
-4
7 0 0 . 4 1 15 X 10 -2 63
0 83
-4
8 -2 0 . 2589 X 10
-4
9 +2 0 . 564 1 X 10 0 83

-4
k o - 0 . 4 1 15 x 10
* 1 29 C
X1
X
-4
0 . 0763 10

Ea - 83
X2 =
10
 104

0 . 0 18
103
•
( 0 . 0 10 )

0 . 026 0 . 007
....-!
,....

I 93 • •
Q)
....-!
0
s
( 0 . 008) ( 0 . 008)

...,
�
'-"
0 . 0 36 0 . 008 0 . 02 3
�
!:il
83 • • •
( 0 . 007) ( 0 . 008) ( 0 . 008)

0.017 0 . 0 16
73
• •
( 0 . 008) ( 0 . 00 7 )

0 . 009

63 •
( 0 . 07)

0 . 2 5 89 0 . 3352 0 . 4115 0 . 4878 0 . 5641

k 10 4 ( s
-1
)
0 X
129 c

FIG . 5 . 4 Or thogonal Design for Ascorbic Acid wi th Calcula ted Average

Res iduals and their S tandard Deviations
 1 05

Q j 0 . 0 1 2 25 - 0 . 00484X 1X2 j
2
- 0 . 00400X1 + 0 . 00 1 5 1X2 + 0 . 00435X1

(5 . 17)

The equat ion was decoded and minimization o f Q was done by the
d ifferential method and is shown in Appendix 5 . 3 . The decoded equat ion
was

3 -3 7 2
Q I -0 . 06 5 1 - 1 . 4904x 1 0 k o + 2 . 6995x 1 0
1 29 C
Ea + 7 . 4 6 5 2x 1 0 k o
1 29 C
- 6 2 . 0238 k o Ea j (5 . 18)
1 29 C

-4 - 1
Minimum Q was ob tained where k o was 0 . 4 3 5 2x 1 0 s and Ea
1 29 C
-1
was 80 . 7 kJ mole Contour plot o f this equation was also made us ing
the computer program ( Appendix 5 . 3 ( e) ) and is shown in Appendix 5 . 3 ( f ) .
The o p t imum point ob tained as the s ta t iona ry point in the plot was f ound
-1 -1
approximately a t k o o f 0 . 43 x 10 -4 s and E a o f 8 1 kJ mole .
1 29 c

The minimum average absolute residual calculated for all exper imental
-4 - 1 -1
runs , wh ere t h e k o was 0 . 43 x 10 s and th e E a was 8 1 kJ mole ,
1 29 c __

was 0 . 006 with the s tandard deviat ion of 0 . 007 .

5.6 DETERMINATION OF KINETIC PARAMETERS FOR RIBOFLAVIN

From the k o and Ea ob tained for ascorb i c acid , the k o and

1 29 c 1 29 c
Ea of ribof lavin were calculated ( Append ix 5 . 5 ( a) ) . The calculation
was based on the de termination of equivalent , process ing t imes us ing the
°
known kine tic re�c t ion of ascorbic acid at each temperature , 1 29 C and
°
1 20 C . These calculated equivalent process ing t imes were plot ted agains t
ln ( c / c ) f ound from the analysis for riboflavin of control and heated
0
samples . The k o and k o f or riboflavin were ob tained from linear
1 29 C 1 20 C
regress ion analys i s . Assuming a linear relationship of ln k and 1 / T ,
the ac tivation energy was calculated . I t was found that the kine t ic
° -4 - l
reac t ion rate of ribof lavin at 1 29 C was 0 . 246 x 1 0 s and the
-1
ac t ivation energy was 8 7 kJ mole . The average absolute res idual
from the quality retenti on calculation was 0 . 006 wi th the s tandard
deviat ion of 0 . 005 .
 106

The experimental desi gn method used f o r de terminati on o f kine tic

parame ters for ascorb i c acid was a ls o used . o The ranges o f the k
1 29 C
and Ea were chosen to cover the values calculated by the equivalent
processing t ime method but , wherever pos s ib le , points used for as corb ic
acid were put into the design to save computation time . The desi gn
i s shown in Table 5 . 4 .

TABLE 5 . 4 Orthogonal Compos i te Design for Ribo f lavin

k ° Ea
l29 C
Point X 1 ** -1 X2 ** -1
s kJ mole

-4
*1 -1 0 . 1826 X 10 1 93
-4
*2 -1 0 . 1826 X 10 -1 73
-4
3 1 0 . 335 2 X 10 1 93
-4
4 1 0 . 3352 X 10 -1 73
-4
5 0 0 . 2 5 89 X 10 0 83
-·

-4
*6 0 0 . 2589 X 10 2 103
-4
*7 0 0 . 2589 X 10 -2 63
-4
*8 -2 0 . 106 3 X 10 0 83
-4
9 2 0 , 4 1 15 X 10 0 83

* Denotes the extra points needed for calculation

-4
k o - 0 . 2589 X 10
1 29 C
** X1 =
-
0 . 0763 X 10 4

Ea - 83
X2
10
 107

The f inal concen tration was calculated b y the quali ty retention

p rogram and the absolute residual was calculated for each run at each
k o and Ea level . The mul tiple linear regress i on was carried out
1 29 C
as in Appendix 5 . 3 .

Taking only the terms o f higher than 80% significance , the regress ion
2
equation ( R = 9 2 . 3% ) was :

! 0 . 00 7 70 - 0 . 00375X1X2 i
2
Q + 0 . 00 148X1 - 0 . 00 1 1 2X2 + 0 . 005 24X1
(5 . 19)

Minimum Q was ob tained where the k o and the Ea were 0 . 2 36

1 29 C
-4 - 1 -1
x 10 s and 79 . 0 kJ mole . These k o and Ea were used in the
1 29 C
quali ty re tention calculation , the average res idual was calculated and
is shown in Tab le 5 . 5 wi th the average residual from the process ing t ime
method and from another p oint in the orthogonal design .

TABLE 5 . 5 Average Abs olute Res iduals and their S tandard Deviations
Resulting f rom �ifferent Levels o f k o and Ea
129 C

k ° x 10 4 Ea Average Absolu te S tandard

129 C
-1 -1
s kJ mole Res idual Deviation

0 . 246 87 0 . 006 0 . 005

0 . 236 80 0 . 006 0 . 005

0 . 259 83 0 . 005 0 . 006

From Tab le 5 . 5 , the average residuals and the standard deviations

were almos t the same but it was decided to do ano ther design to see
whe ther a lower average absolute residual could be ob tained . The new
design i s shown in Figure 5 . 5 w i th the average ab solute residua ls and
their standard deviations .
 108

0 . 009

1 05 . 0 •
(0 . 00 5 )

0 . 0 16 0 . 0 10

�
,...,. '-

I
94. 5 • •
<U
�
0
(0 . 00 7 ) (0 . 00 7 )
s
.....,
� 0 . 02 7 0 . 005 0 . 02 8
'-'

Cl1
J:il 84 . 0 • • •
(0 . 0 12 ) (0 . 00 5 ) ( 0 . 005 )

0 . 0 12 0 . 020

73.5 • •
(0 . 006) (0 . 006)

0 . 0 10

63 .0 •
(0 . 0 7 )

0. 1 1 0 . 18 0 . 25 0 . 32 0 . 39

k X 10 4 (s-1)
1 2 9 °C

FIG . 5 . 5 S econd Orthogonal Compos i te Des i gn for Ribo flavin wi th Average

Absolute Res iduals and their S tandard Deviations
 109

Taking only the terms of higher than 80% signif icance , the regressi on
2
equa t i on ( R = 9 3 . 4%) was :

Q = 1 0 . 00754 + 0 . 00508X 1
2
- 0 . 00 368X 1X2 1 ( 5 . 20)

-4 - 1
Minimum residual was found , where the k o was 0 . 250 x 10 s
1 29 C .
-1
and the Ea was 84 kJ mole , to be 0 . 005 with the s tandard deviation o f
0 . 00 5 .

There fore , i t was concluded that the k o and the Ea of ribof lavin
129 C
-4 - 1 -1
were 0 . 250 x 10 s and 84 kJ mole •

5.7 DETERMINATION OF KINETIC PARAMETERS FOR COLOUR

As in section 5 . 5 , the kinetic parameters found for as corb i c acid

in section 5 . 4 were used for calculating the equivalent p rocess ing t ime s .
The approxima te kinet i c parameters for colour were f ound to b e 1 . 06 3
-4 -1 -1
x 10 kJ mole and 1 20 . 9 kJ mole . The calculation i s i n App endix
5 . 5 (b ) .

The compos i te orthogonal desi gn shown in Figure 5 . 6 was also used ,

- -4 - 1
the k o ranged f rom 0 . 900 x 1 0 4 t o 2 . 100 x 1 0 s and the Ea
1 29 c
-1
ranged f rom 9 2 . 4 to 1 59 . 6 kJ mole . The residuals were calculated
and the mul tiple l inear regression was carried out as in Appendix 5 . 3
where X 1 and X2 were d e f ined as :

-4
k o - 1 . 5 x 10
1 29 C
X1 =
-4
0 . 3 X 10

Ea - 1 26 . 0
X2 =
16 . 8

The average res idual a t each point in the desi gn is shown i n Figure 5 . 6 .
Taking only terms o f higher than 90% significanc e , the multiple regress i on
2
equat ion ( R = 88 . 5%) was :
 l lO

0. 015
159 . 6 •
( 0 . 009)

0 . 02 3 0 . 04 3

.......
,...._ 142 . 8 • •
Q)
I

.......
(0 . 0 1 2 ) (0 . 0 1 7 )
0
s
'J
�
0 . 04 7 0 . 02 8 0 . 1 00
..._,

Cl! 126 . 0 • • •
ILl

( 0 . 0 14 ) ( 0 . 009) ( 0 . 0 16 )

0 . 086
0.011

1 09 . 2 • •
( 0 . 00 7 ) (0 . 0 12 )

0 . 072

92 . 4 •
(0 . 1 5 )

0.9 1.2 1.5 1.8 2.1

4
k X 10 ( s -1)
1 2 9° C

FIG . 5 . 6 Firs t Orthogonal Composite Design for Colour , Y , with Average

Ab solute Res iduals and their S tandard Deviations
 111

j 0 . 02592 - 0 . 0 1 4 16X 1X2 j

2
Q + 0 . 0 1 5 79X 1 - 0 . 0 1 226X2 _+ 0 . 00 104X 1
(5 . 21)

-4 - 1
Minimi zation of Q gave the k o of 1 . 240 x 1 0 s and the Ea
1 29 c
-1
of 1 22 . 1 kJ mole . To get c loser es t ima t ion o f the k o and Ea ,
1 29 C
the des ign in Figure 5 . 7 was used . The absolu te residual and the
s tandard deviation were calculated for each point and are shown in
Figure 5 . 7 .

Taking only terms higher than 90% signif icance , the mul tiple
2
regression equation ( R = 7 7 . 6%) was :

j 0 . 00 7 6 2 - 0 . 00850X 1X2 j
2 2
Q = + 0 . 00459X1 + 0 . 00449X2 ( 5 . 22 )

-4 - 1
Minimi zation o f Q gave the k o of 1 . 200 x 10 s and the
1 29 C
-1
Ea of 1 2 1 . 8 kJ mole The average absolute residual us ing these
k o and Ea was 0 . 00 7 with the s tandard deviation of 0 . 006 .
1 29 c

-4 -1
Therefore , the k o and Ea o f colour , Y , were 1 . 200 x 1 0 s
1 29 C_
-1
and 1 22 k J mole .

5.8 DETERMINATION OF KINETIC PARAMETERS FOR VISCOS ITY

The equivalent processing t ime me thod was also used for calculation
o f the k o and Ea for vj s co s i ty ( Appendix 5 . 6 ( c )). The k o and
1 29 C 1 29 C
-4 - l -�
the Ea o f 1 . 2348 x 10 s and 1 43 . 6 kJ mole were found .

The des ign in Figure 5 . 8 was f i r s t used and the average absolute
residual at each point are shown in Figure 5 . 8 . Taking only terms
2
higher than 80% s igni f icance , the regression equa tion ( R = 6 4 . 4% )
was :

Q = j 0 . 0 2020 - 0 . 00766X2 + 0 . 0 1 282X1

2
+ 0 . 005 30X2
2
- 0 . 0 1 464X1X2 j
( 5 . 23 )
-4 -1
Minimi zation of Q gave the k o of 1 . 7 2 4 x 1 0 s and the Ea
1 29 C
-1
of 1 5 5 . 4 kJ mole • To f ind a c loser approximation of the k o and Ea
1 29 C
 11 2

0 . 025

147 . 0 •
( 0 . 0 14 )

0 . 02 7 0 . 009

1 34 . 4 • •
( 0 . 0 12 ) ( 0 . 00 6 )

r-l
,-....

I
Q)
0 . 030
r-l
0 . 00 7 0 . 02 4
0
s
121 . 8 • • •
1-)
�
(0 . 0 1 2 ) ( 0 . 00 6 ) (0 . 008)
......

Cd
j:Ll
0 . 008 0 . 02 2

1 09 . 2 • •
(0 . 00 7 ) ( 0 . 008)

0 . 024

96 . 6 •
(0 . 1 3 )

1.0 1.1 1.2 1.4 1.5

FIG . 5 . 7 Second Orthogonal Compos i te Des ign for Colour , Y , wi th Average

Absolute Res iduals and their S tandard Deviations
 1 13

0 . 02 4
1 59 . 6
•
( 0 . 0 14 )

0 . 042 0 . 024
1 42 . 8 • •
�
,-....

I (0 . 022) ( 0 . 0 16 )
Q)
�
e
g 0 . 066 0 . 0 15 0 . 075
� 126 . 0 • • •
(0 . 0 3 1 ) (0 . 0 1 7 ) ( 0 . 0 19 )

0 . 02 7 0 . 06 7
109 . 2
• •
( 0 . 0 12 ) ( 0 . 026)

0 . 05 3
92 . 4 •
(0 . 0 4 )

0.9 1.2 1.5 1.8 2.1

FIG . 5 . 8 Firs t Or thogonal Compos i te Des i gn for Viscos i ty wi th Average

Absolute Res iduals and their S tandard Deviations
 l l4

of viscosi ty , the des ign in Figure 5 . 9 was used . The abs olute res idual
at each point was calcula ted and is shown in F igure 5 . 9 .

Taking only terms of higher than 80% s ignif icance , the regress ion
2
equation (R 1 5 . 4%) was :
=

Q = 1 0 . 0 1 19 3 + 0 . 00 1 64X2
2
1 ( 5 . 24 )

-4 - 1
Minimization of Q gave the k o of 1 . 650 x 10 s and the E a
1 29 C
-1
of 1 5 1 . 2 kJ mole . These k o and Ea gave the lowes t average ab solute
129 C
res idual ( F igure 5 . 9) o f 0 . 0 1 1 with the s t andard deviation of 0 . 0 1 0 .

-4 -1
Therefore the k o and E a o f viscosi ty were 1 . 6 50 x 10 s
1 29 c
-1
and 1 5 2 kJ mole .

5.9 CONCLUS ION

The f inal computer program was developed for determining the

qual i ty re tention of food in the can af ter hea t processing by extending
the temperature dis tributiun calculation program developed in Chap ter 4 .
As the purpose of the s tudy was to determine the kine t i c parame ters ,
k o and Ea , which were unknowns in the program , so this program was
1 29 c
wri t ten providing the opportuni ty to use any value of k and Ea . The
time and d imension increment s i zes were s t ud ied as they could effect
the accuracy of qua l i ty retention calculation and it was found that a
t ime increment of 7 2 seconds and a d imensional increment o f 1 0 x 10 were
the best to use . -

The kine tic parame ters were determined roughly by using an equi­
valen t process ing t ime me thod and then the ranges of k o and Ea were
1 29 c
finally determined for an or thogonal composite des ign to sys tematise
the trial and error method . Us ing various k
o and Ea in the des ign ,
1 29 C
the absolute residual was determined for each processing condi t ion at
each k o and Ea level . The residuals were averaged for each temper­
1 29 C
° °
a ture ( 120 and 1 29 C) for each level of k o and Ea . The mul tiple
1 29 c
linear regression o f res iduals (Q ) to b o th kine t i c parame ters , k o
1 29 C
and Ea , was carried out using the average absolu te res iduals . The
 115

0 . 0 17
168. 0 •
(0 . 0 1 3 )

0 . 0 16 0 . 0 12
�
,....

I 159 . 6 • •
Q)
� ( 0 . 0 12 ) ( 0 . 0 10)
0
s
1-j
�
-....;

Cd 0 . 0 16 0.011 0 . 0 14
ILl
15 1 . 2 • • •
( 0 . 0 10 ) ( 0 . 0 10) ( 0 . 0 12 )

0.013 0 . 0 15
1 42 . 8
• •
(0 . 0 1 1 ) ( 0 . 0 15 )

0. 018
1 34 . 4
•
(0 . 1 8 )

1 . 55 1 . 60 1 . 65 1 . 70 1 . 75

k x 10 4 (s-1)
°
12 9 C

FIG . 5 . 9 Second Orthogonal Compos i t e Des ign for Viscosi ty wi th Average

Absolute Res iduals and their S tandard Deviations
 116

ac tual k o and Ea were ob tained f rom ari thme tic op t imi zat ion of Q .
1 29 C

For ascorb i c acid the range was roughly e s t imated from the data
ob tained by Chi t taporn (. 1 9 7 7 ) . By use of one or thogonal des ign , the
-4 - 1
. t 1c
k 1ne • parame t ers were f ound to b e k o o f 0 . 435 x 1 0 s and
1 29 C
-1
Ea of 8 1 kJ mole .

For riboflavin , colour and viscosi ty , the kine tic parame ters were
f i r s t roughly es tima ted by us ing the kine tic parameters ob tained for
ascorbic acid in calculating the equiva lent processing time . Then the
ranges of k o and Ea were u sed in orthogonal composite d e s igns , one to
1 29 C
two designs being nec essary to f ind the k o and Ea . The k
129 C
lo and Ea
1 9 c
-4 - 1
was f ound to b e 0 . 250 x 10
-1 -1
s and 84 kJ mole , 1 . 200 x 1 0 - s and
-1 -4 - 1 -1
1 22 kJ mole , and 1 . 6 50 x 1 0 s and 1 5 1 kJ mole for ribof lavin ,
colour and vis cos i ty , respec t ively .
 117

6. KINETIC PARAMETER DETERMINATION BY

STEADY-STATE PROCEDURE

6. 1 INTRODUCTION

As s tated before , there are two procedures f or de termining the

kine tic parame ters f or thermal degradat ion of food quality : s teady-s tate
and uns teady-s tate . Chap ter 5 dealt wi th an uns teady s tate procedure
where the f ood in a can was subj e cted to dif ferent degrees of heating .
The computer program was cons truc ted to determine the changes in tem­
perature throughou t the can and from this the overall change in the
qual i ty , assuming that the change on heat process ing of the f ood quali ties
s tudied followed a first order reac tion .

In this chap ter , a s teady-state procedure , where food was heated

in tubes , was s tudied to de termine the order o f the degradation reactions
of ascorb i c acid and ribof lavin on heat processing and the kine tic para­
me ters , as wel l as to compare the kine tic parame ters ob t ained wi th those
in Chap ter 5 .

6.2 EXPERIMENTATION

6.2. 1 Sample Prepara tion

The s ample was prepared in exac tly the same way as had been done
for the uns teady-s tate proced ure in the can . The frozen , homogenised
s trained beef and mixed vege tab les baby food prepared for the experiment in
0
Chap ter 5 was thawed for 2� hours in a 30 C water bath , then , i t was
0
heated wi th hand s tirring , to 87 C for gelat ini zation . Some ascorbic
acid had been lost during � t orage , s o ascorbi c acid was therefore added
to make the c oncentration high enough for accurate analysis and in the
s ame range as before . Readj us tment was unnecessary f or r ibof lavin because
0
no loss o f ribof lavin was f ound during s t orage at - 1 0 C .
 1 18

About 0 . 8 - 0 . 9 g of pr ehea ted baby food was f il led into

boros il ic a t e glass v ial s of 3 mm internal d iameter , 1 mm thick and
130 mm long by us ing a 2 5 ml syr ing e . The tubes wer e hea t-sealed
under vacuum by hea t ing the top par t of the tubes to expel the air
and create a vacuum ( Wi lkinson et al , 1 980) . The t emperature o f the
flame used f or seal ing the tubes must be carefully contro lled .
Improperly sealed tub es may resu l t if the t emp erature i s too high
and this c an lead to higher oxygen cont ent in t he tube and explosion
of the baby f ood when it is heated . The prepared v ials were kep t in
°
the dark a t - 1 0 C before heat ing .

6.2.2 Thermal Proc ess ing Sys tem

°
The same thermo s ta t ically controlled o il bath ± 0 . 2 C used by
Wil kinson et al ( 1 980) wa s used . The v ials were hea t ed at spec i f ied
°
temp erature s , 1 1 0 , 1 2 0 , 1 2 9 and 1 3 9 C . I t was f ound by Wilkinson et a l
( 1 980) tha t on hea t ing l iver i n this system , the temperature d if f erenc e
between the centre o f the l iver in the tube and the glass-l iver interface
°
dur ing the initial heat ing per iod was ea 20 C af t er three second s and
°
ea 3 C a f t er 30 second s , theref or e , in 1 5 second s , 90% of the desired
temperature was reached . So Wilkinson et al ( 1 980) conc luded that there
wa s ef f ec t ively ins tantaneous heat ing and coo l ing . As the same o il bath ,
size and typ e of v ials and range of t emperatures were used , this was
a ssumed to b e true f or the s imilar hea t ing o f the baby food .

Four heat ing t imes at each t emperature wer e s tudied for each v itam in
(Table 6 . 1 ) . As the sample sizes required f or analys is of the two
v itamins were d if f eren t , 4 v ials for ascorb ic ac id and 2 vial s for
r ibof lavin were randomly removed a t the spec i f ied heat ing t ime . The
r emoved v ials were immed iately c ool ed in a crushed ice / water bat h .
Af t er cool ing , the v ia l s were wa shed with ethanol and stored in the dark
°
at - 1 0 C unt il analysi s . Control samples which were no t heated were
trea t ed in a similar manner .
 1 19 .

TABLE 6 . 1 Heating Temperature s and Times for S teady-State Hea ting Method

Hea ting Time (minutes)

0
Temperature C
Ascorb ic Acid Ribof lavin

1 10 210 450 690 1 1 40 240 510 840 1 200

1 20 1 10 240 370 -
1 20 270 4 20 600
1 29 40 85 135 195 70 1 50 240 340
1 39 35 75 1 25 175 40 80 1 30 180

6.2.3 Determination o f Ascorbic Acid and Riboflavin

The sample vials were taken from the s torage and cut at b o th ends .
The sample in the vial was blown out by compressed air into the weighed
10 ml volume tric f lask for ascorb ic acid analysis and into the weighed
250 ml erlenmeyer f lask for ribof lavin analysis , then the sample was
weighed . Dupl icate analys is of each sample was carried out by the me thod
described in Append ix 3 . 2 .

6.3 DESTRUCTION OF ASCORBIC ACID AND RIBOFLAVIN ON HEATING

The average concentrations of as corb i c acid and ribof lavin before

and af ter heating are shown in Table 6.2.
 1 20

TABLE 6 . 2 Concentration of Ascorbic Acid and Riboflavin Before and Af ter

Heating

Ascorbic Acid Rib o f lavin

Concentration Concentration
Temperature T ime Temperature Time
X 10
2
o m in 1 o min - 1
c mg g- c �g g

1 10 0 36 . 7 7 1 10 0 26 . 1 1
210 31 . 74 240 25 . 00
450 27 . 7 4 5 10 24 . 39
690 20 . 64 840 2 3 . 24
1 1 50 15 . 72 1 200 22 . 77

1 20 0 2 1 . 57 1 20 0 26 . 7 5
1 10 1 8 . 37 1 20 2 5 . 30
240 1 5 . 45 270 23 . 7 1
370 1 3 . 59 420 2 3 . 08
600 22. 16

1 29 0 3 1 . 29 129 0 2 5 . 85
40 29 . 0 2 70 2 3 . 90
85 24 . 87 1 50 2 2 . 86
1 30 21 . 77 240 22 . 16
195 16 . 9 1 340 2 1 . 73

1 39 0 38. 76 1 39 0 26 . 27
35 30 . 59 40 24 . 37
75 26 . 83 80 23 . 5 1
1 25 24 . 95 1 30 22 . 69
1 75 22 . 08 1 80 2 1 . 74
 121

6.4 DETERMINATION OF THE ORDER OF REACTION

As discussed in Chap ter 2 , mos t degradat ion on heat processing o f

vi tamins in foods was found to follow a f irs t order reaction , so in
Chap ter 5 , where the order of reac tion could not be de termined , degrad­
ation was assumed to f ollow a first order reaction . However , in this
section , the order of reaction could be de termined by regressing different
forms of concentration agains t time .

For zero order reaction :

de (6 . 1)
-k
dt

c - c -kt ( 6 . 2)
0

plotting c - c agains t time , t , will give a s traight line of

0
slop e , -k .

For a first order reaction :

de ( 6 . 3)
-kc
dt
=

ln £__ -kt ( 6 . 4)
c
0

plotting ln( c/ c ) agains t time , t, will give a s traight line of

0
s lope , -k .

For a s econd order reac t ion :

de 2 (6 . 5)
-kc
dt

1 1
= kt (6 . 6)
c c
0

plotting 1 / c - 1 / c 0 agains t time , t , will give a s traigh t line of

slop e , k .
 1 22

Linear regression of ( c - c ) , ln (c /c ) and ( 1 /c - 1 / c ) against t ime

0 0 0
for all the concentra tions in Tab le 6 . 2 gave the correlation coeff icients
2
(R ) shown in Table 6 . 3 . Statistically , the higher correlation coeff icient
indicates a higher consistency in the data at that order o f reaction .

For as corb i c acid , the correlation coefficients were very high excep t
°
at 1 39 C . However , for all 4 tempera tures , the first order relationship
2
gave the highes t average R and the lowes t s tandard deviation which
indicated that over the tempera tur e range s tudied the kinetics of as corbic
acid degradation in baby food were consis tent with the first order kinetics .
As can also be seen in Figure 6 . 1 , the f irs t order relationship , -ln ( c/ c )
0
versus time did give a reasonable approximation o f the experimental resul ts .

The correlation coef f ic ients for r iboflavin were lower than the ones
for as corbic acid for all orders s tudied and were more d iff icult to inter­
pret . The second order reac tion did give s ligh t ly higher correlation
coef f icients . But as can be seen in Figures 6 . 2 and 6 . 3 , at the temper­
°
ature of 1 2 0 C , nei ther f irs t or second order gave a good f i t of the exper­
imental resul ts . This could be due to the only small amounts of ribof lavin
des troyed .

Therefore , i t was concluded that the degradat ion under these heat
processing cond i tions of ascorb ic acid was best described by the f irs t
order kine tics and that the kinetic parameters would be determined based
on f irs t order kinetics . For ribof lavin , both f irs t order and second
order kine tics were s tudied for determination of k o and Ea as the
1 29 C
experimental results did not adequately distinguish between firs t and
second order kine tics .
 1 2 3.

TABLE 6 . 3 Correlation Coeff ic ients of Regress ion Analys is o f Concen tra tion
of As corb ic Acid and Riboflavin with Time o f Hea ting

CORRELATION COEFFICIENT
TEMPERATURE ° C
ZERO ORDER FIRST ORDER SECOND ORDER

Ascorbi c Acid

1 10 0 . 98 7 0 . 990 0 . 9 70
1 20 0 . 988 0 . 99 3 0 . 999
1 29 0 . 99 1 0 . 980 0 . 940
1 39 0 . 9 34 0 . 95 3 0 . 9 70

AVERAGE 0 . 975 0 . 9 7 9. 0 . 9 70
STANDARD DEVIATION 0 . 027 0 .018 0 . 024

Ribof lavin

1 10 0 . 96 7 0 . 969 0 . 97 1
1 20 0 . 956 0 . 956 0 . 956
1 29 0 . 935 0 . 9 40 0 . 946
1 39 a-� 9 6 3 0 . 966 0 . 970

AVERAGE 0 . 955 0 . 958 0 . 96 3

STANDARD DEVIATION 0 . 0 14 0 .013 0 .012
 1 24

1.0

0.8

0.6
0
"'"'

u
u
-

'-'

l=l
I
r-4
0.4

0.2

0.0
0 200 400 600 800 .1000 1 200
Time (min)

FIG . 6 . 1 Degradation Ra te for As corbic Acid in Baby Food on

Heating Described by First Order Kinetics
 125

0 . 22

0 . 20

°
1 10 C
0 . 15
•

0
,.....

(J
-
(J
.......
0 . 10
s::
M
I

0 . 05

o . oo --------�----�------�------_. ______ _. ______ �

0 200 400 600 800 1000 1200
Time (min)

FIG . 6 . 2 Degrada tion Rate for Riboflavin in Baby Food on Heating

Des cribed by First Order Kinetics

0 . 0 10

0 . 008

I
�
°
,.....
1 10 C
I
�
0 . 006
bO •

bO
;:l.
.......

0
(J 0 . 004
-
�

(J
-
�

0 . 00 �----�----._--�
0 200 400 600 800 1000 1 200
Time (min)
FIG . 6 . 3 Degradation Rate for Ribo f lavin in Baby Food
on Heating Described by Second Order Kine tics
 126

6.5 KINETIC PARAMETERS DETERMINATION

6.5. 1 Calculation of Kine tic Parame ters for Firs t Order Reaction

For a f irs t order reac tion , the kinetic reaction rate at each
temperature was de termined f rom the regression analy sis of - l n ( c / c )
0
agains t heating times , forc ing the line through zero a s ins tantaneous
heating and cooling was assumed . Then , the temperature dependence
of the rates was de termined from the regression analysis of ln k
agains t the inverse of absolute temperature as :

-Ea/Rt
k Ae (6 . 7)

Ea
ln k =
ln A - (6 . 8)
RT

where A -1
is the frequency fac tor ( s )
-1
Ea is the activation energy (kJ mole )
R is the gas cons tant (kJ mole- 1 0K- 1 )
0
T is the absolute temperature ( K) .

The k o and Ea could also be de termined by linear regression o f

1 29 c
ln ( ln ( c 0 / c) ) - l n t agains t the inverse o f absolute temperature as :

c
0
ln (-) kt (6 . 4)
c

subs t i tuting "k" by equation (6 . 7 ) , giving

c
- Ea/Rt
ln (_£) Ae t
c

therefore

c
Ea
ln (ln(_£) - ln t) ln A ( 6 . 9)
c RT
=

Linear regres s ion of ( ln ( ln ( c /c) ) - ln t ) agains t the inverse of

0
absolute temp eratures would give a slope o f -Ea/R and an intercep t of ln A .
- - So us ing all data ob tained a t various heating temperatures and times , .
 127

the k o and Ea cou ld b e de termined .

1 29 C

To dis tinguish between these two me thods , the f irs t me thod using
equation ( 6 . 8 ) was called the two-s tep method and the second me thod
using equat ion (6 . 9 ) was called the one-s tep me thod .

6.5.2 Calculation of Kine tic Parame ters for Second Order Reac tion

For second order kine tics , the kine tic reaction rate was determined
from the regress ion ana lysis of 1 / c - 1 / c agains t heating t ime , forcing
0
the line through zero . Then the activation energy was determined from
the regress ion analysis of ln k agains t 1 / T . As in the f irs t order case ,
this method was called the two-s tep method .

Analogous to the first order one-s tep method , the equation used
was modi fied for a second order reac t ion .

From equation ( 6 . 6)

1 1
- - - = kt
c c
0

sub s t i tu ting k by equation (6 . 7 )

1 _
1_ -Ea/RT
=
Ae t
c c
0

1 I Ea +
then ln (- - -) ln A
_

ln t
c c RT
0

1 1 Ea
ln (- - -) - ln t = ln A - - (6 . 10)
c c RT
0

Plot ting ( ln ( 1 / c - 1/c ) - ln t) agains t T gave a s traight l ine of

0
s lope and intercep t equal to -Ea/R and ln A , respectively .
 1 28

In the uns teady-state procedure , the computer progra� was modi fied
for second order kinetics by using :

de 2
= -kc
dt

de
so -kdt
2
c

c de t
f - f kd t
0
=

c 2
0 c

1 1 t
- f kdt
0
- -

c c
0

exp (� (.!. - _) )
1
As k k
Tr R T Tr

1 1 t Ea .!_ ..!.._)
Then - k exp ( ( ) dt (6 . 1 1 )
_ _
-
- f R T Tr
c c o Tr
0

For overall quality retention of the can a f ter time t :

.!. - l_ k f
v
f
t
exp ( -
Ea .!_ 1
( - _) ) d t dv
c c Tr o o R T Tr
0

( 6 . 1 2)

Us ing the graphical integration technique , for small values of �t , the

re tained quality for �v was calculated by

1 1 Ea 1 1
- k exp ( - ( - ) ) �t ( 6 . 1 3)
c Tr ·R T Tr
- - -

c
- -

1 Ea 1 1
k exp ( ( - ) ) �t + _!.._
c Tr c
- - -

R T
-

Tr
0

1 Ea .!_ ..!.._) ) A - 1
Therefore (_ + k exp (- ( t)
_

c
u
=

c Tr R T Tr
0
(6 . 1 4 )

The concentration a t the end o f the f i r s t interval became the ini tial
concentration for the second interval . The calculation was repeated until
the end of process ing . Then the overall quality retention was calculated
. by the summat ion of re tained quali ty of each interation . The computer
program in Chapter 5 was modified based on equation (6 . 1 4 ) and is shown in
Appendix 6 . 1 .
 129

Then the k o and Ea could b e de termined from thi s quality retention

1 29 C
calculation program by the trial and error me thod in section 5 . 4 .

6.5.3 Determination of Kine tic Parame ters for Ascorbic Acid

The kinetic reaction rates for ascorbic acid were de termined and are
shown in Tab le 6 . 4 . The Arrhenius plot of the natural logari thm of k as
a func tion of absolute temperature is shown in Figure 6 . 4 . The ac tivation
energy , frequency fac tor and k o were determined by both the two-s tep
1 29 c
and the one-s tep method as shown in Table 6 . 5 to see whe ther the me thods
led to any d i fference in the es tima tion of· these impor tant parame ters .

The activation energies de termined by either method were in the same

range . The mean ac tivation energy ob tained from the two-s tep method was
lower wi th a higher s tandard deviation . This dif ference could be due to
the inab ility to take the d eviation of the determined kine tic reac tion
rate into account in the two-s tep method whi le in the one-s tep method , all
deviations would be inc luded as all data were used .

°
The predi cted reac tion rates at 1 29 C obtained from the two-s tep
method and the one-s tep method were almos t identical whereas the f requency
fac tor s (A) were d if f eren t as only a small change in k or Ea could cause a
big apparent var iat ion in A . I t wa s considered · safe t o u se the k o only
129 C
wi thin the s tudied temperature range , as the extrapolation of the Arrhenius
plot beyond this temperature was doubtful .

For the one-step method , the error in the raw data was also determin�d ,
a probab i li ty plot was cons tructed o f % res idual , defined as :

% res idual = (c - c ) /c x lOO (6 . 1 5 )

p 0b s p

where c is a predi c ted concentration

p
c is an observed concen tration
obs

The % res idual was calculated based on the de termined E a and A from
the one-s tep method shown in Tab le 6 . 5 . A probability plot (Figure 6 . 5)
as a s traight line indicated that all deviations from the line were
random and due to experimental uncertainty only . The average residual
was 5 . 99% .
 130

TABLE 6 . 4 Kinetic Reac tion Rate Cons tants at Various Tempera tures for
Ascorbic Acid
(Rate for f irs t order kine tics with 9 5% confidence level)

4 !
Tempera ture k X 10 Correlation Coefficient
o -1 2
C s R

1 10 0 . 1 26 + 0 . 0 10 0 . 990
1 20 0 . 2 16 + 0 . 00 8 0 . 99 3
.
129 0 . 49 8 -
+ 0 . 054 0 . 9 80
1 39 0 . 6 19 + 0 . 10 2 0 . 95 3

TABLE 6 . 5 Activation Energy, Frequency Factor and Kinetic Reaction

° ( l)
Ra te a t 1 29 C for Ascorbic Ac id

Two-S tep Method One-S tep Me thod

(2) -1
Ea , kJ mole 77 + 23 8 5 + 10
-1
(kcal mole ") ( 18 . 2 + 5 . 5) ( 20 . 3 ± 2 . 3)

5 -1
A X 10 ' s 3.6 42 . 8

4 -1
k o X 10 s 0 . 40 3 0 .418
1 29 C '

2
( 1) R for the two-s t ep method was 0 . 9 5 7 and for the one-s tep me thod
was 1 . 000 .
(2) Ac tivat ion energy with 95% conf idence level .
 131

- 9

- 10

-11

I
......

CIJ
- 12
._..

.I<:
l=l
......t

-13

- 14
-3
2 . 40 2 . 44 2 . 48 2 . 52 2 . 56 2 . 60 2 . 64 X 10

! /Temperature ( l / °K)

FIG . 6 . 4 Arrhenius Plot for Degradation of Ascorbic Acid and

Riboflavin in Baby Food on Heating

(a &) as corbic acid

(e •) riboflavin
 .. 13
2

Residual ( %)

• •
•
•
•
•
•
•
• • •
•

• •
•
•

•
•

•
•
•

Probability (%)

FIG . 6 . 5 Probability Plo t of Calculated % Residual for Ascorbic Acid

 133

As all data were taken into account a t once i n the one-s tep method ,
so all deviations were included . The one-s tep method should give
more accurate resul ts , k o and Ea , and therefore i t should be used for
1 29 c
de termination of kine tic parame ters in s teady- s tate procedure .

6 . 5. 4 De termination of Kinetic Parame ters for Ribo flavin

Assuming tha t the degrada tion of riboflavin on heat processing could

be describ ed by the firs t order reac tion , the activation energy , frequency
fac tor and k o were determined by both the two-s tep and the one-s tep
1 29 C
methods . The reaction rate cons tants a t v�rious temperatures were deter­
mined by the two-s tep method and are shown in Table 6 . 6 . The Arrhenius
plo t of ln k versus 1 /T is shown in Figure 6 . 4 . The activation energy ,
frequency fac tor and k o ob tained from b o th methods are shown in
1 29 C
Table 6 . 7 .

The % res idual was also calculated as in section 6 . 4 . 3 . A probab ility

plo t (Figure 6 . 6) for riboflavin was also a s traigh t line . The average
absolute residual was 2 . 76 % .

The k o and the Ea ob tained from bo th m� thods were s l ightly

1 29 C
dif ferent . However , as described in sec tion 6 . 4 . 3 , the one-s tep method
gave more accurate results and should be used for determination o f k 1 29 o c

and Ea .

As ribof lav_i n could pos s ib ly be be tter described by second order kine tics ,
the activat ion energy , the frequency factor and the k o were also
1 29 c
determined us ing the me thods describ ed in sec tion 6 . 4 . 2 . The kine tic
reac tion rate cons tants ob tained from the two-s tep method are shown in
Tab le 6 . 8 . The Arrhenius plo t is in Figure 6 . 7 . The ac tivation energy ,
the f requency fac tor and the k o determined by b o th the two-s tep and
1 29 c
the one-s tep methods are shown in Table 6 . 9 .
 1 34

TABLE 6 . 6 Kine tic Reaction Rate Cons tan ts at Various Temperatures for
Ribof lavin

(Ra te for first order kinetics wi th 95% confidence leve l )

4
Tempera ture k X 10 Correlation Coeffi cient
o -1 2
c s R

1 10 + 0 . 00 2
0 . 02 1 - 0 . 969
1 20 + 0 . 006
0 . 05 7 - 0 . 956
129 + 0 . 0 10
0 . 100 - 0 . 940
1 39 + 0 . 0 14
0 . 1 89 - 0 . 966

TABLE 6 . 7 Activation Energy, Frequenc Fac tor and Kinetic Reac tion 1
° !)
Rate at 1 2 9 C for Ribof lavin

Two - Step Method One-S tep Method

- ·

E �2 � kJ mole
-1
+ 15
99 - 105 + 8
(23 . 6 ±
-1
(kcal mole ) 3 . 6) ( 25 . 0 + 1 . 8)

10 , s
5 -1
A X
594 1 89 2

4 -1
k ° 10 s 0 . 09 9 0 . 1 14
129 C X ,

2
( 1) R for the two -s tep me thod was 0 . 9 89 and for the one-step method
0 . 999 .
( 2 ) Ac tivation energy with 95% conf idence level .
 ·. 135 .

Res idual ( %)
10

•
•
• •

•
•
••

•
•
•

5 •
•

•
•
•
•

•
•
••
•
•
•
•
•
••
•
••
0
.,#
/
_

•
___..,.
•
•
•
•
•
• • •

-5 •

Probab i l i ty (% )

FIG . 6 . 6 Probab i l i ty Plot of Calcula ted % Res idual for Riboflavin

·· � 136

TABLE 6 . 8 Second Order Kine tic Reac tion Ra te Cons tants at Various
Temperatures for Ribof lavin
( Rate cons tant with 95% confidence level)

4
Temperature k X 10 Correlation Coefficient
o -1 -1 2
C ].lg g s R

l lO 0 . 0008 -
+ 0 . 0000 0 .971
1 20 0 . 0023 -
+ 0 . 000 1 0 . 966
129 0 . 0042 +
- 0 . 0002 0 . 9 46
1 39 0 . 00 7 8 -
+ 0 . 0003 0 . 970

TABLE 6 . 9 Activation Energy, Frequency Factor, Kinetic Reac tion

Rate at 129 °C for Second Order Kine tics for Ribo flavi & )
1

Two-S tep Method One -S tep Method

E�
2
� kJ mole
-1
100 + 1 4 103 + 7
( 2 3 . 7 .± 3 . 5)
-1
(kcal mole ) (24 . 5 + 1 . 7)

1 0 , ].lg g
5 -1 -1
A X s 33 10 2

-1 - 1
10 , ].lg g . S
4
k ° X 0 . 00 4 1 0 . 0047
1 29 C

2
( 1) R for the two- s tep me thod was 0 . 990 and for the one- s tep method
was 1 . 000 .
(2) Act ivation energy with 9 5% confidence level .
 137

- 16
ln k
-1 -1
( ll g g s )

- 15

0
! /Temperature ( 1 / K)

FIG . 6 . 7 Arrhenius Plot for Degradation of Riboflavin in

Baby Food on Heating Described by Second Order Kine tics
 1 38

The ac tivation energies ob tained from assuming fil;"s t order and second
order kinetics were almos t the s ame . So it could be concluded that the
-1
activation energy of ribof lavin was in the range of 9 6- 1 1 3 kJ mole •
-4 - 1
Howeve r , the k o was o f course dif ferent and i t was 0 . 1 1 4 x 1 0 s
1 29 C
-4 -1 -1
for first order kine t ics and was 0 . 00 47 x 1 0 �g g s for second
order kine t ic s .

6.6 COMPARISON OF KINETIC PARAMETERS DETERMINED BY STEADY-STATE AND

UNSTEADY-STATE PROCEDURES

The kine tic parame ters determined by the one - s tep me thod were compared
wi th the parame ters ob tained from the uns teady-s tate procedure ( Chap ter 5) .

6.6.1 Ascorbic Acid

°
The kine tic reac tion rate cons tant at 129 C and the act ivation energy
of ascorbic acid de termined by the s teady-s tate procedure ( in tubes ) and
the uns teady-s tate p rocedure ( in cans) are tabula ted in Tab le 6 . 1 0 .

TABLE 6 . 10 Comparison of Ea and k o for Ascorbi c Acid Determined by

129 c
Steady- and Uns teady-S tate Procedures

PROCEDURE STEADY- STATE UNSTEADY-STATE

OBSERVATION ( in tubes ) (in cans )

-1 - 81
Ea , kJ mole 85 + 10
-1
(kcal mole ) ( 20 . 3 ± 2 . 3) ( 19 . 2 )

1 -4 -4
k ° s- 0 . 418 X 10 0 . 435 X 10
129 C '
 139

The d i fferences in the parame ters determined a s (abs o lute dif ference
be tween procedures /average of these procedures) , were 4% for k o
129 C
- 1
and 5% for Ea . The ac t iva tion energy o f 8 1 kJ mole determined by the
uns teady- s tate procedure , ac tually fell within the 95% confidence limi ts
of that de termined by the s teady-s tate procedur e . Therefore , i t could be
concluded that there was no s i gnificant difference be tween these two
procedures . Thus , the computer program cons truc ted in Chap ter 5 for uns teady­
s ta te procedure was feasib le and gave a reasonable resul t when the degra­
dation was describ ed by a first order reaction .

I t could be concluded that in this food sys tem , the loss o f as corbic
acid on heat process ing can be des cribed by a first order reac tion wi th
- -1
k o 0 . 4 1-0 . 44 x 1 0 2 s - 1 and Ea 85 + 10 kJ mole •
129 C

6.6.2 Riboflavin

Assuming f irs t order kinetics , the activation energy and the k 1 29 o C

were compared for uns teady-s tate and s teady-s tate procedures (Table 6 . 1 1 ) .

TABLE 6 . 1 1 Comparison of Ea and k o for Ribof lavin D e termined by

1 29 C
Steady- and Uns teady-S tate Procedures
(assuming firs t order kine t i cs )

PROCEDURE STEADY-STATE UNSTEADY-STATE

OBSERVATION ( in tubes ) ( in cans )

-1
Ea , kJ mole 105 + 8 84
-1
(kcal mole ) ( 25 . 0 + 1 . 8) ( 20 . 0)

-1 -4 -4
k ° s 0 . 1 14 X 10 0 . 250 X 10
129 C '
 140

The differences were higher than the ones found f o r ascorbic acid .
The k o determined by the s teady-s tate procedure was only 50% of that
1 29 C
ob tained by the uns teady- s tate procedure . The activation energy was
closer , wi thin about 22% , but was s t ill outside the 95% confidence limi t .
The dif ference in the kinetic parameters determined by these two
d i f ferent methods could be caused by the assump t ion o f a fir st order
reac tion . Therefore , the computer program for uns teady- s tate procedures
for second order kinetics (Appendix 6 . 1 ) was used , and the k o and Ea
1 29 C
of riboflavin were redetermined .

S tarting at the s ame k o and Ea as . in the s teady-s tate heating ,

-4 1 29 c
-1 -1 -1
0 . 0045 x 1 0 llg g s and 1 00 . 9 k J mole , increasing and decreas ing
the k o and Ea ( Tab le 6 . 1 2) , indicated tha t to ob tain the minimum
1 29 C
average res1" d ua 1 a k
-4 -1 -1
o o f hi gh er th an 0 . 00 80 x 10 "g
� g s
1 29 C
-1
and an Ea of less than 9 2 . 4 kJ mole was necessary . The analys is
was , therefore , s topped because these were nearly as far apart as the
first order kine tic parame ters determined for the uns teady-s tate and
s teady-state hea ting .

Ass uming that the s teady-s tate kinetic parameters were the more
exac t , the absolute res iduals were determined for first order and second
order kinetics at these values . For the first order kinetics , the
absolute residual was de termined from equation ( 5 . 20 ) and found to be
-4 - 1 and 105 kJ mole- 1
0 . 04 1 at the k o and Ea of 0 . 1 1 4 x 10 s • For
129 c
the second order kineti cs , the absolute residual was 0 . 0 28 at the k 1 29 o C
-4 -1 -1 -1
and Ea of 0 . 0045 x 10 lJg g s and 10 1 kJ mole . So the second
order kinetics gave sligh t ly b etter agreement between uns teady and s teady
s tate kinet ic parameters .

However , the order of ribof lavin degradation on heat processing was

s till doub t ful . As the loss of riboflavin was very small wi th the max­

imum of only 15% , the plot of d i fferent forms o f c and c agains t time ,
0
t , would therefore g ive virtually s traight lines thus g iving no indication
of the exac t order of reac t ion . Another problem was the error o f analysis .
Because r iboflavin degrada tion was s low , prolonged heating was required
and this could cause browning interference in the analysis as can be seen
in sec t ion 6 . 3 . The rate that the concentration o f ribof lavin decreased
was slower a t prolonged heating times . This error could s ignif icant ly
 141

TABLE 6 . 1 2 Average Res iduals at Various k o and Ea for Ribof lavin

1 29 C
in Uns teady-State Heat ing in Can

4
k
1 29 <� =�
t Ea AVERAGE STANDARD
kJ mole
-1 -1
�g g s (kcal mole ) RESIDUAL DEVIATION

0 . 0040 7 5 . 6 ( 1 8 . 0) 0 . 0267 0. 0 1 1 5
9 2 . 4 ( 2 2 . 0) 0 . 0292 0. 0 1 18
109 . 2 ( 1 6 . 0 ) 0 . 03 1 2 0 . 0121

0 . 004 5 67 . 2 ( 1 6 . 0 ) 0 . 0224 0 . 0 10 9
84 . 0 ( 20 . 0 ) 0 . 02 5 5 0. 01 1 2
1 00 . 8 ( 24 . 0) 0 . 0280 0. 0116
1 1 7 . 6 ( 2 8 . 0) 0 . 030 1 0 . 0 1 20

0 . 00 5 0 75 . 6 0 . 0214 0 . 0 10 6
92.4 0 . 0 244 0 . 01 10
--

1 09 . 2 0 . 0 269 0 . 0 1 14

0 . 00 60 75 . 6 0 . 01 7 1 0 . 00 7 6
92 . 4 0 . 0201 0 . 009 5
1 09 . 2 0 . 0227 0 . 0 1 08

0 . 00 7 0 75 . 6 0 . 0127 0 . 00 5 3
92 . 4 0 . 0 1 63 0 . 00 7 0
109 . 2 0 . 0 1 92 0 . 0086

0 . 0080 92 . 4 0 . 0 1 25 0 . 00 5 2
 142

effect the determination of k and Ea .

Therefore , i t could be concluded that the effect o f heat on

riboflavin in the b aby f ood was nutri tionally no t very s igni f ican t
under normal process ing condi tions as the lo ss of r iboflavin was small .
The exact order o f des truc tion of riboflavin on heat processing could
no t be determined . Thus , the s imp les t form , zero order reaction kine t ics ,
could have been used but this was not chosen as zero order is unlikely
to be in f ac t correct . Also as the change , on heat process ing , of
food qualities and vitamins were mos tly described by first order kinet ics ,
and as the qua l ity re tention calculation program based on first order
kinetics was avai lable , it was sufficiently accurate for present purpose
to estimate the f inal concentration o f r iboflavin af ter processing of
baby f ood us ing first order kine tics . The high d i f ference in the k o
121 C
and Ea ob tained from s teady-s tate compared wi th the uns teady-s tate
procedure was also found in Lenz ( 19 7 7 ) for chlorophyl l in spinach
-1
puree , where k o of 0 . 0 14 + 0 . 004 and 0 . 029 + 0 . 008 min and the
121 C '
-1
Ea of 80 and 9 7 kJ mole were reported for the s teady-state and
uns teady-s tate heating , respec tively . Therefore i t was concluded that
and Ea of 0 . 1 1 4�0 . 250 x 10
-4 - 1 -1
the k o s and 84- 105 kJ mole could
1 29 C
safely be used for riboflavin assuming the f irs t order kinetics .

6.7 CONCLUS ION

Using the same f ood model , beef and mixed vege tables baby food , the
°
kine tic reac t i on rate, at 1 29 C and the activation energy of ascorbic acid
and riboflavin were determined by a s teady- s tate procedure where foods
were heated in small glass vials in a thermostatically controlled o il
bath in whi ch ins tantaneous heating and cooling could be assumed . It
was found that the degradation on heat processing o f ascorb i c acid could
be best described by a f irs t order reac t ion . The kinet i c reaction rate
0 -4 - 1
a t 1 29 C and the ac tivation energy were 0 . 4 18 x 10 s and 85 + 10
-1
kJ mole • These were in a c lose agreement wi th the results from the
un stead y-state procedur e . Therefore , i t wa s concl uded that the comput er
program cons tructed in Chap ter 5 was feasible and could give a reasonable
result where the degradation could be described by a f irs t order reac tion .
 . 1 43

However , for riboflavin , the de termination o f the kine tic parame ters
was d i f f i cul t . The correlation coef f i cients (R ) obtained from regression
2

of various forms of ini t ial and f inal concentration on heating time were
higher than 0 . 9 4 but they were no t s igni f icantly d if ferent . Marked
d i fferences between the k o and Ea for the uns teady-s tate and
1 29 C
s teady-state heating when determined for firs t order and second order
kine t ics were also found . For the s teady-s tate heat ing , the k o and
129 C
-4 - 1
Ea determined for first order kine t ics were 0 . 1 1 4 x 10 s and 105 + 8
-1 -4 -1 -1
kJ mole and for s econd order kine tics were 0 . 00 47 x 10 �g g s
-1
and 103 + 7 kJ mole . The k o were hal f as much and the Ea about
1 29 c
-1
20 kJ mole more compared wi th the uns teady-s tate heating . These
d i f f erences may have been caused by the very small loss of r ibof lavin
in these experiments which made it d i f f icult to calculate accurate
kine t i c parame ters or may have been due to variations in o ther condi tions
in the cans and the tubes .
 144

7. DISCUSS ION

The two me thods developed for s tudying the k ine tics of changes
in ascorbic acid , rib o flavin , colour and viscos i ty during heat processing
of a canned baby food were an uns teady-s tate procedure of heat ing in a
can and a s teady-s tate procedure o f heating in a small tube . In using
these me thods , there are several points to consider .

7. 1 TEMPERATURE PREDICTION IN THE CAN

Us ing the uns teady-s tate procedure , accurate temperature distribution

prediction in the can is necessary . Analyt i cal solutions and numerica l
f in i te d i fference me thods gave nearly identical results and ei ther can
be used to predict tempera tures . Generally , fini te difference methods
should be used because of the shorter computing t ime but where there is
a need for form f i tting because of an unusual temperature his tory in the
can , the analytical s olution is easier to manipulate .

In general , b oth analytical solu tion s and numerical f in i te d i f ference

me thods gave a very good f i t for mos t of the experimental temperatures .
There was a consis tent irregulari ty in the early s t ages o f cooling and
therefore temperature prediction was carried out by using the analy t ical
solution for f i t t ing the ac tual temperatures in the can . The pred i c ted
temperatures from the mod i f ied analy tical program were compared wi th the
experimen tal tempera tures . The residual mean was found to vary from
° ° ° °
0 . 1 C to 0 . 7 C wi th the s tandard deviation varying from 0 . 9 C to 1 . 7 C
for overall proces s . These were considered sufficien t ly accurate as they
were in the range f ound by Lenz ( 19 7 7 ) as the b i o logical variabi li ty o f
physical cons tants .

Prediction of the temperature in the early cooling s tage could have

been done by numerical finite d irference method as the computing cos t
would be cheaper but there was no availab le ins trument for measuring C
and A . Bes ides fur ther inve s t igations were needed to fully exp lain the
phenomenon of the i rregulari ty in the cooling curve .
 145

7.2 USE O F STEADY- STATE KINETICS DATA TO PREDICT QUALITY CHANGES IN

UNSTEADY-STATE HEAT PROCESSING

From the temperature dis tribution predic t ion , the quality re tention
can be determined i f the kine ti c data from s teady-s tate de terminat ion
are availab le . Knowing the order of the reaction kine tics , the kine ti c
react ion rate and the ac tiva t ion energy , quali ty re ten tion can b e
calculated by numeri cal integration based on the predic ted temperatures .
I f the calculated and the experimental quality reten tions are simi lar ,
then the kinet ic parame ters can be assumed to be true for the uns teady­
s tate heating condi tions . This was cer tainly true for ascorbic acid ,
where -4
k o and Ea , from the uns teady-s tate heating were 0 . 4 35 x 10
129 c
-1 -1 -4 - 1
s and 8 1 kJ mole and f rom s teady- s tate heating were 0 . 4 1 8 x 1 0 s
-1
and 85 + 1 0 kJ mole •

However , great care should be taken in assuming the s teady-state

kine tic parameters are true in uns teady-s tate heat process ing . As
was seen in the riboflavi� determination , there c an be inaccuracies
caused by low des truc t ion rates and the assay me thod used . There
--
can also b e disagreement due to some changes in condi tions be tween
the two me thods of hea t ing .

Therefore , there should always be experimental determination o f

the qua l i ty loss in uns teady- s tate heat processing to confirm the
predic ted loss - two temperatures and two processing t imes are enough
to confirm this for the temp erature range and food composi tion s tudied .

7.3 KINETIC ANALYS IS US ING UNSTEADY-STATE HEATING PROCEDURE

Assuming the order of reaction kinetics , the qua l i ty retention can

b e determined where s tandard k and Ea are unknown . The ranges o f
s tandard k and Ea have to b e roughly e s t imated e i ther from any d ata avail­
able on that proper ty , or the data avai lable on a similar property, and they
have to be carefully chosen to cover the possib le ranges of the ac tual
standard k and Ea of that qual i ty . Using an orthogonal composi te
design method to determine the empirical relationships of s tandard k ,
Ea and residual (d i f ference in predic ted and experimental retained
 1 4 6.

quality) , the s tandard k and Ea giving the lowes t residual can be

determined .

The experimental quali ty loss should be determined from using a t

leas t 2 processing temperatures and 3 processing t imes . More experimen­
tal runs can be carried out to get higher accuracy .

The order of reac t ion kine tics is usually first order , however
the deviation from first order kine tics can also be accommodated in this
procedure then the parame ters can be de termined using the same me thod
of calculat ion .

I f i t is possible the accuracy o f the temperature predic tion should

1
be confirmed by s tudying of the known kine tics quality changes , for
example , in this s tudy , ascorbic acid determinat ion confi rmed the
accuracy of tempera ture prediction and therefore gave a basis for the
use of temp erature prediction to determine the k o and Ea of the
129 C
colour and viscosi ty by orthogonal composite design me th od

Where more than one qua l i ty was required , the e s t imation of parame ters
should s tart wi th the one wi th the mos t available information . Then ,
the rough ranges of k and Ea for o ther quali ties could be e s t imated us ing
the equivalent processing t ime method .

7.4 KINETIC PARAMETERS FOR ASCORBIC ACID, RIBOFLAVIN, COLOUR AND

VISCOSITY IN HEAT PROCESSING OF BABY FOOD

For ascorb ic acid , i t was found that the degradation could be

°
described b y firs t order kine tics and the kine tic reaction r ate a t 1 29 C
-1 -1
and the activation energy were 0 . 4 1 8 x 10-4 s and 85 + 1 0 kJ mole
which were 4-5% d i f ferent from those found in the uns teady-s tate procedure
and 8 1 kJ mole •
-4 - 1 -1
- 0 . 435 x 1 0 s

This activat ion energy was almos t the same as found for anaerobi c
decompos i tion a t pH 6 . 0 of as corb ic acid calculated from results of
Huelin ( 19 5 3 ) and Lin and Agalleco ( 1 9 7 9 ) . A higher ac tiva t ion energy
 147

-1
of 1 7 2 k J mole was reported b y Lathrop and Leung ( 1980) f o r peas in
can . This marked dif ference may be due to the environmental conditions
such as mois ture , pH and food product c omposi tion as wel l as the de ter­
- -1
mination method � The kine tic reaction rate at 1 29 ° C of 0 . 4 1 8 x 10 4 s
was also f ound by Garre tt ( 19 5 6 ) in liquid-multivitamin . Thi s is also
- -1
in an agreement with the kine tic react ion rate at 1 29 ° C o f 0 . 26 3 x 1 0 4 s
calculated from Lamb e t a l ( 1 9 5 1 ) for canned tomato j ui ce and tomato
paste . Both higher and lower kine tic reac tion rates were also repor ted .
These variations were , again , due to the difference in environment as
wel l as the method involved .

The activation energies of ribof lavin thermodegradation were 105 + 8

-1
kJ mole wi th 95% c onfidence for s teady- s tate heating procedure and
-
84 kJ mole 1 for uns teady- s tate heating procedure . These were ins igni­
-1
f i cantly d i fferent f rom the 9 7 kJ mole reported by Gi llespy ( 19 6 2 ) .
-1
They were also fairly c lose to 7 8 kJ mole found for mi lk packed in
go ld-pigmen ted BMP ( Singh et a l , 1 9 7 5 ) . The kinetic react ion rates at
0 -1
1 29 C , o f 0 . 1 1 x 10 - 4 s ( s teady-state heating procedure) and o f 0 . 25
- 4 s- 1
x 10 ( uns teady-s tate heating procedure) were also found to be
comparable to the rates for canned green lima bean , whole kernel corn
(Guerrant et al , 1945) and canned luncheon pork (Greenwood et al , 1944)
0
when extrapolated to 1 29 C .

The reac t ion involved in colour change o f baby food , consi s t ing of
beef , peas , potatoes , carro t s , yeas t extrac ts and f lour , could possibly
be mainly the n�n-enzymatic browning reaction . Chlorophyl l des truc tion
could be ano ther minor react ion involved . The ac tivat ion energy o f
-1
1 2 2 kJ mole found for colour change was comparab le to the ac tivation
energies f ound for non-enzymatic browning reaction of liquid foods i . e .
-1 -1
87- 1 1 3 kJ mol e for app le j uice (Hermann , 1 97 0 ) ; 1 1 3 kJ mole for milk
-1
( Burton , 1 9 6 3) ; 1 1 8- 1 66 kJ mole for app le j uice model sys tem (Dr i l leau
and Prioue t , 1 9 7 1 ) . This was found to be higher than the . ac t ivation
energies reported for chlorophyll des truc tion ( Table 2 . 5 ) wi th one excep­
-1
t ion of 1 3 5 kJ mole found for frozen Brussels sprouts during s torage
0 -4 - 1
(Tij skens e t al , 1 9 7 9 ) . The rate o f reac tion at 1 29 C o f 1 . 2 x 10 s
was much s lower than the rate repor ted for milk by Bur ton ( 1 9 6 3) and about
half of the rate reported for app le j uice by Hermann ( 19 7 0 ) . This could
poss ib ly be explained as the e f fect o f food composi tion , pH , oxygen
 148 .

concentration as well as the method used in following the change o f the

colour . As there are at leas t 3 mechanisms that could possibly exp lain
the development of brown colour , so the kine tic s tudies should be
conduc ted for di f ferent food systems and should be applied for only
s imilar food produc ts in whi ch the environmental fac tors such as
c omposi t ion , pH , oxygen concentration are almos t the same . However ,
i t could b e concluded that the colour change was mainly the non-enzyma tic
°
browning reac t ion , the reac tion rate cons tant at 1 29 C and the activation
- -1 -1
energy were 1 . 2 x 10 4 s and 1 2 2 kJ mole •

For viscos i ty , there is l i t t le kine t ic parameter informa tion .

-1
The activation energy of 1 5 1 kJ mole for baby food is in a close
-1
agreement wi th the activat ion energies of 1 30 , 103 , 150 kJ mole
°
reported for cons i s tency change dur ing heating in thin cans a t 1 10- 1 34 C
of f ish pudding , liver pas te and vanilla sauce , respec tively (Ohlsson ,
1 9 80) .

7. 5 APPLICATION TO PROCESSING

As food s are generally c ompo site mater ial s who se cons t i tuents
change with proc essing , so thes e proc edures for determining kinetic
paramet er s and us ing them to fol low pro cess ef fects could be appl ied
to opt imisation of the heat ing process . General ly , there ar e several
qual ity changes oc curr ing together in hea t pro ce s s ing and if the kinet ic
parameters can be determined in a spec ific food sys t em , then the process
c an be studied to f ind the heat ing conditions which will give satisfac tory
microb iologica l safety tog ether with acceptable nutritional and eat ing
qualit ies . The rela t ive importance o f the const ituent s or proper ties
would have to be related on some common basis and f rom this an optimum
proc ess or a t l east some preferred pro cess could b e sought . Once the
equat ions are set up fo r the different parameter s , the dif ferent hea t ing
syst ems can be compared very quic kl y .
 149

8. CONCLUSIONS

To es tab lish the kinetic parame ters for changes of food during
processing , the s teady-s ta te heating procedure should be used wherever
possible as the analysis is s imp ler and gives more exac t results . Als o ,
the order of reac tion kinet ics can b e dire ctly determined . However , some
f ood quali ties require large amount of samp le for analysis , e . g . colour ,
viscosity , f lavour and the uns teady-s tate heat ing procedure mus t be
used . The order of reac tion , ac t ivation energy and the s tandard k can
only be determined indirectly by using a sys t'emat i c trial 1and error method .

In using kine t ic data determined from s teady-s tate s tudies to predi c t

quali ty changes i n food during uns teady-s tate heat processing , i t i s
impor tant to conf irm the pred i c ted changes wi th the exper imental changes a t
at leas t two -diff erent times and temperatures .

The computer me thod , developed to pred ic t temperatures a t dif feren t

points i n the can at different t imes o f heating t o calculate the quality
change , accurately d etermined the des tru ction o f as corbi c acid in heat
p rocess ing during can s terili zation but did not so accurately p redict
ribof lavin des truc t ion . This was poss ibly due to the very small loss
of ribof lavin during can s terilization .

The computer me thod can be used to determine the unknown kine t i c

p arame ters by a - systemat ic trial and error method but i t is impor tant
that the me thod is f i r s t examined for accuracy in the par ticular food
system by using a qual i ty change \·J i th known kine t i c parame ters . Af ter
determining the accuracy of the me thod using the ·ascorbic acid des tru ction,
i t was possib le to determine the Ea and k o for viscos i ty and colour .
1 29 C

I t was conc luded in this food sys tem for the temperature ranges o f
0
60- 1 3 9 C , the kine t ic reac tion rate at 1 29 ° C and the activat ion energy
-4 - 1 -1 -4 - 1
were 0 . 42 -0 . 44 x 1 0 s and 7 7-85 kJ mole , 0 . 1 1-0 . 25 x 1 0 s
- 1 1 . 20 x 10 -4 s - 1 and 1 2 2 kJ mo le - 1 and 1 . 65 x 10 -4 s - 1
and 84- 105 kJ mole ,
-1
and 1 5 1 kJ mole for as corb ic acid , ribof lavin , colour and viscosi ty
respec t ively .
 1 50 .

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 1 67

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 175

APPENDIX 3 . 1 Analys is of Ascorb ic Acid and Riboflavin

( a) Ascorb ic Acid

-1 -2
Concentration mg g X 10
% Accuracy of
Sample
dupl ication*
1 2 3

Control ( 1 ) 24 . 7 1 ( 5 ) 25 . 4 7 ( 7 ) 24 . 28 ( 7 ) 1.8
Heated ( 1 ) 2 3 . 04 (0) 22 . 06 ( 5 ) 2 2 . 59 ( 2) 1.5

Control ( 2 ) 2 3 . 58 (0) 2 3 . 39 (8) 22 . 9 1 ( 9 ) 1.1

Heated ( 2 ) 2 1 . 1 2 (0) 20 . 70 ( 9 ) 2 1 . 03 ( 7 ) 0.8

Control ( 3) 25 . 04 ( 8) 24 . 9 2 (8) 2 4 . 79 ( 0 ) 0.3

Heated ( 3 ) 22. 62 (9) 22 . 43 (8) 22. 10 (9) 0.8

Average 1 . 1 (5)

(b) Riboflavin

-1
Concentrat ion llg g % Accuracy o f
Samp le
dup licati on*
1 2 3 4

Control ( 1 ) 26 . 2 2 ( 0) 26 . 36 ( 3) 26 . 10 (0) 26 . 1 6 (4 ) 0.4

Heated ( 1 ) 24 . 36 ( 5 ) 26 . 1 4 (0) 25 . 28 (0) 24 . 8 1 ( 5 ) 1.6

Control ( 2 ) 26 .-44 ( 2) 25 . 7 7 ( 6 ) 25 . 90 ( 3) 26 . 49 ( 5) 1.2

Heated ( 2 ) 24 . 3 2 ( 4 ) 24 . 1 0 ( 8) 25 . 00 ( 8 ) 24 . 42 ( 1 ) 1. 1

Control ( 3) 25 . 66 ( 9 ) 26 . 1 2 ( 2 ) 26 . 1 3 ( 4 ) 25 . 85 ( 1 ) 0.7
Heated ( 3 ) 24 . 0 2 ( 6 ) 24 . 00 ( 7 ) 24 . 86 ( 1 ) 24 . 0 7 ( 3) 1.3

Average 1 . 1 (5)

* calculated as the mean of the % dif ference , defined a s

! observed concentration-mean concentrat ion !
% d 1. f ference =
mean concen trati on
•
 176

APPENDIX 3 . 2 Ana lyt ical Method

( a) Ascorbic Acid

Ins trument
Spec tronic 20 spec trophotometer ( Bausch & Lomb)
Reagents

Stock ascorbic acid solut ion :

Prepare 0 . 1 % solut ion of ascorbic acid in 0 . 4% oxalic acid
solution .

Working s tandards :
Take 20 ml of s t ock ascorb ic acid solution and make up t o 1 00 ml
with 0 . 4% oxalic acid solut ion . Take 25 , 20 , 1 5 , 1 0 , 5 ml from the
prepared solut ion and make up each to 100 ml with 0 . 4% oxalic acid
solut ion (WS ) .

Stock dye solut ion :

Dissolve ea 200 mg of 2 , 6-Dichlorophenol indo phenol in 1 50 ml hot
wa ter containing 4 2 mg s odium bicarbonate , coo l , d ilu te to 200 ml with
disti lled wa ter . This solution will be s tab le for 5 weeks a t 3 °C .

Standard dye solution:

Take 1 2 ml of s tock dye solut ion and make up to 1 litre with
d is t i lled water • .

Standard Curve

To four absorp tiometer tubes add the following

DW 1 0 ml dis t illed water s - 1 ml WS No . 1 + 9 ml water

No . 1 - 1 ml 0 . 4% oxalic acid No . 2 - 1 ml WS No . 1

Adj us t the Spec tronic 20 to zero absorbance , us ing DW and a green

f i l ter of 520 nm . To tube No . 1 add 9 ml of s t andard dye solution , mix
and record the reading (1 1 ) exac tly 15 seconds af ter add ing the dye .
Then adj u s t the ins trumen t to zero with tube S in the Spec tronic 20 .
 177 ·
. .. ..

To tube No . 2 , add 9 ml dye , mix and read af ter 1 5 s econds (L2) .

Record L 1 and L2 for each working s tandard and cons truct the s tandard
curve wi th concentra t ions of ascorbic acid as abc is sae and (L 1-L2) for
each working s tandard as ordinates .

Method

Macerate 8- 1 0 g of thawed sample wi th 7 0 ml 0 . 4% oxalic acid solution ,

d ilute to exactly 100 ml in volume tric f lask wi th 0 . 4% oxalic acid and
then f i l ter through No . 4 Whatman f i l ter paper . Ob tain L 1 as above .
To tube S add 1 ml fil trate + 9 ml water and adj us t the ins trument to
zero . Then to tube No . 2 add 1 ml filtrate + 9 ml dye and record L2
af ter 15 seconds . Calculate ( L 1 -L2) and ob tain the concentration from
the standard curve .

Remarks

(1) Use only d is t illed water from glass s t ill .

(2) At leas t dup licate read ings o f L 1 and triplicate read ings of L2
are required . Average of L1 and L2 are used .
(3) I n s teady-s tate procedure where small sample s ize was ob tained ,
0 . 8- 1 . 0 g sample was used and d iluted to 1 0 ml . No . 540 Whatman
fil ter paper was used ins tead of No . 4 because darker samples were
ob tained as the heat ing times used were longer than in uns teady­
s ta te procedure .

(b) Ribof lavin

Ins trument
Turner F luorome ter Model 1 1 1 .
Primary f i l ter of 1 1 0-8 1 6 ( 2A) p lus 1 1 0-8 1 3 ( 47 B) where 2A is p laced
neares t to the lamp .
Secondary f il ter of 1 1 0-8 1 8 ( 2A- 1 2 ) .
 1 78

Reagents

-1
Ribof lavin s tock solut ion ( 1 00 �g ml ) ::
Dissolve 50 mg Ribof lavin Reference S tandard , previous ly dried
and s tored in dark in dessicator , in 0 . 0 2 M ace tic acid to make 500 ml .
°
S tore under toluene at ea 1 0 C .

):
-1
Ribof lavin intermediate solution ( 1 0 �g ml
Dilute 1 0 ml s tock solut ion to 100 ml with 0 . 02 M acetic acid .
°
Store under toluene at ea 1 0 C .

)\
-1
Ribof lavin working solut ion ( 1 �g ml
Dilute 1 0 ml intermediate solut ion to 1 00 ml with d istilled
water . Prepare fresh f or each assay .

4 . 0% KMn0 solution :
4
Dissolve 4 . 0 g of KMn0 in distilled water to make l OO ml .
4
Prepare fresh weekly .

3 . 0% H o solution :
2 2
Prepare f resh at the t ime of use .

Sod ium Hydrosulfite :

High purity and s tored to avoid undue exposure to ligh t and air .

Method

Trans fer a thawed sample of approximately 4 g 1 to a 1 25 ml erlenmeyer

f lask , add about 7 5 ml 0 . 1 M HCl . Agitate vigorous ly and wash down s ides
of f lask with 0 . 1 M HCl .

°
Heat mix ture in au toclave a t 1 2 1 - 1 23 C 30 min and cool . Adj us t ,
wi th vigorous ag i ta t ion , to pH 6 . 0-6 . 5 with 1 M NaOH solution; then
immediately add 1 M HCl to pH about 4 . 5 .

D i lute mix ture to exac t ly 1 00 ml in volumetric f lask wi th d i s t i l led

water . Centrifuge and then fi lter through ash-free f i l ter paper (Wha tman
f ilter paper No . 4 1 ) .
 17� ·

2
Take 25 ml fil trate and check for dissolved protein by adding
dropwise , f irst 1 M HCl , and if no precipitation forms , then , with
vigorous agitation , 1 M NaOH to pH 6 . 8 , dilute solu t ion to exac tly
100 ml with d is tilled water in volume tric f lask . I f fur ther preci­
pitation occur , continue as in AOAC . D ilute 5 ml of this solu tion to
3
exactly 1 00 ml wi th distil led water

To each of � 4 tubes , add 10 ml sample solution . To each of

� 2 tubes add 1 ml s tandard working solu t ion and mix and to each of
� 2 remaining tubes , add 1 ml dist illed water and mix .

To each tube , add 1 ml glacial ace tic acid and mix ; add , with
solut ion . Stand f or exac tly 2 min ; then to
mixing , 0 . 5 ml 4 . 0% KMno
4
each tube add , with mixing , 0 . 5 ml 3 . 0% H o solution ; permanganate
2 2
colour mus t be des troyed within 10 s . Shake vigorously unti l excess
0 is expelled .

Measure f luorescence of sample solution containing 1 ml added

s tandard ribof lavin working solution as X and of the sample solution
containing 1 ml added water as B . Add , wi th mixing , 20 mg powder
Na s o to the s ample solut ion containing added water , measure f luore­
2 2 4
scence wi thin 5 s as C .

-1 4
Calculation of concentration (�g g )

B-C 800
X 0. 1 X
X-B w

where W is s amp le we igh t (g)

Remarks ( for ribof lavin analysis of samples from s teady-state pro cedure)

(1) us e 0 . 8 g
( 2) take 50-7 5 ml
( 3) omi t this s tep
-1 B-C 200
(4) concentrat ion (�g g ) x 0. 1 X
X-B w
 1 80

APPENDIX 3 . 3 x, y and Y of Control and Hea ted Samples

Sample X y y

Control 0 . 40 0 . 40 23 . 60
10 2 1 . 60
Heated , F =
6 . 25 0 . 43 0 . 42
121 . 1

Control 0 . 40 0 . 40 23 . 30
lO
Heated , F =
9_, 47 0 . 43 0 . 42 20 . 20
1 21 , 1

Control 0 . 40 0 . 40 22.98
10 1 9 . 50
Heated , F = 1 3 . 47 0 . 43 0 . 42
l21 . 1

Control 0 . 40 0 . 40 23 . 27

Heated , F lO = 16 . 62 0 . 43 0 . 42 1 8 . 85
121 . 1
-·

Control 0 . 40 0 . 40 24 . 50

Heated , �0 =
22 . 86 0 . 43 0 . 42 1 8 . 70
1 21 . 1
 181

APPENDIX 4 . 1 Analytical Solution Computer Program

(a) Flow Chart of the Program

Tlllt • T ll•n; .+ DT
FIX • uu··· I • T UU/Dt/OC
FOX • Dlt't' l 11 r !Ht:/DX/DI

Co\U, -

C1C • 1.0

T(J . I ) • TM!J . l l • (TC-TA)•(I-JCOOL)

 D I ME N S I O N T C S o , s o > , TH C 5 0 , 50 ) , 0 C 1 0 ) , X J I B C 1 0 ) , 8 R A C 1 0 ) ; X J OB C 1 0 ) 00000 1 00
g
100
- -2 0 0 C 0 1- H-1 0 iJ X J U ( 2 0 0 ) ' A R G ( 2 0 0 ) _ _ _ _ __ 0 000 0 200 '-'
3Uo DATA ARG/o , o , o . t , o . 2, 0 · J� 0 . 4, 0 , S, Q , 6, Q • 7' 0 ' 8' 0 • 9' 1 •0' 00000 300
400 * 1 e l 1 l e 2, 1 . 31 1 t41 1 eS, l e 6, l , ?, l .M,1 .9,2 eO, 00000400 (")
500 * 2 e l 1 2 a 21 2 e 31 2 a 41 2 a 51 2 1 61 2 e 7 1 2 a RI 2 a 9# 3 e 01 3 a l # 3 a 21 3 t 31 3 e 4 1 3 t 5' 0 0 0005 00 0
___{;) o_o -- -* J • 6 , 3 • 7 , 3 • a , 3 • 9 , 4 • o , 4 • 1 , 4 _. 2 , 4 • 3 , 4 • 4 , L s , 4 • ..6. L L .J L 4 _._fiLLL. � ..� � • o _, · -- __ _ ooooo6oo 1.§c:
700
_ __ _ _ ___ ___ _ __ _ _

* 5 a l # S a 2 ' 5 • 3 ' 5 • 4 ' 5 • 5, 5 e o, 5 . 7 , s . 6, 5 t 9; 6 , 0 , 6 . 1 , 6 • 2, 6 • 3 ; 6 , 4 , 6 a 5' 0 0 0 0 0 70 0

rt
800 * 6 a 61 6 a 7' 6 • 8' 6 • 9, 7 a 0, 7 a 1 , 7 • 2 , 7 e 3 , 7 t 4, 7 e 5, 7 e 6; 7 a 7, 7 •8, 7 e 9 , e . o, OOOOObOO ro
900 * 8 a l , B a 2 ' 8 ' 3 ' 8 • 4 ' 8 • S, e . 6, 8 , 7 , a . a , a . 9, 9 t 0, 9 a l , 9 a 21 9 a 3 , 9 , 4, 9 e51 00000900 .,
� .o - -* -9- . 6 , 9 • 7 '-9 • 8 , 9 . 9 ; l O . o , l .0 · 1 .- -1 o .- 2 .., 1 0 . 3 .- 1 0 a 4- .L .l-Q ...S. .- � .6 L1 1l ...J' � .l..O ... B l _o o o o 1 o o o ' 1-d
.,
- - -- - _ _ _ . __

1 100 * l 0 , 9; 1 1 t 0 # � 1 • 1 ' 1 1 e 21 l l e 31 l l a 41 1 1 e 51 1 1 a 6 1 1 1 t 7 1 1 1 • 8' 1 1 a 9 1 1 2 • 0 ' 0 0 0 0 1 ! 00

0
1200 * 1 2 • 1 , 1 2 t 2 1 1 2 a 3 1 1 2 e 4 1 1 2 o 5 1 1 2 • 6 1 l ?. t 7 1 1 2 e 8 1 1 2 • 9 ' 1 3 t 0 OU00 1 200 )Q
1 300 * 1 l 3 e l 1 1 3 e 21 1 3 t 31 1 3 t 41 1 3 o �1 1 3 e 61 1 3 e 71 1 3 t 81 1 3 e 91 1 4 e 01 1 4 a 1 1 1 4 e21 OOO O l JOO .,
-li W 0 * 1 4 • 3 ' 1 4 • 4 , 1 4 , 5 , 1 Ll • 6 ' 1 4 • 7 ' 1 4 • 8 ' 1 a , 9 _� _u _. iJ J. ..O.... DJ. ll...a_ 0 L() _. Jl.LQ , aI ___ _ ___ _ __ Q 1H> 0 1 4 Q u_ �
1500 DATA XJO/ l a 0 1 0 t 99 75 , 0 a 9Y00 , 0 • 9776 , 0 a 9604 , 0 e 9 385, 0 • 9 1 20, 0000 1 500
1 600 * O t 88 1 21 0 t 84 6 J , O . R07�, 0 • 7652, 0 • 7 1 96 , 0 e 67 1 1 , 0 t 6 20 1 1 0 e 5669, 0000 1 600
1 700 * O t 5 1 1 U, O e 4554, Q , 3 9dO, O o 3400 , 0 a 2 8 1 8 , 0 t 22 3 ?, Q , l 666, 0 e 1 1 0 4 ' 0000 1 700
1
-8 0 0
900
*
*
O t 0 5 5 3 -, 0 t 0 0 2 �:>� - 0 e 0 4 8 4 , .. 0 , 0 9 6 8 , • 0 e l 4 2 4 , • 0 -. -1 8-§ 0 , • 0 e 2 2 4 3 ,
-o , 260 1 , •U , 292 l , • 0 . 3202 , •u , 34 4 3 , •0 , J6 4 3 , •Q , 380 1 ,
- -
· 0000 1 800
OOOO l YOO
2000 * ·o . J9 1 8 , -u , 39Y2, · 0 . 4026, -u . 40 1 R, -o . 397 t , ·o . 3BB7, oooo2ooo

- • o -. 2 0 9 7 , -- o . 1 7- 7 6 , o . 1 4 4 3 , · v . t l- o -J � -0-7� 8 _, � H )-4- 1 -2��_,

00002 100
- O..U 0 0 2 2 0-0
2100 * • O a 3 7 6 6 , • 0 , 3 6 1 0 , • U , 3 4 2 3 , .. 0 , 3 2 0 S , - 0 . 2 9 1 6 , • 0 , 2 6 9 3 , - U , 2 4 0 4 ,
-2-2 -0 0 - -
_
--- --- - __ _. • - --

2300 * O a 0 2 7 0 1 0 t 0 5 9 9 1 0 t 0 9 1 7 1 0 o l 2 2 0 11 0 e l 5 0 6 1 0 t 1 7 7 3 1 0 1 2 0 1 7 1 0 t 2 2 3 8 # 00002300
24UO * O e 24 3 3 1 0 t 260 1 , 0 a 2 7 40, 0 • 285 1 , 0 • 293 1 ' 0 ' 29 8 1 , 0 e 300 1 , 0 • 299 1 , 00002400
2500 * 0 . 2?5 1 1 0 e 28821 0 e 2 7U61 0 • 26631 0 • 25 1 6, 0 • 2 346 1 0 • 2 1 54 1 0 1 1 944 , 00002500
--2-6-0 a -- - * - i h -1 -7 -1-7 , o • 1 4 7 5 , o . 1 2 2 2 , e . o 9 6 o , o . -{) 6 9 2 , e � 9, o .o 146, oo � -2 6 0-0 -
2 100 * - o . o t 2s , -o , o 39 2 , • o . o 6 5 J , · o . oY o J , •0 . 1 1 4 2, -o . t 3 6 7 , •o • 15 7 7 , oooo2 7oo
280o • ·o . 1 76 6 , -o . l 9 3 9 , • o . 2 090, ·o . 22 1 8 , • 0 • 2 3 2 3 , •o a 2 4 0 3 , •0 • 2 4 5 9 , oooo2aoo
290o
-a-G-o.&
3 100
*
*
· o . 2 4 9o , -o . 2 4 9 6 , · o . 24 7 7 , ·o . 2 4 J 4 , - o . 2 3 6 6 , -o , 2 2 7 6 , • o . t 6 4 ,
- th �3 2- l • () -. M tl t , _ • ..u, � ., -o. 15� R+-!"4.-1 JJo, ·o • 1121,
, •o a 067 7 , •o . o4 46 , - o . o 2 1 3, o . oo2o, o . o25 0; 0 , o 4 77, o10697,
-o g • 902
oooo2Yoo
oooo.J o o o
g o oo 3 1 00
-·

3200 * o . 09081 0 e 1 1 0 8 # 0 e l 2961 0 • 1 46 91 0 e 1 6261 0 t 1 76 61 0 • 1 6871 0 t 1 986, .0003200

3300 * O t 21 0 • 2 1 29; 0 , 2 1 67 ' 0 • 2 1 63' 0 • 2 1 77, 0 • 2 1 S0, 0 • 2 1 0 1 , 0 • 2032, 00003300
---3-4 0 0 --- * - -e-.-1 9 -4 3 , 0 • 1 -6 3 6 , 0 • -1 7 H ' o-. -1 S-7 G- 1 0-• 4- 4 1 ' "0 • 1 2 4 � 0, 1 065,0 •0 875, - --0-o il O l -4- 0-0
3soo * o . o679, o . o476, o . o 2 7 l , O • u0 6� , t . o, t . o , l . o , t . o , t . o/ oooo 3�oo
3600 DATA �/2 • 4048, 5 . 520 1 , 8 • o537, 1 1 . 79 1 51 1 4 . 930 9, 1 8 • 071 1 , o , , o . , o , / 00003�00
3700 DATA XJ I BI O e 5 1 9 1 , •o , 340 J , O t 27 1 5 , •0 , 2 325, 0 , 20 66 , •0 • 1 890 , 0 • , 0 • ' 0 • / 00003700
---:Y&0 6 -- -
-
-R E -A O ( � � I ) U C , 0 X ' 0 I f F h U HT -2 , 0 T ' S C 1 -5 )( # -l -l-, TA, TC, TIME & ,C T H1E - ---- --- - - --{) 0 0 -0 3 8 .0 0 - .
3900 WRIT E ( 6 , 30 ) 0 I F F 1 , 0 I FF2, T I , T A , TC 00003900
4000 Q
WR I TE C 6, 39 l C , 2 t O*nX, 1 1SC, 1 /SX 0 00 0 4 0 0 0
4 100
T H E f< M A L -O l f F U S I V I H '-l N � .fH3-t � -s � t4-/-s -} ::.J.t,
30 FORMA T C 1 HO , ' T H E NMAL D l fFUS I V I T Y I N HE A T I N G PHAS� ( MM / S l =" ' 0 0 0 0 4 1 00
--4-2-0 o -- -* - -F 1 2 • l 0 ' ll , " -- -- - -G- 0 0 0 4 2 0 0
I III I T I A L T U� P R A T l i R E < C > = " , F 1 2 e 2 , / /
- -- --

f.
- ___ -- - -

4300 * F 1 2 . 1 0 , // , " 00004 300

4 400 * " RETORT TEMP E R ATURE < c > = ' , f l � • 2 , // 00004400
; 450o * " COOL I NG T EMPERATURl ( C ): ", F 1 2 • 2 , // ) 00004500
.....
00
N
-4 6 0 0 - -- 39 F O-R �I A H " C A N R A [J I U S C M ) = •• , f t 2 . 5 , ./ - ------- -- - - - - - -· -- -- - - ouoo46oo
" CAN HE I GHT C � ) :", F l 2 ! 5, / 00004700
S I Z E OF O I ME h S I ONL[�S SPACE
*
00004bOO I
4700
4 80 0 * " I NCRE�ENT IN R D I RE C T I ON="'
- '-'- .S I Z [ l+f" .() I M E N S I U N L l � S SPACf
* 00004900
-S -O O o 00005000
4900 F1 2 t 51 /
.. I -N C H E M E N :r -I U- .X - O I R t C T -I O N = " 4
* 00005050
IN
F 1 2 t !H ///
5 1 00
50�0
A
* " TE�PERATURE CAN"/// ) 00005 1 00
5200 T HI E = u
D J STR I�UT ION

_o u .o o 5 J o o
00005�00
---5 .3 ..0 0 N -N �:: ( T I M £ S + .C T I M [ ) I D T
5400 DO 4 2 N= l , NN . 00005400
00005�00
00005600
550 0 T I ME = T I ME + D T
5600
_Q .(J 0 0 5 7 0 0
f" O C • O I F F 1 * T I M E I O C / D C
--5 -1 D o FOX = D i fF 1 • T I M E IO X / D X
5800 DO 58 I = l , SX+ l 000U5BOO
s- 9 o o·- --- - - - -o-r x = r L o A T ' r · t > t s x 00005900
6000 I F C F OX • l T a O e O J ) GO
TO l l u 00006000 I
6 1 00
__ 6 2 0 0 GO TO 80
5LA B ( FOX, VL , b J X )
C A LL Ou006 l OO
_ 00006200
6 300 1 10 Xl�O I X*OX ouoo6Joo
CALL L SL A B ( F QX , Y L , DX , XL )
no s� J= l , sc+ t
6400 OOOU6400
650 o so 00006500
6600
{) 1) 0 0 6 7 0 0
�J C = F L O A T ( J • l > I S C oooo6ooo
07 0 0 - - l f ( F O C a L T • 0 • 0 2 ) G (J T i.J 1 2 0
OD 49 JJ= l 1 6
- -

00006bOO

-ij
6800
6900 00006900
..C A L L C Y U J D _( F O C , Y C 1 B , B R A , X J O B , X J I 13 2
49 BRA C JJ ) :B ( J J ) • D J C
QO
uo
___ _ __ __

GO To 90 ------- �888t�88
0000 200
00 1 20 I f ( O I C • L T • O • l > GO Tu 100 7
00007JOO
380 R=DC *U I C
�
74 �l' 6 y L N 0 ( f 0 C_D c _ ! __Q c_ �_ B L
0
L
0
0000l400
01l"UUT5UU
suo
0

760 0 1 00
H YC=l • O
__

0 0 0 0 7.6 0 0
7100 90 YHE AT=Y C * Y L oooo77oo
J.aO.o _ _ J. u .i � l ) = C 1 • Y H E A T > * C T A • T 1 ) + T I - - -- - - - - -· -- - -- - --- ---- -· -- - -- - - - - - _.£l 0 0 0 7 6 0 0
7900 T F C T I �E a L E e T I ME S l G O T o 2 0 0 00007900
8000 TDEL=T I �E-T I HE S ooooaooo

--$2
8 100

83
g.o ----- -

-
--- -C-F -O- )( ::.. o I F f 2 * T rH
CFOC =u i F F 2•TDEL/OC /uC
.. LID XIUX
00008 1 00

00008 JOO
!) {) .0 .0 8 2 0 0 I

8400
0 C I X= O I X
I F C C FO X e L T e 0 . 0 3 ) G O T O 1 4 5 00008400
8500 0 0 0 0 8 ::> 0 0
'

-8..6.0 0 -- - - G Cl -1' 0 -1 5 5
CALL SLAB C CFOX , C Y L , C I X )
-- ...0 0 0 0 8 6 0 0
I

8700 00008700
--

0 0 0 0 8 tl O O
1 45 C X L =C I X * O X
8800 CALL LSL A � C CfUX , C YL , DX , � X L )
8900
-l -F�C C.. F .u .C _. L T .. 0 • .0 2 > G 0 ! ..!l ...J. .6 5
C I C =O I C 00008900
9 0 0 0--
1 55
-
0 .0 0 0 9 0 0 0 �
(X)
w
 9 100 D O 55 JJ= 1 , 6 U U O O 'J l O O
9200 55 B R A C J J ) = tl ( J J ) * C I C 00009200
9300 C A L L C Y l t·J 0 C C f u C , C Y C , B , !:J f< A , X J 0 8 , X J I 8 ) 00009300
- 9400 GO TO 1 7 5 00009400
9500 1 65 l f ( C I C • L T e O e l l Gn TO l U� 00009500 !
9600 CR=DC*C I C 00009600
9700 C ALL LC YLNO ( CF Oc , c yc , uc , C H ) 00009700
-9� 0 o �n r o 1 7 5 -0 0 0 0 9 ti O 0
1 85
--
9900 C YC• 1 . 0 00009900
1 0000 1 75 Y C OOL=C Y C * � Y L 0 0 0 1 00 00
10100 T C J , I > =T H C J , I ) + ( T C -T A > • < l - Y C O O L l 0 0 0 1 0 1 00
��200 GO T O S6 0001 0200
1 0300 200 T C J, I > =TH C J, I ) 0 0 0 1 0 3 0 ()
SA
1

1 0400 C O N T I NUE 000 1 0400

1 0500 11 R I T E C o , 5 9 > T I M f
T I "1 E C S ) = " , F 1 2 • 2 , I I 8
000 1 0500
_ l .O 6 0 0 59 f. U n 1>1 A T C / I " 000 1 600
X O I R E C T ! Il N A C R U S S , .!i O I R E C T I U N ,. D O ri N " / / )
__ _ _ . _ ____ __ . ___ _ ··- _ _

1 0 70 0 * " 000 1 700

1 0800 DO 60 Jc 1 , SC + 1 0 0 0 1 0 ti O O
1 0900 60 �n i TE C �, 79 l C T C J, J > , J = l , �X + 1 ) 000 1 0900
.1 1 000 79 fORMATC 1 2F 1 0 e 2 ) 000 1 1 000
1 1 1 00 42 C O N T I N�E 000 1 1 1 00
1 1 20o S T 11 P 000 1 1 200 I
1 1 300 £NO OU0 1 1 JOO
_1 1 4 0 0 _ _ .S U B R O U T I N E C Y L IJ O C F u , y c , H , B H A , X J 013 , X J I 8 ) _ _ _ _ 000 1 1 400 I
1 1 50 o O I M E N S I O II: t H 1 0 l , X J I B C 1 0 ) , 8 ,� A C 1 0 ) , X J 0 8 ( 1 0 ) 000 1 1500
1 1 600 C O M M O N X J 0 ( ? 0 0 l , A R G. C 2 0 0 ) 000 1 1 600
1 1700 DO 1 I = ' 6 l . . D..O .Q J J 8J) () '
0001 1 700
lt B Oo .......I F.: C BtiU b .b. T ..e Uu l H l.G lJ T li 3
�2 190 0 -- QUO1 1 .iOJL
1 2000
, 2100 2
0 - 2 . -J.a..1 L1 5 2 --- -- ---
l f C BR A C I ) •A R G C J ) ) 5 , 4 1 2
C O N T I NUE
0 0 0 1 20 0 0
0 00 1 2 1 00
l 2200
- ---
X J OB C I ) • X JO ( J ) 00012200
G O - --1' 0 - -t
4
�*O ·- - - - --0�-0 -1 2 3 0 0
1 2400 5 I r c J . GT a l >J=J· l 000 1 2400
1 2500 XJOB C i l = X JO ( J ) + ( XJO C J+ l > -XJO ( J ) ) / C ARG C J+ l ) •ARG ( J ) ) * 000 1 2500
* 000 1 2600
-- ---
1 2600 C UR A ( I l•ARG C J ) )
.1 .2 1 0 0 ...1.1 0 lO .l 0 0 0 1 2 7 0 .0 ..
3
- ---- -- --- -----· - - - - · - - · - -

, 1 2800 XJOB C I > = < 0 • 7 9 7Y/HR A C 1 ) ) * *0 • 5* ( CO S C URA ( l ) •0 • 7854 ) + 0 • 1 25/ 0001 2d00
1 2900 * BR A C I ) • S I N ( H R A C I ) • O e 7 8 5 4 ) l 000 1 29 00
1 3000 1 CONT I NUE 000 1 3000
-1 � 1 0 0 ¥ C -= O _Q .Q.O l 3 1 0 0
uo 6 1 = 1 , 6
- - ---- ---- ----- ·-

1 3200 000 1 3200

1 3 300 6 Y C=YC+2 e O*XJOB C I ) /H C l ) /XJI 8 C I )*EXP C •B C 1 ) **2*F O ) 0001 3300
1 3400 RETURN 0 0 0 1 3400
� �500 �NO .. 0 o.o 1 3 5 0 .0
.....
00
.p.
 1 3600 SUBROUT INE SLAR < ro, yL, D J OOO l Jb OO
1 3700 YL= 1 • 2 7 32 395* C C OS C 1 e 57 1 4J*U > *E XP C •F0*2 • 46740 1 ) + 0001 3700
c · t > I J . �•cos c 3 . o • 1 . 57 1 4 3•u > •E X P < · Y . O•Fo•r . 46740 1 > + ooo 1 3aoo
1 ) / 5 • u * C 0 S C 5 • u • 1 • 5 7 1 4 3 * 0 h E X P < • 2 5 • 0 * F 0 • 2 • 4 6 7 4 0 U + --- 0 00 1 3900
1 3aoo •
-l-3-9 0 0 * C+ - - - -·
- -- - - -

1 4ooo * c · t > l t . o•cos c 7 . o • t • 5 7 1 4 3*U > •E X P < ·4 9 • 0•Fo•2 • 4674 0 l > + ooo 1 4ooo
1 41 00 * ( + 1 ) /9 , 0* C OS ( 9 , 0* 1 e 5 7 1 43 *D ) * [ X P C • 8 1 • 0*F0•2 • 4674 0 1 ) + 000 1 4 1 00
1 4200 * C • t ) / l l . O*CUS ( 1 1 •0* 1 • 5 7 1 4 3*D > •EXP < • 1 2 1 • 0•FD*2 • 46740 1 ) ) 000 1 4200
-4-4 � 0 - -R£ T U R-N - -- - - - - - -- --- -O Q 0 1 4 l �
1 4400 000 1 4400
--- - ---

END
1 4500 S U B R O U T I N E L C Y L N O C F O� Y C , U C , R > 000 1 4500
1 4600 X= C D C •R ) I 2 • 0 / C F O* D C * *2 • 0 > * * 0 e 5 000 1 4000
-l-4 7 0 0 A -= E R F N < X > - - -- ---·---- - - -- - -- -- - -·.0 -0 0 1 4 7 0-0
-- -

E l =O , S6428958 *EXP C •X • X > • X *A 000 1 4800

000 1 4YOO I
1 4800
1 4900 X 2 = X -+ x
ooo 5ooo l j
- - ----- - 0 0 0 5 .1 .0 0 -- l
E 2 = 0 · 2 � * < A � x 2 • t.: q . ....
-¥ C = 1 • ( ( D C l k ) * * 0 • 5 ·* A + ( D C �� h F G -a O C * -* h -0 ) -*-*- �-§+..4 /.
1 5ooo
-t-5 1 0 0 -- -
OCIR** l e 5*E 1 + ( 9*DC**2 • 0•7 , 0*R * *2 t 0•2 • 0 �UC*R ) / 000 1 5200 1
( ----- - -

1 5200
-

*
1 5300 * C 32 e 0 * D C * * 1 • 5* R * * 2 • 5 > • F D *U C * * 2 • 0 • E 2 ) 000 1 5300
R E T U FHJ
·
1 5400 000 1 5400 '
-t 5 5 0 0 EN0 000 1 5500
S U O R O LJ T I N E
-- - - - ·- -

1 5600 LSLAA C F o, yL, UX, XL ) 000 15600

1 5700 YL= l ; O 000 1 5700
ooo l SbOO '
a o -1 o 2 + = 1 , 3
1 580o xro= C ru•ox• •2 • o > ••o . 5
-1- 5 9 0 o - -- - -- -- - - -- -- --- - !l � o J 5 9 � o
N= I • 1
--- - - - -- - - --

, 1 6000 000 16000

O Y t a ( ( 2*N+ 1 ) *DX•XL ) /2 • 0/XFO 000 1 6 1 00

Ulli 0
. 1 6400
-0 --
Y2= C C 2*N+ 1 ) *0X+XL ) /2t OIXFU
- - +0- 2 --¥-t..a .Y i::J"' (-(.-'!!.l -} -* � < E-R F N .( ¥-1---) + E R FN ( ¥ 2 > ++-
R E T U R iJ
000 1 6200
000-1 ..6-.l-().Q
000 1 6400
1 6500 END
FUNC T I ON
·

ERFN C X )
.
000 1 6500
000 16600
ooo 1 6 1..0..0
6600
- ---()...A T -A --fl-1 -A-1 � -A -2 -* -A J , A-4 #-A �-'4 ..3.4 7 -5 -9- 14-+-0- · 254a295g, •o.2&449674 •
\
, 1670
1 6800
1 6900
* 1 . 42 1 4 1 374 , • 1 . 45 3 1 5203, 1 • 06 1 40543/
I F C X . GT e O e O ) GO T O 1 3
000 1 6800
000 1 6900

1
11 0 0 0
1 1 -0 0 -
1 200
- -- -- - 1 -3
X= C • l ) * X
----l -t -= 1 -. G / { -1 -+ P -* .X .} - - - - - -- - --
---
000 1 7000
-0-Q Q 1 7 1 0 0
000 1 7200
1 lOO
T2=T 1 •T 1
--

T 3cT2•T 1 000 1 7 3 00
1 7400 T4=T 3•T 1 000 1 7400
ii�0g 8 -- ---- - - i�r�-� � � �-( · x • £ )-• C A i ; T-t+ A 2 * T 2 + A J i r3 + A 4- * T 4 + A 5 * T 5 > -

- - -- �81� t�88
1 77 0 RETURW 000 7700
1 7800 END 000 1 7 8 00 I

·------·--- j
--- --- - -· -

.
·- ---

......
00
V1
 T C 50, 50 > , T I C 50, 50 ) 0 0 0 00 2 0 0
200
30 0 REAL K
D I ME NS I UN
00000300 �
"d
4oo � � , 1-> o R ' o x , w .r r -1 , o l -f r -2 , o r � r A .# -N N -#. M� r -1-N , l A H � r A c , l -l � E H . o ..o .o o o 4 o o
�
. _ __ . _ . _ _ _

00000 �00
.

500 * I T l �[C , f R[Q

600 WR I TE t 6, 1 l O i rF 1 , 0 1 Ff2, T I N, y AH, TAC O O O O Ci b O O
::<
H

700 1 FORMA T C 1 Hu , h T H E R M A L D I F F lt S I V I T Y I N H E A T I N G P H A S E C M M / S ) = " ' 00000700

--.8.0.0 * E 1 2 ...._ 1 _u .l._l/ _____
O.O O O O d O O �
f. N
__ _ . _ ___ __ _ __ _ . ____ _____ _ ____ __ . ____ ____ _ . _ __ _

900 * " THERMAL D i fFUS I V I TY I N OOL I N G PHA S E < M M IS > = " , f 1 2 t 1 0 , // 00000900
I N I T I AL TEMPERATURE C C ) z •, f 1 2 • 2, //
1 8
0 0
1 0
* "
" RETORT TEMPERAT�RE C c > :", f 1 2 • 2, //
0000 1 000
0000 1 1 00 z
12 00
*
--*- " COul i N G T £ t4 P £.R-A T U R E ! C ) = " , E 1 2 • 2 .# / / ) - .0 0 0 0 1 � 0 0
D E L X = u X I F L 0 A T 14 M . 1 ) 0000 1 300 �
-- --· -- - __ __ ____ _ --· -- ·

1 300
t1
( I

OELR=oR/FLOAT t NN• l ) O U 00 1 400

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 189

APPENDIX 4 . 3 Thermal Diffus ivi ty Determina tion Results

Thermal Mean Thermal

o S tandard
Re tort ( C) D i f f us ivity Diffus ivity 7
Run No . Deviation x 10
X 10
Temperature 7 x 1Q 7
? -1 2 1 m2 s - 1
m-s m s

7 1 20 . 2 1 . 549 1
3 1 19 . 5 1 . 55 1 1
4 1 19 . 6 1 . 5090 1 . 5429 0 . 0 1 96
9 1 20 . 0 1 . 5459
2 1 19 . 8 1 . 5593

6 1 29 . 1 1 . 5305
1 1 28 . 7 1 . 49 1 6
8 1 28 . 6 1 . 5694 1 . 5277 0 . 0318
5 1 29 . 2 1 . 5452
10 1 29 . 1 1 . 50 1 6

TOTAL MEAN -7
1 . 5353 X 10
.m 2 s - 1

STANDARD
DEVIATI �N
-7
0 . 0 26 1 X 10
m2s -

Tes t of Signi f icant Difference Between Means

x 1 . 5429 s 0 . 0 1 96 n 5
1 1 1
5
.

x =
1 . 5277 s 0 . 0318 n
z 2 2

s
�4 (0 . 0 19 6 ) 2 8 4 ( 0 . 0 3 1 8) 2
+

=
0 . 026 39 3 1 7
S.E 0 . 0 263 9 3 1 7 ;fl5 + l
5
0 . 0 1 1 69
1 . 5429 - 1 . 5 2 7 7
t
0 . 0 1 169
0. 9 102

Therefore , there is no s igni f icant difference betweeen these two

means .
 1 90
APPENDIX 4 . 4 Dis tribution of Res iduals for Determining Ac curacy o f the
Analytical Solut ion for Calculat ing Temperatures

(a) In the Hea ting Phase

Run no . 6 Run no . 8
° °
median -0 . 5 0 C median 0.61 C
° o ·
mean -0 . 45 C 30 .... mean =
0 . 42 c
30 ,__
° o
s tandard deviation =
0 . 80 C standard deviat ion =
0 . 50 c

� 20 1-
,......
1-
:>.
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s::
(.)
f--
Q)
;::1
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10

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1--- 1--
1--
0 I 0 h
-0 . 7 -0 . 3 0. 1 0.5 0.9 1.5
-2 -1 0 1 2

Run no . 7 Run no . 9
o
median median =
0 . 85 c
o
30 mean 60 mean 0 . 90 c
r-
° o
s tandard deviation =
0 . 46 C standard deviation 0 . 46 c

.---- ,......
�
,......
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0 15
. 0 . 75 1 . 35 1 . 95 2 . 55
0
Residual ( C )
 1 91
(b) In the Cooling Phase

Run no . 6 Run no . 8
median o o
-0 . 5 7 c med ian -0 . 94 c
mean o o
- 3 . 00 c mean -3. 27 c
standard deviation o 60 o
60 ' 4 . 38 c standard deviation =
4 . 47 c

,....,
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:>.. 40
:>.. 40 (.)
(.) �
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R e s i d u a L (° C )

Run no . 7 Run no . 9
° °
median -0 . 82 C median -2 . 64 C
° °
mean -2 . 68 C mean - 3 . 30 C
°
r-
° 30 2 . 22 C
r-
30 s tandard deviation - 3 . 8 7 C standard deviation =

r-
,....,
�
•

-
:>.. - 20 r-
20 r-
(.)
�
Q) 1-
::l
0"
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�
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-
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1
0
-5 -1
- 13 -9 -5 -1 0 1 3 - 13 -9

Re s i d u a 1 ( C )
O
 1 92
(c) I n the Overall Process

Run no . 6 Run no . 8
-0 . 14 c -
o °
median =
median -0 . 33 C
o o
mean -0 . 59 C mean = - 1 . 22 c
o oc
c
80
standard devia tion 3 . 35 standard deviation 3 . 15
80

60
60 -
-
-
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o o
Re s i d u a l ( C ) Res i d u a l ( C )

Run no . 7 Run no . 9
o o
median 1 . 26 C median .. -0 . 1 1 C
o o
mean -0 . 3 7 c mean = -0 . 49 C
60 standard devia tion 3 . 02
o
c 60 standard deviat ion = 2 . 54
o
C

-
-
iN!
iN! -
-
40 ?-.
40
?-. ()
()
s::
c:: <li
<li
;:)
;:)
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r::r
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20
<li
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-11 -7 -3 1 5 - 11 -7 -3 3

R e s i d u a l ( °C )
APPENDIX 4 . 5 Modified Analytical So lution Program 1 93

(a) Flow Chart

A • •. L,IA1( 1 - I ) •DC/SC
ALUUT • OC/ At:.
I • FUM.T(J- I ) •DX/SX
XLlliiT • DX/AX
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C A N R A o r u s c M > = '' , F 1 2 . 5 , 1 ooooO J35
"
FoRMAT < ·
J40 HE 1 GH T C M > =" , f 1 2 • 5 , 1 00000 340
SI ZE QE aI MEN S I0NL E.SS SPACE INCR£MEN T I N R D 1 RfC I I 0N = " ' - 8 1.1 0 0 0 _ 3 4 �
* CAN
��S
�0 0000350
* " . _ _

F 12 . � ' '
D l M E N � I U N L t. S S S P A C E I N C R E M E N T I N X
*
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*
''
300
T E 1'1 P t. R A T U R t: u 1 5 T H I iJ U T l 0 N HI 1\ C A �� '' I I I > 00000 365
F12 . ), /l/ 0 0 0 0 0 .3 6 0
J� 5 *
--· -- - - ---· -uu o u tn u -
]r 0 TIME=O 7
375 00000 375
l ij O DO 42 N� l , NN
NN = C T l ME S + C T I ME > I U T
)b5
00000380
T I M E �T I �E + O T 00000 38�
3 � () F o C = D ! F i l * T H1 E / lJ C / D C Ou000 39U
375 F OX=uiF F l *I 1 ME IOXiiJX .. - -. -- - -
0UU00 j9�
BoI X s• Fs L Or A= lT ,( sI •X +t )l / S X
--·-

4U�
4uo guooo4ou
0000405
41o I F C F OX • L T • O • O J ) GO T O 1 1 0
4t5 CA�L �Lfi8CF 0 X , YL D I X ) 000 G0 4 1 �
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GO J ua
·--
'
4'0 oouo0420
XL=O I X • DX
C A L L.. L S L A B. C F O X , Y L , D X , X L )
4�� 110 00000425
4�0 00000430 1
. 3 s-- .
o =- F L O � r J • t > s e
•

4 !4 o oooo044o
f OC • L T • 0 • 0 2 > G O T U
·-

�
�-.
·

f4 5 1 20 0 0 0 00 4 4 5
D O 4 9 J;= 1 , 6
IF
r4 � c . 0000045o
455 4" BAA(JJ - B C JJ >,.01 C � it e 0 0 4 55
·

00000460
465 TO 90
C Y L Nu C F O c , y c , a , �R A , XJUB , X J I B >
GO
400 C ALL

4 0 � If(OI � · L l . O . l ) GO TU
0000046�
00000470
r� 5 R•DCAu C
1 20 1 00
��4 7 �
i 4 ij 0 00000460
GO
C ALL L C Y L NO < Fu c , y c , o c , R >
To
4
4°9�5
90 00000485
411 5
�go t
vHt 1\ = y c w v c
YC• •L 00000490
-- -{) o 1} e e 4 9 5
5VQ 00000�00 1
··
T H C J , � > = C l • Y H�A T > • < T A"T l > + l i
IF C T I H E • L l e T I M ES > GO T O 2 00 00000�05 :
� 0
su
1· s
T O E L = T i t-� E · T i t� t: ::i 00000 � 1 0 I
i5�5 A*F'LUATl i •U*1J X /- 11\lO O !J l !;)

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.
g
oo oo520
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00 00525
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0000054�
CFUC=O l f f 2*TUCLIDCIOC 00000�50

S�a 8b0F fU �C Dlf>t2* f DEL7DX7DX ,8385�8

5�5 800 � =D J F F 3 * f DEL / D C IOC
FOX=U F F 3 • 1 DEL/OXIDX -
- -- ---- - -

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-

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- -- -
-----
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-

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5 �0
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5�5 CFOX==u iFF 1*TDEL/ OX 71JX - --- - - ·· ----- - - -

300 CFOC=J l f f l • fD[L / D C /uC 0 0 0 0 0 !) 9 0
\ tot> 0 0 !> 9 5
6uo 40o c r x= o r x
I t C CfuX . LT • 0 · 03 ) GU TO 14� 00000605
. ooooo6oo
6U5
610 r_;o
C A L L U S 1"
L �A 5B ( -·
C f O- --
T · - -- ----- -- -
X , C Y---- l X -> -
L , C --
00000 6 1 5
000006 1 0
-- -------- ---- -- -- ··- -- -
,

6�0 1 q5 CXL=c i X*uX 00000620

615 -

��� C ALL LSLA� C C�uX , C Y L , U�, CXL ) Ou00062�

6 JO 15� c r c =u t c
6J5 -- ----- - - - -- ··· -- --- - - -
bF
oooooo3o
(��QC • LT • 0 • 02) GIT 4'-tr t -� - -
0 �� JJ= l , b
o-o 0 0 0 6 3 !)
-- · · -

640 00000640
64� 55 B R A ( JJ>=B C J J ) * C I C 0 0 0 00 6 4 5
6�0 CALL CV W U ( CFUC , C Y C , B, BRA, X JOB , X J l B > 00000650
J
I F C l C • Ll • U • 1 ) �0 TL 1 b �
l 6 0- 6· 5 5
660 1 65 00000660
6�� C R=DC * C I C 00000665
w�•r
6(0
• 0
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e�>y
CALL LCYLNO < CFOC, CYC, UC, CR )
-GO· f,6 .t7.S
1 8 5 i ·C '( C D l • !
I . . ' ..,.. . .. . . >
00000670
00006 0 7!)
00 00 0 680
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•

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.
. ' • � I

- __,. _ ( J , I ) 11: Tti< J , I ) + ( T c - T A ) * ( 1 . y c o o L )

00000685
00 0 00 69 0
·

t6 �.9
6"' 5 c.a rn 58
I

'
rroo 500 C I X t: O I X
o uo 0 0 6 9 �
0 0 0 007 o o
. 705 I F C CFOX • LT t 0 • 0 3 ) Gu 1 U 2 45
' 7�0
00000705
C ALL SLAB < C� O X , C Y L , ClXl 00000 7 1 0
�1s
£o 245
eo ro y53 __o o o o 0 7 1 5

i �I
_ _ _ _

C X L =C X *u X 000 0 0 7 20
7�� 00000725

Ofo f �gC J = 1 o, 6_. _a_ 2 ) G(. l D 2Q.L

C ALL L S L Ab C L F UX , C ) L , DX, C XL )
7 Jv 255 00000 7 30
J5 00000 7 35
C •O I C
• •
. 4o
745 B A < J� =a < JJ ) *C I C
---- - w lJlJ07 lfO ..
355 0 0000 7 4 5
C A l� C Y L N D C C F O C , C Y C , B , B R A , X J O B ; X J I B ) 00000750
7��
7�0
GO 0 2� . 00000 7 5 5
·

......
1.0
(j\
 7�0 265 I f l C l C • LT . O . l )GO TL 2B� OUU0U f60
lb5 CR=D�*C I� 0UOJ0 765
C A L L L C Y L N O ( C f O C , <. Y C ,o Q C. ,o C t. U 00000 7 7 0
-W-.
7 (;
7 ti � �85
2 5 YC
G(I l 0 2 7 5
c y c = 1 • ()
l• �� C •• Yl �J
-

- · --- ---
0 0 0 0 0 7 7 !:>
--- ---- --- -o 0 "() 0 0 7 8 0
00000 76�
'( c 0 0 L * ( 'T � 1 M
·

G 5 Yo � I T --�� )-� �
c
- - ]o u8 o8 o8 o8 ts� o� go
_m
l
6 ·o �

6 CJ 5
200
5�
T C J, I >=Th C J, I >
C ONT l NUE .
__ __ - --- - -- - -· ---- --
- -- - - --- - -- - - · - -

0 0 0 0 0 d O !:>
g1 � S']
� �
R I T C , 5 9 l T l ME
OnM I� 11 " _ �i£..(. .!) ) ��£ 1 2 _. _2 2 _/ /
000008 1 0
Q Q O O O ts l �
6� 0 * X D I R EC T I O N A C R O S S , R D I REC T I O N DOWN"// ) 00000820
______ - - - - - - -· _ __

DO 60 J�l , S C + l
"

00000825
·

625
e
�g _jj__ � � � ! � lli 1lia!�� , I >, �-�2_'_
sx+ 1 >
---- --- - - J&8
o o ts
lg I
6� o
e
8��
_ __

42 �NUE
�TOP
. �
o_ o a
0 0 0 oo s 4 0
00000�4�
8�0 UJ o 0 0 0 0 0 tj 5 CJ
e� r::. ���sRu t• I It-1E c Y I tw < r .L , j .C _, .f. , B k J .. .x .J..D. B.L x.J .l fil_ o o o o o () s �
8�0 u Ht E N S I O t-. IH 1 0 l , X J 1 8 { 1 0 1 , 1l R i� C l O-) , X J O B C 1 0 } - - -- - -- - -- - --- - - -- - -- - 00000860
6t 5 C OMMON XJO C 20Q ) , ARb ( 200 ) 00000d65
at o uo 1 I = 1 , 6 oooooa7o
--8.1.' � 1£ CBRACl l..a.!. La..1 L.89 l G(l J f: _J __ _D .O O Q 0 8 7 5 1
aLu o o 2 J = t .. t � 2
_ · ---·

ooooobeo
aus l t C B R A l i ) • A R � ( J ) ) 5 , 4 ,o 2 O u 0 0 0 ti 6 !:>
8 '� 0 2
4
C 0 �J T N E f �
):Joa 1 =x Juc J> . 0 0000b9 0 ,
a9�f.0 Q 0 T CJ 1
ooo o o 11.2. 5.. _ 1
0 o 0 0{) 90 o !
905
• 910
s I r e , T a t > J� J · t
X 0 l )a J C
� -
+ C X J Ci C J + l ) • X J O C J ) ) / C A R G C J + 1 > • A R G C J ) ) *
-- g
oo oo9o5
00 009 1 0
.0..0...2 1.5 '
�0 TO 1
•

9iO 00000�20
•

9�5 3 XJOB < l > = < 0 • 79 7 � /BRA C I ) ) • *0 • 5 • C C �S C BRA ( l )•O e 7654 )+0 • 1 25/ OU000Y25
* f f
9�0
9j5
94 0
1,
BH A C > * � N < �R A C l ) • O t 7 654 ) )
LON I Nli
YCcO
OOOOOY30
�
OO .Q O 't.35
000 0 940
9�5 00 6 1 = 1 1 6 000 0945

g;g
' '
6 p
v • v c +2 • 0 * X JO B < I > I B < l > I X J I B < l > • E x P < · B < l ) * * 2 * F O >
R TURN
ooooo9so 1
OO Q0..0_9.5 5_ I
9oo lNO 00000960
9�5 SUBROUl i NE SLAB C FQ, yL, D > 00000965
9f O YLc1 • 27 323YS* C COSC l e 57 1 � 3*U > •EXP C •F0*2 • 4 6740 1 ) + 00000Y 7 0
9(� � �
- t ) J , O * LU�C 3 ,u • 1 , 571 � 3*U > •EX �� �
· 9aO* f * 2 a 467401 L i O U 0 0 0 Y 7 !:>
'9e
9�5
o·
*
* + 1 ) � . o • C O S C 5 • 0 * 1 • � 7 1 4 3 • D > • E. X � - 2 5 • 0 * 0 * 2 • 4 6 7 4 0 1 ) +
8 � - -· o o O O ll V 8 b
8
*
� i�
( • 1 ) / 7 • 0* C OS C 7 e 0 * 1 • 5 7 1 4 3 * 0 > • X P C •4 9 • *f0•2 • 4 6 7 4 0 ) � 0 000985
·

:�g : !
' 9 • o • o� c 9 . o • t : � 7 4 3 * 0
� �
� � P < -8! • •ro :2 • ! g ! :2 l�
z t >> 8a88��g ......
1.0
. ......
 1 0�0 RETURN ooo o 1 ooo
1005 ENo o --cr o -o 1 --o o s
SUBROUT I NE lC YLND ( f Q, Yt, OC, � )
- - - - -- - -

101 0 0000 1 0 1 0
X • C DC •R ) I 2 . o / C f O * O L * * 2 • 0) * *t e 5

-tm A =ER f N ( X )
0000 1 0 1 5
4� 89 5 b *£Xp C .. X * X T-x * A ----- - -- - --- --- - - - -- -u -o 0 0 t 0 2 5
0000 1020
--------E
"'--; -,1
,-=
--;
-' o
.r.-;.
5-=--;u'---"'
10JO X2=X+X Ou0 0 1 U 30
1 0�� l2�0 · 2�* l A-X2•l 1 ) Ou00 1 0 3�
1 040 Y C = l • ( ( OL /h ) * * O e 5* A + < DL •R ) * ( F0*DC ** 3 • 0 J • •0 . 5/4 / Ou00 1 04 u
10�5 * OCIR**1 e 5*[1+('J*DC**2 • 6•7 , 0•t'. **2a0•2 •0*uC •R> I � uO-G -1 0 4 !>
l o �o
---- - -- - - - --- -

* C J2 , 0*DC* • 1 . 5*R* *2 • 5 > • r o•oc•• 2 · 0•E2 >

RETURN
oooo t o 5o
0 !) 5 0 0 0 0 1 0 5 !)
1 0�0 - ------- - - --- -- - -- - - -
1 -o-t S - SOB R 1JtJ T1n --r- S t:ltff( ru--,-- " t. "� Ll X -, xt: 1 ----- ----- --
END - ·
0000 1 0 60
-D U 0 0 1 0 6 �
10'u YL= 1 e 0
1075
0000 107U
�fO= < Fu*UX•• 2 · G l * * O • �
DO 1 02 1 = 1 , 3
!
0000 1075
10bo
toos
Ou00 1 U8U
��·1·1 -- - -------- - -- -
---- o o o{) 1 v 8 5
0
1 �0 *
Y t = C < � N+ l ) *OX•XL )/� 0 • / X F O 0000 1090
0�5 Y2= C < z• N + l ) * DX+XL ) / 2 • U I �F � 0000 1095

1
YL• Y L• ( ( • l ) * * h * < E H f N ( Y l ) + l k F N < Y 2 ) ) )
RET uRt� ----
1 VQ 102 0000 1 1 00
1us
· · -· -

-o o o o t 1 o 5
END
-

1 10 0000 1 1 1U
1 P5 t U N C T l 0 I,, l R r N ( X ) 0000 1 1 1 �
1 £0

i?5
Jo
*
DATA
1· 4fl413P le 1 , A 2 , A 3 , A 4 , A 5/U • 3 2 759 1 1 , 0 • 2 5 4 d 2 95 9 , •0 • 2 8 4 4 9 6 7 4 ,
7 4' ·t �T 5 70 TIT • Oo 14 05 4
l f X • G T e O e O l GO TO 1 3
o u -o-o--t t 2 5
--- ---
0000 1 1 20

�= Ml > *X
·
0000 1 1 30
l l �s
�

o o o o 1 1 3 !)

f1:�
1 1�0
13 t�:tt2�� 1 +P * X )
T 3�T2*T 1
g��� :�
0000 1 1 50

1 11 �� 05
0000 1 1 55

�
T4=T 3•T l

lt65
TS=T4•T 1 Ou00 1 1 60
R[N=£XP C •x*Xl*C A1* 1 1+A2*1 2+ A3*T3+A4* 1 4+A5*15) �� 0 1 1 6�
0 ETURN
1 7' 5
0000 1 1 70
NO
I
000 0 1 1 75

......
\,()
00
 199

APPENDIX 4 . 6 Comparison of Experimen tal Tempera tures and Pred i c ted Temperatures
from the Mod if ied Analytical Solution Program
( ) exper imental temperatures
(--- --- ) predic ted temperatures

°
(a) Run no . 8 (retort temperature was 1 29 C)

125
12S .......

0
....... u
0
u 120 120
......
......
1 10 1 10
QJ
QJ
;::l
....
H 100
;::l lOO 4-.1
4-.1 Cll
....
Ill .... 90
10 QJ
QJ p.,
p.,
Q)
s 80
s
E-<
10
QJ
E-<
70

r.o 60

so 50

r.o 40

JO lO
1 10 0 10 20 40 60 70 80 90 100 1 10
0 10 20 lO 40 so 60 70 80 90 lOO lO so

Time (mi_n) Time (min)

(a) at r/a =
0.0 , x/h =
0.0 (b) at r/a 0.0 x/h = 1/3

12S

�
....... 12S .......

0
u 120
120
......
'\ ......

Q)
1 10 \ 1 10
QJ
H H
;::l
\
4-.1
;::l
4-.1
lOO 100

\
\
Cll Cll
.... .... 90
QJ 90 QJ
\
p., p.,
s \ s 80
10
QJ \ Q)
E-< E-<
\
\ 10
70

\
\
60
r.o
\
so
so

40
40

lO 30
0 10 20 lO 40 so 60 70 80 90 lOO 110
0 10 20 lO 40 so 60 70 80 90 lOO 1 10

Time (min) Time (min)

(c) at r/a =
1 / 3 , x/h =
1/3 (d) at r/a 0.0 , x/h =
2/3
 2 00

0
(b) Run no . 9 ( re tort temperature was 1 20 C)

,..... ,..... -�--�-

1:0 120

u u
«..... ./"-
�
1 10 1 10

QJ lOO QJ lOO
1-< 1-<
;:J ;:J
cu cu
1-< 1-<
+J 90 +J 90

QJ .iO � QJ 80
0. �
t::;
' � �
� Cl)
E-< '/ E-<
Cl) ]0 ]0

-'/
60 60

50 so

40 40

30 �----l 30

0 10 20 30 40 so 60 70 1:0 90 100 1 10 120 0 10 20 30 40 �0 60 ]0 �il ?0 100 1 10 120

Time (min) Time ( min)

( a) at r/a =
0.0 x/h =
0.0 (b) at r/a =
0 . 0 , x/h = 1/3

,..... - ,.....
120 120

u
\ u
'-"
0 0
'-"
110 1 10

�
\

\
\
A
;:J
QJ 100 100

A
� Cl)

;:J h \
1-< 1-<

cu /, \ cu ;,
A
90

/,
.,.J +J 90

I.
\
A
\
1-< 1-<

0.
I 0. /,
Cl) 80

s s
� 80

\ /,
/,
E-< I. \ E-< I.
Cl) 10 QJ 70

\
60
\ 60

so so

40 40

30 .....___, 30
0 10 20 JO 40 so 60 70 80 90 lOO 1 10 120 0 10 20 JO 40 �0 6� 70 80 IIlO 1 10
?0 120

Time (min) Time (min)

(c) at r/a = 1 / 3 , x/h =

1/3 (d) at r/a = 0.0 x/h = 2/3
 20 1

APPENDIX 4 . 7 Me thod o f Qual i ty Re tent ion Calculat ion for Micro­

Organisms and Ascorbic Acid

For Micro-Organisms

0
For generally basis , z = 10 C ,
. ° °
assum1ng . d was 50 C - 1 30 C .·
tempera ture range s tu d 1e

Ea

2 . 303 X 0 . 0083 X ( 50+2 7 3 ) X ( 1 30+2 7 3)

10

-1
250 kJ mole

From Lund ( 1 9 7 7 ) ; o 2 o was found in the range o f 0 . 48- 1 . 40 min ,

1 1.1 C
and 0 . 1 5 min

o 1 2 1 . 1 o C ave r age = 0 . 6 8 min

-2 . 303
from k
D
2 . 303
0 . 68
. -1
3 . 3868 m1n

lnS lnk + Ea / RT
1 1

lnS ln 3 . 3868 + 250/ (0 . 0083 x ( 1 2 1 . 1 + 2 7 3) )

7 7 . 8L� 0 7
33 -1
s 6 . 3943 x 10 min

From

t -Ea / RT
ln No / N = s f e dt
0

for the time in terval � t ;

-Ea / RT
ln No / N S e �t

where T was the average temperature over t , � t .

 202

So No / N could be calculated from the temperature data , N calculated

at the end o f � t became No for the next � t . The calcula tion was
repeated to ob tain the f inal concentra tion a t the end o f process ing
t ime .

10
Then , F could be d e termined from :
121 . 1
250
-( X 39 4 . 1 )
33 0 . 0083
ln No / N 6 . 39 4 3 X 10 X e

Subs t i tute , f inal No / N from the calcu�a tion , the equivalen t t ime ,
0
t , a t 1 2 1 . 1 C can be determined .

For Ascorbic Acid

From Chi t taporn ( 19 7 7 ) ,

-1
Ea 84 . 2 kJ mole
-3 -1 °
k 840 x 1 0 h a t 1 29 C

14 ; 10
-3
min
-1 °
a t 1 29 C
-3 84 . 2
ln ( 1 4 X 10 ) +
0 . 0083 X 40 2
lnS =

9 -1
3 . 66 32 x 1 0 min

Calculation could be done same as for micro-organisms .

 203
APPEND IX 4 . 8 An Example o f Letha l i ty Calculat ion

(a) Predicted Temperatures and Le thal ity Calculat ion at the Centre Point
for Run no . 6

M I C ROBI OLOGY ASCORBIC ACID

PREDI CTED AVERAGE
° ° -Ea/RT
TEMPERATURE C TEMPERATURE C -Ea/RT
e No/N e No/n

61.0
6 1 .0 6 1 . 00 1 . 8101-14 1 . 000 1
1 . 000 I
1 . 000 1
bl.O 60 . 99 1 . 8101
60 . 99 6 1 . 02 1 . 8 1 35
61 . 15 1 . 8369 1 . 000 I
so
6 1 .05
6 1 . 26 61. 1 . 8978 1 . 000 1
6 1 . 74 6 2 . 14 2 . 0 168 1 . 000 1
62 . 55 62 . 12 2 . 2099 1 . 000 1
6 3 . 69 64 . 40 2 . 49 1 1 1 . 000 1
65. 12 65.95 ' 2 . 87 4 7 1 . 000 1
66 . 79 67 . 72 3 . 3787 1 . 000 1
68 . 6 5 69 . 6 5 5 . 3 394- 39 1 . 0000 4 . 02 3 7 1 . 0002
70.65 7 1 . 69 9 . 0064 1 . 000 1 ·4 . 83 1 6 1 . 0002
72 . 74 73.81 1 . 5 366- 38 1 . 000 1 5 . 8250 1 . 000 3
7 4 . 88 75.97 2 . 6 340 1 . 0002 7 . 0 342 1 . 00 0 3
7 7 . 06 7 8 . 14 4 . 50 1 8 1 . 0003 8 . 4857 1 . 0004
79 . 2 3 80 . 30 7 . 6 1 58 1 . 0006 1 . 0200- 1 3 1 . 0004
8 7 . 38 82 . 44 I . 2 7 2 5- 3 7 1 . 00 1 0 1 . 2 20 8 1 . 0005
1 . 4537 1 . 0006
1 . 7 20 5
8 3 . 50 8 4 . 54 2 . 0959 1 . 00 1 6
85 . 58 86 . 59 3 . 3922 1 . 00 2 6 1 . 0008
87 . 60 88 . 5 8 5 . 39 1 3 1 . 004 1 2 . 02 34 1 . 0009
89 . 5 7 90 . 5 1 8 . 399 5 1 . 00 6 5 2 . 36 3 1 1 . 00 10
9 1 . 46 9 2 . 38 1 . 2 8 35-36 1 . 0099 2 . 74 1 2 1 . 00 1 2
9 3 . 30 94. 18 1 . 9246 1 . 0 1 49 3 . 1 588 1 . 00 1 4
1 . 00 16
I . 00 1 8
9 5 . 06 9 5 . 90 2. 8 2 7 1 1 . 02 19 3 . 6 1 39
96 . 7 5 99 . 56 4 . 0 749 1 .0318 . 4 . 107 1

I . 002 3
9 8 . 37 99 . 1 4 5 . 7656 1 . 04 5 2 4 . 6376 1 . 00 2 0
99 . 9 2 100 . 66 8 . 0 203 1 . 06 3 5 5 . 2055
1 . 08 7 8 5 . 809 1 1 . 0026
I.
101 . 4 1 102 . 1 2 -- 1 . 0 9 7 3-35
102 . 8 3 1 0 3 . 50 I . 4 7 54 1 1 99 6 . 4 4 35 1 . 00 2 8
104 . 1 8 1 0 4 . 82 1 . 9526 1 . 1 6 16 7. 1074 1 . 00 3 1
106 . 08 2 . 5440 1 . 2 1 56 7 . 797 1 1 . 00 3 4
I . 2576
105 . 4 7
106 . 69 107 . 2 7 1 . 2840 8 . 5 1 10 1 . 00 3 7
1 0 7 . 86 108 . 4 1 4. 1 4 2 9 1 . 3742 9 . 2482 1 . 004 1
108 . 9 7 109 . 50 5 . 1 9 60 1 . 4 89 9 1 . 0004- 1 2 1 . 0044
1 . 07 7 5 1 . 004 7
I . 8243 I . 5590
1 10 . 0 3 1 10 . 5 3 6 . 4 1 08 1. 6 35 4

I . 0054
1 1 1.03 Ill.5I 7 . 8353 I . 00 5 1

1 1 1 . 99 1 1 2 . 44 9 . 4 700 2 . 069 1 1 . 2 35 2

I . 0062
1 1 2 . 89 1 1 3 . 32 I . I 3 2 - 34 2 . 3 8 36 1 . 3 148 1 . 00 5 8
1 1 3 . 75 1 1 4 . 16 I . 34 1 2 2 . 7986 1 . 39 5 2
1 14 . 57 1 14 . 95 1 . 5737 3. 3452 1 . 47 54 1 . 00 6 5
1 . 8287 4 . 06 8 2 1. 555 1 1 . 0069
! Ill
1 1 5 . 34 1 1 5 . 70
1 16 . 07 1 16 . 4 2 2. 5 . 0525 1 . 6 352 1 . 0072
1 16 . 78 1 17.03 2 . 3833 6 . 226 1 1 . 706 1 1 . 00 7 5
6 . 64 1 6 1. 7270 1 . 00 7 6
1. 6467
1 1 7 . 29 117.21 - 2 . 4675
117. 13 1 1 6 . 52 2 . 1 5 36 5 . 2200 1 . 00 7 3
1 15 - 92 1 14 . 7 7 1 . 5163 3 . 20 1 1 1 . 4 564 1 . 0064

1 1 3 . 62 112.03 8 . 7 1 2- 3 5 1.9513 1 . 1996 1 . 00 5 3

1 1 0 . 44 108. 5 3 4 . 2429 1 . 3848 9 . 3257- 1 3 1 . 004 1

106 . 6 2 1 0 4 . 50 1 . 824 7 1 . 1 503 6 . 9409 1 . 00 3 1

1 . 0769 5 . 5549 1 . 0024
1 . 00 2 1
1 0 2 . 39 10 1 . 5 2 9 . 6 5 5 6 - 36
100 . 66 99 . 82 6 . 6852 1 . 05 2 6 4 . 88 4 2
98.99 9 8 . 06 4 . 54 7 8 1 . 0355 4 . 26 8 1 1 . 00 1 9

97 . 1 3 96 . 1 2 2 . 9652 1 . 0230 3 . 6747 1 . 00 1 6

95 . 1 1 9 4 . 04 1 . 8652 1 . 0 14 4 3 . 1243 1 . 00 1 4

92.97 9 1 . 86 1 . 1409 1 . 0088 2 . 6305 1 . 00 1 2

90 . 7 5 89 . 6 1 6 . 8346-37 1 . 0053 2 . 1986 1 . 00 10

88 . 48 8 7 . 32 4 . 0 259 1 . 00 3 1 1 . 8269 1 . 0008

86 . 1 7 85.01 2 . 3444 1 . 00 18 1 . 5 1 19 1 . 00 0 7

8 3 . 86 8 2 . 70 1 . 355 7 1 . 00 1 0 1 . 24 8 1 1 . 0005
8 1 . 55 80 . 4 1 7 . 8 1 16-38 1 . 0006 1 . 029 1 1 . 0005

79 . 2 7 78. 14 4 . 50 1 8 1 . 0003 8 . 485 7 - 1 4 1 . 0004

7 7 . 02 75.91 2 . 5983 1 . 0002 7 . 0007 1 . 00 0 3

74 . 8 1 73.73 1. 506 1 1 . 000 1 5 . 7842 1 . 00 0 3

72.65 7 1 . 59 8 . 7803-39 1 . 000 1 4 . 7888 1 . 0002

70 . 54

-8

�g 1 . 1
Final conce n t r a t ion 2 . 3946 x 1 0 No 0 . 8664 No
C a l c u l a te F (min) 5. 1 8 1 3 1 7 . 35 10
 204

10
(b) Calculated Final Concentrat ion and F l Z l . l

Based on Predicted
% Diff erence
Based on Experimental
temperature data
Details
temperature data

run no . 6 ; a t centre point

f inal microbiolog ical

concentration x 10 9 8 . 7 2 1 4 No 2 . 3946 No

f inal ascorbic acid

concen trat ion 0 . 8609 No 0 . 8664 No 0.6
10
F (microbiology ) , min 5 . 4795 5 . 1813 5.4
121 . 1
10
F ( ascorbic acid) , min 1 8 . 1 2 10 1 7 . 35 1 0 4.3
121 . 1

run no . 6 ; r=O . O , x=1 . 8 cm

f inal microbiological
concentrat ion x 10 1 1 3 . 7258 No 5 . 6827 No

f inal ascorbic acid

concentration 0 . 8478 No 0 . 8522 No 0.5

(microbiology) , min
10
F 7 .0904 6 . 9653 1 .8
121 . 1
10
F (ascorbic acid ) , min 19 .9710 1 9 . 3440 3.1
1 21 . 1

run no . 7 ; at centre point

f inal microbiologic A l
concentra tion x 1 0 3 . 1 369 No 1 . 55 7 4 No

f inal ascorbic acid

concentration 0 . 83 9 1 No 0 . 8444 No 0.6
10
F (microbiology) , min 5 . 1016 4 . 6284 9.3
121 . 1
10 3.6
F (ascorbic acid) , min 2 1 . 2242 20 . 46 5 1
12 1 . 1

run no . 7 ; at r•O . O , x• l . 8 cm

f i nal microb iological

concentration x 10 1 0 7 . 4204 No 7 . 8255 No

f inal ascorbic acid

concen trat ion 0 . 8 279 No 0 . 8349 No 0.8
10 11.2
F (mic robiology) , min 6 . 207 1 5.5115
121 . 1

1 2 1 . 1 (ascorbic acid) , min

10 2 1 . 8386 4.4
F 2 2 . 8505
 205

o f the
APPEND IX 4 . 9 Distr ibu t ion o f Residu a l s for Det ermin ing the Accura cy
Tempe rture s
Modif ied Analyt ical Solut ion Program for Calcu lat ing

( a) In the Overall Process

Run no . 6 Run no . 8
o o
median 0 . 24 c median 0 . 67 c
o o
mean o. 71 c mean 0 . 76 c
L 90
o o
standard devia tion = c standard deviation = 1 . 00 c
30 '
30
r---

�
_.....

� '-'
_.....

'-' r---

f- :>-. 20
:>-. 20
(.)
(.)
Cl 1-- Cl
Cl)
Cl)
;::3
;::3
0'
0' Q)
Cl)
,----
1-1

f-
1-1
� 10
� 10

1--

0 � 0
2 . 75 3 . 75
1.5 3.5 5.5 -0 . 75 0 . 75 1 . 75
-2 . 5 -0 . 5
°
R e s i d tJ.a l ( C ) Re s i d u a l ( o c )
Run no . 7 Run no . 9
° o
median 0 . 85 C median 0 . 43 c
° o
mean 0 . 15 C mean 0 . 13 c
° o
standard deviation 1 . 47 C s t andard deviation 1. 4 1 c
60 60

_.....
�
'-'
:>-.
:>-. 40 (.) 40
(.) Cl
Cl Q)
Cl) ;::3
;::3
0'
0' Cl)
Cl) 1-1
1-1
�
�
20 20

0 0
-5 -3 -1 1 3
- 3 . 25 - 2 . 25 - 1 . 25 - 0 . 2 5 1 . 25 2 . 25

R e s i d u a l ( °C )
 206

( b ) I n the Cooling Phase

Run no . 6 Run no . 8
o
median 2 . 13 c median =

o
r-
mean 2 . 27 c mean
30 r-
= =

30
° °
standard devia tion =
1. 70 C standard deviation =
1 . 29 C

- ,.---
- ......-- r---
�
� '-"
'-"
f--
20 f- :>.
20
:>. (.)
(.) r---- c
c (1)
(1)

r---
;j
;j 0"
0" (1)

10 1- f--- ,.----
(1) 1-4

""' 1--
t----
1-4 �
10
1-- - 1--

0
I 0 r- 1. 75 3 . 75
4. 5 6.5 - 1 . 75 0
-1. 5 0.5 2.5
Res i dual ( °C )
Re s i d u a l ( ° C )

Run n9_ • 7 Run no . 9

o med ian o
median - 1 . 46 c =
- 1 . 75 c
o mean o
mean - 1 . 50 c - 1 . 34 c
30 r-
=

30
0 o
s tandard deviat ion =
0 . 91 c standard deviat ion =
1 . 65 c

-
- �
� '-"
'-"
20 f-
20
:>.
:>. (.)
(.) c

r-
c (1)
(1) ;j

r--
;j 0"
0" Cl)

10 1-
(1) 1-4
10
I--
1-4 �
�

r-

f--

1
0
-1
0
-3
3
-1 , 25 -0 . 25 0 . 75 -5
-3 . 25 - 2 . 25
Res i d u a l (° C )
Re s i d u a l ( ° C )
 207
APPEND IX 5 . 1 Analyt i cal Resul t s

(a) A s c o r b i c Ac i d

CONCENTRAT ION x 10 Z mg g
-l
Mean Concen-
2
S t andard Dev-

1 2
Run No . Samp le t r a t ion � 10 i a t ion x 10 2
1 mg g - 1
3 mg g

120°C
7 2 5 . 00 ( 6 ) 24 . 46 ( 7 ) 24 . 0 4 ( 2 ) 0 . 48 ( 8 )
2 1 . 80 ( 4 ) 22 . 34(8)
c on t r o l 24 . 5 0 ( 8 )
heated 23 . 23 (9) 2 2 . 46 ( 7 ) 0 . 72(0)

26 . 48 ( 2 ) 25 . 66 (2) 26 . 2 8 ( 0 )
23 . 72 (4) 2 3 . 7 9 (4)
4 c on t r o l 2 6 . 14 ( 1 ) 0 . 43 ( 8 )
heated 23 . 97 ( 5) 2 3 . 8 3 (8 ) 0 . 13(6)

9 2 5 . 84 ( 2 ) 25 . 9 5 ( 4 ) 26 . 0 5 ( 2 )
2 3 . 54 ( 7 ) 2 3 . 64 ( 6 )
c o n t ro l 25 . 95 (9) 0 . 11(5)
heated 23 . 65 (9 ) 2 3 . 60 ( 9 ) 0 . 06 ( 2 )

2 c o n t ro l 2 3 . 89 ( 7 ) 24 . 48 ( 9 ) 24 . 1 1 ( 3 ) 24 . 1 6 ( 9 ) 0 . 30 ( 9 )
heated 2 1 . 00 ( 1 ) 2 2 . 16 ( 9 ) 2 1 . 95 (4) 2 1 . 7 1 (5) 0 . 62 ( 8 )

129°C
6 25 . 7 5 ( 2 )
24 . 5 3 ( 7 )
contro l 25 . 3 2 ( 0 ) 25 . 47 ( 6) 25 . 68 ( 9 ) 0 . 30 ( 0 )
heated 2 3 . 89 ( 9 ) 23 . 88 ( 0 ) 2 4 . 10 ( 0 ) 0 . 37 ( 1 )

1 23 . 6 1 ( 7 ) 24 . 0 9 ( 8 )
2 2 . 46 ( 1 ) 21. 53(7) 2 1 . 54 ( 3 )
contro l 23 . 9 7 (1) 2 3 . 89 ( 8 ) 0 . 25 ( 1 )
heated 2 1 . 84 ( 4 ) 0 . 5 3 (4)

8 c on t ro l 2 5 . 45 (2 ) 2 5 . 26 (2 ) 2 5 . 16 ( 7 ) 2 5 . 29 ( 1 ) 0 . 15 ( 0 )
heated 23. 20(8) 2 3 . 41(9) 22 . 79(7) 23 . 04(4) 0 . 3 3 ( 4)

24 . 7 1 ( 5 ) 2 5 . 47 ( 6 )
2 3 . 04 ( 0 ) 2 2 . 06 ( 5 )
5 contro l 24 . 2 8 ( 8 ) 2 4 . 82 ( 7 ) 0 . 60 ( 3 )
hea ted 22 . 5 9 ( 2 ) 22 . 56(2) 0 . 49 ( 3 )

2 1 . 12 ( 1 )
10 c on t r o l 23. 58(0) 23 . 39(9) 22 . 9 1 (0) 2 3 . 29 ( 3 ) 0 . 35 ( 5 )
heated _? 0 . 7 0 ( 0 ) 21 . 03 ( 7 ) 20. 95(9) 0 . 22 ( 1 )

(b) Ribo f l avin

IJ g g - 1
CONCENTRATION Mean S tandard
Conc entra t i on Devi a t ion
Run No . Samp l e
1 2 3 4 IJ g g
-1
IJ g g
-1

1 2 0°C
c on t r o l 2 5 . 16 ( 1 ) 25 . 92 ( 5 ) 25 . 14(8)
2 5 . 47 ( 3 ) 23. 98(0)
7 2 5 . 42 ( 0 ) 25 . 4 1 (9) 0 . 36 ( 1 )
heated 25 . 09 ( 0 ) 24 . 0 5 ( 9 ) 2 4 . 65 ( 8 ) 0 . 75 (9)

2 5 . 35 ( 6 ) 25 . 37 (8)
24 . 6 1 ( 1 )
4 c on t r o l 2 5 . 9 5 ( 5 ) 2 5 . 34(6) 2 5 . 59 (0) 0 . 34 ( 0 )
heated 24 . 6 3 ( 6 ) 24 . 8 9 ( 0 ) 23 . 27 ( 2 ) .24 . 3 5 ( 0 ) 0 . 73 (0)

c on t r o l 26 . 0 7 ( 2 ) 26 . 0 3 ( 6 ) 26 . 26 ( 7 )
24 . 2 7 ( 2 )
9 25 . 87(8) 26 . 06 ( 6 ) 0 . 16 ( 0 )
heated 24 . 7 8 ( 9 ) 24 . 8 1 ( 0 ) 24 . 1 7 ( 2 ) 2 4 . 64 ( 2 ) 0 . 25 ( 1)

2 con t r o l 2 5 . 66 ( 9 ) 25 . 1 2 ( 2 ) 26 . 1 3 ( 4 ) 25 . 8 5 ( 1) 25 . 94 ( 2 ) 0 . 23 (9)
heated 2 4 . 02 ( 6 ) 24 . 00 ( 7 ) 24 . 86 ( 1 ) 24 . 0 7 ( 3 ) 24 . 24 ( 7 ) 0 . 42 ( 7 )

6 c on t r o l 2 5 . 5 9 ( 3 ) 25 . 78 ( 2 )
129°C
24 . 9 9 ( 3 ) 24. 76 (9) 25 . 2 8 ( 2 ) 0 . 48 ( 4 )
heated 25 . 14(9) 2 5 . 04 ( 1 ) 24. 25(9) 24 . 52 ( 7 ) 24 . 74 ( 7 ) 0 . 42 ( 4 )

25 . 87 ( 5 )
2 5 . 40 (5 ) 24 . 1 7 ( 8 ) 24 . 32 ( 2) 24 . 6 3 ( 8 ) 0 . 63 (0 )
1 c on t r o l 2 5 . 5 4 ( 4 ) - - 25 . 70 (4) 0 . 19 ( 5 )
heated -

26 . 49 ( 0 )
23 . 65 ( 1 )
8 control 2 5 . 8 8 ( 3 ) 25 . 5 2 ( 5 ) 2 3 . 70 ( 9 ) 2 5 . 40 ( 7 ) 1 . 20 ( 1 )
0 . 28 (9)
� p�
24 . 2 1 ( 3 ) 24. 06 ( 3 )

�� ��
heated 24 . 13 ( 2 ) 24 . 2 5 ( 4 )
5 c on t r o l 26 . 2 2 ( 0 ) 2 6 . 36 ( 4 ) 26 . 10 7 26 . 16 4 26 . 2 l l f 0 . 38
heated 24 . 3 6 ( 5 ) 24 . 14 ( 0 ) 25 . 28 0 24 . 8 1 5 24 . 6 5 5 0 . 51 6

10 con t r o l 2 6 . 44 ( 2 ) 25 . 7 7 (6) 25 . 90 ( 3) 26 . 49 ( 1 ) 26 . 15 ( 1) 0 . 3 7 (0)

heated 2 4 . 32 (4) 24 . 10 ( 8 ) 2 5 . 00 ( 8 ) 24 . 42 ( 1 ) 24 . 46 ( 0 ) 0 . 38 ( 3 )
 208

( c ) Co lour

The co lour of both control and hea ted samples were duplicate
measured . The ins t rumental readings of X, Y and Z were trans ferred
to x, y and Y by :

x = X/ (X + Y + Z )
y Y/ (X + Y + Z )

The x and y of both control and heated samples of each process ing
run are shown below :

X y c/c
0
Run No .
Control Heated Control Heated X y
c c c c
0 0
°
1 29 C
6 0 . 44 0 . 45 0 . 44 0 . 44 1 . 02 1 . 00
1 0 . 44 0- 45 0 . 44 0 . 44 1 . 02 1 . 00
8 0 . 44 0 . 44 0 . 44 0 . 44 1 . 02 1 . 00
5 0 . 44 0 . 45 0 . 44 0 . 44 1 . 02 1 . 00
10 0 . 43 0 . 44 0 . 44 0 . 44 1 . 02 1 . 00

1 20 ° C
7 0 . 44 0 . 45 0 . 44 0 . 44 1 . 02 1 . 00
4 0 . 44 0 . 45 0 . 44 0 . 43 1 . 02 1 . 00
9 0 . 44 0 . 45 0 . 44 0 . 44 1 . 02 1 . 00
2 0 . 44 0 . 45 0 . 44 0 . 44 1 . 02 1 . 00

As can be seen from above figures , c / c of b o th x and y were

0
cons tant . The c / c of x was about 1 . 02 and of y was 1 . 00 . Therefore i t
0
could be concluded that only Y can be used to describe the change of
co lour of baby food caused by heat in this s tudy and the readings , Y ,
are shown in the following tab le .
 ·209

Reading , y
Run No . Sample Mean , Y
1 2

°
1 20 C

7 control 30 . 4 30 . 2 30 . 3
heated 26 . 9 26 . 9 26 . 9

4 control 31 . 2 30 . 7 30 . 9
heated 27 . 2 26 . 6 26 . 9

9 control 30 . 1 30 . 1 30 . 1
heated 25 . 1 25 . 1 25 . 1

2 contro l 30 . 6 - 30 . 7 30 . 6
heated 24 . 2 24 . 0 24 . 1

-·

°
1 29 C

6 control 30 . 8 30 . 2 30 . 5
heated 26 . 2 26 . 0 26 . 1

1 control 30 . 3 30 . 3 30 . 3
heated 25 . 3 25 . 6 25 . 4

8 control 30 . 4 30 . 4 30 . 4
heated 24 . 9 24 . 9 24 . 9

5 control 30 . 1 30 . 3 30 . 2
heated 23 . 2 23 . 8 23 . 5

10 control 30 . 9 30 . 9 30 . 9
heated 23 . 7 24 . 0 23 . 8
 210

( d) Viscosity

Reading of Viscosity S tandard

Run no . Sample Mean Reading
Deviation
1 2 3 4

1 20 ° C

7 contro l 64 . 2 67 . 0 67 . 0 68 . 6 66 . 7 1.8
heated 60 . 1 60 . 6 59 . 6 - 60 . 1 0.5

4 control 63 . 9 63.0 62.5 61.4 62 . 7 1 .0

hea ted 53 . 3 55 . 4 56 . 1 54 . 8 54 . 9 1.2

9 control 60 . 3 60 . 4 59 . 4 - 60 . 0 0.6
hea ted 49 . 6 49 . 7 49 . 6 - 49 . 6 0. 1

2 control 66 . 0 65 . 5 64 . 2 - 65 . 2 0.9
heated 49 . 1 48 . 9 51.7 50 . 8 50 . 1 1.4
--

°
1 29 C

6 control 72 . 0 68 . 0 70 . 3 - 70 . 1 2.0
heated 56 . 8 56 . 3 57 . 9 - 57 . 0 0.8

1 control 71.5 73.5 72 . 4 72. 2 72.4 0.8

heated 57 . 5 57 . 3 57 . 0 - 5 7. 3 0.3

8 control 66 . 8 69 . 4 66 . 1 - 67 . 4 1.7
heated 51.2 52 . 8 53 . 3 - 52 . 4 1.1

5 control 64 . 4 63. 2 65 . 3 - 64 . 3 1.1

heated 49 . 5 49 . 2 47 . 6 - 48 . 8 1.0

10 control 76 . 5 75 . 6 74 . 8 - 75 . 6 0.9
heated 56 . 0 55 . 3 55 . 5 - 55 . 6 0.4
 �
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 217
APPEND IX 5 . 3 An Example o f the Kine tic Parame ters Calculat ion

(a) Cal culat ed ( c / c ) at each k o and Ea Level

0 129 C

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Temper- O o 335 � O o 335� O o 487 � O o 487 � O o 4 1 1� O o 4 1 1� O o 4 1 1� O o 258� O o 564_! Experi-
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a t ure n X 10 X 10 mental
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1 O o 94072 O o 9 3389 O o 9 1 505 O o 90538 O o 9 2 394 O o 9 3 1 19 O o 9 1432 O o 95 1 37 0 89 738 O o 9 1 440
0

8 O o 9 385 1 Oo 93157 O o 9 1 193 O o 90 1 0 3 O o 92031 O o 92857 O o 9 1 049 O o 94960 O o 89254 O o 9 1 1 16

5 O o 9286 1 O o 92177 O o 89 798 0 88834
0 O o 90930 O o 9 1657 O o 89 9 7 3 O o 94 1 85 O o 87796 O o 909 16
10 O o 92703 O o 920 19 O o 89576 O o 886 1 2 0 907 39
0 O o 9 146 7 O o 89783 O o 9406 1 O o 87545 0 89939 0

1 20 7 O o 9 5886 O o 9486 1 O o 94074 O o 92 6 1 5 O o 94 398 O o 95480 O o 9 2949 O o 96435 O o 92407 O o 9 1667

4 O o 94 109 O o 92754 O o 9 1 5 4 7 O o 89636 O o 92052 O o 9 3498 O o 90 180 O o 94 9 2 1 O o 89 2 74 0 . 9 1 1 50
9 0 9 3644
0 O o 92269 O o 90890 O o 889 55 O o 9 1471 O o 92 9 5 1 O o 89589 O o 94547 O o 88510 O o 90942
2 O o 9 2 334 O o 90754 O o 89046 O o 86838 O o 89 7 7 8 O o 9 14 7 9 0 . 87637 0 9 34 38 0 . 86265 O o 89839
0

( b) Calculated Absolute Res iduals

�
Temp e r - O o 335� O o 3 35� O o 487 � O o 487 � O o 4 1 1? O o 4 1 12 O o 4 1 1? O o 258� O o 564_!
4 4 4 4 4 4 4 4 4
a tu r e X 10 X 10 X 10 X 1Q X 10 X 10 X 10 X 10 X 10
o
c 93 73 93 73 83 103 63 83 83

129 6 O o 0 1 144 O o 00525 O o 0 104 1 O o 0 1922 O o 00 304 O o 00 348 O o 0 1 188 O o 02035 O o 02578
1 O o 02632 O o 0 1949 O o 00065 O o 00902 O o 00954 O o 0 1679 O o 00008 O o 03697 O o 0 1 702
8 O o 02 7 35 O o 0204 1 O o 00077 O o 01013 O o 009 1 5 Oo 01741 O o 00067 O o 0 3844 O o 0 1 862
5 O o 0 1945 O o 01 261- O o 01 1 1 8 O o 02082 O o 000 1 4 0 . 007 4 1 O o 00943 O o 0 3 269 O o 0 3 1 20
10 O o 02 764 O o 02080 O o 00363 O o 0 1 327 O o 00800 O o 0 1 528 O o 00 1 56 O o 04 12 2 O o 0 2 394

Average abs o l u t e
res i d ua l s O o 02244 O o 01571 O o 00533 O o 0 1449 O o 00597 O o 0 1 20 7 O o 00472 O o 0 3 39 3 0 . 02 3 3 1
S tandard d e v i a t ion O o 00 700 O o 006 7 3 O o 00 5 1 4 O o 0053 1 O o 004 1 7 O o 00626 O o 0055 1 O o 00820 O o 0057 1

1 20 7 O o 04 2 1 9 O o 0 3194 O o 02407 O o 00948 O o 02 7 3 1 O o 03 8 1 3 O o 0 1 282 O o 04 768 O o 00 740

4 O o 02959 O o 0 1604 O o 00397 Oo01514 O o 00902 O o 02348 O o 00970 Oo 03771 O o 0 1876
9 O o 02 702 O o 0 1 32 7 O o 00052 O o 0 1988 O o 00535 O o 02009 O o 0 1 35 3 O o 03605 O o 02432
2 O o 02495 O o 009 1 5 O o 00793 O o 0 300 1 O o 000 6 1 O o 0 1640 O o 02202 O o 03599 O o 03574

Average abs o l u t e
residua 1 s O o 03093 O o 0 1 760 O o 009 1 2 O o 0 1 863 O o 01057 0 . 02453 O o 0 1452 O o 03936 O o 02 156
S tandard d e v i a t i on O o 00 7 74 O o 00997 O o 0 1040 O o 00870 O o 01 1 70 O o 00952 O o 00527 O o 0056 1 O o 0 1 180

Ove r a l l average
abs o l u t e r e s i d u a l s O o 0262 1 O o 0 1655 O o 00701 Oo 01633 O o 00802 0 .01761 O o 00908 O o 0 36 34 0 .0 2 2 5 3
S tandard deviat ion O o 00819 O o 00 7 8 1 O o 00 7 6 1 O o 00687 O o 008 1 1 O o 00983 O o 00 7 32 O o 00 7 32 O o 00832
 218

(c) Mult iple Regression Analys is

(c) . 1 Us ing average absolute res idual a t each processing tempera ture :

2 2
regression of res iduals (Q) to X 1 , X2 , X 1 , x2 , X1X2 :

Variab le Coeffic ient t-ratio

0 . 00985 4. 11
X1 -0 . 00400 -4 . 3 1
X2 0 . 00 1 5 1 1 . 62
2
X1 0 . 00502 5 . 59
2
X2 0 . 00 1 1 3 1 . 25
X 1X2 -0 . 00484 -3 . 0 1

2
R = 85 . 1% , degree of freedom = 1 2 .

2
As x2 was lower than 80% signif icanc e , therefore , the regress ion
2
was repea ted using only X1 , X2 , x 1 , X 1X2 :

Variab le Coe f f ic ient t-ra tio

0 . 0 1 225 8 . 34
X1 -0 . 00400 -4 . 2 2
X2 0 . 00 1 5 1 1 . 59
2
X1 0 . 00 4 35 5 . 92
X 1X2 -0 . 00484 -2 . 9 5

2
R = 83 . 1 % , degree of freedom = 1 3 . 0 .
 219

(c) . 2 Using individual res iduals :

2 2
regression of residuals (Q) to X 1 , X2 , x 1 , X2 , X 1X2 :

Variab le Coeffi cient t-ratio

0 . 00964 4 . 87
X1 -0 . 00 392 - 5. 11
X2 0 . 00 1 4 5 1 . 89
2
X1 0 . 00505 6 . 80
x2 2 0 . 00103 1 . 38
X1X2 -0 . 00 47 5 -3. 57

2
R = 5 7 . 2% , degree o f freedom = 7 5 .

2
As X2 was lower than 80% s ignifi cance , therefore , the regress ion
2
was repeated using only X 1 , X2 , x 1 , X 1X2 :

Variable Coe fficient t-ra tio

0 . 0 1 1 83 9 . 90
X1 -0 . 00 39 2 -5 . 08
X2 0 . 00 1 45 1 . 88
2
X1 0 . 00444 7 . 42
X1X2 -0 . 004 7 5 - 3 . 55

2
R = 56 . 1% , degree of freedom = 76 .
 220

( d) Decoding the Regres s ion Equat ion and Minimization of Residual

From equation :

Q = j 0 . 0 1 225 - 0 . 00400X 1 + 0 . 00 1 5 1X2 + 0 . 00435X 1

2
- 0 . 00484X 1 X2 j
-4
k o - 0 . 4 1 1 5 x 10
sub s t i tu te X1 by 1 29 C
and
-5
0 . 76 3 X 1 0

Ea - 83
X2 by
10

giving

7
Q = I -0 . 06 5 1 - 1 . 4904x 1 0 -3 k o + 2 . 699x10
-3
Ea + 7 . 4652x 1 0 k o
1 29 c 1 29 c

-62 . 0238 k o Ea j
1 29 C

Minimization of Q was done by :

3 7
- 1 . 4904x 1 0 + 1 4 . 9 304x 1 0 k o - 6 2 . 0238 Ea = 0
1 29 c

E.Q_ - 2 . 6995x 1 0
-3
- 6 2 . 0238 k o 0
dEa 1 29 C

-4 -1
= 0 . 4352x 1 0 s

-1
Ea 80 . 7 kJ mole
 lOO READ ( 51 / ) XH I , X L �, Y H I , Y L O 00000 1 00
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(1)

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900 RE TURN 00000 9 0 0 '1::1
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1 �00 M A x =· 1 • E+ o o o o o1 5 o o )Q
.,
(

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1 U00 DO 1 I -1 , 4 {. ---4> 0-0 0 .1 d 0 0
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C O N T I N Ut .

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N
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 2' 2. 3

(f) Contour Plot Based on Decoded Equa t ion Shown in ( d)

0
147 • 0.;
.9..>

1 26

.--1
,....._

I
Cl)
.--1
0
s
105

t-")
,!G
+
..._,
84
('(j
�

0,�
63
(;:)"
(;:) "

42

0 . 25 0 . 30 0 . 35 0 . 40 0 . 45 0 . 50 0 . 55 0 . 60

+ deno tes the opt imum point

 224

APPENDIX 5 . 4 Es timat ion of k o for the Des ign for Ascorb i c Acid
1 29 c

From equat ion ( 5 . 4 ) , the f inal concentrat ion at the end of a small
time interval , �t , was :

Ea 1 1
o exp (- Bl(T
- 402
where fn (k o , Ea , T) is exp (-k ) ) �t)
1 29 C 1 29 C

If T is cons tant , fn (k o , Ea , T) will be cons tant as well .

1 29 c
So a t the end of the second �t , the f inal concentration will be :

Therefore , at the end of the nth �t , the f inal concentra tion will
be :

0 0
For run no . 6 � assuming the average temperature was 1 10 C or 383 K
over the process ing t ime of 29 5 2 + 2400 second s , k could be calculated
from the measured ini tial and f inal concentration of ascorbic acid of
-2 -2 -1
25 . 68 x 1 0 and 24 . 10 x 1 0 mg g us ing �t o f 7 2 seconds and assuming
-1
that Ea was 84 . 2 kJ mole (Chit taporn , 1 9 7 7 ) .

As

n�t = 29 5 2 + 2400

29 5 2 + 2400
n =

72

� 74
 22 5

So

fn (k 24 . 10 X l Q- Z
o , 84 . 2 , 383)7 4 = ---- -
1 29 c -Z
25 . 68 X 10

fn (k o 84 . 2 , 383) 0 . 99 9 1 9 6
1 29 C '
•

84 . 2 1 1
exp (-k o exp ( ( - )) x 72) = 0 . 999 196
129 C 0 . 0 083 383 402

-4 -1
k o = 0 . 4 1 15 x 10 8
1 29 C
 226

APPEND IX 5 . 5 De termina tion of k o and Ea f or Ribof lavin, Colour Y ,

1 29 c
and Viscos i ty Us ing Equ ivalen t Process ing Time

( a) Ribof lavin

The equivalent process ing time at specif ied tempera tures can be
calculated if the kine t ic reac tion ra te at tha t temperature is known
by :

ln .£.__ -k t
c r r
0

1 c
- k
t ( ln -)
r c
r 0

where t is an equivalent process ing t ime a t reference t emperature , r .

r

-4 - 1
Knowing that the k o o f ascorb ic acid was 0 . 435 x 1 0 s , the
1 29 C
° o , could be calculated f rom
equivalent process ing t ime at 1 29 C , t
- 1 29 C
the experimental of c / c of ascorb i c acid .
0

Run no . (c/c ) , ascorb ic acid min

o exp

6 0 . 9 3844 24 . 3
1 0 . 9 1 440 34 . 3
8 0. 9 1 1 16 35 . 6
5 0 . 909 1 6 36 . 5
10 0 . 89 9 39 40 . 6

As t o for ascorb ic acid and r i b o f lavin should be the same ,

1 29 C
c / c for ribof lavin corresponding to t o was calcula ted :
0 1 29 C

Run no . t ° , min (c/c ) , r ibof lavin

1 29 C 0 exp

6 24 . 3 0 . 9 7 844
1 34 . 3 0 . 95813
8 35 . 6 0 . 94745
5 36 . 5 0 . 94025
10 40 . 6 0 . 93537
 227

Regress ion of ln c / c with t o resul ted i n k o o f 0 . 2459

0 1 29 C 1 29 C
-4 - 1
x 10 s with 9 9 . 9% s igni f icance and 0 . 9 7 3 correlation coe f f icien t .

-1
As the Ea o f ascorbic acid was 8 1 kJ mole , the k o could be
1 20 C
calculated f rom :

Ea ( Tr - T)
k k exp ( - )
Tr RTTr

- 8 1 ( 1 29- 1 20 )
0 · 435 x 1 0 -4 exp < )
0 . 008 3 ( 1 29+2 7 3) ( 1 20+2 7 3 )

-4 -1
0 . 2495 x 1 0 s

°
The equivalent process ing time a t 1 2 0 C was again calculated based
°
on the experimental c/c resul ted f rom 1 20 C process ing tempera ture
0
experiments . These calcula ted equivalent process ing t imes were corres-
°
ponded to experimen tal c / c of r ibof lavin resul ted f rom 1 20 C process ing
0
tempera ture exper iment s as shown be low .

Run no . t ° min (c/c ) , ribof lavin

1 20 C ' 0 exp

7 58 . 1 0 . 9 7 006
4 61.9 0 . 9 5 1 59
9 63 . 4 0 . 94575
2 71.6 0 . 93428

Again , regress ion of ln c / c to t o was done ; k o for ribof lavin

- 4 -?
- 1 20 c 1 20 c
was found to be 0 . 1 3 5 7 x 1 0 s wi th 9 9 . 9 % leve l o f s igni f icance and
0 . 9 64 correlation coe f f icien t .

Then , the a c t ivat ion energy o f r ibof lavin was calculated from :

k 0
1 29 C ( RTTr
Ea ln ( ) )
k o Tr - T
1 20 C

-4
0 . 2459 X 10 0 . 0083 X 402 X 393
ln ( )( )
-4 40 2 - 39 3
0 . 1 35 7 X 10

-1
87 kJ mole
 228

(b) Colour, Y

Same as ribof lavin , the t o for ascorb ic acid and colour Y should
1 29 c
be the s ame . The c / c for colour , Y , corresponding to t o was calcu­
0 1 29 c
lated from the analytical resul ts :

Run no . t ° min (c/c ) colour Y

1 29 C ' 0 exp '

6 24 . 3 0 . 8 1 30
1 34 . 3 0 . 79 16
8 35 . 6 0 . 7 7 82
5 36 . 5 0 . 7578
2
10 40 . 6 0 . 7 3 52

-4 -1
Regress ion analysis gave k of 1 . 06 3 3 x 1 0
o s with 99 . 9%
1 29 c
s ignif icance and 0 . 989 correlation coe fficient .

°
At 1 20 C processing temperature :

Run no . t ° min (c/c ) colour Y

1 20 C ' 0 exp '

7 57 . 8 0 . 90 1 0
4 61.6 0 . 87 5 3
9 63 . 1 0 . 8269
2 71.2 0 . 7684

-4 -1
Regression analysis gave k o of 0 . 46 60 x 10 s wi th 99 . 9%
1 20 c
s ignif icance and 0 . 9 7 3 correlation coeff icient .

-1
The activation energy was 1 20 . 9 kJ mole for colour Y .
 22-9

(c) Viscos i ty

The method as in ribof lavin was used .

At 1 29 ° C processing temperature :

Run no . t min (c/c ) viscos i ty

1 29 °C ' 0 exp '

6 24 . 3 0 . 8 1 30
1 34 . 3 0 . 7916
8 35 . 7 o . 7 782

5 36 . 5 0 . 7578
10 40 . 6 0 . 7352

-4 -1
Regres s ion analysls gave k o of 1 . 2348 x 10 s with 99 . 9%
1 29 C
s ignificance and 0 . 996 correlation coef f icient .

0
At 1 20 C processing temperature :

Run no . t min ( c / c ) exp' viscos i ty

1 20 ° C ' 0

7 57 . 8 0 . 90 10
4 61 . 6 0 . 8753
9 63. 1 0 . 8269
2 71.2 0 . 7684

-4 -1
Regress ion analysis gave k of 0 . 4633 x 1 0
o s with 99 . 9%
1 20 c
signif icance and 0 . 9 3 2 correlat ion coefficient .

-1
The activation energy was 1 4 3 . 6 kJ mole for viscos i ty .
 .

-
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