Optimization of The Concentration of Tomato Juice by Freeze Concentration

OPTIMIZATION OF THE CONCENTRATION OF TOMATO JUICE BY FREEZE
CONCENTRATION
MUHAMMAD HARIZ BIN ABDUL HAMID
UNIVERSITI TEKNOLOGI MALAYSIA

PSZ 19:16 (Pind. 1/13)
UNIVERSITI TEKNOLOGI MALAYSIA
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AND COPYRIGHT
Author’s full name : MUHAMMAD HARIZ BIN ABDUL HAMID
Date of Birth : 20 SEPTEMBER 2000
Title : OPTIMIZATION OF THE CONCENTRATION OF TOMATO

JUICE BY FREEZE CONCENTRATION
Academic Session : 2022/2023 SEMESTER 1
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SIGNATURE OF STUDENT SIGNATURE OF SUPERVISOR
A19ET0149 AP. DR. MAZURA BINTI JUSOH

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“I hereby declare that I have read this dissertation and in my
opinion this dissertation is sufficient in term of scope and quality for the
award of the degree of Bachelor of Chemical Engineering.”
Signature : ________________________________
Name of Supervisor I : AP. DR. MAZURA BINTI JUSOH
Date : 16 FEBRUARY 2022
Signature : ________________________________
Name of Supervisor II : DR. AISHAH BINTI ROSLI
OPTIMIZATION OF THE CONCENTRATION OF TOMATO JUICE BY FREEZE
CONCENTRATION
MUHAMMAD HARIZ BIN ABDUL HAMID
A dissertation submitted in fulfilment of the

requirements for the award of the degree of
Bachelor of Engineering (Chemical)
School of Chemical and Energy Engineering

Faculty of Engineering
Universiti Teknologi Malaysia
February 16, 2023

DECLARATION
I declare that this dissertation entitled “Optimization of The Concentration of Tomato

Juice by Freeze Concentration” is the result of my own research except as cited in the
references. The dissertation has not been accepted for any degree and is not
concurrently submitted in candidature of any other degree.
Signature : ....................................................
Name : MUHAMMAD HARIZ BIN ABDUL HAMID
iii
DEDICATION
This dissertation is dedicated to my family, friends, supervisor, lecturers and

everyone, who have been nicely my supporter and encouraged me attentively with
their fullest and truest attention to accomplish my work with truthful self -confidence.
iv
ACKNOWLEDGEMENT
In the name of Allah, the Most Merciful and Most Gracious. Alhamdulillah, all
praise to Allah the Most Kind in giving me strength, patience, and guidance to
complete this dissertation. Nothing can be accomplished without His help. First of all,
I would like to express my deepest appreciation to all the people involved who were
directly or indirectly giving help through their motivation and support.
In preparing this dissertation, I was in contact with many people, researchers,

academicians, and practitioners. They have contributed towards my understanding and
thoughts. In particular, I wish to express my sincere appreciation to my supervisor,
AP. Dr. Mazura Binti Jusoh, for encouragement and guidance. I am also very thankful
to my co-supervisor Dr. Aishah Bin Rosli for her guidance, advices and motivation.
Without their continued support and interest, this dissertation would not have been the
same as presented here.
My sincere appreciation also extends to all my friends who have provided

assistance at various occasions. Their views and tips are useful indeed. Unfortunately,
it is not possible to list all of them in this limited space as I am grateful to all my family
member.
v
ABSTRACT
Freeze concentration (FC) is known as one of the methods used to concentrate

solution by freezing water molecules into ice crystals so that a highly concentrated
solution is left behind. The aim of this study is to find the effect of operating conditions
on effective partition constant (K) and optimize operating conditions for concentration
of tomato juice through progressive freeze concentration (PFC). In this work, the PFC
system was chosen to concentrate tomato juice and optimize by response surface
methodology (RSM). The design of PFC called as multiple probe cryo-concentration
system (MPCC) was used throughout this process. The effects of different operating
circumstances, including coolant temperature, operation time, stirrer speed on the
effective partition constant (K) were investigated. The optimum system efficiency will
display the lowest value of the effective partition constant (K) in the performance study
that follows utilizing the concentration of tomato juice. A process optimization using
the Response Surface Methodology (RSM) in Design Expert software was used to
investigate the interactions between process variables and identify optimum conditions
for each response. Five different level of central composite design (CCD) was use to
search for optimal concentration of concentrated tomato juice. A full quadratic model
for K was established by using method of least squares. A coefficient of determination
(R2) of this model was found to be 0.71. The optimum conditions were found for
coolant temperature = -9.4 °C, operation time = 49 minutes and stirrer speed = 375
rpm. A validation experiment was conducted to evaluate the accuracy of the
optimization procedure and the best K value was of 0.282 was achieved under the
optimized conditions.
vi
ABSTRAK
Kepekatan beku (FC) dikenali sebagai salah satu kaedah yang digunakan untuk
memekatkan larutan dengan membekukan molekul air menjadi hablur ais supaya
larutan yang sangat pekat tertinggal. Matlamat kajian ini adalah untuk mencari kesan
keadaan operasi ke atas pemalar partition berkesan (K) dan mengoptimumkan keadaan
operasi untuk kepekatan jus tomato melalui kepekatan beku progresif (PFC). Dalam
kerja ini, sistem PFC telah dipilih untuk menumpukan jus tomato dan
mengoptimumkan dengan metodologi permukaan tindak balas (RSM). Reka bentuk
PFC yang dipanggil sebagai sistem kepekatan krio berbilang probe (MPCC) telah
digunakan sepanjang proses ini. Kesan keadaan operasi yang berbeza, termasuk suhu
penyejuk, masa operasi, kelajuan pengacau pada pemalar partition berkesan (K) telah
disiasat. Kecekapan sistem optimum akan memaparkan nilai terendah pemalar
partition berkesan (K) dalam kajian prestasi yang berikut menggunakan kepekatan jus
tomato. Pengoptimuman proses menggunakan Response Surface Methodology (RSM)
dalam perisian Design Expert telah digunakan untuk menyiasat interaksi antara
pembolehubah proses dan mengenal pasti keadaan optimum untuk setiap respons.
Lima tahap reka bentuk komposit pusat (CCD) yang berbeza telah digunakan untuk
mencari kepekatan optimum jus tomato pekat. Model kuadratik penuh untuk K telah
diwujudkan dengan menggunakan kaedah kuasa dua terkecil. Pekali penentua n (R2)
model ini didapati 0.71. Keadaan optimum didapati untuk suhu penyejuk = -9.4 °C,
masa operasi = 49 minit dan kelajuan pengacau = 375 rpm. Eksperimen pengesahan
telah dijalankan untuk menilai ketepatan prosedur pengoptimuman dan nilai K terbaik
ialah 0.282 telah dicapai di bawah keadaan yang dioptimumkan.
vii
TABLE OF CONTENTS
TITLE PAGE
DECLARATION iii
DEDICATION iv
ACKNOWLEDGEMENT v
ABSTRACT vi
ABSTRAK vii
TABLE OF CONTENTS viii
LIST OF TABLES xi
LIST OF FIGURES xii
LIST OF ABBREVIATIONS xiv
LIST OF SYMBOLS xv
LIST OF APPENDICES xvii
CHAPTER 1 INTRODUCTION 1
1.1 Background of Research 1
1.2 Problem Statement 3
1.3 Objectives of Research 4
1.4 Scope of Research 5
1.5 Significance of Research 5
CHAPTER 2 LITERATURE REVIEW 7

2.1 Tomato Juice 7
2.2 Concentration Processes for Fruit Juice 8
2.2.1 Concentration Fruit Juice by Evaporation 8
2.2.2 Concentration of Fruit Juice by Reverse
Osmosis 9
2.2.3 Concentration of Fruit Juice by Freeze
Concentration 11
2.3 Methods of Freeze Concentration 11
2.3.1 Suspension Freeze Concentration (SFC) 12
viii
2.3.2 Progressive Freeze Concentration (PFC) 14
2.4 Progressive Freeze Concentration Exist Design 14
2.4.1 Tubular Ice System 16
2.4.2 Spiral Finned Crystallizer 17
2.4.3 Vertical Finned Crystallizer 18
2.5 Effective Partition Constant, K 19
2.6 Solute Recovery (Y) 20
2.7 Factors Affecting Efficiency PFC System 20
2.7.1 Effect of Coolant Temperature 21
2.7.2 Effect of Stirrer Speed 21
2.7.3 Effect of Operation Time 22
2.7.4 Effect of Initial Concentration 22
2.8 Design of Experiment and Optimization 22
2.8.1 Response Surface Methodology (RSM) 23
2.8.2 Central Composite Design (CCD) 27
2.8.3 Analysis of Variance (ANOVA) 29
CHAPTER 3 RESEARCH METHODOLOGY 31

3.1 Introduction 31
3.2 Flowchart of Methodology 32
3.3 Research Set-up and Procedure 33
3.3.1 Sample Preparation 35
3.3.2 Coolant Preparation 35
3.3.3 Total Phenolic Content (TPC) Determination 36
3.3.4 Multiple Probe Cryo-Concentration (MPCC)
Set-up 36
3.3.5 Experimental Procedure 38
3.4 Effect of Operating Conditions on Performance PFC 40
3.4.1 Coolant Temperature Test 41
3.4.2 Stirrer Speed Test 42
3.4.3 Operation Time Test 42
3.5 Efficiency Assessment 42
3.5.1 Effective partition constant, K 43
ix
3.6 Optimization Process 43
3.6.1 Design of Experiment (DOE) 45
3.6.2 Model Generated 46
3.6.3 Analysis of Variance (ANOVA) 47
3.6.4 Determination of Optimal Condition 48
CHAPTER 4 RESULT AND DISCUSSION 50

4.1 Introduction 50
4.2 Analysis of Performance of PFC System 51
4.3 Effect of Coolant Temperature on PFC System 51
4.4 Effect of Stirrer Speed on PFC System 53
4.5 Effect of Operation Time on PFC System 55
4.6 Optimization of Tomato Juice by Response Surface
Methodology (RSM) 57
4.6.1 Design of Experiment by Central Composite
Design 58
4.6.2 Model Adequacy Check (ANOVA) 60
4.6.3 Response Surface and Contour Plot of K-Value
66
4.6.3.1 Interaction of Coolant Temperature
(X1) and Operation Time (X 2) 66
4.6.3.2 Interaction Coolant Temperature
(X1) and Stirrer Speed (X3) 68
4.6.3.3 Interaction Operation Time (X 2) and
Stirrer Speed (X3) 70
4.6.4 Optimum Operating Conditions for K-Value 72
4.6.5 Validation of Experiment 73
CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS 74

5.1 Conclusions 74
5.2 Recommendations 75
REFERENCES 76
x
LIST OF TABLES
TABLE NO. TITLE PAGE
Table 2.1 Experimental matrices for CCD of two variables (Bezerra

et al., 2008) 29
Table 3.1: Freezing point of ethylene glycol at different volume percentage
(Amran, 2015) 35
Table 3.2 Range for parameters in this research 40
Table 3.3 Value of varied and constant parameter 41
Table 3.4 Experimental range and coded value of variables 45
Table 3.5 Arrangement of experiment using central CCD 46

Table 3.6 ANOVA table (Amran, 2015) 47
Table 3.7 Predicted analysis of optimum condition for K 49
Table 3.8 Optimum values of process parameters in validation

experiment 49
Table 4.1 Experimental result of K value for Design of Experiment 59
Table 4.2 The experimental, predicted and residuals for Response K 62

Table 4.3 ANOVA table 65
Table 4.4 Regression result for K response 65
Table 4.5 Optimum Range for Operation Parameters of K-value 73
Table 4.6 Optimum Value for Operating Parameters of K -value 73
xi
LIST OF FIGURES
FIGURE NO. TITLE PAGE
Figure 1.1 General process of freeze concentration (Samsuri et al.,

2015) 2
Figure 2.1 The difference between normal and reverse osmosis
(Dhapare, 2022) 10
Figure 2.2 Illustration of (a) SFC and (b) PFC system (Samsuri et al.,
2015) 10
Figure 2.3 Schematic suspension freeze concentration system
(Sánchez et al., 2009) 13
Figure 2.4 Conventional design for PFC (Samsuri et al., 2015) 13
Figure 2.5 Tubular ice system for scale-up of PFC (Miyawaki et al.,
2005) 15
Figure 2.6 Schematic diagram of spiral finned crystallizer (Samsuri et

al., 2015) 17
Figure 2.7 General schematic diagram of VFC a) side view and b) top
view of VFC (Amran et al., 2018) 18
Figure 2.8 Step by step procedure for RSM (Aydar, 2018) 19
Figure 2.9 Different types of contour plot of RSM generated from the
quadratic modelling a) maximum b) plateau, c) maximum
outside the experimental region, d) minimum and e) saddle
surface (Bezerra et al., 2008) 26
Figure 2.10 CCD for the optimization of (a) two variables and (b) three
variables (Amran, 2015) 27
Figure 3.1 Flowchart of methodology 33
Figure 3.2 Set up for MPCC in the lab 34
Figure 3.3 Refractometer 34
Figure 3.4 UV-VIS spectrophotometer 34

Figure 3.5 The design with each other part specification of MPCC
(Mohd Rosli et al., 2022) 37
Figure 3.6 The set up for probe cryo-concentration (Mohd Rosli et al.,
2022) 38
Figure 3.7 Ice formed at probe's wall 39
xii
Figure 3.8 Concentrated tomato juice collected from cylindrical tank
after freeze concentration 39
Figure 3.9 Steps in RSM (Amran, 2015) 44
Figure 4.1 Comparison between final concentration, initial

concentration and ice concentration 51
Figure 4.2 Changes of TPC increment and effective partition constant,

K with Coolant Temperature 52
Figure 4.3 Changes of effective partition constant, K and TPC

Increment (%) 54
Figure 4.4 Changes of effective partition constant, K and TPC

Increment (%) 56
Figure 4.5 Predicted versus actual data 63
Figure 4.6 Raw residuals versus predicted data 64

Figure 4.7 Surface plot of K-Value for coolant temperature and
operation time 67
Figure 4.8 Contour plot of K-Value for coolant temperature and
operation time 68
Figure 4.9 Surface plot of K-value for coolant temperature and stirrer
speed 69
Figure 4.10 Contour plot of K-Value for coolant temperature and stirrer
speed 70
Figure 4.11 Surface plot of K-Value for operation time and stirrer speed
71
Figure 4.12 Contour plot of K-Value for operation time and stirrer
speed 72
xiii
LIST OF ABBREVIATIONS
ANOVA - Analysis of Variance

CCD - Central Composite Design
DF - Degree of Freedom
DOE - Design of Experiment
FC - Freeze Concentration
GAE - Gallic Acid Equivalents
PFC - Progressive Freeze Concentration
RO - Reverse Osmosis
RSM - Response Surface Methodology
SFC - Suspension Freeze Concentration
SSHE - Scraped Surface Heat Exchangers
TPC - Total Phenolic Content
UTM - Universiti Teknologi Malaysia
UV-VIS - Ultraviolet-Visible Spectroscopy
VFC - Vertical Finned Crystallizer
SS - Sum of Squares
MS - Mean Squares
xiv
LIST OF SYMBOLS
% - Percentage nutrients in tomato juice

𝐶𝐿 - Solute concentrations in liquid phases
𝐶𝑂 - Initial concentrations of the solution
𝐶𝑆 - Solute concentrations in ice phase
𝑀𝑠,𝐿 - Mass of solute in the concentrated liquid
𝑀𝑠,𝑂 - Mass of solute in initial solution
𝑉𝐿 - Volume of the liquid phase
𝑉𝑂 - Initial volume of the solution
𝑐𝑝 - Replicate number of the central point
𝛽0 - Regression coefficient at centre point
𝛽1 - Linear coefficient for 1st independent variables
𝛽11 - Quadratic coefficients for 1st independent variables
𝛽12 - Second order interaction coefficients
𝛽2 - Linear coefficients for 2nd independent variables
𝛽22 - Quadratic coefficients for 2nd independent variables
+1 - High
+α - Upper high
0 - Centre
-1 - Low
D - Diameter
K - Effective partition constant
k - Factor number
MSreg - Mean square of regression
MSres - Mean square of residuals
MSSSE - Mean of square regression
MSSSR - Mean of square residual
SSreg - Mean square of residuals
SSres - Sum of square residuals
SStotal - Total sum of square
X1 - Coolant temperature
xv
X2 - Operation time
X3 - Stirrer speed
α - Distance from centre of design space to a star point in CCD
xvi
LIST OF APPENDICES
APPENDIX TITLE PAGE
Appendix A Gant Chart 85
Appendix B Result for Effect of Parameters 86

Appendix C Standard F-Table 87
xvii
CHAPTER 1
INTRODUCTION
1.1 Background of Research
Tomato is one of the easiest types of fruit that can be found anywhere. In
addition, tomato also commonly used widely in food industry and variety of forms,
from a daily fresh consumption to the food product like sauce, ketchup, and juices.
Other than that, tomato also used in many traditional dishes especially at
Mediterranean cuisine as they said it’s their symbol of cuisine. Nowadays, food
industry is a one of the most important and lasting in the world because related to the
humans’ food chain. As we know, Tomatoes are widely consumed as fresh vegetables
across the world because of their high quantity of important nutrients like vitamin C,
potassium, folate, vitamin K and antioxidant-rich phytochemicals (Bjarnadottir, 2019).
In tomato content about 95% of water and 5% of nutrients (Barbie Cervoni MS, 2021).
Increasing demand on the tomato juices in industry has brought to research about how
to optimize the concentrate of concentration tomato juices. So, in order to maintain the
flavour, nutrients, functional properties of concentrated fruit juices and colours in
tomatoes, we need to choose the right technology for it.
Freeze concentration (FC) is a method that may be used to concentrate fruit

juices in the food processing sector. FC is a method of concentrating a liquid product
by freezing the water content and resulting in the formation of ice crystals in the system
(Samsuri et al., 2015). FC is one of the common ways to use in handling fruit juices in
order to produce concentrates with an intense flavour. This method allow water to be
removed from a solution by chilling or freezing it until high-purity ice crystals form
and separate, leaving a concentrated fluid behind. Because of the low processing
temperatures, which avoid undesired chemical and biochemical changes and reduce
sensory property loss, the nutritional and sensory quality of freeze-concentrated fruit
juices is greater than that of those concentrated traditionally by evaporation (Sánchez
1
et al., 2009). The basic steps of the FC system are depicted in Figure 1.1. The formation
of proper numbers, sizes, and shapes of ice crystals in a crystallizer is the initial stage
in this process (Samsuri et al., 2015). A crystallizer is an equipment that removes heat
from a sample liquid and converts it into ice crystals
Figure 1.1 General process of freeze concentration (Samsuri et al., 2015)
Freeze concentration of tomato juice can be done by using two method of

freeze concentration which are suspension freeze concentration (SFC) and progressive
freeze concentration (PFC) (Amran & Jusoh, 2016). SFC is a two-phase process that
Figure 1.2 The difference between normal and reverse osmosis (Dhapare, 2022)
begins with the nucleation of ice crystals and ends with the development of ice crystals
from a solution (Rosdi et al., 2020). SFC separate the water content from the tomato
juice Figure 1.3:byGeneral
solution produceprocess of freeze
ice crystals asconcentration
a suspension (Samsuri et al.,solution
in original 2015) and
concentrated product will be gain. Scraped surface heat exchangers (SSHE) are used
to start the creation of seed ice crystals and a stirrer is used as an agitator to speed up
the agglomeration process. But, SFC process more complicated due to the size of the
ice crystals formed in the process is limited and requires a lot of cost especially on
SSHE (Samsuri et al., 2018).
Nowadays, many FC process have switched to PFC due to lower cost and easier
to do (Samsuri et al., 2015). PFC is a type of FC method in which just a single ice
crystal is created on a moving ice front on a cooling wall (Samsuri et al., 2018). PFC
creates a big single ice block by layering a single ice crystal over a cold surface.
Concentration can be achieved by adhering to the increasingly developing single ice
2
front and withdrawing water molecules from the liquid meal (Jayawardena et al.,
2021). After that, by using the correct operational conditions and a slow crystal growth
rate, high concentration efficiency is able to achieve by PFC. Because the concentrated
solution may be drained out of the system to separate the two phases, PFC avoids the
requirement for a complex separation system to remove the ice crystal block.
Furthermore, this method is cheap and affordable due to the only a single large ice
crystal forms in the system and grows on the cooling surface, allowing for simple
separation of the ice crystal from the mother solution. Furthermore, PFC has a low
energy need and a low process temperature which is prevents undesired biochemical
and chemical changes (Rosdi et al., 2020). Thus, PFC is chosen as method of freeze
concentration in this study.
1.2 Problem Statement
Fruit juices are frequently concentrated in order to eliminate the water and
produce juice concentrate, which is a thinner solution like syrup. removal water from
fruit juice helps in reducing the bacterial growth and make the solution doesn't spoil
easily like juice. For the concentration of liquid foods, traditional thermal processes
like evaporation are most frequently used. However, they result in considerable losses
of the original aromatic compounds, and the concentrations that are produced are
frequently regarded as being of inferior quality. High temperature operating conditions
will induce nutrition degradation and damage the biological structure, especially the
total phenolic content (TPC) of the tomato juice itself because evaporation engages
high temperature in the process (Rosdi et al., 2020). Additionally, heat concentration
uses a lot of energy. Freeze concentration uses a lot less energy than evaporation, thus
it will use less electricity. In addition, freeze concentration uses low temperature which
not harm the important substances in tomato juice like flavour, nutrients and functional
properties of concentrated in fruit juice. There is no heat abuse of sensitive food
constituents or components throughout the process.
Optimization concentration of tomato juice solution can be done by using

freeze concentration technique. There are three factors that important to determine the
3
efficiency of FC system. The factors are of efficiency of FC including coolant
temperature, operation time and stirrer speed (Jusoh et al., 2013). Previously, the
classic one-variable-at-a-time technique was the most widely used method for
identifying the optimal or best state of any reaction evaluated (Keshani el al., 2010).
The conventional optimization method is modifying one variable at a time while
maintaining the amounts of the other variables constant. The experiments are simple
and easy to execute but the result will not be accurate and efficient. One factor cannot
be optimized by conducting one factor-at-a time experiments. this situation cannot be
because one-factor-at-a-time analyses ignore the interactions between elements that
are present at the same time. So, the findings do not represent actual changes in the
environment. Furthermore, it will take more experimentation than a factorial design of
experiment, and there is no guarantee that the data will be accurate and presentable
(Montgomery et al., 2001).
In order to get the optimal parameters for FC of tomato juice concentration, we

need to conduct suitable method to overcome such drawbacks. Response surface
methodology (RSM) can be used to determine the optimal parameters for FC of tomato
juice. Response surface methodology (RSM) is a method that is increasingly used for
modelling, interaction analysis, and process and experiment optimization (Keshani el
al., 2010). RSM has been heavily utilised for process optimization in the manufacture
of tropical fruit juice (Chan et al., 2009).
In this study, RSM is used to explore the interactions between a number of

explanatory factors and one or more response variables. RSM was used as a method
to optimize the concentration of tomato juice.
1.3 Objectives of Research
The objectives of the research are:
(a) To study the effect of operating conditions on effective partition

constant, K
4
(b) To optimize operating conditions for concentration of tomato juice
through PFC.
1.4 Scope of Research
In order to achieves the objective above, several scopes were

implemented. The scope is used to determined how to outcome the objectives as
mentioned above.
(a) The range for coolant temperature will be used from -6 to -14 °C
(b) The range of operation time will be used from 20 to 60 minutes
(c) The range of stirrer speed will be used from 200 to 450 rpm
(d) Design Expert Software will be used to carry out response surface
methodology (RSM) to generate experimental design. RSM is used to
define the optimal parameters conditions, which can generate better
result.
1.5 Significance of Research
In this research, freeze concentration is use to optimize the concentration of

tomato juice based on factors including coolant temperature, operation time and stirrer
speed. From this process, it can provide the concentrated of tomato juice that rich with
the sources of vitamin C and other oxidants. This will help in prevent the creation of
free radicals, do the following steps. Cancer is known to be caused by free radicals.
Tomato contain high of vitamin C, E and beta-carotene which good in support heart
health. Furthermore, this research can help in food industry especially in
manufacturing of tomato juice. Optimize tomato juice can be utilize in making a large
number of processed products such as puree, paste, powder, Ketchup, sauce, soup and
canned whole fruit. This research would also give insight into how to construct a high-
productivity PFC system.
5
CHAPTER 2
LITERATURE REVIEW
2.1 Tomato Juice
Tomato juice which is famous as beverage that rich with many useful nutrients,
mineral and antioxidants. In tomato content around 95% of water content and balance
of 5% consists of carbohydrates and fibre. Nutrients content for 100-gram raw tomato
include calories, protein, carbs, sugar, fibre and fat (Bjarnadottir, 2019). Furthermore,
tomato juice also a good source vitamin and mineral like vitamin C, potassium, vitamin
K1 and folate (B9). These vitamins and nutrients are use as antioxidant, blood pressure
control, important for blood clotting and normal tissue growth and cell function
(Bjarnadottir, 2019).
Contents in tomato juice could be useful to improve our health benefits in

prevent from free radical molecules that can cause cancer. In fact, tomato products like
juice, ketchup and pizza sauce are used more in their daily food due to high lycopene
content about 80% (Story et al., 2010). Antioxidant contain in tomato also can help in
heart health. They include antioxidants like lycopene and beta-carotene, which help
lower heart disease risk factors like high blood pressure, cholesterol, and artery fat
formation (atherosclerosis). A study of 584 participants found that persons who ate a
diet high in tomatoes and tomato products had a lower risk of heart disease than those
who ate a low-to-moderate amount of tomatoes (Jacques et al., 2013).
Tomato juice can be obtained manually by squeezing the fresh tomatoes. It can
be made by blending or prepare from tomato paste concentrate. For manufacturing
process of tomato juice involve fresh tomato raw materials selection and cleaning,
manual fruit sorting, tomato crushing, tomato pulp preheating, tomato juice extraction,
tomato juice blending, degassing, sterilization, filling and sealing, tomato juice
container secondary pasteurization, cooling, packaging. The processing technology by
7
using concentrated tomato sauce as the raw material is relatively simple, and you can
refer to the tomato sauce/ketchup processing line. The end products of the tomato juice
can be filled into bottles, tin cans or cartons.
The important of concentration of tomato juice because of because it contains

many good nutrients and flavours in tomato juice. Tomato juice is a popular drink that
provides a wide variety of vitamins, minerals, and potent antioxidants. To preserve the
flavour, colour, and useful qualities of concentrated fruit juices, the technology
employed in the concentration process must be carefully chosen (Samsuri et al., 2018).
Concentrated of tomato juice is one of the powerful sources of antioxidant that have
remarkable health benefits. With concentred tomato juice can help consumer by
protect form certain cancers like prostate cancer and skin cancer. In addition, the uses
of concentrated tomato juice also use in food industry. Concentrated tomato juice can
produce tomato juice drinks and paste for everyday consume because it’s rich with
antioxidant. Iron, potassium, and B vitamins.
2.2 Concentration Processes for Fruit Juice
Generally, there are three common methods use in concentration fruit juice in
food industry which are evaporation, reverse osmosis and freeze concentration
2.2.1 Concentration Fruit Juice by Evaporation
Evaporation is a process used in the food industry to concentrate fruit juice by

removing water from the liquid phase into the vapour or gas phase. It includes boiling
the liquid into a suitable vessel, called evaporator, and extracting the vapour
(Monceaux & Kuehner, 2009). Evaporation has also been used to extra ct volatile
components from a solution such as solvents and fragrance. Evaporation technology
uses convective heat transfer to enhance the concentration of non -volatile compounds
in solution, resulting in increased solute concentration in the final product. Example
of concentration food product from evaporation process include dairy products, syrups,
8
sugar, jams and canned foods. Evaporation typically uses steam or another process
stream as a driving energy source to heat a solution and with the energy being delivered
at constant pressure until the temperature reaches saturation. The heating is continued
until the solution begins to evaporate, at which point the vapour pressure of the
solution equals that of the surrounding air. As a result of the volatile component being
separated from the original solution, the concentration of the solution increases
(Monceaux & Kuehner, 2009). Furthermore, evaporation also has slower operating
cost but can risks destroying vital components of the solution fruit juice such as
fragrance, taste, and nutrition due to the high temperature (Samsuri et al., 2015).
Because of this flaw in the evaporation process, the resulting juice may be considered
poor quality.
Evaporation can be performed at the boiling point of food liquids wh ose quality
is not determined by their aroma composition. However, the scent qualities of most
food liquids are what determine their quality. Low-boiling volatile chemicals make up
almost all aroma and flavour components in foods. As a result, depending on their
thermal stability, they may be eliminated before water removal or destroyed altogether.
The loss of these chemicals is nearly precisely proportionate to the loss of vapour in
this operation, if the liquid has to be concentrated fourfold or more (Thijssen, 1970).
Furthermore, as compared to freeze concentration, evaporation is one of the

processes that uses the most energy. The enthalpy of crystallisation for water, for
example, is 334 kJ/kg, but the enthalpy of vaporisation is 2260 kJ/kg at atmospheric
pressure.
2.2.2 Concentration of Fruit Juice by Reverse Osmosis
Reverse osmosis (RO) causes demineralization or deionization of water by

applying enough pressure across a semipermeable reverse osmosis membrane. In other
words, reverse osmosis happens when water is moved through a membrane between
two media and flows in the opposite direction of normal osmosis (McCabe et al.,
1993). In a typical osmosis process, the solution travels through a membrane from a
9
lower concentration area to a higher concentration area. Initially, two solutions of
varying concentrations will come into contact with one another until a final uniform
concentration is achieved. The uniformed solution is then divided by a semipermeable
barrier, through which the fluid with lower solute concentration flows into the fluid
with greater solute concentration (Binnie et al., 2002). After a short time, the level of
water on one of the medium separated by the membrane will be higher. Osmotic
pressure is the height difference between the two separated solutions at this time. A
reverse effect occurs when an external pressure greater than osmotic pressure is
applied to a concentrated solution. Reverse osmosis is the process. The water will flow
back to the lower-concentration medium on the opposite side of the membrane, leaving
the highly concentrated solution behind. The difference in size or osmotic pressure of
the components in the solution causes the separation of substances. The used
membrane is meant to be semipermeable for allowing just some compounds to flow
through while blocking the rest. Other tiny molecules, usually gases, might travel
through the membrane in addition to water (Binnie et al., 2002). Based on Figure 2.1
shows the difference between normal osmosis and reverse osmosis.
Advantages of RO is energy efficient and simple operation in concentration

fruit juices because can operate at ambient temperature and now also non cellulosic
Figure 2.2: Illustration of (a) SFC and (b) PFC system (Samsuri et al., 2015)
membrane has greatly improved characteristics for retention of aroma and low
10
molecular compounds. With operate with ambient temperature will not cause the
thermal damage to the products. Thus, maintain the higher nutritional, arom a, and
flavour compounds. Furthermore, processing and energy costs are cheaper and high -
quality goods are obtained as a result of the preservation of fragrance and flavour
components as well as those responsible for nutritional properties (Couto et al., 2011).
2.2.3 Concentration of Fruit Juice by Freeze Concentration
Freeze concentration is the process of eliminating moisture fro m a liquid to

make it a highly concentrated liquid. It separates the water from the liquid solution as
ice crystals and leaving behind a highly concentrated solution. It’s one of the methods
that always use for produce pure solutions of fruit with intense flavour. Separation
method by freeze concentration can be used order to maintain flavour, colour and
functional properties of concentrated fruit juices. The concentrated solution may be
used to freeze new goods which can then be combined with water to gene rate a
refreshing juice. The concentrated solution may be used to freeze new goods, which
can then be blended with water to generate a refreshing juice.
Freeze concentration is useful for food industry. One of the advantages for
freeze concentration is being able to control bacterial growth. Freeze concentration
helps to keep them safe by inhibiting harmful germs. They shouldn't be able to cause
food poisoning as long as they are handled carefully at room temperature. In addition,
freeze concentration is cost beneficial for separation process than other method and
avoid corrosion. Freeze concentration has lower cost because needs less maintenance
and with less precipitation. For corrosion, due to low temperature operation cause the
corrosion not significant.
2.3 Methods of Freeze Concentration
There are two types of freeze concentration method which are Suspension
Freeze Concentration (SFC) and Progressive Freeze Concentration (PFC).
11
2.3.1 Suspension Freeze Concentration (SFC)
SFC is a freeze concentration process in which ice crystals develop in a

suspension of the mother liquor and is characterised by the production of an
isothermally expanding crystal size range. (Jusoh et al., 2018). SFC forms ice crystals
in suspension in the mother liquor which in this case is the concentrated solution, while
PFC forms ice crystals as a single block on the chilled surface as shown in Figure 2.2
(Samsuri et al., 2015). Process of SFC includes crystallization, growth, and separation
of ice crystals (Samsuri et al., 2015). SFC comprises a scraped surface heat exchanger
(SSHE) and a crystallizer for separation of ice crystals (Samsuri et al., 2018). After
being pumped from a feed tank, little ice crystals accumulate in the SSHE. In order to
create tiny ice crystals, the SSHE requires a short residence period and a lot of
supercooling. SSHE is the most expensive processing unit in an FC facility, accounting
for 30% of overall investment expenses. Small ice crystals from the SSHE outflow are
delivered to the crystallizer, where they are combined with bigger crystals. The larger
the size difference between big and tiny crystals, the faster the giant crystals will
develop and the smaller crystals will dissolve (Samsuri et al., 2015). The ice nuclei are
sent to the crystallizer to form ice crystals via the Gibbs Thomson effect and then the
ice crystals are separated from the concentrate in a pressured wash column (Sánchez
et al., 2009). The separation and washing of the ice crystals is critical in the SFC
because the solutes in the solution will adhere to the ice crystals and pollute them.
Separating the ice crystals from the concentrated liquid can be done by presses,
centrifuges, and wash columns. Because it combines solid–liquid separation and
counter current washing with pure melt, the wash column is an excellent separation
device (Samsuri et al., 2015). Based on the Figure 2.3 shows the schematic suspension
freeze concentration system (Sánchez et al., 2009)
12
Figure 2.2 Illustration of (a) SFC and (b) PFC system (Samsuri et al., 2015)
Figure 2.4: Schematic suspension freeze concentration system (Sánchez et al., 2009)
Figure 2.5: Illustration of (a) SFC and (b) PFC system (Samsuri et al., 2015)
Figure 2.3 Schematic suspension freeze concentration system (Sánchez et al.,

2009)
SFC has a high capital investment cost since it uses a scraped surface heat
exchanger (SSHE) to manufacture ice crystal seeds, which is quite costly and accounts
for around Figure
30% of2.6:
the entire investment
Conventional expenses
design in an
for PFC FC process
(Samsuri et al.,(Jusoh,
2015)2010). SFC
requires big cost due of its large surface area, separate the ice crystals from the
concentrated liquid. Therefore, this makes SFC is one of the complicated and
Figure 2.7: Schematic suspension freeze concentration system (Sánchez et al., 2009)
expensive method to do.
13
2.3.2 Progressive Freeze Concentration (PFC)
PFC is a kind of freeze concentration (FC) method that develops a huge single
ice block by forming a single ice crystal layer by layer on a cold surface. Concentration
is achieved by adhering to the increasingly developing single ice front and
withdrawing water molecules from the liquid food (Jayawardena et al., 2021). The
concentration efficiency has been demonstrated to be high under proper working
circumstances with a low crystal growth rate. Furthermore, the PFC produces ice
crystals of exceptional clarity. The sluggish pace of development contributes to a better
separation of water and solute (Pham, 2008). Because there is only one block of ice
crystal, separating it from the mother solution is significantly easier and thus resulting
in cheap maintenance costs (Jusoh et al., 2008).
Large ice crystals have less contaminated impurities or quantities of solute than
small ice crystals, hence the purity of ice crystal in PFC is better than in SFC. Despite
the potential for PFC to replace SFC as the main technique of concentration, it is less
efficient than SFC. As a result, several researches have exp lored various aspects of
PFC are required in order to increase PFC efficiency. When assessing the efficiency
of a PFC system, the effective partition coefficient, K is always utilized as a reference
(Samsuri et al., 2015). The effective partition coefficient represents the ratio of solute
concentration in the ice and liquid phase (Gu et al., 2008).
2.4 Progressive Freeze Concentration Exist Design
The PFC method had been studied since the 1960s. It has been demonstrated
by several studies that PFC can be used to concentrate the liquid solution (Matthews
and Coggeshall, 1959). Analysing the contaminants present in organic molecules is
necessary. Impurities may be concentrated even at low quantities using common
processes like distillation and extraction. These methods, however have certain
limitations (Matthews & Coggeshall, 1959).
14
In the conventional design of PFC system as is illustrated in Figure 2.4, which
includes a stainless-steel cylindrical sample vessel, a cooling bath, and a driving
system are all parts of the system. The stainless-steel sample vessel is slowly
submerged into the cooling bath. Additionally, the system has a propeller to mix the
solution, particularly at the ice solution interface, and an exterior hot wire heater to
regulate the level of the ice front of the sample solution, which rises from the bottom
of the sample vessel. To avoid supercooling and assist in the creation of crystal seed
for crystal development, a thin stainless-steel plate with tiny holes is integrated at the
bottom of the sample vessel (Liu et al., 1997).
Figure 2.4 Conventional design for PFC (Samsuri et al., 2015)
Progressive freeze concentration is a more cost-effective technology than

suspension freeze concentration. In comparison to the SFC method, the volume of ice
crystal produced in PFC is lower, but the purity is great. As a result, several researches
Figure 2.8: Tubular ice system for scale-up of PFC (Miyawaki et al., 2005)
have been conducted using diverse PFC designs in order to increase the efficiency of
PFC design and the quality of the end-product. Several types of PFC designs will be
explored inFigure
order 2.9: Conventional
to gain design forofPFC
a better knowledge PFC(Samsuri et al., 2015)
methodologies and to use this
study in the future. Several researchers have developed new designs by using this
conventional design as a guide. The existing designs will be evaluated and described
in the part that follows.
15
2.4.1 Tubular Ice System
Despite the fact that progressive freeze-concentration has been shown to be

successful for high-quality liquid food concentration, the productivity of this approach
using a vertical freezing system is significantly lower than the traditional suspension
crystallization method. Therefore, a tubular ice system was proposed (Shirai et al.,
1999). Coolant is used to cool the surface of the pipe for crystal formation in this
technique. An ice tube was created in a circulator flow for this type of PFC, with a
high purity of ice production. The system consisted of two straight pipes with a
diameter of 35.7 mm and a length of 4 m, as well as curved pipes at the top and bottom
(Samsuri et al., 2015). The solution was circulated inside the pipes using a pump. This
is for allow tubular ice to develop, the straight pipes were chilled from the outside
using coolant. cooling jackets were connected to straight pipes for efficient cooling
and curved pipes were insulated to reduce heat transmission to and from the
environment. Straight and curved pipes were joined and could be removed to remove
the tubular ice crystal that had formed (Samsuri et al., 2015).
In this study, ice seeding was done by adding pure water into the system. The
sample solution was precooled to near-freezing temperature before being introduced
into the tubular system. A tiny drain linked to a fine tube was built at the top of the
system due to the volume increase caused by the phase shift of water to ice. The
drainage capacity of this tiny tube was used to compute the volume of ice generated
(Samsuri et al., 2015). Figure 2.5 shows the schematic of tubular ice system for scale-
up of PFC (Miyawaki et al., 2005)
16
Figure 2.5 Tubular ice system for scale-up of PFC (Miyawaki et al., 2005)
2.4.2 Spiral Finned Crystallizer

Figure 2.10: Schematic diagram of spiral finned crystallizer (Samsuri et al., 2015)
A spiral finned crystallizer has been created and designed to improve the
performance of the
Figure 2.11: PFC process
Tubular by increasing
ice system theofsurface
for scale-up area whichetcan
PFC (Miyawaki al., impacts
2005) the
rate of heat transfer. The spiral finned crystallizer's development is quite similar to that
of the Vertical finned crystallizer (VFC), but the finned configuration is different. The
contact surface of the heat transfer will be increased by adding spiral fins to the
crystallizer. One of the ways to increase performance is to use a spiral fin based on the
Figure 2.6 below. The contact surface area increased by up to 106.67 percent using a
spiral fin (Samsuri et al., 2015). The spiral fin design was used in vertical circulation
to increase the heat transfer rate between the solution and the coolant and to create
turbulent flow from the inlet to the outlet. This is due to increasing the heat transfer by
improving the flow of the solution (Samsuri et al., 2015). Stainless steel was chosen
as design material because of its excellent resistance to corrosion by some solution
compositions (HANIM et al., 2016).
17
Figure 2.6 Schematic diagram of spiral finned crystallizer (Samsuri et al., 2015)
2.4.3 Vertical Finned Crystallizer

Figure 2.12: General schematic diagram of VFC a) side view and b) top view of VFC
(Amran et al., 2018)
The Vertical finned crystallizer (VFC) was created to improve the performance
of the PFC by increasing the heat transmission zone for the crystallisation process. The
Figure 2.13: Schematic diagram of spiral finned crystallizer (Samsuri et al., 2015)
body, fin, stand, lid, and cooling jacket are the five main components of the VFC. The
vertical finned crystallizer's general schematic is shown in Figure 2.7. During the
process, crystallisation took place inside the crystallizer's body which included the
treated fins, while a cooling jacket provided a space for circulating coolant to flow
around the body. The whole system of the new crystallizer (VFC) was composed of
stainless steel and was cylindrical in shape (Amran et al., 2018).
18
Figure 2.7 General schematic diagram of VFC a) side view and b) top view of
VFC (Amran et al., 2018)
2.5 Effective Partition Constant, K

Figure 2.8: Step by step procedure for RSM (Aydar, 2018)
Most of the time, the performance of a progressive freeze concentration system

Figure 2.14: Different types of contour plot of RSM generated from the quadratic
is determined
modelling by the effective
a) maximum partition
b) plateau, constant outside
c) maximum value (K).
the The exclusionregion,
experimental of solute
d)
minimum and e) saddle surface (Bezerra et al., 2008)Figure 2.15: Step
molecules from the moving ice front, the boundary between the ice and solution by step
procedure for RSM (Aydar, 2018)Figure 2.16: General schematic diagram of VFC a)
phases,
side viewis and
the mechanism of VFC
b) top view of concentration
(Amran et(LIU et al., 1997). The value of effective
al., 2018)
partition constant of a solute, K between the ice and liquid phase at the interface can
be calculated by using the Equation (2.1) below:
𝐶𝑆 (2.1)
𝐾=
𝐶𝐿
Where, 𝐶𝑆 is solute concentrations in ice phase while 𝐶𝐿 is solute concentrations in

liquid phases. K can also be calculated experimentally. The integration Equation (2.2)
will give if K is considered to be constant.
(1 − 𝐾 ) log( 𝑉𝐿 /𝑉𝑂 ) = log(𝐶𝑂/𝐶𝐿) (2.2)
19
where 𝑉𝐿 stand for volume of the liquid phase, 𝑉𝑂 stand for initial volume of the
solution, 𝐶𝐿 stand for concentration of solute in the liquid phase and 𝐶𝑂 stand for initial
solute concentration of solution.
2.6 Solute Recovery (Y)
The concentration of solutes in the liquid section of the crystallizer will grow
as the freezing process continues. Depending on the process circumstances, some of
the solutes may be trapped in the ice phase at the same time. As a result, the solute
recovery (Y), which reflects the quantity of solute recovered in the concentrated liquid
from the original solution, may also be used to determine for the process success
(Amran & Jusoh, 2016). The formula for solute recovery (Y) given by Equation (2.3)
below.
𝑀𝑠,𝐿 (2.3)
𝑌=
𝑀𝑠,𝑜
where 𝑀𝑠,𝐿 is the mass of solute in the concentrated liquid and 𝑀𝑠,𝑜 is the mass of
solute in the initial solution.
2.7 Factors Affecting Efficiency PFC System
The performance indicator for the efficiency of a progressive freeze

concentration system is always the effective partition constant. The efficiency is
indirectly proportional to the K value, which implies that if the K value decrease and
the efficiency will increase. According to various research, the lower the K value, the
higher purity the ice crystal created. However, additional factors such as coolant
temperature, stirrer speed, operation time and initial concentration have an impact on
the value of K.
20
2.7.1 Effect of Coolant Temperature
Coolant temperature is one of the most important factors in defining the

efficiency of freeze concentration process. The coolant temperature controls the
formation of ice crystals or the rate of front growth in the freeze concentration process
(Miyawaki et al., 2005). When the coolant temperature was set at lower temperatures,
a higher K value was produced, indicating reduced system efficiency. The ice crystal
front development rate is controlled by the coolant temperature, which increases as the
temperature differential between the entering solution and the surface temperatures
increases. When the coolant temp decreases, the ice front grows faster, resulting in a
low K for their system. More contaminants would be entrained in the ice as the ice
growth rate increased. As a result of the low growth rate, the ice generated is of
excellent purity. As a result, more solute is trapped in the ice and lowering the purity
of the ice produced. This phenomenon is undesirable in this system since it will raise
the value of K and lowering the efficiency of system (Yahya, 2017).
2.7.2 Effect of Stirrer Speed
Stirrer speed is also one of the methods that can be affect the performance of
the concentration system. Since solute inclusion in the ice phase is usual occur at lower
coolant temperatures, a high or appropriate stirrer speed is required to remove trapped
solutes from the crystal and get a highly purified ice and concentrated solution (Amran
& Jusoh, 2016). It's also been proved that a higher stirrer speed results in a layer of
highly pure ice crystals (Ramos et al., 2005). When the target liquid's stirrer speed rate
is sluggish, the content ratio of solute to ice crystals increases, resulting in high
contamination of solutes in the ice crystal produced, raising the value of K (Miyawaki,
2005). In theory, Increased solution flowrate supports higher heat transfer rate for ice
crystallization. The development of planar ice crystals from the cooling wall can be
stimulated under these conditions, therefore rejecting contaminants from the solid-
liquid interface. Furthermore, the trapped solute can be carried away from the ice's
dendrites structure and into the concentrated solution by strong shear force produced
21
at high flowrate. As a result, the concentrate concentration was increased, resulting in
a reduced K value and increase Y values (Amran & Jusoh, 2016).
2.7.3 Effect of Operation Time
In general, a longer operation time might improve the concentration efficiency

of PFC system (Amran et al., 2018). Furthermore, the longer the process is circulated,
the thicker the ice will grow and this will result in a more concentrated solution at the
end of the experiment (Noor, 2012). However, an excessively long operation time is
also bad. It is to reduce the retention time of the concentration process in the PFC
system because the more time spent encouraging the mass transfer of the solute, the
longer it takes to remove the water from the liquid phase. It is not desirable for a
process to take too long since the longer the PFC process takes, the higher the value of
K will be, indicating low system efficiency (Jusoh, 2014).
2.7.4 Effect of Initial Concentration
The solute concentration is changed while the stirrer speed coolant

temperature, and operation time remain unchanged. The system's impact is determined
by the K value. Based on the figure 1, It can be shown that greater initial concentrations
resulted in higher K, thus resulting in lower system efficiency, and vice versa (Jusoh
et al., 2008). Thus, this show that initial concentration of the solute in the solution
effect the efficiency of the system and K is dependent on it.
2.8 Design of Experiment and Optimization
The experimental design is important in many aspects of th e research and

development process. A component of the scientific method is to describe an
experiment with the administration of treatments to an experimental unit based on
22
measurement and multiple responses. As a result, in order to achieve the highest end
result and product quality, careful observation of the process and system performance
is required (Yahya, 2020). The first step in the optimization process is to develop and
design experiments which you must analyse the results. According to prior research,
the optimization method is widely employed in analytical chemistry procedures as a
function for identifying conditions that apply and achieving the greatest possible result
(Yahya, 2020). Optimization involves determining the settings for the important
process variables that result in the best obtainable set of operating conditions for the
process (Montgomery et al., 2021). The selected parameter condition would enable
analysing the response based on the interactions of various factors with one or more
response variables (Aydar, 2018).
Optimization in the analytical chemistry area is usually done by monitoring the

effect of one parameter on an experimental response at a time (Yahya, 2020). The
process of improving a system's performance in order to derive the greatest benefit
from it is known as optimization (Amran, 2015). Furthermore, the specific parameter
is maintained when just one parameter is altered. One-variable-at-a-time is the name
of the approach (Yahya, 2020). As a result, the approach has a drawback in that it
ignores interacting effects among other factors. As a result, the approach only yielded
an incomplete effect parameter on a specific response (Bezerra et al., 2008).
Despite this, response surface methodology (RSM) is the most often used and
relevant method of experimental design for optimization (Yahya, 2020). RSM is a
more efficient approach when compared to other instruments of technique for
determining the ideal parameters for numerous elements and specifying the ideal range
of parameters to get the right output or intended response for the specific process in
the system (Eng, 2013).
2.8.1 Response Surface Methodology (RSM)
The optimization process was carried out utilising a multivariate static

technique, with RSM being the most often utilised technique currently. RSM is thought
23
to be able to improve and overcome the disadvantages of previous techniques. RSM is
a mathematical and statistical collective approach for developing empirical models.
Essentially, the fundamental goal of each experiment is to maximise an output
variable, which is influenced by a number of independent factors (input variable). An
experiment series of test or called runs is investigated and proceed with different forms
of selecting in the RSM tools in order to find the response utilising the change of input
variable. STATISTICA and Design Expert are two typical software applications for
RSM techniques. The RSM step technique was handled as shown in Figure 2.8 in order
to find optimization without any measurement mistake. Furthermore, the adoption of
RSM aims to reduce the high cost of analytical methods. The smooth function of RSM
improves the convergence of optimization processes and allows for the employment
of derivative-based algorithms, reducing the influence of numerical noise in the
process (Aydar, 2018).
RSM is classified as a statistical approach since it combines a number of

mathematical and statistical techniques to provide a result based on the fit of an
empirical model and the organisation of experimental data using a factorial
relationship in an experimental design. As a result of the empirical model's fit, a linear
or square polynomial function will be generated to characterise and analyse the process
system's appropriateness. However, until the optimization is completed, we shall
investigate the model developed based on the experimental conditions. Originally,
RSM was developed by (Box & Draper, 1987) as model response and then converted
into the modelling of numerical experiments (Box & Draper, 1987). After generating
the fitness of a mathematical model, RSM became a graphical viewpoint. The response
surface plot, also known as a three-dimensional graph, and the two-dimensional graph,
also known as a contour plot, are two forms of visualised graphical in RSM.
The aim of visualised graphical is to evaluate the relationship structure between

the answer and the independent variables. Furthermore, response surface plots were
offered in three models which are first order, second order, and three-level fractional
factorial design model. A first-order model is defined as a linear function of
independent variables with low-order polynomial components describing a portion of
the response surface. Meanwhile, all quadratic terms plus all first order terms may be
24
used to create a second order model. When it comes to the curvature of the response
surface, the three-level factorial design is used. First order demonstrates lack of fit,
therefore identifying function curvatures and creating solutions is insufficient (Akçay
& Anagün, 2013). while for second order have the capability and potential to
demonstrate how to conduct quality characteristics of interest on a response surface
and to determine the finer parameter values. As a result, the second order model must
be used to compensate for the first order model's shortcomings. The three-level
factorial can then be used as an alternate strategy if the number of components grows
bigger. Although the three-level factorial design is successful because it allows
researchers to collect data on main effects and low-order interactions, it has a problem
when the number of variables is big since it becomes difficult to distinguish aliased
effects and determine their importance. As a result, the second order model is more
popular among researchers (Bradley, 2007).
The second order model is made up of many different forms of visualised

graphics that are represented on the response surface. As shown in Figure 2. 9, there
are maximum, minimum, ridge or saddle, and plateau. When the experimental factor
is less than three, the contour plot is more helpful, but when the factor is greater than
three, it is hard to visualise and analyse the surface (Bradley, 2007). Knowing the
topography of the response surface plot with maximum and minimum linear and
determining the area of best response of the process will help you understand the
finished RSM research. The purpose is to clearly determine the factor's lowest and
maximum values so that the process' reaction may be optimised.
25
Figure 2.8 Step by step procedure for RSM (Aydar, 2018)
modelling a) maximum b) plateau, c) maximum outside the experimental region, d)
minimum and e) saddle surface (Bezerra et al., 2008)Figure 2.18: Step by step
procedure for RSM (Aydar, 2018)
minimum and e) saddle surface (Bezerra et al., 2008)
Figure 2.8: Step by step procedure for RSM (Aydar, 2018)
minimum and e) saddle surface (Bezerra et al., 2008)Figure 2.20: Step by step
procedure for RSM
26 (Aydar, 2018)
Figure 2.9 Different types of contour plot of RSM generated from the quadratic
minimum and e) saddle surface (Bezerra et al., 2008)
2.8.2 Central Composite Design (CCD)

Figure 2.21: CCD for the optimization of (a) two variables and (b) three variables
(Amran, 2015)Figure 2.9: Different types of contour plot of RSM generated from the
quadratic modelling a) maximum b) plateau, c) maximum outside the experimental
region, The most often
d) minimum andused designsurface
e) saddle for estimating and
(Bezerra et fitting a second-order model for
al., 2008)
the response surface is called the central composite design (CCD) (Park et al., 2008).
Since Box and Wilson introduced this design, CCD is also known as Box-Wilson
Central Composite Design. CCD consists of factorial design (full or fractional), central
points and axial points (Amran, 2015). The distance between the design space's centre
and a star point is ±α if the distance between the centre and a factorial point is ±1 unit
for each factor. Because each factor is examined at five separate levels –α, -1, 0, +1,
27
+α in this design, the interactions between factors as well as quadratic effects
(curvature) are noted and quantified, making CCD a very effective statistical technique
(Lotfy, 2007). The precise value of relies on the design's preferred properties and the
involvement of the 73 experimental elements. The computation of and the
experimental number for CCD is shown in Equations (2.4) and (2.5) (Amran, 2015).
𝛼 = 2(𝑘−𝑝)/4 (2.4)
𝑁 = 𝑘 2 + 2𝑘 + 𝑐𝑝 (2.5)
where k is the factor number and c p are the replicate number of the central point. The
value of α for two, three and four variables are 1.41, 1.68 and 2.00 respectively. Figure
2.10 illustrates the graphical view of a full CCD for optimization of two and three
experimental variables (Amran, 2015), while Table 2.1 shows the coded values of the
experimental matrices for CCD of two variables.
Figure 2.10: CCD for the optimization of (a) two variables and (b) three variables
(Amran, 2015)
Figure 2.22: Flowchart of MethodologyFigure 2.23: CCD for the optimization of (a)
two variables and (b) three variables (Amran, 2015)
Figure 2.24: Flowchart of Methodology
Figure 2.25: Experimental Setup (Amran et al., 2018)Figure 2.26: Flowchart of

MethodologyFigure 2.27: CCD for the optimization of (a) two variables and (b) three
variables (Amran, 2015)
28
Figure 2.28: Flowchart of MethodologyFigure 2.29: CCD for the optimization of (a)
two variables and (b) three variables (Amran, 2015)
Table 2.1 Experimental matrices for CCD of two variables (Bezerra et al., 2008)
X1 X2
Factorial design -1 -1
+1 -1
-1 +1
+1 +1
Axial points -α 0
+α 0
0 -α
0 +α
Central points 0 0
2.8.3 Analysis of Variance (ANOVA)
Analysis of variance (ANOVA) is a statistical test for detecting differences in

group means when there is one parametric dependent variable and one or more
independent variables (Sawyer, 2009). ANOVA is a powerful technique that can carry
out variance analysis, test for equality of variances, and produce different plots. Using
ANOVA is the most trustworthy method to evaluate how well the model was fitted.
The main goal of an ANOVA is to contrast variation resulting from treatment (change
in the combination of variable levels) with variation resulting from random mistakes
that are a natural part of measuring the produced responses. The relevance of the
regression model used to predict answers may be assessed from this comparison taking
into account the causes of experimental variation (Samsuri, 2016).
ANOVA may be used to evaluate the importance of the second-order models.

The statistical significance of the second-order model equation is determined by the F-
value. The null hypothesis, which states that all of the regression coefficients are zero,
is often rejected when the computed F-value is higher than the tabulated F-value
(samsuri, 2016). The p-value and t-value are used to determine the importance of each
variable. More relevance is implied by the relevant variable with a smaller p-value or
a larger magnitude of t-value in the model (Samsuri, 2016). An ANOVA table is used
to display the ANOVA findings. There are columns in this table with the headings "SS
29
or Sum of Squares," "DF for degree of freedom," "MS for mean square," "F-value,"
and “F0.05” (Samsuri, 2016).
30
CHAPTER 3
RESEARCH METHODOLOGY
3.1 Introduction
The objective of this research is to investigate the effect of three operating

parameters on the freeze concentration of tomato juice by multi probe cryo-
concentration (MPCC) and to find the optimize operating condition for tomato juice
in FC. The MPCC was chosen as crystallizer in an attempt to create a more efficient
progressive freeze concentration method by increasing the heat transfer surface
available for crystallisation. The experiment was based on three parameters, which are
coolant temperature, operation time, and stirrer speed as the manipulated parameters.
The experiment was run by manipulating one operating conditions at one time while
others operating conditions will keep constant. Then, the experiment will go through
optimization through RSM technique and Design Expert software will be use in RSM.
This experiment will be conducted through:
(a) Varying the coolant temperature at a fixed initial concentration (1.5

ºbrix), operation time (30 min), and stirrer speed (300).
(b) Varying the operation time at a fixed initial concentration (1.5 ºbrix),
coolant temperature (-8 ºC), and stirrer speed (350 rpm).
(c) Varying the stirrer speed at a fixed initial concentration (1.5 ºbrix),
operation time (30 min), and coolant temperature (-8 ºC).
31
3.2 Flowchart of Methodology
For this study, there were nine stages that need to be done for the optimization
of the concentration of tomato juice by freeze concentration. The first stage is literature
review which the purpose for this to show the importance of optimizatio n for tomato
juice based by PFC. The next stage is problem statement that related to the freeze
concentration process and crystalliser fundamental design.
Experimental setup was done after problem statement by running the multiple
probe cryo-concentration. After that, experimental testing was preparing to ensure that
the crystalliser is able to form ice. But, if this stage is failing, some adjustment towards
the equipment shall be done such as motorized stirrer and cooling bath. If the ice
formation occurs, raw materials preparation for tomato juice.
Next, actual experimental testing was run to investigate the desired parameters
for coolant temperature, stirrer speed, and operation time. For optimization,
experiments was conducted according to a series of experimental arrangement called
a Design of Experiment (DOE) which provide by Design Expert software. The result
was used for optimization process by using 3D surface plot and mathematical model.
Then, optimum condition for operating parameters will be obtain to give. Figure 3.1
illustrates the flowchart of methodology in this study.
32
Figure 3.1 Flowchart of methodology
3.3 Research Set-up and Procedure
Materials and apparatus that involved in this experiment were 3 litre of tomato
juice as sample, ethylene glycol water-based as coolant. For apparatus involved in this
experiment were the cooling system (gas), solution tank, motorized stirrer, insulator, and
probe, refrigerated waterbath, UV-VIS spectrometer, and refractometer. Figure 3.2
shows the apparatus needed for the experiment and analysis for concentration tomato
juice as shown in Figures 3.3 and 3.4.
33
Figure 3.2 Set up for MPCC in the lab
Figure 3.3 Refractometer
Figure 3.4 UV-VIS spectrophotometer
34
3.3.1 Sample Preparation
For the materials in this research, tomato was used as concentration of fruit
juice. The tomato was purchased at nearby shop and then tomato juice was extracted
by the juicer in about 3 litres to be put in the target solution tank before being fed to
the crystalliser (Yahya et al., 2019). Next, the concentration of tomato juice was tested
using a refractometer and the concentration will be set at 1.5 ºbrix (Yahya et al., 2019).
3.3.2 Coolant Preparation
Ethylene glycol water-based solution was used as coolant in this experiment.

Ethylene glycol is frequently used in heat transfer procedures with a low temperature
range percentage (Amran, 2015). Table 3.1 displays the freezing point of ethylene
glycol as a percentage of water. To generate a proper freezing temperature for the
procedure, 50 % by volume of ethylene glycol and water will be use in this research.
Because the PFC process requires a supercooled solution to induce ice nucleation, the
coolant employed must be able to give sufficient cooling energy to the system.
According to Table 3.1, 50% volume of ethylene glycol and water solution would have
an extremely low freezing point and this will be allowing the solution to be
supercooled. Furthermore, the freezing point supplied by the chosen volume
percentage is thought to be capable of preventing the ethylene glycol-water solution
from becoming slushy (viscous).
Table 3.1: Freezing point of ethylene glycol at different volume percentage (Amran,
2015)
Ethylene glycol solution (volume %) Freezing point (ºC)

0 0
10 -3
20 -8
30 -16
40 -25
50 -37
60 -55
35
3.3.3 Total Phenolic Content (TPC) Determination
The Folin-Ciocalteu technique was used to determine the sample concentration

throughout the tests based on TPC (Yunusa et al., 2018). For each experimental run,
0.6 mL of tomato juice samples, representing 1 g of fresh weight of tomato sample,
concentrate, and thawed ice, are collected. With distilled water, 0.6 mL of samples
were diluted to a final amount of 25 mL (Safiei, 2016). The results were expressed as
mg gallic acid equivalents (GAE) per 1 g of material after using gallic acid to prepare
a standard calibration curve (mg GAE/g) (Mohd Rosli et al., 2022). Briefly, 1 mL of
tomato juice sample was mixed with 5 mL Folin-Ciocalteu reagent (10% (v/v)), and
left for 10 min at room temperature. Then, 4 ml of Na2CO3 was added and kept at a
temperature of 37 °C for 45 minutes in the dark. After 30 minutes, UV-Vis
spectrophotometry is used to calculate the sample's absorbance at 760 nm (Mini UV
1240, Shimadzu, Japan).
For each experimental run, 0.6 mL of tomato juice samples, representing 1 g

of fresh weight of tomato sample, concentrate, and thawed ice, were collected. With
distilled water, 0.6 mL of sample are diluted to a final amount of 25 mL.
3.3.4 Multiple Probe Cryo-Concentration (MPCC) Set-up
In this study, the new design called MPCC was used as apparatus for
progressive freeze concentration. Based on the Figure 3.5 shows the design with each
other part specification of MPCC (Mohd Rosli et al., 2022). The basic components of
the MPCC system are a number of probes, a cylindrical stainless-steel solution tank
with a 0.1 cm thickness, and a jacketed water-ethylene glycol solution for cooling
(cucumber). As a result, the solution in the tank can be kept at a temperature just below
freezing (at 2 °C). To prevent a shift in the ambient temperature toward the system,
polyurethane foam was employed as insulation on the tank's outermost surface layer.
The bottom of the tank had a motorized stirrer attached to it. 5 stainless steel hollow
probes were included in the kit and supplied with coolant gas inside the hollow part in
the probe (Mohd Rosli et al., 2022).
36
Figure 3.5 The design with each other part specification of MPCC (Mohd Rosli et
al., 2022)
The probe set was made to be able to rotate the probes 180 degrees apart at a
suitable speed, while the stirrer at the bottom of the tank had an adjustable speed range
of 200 to 400 rpm in order to maximize the formation of ice on the probe's outer surface
and ensure that the solution was thoroughly mixed. The set up for cryo concentration
is shown in Figure 3.6. In order to carry out the concentration process, a probe set was
installed at the top of the tank. This probe set has the ability to rotate at a 180-degree
angle in both directions, allowing for an appropriate distribution of the solution at the
interface while preventing solutes from becoming trapped in the ice that is produced.
When ice crystallization was carried out in the solution, refrigerant was delivered
through a copper tube to give chilling to the submerged probe (Rosdi et al., 2020).
37
Figure 3.6 The set up for probe cryo-concentration (Mohd Rosli et al., 2022)
3.3.5 Experimental Procedure
The experimental procedure is carried out as follows:
The initial concentration of tomato juice was prepared at desired concentration

(ºbrix). Two part of tomato juice was prepared, where the first part of tomato juice is
cooled at a temperature near the freezing point of pure water (2 °C), while the second
part was frozen to form tomato juice cubes. Prior to be feed into the crystallizer for
concentration purpose, the tomato juice cubes were mixed together with the cooled
tomato juice solution in a feed tank to maintain the low temperature during feeding
process. Switch on the water bath that contain 50% by volume of ethylene glycol and
distilled water to reach the desired coolant temperature. When the coolant temperature
reaches desired temperature, the tomato was feed into the tank at volume 0f 3000 ml
(Rosdi et al., 2020). To keep the juice at 2 C, ethylene glycol-water coolant was
subsequently injected into the jacketed wall of the solution tank. Next, the probe set of
MPCC was submerged in the solution and rotated at an angle of 180 degrees. However,
to maximise the production of ice on the probes' outer surfaces and to create a well-
mixed solution, the stirrer speed was set at between 200 and 450 rpm (Yahya, 2020).
After that, the refrigerant was adjusted to the required value, which was a temperature
range of -14 to -6 C. When the cooling is sufficient, ice crystals will begin to form on
the probes' exterior surfaces and the tank will be left with concentrated tomato juice.
38
By adjusting the cooling rate, stirrer speed, duration, and beginning concentration of
the juice solution, the experiments were conducted under the appropriate operating
conditions. Eventually, the coating of ice crystal was thawed and the concentrated
tomato solution was collected as shown in Figure 3.7 and Figure 3.8 below.
Figure 3.7 Ice formed at probe's wall
After certain period, stop the operation and motorized stirrer and tomato juice
was collect from tank and ice formed on the probe. Before collecting samples, the
volume of ice layer forming and concentrate was measured for analysis purpose. Next,
the collecting sample of ice and concentrate for their tomato juice concentration were
analysed by using a refractometer and UV-VIS spectrophotometer. A summary of the
PFC work and for consistent findings, the experiment was carried out two times.
Figure 3.8 Concentrated tomato juice collected from cylindrical tank after freeze
concentration
39
During this experiment, three operating parameters include coolant
temperature, stirrer speed and operation time, were tested in the range between -6 to -
14°C, 200 to 400 rpm, and 20 - 60 minutes. Experiments were conducted out for varied
values of operation time, coolant temperature, and stirrer speed during the efficiency
research where the influence of operational parameters is analysed. While one
parameter is change, the other two remained unchanged. The parameters along with
their range of investigation applied in the experiments are presented in Table 3.2.
Table 3.2 Range for parameters in this research
Parameter Range
Coolant Temperature -6 to -14°C
Stirrer Speed 200 - 400 rpm
Operation Time 40 - 60 minutes
3.4 Effect of Operating Conditions on Performance PFC
As we know in this research, there are three parameters will be investigating

that affect the performance of FC system. The effect of the three operating parameters
which are operation time, coolant temperature and stirrer speed was observed based
on the responses/trends of the effective partition constant (K). One parameter needs to
be varied while other two will keep constant to get the response of K for each
experiment. The summary of varied and constant parameters is shown in Table 3.3
below.
40
Table 3.3 Value of varied and constant parameter
Value of constant parameter

Constant Coolant Initial
Operation Stirrer
temperature concentration
varied time (min) speed (rpm)
(ºC) (ºbrix)
-6
-8
Coolant
-10
temperature - 30 350 1.5
-12
-14
20
30
Operation
40
time -8 - 350 1.5
50
60
200
250
Stirrer speed 300
-8 30 - 1.5
350
400
3.4.1 Coolant Temperature Test
Based on (Miyawaki et al., 2005), The lower the coolant temperature, the better
the heat transfer from the crystallizer wall to the coolant which is necessary for
crystallisation to happen. This is one of three characteristics that contribute to the
system's performance when the temperature varies from -6 to -14 ºC (Samsuri et al.,
2015). The coolant temperature was adjusted at an intermediate point in order to
manage ice development at a sufficient and best rate, resulting in a high-performance
system with high purity of ice crystal formation. The coolant temperature was varied
while the other three parameters were kept constant in this part for coolant temperature
test (Safiei et al., 2016).
41
3.4.2 Stirrer Speed Test
200 to 400 rpm stirrer speeds were used to cause the solution to move (Liu et
al., 1999) as tabulated in Table 3.3. According to earlier study, the formation of a pure
ice layer and the likelihood of protein breakdown are both influenced by stirrer speed.
The other two parameters include operation time at 30 minutes and probe temperature
at -8 °C, were held constant for the purpose of examining the impact of stirrer speed.
Analysis of the yield of the finished tomato juice solution was made possible by the
study on the impacts of stirrer speed (Yahya, 2020).
3.4.3 Operation Time Test
Knowing the appropriate time for an experimental run can help a PFC process
achieve its best performance. The operation time was altered from 40 to 60 minutes in
this study, whereas the constant value of operation time for the other three operational
parameters is set at 30 minutes. With suitable operation time can produce lowest value
of K which is shows the best efficiency for experiment.
3.5 Efficiency Assessment
The effectiveness of the PFC process was assessed using the crucial parameter
which is the effective partition constant, K (Miyawaki et al., 2005). The response/trend
of these determinant parameters to changes in the three operational parameters
investigated in the study was notice. The sections that follow give further details on
how the K values for this investigation will be calculate.
42
3.5.1 Effective partition constant, K
The efficiency of the PFC system was evaluated based on the value of effective
partition constant, K as defined by the previous Equation (2.2) in Chapter 2.
𝐾 = 𝐶𝑆/𝐶𝐿 (3.1)
where, CS and CL are the concentration of total phenolic content in the ice and
concentrate of tomato juice, respectively. In this study, the data obtained from the
experiment were used to calculate the value of K by using an Equation (3.2) shown
below.
(1 − 𝐾 ) log( 𝑉𝐿 /𝑉𝑂 ) = log(𝐶𝑂/𝐶𝐿) (3.2)
where Co, Vo and VL are the initial tomato juice concentration in the solution, initial
volume of the solution and volume of concentrate, respectively. The values of C L and
CO is calculate using Equation (3.2) and the concentrations of phenolic content in the
concentrate and starting solution which are measured using a UV-VIS
spectrophotometer after the experiment. Based on the research, that a lower value of
K is preferred in the PFC process since it indicates a greater separation efficiency of
the system. To put it another way, the quantity 𝐶𝑆 in Equation (3.1), which denotes the
solute concentration in the ice phase (ice purity), should be as low as feasible. As a
result, the method will result in improved ice purity and a solute increase in the
concentrate.
3.6 Optimization Process
The Design Expert software for Response Surface Methodology (RSM) was
used in this study to find the best parameters for tomato juice concentration and to
improve the process's operating conditions. The trend of the effect of operating
conditions may be seen in the performance research. The optimum performance of the
system may also be determined by knowing the value of each parameter. The
43
experiment from this study, on the other hand, is based on one element at a time
(Samsuri, 2016). Only one parameter is changed, while the others stay the same. As a
result, the interaction of other parameters is hidden. As a result, the optimization will
be carried out using RSM's central composite design (CCD) (Samsuri, 2016). The
CCD experiment was constructed based on the arrangement of combined components
at five separate levels, allowing for a more precise prediction of the optimal value.
In this study, the effect of three independent variables (coolant temperature,

stirrer speed, and operation time) on the determinant parameters or response variables,
K was investigated. The goals of RSM were to quantify the relationship between the
values of certain measurable response variables and the values of a set of experimental
factors thought to influence the responses and to determine the values of the factors
that yield the optimal value or values of the responses (Samsuri, 2016). Concentration
study was done using a refractometer to evaluate changes in tomato juice concentration
dependent on sugar brix in the PFC process. The steps of RSM as an optimization
process are depicted in Figure 3.9 (Amran, 2015).
Figure 3.9 Steps in RSM (Amran, 2015)
44
3.6.1 Design of Experiment (DOE)
CCD was used to investigate the interactions between variables and predict the
best process conditions for the PFC process. In this study, DOE was carried out using
CCD which is a common class of second order designs that is more adaptable than
other designs (Langhans, 2000). Table 3.4 shows the range and coding level of the
PFC process variables. Coolant temperature (X1), operation time (X2) and stirrer speed
(X3) were the three variables. Each variable is divided into three levels: low (-1),
medium (0), and high (+1) (Samsuri et al., 2018). The central composite design (CCD)
was used to perform the extreme measures and presented by –α and +α (Safiei, 2016).
In addition, CCD requires five levels if α≠1, for lower limit, low, centre, high and
upper limit which are coded as -α, -1. 0. +1 and +α which are shown in Table 3.4
(Yahya, 2020).
Table 3.4 Experimental range and coded value of variables
Range and levels

Variable Symbol
-α -1 0 1 +α
Coolant
Temperature, X1 -14.0 -12. 4 -10.0 -7.6 -6.0
(°C)
Stirrer speed,
X2 250.0 290.5 350.0 409.5 450.0
(rpm)
Operation
time, X3 20.0 28.1 40.0 52.0 60.0
(minutes)
Based on the chosen range of each independent variable, a three-factor CCD

of RSM experiment was used to construct the table. Before the optimization of PFC
system is carried out, 17 runs must be performed. Following the completion of the
procedure, the data with two responses was analysed, and the last 18 runs was run
based on the determined ideal parameter. The last section is run to make sure the ideal
settings may produce satisfactory results for both answers (Yahya, 2020). The order
of the tests is depicted in Table 3.5.
45
Table 3.5 Arrangement of experiment using central CCD
Manipulated variables
Run Coolant Operation time, Stirrer speed, Response, K
temperatures, X1 X2 X3
1 -12.4 28.1 290.5 -
2 -7.62 52.0 409.5 -
3 -10.0 20.0 350.0 -
4 -10.0 40.0 350.0 -
5 -12.4 28.1 409.5 -
6 -7.6 28.1 409.5 -
7 -10.0 40.0 250.0 -
8 -12.4 52.0 290.5 -
9 -10.0 40.0 450.0 -
10 -10.0 60.0 350.0 -
11 -12.4 52.0 409.5 -
12 -7.6 52.0 290.5 -
13 -6.0 40.0 350.0 -
14 -14.0 40.0 350.0 -
15 -10.0 40.0 350.0 -
16 -7.6 28.1 290.5 -
17 -10.0 40.0 350.0 -
3.6.2 Model Generated
The second polynomial model equation for three independent variables was
used to generate the regression model. The complexity and quantity of the influences
determine the order model. Equation (3.3) was used to determine a predicted response
when the chosen parameters are substituted into the final model (Amran, 2015).
𝑌 = 𝛽0 + 𝛽1 𝑋1 + 𝛽2 𝑋2 + 𝛽3 𝑋3 + 𝛽4 𝑋4 + 𝛽12 𝑋1 𝑋2 + 𝛽13 𝑋1 𝑋3 + 𝛽14 𝑋1 𝑋4

+ 𝛽23 𝑋2 𝑋3 + 𝛽24 𝑋2 𝑋4 + 𝛽34 𝑋3 𝑋4 + 𝛽11 𝑋1 2 + 𝛽22 𝑋2 2
+ 𝛽33 𝑋3 2 + 𝛽44 𝑋4 2 (3.3)
46
where Y is the predicted response of K-value and Y, βo is the regression coefficient at
centre point, β1, β2, and β3 are linear coefficient; β12, β13, and β23, are second order
interaction coefficients and β11, β22, β33 and β44 are quadratic coefficients.
Meanwhile, X1, X2, X3 and X4 are the factors influential in the process as mentioned
in Table 3.5.
3.6.3 Analysis of Variance (ANOVA)
Analysis of variance (ANOVA) was used to determine whether the empirical

mathematical model is significant (Mohd Rosli et al., 2022). To put it another way,
they assist you in determining whether you should reject the null hypothesis or accept
the alternate hypothesis (Kenton, 2022). The ANOVA method used to determine the
significance of second-order models. The F-value was used to estimate the statistical
significance of the second order model equation. Based on the Table 3.6 demonstrates
how multiple regressions were used in this study's analysis of variance (ANOVA) to
fit the mathematical model to the experimental data set (Amran, 2015). N refers to the
number of experiments, while P represents the number of terms in the model or
equation. On the other hand, sum of square regression (SS reg) is created from the
disparity between the residual (SSres) and the total sum of square (SStotal).
Table 3.6 ANOVA table (Amran, 2015)
Source of Sum of square Degree of Mean square F-value

variation freedom (MS)
Regression SS regression P-1 (SSreg)/(P-1) F=MSreg/MSres
(SSR) (SSreg)
Residual SS residue N-P (SSres)/(N-P)
(SSres)
Total (SST) (SStotal) N-1=(P-1)
+(N-P)-N-1
From the Table 3.6, the significance of regression (F-value) was evaluate by
the ratio between the mean square of regression (MSreg) and the mean square of
residuals (MSres). This ratio shows how accurately the components account for the
47
statistical variance (Samsuri, 2016). The Fisher distribution (F-test) approach was then
used to compare the variation sources. The statistically significant value for the ratio
must be greater than the tabulated value for F in order to show that the mathematical
model fits the experimental data effectively. Additionally, the model's applicability
may be checked using the coefficient of determination (R-squared) which measures
how well the model captures the true relationship between the components under
analysis. If the value of R2 is near 1 that shows the model in real situation well (Keshani
et al., 2010).
To reject the null hypothesis, when all the regression coefficients are zero, the
computed F-value should be bigger than the tabulated F-value. The ratio between mean
of square regression (MSSSR) and mean of square residual (MSSSE), where MSSSR and
MSSSE are determined by dividing sum of squares (SSR) and sum of residual (SSE) by
degree of freedom (DF), respectively, yields the estimated F-value. For regression and
residual, tabulated F-values are derived from F distributions based on DF at a particular
level of significance, which is indicated as α-value.
3.6.4 Determination of Optimal Condition
To understand the interactions of the factors tested and to identify the critical
point for the anticipated model as maximum, minimum, or saddle, a response surface
and two-dimensional plots (contour plots) was constructed. Minimum point
coordinates are considering the optimal values for K response, because the goal of this
study is to have the lowest K response. Exact optimum values are generated from
critical points in the software based on the Table 3.7. Finally, an experiment was run
under the projected optimal condition, using the K value as the major response
parameters, to test the optimization findings as shown in Table 3.8.
48
Table 3.7 Predicted analysis of optimum condition for K
Parameters Observed Critical values Observed

minimum maximum
Coolant - - -
temperature, (°C)
Operation time, - - -
(min)
Stirrer Speed - - -
(rpm)
Table 3.8 Optimum values of process parameters in validation experiment
Response Coolant Operation Stirrer Predicted validation

temperature, time, X2 speed, X3
X1
K - - - - -
Plotting the response surface is the primary analytical step following regression
analysis (model adequacy check) and ANOVA. The effect in a 2k factorial design can
be readily converted into a regression model and used to forecast the response surface
at any moment. The response and the independent variables (X1, X2, and X3) have
been plotted on a three-dimensional response surface on the Y-axis and the interaction
between the independent variables has been plotted on the Z-axis with several
permutations for each representing. There were three forms of graphing available
include horizontal axis, perpendicular axis, and vertical axis. Only two-factorial can
be presented at a time with a single response. In the ideal situation, the second -order
model explains the response surface to allow for a more extensive analysis (Yahya,
2020). The second order also illustrates the wide variety of shapes of response surface
such as maximum, minimum, plane, ridge, saddle, bowl, bell and cradle.
49
CHAPTER 4
RESULT AND DISCUSSION
4.1 Introduction
In this experiment, the outcome presented in this chapter was based on the
objectives and parameters of the suggested study. The coolant temperature, rotation
time, rotation speed, and beginning concentration are the three key variables in
progressive freeze concentration. However, the purpose of this study was to predict,
using just two factors, the experimental values of the effective partition constant (K)
of a MPCC system. This chapter contains every justification and explanation possible
to support up the results of the PFC process by using MPCC crystallizer. In addition,
the response analyses for this study are reviewed in light of the findings from
refractometer and UV-vis data, and their interpretation is based on the determination
of effective partition constants (K) for each operational parameter to enable monitoring
of the process performance.
The result for optimization of tomato juice by PFC process are shown in this
chapter to analyse the optimum value of 3 parameters including coolant temperature,
operation time and stirrer speed. RSM was used to determine the best value for each
operational parameter that would produce the best value for the effective partition
constant (K) as well as to create a regression model that could mathematically describe
the process parameters.
In this section, the experimental result for effect of parameter on partition

constant, K and optimization process are shown for efficiency of PFC system.
Efficiency of PFC system will be analysed based on the trend between operating
conditions and effective partition constant, K. Then, critical values will be generated
based on the interactions between three operating conditions in this PFC system. From
that, the exact optimum values will be test and validate the result.
50
4.2 Analysis of Performance of PFC System
As we know the, highest PFC performance can be obtained at the optimum

operating condition. From previous reading show that the numbers of operating
conditions that appears to affect the performance of FC. In this study, performance of
FC system can be evaluated through effective partition constant (K) based on the three
operating conditions including coolant temperature, operation time, and stirrer speed.
In this analysis, tomato juice is the target solution. Figure 4.1 shows the comparison
between final, initial and ice concentration in the experiment.
Figure 4.1 Comparison between final concentration, initial concentration and ice
concentration
4.3 Effect of Coolant Temperature on PFC System
Because removing the water content from the solution requires cooling, the
effect of coolant temperature during the freeze concentration process was a crucial
element that required discussion. For this parameter, all three of the other operational
parameters which are operation time, stirrer speed, and initial concentration were
maintained constant at 30 minutes, 300 rpm, and 1.5 ºbrix, respectively, to allow for
the evaluation of the impact of coolant temperature on the process's performance.
Based on the Figure 4.2 shows the result for K-values at different coolant temperatures.
51
Figure 4.2 Changes of TPC increment and effective partition constant, K with
Coolant Temperature
Based on the graph, it can be shown that from a coolant temperature of -6 °C

to -10 °C, the value of K decreases. But these trends of K values changed from -10 °C
to -14 °C, where the value of K begins to increase. This phenomenon demonstrates
that the process's maximum efficiency was achieved at a coolant temperature of -10
°C, where the lowest K value of 0.307 was measured. Since the concentration of the
solute in the ice that is generated is lower than that in the liquid that is formed, the PFC
process through the MPCC system performed most effectively and completely at a
temperature of -10 C based on the lowest K-value.
Coolant temperature is a crucial factor that has a significant impact on the PFC
system as it influences the rate of ice front growth and the creation of ice crystals. At
temperature -6˚C to -10˚C, shows the K values decrease due to the decreasing
temperature of probe in the tomato solution. Lower coolant temperature produces
larger size of ice crystal formed (Rosdi et al., 2020). However, a too low coolant
temperature will cause the ice growth rate per unit time increase. Then, when there is
a significant temperature difference between the probes where the coolant gas is
channelled and the solution entering them, the rate of ice development is accelerated.
This circumstance will make it more likely that the solute will become stuck in the ice
front's outward motion (Rosdi et al., 2020). This will result the PFC system will not
perform well since the effective partition constant K will be high. This justification
demonstrates why the K value spiked when the temperature approached -12 to -14 °C.
52
Low temperature of the coolant could improve heat transfer within the probe
wall and the coolant for the concentration process through ice crystallisation. Or, to
put it another way, low surface temperatures might offer the initial supercooling that
is required for ice nucleation (Amran, 2015). This situation demonstrates the increase
in process efficiency by explaining in detail the decrease in K value when the coolant
temperature declined from -6 °C to -10 °C. According to this data, the process was
most effective at -10 °C, where the most solute was also recovered.
However, lowering the coolant temperature further more can result in the ice
crystal's inclusion of solutes (Jusoh et al., 2008). Ice formation rate increased as the
temperature differential between the crystallizer wall and the entering solution
increased (Flesland, 1995). A part of the solute may become trapped inside the ice
crystal created if the crystal development rate is higher than the solute's outward
movement under certain circumstances. The best explanation for this case is that the
solute's inability to overcome the rate of ice crystal formation. As a result of the solute
contamination, the quality of the ice generated decreases.
4.4 Effect of Stirrer Speed on PFC System
In this experiment, based on (Yahya, 2020) The screening procedure continued

at a speed of 200 rpm until the first layer of ice formed on the probe's surface. For the
maximum stirrer speed was set at 400 rpm was made in due to the fact that the
thickness of the ice decreased below the speed screened. The range of stirrer speed is
employed between 200, 250, 300, 350, 400 rpm with constant operation time, coolant
temperature, and initial concentration were maintained at 30 minutes, -8 °C, and 1.5
ºbrix respectively. Figure 4.3 shows the findings of the variations in K values at various
stirrer speed.
53
Figure 4.3 Changes of effective partition constant, K and TPC Increment (%)
From the graph shows, K-value was found to be higher at 200 rpm and slightly
decreased when the stirrer speed was increased to 250 rpm with K-value 0.383 which
shows the highest efficiency of the system in this study. Then, K value increased back
at 300 rpm. This case happened as a result of a decrease in the driving force needed to
remove the solute from the ice crystal layer and a tendency for the ice p hase to
accumulate more solute than the liquid phase (Gunathilake et al., 2014). Additionally,
at that temperature, the solute is heavily accumulated at the ice-liquid interface causing
a higher concentration of solute in the ice formed and necessitating swift washing from
stirrer speed in order to avoid poor separation as a result of the low purity of the ice
produced (Robles et al., 2016). Stirrer speed that is too high would wash away the ice
and increase the amount of solute in the liquid phase (Moreno et al., 2015)
A stirrer was specifically utilised in this study to thoroughly combine the

solutes in the target solution which afterwards might improve the production of highly
concentrated concentrate and highly purified ice. In general, a higher stirrer speed
resulted in a higher separation efficiency. If a higher stirrer speed is used, a faster
mixing rate can promote mass transfer at the interface, which indicates that the solute
will be distributed evenly in the solution. As a result, there might be less solute trapped
inside the ice. The amount of solute and contaminants at the solid-liquid interface can
be decreased with proper mixing, resulting in less solute being transported into the ice
(Moreno et al., 2015). The decrease in K value when the stirrer speed rose from 200
to 250 rpm may be plainly explained by this situation. It also demonstrates that a large
54
amount of solute was recovered in the concentrate when the amount of trapped solute
in the ice was low at a higher shaking speed.
A stirrer was utilised in this study specifically to evenly distribute and blend
the solutes in the target solution, which afterwards might improve the manufacture of
highly concentrated concentrate and highly purified ice. In general, a higher stirrer
speed led to a higher separation efficiency. The solute will be dispersed evenly
throughout the solution if a higher stirrer speed is used because it can stimulate mass
transfer at the interface. As a result, the quantity of solute trapped in the ice could be
decreased. Therefore, less solute will be transferred into the ice, proper mixing helps
to lower the amount of solute and contaminants at the solid-liquid interface. This
occurrence provides a clear explanation for both the drop in K value and the rise in Y
value as the shaking speed was raised from 200 to 250 rpm. It also demonstrates that
a large amount of solute was recovered in the concentrate when the amount of trapped
solute in the ice was low at a higher stirrer speed.
However, further increase of the stirrer speed had caused a decrease in

separation efficiency portrayed by higher value of K. The volume of ice formed when
the stirrer speed was increased decreased, which is the cause of this outcome. The
reduction in ice volume produced when the stirrer speed was increased can be
explained with this result. Although adding a stirrer to the system could improve the
solute distribution in the solution, excessively fast mixing could prevent ice from
forming on the crystallizer's wall. The greatest explanation for this condition is that
the slushy shape in which the front growth of the ice is growing makes it ea sily
washable away or eroded from the stiff ice layer by the vigorous speed.
4.5 Effect of Operation Time on PFC System
Using a similar process, the impact of operation time on the efficiency of this
technique is examined. The range for operation time uses in this analysis is between
20 to 60 minutes. The remaining operational parameters are kept constant at -8 °C for
the coolant temperature, 350 rpm for the stirrer speed, and 1.5 ºbrix for the initial
55
concentration. As previously noted, the value of the effective partition constant (K)
and represent the performance of the VFC in this research. Theoretically, Longer
operation times could boost the PFC process's concentration efficiency (Rosdi et al.,
2020). Figure 4.3 shows the changes in K values at different operation time.
Figure 4.4 Changes of effective partition constant, K and TPC Increment (%)
Based in Figure 4.4 shows the change on K value at different operation time.
Based on the graph, it can be seen that the K value decreases from 20 to 40 minutes of
operation times. However, after 50 minutes of operation, the trend changed and the K
value began to rise. The increased K-value was caused by the impurity of the ice which
grew with increasing concentration over time. For 20 minutes was not enough time for
the freezing process to produce complete ice layer creation during the first period and
the ice fraction had an impact (Moreno et al., 2015). Due to an incomplete freezing
process, this situation would be regarded as an unstable state for the solid ice phase.
Then, the best K-value obtained from the graph at 40 minutes among the
various operating times which is 0.201. The mass and heat transfer of the process was
at an equilibrium phase at the time which corresponds to the solute inclusion limitation,
and thus caused the initial concentration to evolve (Yahya, 2020). The steady state of
ice growth on the probe’s cold surface and fraction of solute must be balanced by
diffusion of solute away from the interface into the bulk of solution (Flesland, 1995).
The ice crystal lattice typically rejects solute because of their excessive molecular size
when crystallised ice first appears and begins to expand (John et al., 2019). the
56
impurities are expelled to build up pure ice crystal lattice (Nakagawa et al., 2010).
However, after 40 minutes the value for k is increased over the time. At 50 and 60
minutes, the graph shows K value are 0.215 and 0.219. this situation happens because
solute was lost more in the ice than in the liquid phase.
In general, a longer operation time could give the PFC process a higher
concentration efficiency. When the freezing process began, the generated ice layer had
a low degree of crystallinity due to the presence of dendrites. By allowing for more
time for operation, the ice layer thickens and leaving the unfrozen solution in a
condition that is getting close to saturation. in another way, the procedure needs
enough time to obtain the high concentration of the unfrozen fluid which is
concentrated (Amran, 2015).
However, excessive operation time may cause the saturation of the solute in
the concentrate to change the trend of solute concentration in the ice. This situation
can be explained by the development of ice layers that have almost completely taken
over the crystallizer's interior area, especially after 40 minutes of concentration.
Hence, high number of solutes in the concentrate can easily be trapped into the ice
layers if the concentration process continued, thus lowering the amount of solute
recovered in the concentrate as well as process efficiency.
4.6 Optimization of Tomato Juice by Response Surface Methodology (RSM)
In this research, central composite design (CCD) by RSM was used as a method
to determine the optimum conditions by predict the suitable value for effective
partition constant (K). RSM was applied to find the optimum values for the three
operating conditions include coolant temperature, stirrer speed and operation time by
using multiple probe cryo-concentration (MPCC) system. The suitable range for each
process parameters has been yielded by the investigation the effect of parameters done
by previous subtopic which are -8 to -14 °C for coolant temperature, 250 to 450 rpm
for stirrer speed, 20 to 60 minutes for operation time.
57
Central Composite Design was used in this experiment to conduct
experimental design in order to collect sufficient data for the subsequent optimization
phase (Samsuri, 2016). RSM was used to generate regression model that would
mathematically describe the process variables the best and to predict the ideal value
for each operating parameter that would produce the best value for the effective
partition constant (K). ANOVA was used to evaluate the model whether the equation
is significant or not. Then, optimum values will be generated from the critical points
by the software and one experiment will be conducted to validation value of K.
4.6.1 Design of Experiment by Central Composite Design
The effective partition constant (K), which represents the degree of solute
separation that may be completed by the process is typically used to assess the
efficiency of a PFC process. A lower K value means a greater separation efficiency.
Choosing the range of variables based on the minimum and maximum value, as well
as the middle and extreme values, was the first step in the RSM process. Design of
experiment (DOE) was the procedure used to determine the appropriate experimental
value to be used in the experimental section. From the DOE the combinations of three
parameters will be generated as shown in Table 4.1. Table 4.1 shows the experimental
values of K for each run.
58
Table 4.1 Experimental result of K value for Design of Experiment
Run Manipulated variables Response, K

Coolant Operation time, Stirrer speed,
temperatures, X1 X2 X3
1 -12.40 28.10 290.50 0.38
2 -7.62 52.00 409.50 0.33
3 -10.00 20.00 350.00 0.35
4 -10.00 40.00 350.00 0.24
5 -12.40 28.10 409.50 0.38
6 -7.60 28.10 409.50 0.23
7 -10.00 40.00 250.00 0.17
8 -12.40 52.00 290.50 0.35
9 -10.00 40.00 450.00 0.34
10 -10.00 60.00 350.00 0.33
11 -12.40 52.00 409.50 0.27
12 -7.60 52.00 290.50 0.35
13 -6.00 40.00 350.00 0.38
14 -14.00 40.00 350.00 0.38
15 -10.00 40.00 350.00 0.24
16 -7.60 28.10 290.50 0.33
17 -10.00 40.00 350.00 0.25
Based on the Equation (4.1) in Chapter 3 presents a second order polynomial

model that was used to correlate the response of K value with the three parameters
under investigation. A regression analysis was used to determine the importance of
each parameter. Equation (4.1) presents a regression equation for K as a function of
the three variables (X 1, X2, X3) and their interaction utilising linear and quadratic
regression coefficients followed by second order interaction coefficients.
Y = 1.18977 + 0.13100𝑋1 − 0.00786 𝑋2 − 0.00096𝑋3 + 0.00114𝑋1 𝑋2

− 3.53553𝑋1 𝑋3 + 3.16083 × 10−19 𝑋2 𝑋3 + 0.00845𝑋1 2
+ 0.00024𝑋2 2 + 1.01258 × 10−6 𝑋3 2
(4.1)
59
Where X1, X2, and X3 are independent variables or factors that have an impact on K-
value, and Y is the predicted response (K-value). One-factor coefficients show the
specific factor or linear coefficient interaction, two-factor coefficients show the
quadratic influence of the factor, and three-factor coefficients show the interaction
effect of those three factors. In contrast, the constant is the coefficient without the
factor. The greatest order of polynomials that provide a significant model for the
response K-value as a function of each variable and are not aliased were used to derive
the regression models (Yahya, 2020).
The synergistic impact is represented by the positive sign in front of these four
phrases, and the antagonistic effect is represented by the negative sign (Samsuri,
2016). The highest order of polynomials that provide a significant model for the
response K-value as a function of each variable and are not aliased were used to derive
the regression models (Jusoh, 2010). The effects of each individual factor are shown
by the coefficients with one factor for coolant temperature, operating time, and stirrer
speed. The coefficients with two factors show the interaction between the two
components, while others with second order terms reveal the quadratic effect.
4.6.2 Model Adequacy Check (ANOVA)
A model evaluation based on a number of model verification criteria has been

conducted in order to make sure that the produced mathematical model could give a
suitable approximation of the genuine response surface. The model can provide an
accurate representation of the real result and trend of performance in the MPCC
system; thus, the model adequacy check is an essential thing need to do for
optimization analysis discussion. In order to assess the significance or suf ficiency of
each combination of variables relying on the K-value, the experimental data as well as
the effects of each interaction of variables were examined.
Based on the data gathered from the experiments at the Table 4.1, the Design
Expert software created the regression model shown in Equation (4.1). The effects of
interaction between each factor were then examined to determine the significance or
60
acceptability of each combination of variables using the K-value. When analyzing the
data from a DOE, the results of numerous trials in terms of an empirical model would
be helpful. Additionally, it offers recommendations for the validity and reliability of
the findings which can be used to demonstrate that the tests were likely to contain
errors or to provide a degree of confidence to a statement.
The first thing to check in this study is the value of R2 which serve for
evaluating the accuracy of the produced model. The R-squared or R2 is a significant
criterion that was initially assessed in connection to the model's dominance and
suitability in order to calculate the regression coefficient and gauge the strength of the
linear relationship. The nearer the R2 number is to 1.0, the more accurately the response
may be anticipated by the model (Myers and Well, 2003).
In this MPCC system, the value of R2 for the regression model is 0.71. This
shows that the experimental variables under study explain s for 71% of the entire
variation in K and for balance 29% indicates for total variation that not explain ed by
the model. For equation 6.1, the R2 of 0.71 is regarded as moderate to justify the fit,
which could result in significant variation in the K predicted from this model. The R2
is still acceptable since it greater than 0.7. The R-Squared above 0.7 would generally
be seen as showing a high level of correlation7 would generally be seen as showing a
high level of correlation (Fernando, 2022). Based on the Table 4.2 show the predicted
value for response K in each run of the experiment using the regression model and
illustrated by graph as shown in Figure 4.5 and Figure 4.6.
61
Table 4.2 The experimental, predicted and residuals for Response K
Run Experimental Predicted Residuals
1 0.38 0.36 0.02

2 0.33 0.35 -0.02
3 0.35 0.34 0.01
4 0.24 0.25 -0.01
5 0.38 0.39 -0.01
6 0.23 0.29 -0.06
7 0.17 0.25 -0.08
8 0.35 0.3 0.05
9 0.34 0.26 0.09
10 0.33 0.34 -0.01
11 0.27 0.32 -0.05
12 0.35 0.35 0.00
13 0.38 0.36 0.02
14 0.38 0.4 -0.02
15 0.24 0.25 -0.01
16 0.33 0.29 0.04
17 0.25 0.25 0.00
The graphs of predicted versus experimental K values show the performance

of the model performed. Figure 4.5 shows the actual versus predicted value of response
K. Based on the Figure 4.5, the values presented show that the observed values
somewhat depart from the straight line as predicted by the value of R-squared of 0.71,
based on the values. The graph clearly demonstrates that the majority of the observed
points are located close to the linear line that corresponds to the expected value of
response K. This trend demonstrates that the correlation between the three factors and
the response of K-value provided by the model created is appropriate, as predicted by
the reassuringly high value of R 2.
62
Figure 4.5 Predicted versus actual data
The residuals show how well the model satisfies the ANOVA assumptions by
comparing the predicted and actual values at each point. Figure 4.6 shows the graph
for raw residuals versus predicted values. The residuals are displayed as a randomly
formed plot and demonstrating that the variance of the observed values is constant for
all response values. Based on the graph, the residuals are shown randomly scattered
around 4.82% in the plot of the raw residuals versus expected values. However, some
residuals fall between -0.29 and 0.31, indicating 95% degree of confidence. An
operating error in the experimental data or a potential model error results from any
residual outside of this range. The residuals show a random distribution, proving that
the model is a good fit for the process (Samsuri, 2016).
63
Figure 4.6 Raw residuals versus predicted data
The analysis of variance (ANOVA) method was used to further assess the
adequacy of the generated prediction model. Table 4.3 shows the ANOVA table for
this analysis. The F-value, which shows the ratio of mean square regression to mean
square residual, must be observed when using the method. The estimated F-value must
be higher than the tabulated number displayed in Appendix B in order to accept the
prediction model as appropriate. Calculated F-value for the response K-value was 3.77,
while tabulated F-value for 95% confidence level (F9,7,0.05) was 3.68. Thus, the
prediction mathematical model is considered to have a good agreement based on the
data obtained.
64
Table 4.3 ANOVA table
Sum of Degree of Mean

Sources Squares, Freedom, Squares, F-value F0.05 R2
(SS) (DF) (MS)
Regression
0.1925 9 0.0214 3.77 3.68 0.71
(SSR)
Residual 0.0568 7
Total
0.2493 16
(SST)
The variables that have a significant impact on the process for each variation
factor were then identified in the subsequent study after verifying and assessing the
validity and suitability of the regression model. Table 4.4 shows the arranged multiple
regressions result which lists all the significant or insignificant values for each factor
and the interaction between factors that involved in the model. the F-value refers to
means of Fisher’s test (F-test), which was used to determine the signif icance of the
regression coefficients of the parameters (Amran, 2015). Then, the p-value was used
to evaluate the importance of each component and the interaction between factors. The
factors with bold values have a considerable impact on the process, with the top factor
having the biggest influence.
Table 4.4 Regression result for K response
Factor Regression Standard error F P

coefficient
X 1X 1 0.00845 0.0172 7.75 0.0272
X3 -0.00096 0.0204 9.37 0.012
X1 0.131010 0.0204 2.99 0.1146
X2 -0.007865 0.0204 1.52 0.2452
X 1X 2 0.001149 0.0266 1.04 0.3315
X 1X 3 -0.000035 0.0266 0.6198 0.4494
X 2X 2 0.000238 0.0198 0.3199 0.5842
X 3X 3 1.0125x10 -6 0.0198 0.0021 0.9640
65
X 2X 3 3.16084x10-19 0.0266 0.01775 0.6824
According to Table 4.4, the variable or factor with the highest F-value and
lowest p-value is regarded as the most significant factor, and the other variables or
factors are arranged in decreasing order of significance which starting with the most
significant factor and ending with the least significant factor. The influence of a factor
is considered significant if the p-value is less than 0.05 in accordance with the
confidence level set for the ANOVA analysis that was used.
4.6.3 Response Surface and Contour Plot of K-Value
The effects of any two process variables or factors on the response of K were
also evaluated by plotting a three-dimensional (3D) surface plot of the response against
the two selected factors, while the other two unselected factors were kept at the middle
of their range. The middle values for operating time, stirrer speed, and coolant
temperature are, respectively, -10 °C, 40 minutes, and 350 rpm. This 3D surface
graphic is frequently used to show how many elements interact. An ellipse contour
plot accurately depicts a process variable's interaction with other variables. The surface
was also used to create a regression model that depicts the interaction between the two
chosen variables. A reasonable range for the displayed variables that would produce
the best value for the K value is then recommended in a two-dimensional (2D) fitted
response profile known as a contour plot.
4.6.3.1 Interaction of Coolant Temperature (X 1) and Operation Time (X 2)
Based on the Figure 4.7 shows surface plot of K value as a function of coolant
temperature (°C) and operation time (min). Figure 4.7 shows the effects and
interactions of coolant temperature and operation time on the K-value at a constant
stirrer speed of 350 rpm. From the Figure, the K-value start decrease after 30 minutes
of operation time. The pattern has changed to an increasing K value after more solution
iterations above 50 minutes. The solution is saturated with solutes after 30 minutes,
66
which results in some inclusions of the solute in the ice that has formed. For this PFC
procedure, operation times more than 50 minutes are not appropriate. The K-value is
high anywhere outside of this range due to the decreasing coolant tempera ture and
operation time. This can be seen by the contour plot in Figure 4.8, a two-dimensional
(2D) fitted response profile. The equation 4.2 shows the regression model for the trend
of the graph that describes the interaction between the coolant temperatu re and
operation time.
Figure 4.7 Surface plot of K-Value for coolant temperature and operation time
𝑌 = 0.85412 + 0.13100 𝑋1 − 0.00786𝑋2 + 0.00114 𝑋1 𝑋2

− 1237.43551 𝑋1 + 3.16083 × 10 −19 𝑋2 𝑋3 + 0.00845𝑋1 2
+ 0.00024 𝑋2 2 (4.2)
The contour plot in Figure 4.8 shows an appropriate range for the plotted
variables that would produce the lowest K-value. The optimum ranges for coolant
temperature and operation time are -9 to -11 °C and 34 to 45 minutes, respectively.
This shows how a lower coolant temperature would promote better ice crystal
formation whereas a lower coolant temperature would cause the solute to become
trapped in a dendritic ice crystal due to the cold environment (Yahya et al., 2017). To
ensure that the ice is formed in a place and to prevent supercooling phenomena, good
ice creation requires a lengthy operation time (Jusoh et al., 2014). It is important to
67
keep in mind that the longest operation time may not always produce the best K-value.
This is because the ice contains a lot of solute since the coolant temperature is too low.
Therefore, the combination of these factors causes the process to keep a lot of solute
in the solution and reduce the response of K-value.
Figure 4.8 Contour plot of K-Value for coolant temperature and operation time
4.6.3.2 Interaction Coolant Temperature (X 1) and Stirrer Speed (X 3)
The 3D surface and contour plot of K against coolant temperature and stirrer
speed was generated with operation time being held constant at 30 minutes in order to
visualize the interaction of coolant temperature and operation time and their effects on
K. Figure 4.9 and Figure 4.10 shows the 3D surface for coolant temperature and Stirrer
Speed and contour plot. From the Figure 4.9 and 4.10, it is shown that the range of -9
to -11 ˚C for the X1 factor and range of 320 to 380 rpm with the lowest response of K-
value are appropriate for the interaction between coolant temperature (X 1) and stirrer
speed (X3) towards the response of K-value. A lower K-value would result from a
higher stirrer speed and a lower coolant temperature given the relationship between
the two main factors that affect that temperature. The Equation (4.3) shows the
68
regression model for the trend of the graph that describes the interaction between the
coolant temperature and stirrer speed.
Figure 4.9 Surface plot of K-value for coolant temperature and stirrer speed
Y = 1.16997 + 0.13100 𝑋1 − 0.00096𝑋3 + 0.03421𝑋1 − 3.53553 𝑋1 𝑋3

+ 9.48249 × 10−18 𝑋3 + 0.00845 𝑋1 2
+ 1.01258 × 10−6 𝑋3 2 (4.3)
Based on the observation, it can be stated that the separation process would
become less effective if the highest X1 and X3 or the lowest X1 and X3 caused an
increase in K-value (Yahya et al., 2019). This indicates that based on the observation,
the appropriate range is at a value that falls halfway between the two components that
were noticed. If the stirrer speed is too slow and the coolant temperature is too high,
the ice on the probe will not form properly. However, because of the tremendous sheer
force of stirrer speed, the ice would be washed out and combined with the bulk
solution. Meanwhile, as soon as the coolant temperature began to fall to the lowest
temperature, the solute could be confined in the ice form (Yahya et al., 2019). Given
that the value and trend are quite similar to the parameters, the considerable interaction
between the variables and K-value in those ranges demonstrates the ability of the
MPCC process to be used to produce the best output.
69
Figure 4.10 Contour plot of K-Value for coolant temperature and stirrer speed
4.6.3.3 Interaction Operation Time (X2) and Stirrer Speed (X3)
Figures 4.11 and 4.12 show a 3D response surface and a 2D contour plot,
respectively which to analyze each combination of variables and identify the ideal
condition. The effects and interactions of operation time and stirrer speed while
keeping coolant temperature which -10 °C. Figures 4.11 and 4.12 show that the K-
value increases when the operation time is either too short or too lengthy. Similar to
stirrer speed, K-value is high when the PFC process is using an excessively low or
excessively high stirrer speed. When the operation time is in the range of 34 to 45
minutes and the stirrer speed is between 290 and 350 rpm, the high efficiency of the
process shown by the lowest value of K can be seen. The best value of K in these
interactions was produced by both. In addition to mixing the solute in the target
solution, stirrer speed also spreads heat transfer and induces mass transfer at the
interface. Meanwhile, a more stable ice layer can be attached to the probe thanks to
longer contact time between the cooled probe surface and the solution due to larger
operation time. The Equation (4.4) shows the regression model for the trend of the
graph that describes the interaction between the operation time and stirrer speed.
70
Figure 4.11 Surface plot of K-Value for operation time and stirrer speed
Y = 3.34477 − 0.00786 𝑋2 − 0.00096𝑋3 + 0.01140 𝑋2 − 35.35530 𝑋3

+ 3.16083 × 10−19 𝑋2 𝑋3 + 0.00024𝑋2 2
+ 1.01258 × 10−6 𝑋3 2 (4.4)
Based on the observation, the optimum range of the factor for stirrer speed is
290 to 350 rpm while for the factor of operation time is 34 to 45 minutes to reach the
lowest response of K-value. This explains the relationship between stirrer speed and
operation time, which is consistent with the trend from the previous chapter. A strong
effect of heat transfer distributed by increasing stirrer speed and longer operation time
could accelerate the growth rate of ice and prevent the inclusion of solute in the ice.
However, if the stirrer's speed and operating time are too slow and short, the solution's
solubility will decrease, which will result in an inadequate washing action for the
solute trapped in the ice (Osorio et al., 2018). Otherwise if stirrer speed is too fast and
operation time is longer, the crystal ice is believed to be enlarged due to the interface
between ice and solution and as a consequence, the ice morphology would entrap the
solute (Miyawaki et al., 2016)
71
Figure 4.12 Contour plot of K-Value for operation time and stirrer speed
4.6.4 Optimum Operating Conditions for K-Value
The Table 4.5 generated by the statistical software reveals the best range for
each factor with respect to K-value. The optimal range of the three independent
variables was effectively identified and predicted using the developed re gression
model. The trend of the 3D response surface and 2D contour plot related to the
interaction of two elements at once was used to determine the ideal range of conditions.
The lowest K-value response is actually not all that different from the predicted and
actual results. According to the statistical software, it is found that the best value of K
the system could achieve is 0.267 when the process is operated at coolant temperature
of -9.4 °C, operation time of 49 minutes, and stirrer speed of 375 rpm.
72
Table 4.5 Optimum Range for Operation Parameters of K-value
Interaction Optimum Range for Independent Variables

Combination Coolant Operation time, Stirrer speed, X3
Factors temperature, X1 X2
X1X2 -7.8 to -11 °C 30 to 50 minutes
X1X3 -9 to -11 °C 320 to 380 rpm
X2X3 34 to 50 minutes 290 and 350 rpm
4.6.5 Validation of Experiment
The best effective partition constant (K) value was accurately predicted using
regression models created based on the chosen experimental design (DOE).
Additionally, the optimization of the response variables has been examined using
multiple suitable RSM phases. The optimum value for each parameter concerned is
summarized in Table 4.6 accordingly. Confirmatory tests were run in order to validate
the anticipated values, and the results are shown in the table as an experimental
response.
Table 4.6 Optimum Value for Operating Parameters of K -value
Response Coolant Operation Stirrer Predicted validation

temperature, X1 time, X2 speed, X3
K -9.4 49.0 375.0 0.267 0.282
73
CHAPTER 5
CONCLUSIONS AND RECOMMENDATIONS
5.1 Conclusions
In conclusions, freeze concentration is one of the efficient ways to concentrate

tomato juice, and MPCC design is one of the crystallizers that can be used to assess
the effectiveness of the FC. The objectives of this study are analyzing the effect of
coolant temperature, operation time and stirrer speed on effective partition constant,
K. The optimization process which determine the optimum conditions in concentrating
tomato juice through FC system. In this study, the details analysis of experiment is
listed below:
(a) For effect of coolant temperature, the K value decrease from -6 °C to -10 °C
and recorded the best K value at -10 °C which 0.307 and rise back at -12 °C to
-14 °C. the decrease of K value due to lower coolant temperature promotes
larger size of ice crystal formed. Meanwhile, increase of K value due to the ice
formation rate increased as the temperature differential between the probe wall
and the entering solution increased. This will cause solute will become stuck
in the ice front's outward motion.
(b) For effect of operation time, the K value decrease from 20 to 40 minutes and
recorded the best K value at 40 minutes which 0.201 and rise back at 50
minutes of operation. the decrease of K due to the ice layer thickens
and leaving the unfrozen solution in a condition that is getting close to
saturation. Meanwhile, increase of K value caused by the impurity of the ice
which grew with increasing concentration over time.
(c) For effect of stirrer speed, the K value decrease from 200 to 250 rpm and
recorded the best K value at 250 rpm which 0.362 and rise back at 200 to 250
rpm. the decrease of K due the solute is dispersed evenly throughout the
74
solution if a higher stirrer speed is used because it can stimulate mass transfer
at the interface. As a result, the quantity of solute trapped in the ice could be
decreased. Meanwhile, increase of K value caused by solute is heavily
accumulated at the ice-liquid interface causing a higher concentration of solute
in the ice formed
(d) Through the use of RSM, the process parameters were successfully optimised
and the optimum conditions for generating the optimum K value were found to
be a coolant temperature of -6.4 °C, an operation time of 49 minutes, and a
stirrer speed of 375 rpm, the K-value reaches 0.282 which represents the high
efficiency of the FC process. An effective experimental design method was used
to optimise the process parameters, and then a regression model and model
analysis were used to fit the response data. Each response's computed R 2 and
f-value showed that the regression model produced a good approximation. The
results and discussion in the previous performances analysis, as well as the
theory, were determined to be consistent with the effects and interactions
between process factors. As a result, the use of RSM in this optimization
procedure is reliable. When the best scenario for K value response was
validated, there were little differences between the validated and predicted
values for both answers and proving the viability of the prediction model.
5.2 Recommendations
(a) MPCC system could be improved with the installation of fully automated
version for easier monitoring of the product.
(b) MPCC system should be installed with efficient cooling gas system that can be
set with different decimal temperature range for cooling process.
(c) The tank could be place with suitable position to ease the cleaning process after
experiment.
75
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84
Appendix A Gant Chart
85
Appendix B Result for Effect of Parameters
Parameter condition Constant Result/Response

Coolant temperature, Operation time, TPC Increment,
Manipulated Stirrer speed, (rpm) K
(ᵒC) (minutes) (%)
-6 0.400 42.96
Coolant -8 0.370 62.63
temperature, -10 - 30 350 0.307 95.46
(ᵒC) -12 0.352 83.32
-14 0.357 85.75
20 0.216 49.62
Operation 30 0.213 64.33
time, 40 -8 - 350 0.201 107.02
(minutes) 50 0.215 57.77
60 0.219 84.82
200 0.424 94.19
Stirrer 250 0.362 103.76
speed, 300 -8 30 -0.2 0.383 83.05
(rpm) 350 0.426 14.92
400 0.450 5.54
86
Appendix C Standard F-Table
87

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OPTIMIZATION OF THE CONCENTRATION OF TOMATO JUICE BY FREEZE

MUHAMMAD HARIZ BIN ABDUL HAMID

UNIVERSITI TEKNOLOGI MALAYSIA

DECLARATION OF THESIS / UNDERGRADUATE PROJECT REPORT

Date of Birth : 20 SEPTEMBER 2000

Title : OPTIMIZATION OF THE CONCENTRATION OF TOMATO

Academic Session : 2022/2023 SEMESTER 1

I declare that this thesis is classified as:

CONFIDENTIAL (Contains confidential information under the

RESTRICTED (Contains restricted information as specified by

✓ OPEN ACCESS I agree that my thesis to be published as online

1. I acknowledged that Universiti Teknologi Malaysia reserves the right as

SIGNATURE OF STUDENT SIGNATURE OF SUPERVISOR

A19ET0149 AP. DR. MAZURA BINTI JUSOH

Date: 16 FEB 2023 Date: 16 FEB 2023

MUHAMMAD HARIZ BIN ABDUL HAMID

A dissertation submitted in fulfilment of the

School of Chemical and Energy Engineering

February 16, 2023

I declare that this dissertation entitled “Optimization of The Concentration of Tomato

This dissertation is dedicated to my family, friends, supervisor, lecturers and

In preparing this dissertation, I was in contact with many people, researchers,

My sincere appreciation also extends to all my friends who have provided

Freeze concentration (FC) is known as one of the methods used to concentrate

CHAPTER 2 LITERATURE REVIEW 7

CHAPTER 3 RESEARCH METHODOLOGY 31

CHAPTER 4 RESULT AND DISCUSSION 50

CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS 74

TABLE NO. TITLE PAGE

Table 2.1 Experimental matrices for CCD of two variables (Bezerra

Table 3.3 Value of varied and constant parameter 41

Table 3.4 Experimental range and coded value of variables 45

Table 3.5 Arrangement of experiment using central CCD 46

Table 3.7 Predicted analysis of optimum condition for K 49

Table 3.8 Optimum values of process parameters in validation

Table 4.1 Experimental result of K value for Design of Experiment 59

Table 4.2 The experimental, predicted and residuals for Response K 62

Table 4.4 Regression result for K response 65

Table 4.5 Optimum Range for Operation Parameters of K-value 73

Table 4.6 Optimum Value for Operating Parameters of K -value 73

FIGURE NO. TITLE PAGE

Figure 1.1 General process of freeze concentration (Samsuri et al.,

Figure 2.6 Schematic diagram of spiral finned crystallizer (Samsuri et

Figure 2.8 Step by step procedure for RSM (Aydar, 2018) 19

Figure 3.2 Set up for MPCC in the lab 34

Figure 3.3 Refractometer 34

Figure 3.4 UV-VIS spectrophotometer 34

Figure 3.9 Steps in RSM (Amran, 2015) 44

Figure 4.1 Comparison between final concentration, initial

Figure 4.2 Changes of TPC increment and effective partition constant,

Figure 4.3 Changes of effective partition constant, K and TPC

Figure 4.4 Changes of effective partition constant, K and TPC

Figure 4.5 Predicted versus actual data 63

Figure 4.6 Raw residuals versus predicted data 64

ANOVA - Analysis of Variance

% - Percentage nutrients in tomato juice

APPENDIX TITLE PAGE

Appendix A Gant Chart 85

Appendix B Result for Effect of Parameters 86