1
Kinetics of Oxidation of Acetone and Acetophenone by
Persulphate Ion in presence of Silver Ion as a catalyst
MISON MUSTAFA HASSAN MADANI
B.Sc in chemistry, Alneelain University (2005)
A Dissertation
Submitted to the University of Gezira in Partial Fulfillment of
the Requirements for the Award of the Degree of Master of
Science
in
Chemistry
Department of Applied Chemistry and Chemical Technology
Faculty of Engineering and Technology
January, 2014
2
Kinetics of Oxidation of Acetone and Acetophenone by
Persulphate Ion in presence of Silver Ion as a catalyst
Mison Mustafa Hassan Madani
Supervision Committee:
Name Position Signature
Dr.Fathelrahman Abbas El Sheikh Main Supervisor …….…..
Dr. Mohamed Osman Babiker Co-supervisor ………….
Date: January, 2014
3
Kinetics of Oxidation of Acetone and Acetophenone by
Persulphate Ion in presence of Silver Ion as a catalyst
Mison Mustafa Hassan Madani
Examination Committee:
Name
Position
Signature
Dr. Fathelrahman Abbas Elsheik
Chair Person ……………
…….
Dr. Kamal Mohamed Saeed
External Examiner ……………
…….
Dr. Abobaker Khidir Ziyada
Internal Examiner …………
Date of Examination: 31/01/2014
5
AKNOWKEDMENT
One day a friend said to me that sometimes it is
necessary to touch the thorn of the rose to reach the
flower, and I wish to say thanks to all of those people
that helped and supported me during this journey. I
would like to express my special thanks of gratitude to
my supervisor Dr.Fathelrahman Abbas Elsheikh His wise
advise, insightful criticism, and patient encouragement
aided me in writing this work and my thanks to all
laboratories members faculty of pharmacy in Khartoum
collage of medical sciences and i don’t forget to thank my
lovely sister Amna Mustafa whose steadfast support on
my acadimic journey. Last but not least thanks again to
all who helped me and most of all to the almighty Alla
who gave me strengths and good health while doing
this project.
6
Kinetics of Oxidation of Acetone and Acetophenone by
Persulphate Ion in presence of Silver Ion as a catalyst
MISON MUSTAFA HASSAN MADANI
Abstract
The ketones are relatively hard to oxidize at ordinary temperature, but
they do undergo oxidation reaction at extreme temperatures. The
oxidation of ketones, Investigated, to study the oxidation reaction
kinetics of (acetone and acetophenone) by peroxodisulphate, to find the
order and effect of the structure of the two compounds and determine the
activation energy, the entropy, the enthalpy and free energy of activation.
The kinetics runs were carried out by potassium peroxodisulphate ion in
aqueous sulfuric acid medium in presence of silver nitrate as catalyst in
70oC and there were variable concentrations of peroxodisulphate and
silver ion and a plot of variable concentration of titre against time were
established. From the curve, the initial rate for each concentration was
obtained and plotted against the log of [potassium peroxodisulphate] and
secondly versus [silver]. From the slope of the straight line the order of
reactions were determined, the reactions obeyed first –order for each. on
the other hand the concentration of substrates were variable while the
concentrations of silver and potassium peroxodisulphate were constant
and a plot of concentrations of titre against time was established, from
the curve initial rate for each concentration was obtained and plotted
against the log of [substrate] . A straight line was obtained and from
slope determined the order of reactions for substrate. The reactions
obeyed first –order for acetone and half- order for acetophenone .the
activation of energy [26kJ] for acetone and [93Kl] for acetophenone ,and
the enthalpy of activation to acetone [23.15Kj] and [90.19Kj ] for
acetophenone ,entropy of activation [-235.5J] for acetone and [-247J] for
acetophenone and free energy of activation for acetone[79.5Kj] and
[83.4Kj]for acetophenone.The kinetics have been evaluated by
determining the rate constants at different temperatures.Differences may
be due to benzene ring acetophenone. For this, it is recommended that
the effect of the benzene ring on the oxidation of ketones must be studied
by choosing aliphatic ketone. The products of the reaction have been
identified as carboxylic acid.
7
بيرسلفيتاكسده االستون واالسيتوفينون بواسطه ايون ال ةحركي في وجود ايون
الفضه كعامل مساعد
ميسون مصطفي حسن مدني
ملخص الدراسه
صعبه في ) االليفاتيه واالروماتيه(تم دراسة حركية اكسدة الكيتونات ووجد أن اكسده الكيتونات
وفي هذه الدراسه تم درجه الحراره العاديه ووجد أنها تحدث في درجه حراره عاليه نسبيا,
بواسطه أيون بيروكسي ثنائي كبريتات اكسدة التفاعل لالستون واالسيتوفينوندراسة حركية
وايجاد درجة التفاعل وتاثير الصيغه الكيميائيه علي اكسدة الكيتونات وتم تحديد البوتاسيوم
في ركيه آكسده الكيتونات ح االنتروبي واالنثالبي وايجاد طاقه جبس الحره وقد تمت دراسة
في وجود نترات الفضه كعامل مساعد وفحصت في الكبريتيك المائي( وسط حمضي) حمض
ا بينملبوتاسيوم ا كبريتاتبيروكسي ثنائي , وقد اخذ تركيز متغير من 70OCدرجه حراره ثابته
, ومن جهة اخري اخذ تركيز ثابتاونترات الفضه ظل )االستون, واالسيتوفينون(كيتونتركيزال
الكيتون والبيروكسي تنائي كبريتات البوتاسيوم ثابتا, ومنهامتغيرلنترات الفضه وظل تركيز
لمحلول المعاير ومنها وجدت السرعه االبتدائيه للتراكيز امنحني برسم الزمن مع تركيزحدد
ورسم معادله ل بيركسي ثنائي كبريتات البوتاسيوم ونترات الفضه في كل حاله ومنها المختلفه
مره المختلفه مره,ونترات الفضه البيروكسي ثنائي البوتاسيوم تركيز الخط المستقيم للوغريثم
ومنها حدد درجه التفاعل المتحصل عليها لكل تركيز مقابل لوغريثم السرعه االبتدائيهاخري
و في كلتا الحالتين , ووجد انها من الرتبه االولي لالستون والرتبه االولي بالنسبه لالسيتوفينون
ثابتا وتركيز نترات الفضه ثابتا يروكسي ثنائي كبريتات البوتاسيوم ايون بعندما كان تركيز
ل االسيتون قدرت درجه التفاعل و,بينما كان تركيز الكيتون )االستون, واالسيتوفينون( متغيرا
مقابل التراكيز رسم منحني المعايره ب [70OC] واالسيتوفينون عند درجه حراره ثابته
سرعه االبتدائيه وبرسم معادله الخط المستقيم لوغريثم السرعه ال تحددو المختلفه للكيتون
حيث منها حدد الميل من معادله الخط المختلفه كيز الكيتونااالبتدائيه للكيتون مقابل لوغريثم تر
الرتبه االولي بالنسبه لالستون والدرجه المستقيم والذي يمثل درجه التفاعل حيث وجد انها من
تم تقييم طاقه التنشيط وقيم االنثالبي واالنتروبي عن طريق قياس يتوفينون.النصفيه بالنسبه لالس
( لالسيتون 26kJ, ووجد ان طاقه التنشيط تساوي ) ثابت السرعه عند درجات حراره مختلفه
ي قيم االنثالبي ووجد قيمتها تساولالسيتوفينون وقد حسبت بناء علي طاقه التنشيط kJ 93و
23.15kJ ( 90.19لالستونkJ وجددت)( لالسيتوفينون وقيم الطاقه العشوائيه )االنتروبي
( ووجدت قيم الطاقه الحره لالسيتون )(247jلالسيتوفينون 235.5J-)لالسيتون
(kJ79.5(وكذلك قدرت الحركيه بتقدير ثابت معدل التفاعل في درجات 83.4ولالسيتوفينون.)
تفاعل لالسيتون واالسيتوفينون وعزز ووجد ان هنالك اختالف في معدل ال حراره مختلفه
االختالف ربما يرجع لوجود حلقة البنزين في السيتوفينون خالفا لالسيتون الذي يعتبر مركبا
الفاتيا. لذلك نوصي لدراسة ااكسدة الكيتونات يجب اختيار مركبات الفاتيه بديال عن المركبات
ناتج التفاعل كحامض كربوكسيلي العطريه . وقد ميز
8
LIST OF CONTENTS
I Supervision Committee
II Examination Committee
III Dedication
IV Acknowledgement
V English abstract
VI Arabic abstract
VII List of contents
X List of tables
XII List of figures
CHAPTER ONE
Introduction
1 .Chemical kinetics1-1
2 1-1-1. The objective of this research
2 1-2. Reaction Rates
2 1-2-1. Factors affecting reaction rate
2
1-2-1-1. Nature of the reactants
2 1-2-1-2. Physical state
2 1-2-1-3. Concentration
9
3 1-2-1 -4.Temperature
3 1-2-1-5. Catalysts
3 1-2-1-6. Pressure
3 1-2-1-7. Equilibrium
3 1-2-1-8. Free energy
3 1-2-2. Rate Law & Reaction Order
4 1-2-3. Units for the rate constant
4 1-3. Rates and Rates equations for chemical reactions
4 1-3-1. Zero –order Reaction
4 1-3-2. First-order Reaction
5 1-3-3. Second-order Reaction
5 Half-Life: 1-3-4.
5 1-4. Activation Energy
6 1-5. Chemical persulphate
8 1-5-1. Persulfate Oxidation Chemistry
10
9 Oxidation of carbonyl group 1-6.
CHAPTER TWO
Materials and method
13 2-1. Materials
14
2-2. Apparatus
14 2-3. Methods
14 2-3-1.Preparation of solution
15 2.3.2. Kinetics Measurement
CHPTER THREE
Results and discussion 42 3-1. Determination of activation Thermodynamic
Function
54 3-2. Calculation of H, G and S
56 3-3. Results and discussion
56 3-3-1. Acetone
56 3-3-1-1. The order with respect to[S
2O
8-2
]
57 3-3-1-2. The order with respect to [Ag+]
57 3-3-1-3.The order with respect to [ acetone]
57 3-3-2. Acetophenone
58 3-4. Mechanism
61 3-5. Conclusion
61 3-6.Recommendations
References
11
LIST OF TABLES
Page Name of Table Table
17 Variation of titre with time at different
concentration of[S2
O8
-2] for Acetone
3-1
19 Variation of Log Initial Rate with Log Initial
Concentration of[S2O
8-2
] for Acetone
3-2
21 Variation of titre with time at different
concentration of Acetone
3-3
23 Variation of Log Initial Rate with Log Initial
Concentration of Acetone
3-4
24 Variation of titre with time at different
concentration of [Ag+]for Acetone
3-5
27 Variation of Log Initial Rate with Log Initial
Concentration of [Ag+]for Acetone
3-6
29 Variation of titre with time at different
concentration of [S2O
8-2
]for Acetophenone
3-7
31 Variation of Log Initial Rate with Log Initial
Concentration of[S2O
8-2
]for Acetophenone
3-8
33 Variation of titre with time at different
concentration of Acetophenone
3-9
35 Variation of Log Initial Rate with Log Initial
Concentration of Acetophenone
3-10
37 Variation of titre with time at different
concentration of [Ag+] for Acetophenone
3-11
12
39 Variation of Log Initial Rate with Log Initial
Concentration of [Ag+] for Acetophenone
3-12
41 The Order with Respect to the Reactants 3-13
44 Variation of titre with time [60 o C]for Acetone 3-14
45 Variation of titre with time [65o C]for Acetone 3-15
46 Variation of titre with time [70 o C]for Acetone 3-16
48 Effect of Temperature of the Reaction case of
Acetone
3-17
49 Variation of titre with time [60 o C]for
Acetophenone
3-18
50 Variation of titre with time [65 o C]for
Acetophenone
3-19
51 Variation of titre with time [70 o C]for
Acetophenone
3-20
53 Effect of Temperature of the Reaction case of
Acetophenone
3-21
55 The values for G, H, and S of acetone for
different temperatures
3-22
55 The values for G, H, and S of acetone for
different temperatures
3-23
13
LIST OF FIGURES
Page Name of Figure Figure
18 A plot of Concentration of Titre against Time 3-1
20 A plot of Initial Rate against Log [S
2O
8-2
] 3-2
22 A plot of Concentration of Titre against Time 3-3
24 A plot of Initial Rate against Log [CH3COCH3] 3-4
26 A plot of Concentration of Titre against Time 3-5
28 A plot of Initial Rate against Log [Ag+] 3-6
30 A plot of Concentration of Titre against Time 3-7
32 A plot of Initial Rate against Log [S
2O
8-2
] 3-8
34 A plot of Concentration of Titre against Time 3-9
36 A plot of Initial Rate against Log [Acetophenone] 3-10
38 A plot of Concentration of Titre against Time 3-11
40 A plot of Initial Rate against Log [Ag+] 3-12
42 A plot of titre against time at [60 o C] of Acetone 3-13
44 A plot of titre against time at [65 o C] of Acetone 3-14
46 A plot of titre against time at [70 o C] of Acetone 3-15
48 A plot of Log K against 1/T for Acetone 3-16
49 A plot of titre against time at [60o C] of
Acetophenone
3-17
50 A plot of titre against time at [65 o C] of
Acetophenone
3-18
51 A plot of titre against time at 70 o C] of
Acetophenone
3-19
53 A plot of Log K against 1/T for Acetophenone 3-20
14
Chapter One
Introdution and literature review
Introduction
1-1.Chemical kinetics:
Chemical kinetics, as a science, began in the middle of the 19th century;
whenWilhelmy was apparently the first to recognize that the rate at
which a chemical reaction proceeds follows definite laws. Although his
work paved the way for the law of mass action of Waage and Guldberg,
it attracted little attention until it was taken up by Ostwald towards the
end of the century. Wilhelmy realized that chemical rates depended on
the concentrations of the reactants [L. F.Wilhelmy (1850)].
Chemical kinetics, (Laidler, 1987; Houston, 2001; Atkins and de Paula,
2006) is a branch of dynamics, (the science of motion) and it is that body
of concepts and methods used to investigate and understand the rates and
mechanisms of chemical reactions, typically occurring either in a well-
mixed, homogeneous gaseous or liquid system or on a catalytic surface
(Freund and Knozinger, 2004).
Chemical kinetics, also known as reaction kinetics, is the study of rates
of chemical processes. It is includes investigations of how different
experimental conditions can influence the speed of a chemical reaction
and yield information about the reaction's mechanism and transition
states, as well as the construction of mathematical models that can
describe the characteristics of a chemical reaction. In 1864, Peter Waage
and Cato Guldberg pioneered the development of chemical kinetics by
formulating the law of mass action, which states that the speed of a
chemical reaction is proportional to the quantity of the reacting
substances.
Chemical kinetics deals with the experimental determination of reaction
rates from which rate laws and rate constants are derived. Relatively
simple rate laws exist for zero-order reactions (for which reaction rates
are independent of concentration), first-order reactions, and second-order
reactions, and can be derived for others. In consecutive reactions, the
rate-determining step often determines the kinetics. In consecutive first-
order reactions, a steady state approximation can simplify the rate law.
15
The activation energy for a reaction is experimentally determined
through the Arrhenius equation and the Eyring equation. The main
factors that influence the reaction rate include: the physical state of the
reactants, the concentrations of the reactants, the temperature at which
the reaction occurs, and whether or not any catalysts are present in the
reaction.
1-1-1.Objective:
- To study the oxidation reaction kinetics of acetone and Acetophenone
by peroxodisulphate ion.
- To find the order for the two compounds and measure how the
concentration of a reactant or product varies with time and then make
characteristic kinetics plots.
- To study the effect of the structures of the two compounds on their
oxidation reaction kinetics.
- To determine the activation energy, the entropy of activation, enthalpy
of activation and free energy of activation for them.
1-2. Reaction Rates:
Reaction Rate: The change in the concentration of a reactant or a
Product with time (M/s).
Reactant → Products
A → B
Average rate= change in number of moles of B /change in time
1-2-1. Factors affecting reaction rate:-
1-2-1-1. Nature of the reactants:-
Depending upon what substances are reacting, the reaction rate varies.
For example acid/base reactions, the formation of salts, and ion
exchange are fast reactions.
1-2-1-2. Physical state:-
The physical state (solid, liquid, or gas) of a reactant is also an important
factor of the rate of change.
1-2-1-3. Concentration:-
The reactions are due to collisions of reactant species. The frequency
with which the molecules or ions collide depends upon their
concentrations. The more crowded the molecules are, the more likely
they are to collide and react with one another. Thus, an increase in the
concentrations of the reactants will result in the corresponding increase
16
in the reaction rate, while a decrease in the concentrations will have a
reverse effect.
1-2-1-4.Temperature:-
Temperature usually has a major effect on the rate of a chemical
reaction. Molecules at a higher temperature have more thermal energy.
1-2-1-5. Catalysts:-.
A catalyst is a substance that accelerates the rate of a chemical reaction
but remains chemically unchanged afterwards. The catalyst increases
rate reaction by providing a different reaction mechanism to occur with
lower `activation energy.
1-2-1-6. Pressure:-
Increasing the pressure in a gaseous reaction will increase the number of
collisions between reactants and product increase the rate of reaction.
This is because the activity of a gas is directly proportional to the partial
pressure of the gas. This is similar to the effect of increasing the
concentration of a solution.
1-2-1-7. Equilibrium:-
It has a major effect on the rate of a chemical reaction.
1-2-1-8. Free energy:-
The free energy change (ΔG) of a reaction determines whether a chemical
change will take place, but kinetics describes how fast the reaction is. A
reaction can be very exothermic and have a very positive entropy change
but will not happen in practice if the reaction is too slow. If a reactant
can produce two different products, the thermodynamically most stable
one will in general form, except in special circumstances when the
reaction is said to be under kinetic reaction control. The Curtin–Hammett
principle applies when determining the product ratio for two reactants
interconnecting rapidly, each going to a different product. It is possible
to make predictions about reaction rate constants for a reaction from
free-energy relationships.
1-2-2. Rate law and Reaction Order:
The rate law is an expression relating the rate of a reaction to the
concentrations of the chemical species present, which may include
reactants, products, and catalysts?
Many reactions follow a simple rate law, which takes the form
ν = k [A]a [B]b[C]c
17
I.e. the rate is proportional to the concentrations of the reactants each
raised to some power.The constant of proportionality, k, is called the
specific rate constant. The power a particular concentration is raised to
is the order of the reaction with respect to that reactant [G.K.Vemulapalli
(2006)].
1-2-3. Units for the rate constant:
The units of a rate constant will change depending upon the overall
Order. The units of rate are always M/s or Ms–1
To find the units of a rate constant for a particular rate law, simply divide
the units of rate by the units of molarities in the concentration term of the
rate law (Barrow.M, 2006).
Rate (Ms–1
) = k [A] 1st order
k (units) Ms–1
/ Ms–1
1-3. Rates and Rates equations for chemical reactions:-
The rate of a reaction gives information on the decrease in the amount of
one of reactants or on the increase in the mount of a product that occurs
in some time interval. If the reaction system is one of constant or near
constant volume the change in the mount of reagent will correspond to a
change in the concentration of that reagent .for liquid systems the rate of
a reaction is often expressed in terms of the rate of change of the molar
concentration of a reagent. For constant volume gaseous systems it is
generally more convenient to deal with the partial pressure is
proportional to the concentration n/v. The rate of a reaction define as the
derivative with respect to time of the extent of the reaction .there are a
large number of reaction have rates that, at a given temperature, are
proportional to the concentration of one or two of the reactant raised to a
small integral power. If reactions are considered in which A and B
represent possible reactants, the rate equations for reactions with such
concentration dependence would be of the form:
Rate =k [A] first order
Rate=k [A] 2 or k [A] [B] second order
1-3-1.Zero–order Reaction:-the rate does not depend on the
concentration of any of the species participating in the reaction.
Rate=k unit Ms-1
18
1-3-2. First-order Reaction:-rates depend on the first power of the
concentration. The first order rate law can be written:
Rate = k [A] unit s-1
The rate constant (K) is then a positive quantity band has the units of the
reciprocal of time (Barrow.M, 2006)
1-3-3. Second-order Reaction:
Second Order Reactions are characterized by the property that their rate
is proportional to the product of two reactant concentrations (or the
square of one concentration). Suppose that
Rate=K [A] 2
A ---> products is second order in A
d [A]/dt=-k[A]2
(for 2A ---> products)
Rate =k [A] [B]
dc/dt = -k [A][B]
(For A + B ---> products) [G.K.Vemulapalli, (2006)].
For a Second Order Process:
A → Products
Rate = k [A] 2
Rate (Ms- 1) = d [A]/dt =k [A] 2
Integrating and rearranging:
1/ [A] = kt +1/ [A]o
A plot of 1/ [A] versus t is a straight line with slope K and intercept
1/ [A] o for a second order reaction, a plot of in [A] vs. t is not linear.
1-3-4. Half-Life:
The order of reaction may be determined by measuring the time it takes
for half of the original material to react. Half-life is independent of the
initial concentration for first-order reaction.
1-4. Activation Energy:
19
The activation energy for a reaction is experimentally determined
through the Arrhenius equation and the Eyring equation
Arrhenius Molecules must possess a minimum amount of energy to
react:
- In order to form products, bonds must be broken in the reactants.
- Bond breakage requires energy.
- Molecules moving too slowly, with too little kinetic energy, don’t react
when they collide.
The Activation energy, Ea, is the minimum energy required to
Initiate a chemical reaction.
Ea is specific to a particular reaction.
Arrhenius equation
k=Ae-Ea/Rt
Both A and Ea are specific to a given reaction.
K: is the rate constant.
Ea: is the activation energy.
R: is the ideal-gas constant (8.314 J/K mol).
T: is the temperature in K.
A: is known the frequency or pre–exponential factor
In addition to carrying the units of the rate constant, “A” relates to
The frequency of collisions and the orientation of a favorable.
1-5.Chemical persulphate:
Persulphate, known also as peroxydisulfate or peroxodisulfate, is a
sulfate peroxide with the chemical structure [O3S-O -O -SO3]2-
(Ahmad, 2008; house, 1962; Liang et al., (2004). Persulfate has been used as an agent in a number of industrial
applications such as an initiator for olefin polymerization in aqueous
systems, as a micro-etchant for printed Circuit boards, for leaching of
textiles, and in studies related to industrial wastewater Treatment (killian
et al., 2007). There are three possible salts of persulfate: potassium,
ammonia and sodium.
The Solubility of potassium persulfate is very low for environmental
applications, and the reaction of ammonium persulfate results in an
ammonia residual, which is an undesirable reaction product. Therefore,
sodium persulfate (Na2S2O8) is the most common and feasible form
20
used to date in isco, with a high solubility (73 g/100 g H2O at 25oc)
(Behrman and Dean, 1999; epa, 2006; fmc, 1998).
Persulfate salts are dissociated in water to the persulfate anion [S2O8-2]
which despite having a strong oxidation potential (Eo= 2.01V), is
kinetically slow to react with many organic compounds. Studies have
indicated that Persulfate anions can be activated to generate sulfate
radicals (SO4•-), which are stronger oxidants compared to the Persulfate
anion (EO= 2.6 V) (Liang et al., 2007; watts and teel, 2006).
Conventional oxidants can accept electrons from persulfate ions to form
the Sulfate anion radical, but the reaction rate is extremely slow.
Therefore, the oxidation of Target contaminants by this oxidant has to be
accelerated by activation of persulfate, thus increasing the rate persulfate
decomposition and the rate of sulfate free radical formation (Liang et al.,
2007; todres, 2003).
To the date, the methods that have been extensively used for the
activation of Persulfate include heat, light, gamma radiation, and
transition metals (anipsitakis and Dionysiou, 2004; Liang et al., 2007;
waldemer et al., 2007).
Their initiation reactions, which result in the formation of sulfate
radicals, are:
S2O82- heat, hv activation 2SO4
2-………… (1.1)
S2O8+ Mn+ metal activation SO4.-
+SO42-+M
+ (n+1) ……….. (1.2)
Another common approach to activate the generation of sulfate radicals
is the use of base (Liang et al., 2007). Recent studies have demonstrated
the influence of pH on the generation of reactive oxygen species in base-
activated persulfate systems (Corbin, 2008). Under these conditions most
sulfate radicals are converted to hydroxyl radicals (OH•) (Equations 1.3
to 1.9), which can proceed through propagation reactions to give the
same reactive species (hydroxyl radicals, hydro peroxide, superoxide,
and hydrogen Peroxide) (Gonzalez and martire, 1997; dogliotti And
hayon, 1967; Liang et al., 2007). Therefore, the reactive species formed
in neutral and alkaline conditions are
SO4. - + OH
- OH
. + SO4
-2…………..…….. (1-3)
21
SO4.- + H2O H SO4
- + OH.………………... (1-4)
OH. + OH
. H2O + 1/2 O2
……………....… (1-5)
S2O82 - + OH
. H SO4
- + SO4. - + 1/
2 O2……. (1-6)
S2O82- + OH
. S2O8
- + OH-………..…….. (1-7)
SO4. - + OH
. SO4
2- +1/2 O2 ……………….. (1-8)
SO4. - + S2O8
2- SO42- + S2O8
- ……………. (1-9)
However, this mechanism implies that the initial step to generate sulfate
radicals is carried out by heat or UV (equation 1.1).
1-5-1. Persulfate Oxidation Chemistry
The persulfate anion is a strong oxidant, with an oxidation potential of
2.12 V:
S2O82-+ 2 H+ + 2 e- 2 HSO4
-
However, the persulfate anion typically has slow oxidative kinetics at
ordinary temperatures for most contaminant species and really can only
be applied to a limited number of contaminants, such as xylene, to be
effective. As a result, persulfate is typically activated, for use to oxidize
most contaminants or concern. In the presence of certain activators,
persulfate anion can be converted to the sulfate radical, an even stronger
oxidant with an oxidation potential of 2.6 V
S2O82-+ activator SO4
·- + (SO4·- or SO4
-2)
Under acidic conditions, persulfate anion can hydrolyze to form
hydrogen peroxide:
S2O82-+ 2 H2O H2O2 + 2HSO4
-
Sulfate radicals can react with water also to form hydroxyl radicals.
Under stronger acidic conditions, persulfate can form
peroxymonopersulfate anions, with an oxidation potential of 1.44V
S2O82-+ 2 H2O HSO5
- + HSO4-
As a result, persulfate solutions may contain several different oxidant
and radical species. One consequence of this mixture of oxidizing
species is that multiple pathways for contaminant oxidation may exist,
22
increasing the probability of reducing the target compound
concentrations. However, such diversity of oxidant species makes the
assessment of the “stoichiometric” amount of persulfate needed to
destroy a given concentration of contaminant problematic, and thus it is
common practice to revert back to the basic, two electron transfer
associated with the persulfate anion (seen in first equation above) to
determine the stoichiometric persulfate demand.
1-6. Oxidation of carbonyl group:-
Kinetics and mechanism of oxidation of aliphatic and aromatic ketones
by peroxomonosulphate were studied by Gurusamy
Manivannan and Pichai Maruthamuthu (J. Chem. Soc., Perkin Trans.
2, 1986, 565-568) and found The kinetics of oxidation of ethyl methyl
ketone, isobutyl methyl ketone, and acetophenone by
peroxomonosulphate (PMS) was carried out in aqueous H2SO4 medium
(0.20M-1.00 M) and in aqueous acetic acid medium (40% acetic acid
v/v) respectively in the temperature range (30°C-60 °C ) The reactions
obey total second-order kinetics, first order each with respect to [ketone]
and [PMS] for all the ketones. They exhibited acid catalysis with the
concurrent occurrence of acid-independent reaction paths conforming to
of
d [PMS]/dt=ka [PMS] [ketone] [H+] + kb [PMS] [ketone]
The reaction stoicheiometry, [ketone]: [PMS] 1:1, for all the ketones
indicated the absence of self-decomposition and carbonyl-assisted
decomposition of PMS. The kinetic and thermodynamic parameters
strongly suggest the mechanism of a fast nucleophilic attack of the
oxidant (PMS) on the ketone followed by slow, rate-determining acid-
catalysed and uncatalysed decomposition of the intermediate to the
product.
Formaldehyde and acetaldehyde are oxidized to the corresponding acids,
RCHO+ S2O8-2 +H2O RCOOH+2HSO4
Subbarman and Santappa [Subbarman and Santappa, 1966] studied the
oxidation of formaldehyde and acetaldehyde, both in the present and
absent of silver ions, when the concentration of aldehyde is much low
than that of peroxodisulphate, the rate equation for reaction in absence of
silver ions is:
23
-d [S2O8-2]/dt =k [S2O8
-2] 1/2 [RCHO] 1/2
With excess of formaldehyde the rate equation becomes:
-d [S2O8-2]/dt =k [S2O8
-2]1 /2 [HCOH] 1/2
Oxygen inhibits the oxidation of both aldehyde subbarman and santappa
[Subbarman and Santappa, 1966] suggest that the hydrated form the
aldehyde reacts via chain mechanism similar to those proposed for
alcohols [Edward and Melssa, 1966].
[Schorder and Griffith [Schorder and Griffith 1979]report that the
product of aldehyde oxidation of with oxygen on presence of
peroxodisulphate were the corresponding acid .Different kinetic laws
have been established and different mechanism is proposed for the
oxidation of aldehyde by peroxodisulphate this mainly due to :
(1) The reaction mixture is not completely from dissolved oxygen.
(2) The influence of reaction concentration on the reaction rate has not
been studied over a wide range.
(3) Each elementary reaction has not yet been sufficiently studied the
following general mechanism has been proposed for oxidation of RCHO
[House, 1961], at higher aldehyde concentration.
S2O8-2 k1 2SO4
.
SO4. +RCHO K2 HSO4
-+RC
.O
RC.O + S2O8
-2 + H2O k3 RCOOH +HSO4- + SO4
.
RC.O + SO4
. + H2O k4 HSO4
-+RCOOH
2 RC.O + H2O k5 RCOOH+RCHO
The above mechanism is lead to the following rate law:
-d [S2O8-2] /dt =k3 (k1/k5)1/2
[S2O8-2] 3/2
The effect of added salt to the kinetic of oxidation of propanal aldehyde
by S2O8-2 was studied as function of concentration and temperature.
The overall order of Ag+ catalyzed reaction was one, and zero with
respect to propanal aldehyde. An induction period was observed at high
concentration of EtCHO. The presence of cautions decreased the
oxidation rate in the order k+>Na+>mg++. The activation energy of Ag+
24
catalyzed reaction was 49.7kj.mol-1 between 25OC and 45O
C temperature
coefficient was 1.86 [Khulble and Srivastava, 1964]. The catalytic
oxidation of formaldehyde by was studied at Ph 9-2-13 ,the order with
respect to [Khulble and Srivastava,1962].The catalytic activity for
HCOH oxidation decreased in the order Pt,Cu,Ni,Ag and Au catalytic
interaction of [S2O8-2] with HCOH consist of electrochemical reaction
occurring on the metal surface two stoichiometric equation are obtained
[House, 1961]
Pt and partially on Ni
HCHO+ S2O8-2 +3OH HCOO-+2SO4
-2+2H2O
On Cu, Ag and partially Ni
HCOH + S2O8-2 +4OH- HCOO-+2SO4
-2+2H2O
In the silver ion catalyzed oxidation of acetone by peroxodisulphate it
was shown [Bekier and Kijowsk, 1935] that acetic acid and carbon
dioxide are formed according to the equation:
CH3COCH3+4K2S2O8-2 +3H2O CH3COOH+CO2+8KHSO
The salt effect on this reaction is negative. The copper catalyzed
oxidation of acetone by peroxodisulphate was studied [Agrawal, 1982]
and unanalyzed, oxidation of acetone by peroxodisulphate was studied
[Hala, 1992], the reaction follows first order in peroxodisuphate and zero
order in acetone in silver catalyzed oxidation of some cyclic ketone by
peroxodisulphate.
The kinetics of oxidation of aliphatic ketones (acetone, ethyl methyl
ketone and diethyl ketone) by chloramine-T in presence of hydrochloric
acid (0.1 to 0.3M) has been investigated at 30 °C. The rate of
disappearance of chloramine-T has been found to be first order each with
respect to oxidant, ketone and [H+], in the range of the acid
concentrations studied. The thermodynamic and kinetic parameters have
been evaluated by determining the rate constants at different
temperatures. The products of the reaction have been identified as
chloroketones by their NMR spectra. The solvent isotope effect has been
studied in the case of the oxidation of acetone and ethyl methyl ketone.
Nafisa [Nafisa2002] studied the unanalyzed, reaction of butanone and 3-
pentanone with the reaction follows first order in peroxodisulphate and
zero order in substrate, she suggested the following mechanism
25
S2O8-2 K1 2 SO4
-
SO4- + H2O K2 HSO4
-+OH-
R RCO + OH- K3 RC.O + ROH
RC.O + SO4. K4 RC [SO4
-] O
RC [SO4-] O + H2O k5 RCOOH+H SO4
-
RCOOH + SO4- K6 RCOO
. +H SO4-
R/OH +H SO4- K7 R/+H2O+ SO4
-
RCOO. +R
/ K8 RCOOR
/
26
Chapter Two
Materials &Methods
2-1. Materials:-
Chemical used were further purified. Their sources and some of their
physical properties are outlined as follows:-
1. Potassium Peroxodisulphate (K2S2O8):
Analar, the British Drug House Ltd., B.D.H Laboratory, Chemicals
Group, Poole England. (M.wt=270).
2. Sodium Thiosulphate (Na2S2O8.5H2O):
Loba chemie Pvt.Ltd.107, Wodehouse Road, Mumbai 400005.india.
General purpose Reagent, (M.wt. =248.17
3. Sodium Bicarbonate (NaHCO3):
BDH Poole, BH151TD England
(M.wt. =84.0).
4. Potassium Iodide (KI):
Scharlau Chemie S.A. (M.wt. =166.0).
5. Sulphuric Acid (H2SO4)
Scharlau, Conc. =98% v\v
Wt.per ml=1.84 g\ml), M.wt=98.08)
6. Silver nitrate AgNO3:
Fisons, (M.wt=169.87)
7. Starch:
Analar, BDH chemicals Ltd., Poole England.
8. Acetone (CH3COCH3):
27
Lobe Chemie Pvt Ltd 107, Wodehouse Road, Mumbai, India M.wt.
=58), (Sp.d=0.791), (z=98%)
9. Acetophenone (ARCOCH3):
Lobe Chemie Pvt Ltd 107, Wodehouse Road, Mumbai, India M.wt. =
(120.15)
10. Double Distilled water:
It was prepared by redistilling ordinary distilled water over alkaline
potassium permanganate and it was used in all kinetic
experiment.
2-2 Apparatus:-
Thermostat Analytical balance and Glassware.
2-3. Methods
2-3-1.Preparation of solutions:
Potassium peroxodisulphate (0.2M):
5.4g of K2S2O8 were dissolved in 100ml volumetric flask with distilled
water to obtain 0.2M solution. It was always freshly prepared and never
used after more than 24hours.
Sodium Bicarbonate solution (4%):
10g of NaHCO3were dissolved in 250 ml volumetric flask with distilled
water to obtain 4%.
Potassium Iodide solution (20%):
20g of KI were dissolved in 100ml distilled water to obtain 20% KI
solution .A freshly prepared solution was used every time.
Sulphuric Acid solution (0.5M):
7ml of H2SO4 conc. were diluted in 250ml distilled water to obtain
0.5M solution.
28
Silver Nitrate solution (0.02M):
0.85g of AgNO3 dissolving in 250ml distilled water in a volumetric
flask to obtain 0.02M solution.
Starch solution:
1g of soluble starch was dissolved in 30ml of distilled water and the
mixture was heated until it was clear then used as indicator. Afresh
solution was prepared for every kinetic run.
Sodium thiosulphate Solution (0.01M):
2.48g of Na2S2O3 were dissolved in 1000cm3 of distilled water to
obtain 0.01M solution. This was used as a stock solution for (4-5) days.
Acetone solution:
7.46 ml of acetone (Sp.d = 0.789- 0.792 g\ml) were diluting in double
distilled water in 500 ml volumetric flask to prepared 0.2M solution.
Acetophenone:-
0.2M solution of acetophenone was prepared by dissolving 11.83 of
acetophenone in double distilled water and the volume of the solution
was completed to 500 ml.
2.3.2. Kinetics Measurement:-
The reaction of peroxodisulphate with acetone and acetophenone is very
slow at room temperature but it has measurable rate at 70Oc
There for, this range was selected for the kinetic measurement. Various
kinetic runs were carried out as follows:
Mixture of 10 ml the substrate and10 ml of catalyst (AgNO3) solution in
around –bottomed flask was thermostatic at70OC for 20-30 minutes.
Simultaneously the appropriate volume of the persulphate solution
(necessary to make the required persulphate concentration) plus the
amount of water required to mark the total the reaction mixture 100ml
were the thermostatic for the same period.
29
After thermostating, the two solutions were mixed, and the reaction
mixture was shaken from time to time to insure through mixing. At 5
minutes intervals, 5ml samples were withdrawn by pipette and analyzed
for S2O8-2 ion as follow, The sample was discharged into a 100ml
conical flask which contained 5ml of 4% sodium bicarbonate, 1 ml of
sulphuric acid and 5ml of 20% potassium iodide solution, and placed in a
dark place for 10 minutes .The liberated iodine was titrated against
sodium thiosulphate (which is represented as titre).The concentration of
the reactants under investigation were changed for each run by changing
the volume of that reactant in the mixture.
The concentration of titre at various time intervals was subjected to
regression for a polynomial fit. At zero time was found and considered
as the initial rate of the reaction.
30
Sample (1):-[Acetone]
The results of oxidation of Acetone by peroxodisulphate ion are shown
in the following tables and figs.
Table (3-1)
Variation of the titre with time at different initial concentration of
[S2O8-2] while the concentration of acetone and silver are constant
[Acetone] =2x10-2 mol .L-1
[Ag+]=2x10-3 mol .L-1
0.01 0.015 0.02 0.025 0.03 0.035 0.04
S2O8-2
Volume of titer (ml)
Time
min
22.5 18.5 17 14.2 10.2 7.5 5.9 0
17.2 16.2 15.2 13.1 9.5 6.3 4.5 5
15.5 14.5 13 11.5 8.5 6 3.6 10
14.7 13.8 11.2 10.5 7 5 3.2 15
13.2 12.1 10 9.3 6.3 4 2.4 20
12.2 10.6 8.8 8.8 5.1 2.9 2 25
11.1 10.1 8 7.7 4.2 2.5 1.8 30
10.2 9 7.5 6.5 3.5 2 1.5 35
9.6 8.3 6.8 5.3 3 1.7 1 40
31
Fig (3-1): A plot of Concentration of Titre against Time
y = 0.0004x2 - 0.0878x + 3.9291
y = 0.0015x2 - 0.1659x + 6.2158
y = 0.0015x2 - 0.1753x + 7.7061
y = 0.0009x2 - 0.1818x + 10.008
0
2
4
6
8
10
12
0 5 10 15 20 25 30 35 40 45
titr
e
Time
1سلسلة
2سلسلة
3سلسلة
4سلسلة
y = 0.0016x2 - 0.2224x + 11.865
y = 0.0004x2 - 0.1894x + 13.973
y = 0.0018x2 - 0.3077x + 17.072
0
2
4
6
8
10
12
14
16
18
0 5 10 15 20 25 30 35 40 45
Titr
e
Time
2سلسلة
3سلسلة
4سلسلة
32
Table (3-2)
Variation of Log Initial Rate with Log Initial Concentration of
[S2O8-2] while the concentration of acetone and silver are constant
[Acetone]=2x10-2 mol.L-1
[Ag+] =2x 10-3 mol.L-1
Log
initial[Rate]+3
Initial Rate
mol.ml
Log[S2O82]+2
[S2O8-2]
mol-1. L-1
2.317227 0.002076 0 0.01
2.495197 0.003128 0.176091 0.015
2.685742 0.00485 0.30103 0.02
2.775064 0.005958 0.39794 0.025
2.802089 0.00634 0.477121 0.03
2.872331 0.007453 0.544068 0.035
3.342975 0.022028 0.60206 0.04
33
Fig (3-2): A plot of Log initial Rate+3 against Log [S2O8-2] +2
The equation of straight line is: - y=1.4763x+0.2671
The slop of this plot shows that the order of reacn w.r.t [S2O8-2] is (1)
y = 1.4493x + 0.2793 R² = 0.9876
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Log
Init
al R
ate
+3
Log [S2O8-2]+2
1سلسلة
34
Table (3-3)
Variation of the titre with time at different Initial Concentration of
acetone while concentration of silver and [S2O8-2] are constant
[S2O8-2]=2X10-2M
[Ag+]=2x10-3M
Volume of titer (ml)
Time
min
18.5 16.8 15 14.2 14 13.5 13.2 0
16.5 14 13.2 12.6 12 11.5 11.2 5
12.8 11.2 10.6 9.8 9.5 9.2 10.2 10
10.9 9 8.2 7.8 7.7 7.3 6.6 15
9.3 8.3 6.6 6.4 6.5 5.8 5.4 20
8.5 7 5.7 5.5 5.2 5 4.3 25
7.3 5.3 4.8 4.2 4 3.8 3.2 30
6.2 4.6 4 3.8 3.5 2.8 2.6 35
5.3 4 3.4 3 2.8 2 1.8 40
0.04 0.035 0.03 0.025 0.02 0.015 0.01
CH3COCH3
Mol-1. L-1
35
Fig (3-3):- A plot of Concentration of Titre against Time
y = 0.0038x2 - 0.4111x + 12.108
y = 0.0045x2 - 0.4658x + 13.507
y = 0.0048x2 - 0.4704x + 13.978
y = 0.005x2 - 0.4849x + 14.663
0
2
4
6
8
10
12
14
16
0 5 10 15 20 25 30 35 40 45
Titr
e
T ime
0.01 M
0.015 M
0.02 M
0.025 M
y = 0.0062x2 - 0.5432x + 15.273
y = 0.0062x2 - 0.5576x + 16.565
y = 0.0064x2 - 0.5812x + 18.564
0
2
4
6
8
10
12
14
16
18
20
0 10 20 30 40 50
Titr
e
Time
0.03 M
0.035M
0.04 M
36
Table (3-4)
Variation of Log Initial Rate with Log Initial Concentration of acetone
while concentration of [Ag+] of and [S2O8-2] are constant.
[Ag+]=2X10-3M,
[S2O8-2] =2X10-2 M
Log Initial Rate+3
[Initial Rate
mol.ml
[Log
Acetone]
[Acetone]
mol-1. L-1
0.693199 0.004934 0 0.01
0.844291 0.006987 0.176091 0.015
0.991137 0.009798 0.30103 0.02
1.11059 0.0129 0.39794 0.025
1.20412 0.016 0.477121 0.03
1.290035 0.0195 0.64424 0.035
1.383815 0.0242 0.60206 0.04
37
Fig (3-4):- A plot of Initial Rate+3 against Log [CH3COCH3] +2
The equation of straight line is: - y=1.0826x+0.6759
The slop of this plot shows that the order of reacn w.r.t [CH3COCH3] is
(1).
y = 1.0826x + 0.6759 R² = 0.9937
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 0.1 0.2 0.3 0.4 0.5 0.6
Log
Init
al R
ate
+3
Log [CH3COCH3]+2
1سلسلة
38
Table (3-5)
Variation of the titre with time at different Initial Concentration of [Ag+]
while concentration of acetone and [S2O8-2] are constant
[CH3COCH3]=2X10-2mol.L-1
[S2O8-2] =2X10-2 mol. L-1
0.004 0.0035 0.003 0.0025 0.002 0.0015 0.001
[Ag+]
mol-1. L-1
Volume of titer (ml)
Time
min
12 11 10.5 10 9.5 8.9 8.7 0
11 10.4 9.5 9.4 8.5 8.2 8 5
10.5 9.6 9 8.5 7.9 7.6 7.2 10
9.7 9 8.2 7.6 7.2 6.5 6.4 15
8.4 8 7.4 7 6.6 6 5.8 20
7.9 7.5 7 6.6 6 5.2 4.8 25
7.3 6.6 6.3 5.9 5.6 4.5 4.3 30
6.6 6.2 5.8 5.5 5 4 3.8 35
6.5 6 5.3 5 4.3 3.7 3.5 40
39
Fig (3-5):- A plot of Concentration of Titre against Time
y = 0.0022x2 - 0.2201x + 8.0236
y = 0.001x2 - 0.1753x + 9.0206
y = 0.0007x2 - 0.1522x + 9.3733
y = 0.0012x2 - 0.1743x + 10.084
0
2
4
6
8
10
12
0 5 10 15 20 25 30 35 40 45
Titr
e
Time
1سلسلة
2سلسلة
3سلسلة
4سلسلة
y = 0.0009x2 - 0.1642x + 10.442
y = 0.001x2 - 0.1719x + 11.152
y = 0.0014x2 - 0.1994x + 12.09
0
2
4
6
8
10
12
14
0 5 10 15 20 25 30 35 40 45
Titr
e
Time
0.003 M
0.0035 M
0.004 M
40
Table (3-6)
Variation of Log Initial Rate with Log Initial Concentration of [Ag+]
while concentration of acetone and [S2O8-2] are constant.
[Acetone] =2x10-2 M
[S2O8-2] =2X10-2 M
Log Initial
Rate+3
Initial Rate}
Mol.ml
Log[Ag+]
[Ag+]
mol-1. L-1
1.199206 0.000158 0 0.001
1.418301 0.000262 0.176091 0.0015
1.553762 0.000358 0.30103 0.002
1.670246 0.000468 0.39794 0.0025
1.841109 0.000694 0.477121 0.003
2.050573 0.001124 0.544068 0.0035
2.236638 0.001724 0.60206 0.004
41
Fig (3-6):-A plot of Initial Rate+3 against Log [Ag+] +2
The equation of straight line is: - y=1.0153x+1.2906
The slop of this plot shows that the order of reacn w.r.t [Ag+] is (1)
y = 1.0153x + 1.2906 R² = 0.9237
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
0 0.1 0.2 0.3 0.4 0.5 0.6
Log
[In
ital
Rat
e]+
3
Log [Ag+]+2
42
Sample (2):-[Acetophenone]
Table (3-7)
Variation of the titre with time at different initial concentration of
[S2O8-2] while the concentration of acetophenone and silver are
constant
[Acetophenone] =2x10-2
[Ag+]=2x10-2 M
0.04 0.035 0.03 0.025 0.02 0.015 0.01
[S2O8-2]
Volume of titer (ml)
Time
min
16.8 13.6 12 10 7.7 6.2 4 0
15.7 13.7 10.5 9.2 7 5.6 3.5 5
14.5 11.8 10 8.2 6 4.5 3 10
13 11.3 8.8 7.5 5.3 4 2.6 15
11.6 10.5 8 6.6 4.8 3.5 2.4 20
10.2 9.2 7.5 6 4.4 3.2 2 25
9.3 8.7 6.5 5.4 3.9 2.6 1.8 30
8.5 7.5 6 4.8 3.5 2.2 1.4 35
7.8 7.2 5.5 4 3.1 2 1 40
43
Fig (3-7): A plot of Concentration of Titre against Time
y = 0.0013x2 - 0.1488x + 4.9642
y = 0.0015x2 - 0.1659x + 6.2158
y = 0.0015x2 - 0.1753x + 7.7061
y = 0.0009x2 - 0.1818x + 10.008
0
2
4
6
8
10
12
0 5 10 15 20 25 30 35 40 45
titr
e
Time
1سلسلة
2سلسلة
3سلسلة
4سلسلة
y = 0.0016x2 - 0.2224x + 11.865
y = 0.0004x2 - 0.1894x + 13.973
y = 0.0018x2 - 0.3077x + 17.072
0
2
4
6
8
10
12
14
16
18
0 5 10 15 20 25 30 35 40 45
Titr
e
Time
2سلسلة
3سلسلة
4سلسلة
44
Table (3-8)
Variation of Log Initial Rate with Log Initial Concentration of [S2O8-
2] while the concentration of acetophenone and silver are constant
[Acetophenone]=2x10-2 M
[Ag+] =2x 10-3 M
Log initial Rate
Initial Rate
mol.ml
Log [S2O8-2]
[S2O8-2]
mol-1. L-1
2.14613 0.0014 0 0.01
2.395938 0.002489 0.176091 0.015
2.544812 0.003506 0.30103 0.02
2.681919 0.004808 0.39794 0.025
2.824451 0.006675 0.477121 0.03
2.821448 0.006629 0.544068 0.035
3.090187 0.012308 0.60206 0.04
45
Fig (3-8): A plot of Log initial Rate+3 against Log [S2O8-2] +2
The equation of straight line is: - y=1.4353X+2.1313
The slop of this plot shows that the order of reacn w.r.t [S2O8-2] is (1)
y = 1.4353x + 2.1313
R² = 0.9685
0
0.5
1
1.5
2
2.5
3
3.5
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Log
[In
ital
Rat
e]+
3
Log [S2O8-2]+2
46
Table (3-9)
Variation of the titre with time at different Initial Concentration of
acetophenone while concentration of silver and [S2O8-2] are constant
[S2O8-2]=2X10-2M
[Ag+]=2x10-3M
0.04 0.035 0.03 0.025 0.02 0.015 0.01
ARCOCH3
mol-1. L-1
Volume of titer (ml)
Time
min
9.7 9.5 9 9.3 8.7 8 7.7 0
9.2 9 8.8 8.5 8.4 7 7.3 5
8.8 8.5 8 7.5 7.4 6 6.2 10
8 7.4 7.3 6.9 6.9 5.4 5.5 15
7.6 7 6.6 6.2 5.8 3.9 4.8 20
6.4 6.2 6 5.8 5.2 3.5 4.1 25
5.4 5 4.8 4.9 4.7 2.8 3.8 30
4.8 4.4 4.2 4.2 4 2.5 3.1 35
4.5 4 3.7 3.9 3.7 2 2.2 40
47
Fig (3-9):- A plot of Concentration of Titre against Time
y = 0.0015x2 - 0.2028x + 7.7121
y = 0.0014x2 - 0.195x + 8.1988
y = 0.0007x2 - 0.1612x + 8.9321
y = 0.0008x2 - 0.1696x + 9.2715
0
1
2
3
4
5
6
7
8
9
10
0 5 10 15 20 25 30 35 40 45
Titr
e
Time
0.01 M
0.015 M
0.02 M
0.025 M
y = -0.0006x2 - 0.1183x + 9.1952
y = -0.0003x2 - 0.1339x + 9.6364
y = -0.0006x2 - 0.1157x + 9.8327
0
2
4
6
8
10
12
0 5 10 15 20 25 30 35 40 45
Titr
e
Time
0.03 M
0.035 M
0.04 M
48
Table (3-10):
Variation of Log Initial Rate with Log Initial Concentration of
[Acetophenone] while concentration of [Ag+] and [S2O8-2] are
constant.
[Ag+] =2x10-3 M
[S2O8-2] =2X10-2 M
Log
Initial
Rate+3
Initial Rate
Mol.ml
Log
[Acetophenone]
[ACETOPHENONE]
mol-1. L-1
0.307068 0.002028 0 0.01
0.466126 0.002925 0.176091 0.015
0.482874 0.00304 0.30103 0.02
0.579784 0.0038 0.39794 0.025
0.549003 0.00354 0.477121 0.03
0.670849 0.004687 0.544068 0.035
0.665393 0.004628 0.60206 0.04
49
Fig (3-10): A plot of Log initial Rate+3 against Log [ARCOCH3] +2
The equation of straight line is: - y=0.5296x + 0.261
The slop of this plot shows that the order of reacn w.r.t [Acetophenone]
is (0.5).
y = 0.5296x + 0.261
R² = 0.997
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 0.1 0.2 0.3 0.4 0.5 0.6
Log
init
al R
ate
+3
Log [ARCOCH3]+2
50
Table (3-11)
Variation of the titre with time at different Initial Concentration of [Ag+]
while concentration of acetophenone and [S2O8-2] are constant
[ARCOCH3]=2X10-2M
[S2O8-2] =2X10-2 M
0.004 0.0035 0.003 0.0025 0.002 0.0015 0.001
[Ag+]
mol-1.
L-1
0 16.3 14.8 13.7 12.9 12.3 11.8 11.0
5 14.7 13.0 11.5 11.0 10.5 9.4 9.0
10 13.0 11.4 10.2 9.5 9.1 8.0 7.8
15 11.9 10.2 8.6 8.0 7.3 6.5 6.0
20 11.0 9.4 7.8 7.0 6.2 5.7 5.1
25 9.5 8.4 6.9 6.2 5.7 5.0 4.3
30 8.0 7.5 6.0 5.3 4.8 4.4 3.5
35 7.7 7.0 5.2 4.5 4.0 3.4 2.9
40 7.0 6.4 4.8 4.0 3.6 2.9 2.5
Time
Volume of titer (ml)
51
Fig (3-11):- A plot of Concentration of Titre against Time
y = 0.0025x2 - 0.3347x + 16.298
y = 0.0034x2 - 0.3394x + 14.659
y = 0.0037x2 - 0.3639x + 13.473
y = 0.0035x2 - 0.3595x + 12.781
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
16.0
18.0
0 5 10 15 20 25 30 35 40 45
Titr
e
Time
y = 0.0039x2 - 0.3717x + 12.27
y = 0.004x2 - 0.3678x + 11.432
y = 0.0041x2 - 0.3711x + 10.91
0.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
0 5 10 15 20 25 30 35 40 45
Tite
r
Time
52
Table (3-12)
Variation of Log Initial Rate with Log Initial Concentration of [Ag+]
while concentration of acetophenone and [S2O8-2] are constant.
[Acetophenone] =2x10-2 M
[S2O8-2] =2X10-2 M
[Ag+]
Mol.L-1
Log [Ag+]
+2
Initial rate
mol ml-1
Log[initial
rate]+3
0.0010 0.00 0.00038 0.58
0.0015 0.18 0.00050 0.70
0.0020 0.30 0.00074 0.87
0.0025 0.40 0.00088 0.94
0.0030 0.48 0.00113 1.05
0.0035 0.54 0.00125 1.10
0.0040 0.60 0.00146 1.16
53
Fig (3-12): A plot of Log initial Rate+3 against Log [Ag+] +2
The equation of straight line is: - y=0.99x+0.5575
The slop of this plot shows that the order of reacn w.r.t [Ag+] is (1).
y = 0.9991x + 0.5575 R² = 0.9907
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
0.00 0.10 0.20 0.30 0.40 0.50 0.60 0.70
54
The orders obtained from the previous plots are tabulated in table (3-13)
Table (3-13)
Order with Respect to the Reactants
[Substrate] [Ag+] [S2O8-2] Reactant
Substrate
1 1 1 Acetone
0.5 1 1 Acetophenone
55
Chapter three
Results and Discussion
3-1.Determination of activation Thermodynamic Function:
These functions are calculated from activation energy which is
determined from absolute rate constant temperature.
[Ketone]= 2.0x10-2
[S2O8-2]= 2.0x10-2
[Ag+]= 2.0x10-3
From the rate of the reaction at zero time:
Ratet =0
=k [S2O8-2] [Ketone] [Ag+]
And specific rate constant k was evaluated from the reaction:
[Rate] 0
=k [S2O8-2]
n [Ketone]
m [Ag+]
o
Where n, m, and o are the order w.r.t. each reactant
The variation in rate constant with temperature is found to obey
Arrhenius equation:
K=Ae-Ea/Rt
Where the constant A is called pre-exponential factor and Ea is called the
activation energy .An alternative form of this expression is
InK=- Ea/RT + In A
Or
LogK=- Ea/2.303R
1
/T + LogA
On plotting Log K values versus reciprocal of absolute temperature
straight lines were obtained figs (3-19) (3-21) from the slop, the energies
of activation were calculated using the equation:
E= (-) slop x2.303 x8.314 joule.mol-1
Table (3-14) to (3-16) show the variation of titre volume with times for
three temperatures 60, 65 and 70oC.These results are plotted in fig (3-13)
to (3-15),from these results the values of the rate constant K at this
temperature was found by using the orders obtained before acetone, and
acetophenone.
These values are used in the Arrhenius equation as shown in table
56
(3-17) and (3-21) and plotted in figs (3-16) and (3-19)
The of activation energy ∆E was then found. The other thermodynamic
values for ∆H, ∆S and ∆ G were then calculated and summarized in
tables (3-22) and (3-22) of acetone and acetophenone respectively.
The effect of temperature is shown in tables (3-14) to (3-16) and figs (3-
7) to (3-9) for acetone and in tables (3-17) to (3-19) and figs (3-10) to (3-
12) for acetophenone.
57
Table (3-14)
Variation of Titre with Time {at 60O
C}
[S2O8-2]= 2X10-2 M
[Acetone] =2x10-2 M
[Ag+] = 2X10-3 M
Titre Per ml Time Per min
9 0
8.3 5
6.7 10
5.2 15
4.8 20
4 25
3.4 30
2.9 35
Fig (3-13):- A plot of Titre against Time at 60O
C of Acetone
y = 0.0031x2 - 0.2877x + 9.2292 R² = 0.9882
0
1
2
3
4
5
6
7
8
9
10
0 5 10 15 20 25 30 35 40
Titr
e
Time
58
Table (3-15)
Variation of Titre with Time {at 65O
C}
[S2O8-2]= 2X10-2 M
[Acetone] =2x10-2 M
[Ag+]=2X10-3 M
Titre Per ml Time Per min
8.8
0
7.2 5
6.5 10
5 15
3.8 20
3 25
2.5 30
2 35
Fig (3-14):- A plot of Titre against Time at 65O
C of Acetone
y = 0.003x2 - 0.3038x + 8.8333
R² = 0.9939
0
1
2
3
4
5
6
7
8
9
10
0 5 10 15 20 25 30 35 40
Titr
e
Time
59
Table (3-16)
Variation of Titre with Time {at 70O
C}
[S2O8-2]= 2X10-2 M
[Acetone] =2x10-2 M
[Ag+]=2X10-3 M
Fig (3-15):- A plot of Titre against Time at 70O
C of Acetone
y = 0.0042x2 - 0.3561x + 9.2458
R² = 0.98
0
1
2
3
4
5
6
7
8
9
10
0 5 10 15 20 25 30 35 40
Titr
e
Time
Titre per ml
Time per min
8.8 0
8 5
6.7 10
4.5 15
3.5 20
2.8 25
2.4 30
2 35
60
From Fig (3-13), initial rate was equal
[2.8x10-3]0 =k1 [0.002]
1 [0.0002]
1 [0.002]
1
[2.8x10-3]0
=K1
8X10-7
K1
=3625 dm3 mol-1 min-1
From Fig (3-14), initial rate was equal
[3.038x10-3]0 = K2 [0.002]
1 [0.0002]
1 [0.002]
1
[3.038x10-3]0
=K2
8X10-7
K2
=3650 dm 3 mol-1 min-1
From Fig (3-15), initial rate was equal
[3.561x10-3]0 = k3 [0.002]
1 [0.0002]
1 [0.002]
1
[3.561x10-3]0
=K38X10-7
K3
=4375dm3 mol-1 min-1
61
Table (3-17)
Effect of temperature of the reaction case of acetone
∆E = (-)Slopx2.303x8.314 Joule
∆E = 940.37x3.303x8.314
∆E = 26 K joule
Fig (3-16):-A plot of Log k against 1/T for Acetone
y = -940.37x + 8.2852 R² = 0.999
5.45
5.46
5.47
5.48
5.49
5.5
5.51
5.52
5.53
5.54
5.55
0.0029 0.00292 0.00294 0.00296 0.00298 0.003 0.00302
Log
K
1/T
Log[k] 1/T k
-1
Kdm3
mol-1min-1
Temperature
Co
3.544407 0.003003 3500 60
3.56229 0.002967 3650 65
3.64098 0.002915 4375 70
62
Table (3-18)
Variation of Titre with Time {at 60O
C}
[S2O8-2]= 2X10-2 M
[Acetophenone] =2x10-2 M
[Ag+]= 2X10-3 M
Fig (3-17):- A plot of Titre against Time at 60O
C of Acetophenone
y = 0.0024x2 - 0.2657x + 9.2058
R² = 0.9946
0
1
2
3
4
5
6
7
8
9
10
0 5 10 15 20 25 30 35 40
Titr
e
Time
Titre Per ml
Time Per min
9 0
8.4 5
7.9 10
7 15
6.3 20
6.5 25
5.4 30
4.8 35
63
Table (3-19)
Variation of Titre with Time {at 65O
C}
[S2O8-2]= 2X10-2 M
[Acetophenone] =2x10-2 M
[Ag+]=2X10-3 M
Titre Per ml
Time Per min
8.1 0
8 5
7 10
6.2 15
5.8 20
4.9 25
4.5 30
4 35
Fig (3-18):- A plot of Titre against Time at 65O
C of Acetophenone
y = 0.002x2 - 0.2079x + 8.9095
R² = 0.9942
0
1
2
3
4
5
6
7
8
9
10
0 5 10 15 20 25 30 35
Titr
e
Time
64
Table (3-20)
Variation of Titre with Time {at 70O
C}
[S2O8-2] = 2X10-2 M
[Acetophenone] =2x10-2 M
[Ag+] =2X10-3 M
Fig (3-19):- A plot of Titre against Time at 70O
C of Acetophenone
y = 0.0002x2 - 0.149x + 8.95
R² = 0.9905
0
1
2
3
4
5
6
7
8
9
10
0 5 10 15 20 25 30 35 40
Titr
e
Time
Titre Per ml
Time Per min
9
0
8 5
8.5 10
7.2 15
5.8 20
5.2 25
4.6 30
4.1 35
65
From Fig (3-17), initial rate was equal
[0.149x10-3]0 =k1 [0.002]
1 [0.0002]
1 [0.002]
0.5
[0.149x10-3]0
=K1
(2.6) (10-6)
K1
=50 dm3 mol-1 min-1
[0.20x10-3]0 =K2 [0.002]
1 [0.0002]
1 [0.002]
0.5
[0.20x10-3]0
=K2
(2.6) (10-6)
K2
=70 dm3 mol-1 min-1
From Fig (3-18), initial rate was equal
[2.6x10-3]0 =k3 [0.002]
1[0.0002]
1[0.002]
0.5
[2.6x10-3]0
=K3
(2.6) (10-6)
K3
=100 dm3 mol-1 min-1
66
Table (3-21)
Effect of temperature of the reaction case of acetophenone
∆E=Slopx3.303x8.313 J
∆E=93K J
Fig (3-20):-A plot of Log k against 1/T for Acetophenone
y = -3419.5x + 11.965 R² = 0.9991
1.65
1.7
1.75
1.8
1.85
1.9
1.95
2
2.05
0.0029 0.00292 0.00294 0.00296 0.00298 0.003 0.00302
Log
K
1/T
Log[K] 1/T k
-1
K dm3
mol-1
min-1
Temperature /
c0
3.544068 2 100 60
3.579441 1.8451 70 65
3.648458 1.696 50 70
67
3-2. Calculation of ∆ H, ∆G and ∆S
the value of activation energies and frequency factors were further used
to calculate the enthalpy of activation,entropy of activation and free
energy of activation using the equation:
∆ H = ∆E -RT
∆S = 2.303 R [Log A - Log RT/Nh]
∆ G = ∆ E -T ∆S
The results are summarized in table 22 and 23
68
Table (3-22)
The values for ∆S, ∆G and ∆H of acetone for different temperature are:
∆G (KJ)
∆S (J)
∆H( KJ)
T(K)
78 -235.5 23.23
333
79.9
-235.7 23.19
338
80.4 -234.5 23.15
343
∆H = 23.15 kJ
∆ S = - 235.5 J
∆G=79.5 kJ
Table (3-23)
The values for ∆S, ∆G and ∆H of acetophenone for different temperature
are:
∆G(KJ)
∆S(J)
∆H(KJ)
T(K)
81.07 -243.2 90.23
333
83.51 -246.8 90.19
338
85.91 -250.2 90.15
343
∆H = 90.19 kJ
∆S= -246.7 J S
∆G= 83.4 kJ
69
3-3 Results and Discussion:
Kinetics investigation of the oxidation of acetone and acetophenone by
peroxodisulphate was made at several concentrations by keeping the
concentrations of [S2O8-2] and [Ag+] constant, the silver ion catalyzed
oxidation of acetone by peroxodisulphate it was shown [Bekier and
Kijowsk, 1935] that acetic acid and carbon dioxide are formed according
to the equation:
CH3COCH3+4K2S2O8-2+3H2O Ag+ CH3COOH+CO2+8KHSO
P.S.Sheeba and T.D.Radhahishnan Nair reported that the kinetic of
oxidation of acetophenone by potassium permanganate have been
studied in 50% aqueous acetic acid medium the reaction is first order
with respect to oxidant and half order to substrate.
While Nafisa [Nafisa2002] studied the unanalyzed, reaction of
butanone and 3- pentanone with the reaction follows first order in
peroxodisulphate and zero order in substrate.
The copper catalyzed oxidation of acetone by peroxodisulphate was
studied by [Agrawal, 1982] and unanalyzed, oxidation of acetone by
peroxodisulphate was studied by [Hala, 1992], the reaction follows first
order in peroxodisuphate and zero order in acetone in silver catalyzed
oxidation of some cyclic ketone by peroxodisulphate.
In this work two ketones were chosen, namely Acetone and
acetophenone as substrate in the reaction of catalyzed oxidation by
peroxodisulphate the catalyst is silver ion, the kinetic runs were
performed as usual by drawing samples were analyzed for the oxidant,
peroxodisulphate by the iodometric method ,for each run a plot of [S2O8-
2] Against [T] was prepared, Curve was given and the slop of the curve
at zero time is taken as initial Rate of the reaction, the curve nearly
straight out at zero time.
3-3-1 Acetone:
3-3-1-1 Determination of order with respect to [S2O8-2]:
70
At constant[Ag+]and [Acetone],the variation of titre with time at
different [S2O8-2] is shown in table(3-1) where the initial rate is
obtained as the slop of the curve at zero time for each values of [S2O8-2].
Variation of initial rat with [S2O8-2] is summarized in table (3-2) and a
plot of log [initial rate] against log [S2O8-2] is given in fig [3-2].
The plot is straight line, the slop of which is the order with respect to
[S2O8-2] the order was found to be one.
3-3-1-2.the order with respect to [Ag+]:
The above procedure was repeated by replacing [Ag+] for [S2O8-2]
And the results as shown in table (3-5 and 3-6) and the plots in fig (3-5)
and (3-6) the order was found to be one.
3-3-1-3. the order with respect to [Acetone]:
The procedure is the same as above and the data are shown in table (3-3
and 3-4) and the plot is shown in fig (3-4).the order was found to be one.
3-3-2. Acetophenone:
Atypical procedure like that for Acetone was followed for
Acetophenone, the respectively data for the determination of order with
respect to [Ag+] and [S2O8-2] [Acetophenone ketone] are shown in
table [3-7 to 3-12] and the plot is shown in figs [3-6 to 3-12]. The order
with respect to the reaction component was found to be one for [S2O8-
2], one for [Ag+] and half for [Acetophenone Ketone] respectively.
Table (3-13) summarizes the orders for both Ketones.
To compare these results with literature, the order with respect to [S2O8-
2], agree with respect to catalyst [Ag+] was found to be one. It is
agreement with almost all workers.
The order with respect to the substrates was found to be one for Acetone
and half for Acetophenone. These values are in disagreement with
almost all workers who reported the order to be zero with respect to
Acetone.
71
All these different in order of reaction necessitates a look into the
experimental methods of determining these order, the task which is
under taken by this work.
Mechanisms are proposed which agree with the deducted rate equations
according to the orders with respect to the components of the reaction.
3-4. mechanism:
The following mechanisms were proposed which leads to the
experimental rate laws:
S2O8-2 K1 2 SO4
.
SO4.+ H2O K2 HSO4
-+OH.
R RCO + OH. K3 RC.O + ROH
R.CO + S2O8-2 K4 RC [SO4
-] O+ SO4-
or
R.CO+ SO4- K5 RC [SO4
-] O
RC [SO4-] O + H2O k6 RCOOH+H SO4
-
RCOOH + SO4. K6 RCOO
. +H SO4-
R/ +H SO4- K7 R/ +H2O+ SO4
-
RCOO. +R
/ K9
RCOOR
/
The rate law of the reaction according to the above mechanism can be
expressed as follows:
-d [S2O8-2]/dt =K1 [S2O8
-2] +K4 [RC.O] [S2O8-2]…………….. (1)
On applying the steady state treatment to the formation of radicals
SO4- , OH
. , RC
.O, RCOO
. and R
/
[I]d [SO4-]/dt =0
k1
[S2O8-2] + k
4 [RC
.O] [S2O8
-2] +k8[R
/] [H SO4
-]
[II] d [OH.]/dt = 0
72
K2 [SO4
-][ H2O]+
k
5[SO4
-][RC
.O]+ k
7[SO4
-][RCOOH]………(2)
K2 [SO4
-] [H2O] + K3 [R
/RCO][ OH
.]…………………………... (3)
[III] d [RC.O]/dt=0
K3= K4 [RC.O] [S2O8
-2] + K5 [RC.O] [SO4
-]………………… (4)
(IV) d [RCOO. ]/dt =0
K7 [RCOO.] [SO4
-] =K9 [RCOO
.][R
.]………………………… (5)
(V) d [R/]/dt =0
K8 [R/OH] [HSO4
-] =K9 [RCOO
. ]
[R
.]……………………….. (6)
From equation (3) and (4)
k2 [SO4
-] [H2O] = k4 [RC
.O] [S2O8
-2] + K5 [RC.O] [SO4
-]…..(7)
From equation (5) and(6)
k7 [RCOO.] [SO4
-]= k8 [R
/OH] [HSO4
-]………………………. (8)
From equation (7) and (8) equation (2) become:
k1
[S2O8-2] = 2k5 [RC.O] [SO4
-]……………………………… (9)
Then:
[SO4-]= k
1 [S2O8
-2]/ 2k5 [RC.O]………………………………. (10)
Substitute equation (10) in (2) and from equation (8) we get
[S2O8-2]+ k4 [RC
.O] [S2O8
-2] =
k2 [H2O] k1
[S2O8-2]/2k5[RC.O]+K5[RC
.O]k
1[S2O8
-
2]/2k5[RC.O](11)
[S2O8-2] K2[H2O] k
1/2 K5[RC
.O]+( K5[RC
.O])[ k
1/2
K5[RC.O]]..(12) k
1+ k4 [RC
.O] =k
1 k
2 [H2O]/ 2 k5 [RC
.O] +1/2 k
1.
(13)
2k1
k5[RC.O]+ 2k
4 k5[RC
.O]
2 =2k
1 k5[RC
.O]+
k1k2[H2O]……….(14)
73
2k1
k5 [RC.O]
2=2k
1k5[RC
.O] + k
1k2 [H2O] =0………........... (15)
The rates of these second order equations are:
RC.O] =-k
1k5+ [( k
1k5)2] +8 k
1k2
k4k
5 (H2O)]
1/2/4 k
4k5
…………(16)
Considering only positive value of [RC.O]
[RC.O]=- +[( k
1k5)2]+ +[( k
1k5)2]+8
k1k2
k4k
5(H2O)]
1/2/4k
4k
5………(17)
[H2O] is constant as water is present in large excess so:
[RC.O]=K……….……………………………………………… (18)
There for equation (1) becomes
-d [S2O8-2] /dt = k
1 [S2O8
-2] +k4
k/
[S2O8-2]
= [S2O8-2] (k
1+ k
4k/)
= k0
[S2O8-2]
Where
k0
= (k1
+ k4k
/)
The stoichiometric equation can be written as:
R/RCO+ K2S2O8+ H2O RCOOR
/+2KHSO4
This mechanism similar to the mechanism which was proposed by
Nafisa (Nafisa2002).
74
3-5.Conclusion
The results of this study show that there is a difference in order of
substrate (ketones) in the oxidation kinetics of the Aliphatic and
Aromatic ketones. It was found to be (1) in the case of Acetone and (0.5)
in the case of Acetophenone. This may be due to the difference in
structure of ketones (ring in the acetophenone).
3-6.Recommendations
It is recommended that the effect of the aliphatic ketone on the oxidation
of ketones with persulphate be studied by employing aliphatic ketones
like acetone, butanone and hexanone in addition to different Aromatic
ketones.
75
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