PYROLYTIC KINETIC STUDY OF SALVIA

AEGYPTIACA HYDROGEL (TUKM-E-BALANGO)

WITH NON-LINEAR METHODS

A thesis submitted on completion for the degree of M.phil (Organic Chemistry)

by

SADIA MASOOD

Roll No. PCHF14E049

(2014-2016)

Department of Chemistry

University of Sargodha.

Sargodha, Pakistan.

I
II
 PYROLYTIC KINETIC STUDY OF SALVIA
AEGYPTIACA HYDROGEL (TUKM-E-BALANGO)
WITH NON-LINEAR METHODS
A THESIS SUBMITTED
TO THE

UNIVERSITY OF SARGODHA

FOR THE

DEGREE OF MPHIL ORGANIC CHEMISTRY

(2014-2016)

BY

SADIA MASOOD

ROLL NO. PCHF14E049

Department of Chemistry

University of Sargodha

Sargodha, Pakistan

III
 DEDICATION

Dedicated

To

My Loving Parents

Whose Prayers and Encouragement Enabled

Me to Accomplish My Research Work

IV
 DECLARATION

It is certified the research work mentioned in this thesis entitled Pyrolytic kinetic

study of Salvia aegyptiaca hydrogel (Tukm-e-balango) with non-linear methods. by

Sadia Masood is original and nothing been stolen/copied/plagiarized from any source.

Dr. Jamshed Akbar

Name & Signature of Supervisor with official stamp

Department of Chemistry,
University of Sargodha,
Sargodha.

DECLARATION

It is certified the research work mentioned in this thesis entitled Pyrolytic kinetic

study of Salvia aegyptiaca hydrogel (Tukm-e-balango) with non-linear methods. by

Sadia Masood is Original and nothing been stolen/copied/plagiarized from any source.

Sadia Masood
Name & Signature of Student
Department of Chemistry,
University of Sargodha,
Sargodha.

V
 Certificate

It is certified that the research work contained in the thesis entitled Pyrolytic kinetic
study of Salvia aegyptiaca hydrogel (Tukm-e-balango) with non-linear methods. by
Sadia Masood is original and the research work reported in this thesis has been
completed according to the requirement of HEC & UOS.

Signature of Student Signature of supervisor with official stamp

Name Name

VI
 APPROVAL CERTIFICATE

This thesis titled Pyrolytic kinetic study of Salvia aegyptiaca hydrogel (Tukm-e-

balango) with non-linear methods submitted by Sadia Masood, Roll No.

PCHF14E049, session 2014-2016, under my supervision on completion for the degree

of MPhil Organic Chemistry is hereby approved.

Supervisor:

Dr. Jamshed Akbar

Associate Professor

Department of Chemistry,

University of Sargodha,

Sargodha

Dr. Muhammad Sher

Chairman Department of Chemistry,

University of Sargodha,

Sargodha.

VII
All praises are for Omnipotent Allah, the most beneficent, ever merciful and tremendous

respects are for the guardian of all the humanity, the Holy Prophet Mohammad (peace

and blessings of Allah be upon him), who exhorted his followers to seek for knowledge

from cradle to grave.

I am greatly honored to pay my sincere thanks and heartiest obligations to my Research

Supervisor Jamshed Akbar, Associate Professor of Organic Chemistry. His proper

supervision, experience, time devotion and keen interest enabled me to accumulate this

humble work. I acknowledge Dr. Muhammad Sher, Chairman, Department of Chemistry

for the provision of research facilities during my studies. I also acknowledge all of the

teachers of department as well for enabling me to accomplish this task.

Special thanks are also due to my friends and class fellows, especially Rabia Hassan and

Mehwish Bashir for moral support and thanks to all my family members, my younger

sisters who help me in one way or the other.

Finally I express my heartiest gratitude and respect to my parents, my sisters and my

husband whose prayers, love, patience, encouragement and spiritual inspiration was a

great source of motivation at every stage of my education. May Allah provide me the

way to fulfill their promises.

Sadia Masood

VIII
 DECLARATION

I declare that the work described in this thesis was carried out under the Supervision of

Dr. Jamshed Akbar, Assistant Professor at the Department of Chemistry, University of

Sargodha, Sargodha, Pakistan, for the MS Examination. I also hereby declared that the

substance of this thesis has neither been submitted elsewhere nor is being concurrently

submitted for any other degree. I further declared that the work embodied in this thesis is

the result of my own research work and where work of any other investigator has been

used, this has been fully acknowledged.

Sadia Masood

IX
 ABSTRACT

The purpose of present work was to study the pyrolytic kinetics of hydrogel, using non-

linear methods, isolated from Salvia aegyptiaca. The hydrogel was isolated and its

thermal degradation kinetics was studied to determine different thermodynamic

parameters.

The natural hydrogel material exhibited a three stage decomposition behavior as

characterized by use of Thermogravimetric (TGA) analysis and Differential Scanning

Calorimetry (DSC) in temperature range from ambient to 680oC. Thermal transition and

thermal parameters i.e Activation energy, pre-exponential factor, entropy, enthalpy and

free energy changes were determined for each stage of decomposition using model-

fitting and model-free isoconversional methods.

The activation energy of decomposition Salvia aegyptiaca obtained by KAS method was

found to be 162.78 kJmol-1 for major decomposition step. The reaction model, g (), was

found to be D4 for major stage of decomposition determined by master plot method. The

activation energy, pre-exponential factor, and g () model were: 162.78 kJmol-1,

31.428min-1 (lnA=3.447) and D4 respectively.

The application of non-linear method provided activation energy, pre-exponential factor,

and g () model to be 4.69 kJmol-1, 6.30 e13min-1 (lnA=31.77) and D8 respectively for

major stage of decomposition of the hydrogel. The non-linear algorithm minimizes the

error between experimental and theoretical results. The residual sums of squares (RSS)

error values for non-linear method was found sufficiently low (RSS < 0.1).

X
TABLE OF CONTENTS

1. INTRODUCTION

1.1 Thermal Analysis.....01

1.2 Techniques of Thermal Analysis ...02

1.2.1 Thermogravimetric Analysis(TGA)02

1.2.1.1 Advantages of TGA.03

1.2.2 Differential Thermal Analysis (DTA).....04

1.2.3 Differential Scanning Calorimetry .04

1.2.3.1 Heat flux DSC .05

1.2.3.2 Power Compensation DSC...05

1.2.3.3 Applications of DSC06

1.2.4 Limitation of Thermal analysis Techniques...06

1.3 Thermal analysis kinetics ....07

1.3.1 Kinetic Triplet.....08

1.3.2 Thermal Parameters.....08

1.4 Thermal Degradation Analysis...09

1.5 Kinetic Analysis Equation...10

1.5.1 Arrhenius equation 10

1.6 Model Fitting Methods....12

1.6.1Coats Redfern Method....12

1.6.2 Broido Method...12

1.7 Model free methods.13

1.7.1 Isoconversional method...13

1.7.2 Differential Isoconversional method .....14

1.7.2.1 Drawbacks of Differential Isoconversional Method 15

1.7.3 Integral Isoconversional Method.15

XI
1.8 Natural polysaccharides18

1.8.1 Applications of plant hydrogels...19

1.8.2 Mucilage in plant parts.21

1.8.3 Labiatae....21

1.8.4 Salvia Aegyptiaca...21

1.8.4.1 Origin and distribution......22

1.8.4.2 Chemical profile....22

1.8.4.3 General Uses.23

1.8.4.4 Medicinal Effects..24

2. LITERATURE REVIEW
2.1 Literature review.25
2.2 Aims and objectives.....31

3. EXPERIMENTAL
3.1 Materials and methods ...32
3.1.1 Materials...32
3.1.2 Methods ...32
3.1.2.1 Isolation of hydrogel from Salvia aegyptiaca32

3.1.2.3 Thermal Analysis...33

3.1.2.3.1Model fitting analysis: Broido method.33

3.1.2.3.2Model free isoconversional analysis ...34

3.1.2.3.3Non linear regression analysis ...36

4. RESULTS AND DISCUSSION

4.1 Isolation of hydrogel....37
4.2 Thermal degradation kinetics..37
4.2.1Model-Fitting analysis: Broido method........37

XII
 4.2.2 Model-Free isoconversional analysis......43
4.2.2.1 Isoconversional Thermal Analysis of SA hydrogel 43

4.2.2.2 Thermal degradation mechanism.....45

4.2.2.3 Non-linear regression analysis.58

4.3 Conclusion...62
References...........................63

XIII
Chapter1
Introduction

1.1 Thermal Analysis:

Thermal analysis is termed as heating of sample at some high temperature followed by

measurement of the properties with time under isothermal conditions [1].

Thermal analysis (TA) contains family of various techniques. The techniques involve in

thermal analysis are used to measure a materials reaction to being heated or cooled. The aim

is to develop a connection between physical properties of materials and temperature. Thermal

analysis is used for describing the mechanical and thermal properties of material, for

calculating actual physical properties of material, for estimating their lifetimes in various

environments and for illustrating and scheming processes used in their manufacture. Thermal

analysis is the most important quality control and research method in the manufacture and

development of various polymeric materials.

The thermal analysis comprises various methods that measure many properties during the

pyrolysis of a sample. Differential scanning calorimetry, the property is the flow of heat into

and out of the sample and Thermogravimetry, where the property studied is weight changing

in sample [2].

Thermogravimetry (TG) analysis is a technique in which substance weight is recorded as a

function of time or temperature. After performing TG experiment data acquired is in the form

1
of graph having weight percent on y-axis and temperature or time plotted on x-axis. Lot of

polymeric materials can be analyzed by thermogravimetric technique and there are various

applications of TG for characterization of material [3].

Differential scanning calorimetry or DSC is defined as a technique in which the heat

difference required to rise the temperature of a reference and sample is calculated as a

function of temperature. Throughout the experiment both the reference and sample are kept

at same temperature. The Digital Scanning Calorimeter is used to study the thermal changes

taking place in the compound. The enthalpy of fusion, which is characteristics for pure

substances, drugs or formulation additives, may be calculated from the corresponding first

order transition in DSC thermograms. Purity analyses by DSC can also be done [4, 5].

1.2 Techniques in thermal analysis.

1.2.1 Thermogravimetric Analysis (TGA)

Thermogravimetry is a technique that calculates the variation in mass of a sample as a

function of time or temperature. Thermal events like glass transition, crystallization and

melting do not cause change in the mass of a sample. However, thermal changes like

vaporization, absorption, desorption and decomposition accompanying mass change can be

measured by TG. TGA can give information about various other chemical phenomenon like

chemisorption, desolvation (dehydration), gas-solid reactions [6] and oxidative mass losses

are the most common losses in TGA. Combustion process occurring during TG analysis is

recognized by discrete traces in the TGA thermograms [7].

Sample in any physical form of sample i.e gel, solid or liquid and in different shapes

(powder, films, granules, fiber, fabrics, plate etc.) is applicable. A small amount of sample is

needed (0.1 mg-10 mg).

2
Thermobalance measures the change in mass of given sample with temperature. This is a

combination of a furnace connected to electronical microbalance and a temperature

programmer. Suitable enclosed system is used for balance so that the atmosphere can be

controlled. Thermobalance are placed in metal system or glass so that it allow for functioning

at pressure ranging from a low pressure (< 10-4 Pa) to very high pressure (>3000 kPa) of

different types of inert and corrosive gases. Gases used in TG analysis are air, Ar, H2, HCN,

N2 and SO2. The gaseous products evolved during TG measurements are measured by

coupling an appropriate instrument to the TG apparatus e.g Mass spectrometers, infrared

spectrometers and gas chromatographs.

The results obtained from Thermogravimetric analysis are described as (1) mass loss rate

versus temperature curve, called as Derivative Thermogravimetric. (2) Mass versus

temperature (or time) curves, called as Thermogravimetric curve [3].

1.2.1.1 Advantages of TGA:

The TG has its widespread use in technology and science because it can generate quantitative

based date from any class of materials. The applications of TG are given below:

Thermal Stability: Many structurally closed materials can be matched at high temperatures

under the any pressure. The Thermogravimetric curve can help to explain pyrolytic

mechanism of various materials.

Industrial processes simulation: Thermobalance furnace used in TG is considered as a

mini-reactor, which is capable to minimize the conditions in industrial reactor.

Compositional analysis: Much type of complex materials can be analyzed by decomposing

their component selectively. This method is used to analyze e.g. polymeric filler contents,

carbon and ash in coals, carbon black in oils and the moisture content of many materials.
3
Material preparation: Using it for the preparation of many anhydrous compounds and

hydrates can be done by care full choice of temperature conditions [8, 9].

1.2.2 Differential Thermal Analysis (DTA)

In DTA, the temperature changes are programmed and sample temperature is compared with

reference material. During the thermal events the temperature must be kept constant. When

the thermal event is endothermic then the sample will lag behind that of the reference and on

curve minimum will be observed. On the other side, if the thermal event is exothermal then

sample temperature will leads that of the reference and on curve a maxima will be observed.

The area under the curve shows the enthalpy change H of both thermal event [6, 10].

DTA modes can be used to determine the followings properties of a polymer.

Melting points

Glass transition temperatures

Volatile content

Moisture

Purity

Thermal and oxidative stability

Transformation of temperature

1.2.3 Differential Scanning Calorimetry (DSC)

Differential Scanning Calorimetry is defined as a method in which the difference of heat

flow rate between a reference and a substance is calculated as a function of temperature,

whereas sample is taken at a controlled temperature program. The majority of uses of the

DSC are in the pharmaceutical and polymer fields. The applications of DSC are the fast and

4
easy measurement of the glass transition temperature, heat of reaction, heat of fusion,

estimation of purity and heat capacity determination. In DSC, enthalpy change is measured

from the temperature difference between the reference and given sample. In endothermic

process the enthalpy of the system increases, while in exothermic processes the enthalpy and

the internal energy of the system decreases. There are two types of DSC instruments: heat

flux DSC and power compensation DSC [11].

1.2.3.1 Heat Flux DSC:

Heat flux DSC is consisting of furnace designed with a temperature sensor and both the

reference pans and the sample located within the same furnace. In its construction the

reference and sample pans are kept in specific locations and the heating of furnace is done at

the programmed temperature. The difference in temperature is produced between reference

and sample when the transitions in takes place. As system approaches to equilibrium

transition this difference in temperature between reference and the sample decreases and this

difference act as a signal that is calculated. This signal is changed into the heat flow

equivalent by analyzer and this is shown as a function of temperature or time. The heat flux

DSC analyzers is applicable from very low temperature to high temperature around 700oC

like the power compensation DSC using temperature DTA analyzers that gives a calibrated

DTA signal [12].

1.2.3.2 Power Compensation DSC:

In power compensation differential scanning calorimeter, the sample holder unit base is in

direct contact with a reservoir of coolant. The sample and the reference holders are

individually equipped with a resistance sensor which calculates the temperature of the base

of the holder and a resistance heater. Electric power is supplied to detect the temperature

5
difference between the sample and reference that takes place due to the phase change taking

place in the sample. Due to supply of electric power that the temperature difference falls

below a threshold value, typically <0.01 K. The DSC curve gives the power input per unit

time, as a function of either the programmed temperature or the time. The maximum

sensitivity of a power compensation DSC is 35 mW. Energy and temperature calibrations are

carried out by using standard reference material. Comparing with a heat-flux DSC, higher

scanning rates can be used with a power compensation DSC, with a maximum reliable

scanning rate of 60 K min-1. By maintaining the linearity of the instrument baseline can pose

problems at the high operating temperatures or in the sub-ambient mode [12].

1.2.3.3 Applications of DSC:

Applications of DSC includes the heat-sealing property of polyethylene, the binding of

polyethylene by peroxides and determination of additives [11]. Differential scanning

calorimeter (DSC) is used in determination of melting point of many Easters and fatty acid

[13], determination of purity of low molecular mass compounds [14], for the quality control

of raw materials used in pharmaceutical products [15] , for measuring melting temperature of

many materials [16] and to measure degree of crystallinity [17].

1.2.4 Limitations of Thermal Analysis:

The reference temperature during kinetic analysis should be same as of the sample. But

sometime sample temperature deviate from reference it because of thermal conductivity

variations or sometime self-heating or cooling takes place. This problem is mostly associated

with large sample amount and fast heating rate [18].

6
1.3 Thermal Analysis Kinetics:

Kinetic analysis helps in investigating degradation mechanisms and in forecasting the

thermal stability of polymeric substance. Such goals are achieved only by using appropriate

methods for kinetic determination. Most analysis are done by fitting the kinetic data into

various reaction models, which gives Arrhenius parameters whose consistency is subjected to

the proper selection of the reaction model [19].

Kinetic evidence is vital for estimating the temperature and times associated with the

processing, storage of materials and service lifetimes. It is also important for analyzing the

thermal processes mechanism. The rate of many thermally activated processes at constant

pressure defined as a function of two variables the extent of conversion () and the

temperature (T). User controls the temperature in TGA and the extent of conversion is easily

calculated by mass loss measurement [2]. At a given temperature, is defined as

mi mT

mi m f
(1)

mT is mass at temperature T

mf is final mass

mi is initial mass

The kinetic analysis provided kinetic parameters e.g. the pre exponential factor, reaction

model and energy of activation. These parameters are then commonly used for mechanistic

explanations and kinetic estimation. Applications of kinetic analyses are linked with

obtaining mechanism understandings and performing kinetic predictions. The kinetic analysis

offers only limited understandings into reaction mechanisms. The shape of the isothermal

curve can give insight into the mechanistic model leading the process. Independence of Ea on

7
 shows the presence of a single rate determining step, a step in which increase in Ea occurs

shows the presence of two successive rate determining steps [20].

1.3.1 Kinetic Triplet:

A combination of the pre-exponential factor, reaction model and activation energy is called

as kinetic triple. For the process having more than one step, every step is likely to have

different kinetic triplets. For the two-step kinetic equation two kinetic triplets are involved:

A1, f 1 (), E1 and A2, f 2(), E2

1.3.2. Thermal Parameters:

Entropy, enthalpy, Gibbs free energy and energy of activation are the thermal parameters.

The entropy is defined as the difference between the entropy of the transition state and the

summation of entropies of the reactants. Gibbs free energy is the difference between the

enthalpy of the transition state and the sum of enthalpies of the reactants in their ground state.

Enthalpy is designated by the letter "H", that comprises of the internal energy of the system

(U) and pressure (P) volume (V) product of the system. The minimum amount of energy

which is required for reactants to cross a barrier for a reaction to proceed is known as

activation energy. Entropy (S), enthalpy of activation (H), Gibbs free energy (G) are

calculated by these equations respectively

( S / R )
A (kT / h)e
(2)

H U PV (3)

G H T S (4)

8
1.4 Thermal degradation analysis:

Solid polymeric materials upon heating material may experience changes both physically and

chemically. This causes the unwanted changes in the materials properties. A strong

discrimination need to be made between thermal degradation and thermal decomposition.

The American society for testing and materials (ASTM) defines thermal decomposition as

procedure of widespread chemical changes occurs by heating. Thermal degradation is the

method where the action of heat on material causes a loss of physical and chemical properties

[21]. Thermal degradation of the polymer occurs using a free-radical method [22] including

three steps initiation, propagation and termination.

The stability and the mechanism of thermal degradation of a polymer depends primarily on

the molecular structure of the polymer. For example, tertiary carbon atoms in the chain

weaken the adjacent C- C bonds in the chain. Quaternary carbon atom is even much effective

in this respect than tertiary carbon atoms. Abundance of hydrogen in the chain leads to the

formation, through random scissions, of volatile products which differ in size from those

containing one carbon atom to those containing as many carbons as will allow the fragments

to vaporize at the temperature employed in the pyrolysis. On the other way scarcity of

hydrogen on the main chain will cause the formation of monomers by an unzipping method

at the original chain ends as well as at the new ends formed by random scissions. With

respect to the nature of thermal degradation, several types of polymers should be

differentiated: (1) Polymers having branching in the main chain. These polymers vaporize at

high temperatures. (2) Polymers in which the branching occur between the main chain and

the substituent. Such scissions form double bonds or cross linking. On further heating such

polymers become more or less stabilized in the form of a partially carbonized residue. (3)

9
The polymers which are highly cross linked. Such polymers on heating are converted into a

combed structure of carbon residue [23].

1.5 Kinetic Analysis Equations:

Reaction rate affect the kinetic parameters. Extent of reaction is determined by TGA data

[24]. In kinetic analysis of decomposition process Arrhenius equation and reaction models

are used. The reaction models are grouped into following type diffusion model, nucleation

model and reaction order model. These models depend on the extent of reaction (). For

every model kinetic parameter are measured and the fitness of data is determined. Kinetic

parameters were measured from integral rate law and solid state rate reaction. These rate

laws gives the kinetic information that is useful for evaluating the times and temperatures

linked with the handling, storage of materials and service lifetimes. It is also important for

understanding the mechanisms of thermal processes. The general equation used for kinetic

analysis is given below

d
k (T ) f () (5)
dt

g () k (T ) (6)

Where k(T) is the rate constant and f() is the reaction model and g() is an integral reaction

model. The rate of a process involving two parallel reactions can be described as:

d
k1 (T ) f1 () k2 (T ) f 2 ()
dt (7)

1.5.1. Arrhenius Equation:

The temperature dependence is explained by the Arrhenius equation. It leads to the

measurement of activation energy. Where A and E are Arrhenius parameters the pre-

10
exponential factor and the energy of activation, respectively and R is the general gas

constant.

E
k (T ) exp
RT (8)

Substituting the value of equation (8) into equation (5) we get.

d E
exp f ( ) (9)
dt RT

The rate of reaction depends upon the extent of conversion, which may be characterized by a

reaction model f() [25].

Upon integrating the equation (9) at constant heating rate we get

d E
T
g ( ) exp dT
f ( 0 RT
0 (10)

RTE
T
g () e dT
0
(11)

Replacing [ ]by x and applying the limit in above equation.

E
RT 0
g ( ) e x x 2 dx
(11.1)

The exponential integral is replaced by p(x) which has no analytical solution but has

approximation.

E
g ( ) p ( x) (12)
RT

From it energy of activation and rate constant can be calculated. Arrhenius equation also

finds its application in activated complex theory for determination of activation enthalpies

(H ), and activation entropies (S ) [26]. Comparison of slope of Arrhenius plot in high

11
and low temperature region will permit us to estimate the energy barrier and relative defect

formation energy in case of solid materials[27, 28].

1.6 Model Fitting Method:

From non-isothermal rate law and using model-free and model-fitting method kinetic

parameters are obtained. In model-fitting method fitting of different reaction models to the

extent of reaction, temperature curves and the calculation of the activation energy and

frequency factor is done. There are numerous non isothermal model-fitting methods

available, one of the most famous method is the Coats Redfern method [29].

1.6.1 Coats Redfern Method:

Coats Redfern method considers various reaction models and compare the linearity in each

case in order to choose the order of reaction. It also involves the thermal degradation

mechanism [30]. The Coats Redfern equation is given as.

g ( ) AR 2 RT ' E
ln 2 ln 1 (13)
T E RT

( )
T is mean of experimental temperature. Plotting [ ] Verses 1/T give E and A from slope

and intercept respectively. If 2RT/E << 1 then above equation becomes

g ( ) AR E
ln 2 ln (14)
T RT

1.6.2 Broido Method:

Broido equation, is used to find the kinetic parameters for the first and second stage. Broido

equation is given as

1 E RAT m
ln ln ln (15)
y RT E
12
Where y is the number of initial molecules that are not decomposed, R is gas constant (kJ

mol-1K-1) T is the temperature (K) and Ea is the activation energy (kJ mol-1). Tm is the

temperature of the maximum decomposition rate (K), is the heating rate (K min-1) and Z is

the frequency factor. A straight line is obtained if a graph is plotted between ln[ln(1/y)]

versus 1/T, where slope gives Ea and intercept gives A [31].

1.7 Model free methods:

1.7.1 Isoconversional methods

Isoconversional principle explains that the reaction rate is only the function of temperature if

the extent of conversion is constant. All isoconversional methods are developed based on this

principle. It can be revealed by taking logarithmic derivative of the rate of reaction at

= constant.

d
k (T ) f () (16)
dt

ln(d / dt ) ln k (T ) ln f ( )
1 1 1
T T T
(17)

is isoconversional value. If = constant then f () is also constant, and on right side of the

Eq. (17) the second term is zero. Thus above equation reduced as:

ln(d / dt ) Ea
1
T R (18)

13
From Eq. (18) it is clear the dependence of isoconversional rate on temperature can be used

to calculate the value of activation energy without using any reaction model. Due to this

reason, isoconversional methods are also called as model-free methods.

The dependence of Ea is very important for calculating and finding multistep kinetics. A

major variation of Ea with shows the complex process. The multi-step process does not

cancel the importance of the isoconversional principle. As isoconversional principle can

explain the kinetics of multistep process by using multiple single step kinetic equations.

Infect the Ea dependencies that are calculated by an isoconversional method allow kinetic

analysis mechanistic analysis as well as kinetics predictions can also be done [20, 32].

The isoconversional principle has wide applications as it laid foundation of various

isoconversional computational methods. They can be divided in two categories: integral and

differential. These are discussed below.

1.7.2 Differential isoconversional methods:

Friedman method is the most common differential isoconversional method [33]. The

Friedman equation is given as eq.19.

d Ea
ln ln[ f () A ]
dt ,i RT ,i
(19)

Eq. 19 can be applied to any temperature program. If the graph is plotted between ln

(d/dt),i and 1/T,i then the slope of this graph gives the value of Ea. The index i is used to

denote different temperatures. In case of isothermal programs, i denote an individual

14
temperature. For linear non isothermal programs i identify every single heating rate. In the

latter case, Eq. (19) is used in the following form

d Ea
ln ln[ f () A ]
dT ,i RT ,i
(20)

The resulting Eq. (20) infers that T ,i changes with the time in a linear way. The actual

sample temperature for T,i in Eq. (20) cannot be substituted. But, Eq. (19) can be used for

this substitution. It is important to note that both of these equations are related to that process

that occurs on low temperature or on cooling for which ( < 0) like crystallization.

1.7.2.1 Drawbacks of differential isoconversional methods:

Differential isoconversional method has certain inaccuracy. Firstly, inaccuracy in

determination of rate values occur when various methods are applied to differential data this

is due to difficulty in determination of baseline [34]. Inaccuracies also arise when the

reaction heat depends on heating rate. Due to these problems, the integral method can be

considered as an accurate and precise than differential method.

1.7.3 Integral isoconversional methods:

By applying isoconversional principle to integral equation (21) Integral isoconversional

methods originated. There is no analytical solution is present for the integral in Eq. (21) for

any temperature program. But for isothermal temperature program analytical solution can be

found as given:

E
t
d
g ( ) A exp dt
f ( ) RT
0 0 (21)

15
 E
g () A exp t
RT (22)

By rearranging the above equations and applying isoconversional principle a new equation

(23) is developed.

g () E
ln t ,i ln
A RTi (23)

where t,i is the time to reach a given extent of conversion at various temperatures Ti. The

equation (23) is applyied in isothermal conditions for an integral isoconversional method.

The slope of plot of lnt,i vs. 1/Ti gives the value of Ea. There are a lot of integral

isoconversional methods that differ from each other in temperature integral approximation.

Most of these approximations become the basis of linear equations of the general form [34]

E
ln i
T const C
,i RT (24)

where and C are the parameters find by the type of the approximation of temperature

integral. A very solid approximation is given by Doyle [35] according to it C = 1.052 and =

0 so that Eq. (24) take another form that is commonly known as the Ozawa [36], and Flynn

Wall (FWO) [37] equation:

E
ln(i ) const 1.052
RT (25)

More precise approximation is given Murray and White according to it C = 1 and = 2 and this

equation leads to another most famous Kissinger-Akahira-Sunose (KAS) equation (26) [38].

16
 E
ln 2i
T const
,i RT (26)

As compared to the Flyn-Wall-Ozawa method, the KissingerAkahiraSunose method

proposes an improvement in the exactness of the Ea values. According to Starink, more exact

evaluations of Ea can be done when setting C = 1.0008 and = 1.92 so that Eq. (24) changes

into:

i E
ln 1.92 const 1.0008
T
,i RT (27)

Since the mentioned Eqs. (24), (25), (26) and (27) can be solved by using linear regression

analysis. Further increase in the precision can be done by making use of numerical

integration. Integral isoconversional methods developed by Vyazovkin [39-41] is an example

of such approach. The Ea value can be find by minimizing the following function.

n n I [ E , T ,i )] j
( E )
i 1 j i I [ E , T , j )]i
(28)

where the temperature integral is :

E
T

I ( E , T ) exp dT
0 RT (29)

To fine dependence of of Ea on minimization is done for each value of .

The E value can also find by minimizing another function given in equation (30).

17
 n n
J [ E , Ti (t )]
( E )
i 1 j i J [ E , T j (t )]
(30)

where the integral with respect to the time:

E
t

J [ E , T (t )] exp dt
0 RT (t ) (31)

is solved numerically. Minimization is again done for each value of to find a dependence of

Ea on .

Application area of integral isoconversional methods is expanded by performing integration

with time. Firstly, by replacing sample temperature variation for Ti(t) effect of self-heating or

cooling can be studied. Secondly, many integral methods are also explained by it that apply

to those process that happens on cooling such as crystallization.

1.8 Natural Polysaccharides:

Polysaccharides are more versatile class of polymers. In nature the polysaccharides perform

different functions. Polysaccharides behave as energy storage materials like glycogen, starch.

Some plant seed polysaccharide gums also act as energy storage materials like guar gum and

locust bean gum. Some polysaccharides also have role in the formation of cell structures like

chitin and cellulose. Similarly in animal world like chondroitin sulphate, hyaluronate and

other related polysaccharides play an important part in the structure to build-up of the

intercellular matrix [42]. Some biomaterial taken from polysaccharide play a vital role in

various biomedical fields. Important properties of the polysaccharides include

biodegradability, controllable biological activity and its ability to form hydrogels [43].

18
Polysaccharides also act as natural absorbent materials or super absorbents. They have ability

to absorb water, saline solutions ,biological fluids and they have ability to retain these fluids

[44]. Polysaccharides also have applications in remediation, catalysis and adsorption. Natural

polysaccharides are well known as support for gelling agents as they have ability of

scattering of hydrocolloids. However, due to the low surface area they have less ability to

diffuse in dry state [45].

Natural gums and their derivatives are the polysaccharides and have lot of applications in

pharmaceutical industry. These natural polysaccharides are more important than synthetic

polymers because of their nontoxicity, cheap and free availability. Natural gums can also

used as an important materials for drug delivery systems and these compete with the

synthetic biodegradable materials [46].

1.8.1 Application of plant hydrogels:

Polysaccharide hydrogels are three-dimensional in structure, polymeric networks,

hydrophilic, capable of absorbing large amounts of water or other biological fluids [47].

Natural hydrogels are mostly preferred over synthetic hydrogels for being biocompatible,

easy availability, lower toxicity, favorable economics, higher water absorption capacity and

service life. Polysaccharide based materials among all other natural hydrogel have obtained

much attention in the controlled drug delivery technology. Modification of the natural

polysaccharide hydrogels can be easily done to alter their physio-chemical properties and to

fit them for different pharmaceutical uses. These materials, safe and biocompatible, are an

attractive choice not only for pharmaceuticals but also for food industries [48]. Chemically

modified plant hydrogels find its lot of applications in industry. Hydrogel alteration improves

19
the soil solutions by lowering the level of salt due to its buffering capacity and increased

Ca2+ uptake [49]. The effect of various types of hydrogels in varying amount added to sandy

soil on the vegetative growth, emergence, and drooping time of corn plant was studied. As

the level of hydrogel increased, the height of plant, width of leaf, crop production and wilting

time also increased. It is also observed that the PAAm/PAAcK hydrogels can improve sandy

soil properties for farming, because they can reduce watering frequency of the plants absorb

and improve the water retention capacity of soil matrix that caused an increase in plant

performance and growth [50]. Cellulose-based hydrogels can be made by cross linked

cellulose ethers in aqueous solution such as hydroxypropyl methylcellulose (HPMC),

methylcellulose (MC), ethyl cellulose[43] and sodium carboxymethylcellulose (NaCMC) and

hydroxyethyl cellulose (HEC) among which the most widely used cellulose derivatives. It is

worth importance that all these above polymers find a variety of application as emulsifying

agents in the food, thickeners, pharmaceutical and cosmetics industries due to their non-toxic

character and being cheap. Cellulose based hydrogel found its applications in devices for

controlled drug delivery, wound dressings scaffolds for regenerative medicine, stomach

bulking agents [10]. By using chemically modified acrylamide (AAm) and cashew gum

(CGMA) as reactants various super absorbent hydrogels are formed. Applications in the

agriculture field such as soil conditioner are being investigated [51]. Calcium-deficient

hydroxyapatite that is deposited in a bacterial cellulose hydrogel is considered as a novel

composite material and it is used as an orthopedic biomaterial [52]. Xylan-rich hemicellulose

base hydrogel was synthesized as a bio-adsorbent by co-polymerization of acrylic acid [5]

and xylan rich hemicellulose it can absorb many heavy metals like (Cd2+, Pd2+ and Zn2+)

from aqueous solutions [53].

20
1.8.2 Mucilage in plants parts:

Polysaccharide hydrocolloids having mucilage, glucans and gums are most rich in nature and

mostly found in highly developed plants. Mucilage is present in high concentration in various

plant organs and there are lots of classes in which the physiological functions of mucilage are

not clear. The organs containing mucilage are rhizome, endosperm of seed and root these are

main energy reservoir and storage organs however foliar mucilage do not serve as storage

form of carbohydrate [54]. Mucilage in plants means those carbohydrates that swell upon

addition of water and precipitated on addition of alcohol. Mucilage is present in plants in two

forms as a part of cell sap or in the wall[54].

1.8.3 Labiatae:

Salvia L. has more than 900 species and it is the larger genera in the Labiatae (Lamiaceae).

Labiatae is divided into four sub-genera: Leonia, Salvia, Sclarea and Calosphace. While

subgenera Sclarea are Salvia majorly found in European and Asiatic, Salvia subgenus

Calosphace is majorly present in South and Central America.

The genus Salvia contains many medicinal plants. For example S. aegyptiaca, S. canariensis,

S. fruticosa, S. aegyptia, S. lavandulifolia and S. officinalis [55]. Clerodanedi-terpenoid is

present in most of Salvia species. There seems to be clearly phytochemical differentiation

between subgenera Sclarea and Leonia, Salvia on the other hand, and the American subgenus

Calosphace on the other. Penta cyclic triterpenoids are most common in Salvia specie [56].

1.8.4 Salvia Aegyptiaca:

Salvia is a famous genus is mostly used in folk medicines as well as in flavoring. This genus

is of large importance due to chemical composition. The unique property of this genus is the

presence of 160 types of poly phenols. A large number of these polyphenolic compounds are

21
created from the caffeic acid through lot of condensation reactions. Seeds are used for

diarrhea also in haemorrhoids. Seeds yield mucilage and gum which contain aldotriouronic

acid and aldobiuronic acid. The mucilage on hydrolysis yields D-galactose, L-rhamnose, L-

arabinose and galacturonic acid.

1.8.4.1 Origin and distribution:

S.aegyptiaca is intricately branched and 10-20 cm high usually grows in sandy and compact

soil. S.aegyptiaca is located in Cape Verde Islands, Pakistan, N. Africa, Arabian peninsula,

Canary Islands, Afghanistan, Iran and India .Arid areas from Delhi west wards in Rajasthan

and Punjab , southwards in Maharashtra and Gujarat. In Pakistan Salvia aegyptiaca growth

was found on the LahoreIslamabad motorway M-2 Sawat [57].

1.8.4.2 Chemical profile:

From salvia specie the major isolated compounds include 6-methyl-epicryptoacetalide, 6-

Methylcryptoacetalide and 6-methylcryptotanshinone. Moreover, these unique diterpenoids,

13(18)-dien-28-oic acid, 3-hydroxy-oleana-11, 3-hydroxy-olean-12-en-28-

oic acid, sitosterol-3-glucoside, sitosterol, and 6-dihydroxy-7,3,4-trimethoxyflavone were

isolated [58]. The HPLC technique can easily detected the presence of many phenolic acids,

particularly the derivativde of caffeic acid along with phenolic diterpenes and flavonoids

[59] however, S. aegyptiaca was characterized by the be current of linoleic acid [60]

Further the known compounds b-amyrin 8 , D-glucopyranoside, lupeol, 3-hydroxy-24-

alkylcarboxylate-12-oleanan-28-oic acid, D-glucopyranoside.

Chromatographic separation of this shows the presence of the non-volatile material having

mixture of fatty acid esters of many oleanane-triterpenoid. From spectral data fatty acids are

easily identified and isolated [55].

22
Gas chromatographic analytical data of the essential oil of S. aegyptiaca is given below.

% Identification

1.14 Aromadendrene

19.29 1(10) Aristolene

6.14 Butylatedhydroxytoluene

3.43 9-Aristolene

1.29 Alloaromadendrene

18.43 Diphenyl amine

1.71 Phthalate ester

2.43 1-Hexadecanol

10.57 Methyl palmitate

2.86 Octadecane

3.71 Methyl linoleate

8.00 Methyl linolenate

1.57 Hexadecane

2.00 Phytol

1.43 Phthalate ester

7.00 E,E,E-Cembrene A

1.8.4.3 General uses:

Salvia aegyptiaca (tukhm-balango) widely used in traditional medicine like stomach soother

that helps in the digestion of undigested food. Seeds made into drink, for gonorrhea used as

23
demulcent, in diarrhea and piles[61], in the treatment of eye disease[62]. It is also used as

poultice[63].

1.8.4.4 Medicinal effect:

Salvia aegyptiaca is used to treat nervous disorders, used as demulcent, trembling, dizziness

and diarrhea etc. The reported tanshinone and royleanonediterpeneuinones are the subject of

great interest because of their anticancer and antimicrobial properties. The petrol extract of

S.A roots showed the potent inhibitory activity against staphylococcus aureus, pseudomonas

aeruginosa and candida albicane [64]. S.A extract also have antipyretic and anti-

inflammatory actions and CNS depressant properties [65]. S.A extract also inhibits the

growth of many bacteria and dematophytes that cause unpleasant odors and many of the

microorganisms are resistant to its extract like Cryptococcus neoformans and Candida

albicans [66].

24
Chapter 2
Literature Review

2.1 Literature Review

Zohuriaan, M. J., & Shokrolahi, F.et.al.(2004) [67] characterized Various gums (i.e.,

tragacanth gum, xanthan gum, hydroxyethylcellulose, gum Arabic, chitosan, methylcellulose

and carboxymetylcellulose). During analysis techniques employed were differential scanning

calorimetry (DSC) and thermogravimetric analysis (TGA) under nitrogen atmosphere.

Activation energies and thermal transitions were determined. Tragacanth gum and

hydroxyethyl cellulose exibit (258 kJ/mol) and (121 kJ/mol) activation energy during

pyrolysis respectively. The DSC curves shows a major exothermic transition around

temperature 300C followed by weaker exotherms. However, intense exotermic transition is

shown by Methylcellulose. Based on TGA thermograms, the integral procedural

decomposition temperature (IPDT) values were determined. The chitosan have IPDT value

417C, carboxymethylcellulose IPDT value was 412C and methylcellulose IPDT 386C

were considered to be more thermally stable than the other polysaccharide.

Villetti, M. et .al.(2002)[68] evaluated the thermal degradation of xanthan, methylcellulose

and sodium hyaluronate by infrared and thermogravimetric analysis. Activation energy and

pre-exponential factor were calculated using the Ozawa and Freeman-Carroll methods. The
25
finding shows the fraction of mass loss with changes in the degradation mechanism for

polysaccharides. The values of activation energy calculated by the FreemanCarroll method

were found higher than that value which is calculated by the Ozawa method under the same

conditions. Low thermal stability was obtained for poly anions e.g. xanthan(XT) and sodium

hyaluronate as compare to methylcellulose which is a neutral polysaccharide.

Akbar, J. et. al.(2012)[69] studied the thermal degradation mechanism and kinetics of

pentose and hexose based polysachhrides that are extracted from Ocimum

basilicum (OB) Plantago ovate (PO) and Salvia aegyptiaca (SA). Isoconversional method

was used during analysis. The materials showed two-stage degradation. The loss of weight

that occurs at ambient to 115 C corresponds to loss of moisture content from sample and it

is determined by low activation energy. Activation energy, pre-exponential factor and

reaction model of the materials were determined. The major pyrolytic stage indicated that the

high boiling volatile sample evolve from sample and this stage was exothermic. Above

340 C about 1015% residue left that shows complete degradation. Master plot method was

used to determine and differentiate the degradation mechanism of hexose-based OB and SA

polymers and pentose-based PO polymer. The master plot method showed that the hexose-

based polymers showed A4 type degradation mechanism and pentose-based carbohydrate

polymer showed D4 type mechanism.

26
Iqbal, M. S. et. al.(2013)[70] reported the isoconversional thermal analysis of some

polysaccharides. Kinetic triplet i.e E, A and g() [71] were determined, and the fitness of data

to different models was analyzed that describe the degradation kinetics of polysaccharides.

The polysaccharides from Plantago ovata , Argyreia speciosa , Acacia nilotica ,

Acacia modesta, Mimosa pudica and ovata showed multistep degradation while those from

Astragalus gummifer, Ocimum basicilicum and Salvia aegyptiaca degraded mainly in single

step. The degradation was exothermic. FlynnWallOzawa method was used to determine

average Ea values that were in the range of 132187 kJ mol1. The mean comprehensive

index of thermal stability[14] was 0.330.43. The entire sample under examination except

those from Salvia aegyptiaca and Argyreia speciosa were found to be as stable. Model-fitting

analysis indicated that the major degradation step follows first-order kinetics.

Akbar, J. et. al.(2011)[71] Isolated and thermally characterized the hydrogels from Plantago

ovate (PO), Ocimum basilicum (OB), Mimosa pudica (MP) and Salvia aegyptiaca (SA). In

order to study the effect of variation on pyrolytic behaviour, the hydrogel acquired from PO

was altered by carboxymethylation, ethylation and cross-linking. Pre-exponential factor,

activation energy, entropy, enthalpy, comprehensive index of intrinsic thermal stability[14]

and free energy change were calculated from the thermograms. A good thermal stability of

the hydrogels was indicated by ITS values. Other hydrogels do not showed significant

difference only PO gel and its modified forms showed difference in thermal profile. The

27
modified gels showed good thermal stability. The GCMS analysis of these hydrogels was

done and formation of water, 3-hydroxypropanal and 2-hydroxybutanedial as degradation

products was detected.

Archana, G., Sabina, K., et. al.(2013)[72] extracted the mucilage from waste of Abelmoscus

esculentus using two different solvents (Methanol and Accetone) and further compared with

seaweed polysaccharide. The emulsifying capacity, swelling index and percentage yield of

this mucilage were determined. The okra waste and macro algae showed high % yield (8.6%

and 22.2% respectively) and good emulsifying capacity (0.28% and 11.3%; EC% = 50%)

(PH = 7) with methanol and (EC% = 54.76% and 52.38% respectively) with acetone. The

emulsifying capacity with acetone as found to be good. Swelling index was found to be

greater with methanol than acetone. In order to explore the chemistry of mucilage the I.R

spectrum was recorded. TGA (Thermal Gravimetric Analyzer) and DSC (Differential

Scanning Calorimeter) of mucilage revealed great thermo stability of both okra and algal

hydrogels.

Chen, C., Ma, X., & Liu, K. (2011)[73] conducted an experiment in which the combustion

behavior of Chlorella vulgaris was explored in a thermogravimetric analyzer (TGA) from

ambient to 800 C. The effects of different oxygen concentrations and different heating rates

on the pyrolysis of Chlorella vulgaris has been analyzed. The findings revealed that the

ignition processes of Chlorella vulgaris can be distributed into three stages. For the kinetic

28
analysis of the main decomposition process of Chlorella vulgaris (FWO) and (KAS) methods

were employed. The findings showed that, when amount of oxygen changes from 20-80

vol% the activation energy values increase from 134.5-242.33 kJ mol1 by KAS method and

134.03 to 241.04 kJ mol1 by using FWO method. So the optimum concentration of oxygen

for Chlorella vulgaris combustion was found to be 25-35 vol.%.

Poletto, M. et. al.[74] compared the thermal stability of the sawdust of different wood

species. The composition of two wood species Eucalyptus grandis and Pinus taeda was

determined in order to assess the effect of the main woody component on the thermal

stability of sample. To evaluate the activation energy the thermogravimetric analysis of both

species was done at different heating rates. For the calculation of activation energy method

used were the Flynn-Wall-Ozawa (FWO) and Kissinger methods. The findings recommend

that the great thermal stability of wood is related to large quantity of hemicellulose and

lignin. The Ea values calculated for the both species were in the range of 146-165 kJmol-1.

Tonbul, Y. (2007)[75] studied thermal degradation kinetics and characteristics of various

small sizes pistachio shells. Thermal degradation analysis has been performed by using a

thermogravimetric analyzer from ambient to 800C in N2 atmosphere at different heating

rates. By using Coats-Redfern method and Flynn-Wall-Ozawa method kinetic parameters

were calculated. Two distinct degradation zones were observed in TG and DTG curves.

29
Liu, X. et. al. (2010)[76] used TGA and studied the pyrolysis of corn starch having different

amylose/amylopectin ratios under nitrogen conditions using TGA. To calculate the activation

energy of different starches various decomposition models including Friedman, modified

Coast-Redfern methods, Kissiger and Flynn-wall-Ozawa was used. The finding reveals that

all corn starches showed multiple-step mechanism of thermal decomposition. The order of

activation energy for the corn starches which corresponds to amylopectin content was

waxy>maize>G50>G80. The greater activation energy for corn starch with more

amylopection content can be elucidated by its more 1,6 bonds and higher molecular weight.

Li-Chan, E. C. Y.et.al. (2002)[77] investigated the thermal properties of proteins isolated

from flaxseed as well as meal by using differential scanning calorimetry (DSC). A large

amount of flaxseed protein was extracted by anion exchange chromatography and a high

denaturation temperature (Td) of 114.70 C was observed that represents the 11-12 S stored

globulin protein. Thermal analysis of the major fraction in the presence of chaotropic salts or

protein structure recommended the influences of ionic interactions and hydrophobic,

disulfide linkages and hydrogen bonding. This contributes to the stability of flaxseed protein.

However, no report is available in literature on the pyrolytic kinetics of SA hygrogel

with non-linear methods. The objective of present study is to explore the degradation kinetics

of SA hydrogels with non-linear techniques and to predict its stability profile.

30
The thermal degradation behaviour of various polysaccharides and other polymers can be

studied either by multiple heating rates (model-free, isoconversional) methods, or single

heating rate (model-fitting) methods. However, single-heating rate methods do not provide

precise information about kinetic parameters. Moreover, recently non-linear methods such as

distributed reactivity model (DRM), non-linear least square method and Vyazovkin method

have proven better techniques. These methods can provide better estimate of thermal kinetic

parameters and give better information about the kinetics of thermal degradation of materials.

These methods eventually results in good prediction of the thermal stability profile and shelf-

life of the materials as well as kinetics of degradation. This work focuses on the study of

pyrolytic behaviour of hydrogel isolated from Salvia aegyptiaca and kinetic modelling of

their thermal degradation by non-linear methods.

2.2. Aims and objectives:

The aims and objectives of this study are

Study of thermal degradation kinetics and mechanisms of the hydrogel, isolated from

seeds of Salvia aegyptiaca by non-linear methods.

Non-linear estimation of kinetic triplet for pyrolytic degradation process.

Estimation of stability profile of the hydrogel under study.

31
 Chapter3

Experimental

3.1 Materials and Methods

3.1.1 Materials

The seeds of Salvia aegyptiaca (SA) was purchased from the native market. During the study

double-distilled water and methanol was used.

3.1.2 Methods:

3.1.2.1. Isolation of Hydrogel from Salvia Aegyptiaca:

Seeds of Salvia aegyptiaca (10g) were cleaned with distilled water and transferred to 2-L

beaker having distilled water (500 cm3). Seeds were dipped in distilled water for 6 hours then

the seeds was crushed and mixed with blunt blades by using kitchen blender. Using mulsin

cloth the mucilage was separated from seeds. The mucilage was then precipitated by treating

with ethanol. Coagulated material was obtained, filtered, dried in air and powdered by using

kitchen grinder.

32
3.1.2.3 Thermal Analysis:

The grounded hydrogel was analyzed by TGA and DSC. The scans were simultaneously

recorded by use of thermal analyzer SDT, Q-600 (TA instruments, USA). A small amount of

sample (3mg) was used under nitrogen atmosphere at a flow rate of 100oC min-1. Four

different heating rates; 5, 10, 15 and 20oC min-1 were used to obtain the thermal data over a

temperature range from ambient to 600oC. The data obtained was analyzed by using single

heating rate model-fitting Brodio method, multiple heating rate model-free isoconversional

methods and non-linear optimization methods.

3.1.2.3.1.Model fitting analysis:

The Broido equation (eq. 15) was used to calculate the kinetic parameters for the first and the

second thermal decomposition stages.

1 E RAT m
ln ln ln
y RT E

where, y is the fraction of the number of initial molecules not yet decomposed, R is the

general gas constant (kJ mol-1 K-1), T is the temperature (K) and Ea is the energy of activation

(kJ mol-1). Tm is the temperature of the maximum decomposition rate (K), is the heating

rate (K min-1), and A is the frequency factor. A straight line is obtained if a graph is plotted

between ln[ln(1/y)] versus 1/T, where slope gives Ea and intercept gives A [31].

Using Broido equation Activation energy and frequency factor A were calculated. The

thermodynamic parameters; entropy of activation (S*),enthalpy of activation (H*) and

gibbs free energy of activation (G*) were determined using standard equations (eq. 2,3,4).

33
3.1.2.3.2.Model free isoconversional analysis:

The FWO method [36] given in eq. (25) was used to determine activation energy.

E
ln(i ) const 1.052
RT

AE
where const is ln 5.331 . graph was ploted between ln against 1/T at different .
Rg ( )

Slope of this graph gives activation energy. Another method called as KAS (eq.26) [38].

method was employed for the calculation of activation energy.

E
ln 2i
T const
,i RT

AR
where constant is ln graph was plotted against ln 2i and 1/T and from the slope
Eg ( ) T
,i

of this graph activation energy was calculated.

Coats redfern equation (eq. 13) was used to calculate value of frequency factor.

g ( ) AR 2 RT ' E
ln 2 ln 1
T E RT
( )
where T is the mean experimental temperature. Plotting [ ] VS [1/T] give Ea and A

from slope and intercept respectively. Compensation parameter a and b were determined

from slope and intercept of graph of Ea plotted against lnA. Compensation effect relation was

finally used to determine the value of frequency factor.

ln A a bE (32)

Various g ( ) models (Table 1) were used to solve Coats-Redfern equation and Master plot

method was also used to determine value of frequency factor.

34
Table 1: Various Kinetic models

35
3.1.2.3.3 Non-linear Regression Analysis:

Non-linear regression was used to reduce the difference between the theoretical and

experimental data. It is denoted as (RSS):

RSS Yexp Ycalc min

2
(33)

Using master plot method the values of yexp and ycalc can be obtained from the experimental

g() and theoretical g(). A minimum value of RSS is calculated mathematically by changing

values of different kinetic parameters for the separate steps individually. Some rate equations

can be analyzed and linearized with the help of methods such as linear regressions. However,

linearization can increase the kinetic parameters sensitivity to small values. However, non-

linear regression methods are comparative to extents of conversion and can simply optimize

reaction rates or both at the same time.

36
Chapter4

Results and Discussion

4.1 Isolation of Hydrogel

The hydrogel isolated from the given material was found slightly brown in color. A

good yield (8%) was obtained for SA hydrogel. The hydrogel material thus obtained showed

a good swelling property in water and it was light weight. It can be used for various

applications such as in planning controlled drug delivery devices.

4.2 Thermal Degradation Kinetics

Both model-fitting and model-free methods were used to investigate the thermal degradation

kinetics of material.

4.2.1 Model-Fitting analysis: Broido Method:

The natural hydrogel materials exhibited a three-stage decomposition behavior as shown in

TGA. (Fig.1). The SA hydrogel exhibited a weight loss of 7.4% at the start in temperature

range 80-120oC. The reason for this endothermic transition is the loss of entrapped water

[78]. The major decomposition of SA hydrogel takes place in second stage. The initial

decomposition temperature (IDT) was found between the ranges of 30-130C for first stage

while the final decomposition temperature (FDT) was found to be in the range of 215-335C.

37
Fig. 1: TGA, DTG and DSC thermograms of hydrogel isolated from Salvia Ageptiaca.

38
This is due to the small exothermic enthalpy change with considerable weight loss (46%)

which indicates the loss of some high mass volatile components [79].

During later stage (stage-III), the hydrogel was decomposed almost completely to gaseous

products such as CO2, H2O, CO etc. leaving behind a residue rich in carbon (7.4%). In order

to calculate the thermal parameters, Broido plots (Fig. 2) and standard equations were used.

The Ea values was found to be 101.68-104.56 kJ mol-1 which are comparable with other

naturally occurring polysaccharides [67].

The IPDT and ITS values were used to assess the overall thermal stability of which were

found to be 321.94C and 0.53 respectively. The values indicated a better thermal stability of

the SA hydrogel and these values are analogous to commercially available polymeric

materials [67]. In case of SA hydrogel positive G* values shows a non-spontaneous

degradation (183.57 kJ mol-1) while S* values shows more ordered activated complex

(-114.14J K-1mol-1). The Ea value for SA hydrogel was found to be 101.68-104.56 kJmol-1.

This reflected sufficient thermal stability of SA hydrogel which would result in a slower rate

of decomposition. The kinetic parameters obtained by Broidos method are given in Table 2.

39
 1.5
1 y = -12.231x + 21.268
0.5 R = 0.9866
0
ln(ln(1/y))

-0.5
-1
-1.5
-2
-2.5
-3
-3.5
1.5 1.7 1.9 2.1 2.3 2.5
-1
1000/T(K )

(a)

1.5
y = -12.259x + 20.914
1
R = 0.9844
0.5
0
ln(ln1/y)

-0.5
-1
-1.5
-2
-2.5
-3
-3.5
1.6 1.7 1.8 1.9 2
1000/T(K-1)

(b)

40
 y = -12.577x + 21.2
1.5 R = 0.9837
1
0.5
0
ln(ln1/y)

-0.5
-1
-1.5
-2
-2.5
-3
-3.5
1.6 1.7 1.8 1.9 2
1000/T(K-1)

(c)

1.5
1
0.5
y = -12.48x + 20.884
0 R = 0.9866
-0.5
ln(ln1/y)

-1
-1.5
-2
-2.5
-3
-3.5
1.55 1.6 1.65 1.7 1.75 1.8 1.85 1.9 1.95
1000/T(K-1)

(d)

Fig. 2: Broido Plots to calculate Activation Energy

41
Table 2: Thermal parameters for hydrogel under study by Broidos method

Temp. Mass Mass at

Sample rangea loss Ea H* S* G* IPDT 600C
code (C) (%) (kJ mol-1) (kJ mol-1) (JK-1mol-1) (kJ mol-1) lnA (C) ITS (%)

101.68-
SA 250-325 39.22 104.56 113.26 -114.14 183.57 16.45 321.94 0.53 7.14

a
Temperature range for the main stage of decomposition. lnA, E, H*, S*and G* are calculated for this stage. IPDT and ITS are

calculated for the entire thermogram.

42
In order to assess the thermal stability of materials a quick estimate of kinetic parameters can be

obtained from single heating rate methods (i.e. Broido method). But, these methods are being

criticized for provision of a rough estimate of kinetic parameters. Due to this reason model-free

isoconversional analysis was performed. This approach gives a stable estimate of kinetic

parameters and it can also be used to guess the behavior of materials under isothermal conditions

and gives a better insight into the degradation kinetics and mechanism.

4.2.2 Model-Free Isoconversional Analysis:

The DSC and TGA scans were simultaneously recorded on powdered polymer by use of thermal

analyzer SDT, Q-600 (TA instruments, USA). The 3.0-10 mg of samples was used under

nitrogen atmosphere at a flow rate of 100 Four different heating rates: 5, 10, 15 and

20 C min-1were used to get the thermal data over a temperature range from ambient to 360 C.

The data was further analyzed by using MS Excel 2010, Universal Analysis 2000 software,

version 4.2E (TA Instruments, USA).

4.2.2.1 Isoconversional Thermal Analysis of SA hydrogel:

The TGA curves of SA hydrogel showed three discrete regions of weight loss (Fig. 3). These are

(i) Region I: ambient to 130C,

(ii) Region II: 215-365C,

(iii) Region III: >365oC

43
Fig 3: TGA curves for SA at different heating rates

44
For region I the activation energy is low (57.74 kJ mol-1 by FWO method, 55.25 kJ mol-1 by KAS

method) (Fig 4a, 5a and 6a) showed the removal of moisture. The lnA value for stage I come out

to be 17.154. The degradation of SA hydrogel was initiated in the region II. The average Ea for

this region =0.05 to =0.95, calculated by FWO and KAS method (Fig.4b, 5b and 6b) comes

out to be 163.83 kJmol-1, 162.78 kJmol-1 respectively. The Ea was almost found to be constant at

different degree of conversions (Fig 7).

4.2.2.2 Thermal degradation mechanism:

The isoconversional principle states that at any degree of conversion (), the rate of

reaction is independent of reaction mechanism and it depends only upon temperature. This

statement makes base for the formation of model-free method which helps for evaluation of

thermal data. The integral kinetic equation given below in Eq. (25). This equation is obtained by

using an approximation

E
ln(i ) const 1.052
RT

where and C parameters in above equation refers to a specific type of approximation applied on

a specific integral isoconversional method. The isoconversional method which was suggested by

Flynn and Wall and Ozawa, (FWO) is being more extensively used C is taken as 1.052. However

the most dependable values of activation energy (Ea) can be achieved by putting C = 1. The

result achieved is called Kissinger-Akahira-Sunose (KAS) equation[70], shown below in Eq.

(26).

E
ln 2i
T const
,i RT

45
 1
0.9
0.8
0.7
0.6 5 C
0.5 10 C

0.4 15 C
0.3 20 C
0.2
0.1
0
200 250 300 350 400 450 500
T(K)

(a)

1
0.9
0.8
0.7
0.6 5 C
0.5 10 C

0.4 15 C
0.3 20 C
0.2
0.1
0
400 450 500 550 600 650 700
T(K)

(b)

Fig 4: -T profile of SA hydrogel (a) Stage I, (b) Stage II

46
 0.05
0.10
0.15
3.50 0.20
0.25
3.00 0.30
0.35
2.50 0.40
0.45
ln (

2.00 0.50
0.55
1.50 0.60
0.65
1.00 0.70
0.75
0.80
0.50 0.85
2.00 2.50 3.00 3.50 0.90
1000/T (K-1) 0.95

(a)

0.05
0.10
0.15
3.50 0.20
0.25
3.00 0.30
0.35
2.50 0.40
ln (

0.45
2.00 0.50
0.55
1.50 0.60
0.65
1.00 0.70
0.75
0.50 0.80
1.40 1.90 0.85
0.90
1000/T (K-1) 0.95

(b)

Fig. 5: FWO analysis plot to calculate Ea (a) Stage I, (b) Stage II

47
 0.05
-8.00 0.10
0.15
-8.20
0.20
-8.40 0.25
0.30
-8.60
0.35
log (/T2

-8.80 0.40
-9.00 0.45
0.50
-9.20 0.55
-9.40 0.60
0.65
-9.60 0.70
-9.80 0.75
0.80
-10.00 0.85
2.00 3.00 4.00 0.90
1000/T (K-1) 0.95
(a)

0.05
-8.00 0.10
0.15
-8.50 0.20
0.25
-9.00 0.30
0.35
-9.50
log (/T2

0.40
0.45
-10.00
0.50
-10.50 0.55
0.60
-11.00 0.65
0.70
-11.50 0.75
0.80
-12.00 0.85
1.40 1.90 2.40 0.90
1000/T (K-1) 0.95

(b)

Fig. 6: KAS analysis plot to calculate Ea (a) Stage I, (b) Stage II

48
 250 Region I Region II

200
150
100
E

50
0
-50
-100
0.10 0.30 0.50 0.70 0.90 1.10

(a)

250 Region I Region II

200
150
100
E

50
0
-50
-100
0.10 0.60 1.10

(b)

Fig 7. -E profile, (a) FWO plot, (b) KAS

49
In Eq. (26) R represents general gas constant; Ea refers to the activation energy; while denotes

the heating rate and T represents the temperature at a degree of conversion . The degree of

conversion can be described as ( )/( ). In this refers to the weight of the

sample at any temperature T, while indicates initial weight and refers to the final weight at

the temperature where the mass losses are almost insignificant. The data obtained at multiple

heating rates was analyzed by KAS method and at a given value of , a graph of ln (/T) vs 1/T

gives a straight line (Fig 6).From the slope The values of Ea were calculated.

The pre-exponential factor A cannot be directly estimated from KAS method. For this

purpose master plot method[80] or the compensation effect method[20] can be used. In this

study we used compensation effect relationship Eq. (32)

ln A = a + b Ea

where a and b represents the compensation effect parameters and these factors were calculated

by using model-fitting approach given by Coats-Redfern Eq.13

g ( ) AR 2 RT ' E
ln 2 ln 1
T E RT

50
Where T denotes the average experimental temperature. The Eq. (13) was solved by using

various g () models (Table 1). To determine the pre-exponential factor A, the average values of

(from KAS method) and compensation parameters (a and b) were obtained from equation 32

by putting various models. A set of kinetic parameters, A and were obtained by plotting a

graph between ln(g()/ ) vs1/T in this equation and the values of a and b were calculated

according to Eq. (32). The selection of model was made by observing to factors (i) the activation

energy closeness with that calculated by KAS method (ii) the correlation coefficient. Various g

() models are given in Table 1. The values of thermal parameters G *, S* and H* were

determined by standard equations [70]. The kinetic model determination for all 3 stages is shown

in (Fig 8,9,10) .

51
 25

20
g()/g(0.5)

15

10 D3
5C/min
10C/min
5 15C/min
20C/min
0
0.00 0.20 0.40 0.60 0.80 1.00

(a)

16

14

12 y = 2E-05x + 0.5242
R = 0.7724
10
g()

0
0 200000 400000 600000 800000 1000000
[p(x)E/T]*10^13

(b)

52
 2.5

1.5
g()

A3/2
1
5C/min
10C/min
0.5 15C/min
20C/min

0
0.00 0.20 0.40 0.60 0.80 1.00

(c)

fig 8: Determination of kinetic model for SA hydrogel decomposition in region I, (a)

Fitting of Experimental data to theoretical model, (b) determination of g() model, (c)

reconstructed g() model

53
 13

11

9
g()/g(0.5)

D3
5
5C/min
10C/min
3
15C/min
1 20C/min

-10.00 0.20 0.40 0.60 0.80 1.00

(a)

7.5
y = 31.429x - 0.0348
6.5 R = 0.997

5.5

4.5
g()

3.5

2.5

1.5

0.5
0.05 0.1 0.15 0.2
[p(x)E/T] x1013

(b)

54
 2.5

1.5
A3/2
g()

5C/min
1 10C/min
15C/min
20C/min
0.5

0
0.00 0.20 0.40 0.60 0.80 1.00

(c)

Fig 9. Determination of kinetic model for SA hydrogel decomposition in region II, (a)

Fitting of Experimental data to theoretical model, (b) determination of g() model, (c)

reconstructed g() model

55
equation. The kinetic triplet for region I was found to be: g () =F2, E=55.25 kJmol-1, A= 1.8310-5

min-1(lnA= -10.90). The F2 is second order kinetic equation. The kinetic triplet for region II was found

to be g () = D4, E=162.78 kJmol-1, A=31.428 min-1(lnA=3.447) (Table 3). The D4 reaction model is

the Ginstling-Brounstein equation (Table 1).

56
 Table 3: Thermal parameters for hydrogels obtained by isoconversional methoda

Sample Decomposition Temp. Ea

(kJ mol-
Code Stage rangea 1 MPb CEb
)
(C) KAS FWO lnA A B R2 lnA Mechanism

SA I 25-130 55.25 57.74 -10.90 1.83 -2.947 0.996 17.15 F2

II 215-360 162.78 163.83 3.44 31.42 0.2133 0.998 31.77 D4

a
The temperature ranges are from all heating rates
b
MP and CE are master plot and compensation effect methods respectively for the determination of lnA

57
4.2.2.3 Non- linear regression analysis:

Non-linear regression is used for fitting of different single and multi-step, it reduces the

difference among the theoretical and experimental data. The least squares process assesses the

difference as residual sum of squares denoted as (RSS): The equation is

RSS Yexp Ycalc min

2

The values of yexp and ycalc can be obtained from the experimental g() and theoretical g() and

calculated by using master plot method. A minimum of RSS can be calculated mathematically by

changing the values of different kinetic parameters for the separate steps. From the values which

assure a minimum of RSS Approximations or estimations of the kinetic parameters are achieved

Fig 11 and 12. Linearization will increase the sensitivity of kinetic parameters to small values

[20]. Following the above procedure the region I was found to follow D6 mechanism=Anti-

Jander equation majorly. The kinetic triplet for this region was found to be g () = D6, E=19.17

kJmol-1, lnA= (16.09) and RSS value 0.02

The region II was found to follow D8= Anti-Jander equation. D6 and D8 both follow anti-jander

equation, which was observed to follow three dimentional diffusion mechanism. The Anti-jender

model could be treated as reverse of jender model. The kinetic triplet for this region was found to

be g () = D8, E=4.69 kJmol-1, A= 6.30 e13 min-1(lnA=31.77) and RSS value was 0.00184 (Table

4).

58
 2.5

2
g()/g(0.5)

1.5 D8

1
5C/min

0.5

0
0.00 0.20 0.40 0.60 0.80 1.00

(a)

2.5

2
g()/g(0.5)

1.5

1 D3

10C/min
0.5
20C/min
0
0.00 0.20 0.40 0.60 0.80 1.00

(b)

59
 2.5

2
g()/g(0.5)
1.5

1 D8

0.5 15C/min

0
0.00 0.20 0.40 0.60 0.80 1.00

(c)

Fig 11. Determination of kinetic model for SA hydrogel by nonlinear regression for stage 1

2.5

2
g()/g(0.5)

1.5

1 D3
5C/min
10C/min
0.5 15C/min
20C/min
0
0.00 0.20 0.40 0.60 0.80 1.00

Fig 12. Determination of kinetic model for SA hydrogel by nonlinear regression for stage II
60
 Table 4: Kinetic triplet for hydrogels obtained by non-linear regression method.

Sample Decomposition Mechanism E A LnA RSS

Code Stage g(a) (kJ mol-1) (min-1)

SA I D6 19.17 9779321.63 16.09 0.02

II D8 4.691 6.30 e13 31.77 0.00184

61
4.3 Conclusion

The hydrogel was isolated in good yield by use of the experimental procedures. The hydrogel

was thermally stable upto 215C and decomposed after that releasing various products leaving a

residue of about 7.4%. The non-linear regression method was used to minimize the error between

experimental and theoretical data. The value of residual sum of square (RSS) was found lower

than master plot method and it provides better estimate of kinetic parameters. The material

showed good stability profile at room temperature and therefore possesses an acceptable shelf-

life and as such can be used as pharmaceutical excipients and in food industry.

62
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