Kinetics of Oxidation of Acetone and Acetophenone by ...

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



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



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

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DEDICATION

TO MY MOTHER,

TO MY FATHER

&

MY SISTERS

FOR THEIR UNWAVERING SUPPORT

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.

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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.

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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

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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

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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

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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

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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


concentration of Acetone

3-3


Concentration of Acetone

3-4


concentration of [Ag+]for Acetone

3-5


Concentration of [Ag+]for Acetone

3-6


concentration of [S2O

8-2

]for Acetophenone

3-7


Concentration of[S2O

8-2

]for Acetophenone

3-8


concentration of Acetophenone

3-9


Concentration of Acetophenone

3-10


concentration of [Ag+] for Acetophenone

3-11

12


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


Acetophenone

3-19


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

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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


24 A plot of Initial Rate against Log [CH3COCH3] 3-4


28 A plot of Initial Rate against Log [Ag+] 3-6


32 A plot of Initial Rate against Log [S

2O

8-2

] 3-8


36 A plot of Initial Rate against Log [Acetophenone] 3-10


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



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

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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.

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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

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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

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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


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 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


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


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 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]


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


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


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


51


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 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)


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


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)


C}

[S2O8-2]= 2X10-2 M

[Acetone] =2x10-2 M

[Ag+]=2X10-3 M


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


[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


[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)


C}

[S2O8-2]= 2X10-2 M


[Ag+]= 2X10-3 M


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)


C}

[S2O8-2]= 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


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)


C}

[S2O8-2] = 2X10-2 M


[Ag+] =2X10-3 M


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


[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


[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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