Intensification of Sonochemical Reactions

Study of intensification of sonochemical reactions using gaseous additives
Thesis submitted to for the degree of
MASTER OF CHEMICAL ENGINEERING
Suraj S. Shaha
Department of Chemical Engineering Institute of Chemical Technology, Mumbai Maharashtra, India
2012
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Study of intensification of sonochemical reaction using gaseous additives
Thesis submitted to Institute of Chemical Technology, Mumbai For the award of the degree of
MASTER OF CHEMICAL ENGINEERING

by
Suraj S. Shaha
under the supervision of
Professor (Dr.) Parag R. Gogate
Department of Chemical Engineering Institute of Chemical Technology, Mumbai Maharashtra, India May 2012 2012, Suraj S. Shaha, All rights reserved
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INSTITUTE OF CHEMICAL TECHNOLOGY, MUMBAI
Approval of the Research Supervisor and the External Examiner
Certified on
, that the thesis titled Study of intensification of sonochemical
reaction using gaseous additive submitted by Mr. Suraj Sudhir Shaha to the Institute of Chemical Technology, Mumbai, for the award of the degree Master of Chemical Engineering has been accepted by the external examiners, and that the student has successfully defended the thesis in the viva voce examination held today.
Signature:
Research Supervisor: Prof. (Dr.) Parag R. Gogate Affiliation: Institute of Chemical Technology, Mumbai, Maharashtra, India
Signature:
External Examiner: Affiliation:
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CERTIFICATE
This is to certify that the thesis titled titled Study of intensification of sonochemical reaction using gaseous additive submitted by Mr. Suraj Sudhir Shaha to the Institute of Chemical Technology, Mumbai, for the degree of Master of Chemical Engineering is a bona fide record of the research work carried out by him in the Department of Chemical Engineering, Institute of Chemical Technology, Mumbai, under my supervision. Mr. Suraj Sudhir Shaha has worked on this topic from February 2007 till February 2011 and the thesis, in my opinion, is worthy of consideration for the award of the degree Master of Chemical Engineering in accordance with the regulations of this Deemed-to-be University. The results embodied in this thesis have not been submitted to any other University or Institute for the award of any degree, diploma, or certificate.
Signature:
Research Supervisor: Prof. (Dr.) Parag R. Gogate Affiliation: Date: Institute of Chemical Technology, Mumbai, Maharashtra, India
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Dedicated to my family and friends..!!
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ACKNOWLEGMENT It is indeed a pleasure to get an opportunity to thank all those who have helped me to complete my M. Chem. Eng course and for showering me their blessings. Words and actions are not sufficient to show how thankful I am to my parents, sister (Sayali) and mausi. I am indeed proud to thank my research guide Dr.Parag Gogate who has put in all his efforts and has helped me by giving suggestions on how to work and go about my project. I will never forget his boundless passions and efforts to make students perfect in everything. I am very much thankful to him for the freedom he has given to me in my research work. He was a constant source of encouragement & motivation as well as a principle cantered person. His overtly enthusiasm and integral view on research always had a deep impression on me and gave me confidence to go about and complete my project successfully. I am indebted Dr.Amit Pratap for his due help and knowledge he imparted to me for my future and career. The friendly environment in the lab kept me cheered up during my work. I am really obligated to my senior lab mates Pankaj, Bagal Madam, Kiran, and Chandu for their support all throughout my research period. I would like to thank my lab mates Ghanshyam, Sanket, Amar and Kavita for their support and help during critical situations. My special thanks for Ghanshyam and Sanket for their support, help, counselling and many other things. Also would like to thank Atchut, Tushar, Prashil, Inder, Pallavi, Dhanashri and Kavita for their valuable help in lab. Transition from B. Tech Oils to Chemical Engineering was indeed a very difficult job for me but thanks to Patle, Viplav, Shefali, Southy and Gaurav, who gave their valuable time during exam period & throughout the year and have helped me a lot in my study and made my tedious journey easy. I would want to thank Shraddha, Shefali, Southy, Gaurav, Patle, Ghanshyam, Ankush, Rikku, Ankita, Shilpa, Rohini, Suma & Karan who had been there to entertain me with their laughter and talks. There were many trips and outings with them which helped me feel refreshed to work ahead.
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I would also like to thanks all my classmates Pratik, Aniket, Gaja, Avinash, Santosh, Ritesh, Parag and all placement co-ordinators (Nikhil, Navneet, Sanket, Rohini, Shilpa and Darshan who worked with me during whole placement cell. Without all of them my social life would have been incomplete. I would like to thank my roommates- Magar, Gund, Kulkarni, Kabade, Khandare, Ankur, Dhumal, Raybole as well as all my hostel & trekking friends specially Bhogale, Mukesh, Parag, Patil, Chavan, Sanket, Venu, Labade, Rathod, Sahare who added to the fun trips and enjoyments to the research life. I want to give my special thanks to Ghanshyam, Sanket, Ankur, Dhumal, Chandan, Magar, Darade, Smita, Amruta, Purva, Pradnya who had been there to encourage & help me in every tough situation; moreover they were always there with me in all the good & bad times. Last but not the least I am very much grateful to the non-teaching staff, watchmen, Mess workers and the most important Munnaji without whom my 6 years of ICT would have been impossible. I wish my juniors all the very best for their future and regret if I have missed out anyone in my acknowledgment. Thank you to everyone and above all God. Suraj Shaha
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DECLARATION
I certify that, - the work contained in this thesis is original and has been done by me under the guidance of my research supervisor / supervisors. - the work has not been submitted to any other University or Institute for the award of any degree, diploma, or certificate. - I have followed the guidelines of the Institute in preparing the thesis. - I have conformed to the norms and guidelines given in the Ethical Code of Conduct of the Institute. - whenever I have used materials (data, theoretical analyses, figures, text, etc.) from other sources, I have given due credit to them by citing them in the text of the thesis and giving their details in the references. Further, I have taken permission from the copyright owners of the sources, whenever necessary. - I hereby grant to the university and its agents the non-exclusive license to archive and make accessible, my thesis, in whole in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis. I also retain the right to use in future works (such as articles or books) all or part of this thesis.
Signature: Research Scholar: Mr. Suraj S. Shaha
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List of Figures
Figure No. 1.1 Growth collapse cycle of cavitation bubbles 1.2 The compression and expansion cycle of ultrasound 1.3 Classification of different types of cavitation 1.4 Schematic of acoustic cavitation Figure Caption Page No. 22 22 24 25
3.1 Calibration curve of Iodine on UV-spectrophotometer 3.2 Calibration curve of salicylic acid using HPLC 3.3 The schematic view of experimental setup for ultrasonic horn 3.4 The schematic view of experimental setup for ultrasonic longitudinal horn of 36 kHz and 25 kHz
45 46 48 51
4.1 Sonication of 100 ppm KI on different reactors in absence of any gases 4.2 Sonication of 100 ppm KI on different reactors in presence of air 4.3 Sonication of 100 ppm KI on different reactors in presence of oxygen 4.4 Sonication of 100 ppm KI on different reactors in presence of nitrogen 4.5 Sonication of 100 ppm KI on different reactors in presence of carbon dioxide 4.6 Sonication of 100 ppm S.A. on different reactors in absence of any gases 4.7 Sonication of 100 ppm S.A. on different reactors in presence of air 4.8 Sonication of 100 ppm S.A. on different reactors in presence of oxygen 4.9 Sonication of 100 ppm S.A. on different reactors in presence of nitrogen
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4.10 Sonication of 100 ppm S.A. on different reactors in presence of carbon dioxide 4.11 Effect of initial concentration of potassium iodide on sonolysis using 20 KHz horn in absence of any gases 4.12 Effect of initial concentration of potassium iodide on sonolysis using 20 KHz horn in presence of air 4.13 Effect of initial concentration of potassium iodide on sonolysis using 20 KHz horn in presence of oxygen 4.14 Effect of initial concentration of potassium iodide on sonolysis using 20 KHz horn in presence of nitrogen 4.15 Effect of initial concentration of potassium iodide on sonolysis using 20 KHz horn in presence of carbon dioxide 4.16 Effect of initial concentration of potassium iodide on sonolysis using 25 KHz longitudinal horn (1 Kw) in the absence of any gases 4.17 Effect of initial concentration of potassium iodide on sonolysis using 25 KHz longitudinal horn (1 Kw) in presence of air 4.18 Effect of initial concentration of potassium iodide on sonolysis using 25 KHz longitudinal horn (1 Kw) in presence of oxygen 4.19 Effect of initial concentration of potassium iodide on sonolysis using 25 KHz longitudinal horn (1 Kw) in presence of nitrogen 4.20 Effect of initial concentration of potassium iodide on sonolysis using 25 KHz longitudinal horn (1 Kw) in presence of carbon dioxide 4.21 Effect of gaseous additives on KI (100 ppm) oxidation (using 20 KHz horn) 4.22 Effect of gaseous additives on KI (300 ppm) oxidation (using 20 KHz horn) 4.23 Effect of gaseous additives on KI (500 ppm) oxidation (using 20 KHz horn) 4.24 Effect of gaseous additives on S.A. (100 ppm) oxidation (using 20 KHz horn)
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4.25 Effect of gaseous additives on KI (100 ppm) oxidation (on 25 KHz reactor) 4.26 Effect of gaseous additives on KI (300 ppm) oxidation (on 25 KHz reactor) 4.27 Effect of gaseous additives on KI (500 ppm) oxidation (on 25 KHzreactor) 4.28 Effect of gaseous additives on S.A. (100 ppm) oxidation (on 25 KHz reactor) 4.29 Effect of air flow rate on sonolysis of 300 ppm KI (20 KHz horn) 4.30 Effect of air flow rate on sonolysis of 300 ppm KI (36 KHz longitudnal horn) 4.31 Effect of air flow rate on sonolysis of 300 ppm KI (25 KHz reactor) 4.32 Effect of air flow rate on sonolysis of 100 ppm S.A. (20 KHz horn) 4.33 Effect of air flow rate on sonolysis of 100 ppm S.A. (36 KHz longitudnal horn) 4.34 Effect of air flow rate on sonolysis of 100 ppm S.A. (25 KHz longitudnal horn)
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List of Tables
Table No. 1.1 Overview of the applications of cavitation Table Caption Page No. 27
2.1 Research work in cavitations field using potassium iodide and salicylic acid dosimetry
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3.1 Data obtained from UV- spectrophotometer 3.2 Data obtained from HPLC
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4.1 Effect of reaction temperature on cavitational yield of sonolysis of potassium iodide 4.2 Effect of reaction temperature on cavitational yield of sonolysis of salicylic acid 4.3 Effect duty cycle percentage on cavitation yield of potassium iodide 4.4 Effect duty cycle percentage on cavitation yield of salicylic acid 4.5 Effect of power supply on sonolysis of potassium iodide 4.6 Effect of power supply on sonolysis of salicylic acid 4.7 Comparison study of three different reactors using different initial concentrations of potassium iodide 4.8 Study of effect of initial concentration on iodine liberation using 36 kHz reactor in presence of different gases (all values approximate and are in ppm) 4.9 Effect of gaseous additives on sonochemical reactions ( using 36 kHz reactor)
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List of Abbrevation
CO2 HPLC KI N2 O2 SA UV Carbon Dioxide High pressure liquid chromatography Potassium iodide Nitrogen Oxyegn Salicylic acid Ultra-violate spectroscopy
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Abstract
Due to its large potential of intensification of physical as well as chemical processes, cavitation can be used in many industrial applications. Tremendous research has been done in finding its applicability in different fields. But it is observed that due to lack of economical operation and reliable design of sonochemical reactors based on the use of ultrasonic irradiation, industrialization of this phenomenon is nearly negligible. So to make it industrially feasible, intensification of cavitation is required. To study the intensification aspects of sonochemical reactors oxidation of potassium iodide and salicylic acid degradation using ultrasonication have been studied in the present work. Initially effect of different operating parameters such as temperature, power, duty cycle and initial concentrations of reaction solution has been investigated with experiments in the available different geometries and capacity of reactors. Intensification of these sonochemical reactions using different gaseous additives such as air, oxygen, nitrogen and carbon dioxide has been then investigated. Effect of air flow rate on sonochemical reactions in different sonochemical reactors has also been examined. The experimental results show that the cavitational yield is strongly influenced by the operating parameters and type of the reactor. Also it is observe that presence of gases increase the extent of oxidation of potassium iodide and degradation of salicylic acid. This extent is different for different gases and depends on the nature of the gas and physical properties of gases like polytropic index, vapor pressure etc. In the study of effect of air flow rate on sonochemical reaction, increase in cavitational yield is observed in the presence of air up to a certain flow rate and after that it has been observed to decrease.
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CONTENTS Page No. Cover Page Title page Approval of supervisor(s) and external examiner Certificate by the supervisor(s) Dedication Acknowledgements Declaration by the student List of figures List of tables List of abbreviations Abstract and keywords Contents 1 2 3 4 5 6 8 9 12 13 14 15
Page No. Chapter 1 Introduction 1.1 History 1.2 Advantages using ultrasouns 19-31 19 20
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1.3 Cavitation 1.4 Types of cavitation 1.4.1 Acoustic cavitation 1.4.2 Hydrodynamic Cavitation 1.4.3 Particle cavitation 1.4.4 Optic Cavitation 1.5 Acoustic cavitation 1.6 Theory of cavitation 1.7 Factors affecting cavitation 1.8 Application of cavitation 1.9 Limitation of ultrasonic cavitation 1.10 Objective of present work
21 23 23 23 23 23 24 25 26 27 29 30
Chapter 2
Literature survey
33-41
Chapter 3
Experimental 3.1 Reaction scheme 3.2 Materials 3.3 Analytical procedure
42-52 42 42 43
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3.3.1 Iodine measurement 3.3.2 Calibration curve for salicylic acid 3.4 Experimental Set-up of ultrasonic horn reactor 3.5 Parameter optimization 3.5.1 Procedure for optimization of reaction temperature 3.5.2 Procedure for optimization of duty cycle 3.5.3 Procedure for optimization of power 3.6 Experimental procedure for sonolysis of reaction solution in the presence of gases using horn reactor 3.7 Experimental Set-up of ultrasonic longitudinal horn reactor 3.8 Experimental procedure for sonolysis of reaction solution using longitudinal horn reactors of different capacity
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Chapter 4
Results and Discussion 4.1 Effect of temperature 4.2 Effect of duty cycle 4.3 Effect of power 4.4 Comparison of different sonochemical reactors 4.5 Effect of initial concentration on sonochemical reactions
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4.6 Effect of different gaseous additives on sonochemical reactions 4.7 Effect of air flow rate on sonochemical reactions
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Chapter 5
Conclusion
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Chapter 6
Future work
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Chapter 7
References
91-97
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1. Introduction
1.1 History Cavitation dates back to 1800s. During field tests of the first high-speed torpedo boats in 1894, Barnaby and Thornycroft I et al., (1895) discovered severe vibrations from rapid erosion of the ship's propeller. It was postulated that the formation and collapse of bubbles were the reason behind the observation of the formation of large bubbles (or cavities) on the spinning propeller. By increasing the propeller size and reducing its rate of rotation, this difficulty of "cavitation" could be minimized. However with increasing ship speed, this became a serious concern and the Royal Navy commissioned Lord Rayleigh (1917) to investigate this phenomenon. He confirmed that the effects were due to the enormous turbulence, heat, and pressure produced when cavitation bubbles imploded on the propeller surface. Such phenomenon of cavitation is observed in liquids not only during turbulent flow but also under high-intensity sound wave irradiation. Audible sound has a frequency between 10 and 18 kHz, but this is generally of too low an energy to have any influence to cause cavitation. However, ultrasound with a frequency between 20 kHz and 2 MHz are reported to show a remarkable effect to produce the same, leading to the physical and chemical consequences. These effects of ultrasounds on chemical reactions are referred as sonochemistry. Application of ultrasound was first reported by Richards and Loomis in 1927. Ten years later Brohult (1937) discovered that ultrasound led to the degradation of a biological polymer. Research in this field of ultrasonics led to research in the area of degradation of synthetic polymers by Schmid and Rommel in 1939. Since 1950 there have been several new and exciting developments in the field of sonochemistry. Noltingk and Neppiras (1950) performed the first computer calculations modeling on a cavitating bubble. Three years later work on sonolysis of an organic liquid (Schultz and Henglein, 1953) was reported. Elder et al. (1954) suggested that bubble-induced micro-streaming was one of the factors leading to the well-known ultrasonic cleaning effects in heterogeneous systems. Sonochemistry gained inportance in the 1980s (Caupin et al., 2006) and over
Study of intensification of sonochemical reactions using gaseous additives Page 19
these past few years, intense research has been going on for effective utilization of acoustic energy for cavitationally induced transformations. Reactions involving solid surfaces as reagents or catalysts were improved by the mechanical effects associated with the collapse of a bubble. They are the cleaning and oxide removal from the surface enhancing its reactivity enabling the molecules to be efficiently swept over the surface (Caupin et al., 2006). But in case of homogeneous liquid phase, ultrasonic irradiation induces the production of cavitational bubbles in the liquid medium through which it is transmitted. These microbubbles act as micro-reactors, which produce very high temperature and pressure on collapsing, leading to sonolysis (formation of hydroxyl radical from water) (R. dAuzay et al. (2010), Cravotto et al. (2006). The radical species produced can react and recombine with other gaseous species present in the cavity, or diffuse out of the bubble into the bulk fluid medium where they can react with the solute molecules (Merouani et al., 2010). These effects can be effectively worked upon for the intensification of physical and chemical processing applications such as chemical synthesis, wastewater treatment, textile processing, biotechnology, crystallization, polymer chemistry, extraction, emulsification and petrochemical industries, etc. (Sutkar et al., 2009). 1.2 Advantages using Ultrasound: Before using any technology it is desirable to know its benefits. The benefits of ultrasound are many folds. It has been studied extensively in the field of chemical reactions with respect to synthesis and kinetic aspects. To carry out chemical reactions we require removal or addition of energy, in one form or another to proceed and ultrasonic irradiation has number of advantages over traditional energy sources, such as high heat, light, electricity or ionizing radiation. Some of the advantages are given below. Use of ultrasound, Accelerates the rate of reaction Enhances radical reactions and catalyst efficiency Permits the use of less forcing conditions
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Revitalizes older discarded synthetic techniques by enhancing the reactivity of reagents Reduces the number of steps required and induction period Initiates stubborn reactions 1.3 Cavitation Very high densities (~1018 kW/m3) can be produced over a small location using the cavitation phenomenon, which involves generation, growth and collapse of cavitites in a liquid (Gogate et al. 2006). Ultrasound can be used to bring about cavitation events in sonochemical reactors. In the case of sonochemical reactors, the cavitation events are brought about by the passage of ultrasound. Ultrasound when transmitted through a medium creates a time-varying pressure field which induces vibrational motion to the molecules leading to compression and stretching of the molecular structure of the medium. Thus, the molecules oscillate around their mean position leading to variation in the distances among them. If the intensity of ultrasound in a liquid is increased, a point is reached at which the intramolecular forces are not able to hold the molecular structure intact. Consequently, it breaks down and a cavity is formed, shown in the figure 1.1. This cavity is called cavitation bubble and the point where it starts is known as cavitation threshold or the inception of cavitation. A bubble responds to the sound field in the liquid by expanding and contracting, i.e. it is excited by a time-varying pressure, shown in the figure 1.2. Such bubbles grow by a process known as rectified diffusion i.e. small amounts of vapour (or gas) from the medium enters the bubble during its expansion phase and is not fully expelled during compression. The bubbles grow over the period of a few cycles to an equilibrium size for the particular applied frequency.
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Figure 1.1: Growth collapse cycle of cavitation bubbles, Suslick (1998)
Figure 1.2: The compression and expansion cycle of ultrasound, Suslick (1998) In the subsequent compression cycles, the collapse phase of the bubbles is usually very fast as compared to the growth phase of the bubbles. This rapid adiabatic collapse of the cavities generates the energy levels suitable for significant intensification of many chemical and processing applications as mentioned earlier.
Cavitation events can occur at countless locations in the reactor simultaneously in an actual reactor. It generates different physical and chemical effects suitable for process intensification (Gogate and Pandit 2004; Gogate, 2002; Gogate, 2008; Gogate et al. 2006). Physical effects of local turbulence and liquid microcirculation are a result of cavitation and for applications limited by transport processes; cavitation can be used to enhance the rates of transport process, leading to process intensification. Cavitation also results in chemical effects such as the generation of hot spots (conditions of very high temperatures and pressures) and reactive free radicals, which can intensify the chemical processing applications limited by intrinsic chemical kinetics (Gogate 2008). In actuality, the combination of the physical and chemical effects of cavitation leads to net intensification of the process. In actual practice, depending on the operating conditions, two forms of cavitation are observed, stable and transient. In stable cavitation the bubbles oscillate around their equilibrium position over several refraction/compression cycles. In transient cavitation, the bubbles grow over one (sometimes two or three) acoustic cycles to a maximum size which can be in multiples of the initial size and finally collapse violently over a quick time duration (Thompson and Doraiswamy, 1999). 1.4 Types of Cavitation: 1.4.1 Acoustic cavitation: In this case, passage of sound waves usually ultrasound (16 kHz 100 MHz) causes pressure variation. 1.4.2 Hydrodynamic cavitation: Cavitation is produced by pressure variation, which is obtained using geometry of system creating velocity variation. For example based on the geometry of system, the interchange of pressure and kinetic energy can be achieved resulting in the generation of cavities as in the case of flow through orifice, venturi etc. 1.4.3 Particle cavitation: It is generated by any type of elementary particle rupturing a liquid, as in a bubble chamber. 1.4.4 Optic cavitation: It is produced by photons of high intensity light (laser) rupturing the liquid continuum.
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Thus, the tensions prevailing in a liquid leads to acoustic and hydrodynamic cavitations and local deposition of energy results in optic and particle cavitations. The classification of the phenomenon of cavitation has been shown schematically in Figure 1.3.
Figure 1.3: Classification of different types of cavitation 1.5 Acoustic Cavitation: The mechanism of acoustic cavitation consists of Liquid being exposed to the acoustic field Cavity formation due to pressure waves which contain small quantities of dissolved gases and vapours from the surrounding medium Expansion of bubble or cavity due to compression and rarefaction cycles Attaining a maximum bubble size depending on operating conditions Collapse of bubble releasing large amount of energy creating conditions with extreme pressures and temperatures. (Patil et al., 2007). Under these conditions, gas molecules entrapped in the cavitation bubbles are thermally fragmented (by pyrolysis) to dissociate into a variety of short-lived energetic free radical species. The impact of a collapsing bubble on the contents of the surrounding liquid depends on the vibrational frequency of the applied field: if the frequency is low (20100 kHz) mechanical effects are dominant, whereas in the medium to high range frequency (300800 kHz) chemical effects dominate (Kidak and Ince, 2006).
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Figure 1.4: Schematic of acoustic cavitation (Maikel M., 2008). 1.6 Theory of Cavitation: Two theories have been reported to explain the observed sonochemical effects Hot-spot theory (Flynn, 1964) Electrical theory (Margulis, 1981).
Hot spot theory says that, a small gas bubble subjected to acoustic pressure amplitude of more than a few bars, experience violent pulsation such that the wall velocity for collapsing bubble approaches the velocity of sound. At this point, the bubble shatters upon collapse and results in adiabatic heating. The conditions so induced are in thousands of degrees temperature and thousands of atmospheres of local pressure and are described as in hot spots. These hot spots can also result in the dissociation of the water molecules or other chemical species entrapped in the cavitating bubble and result in the formation of the free radicals. This is the most common accepted explanation for chemical effects involving cavitation. (Flynn, 1964; Noltingk and Neppiras, 1950). Margulis (1981) showed that some observations could not be completely explained by the hot-spot theory and proposed an alternative electrical theory. This considers the
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charge distribution due to dipoles in water and their distribution around a bubble. It was lso shown that during bubble formation and collapse, enormous electrical field gradients in the region of 1011 V/m can be generated which are sufficiently high to cause bond breakage and chemical activity. 1.7 Factors affecting cavitation The magnitudes of collapse pressures, temperatures and the number of free radicals generated are a measure of how optimized a cavitation event has been. They are strongly dependent on the operating parameters of the equipment: intensity and frequency of irradiation; geometrical arrangement of the transducers in the case of sonochemical reactors and the liquid phase physicochemical properties, which affect the initial size of the nuclei and the nucleation process. Gogate P.R. (2010) had studied the influence of various parameters on cavitation and operational parameters for optimal cavitation effects have been presented. It was observed that the intensity of irradiation influenced the collapse pressure of a single cavity and also the number of cavities generated. In order to enhance this effect it is suggested to use a wide area of irradiation and also operate at optimum power dissipation. The intensity study was done within the range of 1-300 W/cm2. Effect of frequency was studied in the range of 20-200 kHz and it was observed that the frequency of irradiation affected the collapse time of the cavity and the final pressure & temperature pulse. Operation at optimum frequencies leads to desired effects. The liquid vapor pressure (range: 40-100 mm Hg at 30 oC) influences the cavitation threshold, intensity of cavitation, rate of chemical reaction. The viscosity of liquid governs the transient threshold and hence liquids of low viscosity are preferred to lower the threshold. Effect of surface tension was studied in the range of 0.03-0.72 N/m. It plays a crucial role in determining the size of nuclei, in order to generate nuclei of lower sizes low surface tension liquids must be used. Bulk liquid temperatures used affect the intensity of collapse, rate of reaction, threshold nucleation and other physical properties mentioned above. Optimum value of the bulk
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temperature varies with system used and has to be determined. It was studied in the range of 30-70 oC. The geometry of reactor is quite instrumental in determining the number of cavitational events and the distribution of cavitational activity distribution. Shape and number of transducers should be optimized for enhanced performance. The dissolved gas used determines the gas content, nucleation collapse phase and intensity of cavitation events. Gases with low solubility, high polytropic constant and low thermal conductivity (preferable monoatomic gases) should be used. 1.8 Applications of Cavitations: It is worthwhile to overview the different applications, where cavitation can be used efficiently. Few of the important applications are mentioned in the table 1.2. Table 1.1: Overview of the applications of cavitation
Area Physical Processes
Application Degassing Filtration Emulsification Crystallization Surface cleaning Particle Fusion Agglomeration
References Gandhi K. S. et al., (1994) Martin (1993) Mason, (1990)
Mechanical Engineering
Cutting and drilling Machining Metal Tube Drawing
Mason, (1990) Gandhi K. S. et al., (1994)
To degrade compounds which are present 1) Kotronarou et al., Waste treatment water in waste water stream like, P-nitrophenol [1] 1991; Sivakumar et al., (2001)
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Rhodamine B [2] 1,1,1 Trichloroethane [3] Phenol [4] CFC 11 and CFC 113 [5] o-dichlorobenzene dichloromethane [5] potassium iodide,
2) Shivkumar Pandit., (2001)
and
3) Toy et al., (1990) 4) Petrier et al., (1994) and and 5) Bhatnagar Cheung , (1994)
and sodium 6) Shirgaonkar Pandit, (1997) cyanide, carbon tetrachloride [6] Ando et al.(1984) Javed et al. (1995) Lie Ken Jie and Lam, (1995) Li et al., (1996) Thompson Doraiswamy, (1999) and
The different ways in which cavitation Chemical processing applications can be used. Like, Reaction time reduction Reduction in the induction period of the desired reaction Increase in the cavitational yield Use of less forcing conditions (temperature and pressure) as compared to the conventional routes Possible switching of the reaction pathways resulting in increased selectivity Increasing the effectiveness of the catalyst used in the reaction Initiation of the chemical reaction by way of generation of the highly reactive free radicals Biotechnology
Cell disruption for recovery of 1) Harrison and Pandit, intracellular proteins. [1,2] To selectively release (1992). the 2) Save et al., 1994, 1997.
intracellular enzymes or enzymes
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present in the cell wall. [3] Miscellaneous applications Retaining the activity of the leached out enzymes. [2]
3) Balasundaram Pandit, (2001)
and
In petroleum industry for refining 1) Patra fossil fuels, determination of (2006)
and
Das
composition of coal extracts, 2) Gogate et al, (2001) extraction of coal tars, etc. [1] In textile industry for enhancing the efficacy of dyeing of clothes and in wet processing. [2] To synthesis of nanocrystalline materials, preparation of high quality quartz sand, preparation of free disperse system using liquid hydrocarbons and dental water irrigator. [3] For solvent extraction of herbs. [4] 3) Vinatoru M. (2001)
1.9 Limitations of ultrasonic Cavitation The factors causing hindrance to successful application of sonochemical reactors on an industrial scale are multifold. Firstly (Mason, 2000), there is a lack of suitable large-scale design strategies. Also, intense cavitational activity occurs very close to the transducer which is the device used for generating ultrasound. This intense activity could prove detrimental to the functioning of transducer. Secondly, substantial efficacy at larger scales of operation is a challenge with the existing conventional designs. The operating temperature of the equipment has to be below 70 C. Thirdly, the frequent erosion of the ultrasonic surfaces hinders the pilot plant scale operation. The whole process cavitation occurs in extremely short period of time. Thus, in spite of extensive research, there is hardly any chemical processing based on ultrasonic cavitation phenomenon carried out on
an industrial scale .The lack of expertise required in diverse fields such as material science, acoustics, chemical engineering, etc., for scaling up successful lab-scale processes has also limited its application. . Ultrasonic transducer, which works on the principle of magneto striction capable of handling large scale volumes are now available in the commercial application. Theses transducers are capable of being operated at relatively higher temperature and continuously for 24 hrs. The recent past has seen the successful use of Multiplefrequency multiple transducer reactors. These reactors are an improvement when compared to the conventional designs such as ultrasonic horn or ultrasonic bath. Such reactors have substantially higher processing capacities (in the range of 11000 L). However, acoustic cavitation reactors still lack the continuous large scale industrial operation in spite of all these available designs 1.10 Objectives of the present work: As discussed in earlier section, there are large numbers of promising prospective applications of sonochemical reactors, but there are very few numbers of applications which are successful over industrial scale operation. One of the reasons for this lack of successful applications is the lower rates of processing at large scale applications, which can be overcome by the use of different additives as process intensifying parameters. The present work is concentrated in evaluating the efficiency of different gaseous additives at laboratory scale operation and also understands the dependency of the observed effects on the scale of operation by performing experiments at three different scales of operation. Specific hydroxyl radical dosimeters are adequate methods to standardize the characterization of sonochemical processes. Monitoring the generation of OH radicals in sonochemical reactors is essential to know the potential applicability as an advanced oxidation process. In cavitation processes, the hydroxyl radicals are generated inside the bubbles. Therefore, in order to react with the substances in the liquid phase the radicals have to diffuse through the gas phase, the interface and the liquid phase. In this process, the radicals tend to recombine, eventually leading to an underestimation of the OH radicals generation. Thus, dosimetry in cavitation systems has to guarantee the
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accessibility of the substrate to the OH radicals. Taking into account the previous studies (Sutkar and Gogate (2009), Martnez-Tarifa A. et al. (2010)), the present study is being focused on salicylic acid and iodide dosimetry as the method to estimate the OH radicals generation in the cavitation process (Martnez-Tarifa A. et al. (2010)). These approaches offer some advantages like, 1. Organic dosimetries quantify hydroxylated products that are obtained exclusively due to the action of OH radicals. No intermediate products affect the results. 2. The reaction products of salicylic acid/ Iodide dosimetry can be easily analyzed. Different types of additives used in the present work include air, oxygen, nitrogen and carbon dioxide. They are used to ease the process of cavity generation and intensify cavitational activity in the reactor. The presence of additives in the sonochemical reactors results in intensification due to the any of the following simultaneously acting mechanisms: Provide additional nuclei so that the number of cavitation events in the system increases leading to enhanced effects. Promote enhanced generation of free radicals or generation of additional oxidizing species in the system. Alter the physicochemical properties of the liquid medium thereby facilitating the ease of generation of cavitation events. Alter the distribution of the reactants at the site of cavity collapse.
Objectives: 1) Quantification of cavitational activity using salicylic acid and potassium iodide dosimetry and optimizing the parameters to increase the overall yield of the process. 2) Understand the effect of the presence of air and effect of flow rate of air on the reaction at optimized conditions.
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3) Understand the effect of presence of different gases on the sonochemical reaction in the ultrasonic horn and ultrasonic bath. So the present research topic focuses on the studies related to the intensification of cavitational activity using gaseous additives like air, oxygen, nitrogen and carbon dioxide. The cavitational activity has been quantified using salicylic acid and potassium iodide dosimetry.
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2. Literature Survey: As discussed earlier specific hydroxyl radical dosimeters are adequate methods to standardize the characterization of sonochemical processes. A lot of research was done in cavitation field using potassium iodide and salicylic acid dosimetry. Table 2.1 gives an overview about the use of these dosimetries. Table 2.1: Research work in cavitations field using potassium iodide and salicylic acid dosimetry. Research Description Potassium iodide dosimetry was used to standardize To standardize individual showed the ultrasonic power of Reference
ultrasonic that the
devices. potassium
Results iodide Kimura T. et al., (1996)
ultrasonic power for sonochemical reaction.
dosimetry, which can be regarded as a chemical dosimeter for measuring acoustic energy, was directly and linearly related to the calorimetrically determined ultrasonic power The influence on of several the operational
parameters
sonochemistry
dosimetries namely KI oxidation, Fricke To study the influence reaction of and H2O2production parameters using
experimental 300 kHz ultrasound was investigated. The Merouani S. et on main experimental which al., (2010)
parameters sonochemistry dosimetries
using showed significant effect in KI oxidation dosimetry were initial KI concentration, acoustic power and pH. The solution temperature showed restricted influence on KI oxidation.
To
enhance
the An examination of the efficacy of power- Dominick J. et al.,
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sonochemical activity modulated pulsed (PMP) sonochemistry (2005) in using modulated ultrasound A model has been developed for batch Modelling of a batch sonochemical reactor. sonochemical reactor using various Naidua D. V. P. et al., (1994) aqueous media was done by exploring the effects of pulse power- type and pulse frequency on the oxidation pulsed of potassium iodide.
assumptions was verified by conducting experiments with KI solutions of different concentrations
To investigate acoustic Acoustic cavitation energy distributions Younggyu Son et cavitation energy in a were investigated for various frequencies al., (2009) large-scale sonochemical reactor. For comparison of The work deals with evaluation of different configurations of sonochemical reactors of using a model reaction, potassium iodide oxidation, also known as the Weissler reaction, with justification on the basis of cavitational activity predictions of Levente C. et al., (2011) such as 35, 72, 110 and 170 kHz in a largescale sonochemical reactor.
cavitational activity in different configurations
sonochemical reactors supported theoretical simulations. with
theoretical simulations.
To study the effect of The sonochemical oxidation efficiency of a resonance power frequency, commercial titanium alloy ultrasound horn input, and has been measured using potassium iodide Rooze J. et al.,
saturation gas type on as a dosimeter at its main resonance (2011) the efficiency oxidation frequency of (20 kHz) and two higher
an resonance frequencies (41 and 62 kHz).
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ultrasound horn. The generation of OH radicals inside hydrodynamic cavitation bubbles was
monitored using a salicylic acid dosimeter. This method has been applied to study the To hydrodynamic cavitation advanced process as evaluate influence of the flow-rate and the solution pH for a given cavitation chamber Arrojo S. et al., (2007)
an geometry. The salicylic dosimetry has especially suitable for the
oxidation proven
characteristic time scales of hydrodynamic cavitation (higher than those of ultrasonic cavitation), which usually gives rise to recombination of radicals before they can reach the liquid-phase. In the present work, the effect of different
To
study
the of radical in
operating parameters viz.
pH,
power
intensification hydroxyl production
dissipation into the system, effect of Chakinala A. G. additives such as air, haloalkanes, titanium et al. (2007) dioxide, iron and oxygen on the extent of hydroxyl radical formation have in a been
sonochemical reactors.
sonochemical
reactor
investigated using salicylic acid dosimetry. The most significant parameters were For the statistical determined by designing a 25 factorial set of of experiments and applying some Martnez-Tarifa A. et al. (2010)
determination
significant parameters statistical tools to the results obtained with in a sonochemical the dosimeter. When operating within a limited range (typical range of standard sonochemical reactors) the statistical tools
reactor
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showed
that
only
the
dosimeter
concentration and the reactor geometry were mathematically significant in the process. Ultrasound works successfully with easily For the chemical oxidative organic matter, like salicylic acid, demand at optimised conditions. But the COD Canals A. et al., (COD) determination values obtained with more difficult organic (2002) oxygen assisted by ultrasonic matter are poor and still much more radiation research efforts must be done in order to improve the instrumental set-up. The focus of the project is on the intensification of sonochemical reactions using gaseous additives. A detailed literature survey has been done to analyze the existing data on the intensification of different sonochemical reactions using gaseous additives. The objective was to get the proper knowledge of the mechanism of intensification processes and also to finalize the set of important operating parameters affecting the extent of conversion as well as the extent of intensification. Katekhaye and Gogate (2012) have investigated the effects of different additives such as air, solid particles (cupric oxide and titanium dioxide), salts (sodium chloride and sodium nitrite) and radical promoters (hydrogen peroxide, ferrous sulphate, iron metal, carbon tetrachloride and t-butanol) on the degradation of potassium iodide. Combination of additives has also been investigated for examining the possible synergistic effects in comparison to the use of individual additions. They reported that the use of different additives results in enhanced cavitational effects as quantified by an increase in the iodine formation. Also the comparison between air and other solid additives has been done and it was reported that some solid additives like titanium dioxide gives higher yield than air at same conditions. It has been established that those additives which give additional reactive capability to generate enhanced quantum of free radicals are more effective as compared to those additives which merely enhance the cavitational activity by virtue of
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surface cavitation. They have also observed that using different additives in combination for intensification of sonochemical oxidation would be dependent on the type of additive and its mechanism of intensification. Chakinala A. G. et al., (2007) have studied the intensification of hydroxyl radical production in sonochemical reactor with different additives such as air, haloalkanes, titanium dioxide, iron and oxygen. They have taken salicylic acid dosimetry as the model reaction and found out that acidic condition under optimized power dissipation in the presence of iron powder and oxygen resulted in maximum liberation of hydroxyl radicals as quantified by the kinetic rate constant for production of 2, 5- and 2, 3dihydroxybenzoic acid. Also it was reported that the presence of oxidant in the form of air in combination with fenton chemistry might also play some role in enhancing the reaction rate. Pang Y. L. et al., (2011) have studied the sonochemical methods in the presence ozone as an additive for the treatment of organic pollutants in wastewater and observed the improvement in degradation efficiency. Mechanism offered for this intensification as the increased mass transfer of ozone from the gas phase to the bulk solution to react with substrate by mechanical effects of ultrasound. The cavitation bubbles can more readily induce O3 decomposition under mild conditions. Decomposition of O 3 yields molecular O2 and triplet atomic oxygen ( O(3P)) state O atoms produced are un-reactive and may react back with O3, they can also contribute to increase the formation of OH. Therefore it was reported that combined sonolysis and ozonolysis is an effective oxidation method compared to its individual oxidation methods as two OH are formed for every O3 molecule consumed. In bulk aqueous phase, the remaining dissolved O 3 could be decomposed by species originating from H2O molecules during sonolysis and ozonolysis such as OH, O2 and O3 to yield OOH and OH as shown in reactions. These reactive radicals may react with the target substrates and their initial degradation by-products. Also studies showed that decomposition using ozone as a additive was maximum at high pH and at optimum feed rate. Mohod and Gogate (2011) have worked on intensification of ultrasonic degradation of polymers like carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA) using air as
an additive. Yield polymer degradation as reflected by a significant reduction in the intrinsic viscosity or the molecular weight. The experimental results showed that the viscosity of polymer solution decreased with an increase in the ultrasonic irradiation time and approached a limiting value. Use of air helped in increasing the extent of viscosity reduction. The extent of viscosity reduction increases by using aeration. This was attributed to the fact that, presence of the dissolved gases in the liquid significantly increases the cavitational effect by supplying nuclei for the process. Kojima Y. et al. (2005) have studied the sonochemical degradation of MCPA ((4-chloro2-methylphenoxy) acetic acid) in dilute aqueous solutions using ultrasound. The effect of gas atmosphere on MCPA degradation was investigated in nitrogen (N2), air (O2/N2), oxygen (O2), argon (Ar) and Ar/O2 (60/40% v/v) atmospheres. For sonochemical degradation of MCPA in N2, air (O2/N2), O2 and Ar atmospheres, and the rate enhancement of MCPA decomposition by sonolysis was found to be more effective in an O2- enriched atmosphere compared to Ar atmosphere. It was considered that a higher amount of oxidants was formed in a higher O2 partial pressure, which accelerated MCPA decomposition in a radical reaction system. On the other hand, both dechlorination and total organic carbon (TOC) removal rates were higher in Ar atmosphere, compared to those in O2/N2 atmosphere. It was found that, MCPA was most effectively decomposed by sonication in Ar/O2 (60/40% v/v) atmosphere, with higher rates of decomposition, dechlorination and TOC removal. Wayment D. G. et al., (2002) have worked on the effect of ultrasonic frequency on the sonochemical degradation of alachlor, which is widely employed herbicide that was used to control most annual grasses and many broadleaf weeds. Effect of dissolved gases such as air, oxygen and argon was also studied. It was observed that the rate of degradation was increased by approximately 1.5 at 300 kHz and by a factor of two at 446 kHz for an argon-saturated atmosphere compared to oxygen, while the rate did not change with air. At 300 kHz, the rates were followed the order argon > oxygen > air = nitrogen, while at 446 kHz the rate appears to follow the order argon > air ~ oxygen. Nagata Y. et al. (2000) have studied the sonochemical degradation of dilute aqueous solutions of 2-, 3- and 4-chlorophenol and pentachlorophenol under air or argon
atmosphere. Under specified experimental conditions the investigation of dependency on time of the degradation of 2-, 3-, 4-chlorophenol and pentachlorophenol and liberation of chloride anions during sonication under argon or air atmosphere was studied. It was observed that the rate of degradation was faster in argon than in air. They justify this as the temperature in a collapsing cavity was defined as Tfin= Tin[Pfin(1)/Pin] where Tfin and Pfin were the final temperature and pressure, and Tin and Pin were the initial temperature and pressure in the cavities. =Cp/Cv was the ratio of the specific heat at constant pressure to the specific heat at constant volume of the gas in the bubble. The value was higher under argon (1.67) than in air (1.40); therefore, the cavitation effect was observed higher under argon than under air and hence the acceleration of the reaction by oxygen appears to be small. Adewuyi and Oyenekan (2007) worked on optimization of a sonochemical process using a novel reactor and Taguchi statistical experimental design methodology. For this study they had selected the model reaction, the sonochemical oxidation of carbon disulfide, and the response measured was the amount of sulfate (i.e., the predominant oxidation product) formed during the ultrasonic irradiations. The effect of gaseous additives like helium, air, oxygen, argon, and 75% argon/25% oxygen mixtures in the temperature range of 5-50 C were examined. It was observed that at 581 kHz, the optimum conditions were 35 C, 49 W, and oxygen, while the contributions of the temperature, power, and gas were 5%, 20% and 75% respectively. At 611 kHz, the optimum conditions were 35 C, 39 W and helium while the contributions of the temperature, power and gas were 6.5%, 58% and 35.5% respectively. At 1.3 MHz, the optimum conditions were 35 C, 90 W and oxygen while the contributions of the temperature, power, and gas were 21%, 29% and 50% respectively. Entezari and Kruus (1996) have studied the effects of different parameters on the potassium iodide sonochemical oxidation. It was observed that with 20 kHz irradiation, the reaction rate in a degassed solution is lower than that in an aerated solution. However, the rate with argon present is greater than that with air, and independent of whether there is continuous introduction of argon. The nature of the gas present does therefore affect the reaction rate, and any degassing during ultrasonic irradiation does not seem to be
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significant. The gas affects the ratio of specific heats and the thermal conductivity of the bubble contents. O2 can also participate in the secondary reactions that can occur around the cavitation bubble. The order of the rate at 20 kHz was argon>air>degassed, whereas at 900 kHz it is air>degassed>argon. No reasonable explanation can be offered for the low rate of reaction in degassed solutions using 20 kHz ultrasound. It may be due to a lack of nucleation centres. Hart and Henglein (1985) have conducted experiments by irradiating aqueous solutions of KI in a batch reactor with 300 kHz ultrasound under argon, oxygen and Ar-02 mixtures of different compositions. The products formed were determined to be I and H 2O2. The study showed that the rate of formation of I 2 increased with increasing KI concentration, but reached a plateau value at very high concentrations of KI. Also the rate of I 2 formation reached a maximum at a gas composition of 30% oxygen-70% argon. It was observed that the ratio of specific heats () for argon is higher than that of O 2 and thus, with the increase in O. content of the bubble, decreases, and the collapse temperature of the bubble also decreases. This leads to the generation of fewer hydroxyl radicals. At the same time, as the O2 concentration increases, the formation of hydroxyl radicals should also increase. Thus, a composite effect exists at an intermediate point, resulting in a maximum. Rooze J. et al. (2011), have studied the effect of resonance frequency, power input, and saturation gas type such as air, oxygen, nitrogen, carbon-dioxide and argon and helium on the oxidation efficiency of an ultrasound horn. It was observed that cavitational yield increases with increase in frequency for all saturation gases. At low frequency oxidation efficiency was maximum under argon saturation than air and oxygen but at high frequencies air saturation showed maximum cavitational yield than oxygen and argon. Also it was mentioned that in presence of carbon dioxide, bubble grows faster due to large solubility of carbon dioxide in potassium iodide solution. Hence higher oxidation efficiency was observed under carbon dioxide saturation. Sivasankar and Mohalkar (2009) have worked on intensification of sonochemical degradation of phenol using four different gases as a additives viz. argon, oxygen, nitrogen and air. It was observed that degradation of phenol was more than nitrogen,
argon and air. Also combinations of gases were studied and observed that combination of oxygen-argon gave the maximum degradation. Combination of gases with FeSO 4 were also studied and resulted in maximum degradation of phenol using combination with oxygen. Reaction mechanisms were offered for all the gases. Shimizu N. et al. (2008) have investigated the effect of dissolved gases on the generation of OH radicals in the presence of TiO2 catalyst. It was observed that in a sonochemical reactor of operating frequency of 36 kHz and power rating of 200W, maximum rate was given by Xenon followed by Ar, O2 and N2.
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3. Materials and Methods: 3.1 Reaction scheme: Reactions considered for the quantification of cavitational activity are oxidation of potassium iodide and salicylic acid dosimetry. The reaction scheme for oxidation of potassium iodide can be shown as follows.
Similarly, reaction scheme for salicylic acid docimetry can be shown as follows.
It can be seen that both the reactions are driven by hydroxyl radicals and hence are true indicator of the cavitational activity. 3.2 Materials: AR grade potassium iodide (KI) and salicylic acid (SA), sodium hydroxide and phosphoric acid were procured from S.D Fine-Chem Pvt. Ltd., Mumbai, India. Potassium iodide and salicylic acid were diluted to required concentrations using distilled water for
Page 42
experimental studies. Compressor was used for air sparging. Oxygen, Nitrogen and Carbon Dioxide cylinders were obtained from Alchemi gases. All the chemicals were used as received from suppliers. 3.3 Analytical Procedure: Analysis of samples of potassium iodide oxidation was obtained using Thermo Scientific SPECTROSCAN UV 2600 spectrophotometer and analysis of samples of salicylic acid dosimetry was performed using high pressure liquid chromatography (HPLC). Column used for the HPLC was C18 column having inner diameter of 4mm and length as 25 cm. The mobile phase used was a mixture of phosphate buffer (pH=2.5) and methanol (45:55 %), isocratically delivered (constant composition and flow rate) by a pump at a flow rate of 1 ml/min. The wavelength set for UV detection was 291 nm. Calibration Curve: In analytical chemistry, a calibration curve is a general method for determining the concentration of a substance in an unknown sample by comparing the unknown to a set of standard samples of known concentration. The concentrations of the analyte and the instrument response for each standard can be fit to a straight line, using linear regression analysis. This yields a model described by the equation y = mx, where y is the instrument response and m represents the sensitivity. The analyte concentration(x) of unknown samples may be calculated from this equation. 3.3.1. Iodine Measurements: Concentration of iodine liberated was obtained by measuring the absorbance of standard iodide solution with the help of the calibration curve. Procedure: 1) Initially 500 ml of distilled water was taken in the glass beaker. Then 350 mg iodine was added into it.
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2) From this solution, 5 ml was taken in the test-tube and 5 ml of distilled water was added so that total volume in the test tube became 10 ml. 3) Using step 2 (with different volumes) different concentration of iodine over the range of 50 ppm to 500 ppm were prepared. 4) Distilled water was used as a blank sample and the spectrophotometer was set at auto zero. 5) Set the spectrophotometer at = 352 nm and analyze the samples which gives the maximum absorbance for iodine. 6) From the readings taken, a graph of absorbance values against concentration was plotted as shown in figure 3.1, while the obtained data have been given in table 3.1. 7) The extent of iodine liberation, which gives a net quantification of the cavitational activity, can be estimated from the absorbance values using the calibration equation. Table 3.1: Data obtained from UV- spectrophotometer. Concentration (ppm) 0 50 100 150 200 250 300 350 400 450 500 0 0.06 0.094 0.135 0.181 0.205 0.257 0.278 0.317 0.363 0.394 Absorbance
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0.45 0.4 0.35 Absorbance 0.3 0.25 0.2 0.15 0.1 0.05 0 0 200 400 600 Concentration (ppm) Linear (Standerdization curve- Iodine) Standerdization curve- Iodine
y = 0.0008x R = 0.9908
Figure 3.1: Calibration curve of Iodine on UV-spectrophotometer 3.2.2. Calibration curve for salicylic acid: The procedure for salicylic acid calibration has been given as follows: Procedure: 1) Initially 500 ml of distilled water was taken in the glass beaker. Then 50 mg salicylic acid was added into it. 2) From this solution, 5 ml was taken in the test-tube and 5 ml of distilled water was added so that total volume in the test tube became 10 ml. 3) Using step 2 (with different volumes) different concentration of salicylic acid over the range of 10 ppm to 100 ppm were prepared. 4) Every sample prepared was analysed on HPLC to give corresponding peak area. 5) The areas obtained, shown in the table 3.2, were plotted versus the concentration of salicylic acid solutions, as shown in the figure 3.2. 6) From the graph, we get a linear line passing through zero. The line is thus described by equation y = mx in which y is area of peak and x is concentration of sample. m represents slope of the line. 7) The extent of salicylic acid degradation, which gives a net quantification of the cavitational activity, was estimated from the absorbance values using the calibration equation.
Table 3.2: Data obtained from HPLC. Concentration (ppm) 10 20 30 40 50 60 70 80 90 100 Area under Curve 61.23 262.177 613.45 904.87 1217.68 1543.67 1934.54 2202.85 2532.76 2876.25
3500 3000 Area under curve 2500 2000 1500 1000 500 0 0 50 100 150 Concentration (ppm) y = 27.044x R = 0.9692 Calibration on Agilent HPLC Linear (Calibration on Agilent HPLC)
Figure 3.2: Calibration curve of salicylic acid using HPLC
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3.4 Experimental Set-up of ultrasonic horn reactor: Three different ultrasonic reactors were used for characterizing the effects of different gaseous additives such as air, oxygen, nitrogen and carbon dioxide. Ultrasonic horn reactor: The unit consists of an ultrasonic horn equipped with generator and was procured from Dakshin India Ltd., Mumbai. The reactor operates at a frequency of 20 kHz. The maximum rated power output of the generator is 240 W. The tip diameter of the transducer was 2.1 cm with an active acoustical vibrational area as 3.46 cm2. The reactor was operated at optimized conditions and experiments were conducted in a 500 ml glass reactor. Experiments were conducted using 300 ml reaction solution of 100ppm, 300 ppm, 500 ppm concentrations of potassium iodide and 100 ppm concentration of salicylic acid. It was observed that during sonication reaction temperature increased due to heat dissipation induced by cavitational events during. Hence to achieve a constant temperature throughout the reaction time glass reactor was kept in the ice bath. Temperature for sonication of potassium iodide was maintained at 15 0 C and for salicylic acid reaction temperature was maintained at 200 C. L-shaped sparger was used having inner diameter of 3.5 mm and hole diameter of 1 mm. Rota-meter of capacity 100 liter per hour was used to measure the gas flow. The schematic view of experimental setup is shown in figure 3.3.
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Figure 3.3: The schematic view of experimental setup for ultrasonic horn. 3.5 Parameter optimization: The magnitudes of collapse pressures and temperatures as well as the number of free radicals generated at the end of cavitation events are strongly dependent on the operating parameters of the equipment. Hence for getting a sufficient cavitational yield using ultrasonic horn reactor, operating parameters like temperature, power supplied and duty cycle were optimized. One parameter at a time method was used for parameter optimization. 3.5.1 Procedure for optimization of reaction temperature: 1) 300 ml of reaction solution (potassium iodide of concentration 300 ppm) was prepared and taken in the glass reactor of capacity 500 ml. 2) The output power was adjusted at 60 W and 50% duty cycle was provided by adjusting on and off timing as 20 seconds. 3) Initially for the first set temperature was maintained at 10 0C using ice bath. 4) Sonication was done for one hour and sample was withdrawn at the end of the sonication. 5) Sample was analyzed on UV-spectrophotometer.
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6) Same procedure was carried out at different reaction temperature such as 15 0C, 20 0C, 25 0C and 30 0C. 3.5.2 Procedure for optimization of duty cycle: 1) 300 ml of reaction solution (potassium iodide of concentration 300 ppm) was prepared and taken in the glass reactor of capacity 500 ml. 2) The reaction temperature was maintained at 15 0 C using ice bath and the output power was adjusted at 60 W. 3) The first set, 20% duty cycle was provided by adjusting on and off timing as 10 seconds and 40 seconds respectively. 4) Sonication was done for one hour and sample was withdrawn at the end of the sonication. 5) Sample was analyzed on UV-spectrophotometer. 6) Same procedure was carried out at different percentage of duty cycles such as 40, 50, 60, and 80. 3.5.3 Procedure for optimization of power: 1) 300 ml of reaction solution (potassium iodide of concentration 300 ppm and salicylic acid of concentration 100 ppm) was prepared and taken in the glass reactor of capacity 500 ml. 2) The reaction temperature was maintained at 15 0C for potassium iodide and 20 0C for salicylic acid using ice bath and the duty cycle was adjusted at 60 %. 3) In the first set, 30W power was provided using power generator. 4) Sonication was done for one hour and sample was withdrawn at the end of the sonication. 5) Sample of potassium iodide was analyzed on UV-spectrophotometer and sample of salicylic acid was analyzed on HPLC. 6) Same procedure was carried out at different power such as 60W, 90W and 120W.
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3.6 Experimental procedure for sonolysis of reaction solution in the presence of gases using horn reactor: 1) 300 ml of reaction solution was taken in the glass reactor having capacity of 500 ml. 2) 1 cm length of the horn was dipped in the reaction solution. 3) The output power of the reactor was adjusted at 60 W. 60% duty cycle was provided by adjusting the on and off time of the reactor. 4) First sonication was done for 1 hour without using any gases additives. Sample was taken out after every 10 minutes. 5) Another 300 ml reaction solution was prepared and taken in the glass reactor. Lshaped sparger was inserted in the reaction solution. 6) 1 hour sonolysis was carried out with continuous sparging of air in it at atmospheric pressure. Flow rate of air was 5 liter per hour measured using rotameter. Sample was taken out after every 10 minutes. 7) Same procedure was followed for other gaseous additives such as carbon dioxide, oxygen and nitrogen. 8) Samples of potassium iodide were analyzed on UV-spectrophotometer and samples of salicylic acid were analyzed on HPLC. 3.7 Experimental Set-up of ultrasonic longitudinal horn reactor: Second reactor used was ultrasonic longitudinal horn. The experimental set up consists of single large transducer having longitudinal vibrations and was procured from Roop Telsonic Ultrasonics, Mumbai, India which had an operating frequency of 36 kHz and rated power output of 150 W. The bath was divided into two sections. The upper section had dimensions like 33 cm length, 20 cm width and 15 cm height. The lower section was a V shaped channel of height 3 cm. The total body was made up of stainless steel. A drainage valve was also provided at the bottom of the bath. The internal of the bath consists of a horn which was fitted at the bottom of the bath horizontally along the length of bath. A transducer was attached to one end of the horn and the energy to this transducer is provided by a generator which is a separate unit. The reactor had a
Page 50
maximum capacity of 9.5 liter. L-shaped sparger was inserted in to the reactor for sparging of gaseous additives as shown in the figure 3.4.
Figure 3.4: The schematic view of experimental setup for ultrasonic longitudinal horn of 36 kHz and 25 kHz Third reactor used was ultrasonic longitudinal horn. The experimental set up similar to the second reactorand was also procured from Roop Telsonic Ultrasonic, India. The ultrasonic bath had an operating frequency of 25 kHz and rated power output of 1 kW. The bath was divided into two sections. The upper section had dimensions as 35cm length, 12cm width and 17cm height. The lower section was a V shaped channel of 3 cm height. The reactor body was made up of stainless steel. A drainage valve was also provided at the bottom of the bath. The internal section is similar to the second reactor.
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3.8 Experimental procedure for sonolysis of reaction solution using longitudinal horn reactors of different capacity: 1) Firstly the reactors were filled up with the reaction solution. Volume required for the longitudinal horn reactor having capacity of 1 kW was 7 liters and that for 150 W capacity reactor was 9 liters. 2) First sonication was done for 1 hour without using any additives. Sample was taken out after every 10 minutes. 3) Again reaction solutions were prepared and taken in to the reactor. L-shaped sparger was inserted in to the reaction solution. 4) 1 hour sonolysis was carried out with continuous sparging of air at the atmospheric pressure. Flow rate of air was maintained at 20 liters per hour for the sonolysis in the reactor having 1 kW capacity and 25 liters per hour for reactor having 150 W capacity. Sample was taken out after every 10 minutes. 5) Same procedure was followed for other gaseous additives such as carbon dioxide, oxygen and nitrogen. 6) Samples of potassium iodide were analyzed using UV-spectrophotometer and samples of salicylic acid were analyzed using HPLC.
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4. Result and Discussion 4.1 Effect of Temperature It was observed that cavitational yield decreases with an increase in the temperature. It is mainly due to the fact that vapours pressure of the liquid medium increases with the temperature. Also vapors which enters the bubble during its formation cushions the collapse of the bubble. This 'vaporous' or 'transient' cavitation is expected to be the predominant effect when little dissolved gas is present. This predicts that as the bulk temperature increases, the temperature of the 'hot spot' formed by the cavity collapse decreases (Entezari and Kruus, 1996). Results of sonolysis of potassium iodide have been shown in the table 4.1 and that for salicylic acid have been shown in the table 4.2. Table 4.1: Effect of reaction temperature on cavitational yield of sonolysis of potassium iodide. Temperature ( 0 C) 10 15 20 25 30 Iodine Liberated (ppm) 198.25 185.00 163.25 141.25 115.00
Table 4.2: Effect of reaction temperature on cavitational yield of sonolysis of salicylic acid. Temperature 10 15 20 25 30 % degradation 32.01 32.67 31.83 10.85 7.3
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For further experiments 150 C temperature was chosen as the optimum for the sonolysis of the potassium iodide and 20 0C for the sonolysis of the salicylic acid, because below this reaction temperature, only marginal variation in the cavitational yield is obtained. 4.2 Effect of duty cycle It was observed that sonication yield increases with an increase in the percentages of duty cycle. It is attributed to the fact that more the duty cycle more is the power dessipatation, results in the increased cavitational yield. Results of sonolysis of potassium iodide have been given in the table 4.3 and for salicylic acid have been given shown in the table 4.4. Table 4.3: Effect duty cycle percentage on cavitation yield of potassium iodide. % duty cycle On time (sec.) Off time (sec.) Iodine liberated (ppm) 20 40 50 60 80 10 20 25 30 40 40 30 25 20 10 78.75 108.25 141.25 171.00 200.25
Table 4.4: Effect duty cycle percentage on cavitation yield of salicylic acid. % duty cycle 20 40 50 60 80 On time (sec.) 10 20 25 30 40 Off time (sec.) 40 30 25 20 10 9.2 19.42 23.56 28.83 36.76 Degradation obtained (%)
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For the further experiments 60 % duty cycle has been selected for the both the cases, because at this value percentage a sufficient cavitation yield was observed than that obtained at lower percentages of duty cycle. Also energy conservation and instrument maintenance will be better at 60 % compared to that at higher percentage of duty cycle. 4.3. Effect of power It was observed that sonication yield increases with an increase in the power supply. It can be attributed to the enhanced mixing and circulation currents with an increase in the ultrasound power (Toukoniitty et al.2006; Hingu et al. 2010). Also Merouani S. et al., (2010) explain the iodine liberation on the basis of increase in the number of active cavitationa bubbles with power. That is when power is increased, transmittance of ultrasonic energy into the reactor increases. Due to this energy, the pulsation and collapse of bubble occur more rapidly, the number of cavitation bubbles increases and realizing a higher concentration of OH radicals into the aqueous solution of potassium iodide. Thus, an increase in ultrasonic power results in an increase in acoustic amplitude, which favors more violent cavitation bubble collapse because the bubble collapse time, the transient temperature, and the internal pressure in the cavitation bubble during collapse are all dependent on the acoustic amplitude. Results of sonolysis of potassium iodide have been given in the table 4.5 and of salicylic acid were shown in the table 4.6. Table 4.5: Effect of power supply on sonolysis of potassium iodide. Power supplied (W) 30 60 90 120 Iodine Liberated (ppm) 46.25 93.75 172.00 210.00
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Table 4.6: Effect of power supply on sonolysis of salicylic acid. Power supplied (W) 30 60 90 120 Degradation obtained (%) 12.34 21.46 30.32 34.65
For further experiments 90W power supply has been selected for both the cases, because at this value a sufficient cavitation yield was observed than that at lower amount of power supply. Also energy conservation and instrument maintenance will be better at 60W compared to that at higher powers. 4.4 Comparison of different sonochemical reactors: Three low frequency (20 kHz, 25 kHz and 36 kHz) reactors were used in the present work. Sonication of three different concentrations of potassium iodide (100 ppm, 300 ppm and 500 ppm) and 100 ppm of salicylic acid were studied in all three reactors. Sonication was performed in the presence of different gases such as air, oxygen, nitrogen and carbon dioxide. Firstly sonolysis of potassium iodide of concentration 100 ppm was investigated using three sonochemical reactors in the absence of any gases. Reactions were carried out at optimized conditions for one hour. Iodine liberated with time was plotted for all three reactors, as shown in the figure 4.1. It was observed that iodine liberated in the 20 kHz, 25 kHz and 36 kHz sonochemical reactors at the end of one hour was 61.25 ppm, 50 ppm, and 20 ppm respectively. Similar study was done but in the presence of different gases. In the presence of air it was observed that iodine liberation at the end of 60 minutes sonication in each case was larger than the sonication in the absence of air. The reason of that is discussed in later section. But it was also observed that the order of the increase in iodine liberation with respect to type of reactor remain the same. The obtained results are given in the figure 4.2. It was seen that 20 kHz reactor gave 70 ppm of iodine liberation
in the presence of air whereas 25 kHz and 36 kHz had gave 60 ppm and 30 ppm of iodine liberation respectively. This trend is attributed to the fact that in the 20 kHz reactor power dessipatition per liter of volume is larger followed by 25 kHz and 36 kHz reactor. And more power dessipatation results in more cavitational yield.
70 60
Iodine Liberated (ppm)
50 40 30 20 10 0 on 36 KHz longitudnal horn on 20 khz horn On 25kHZ longitudnal horn
20
40
Time (min)
60
80
Figure 4.1 : Sonication of 100 ppm KI in different reactors in the absence of any gases Similar effect was observed when 100 ppm of potassium iodide was sonicated in these three reactors in the presence of oxygen, nitrogen and carbon dioxide. Figure 4.3 shows that in the presence of oxygen, maximum iodine liberation was given by 20 kHz reactor (80 ppm) followed by 25 kHz (70 ppm) and 36 kHz reactor (40 ppm). Similarly figure 4.4 and 4.5 shows the comparison of the three reactors on the basis of cavitational yield using nitrogen and carbon dioxide respectively. It was observed that in the presence of nitrogen 20 kHz, 25 kHz and 36 kHz reactors gave 63 ppm, 58 ppm and 27 ppm of iodine liberation from 100 ppm of potassium iodide respectively. In the presence of carbon dioxide the yields are 85 ppm, 80 ppm and 46 ppm of iodine liberation for the 20 kHz, 25 kHz and 36 kHz reactors respectively.
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80.00 70.00 Iodine Liberated (ppm) 60.00 50.00 40.00 30.00 on 20 KHz horn on 25 kHz longitudnal horn 36 KHz longitudnal horn
20.00
10.00 0.00 0 20 40 Time (min) 60 80
Figure 4. 2 : Sonication of 100 ppm KI in different reactors in the presence of air.
90.00 80.00 70.00 Iodine liberated (ppm) 60.00 50.00 on 20 kHz horn 40.00 30.00 20.00 10.00 on 25 kHz longitudnal horn
on 36 kHz longitudnal horn
0.00
0 20 40 Time (min) 60 80
Figure 4.3: Sonication of 100 ppm KI in different reactors in the presence of oxygen.
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70.00 60.00 Iodine Liberated (ppm) 50.00
40.00
30.00 20.00 10.00 0.00 0 20 40 60 80
Using 20 KHZ horn Using 25 kHz longitudnal horn Using 36 KHz longitudnal horn
Time (min)
Figure 4.4 : Sonication of 100 ppm KI in different reactors in the presence of nitrogen.
90.00 80.00 Iodine Linerated (ppm) 70.00 60.00 Using 20 KHz horn Using 25 kHz longitudnal horn Using 36 KHz longitudnal horn
50.00
40.00 30.00 20.00 10.00 0.00 0 20 40 Time (min) 60 80
Figure 4.5: Sonication of 100 ppm KI in different reactors in the presence of carbon dioxide.
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Salicylic acid with 100 ppm concentration was also examined to study the effect additives in of different reactors. Figure 4.6 shows the comparison of the three reactors on the basis of salicylic acid degradation with respect to time. It was observed that percent degradation was larger in 20 kHz reactor. 28 % degradation was observed in this reactor in absence of any gases. The 25 kHz reactor yields lesser cavitational yield and 22 % of degradation was achieved using this reactor in the same operating time. The 36 kHz reactor gave the lowest cavitational degradation (13 %) of 100 ppm salicylic acid in absence of any gases in 60 minutes.
35.00 30.00 25.00 % change in SA 20.00 using 36 KHz longitudnal horn 15.00 10.00 5.00 0.00 0 20 40 Time (min) 60 80 using 25 kHz longitudnal horn usig 20 kHz horn
Figure 4.6: Sonication of 100 ppm S.A. in different reactors in the absence of any gases. Cavitational degradation of salicylic acid was also examined in the three reactors in the presence of gases. Nitrogen, oxygen, air and carbon dioxide were the gases used in the study. It was observed that with the effect of gases, was similar as compared to liberation of iodine. 20 kHz reactor gave the largest percent of degradation followed by 25 kHz and 36 kHz reactor. This means that 20 kHz was more efficient in generating higher intensity of cavitation activity than other two. 36 kHz reactor had shown the lowest efficiency in terms of cavitational yield.
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Percent degradation of 100 ppm salicylic acid in these 3 reactors in the presence of different gases, have been presented in figure 4.7 to 4.10. Air- Figure 4.7 shows that in the presence of air, 20 kHz reactor gave 40 % of degradation of 100 ppm salicylic acid. The percent degradation was 29.5 in the case of 25 kHz reactor and 18 % in the case of 36 kHz reactor. Oxygen- Figure 4.8 shows that in the presence of oxygen, 20 kHz reactor gave 44 % of degradation of 100 ppm salicylic acid. The percent degradation was 27% in the case of 25 kHz reactor and 27 % in the case of 36 kHz reactor. Nitrogen- Comparison has been shown in the figure 4.9 and it was observed that 20 kHz reactor gave 30 % degradation of salicylic acid in the presence of nitrogen. The degradation observed was 25.5 % and 17 % in the case of 25 kHz and 36 kHZ reactor respectively. Carbon dioxide- From figure 4.10, it was seen that 48 % of degradation of salicylic acid was given by 20 kHz reactor in the presence of carbon dioxide. This yield was 42% in the case of 25 kHz and 31 % in the case of 36 kHz reactor.
45.00 40.00 35.00 % change in SA conc. 30.00 25.00 20.00 15.00 10.00 Using 36 KHz Longitudnal horn Using 25 kHz longitudnal horn Using 20 kHz horn
5.00
0.00 0 20 40 Time (min) 60 80
Figure 4.7: Sonication of 100 ppm S.A. in different reactors in the presence of air.
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50.00 45.00 40.00 % change in SA conc. 35.00 30.00 25.00 20.00 15.00 Using 36 KHz longitudnal horn Using 25 kHz longitudnal horn using 20 KHz horn
10.00
5.00 0.00 0 20 40 Time (min) 60 80
Figure 4.8: Sonication of 100 ppm S.A. in different reactors in the presence of oxygen.
35.00 30.00 % change in SA conc. 25.00 20.00 15.00 10.00 5.00 0.00 0 20 40 Time (min) 60 80 using 36 KHz longitudnal horn Using 25 kHz longitudnal horn Using 20 KHz horn
Figure 4.9: Sonication of 100 ppm S.A. in different reactors in the presence of nitrogen.
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60.00 50.00 % change in SA conc. 40.00
30.00
20.00 10.00 0.00 0 20 40 Time (min) 60 80
Using 36 kHz longitudnal horn Using 25 kHz longitudnal horn Using 20 KHz horn
Figure 4.10: Sonication of 100 ppm S.A. in different reactors in the presence of carbon dioxide. Studies were also carried out using 300 ppm and 500 ppm of potassium iodide. All results of sonication using 300 ppm and 500 ppm potassium iodide in all the reactors and in presence of different gases are shown in the table 4.7. All values in table are showing the ppm concentration of iodine liberated in respective system. Though it was reported that (Rooze J. et al., 2011) sonochemical reactors efficiency should increase with the frequency, but it was observed in the study that the maximum iodine liberation was obtained in lower frequency reactor that is in the 20 kHz reactor followed by 25 kHz and 36 kHz reactor. That is iodine liberation increased from lower frequency reactor to higher. So it is the fact that the sonochemical reactors were influenced by some other reactor parameter like power than the frequency of the reactor. Hence the observed trend of iodine liberated can be explained on the basis of power dissipate per liter of reaction solution in the different reactors.
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Table 4.7: Comparison study of three different reactors using different initial concentrations of potassium iodide. Reactor > 300 ppm KI No gas Air Oxygen Nitrogen Carbon Dioxide 170 250 198 177 20 kHz 500 ppm KI 230 190 275 250 300 ppm KI 118 150 168 132 25 kHz 500 ppm KI 185 205 232 193 300 ppm KI 31 41 54 36 36 kHz 500 ppm KI 43 60 82 52
Gas
221
295
190
252
68
107
20 kHz sonochemical horn was operated at 90 W i.e. 90 J/sec. Horn was operated for one hour with 60 % duty cycle. Therefore total working time of the reactor was 36 minutes i.e. 2160 seconds. Therefore total power supplied to the reaction solution was 194400 Joules (supplied power X time). Volume of reaction solution was 300 ml. Hence total energy supplied per liter was 648 kJ. In case of 25 kHz sonochemical reactor which worked at 1 kW i.e. 1000 J/sec and having capacity of 7.5 liters was operated for one hour. Therefore total energy supplied to the reaction solution was 36,00,000 Joules. Total volume of reaction solution was 7.5 liters which was the maximum volume capacity of the reactor. Hence total energy supplied per liter of reaction solution was 480 kJ. Similarly, in the case of 36 kHz sonochemical reactor which worked at 150 W i.e. 150 J/sec and having capacity of 7.5 liters was operated for one hour. Hence total energy supplied per liter of reaction solution was 56.8 kJ.
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It is cleared from the above calculation that due to comparatively larger power dissipatation in the 20 kHz reactor, it shows the higher cavitational yield. In other words the performance of the reactor is directly proportional to the power dissipated per liter of reaction solution. It is attributed to the fact that as the power dissipatation increases mixing of the reaction solution and circulation current increases which results in enhanced cavitational yield (Hingu et al., 2010). 4.5 Effect of initial concentration on sonochemical reactions: For study of effect of concentration, 3 different concentrations were used (100, 300 and 500 ppm). Study was carried out in all three reactors using different gases additives such as air, nitrogen, oxygen and carbon dioxide. It was observed that in all cases iodine liberation increased with initial concentration of reaction solution. Iodine liberation is highest in the case of 500 ppm initial concentration followed by 300 ppm and 100 ppm respectively. For comparison study, iodine liberation was plotted against the time of treatment in each case. In figure 4.11 results of sonication of 100 ppm, 300 ppm and 500 ppm potassium iodide using the 20 kHz horn reactor have been given. Sonication was done in absence of any gases and at optimized conditions. The figure shows that iodine liberation in the case of 100 ppm initial concentration of potassium iodide was 60 ppm and in the case of 300 ppm it was 160 ppm where as in the case of 500 ppm, 220 ppm of iodine liberated. Similar results were obtained (with additional effect of gases) when sonication was done in the presence of different gases like air, oxygen, nitrogen and carbon dioxide. In the presence of air, iodine liberation was around 70 ppm, 190 ppm and 260 ppm for 100, 300 and 500 ppm of initial concentration respectively, as shown in the figure 4.12. Similar increment was observed for other gases. For oxygen it was 80 ppm to 175 ppm to 265 ppm, as shown in the figure 4.13. For nitrogen it was 77 ppm to 168 ppm to 250 ppm, as shown in the figure 4.14. For carbon dioxide the increment was as 85 ppm to 220 ppm to 300 ppm which is shown in the figure 4.15. All increments discussed above were for 100 ppm, 300 ppm and 500 ppm of initial concentrations respectively.
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In the case of 25 kHz reactor (reactor volume 7.5 liters) similar studies were carried out on effect of initial concentration of reaction solution. Initially sonication of potassium iodide of different concentrations, as discussed above was carried out in absence of any gases. It was observed that iodine liberated was lower than that of 20 kHz ultrasonic horn. It is due to difference in the power dissipatition of the different reactors as discussed in earlier section. But the increasing trend of iodine liberation with concentration remained same. Results have been given shown in the figure 4.16. It shows that for 100 ppm of initial concentration, 50 ppm of iodine was obtained at the end of 60 minutes. In the case of 300 ppm of initial concentration 115 ppm and in case of 500 ppm of initial concentration, 180 ppm of iodine was obtained at the end of 60 minutes under same conditions. It was clearly indicating that iodine liberation was maximum for 500 ppm of initial concentration followed by 300 ppm and 100 ppm. Studies of effect of initial concentration were also carried out in this reactor in the presence of gases additives. Iodine liberation for 100 ppm, 300 ppm and 500 ppm of initial concentration of potassium iodide in the presence of gases has been shown as per following description: For air iodine liberation was increased as 60 ppm to 155 ppm to 200 ppm, (figure 4.17). For oxygen iodine liberation was increased as 70 ppm to 165 ppm to 230 ppm, (figure 4.18). For nitrogen iodine liberation was increased as 55 ppm to 150 ppm to 185 ppm, (figure 4.19). For carbon dioxide iodine liberation was increased as 80 ppm to 190 ppm to 245 ppm, (figure 4.20). Third reactor that is 36 kHz longitudinal horn which has reactor capacity of 9.5 liters was also used to study the effect of initial concentration on iodine liberation. Iodine liberation in this reactor was much lesser than above two reactors. But the trend of change in amount of iodine liberation with initial concentration was same as the above two reactors. The results on this reactor have been given in the table 4.8. Table 4.8: Study of effect of initial concentration on iodine liberation using 36 kHz reactor in presence of different gases. (all values are in ppm)
Gas additive\ reactor No gas Air Oxygen Nitrogen Carbon Dioxide
100 ppm 20 30 40 34 50
300 ppm 31 40 55 45 70
500 ppm 43 60 80 70 110
This enhancement in iodine liberation with initial concentration can be attributed to the fact that, increase in initial concentration of potassium iodide may increase the surface tension and ionic strength of the reaction medium (Merouani et al, (2010), Kirpalani & McQuinn, (2006)). Also, as concentration of potassium iodide increases the vapor pressure of the medium decreases. Due to the changes in the physical property collapse conditions are also changed. As the surface tension and ionic strength increases interfacial energy of the bubble and medium also increased and hence given more energy release at the cavity collapse. Also due to decrease in vapor pressure cavity formation is easier. Both factors results in the collapsing of the bubbles more violently. It means that temperature and pressure at cavity collapse increase with an increase in initial concentration of potassium iodide. This helps in producing more hydroxyl radicals available for the oxidation of potassium iodide. Increase in cavitation yield can also be attributed to the fact that as concentration of KI increases more molecules of potassium iodide are available for the oxidation reaction with increased hydroxyl radicals. Hence the probability of recombination of reaction radicals gets reduced Naidu et al., (1993) and Seymour et al., (1997). As possibility of recombination of radicals get reduced, less peroxide formation takes place. Hence maximum hydroxyl radicals are consumed by iodide ions which increase with potassium iodide concentration. This helps in improvement in amount of iodine liberation.
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250.00
200.00 150.00 100.00 wiyhout using any gases-300 ppm wihout any gases-100 ppm without any gases - 500 ppm 0 20 40 Time (min) 60 80
50.00
0.00
Figure 4.11: Effect of initial concentration of potassium iodide on iodine liberation using 20 KHz horn in absence of any gases.
300.00 250.00
200.00 150.00 100.00 50.00 0.00 Using air horn- 300ppm Using air horn - 100 ppm Using air - horn- 500 ppm
20
40
Time (min)
60
80
Figure 4.12: Effect of initial concentration of potassium iodide on iodine liberation using 20 KHz horn in the presence of air.
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300.00 250.00 Iodine Liberated (ppm) 200.00 150.00 100.00 Horn- Using Oxygen 300 ppm Horn- Using Oxygen- 100 ppm Horn- Using air- 500 ppm
50.00
0.00 0 20 40 Time (min) 60 80
Figure 4.13: Effect of initial concentration of potassium iodide on iodine liberation using 20 KHz horn in the presence of oxygen.
300.00 250.00 Iodine Liberated (ppm) 200.00 150.00 100.00 50.00 0.00 0 20 40 Time (min) 60 80 Horn- using nitrogen - 300 ppm Horn- Using nitrogen- 100 ppm Horn- Using Nitrogen- 500 ppm
Figure 4.14: Effect of initial concentration of potassium iodide on iodine liberation using 20 KHz horn in the presence of nitrogen.
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350.00 300.00 Iodine Liberated (ppm)
250.00
200.00 Horn- Using CO2- 300 ppm 150.00 100.00 50.00 0.00 0 20 40 Time (min) 60 80 Horn- Using CO2- 100 ppm Horn- Using CO2- 500 ppm
Figure 4.15: Effect of initial concentration of potassium iodide on iodine liberation using 20 KHz horn in the presence of carbon dioxide.
200 180 160 Iodine liberated (ppm) 140 120 100 80 60 40 20 0 0 20 40 Time (min) 60 80 1 Kw- Nogase- 100ppm 1 Kw- no gas- 300 ppm
1 Kw- no gase- 500 ppm
Figure 4.16: Effect of initial concentration of potassium iodide on iodine liberation using 25 KHz longitudinal horn (1 kW) in the absence of any gases.
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250
200 Iodine liberated (ppm)
150 1 Kw- Using air- 100 ppm 100 1 Kw- using air- 300 ppm 1 kw- using air- 500 ppm 50
0 0 20 40 Time (min) 60 80
Figure 4.17: Effect of initial concentration of potassium iodide on iodine liberation using 25 KHz longitudinal horn (1 kW) in the presence of air.
250
150 1kw- using oxygen- 100ppm 100
1 Kw- using oxygen- 300 ppm

1 Kw- using oxygen- 500 ppm
50
0 0 20 40 Time (min) 60 80
Figure 4.18: Effect of initial concentration of potassium iodide on iodine liberation using 25 KHz longitudinal horn (1 kW) in the presence of oxygen.
250
150
1 Kw- using nitrogen- 100 ppm 1 Kw- using nitrogen- 300 ppm 1 Kw- using nitrogen- 500 ppm
100
50
0 0 10 20 30 40 50 60 70 Time (min)
Figure 4.19: Effect of initial concentration of potassium iodide on iodine liberation using 25 KHz longitudinal horn (1 kW) in the presence of nitrogen.
300 250 Iodine liberated (ppm) 200 150 100 50 0 0 10 20 30 40 50 60 70 Time (min) 1 Kw- using CO2- 100 ppm 1 Kw- using CO2- 300 ppm 1 Kw- Using CO2- 500 ppm
Figure 4.20: Effect of initial concentration of potassium iodide on iodine liberation using 25 KHz longitudinal horn (1 kW) in the presence of carbon dioxide.
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4.6 Effect of different gaseous additives on sonochemical reactions: Gases such as air, oxygen, nitrogen and carbon dioxide were used to study the effect as an additive on the selected sonochemical reactions, potassium iodide oxidation and salicylic acid degradation. Studies were carried out in three different reactors (20 kHz, 25 kHz and 36 kHz). It was observed that cavitational yield that is iodine liberation by oxidation of potassium iodide and percent degradation of salicylic acid increases due to the use of these gases. In 20 kHz reactor, to study the effect of gases as an additive, initially 300 ml of potassium iodide solution of concentration 100 ppm was taken. Flow rate of each gas was kept constant at 5 liter per hour (lph). Results of sonication in the presence of gas at the end of 60 minutes were shown in the figure 4.21. It was observed that in the absence of any gases one hour sonication liberates around 60 ppm of iodine. After the initial experiments, air was passed at given flow rate through reaction solution simultaneously during sonication. It was observed that because of presence of air, amount of iodine liberation at the end of one hour sonication increased up to 71 ppm. It means that air increased the amount of iodine liberation by 16.6 %. Nitrogen also showed similar effect on the amount of iodine liberation, and iodine liberation increased up to 65 ppm. Thus use of nitrogen increased iodine liberation increased by 7 %. Similarly increased iodine liberation was observed in the case of oxygen and carbon dioxide. In the presence of oxygen, 77 ppm of iodine was obtained and in the presence of carbon dioxide, 80 ppm of iodine was obtained. Iodine liberation observed to be increase by 28 % due to oxygen and 33 % due to carbon dioxide. Similar study was carried out for the 300 ppm and 500 ppm of potassium iodide keeping other operating parameters constant. It was observed that the trend of effect of gaseous additives is same but with additional concentration effect (The relation of iodine liberation with initial concentration has been already discussed in the previous section.). Sonication in the presence of air gave the increment of 12 % in 300 ppm initial concentration and 13 % in 500 ppm initial concentration of potassium iodide. Similar increment of iodine liberation was observed in the presence of oxygen (16.5 % and 18 %), Nitrogen (5 % and 7.5 %) and carbon dioxide (20.5% and 24 %) for 300 ppm
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and 500 ppm of initial concentration of potassium iodide, as shown in the figure 4.22 (for 300 ppm KI) and 4.23 (for 500 ppm KI). Studies were also carried out using 100 ppm salicylic acid using same reactor. Same gases were used to study the effect at optimized conditions. It was observed that similar to iodine liberation in the case of potassium iodide, extent of salicylic acid degradation also increased in the presence of gases. Order of increment was observed to be same as that observed for iodine liberation, i.e. extent of degradation was in the following order for different gases as CO2 > O2 > Air > N2. Results have been shown in the figure 4.24. From this figure, it can be established that increase in degradation of salicylic acid in the presence of air was 17 %, for oxygen it was 39 % and for nitrogen it was 8.5 %. It shows maximum increase in the presence of carbon dioxide as 50 %.
90.00 80.00 iodine liberation (ppm) 70.00 60.00 Without any gases Using Air
50.00
40.00 30.00 20.00 10.00
Using Oxygen
using Nitrogen Using Carbon Dioxide
0.00
0 20 40 Time (min) 60 80
Figure 4.21: Effect of gaseous additives on KI (100 ppm) oxidation (using 20 KHz horn)
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250.00
200.00 iodine liberation (ppm)
150.00
Using Air Using oxygen
100.00
Using Nitrogen Using Carbon Dioxide
50.00
Without any gases
0.00 0 20 40 Time (min) 60 80
350.00 300.00 iodine liberation (ppm) 250.00 200.00 150.00 100.00 50.00 0.00 0 20 40 60 80 without any gases Using Air Using Oxygen Using Nitogen Using Carbon Dioxide
Time (min)
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50.00 45.00 40.00
% degradation
35.00 30.00 25.00 20.00
Sonication without gases Using Air
Using Oxygen
Using Nitrogen Using Carbon Dioxide 0 20 40 60 80
15.00
10.00 5.00 0.00
Time (min)
Figure 4.24: Effect of gaseous additives on S.A. (100 ppm) oxidation (using 20 KHz horn) In the case of 25 kHz reactor (reactor capacity 7.5 liters) studies were carried out to study the effect of various gases as an additives. All gases were passed through the reaction solution at constant flow rate i.e. at 15 liter per hour. Initially sonication of 100 ppm of potassium iodide was carried out in the absence of any gases. Iodine liberated at the end of 60 minutes was 50 ppm. But when air was passed simultaneously during the sonication it was seen that iodine liberation increased up to 63 ppm i.e. by 26 %. Sonication of 100 ppm of potassium iodide was also done in the presence of oxygen, nitrogen and carbon dioxide using same reactor. Results have been given in the figure 4.25. It cab be seen from figure that iodine liberation increased in the presence of other gases also. But the extent of increase was different for different gases. For oxygen 40 % increment was observed. Similarly iodine liberation was increased by 15 % in the presence of nitrogen and by 60 % in the presence of carbon dioxide. 300 ppm and 500 ppm potassium iodide were also sonicated using same reactor in the presence of above mentioned gases. Results for these two were plotted against the time and shown in the figure 4.26 and 4.27 respectively. It was observed that gases affect the sonication of these two solutions. The trend of effect of different gases was same as that
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for the sonication of 100 ppm potassium iodide. It means that maximum increment was observed in the case of carbon dioxide followed by oxygen, air and nitrogen. But if compared quantitatively i.e. on the basis of amount of iodine liberated then results showed some difference. The attributes of this difference were already discussed in previous session. In the case of sonication of 300 ppm of potassium iodide, 118 ppm of iodine liberation was observed in absence of any gases. Using air iodine liberation increased by 26.5%, whereas by using oxygen it went up by 41 % and for nitrogen by 13%. In the case of carbon dioxide, the extent of increase in the iodine liberation was maximum as 55 %, as shown in the figure 4.26. Similarly in the case of sonication of 500 ppm of potassium iodide 14 %, 24 %, 9 % and 42 % increase of iodine liberation was observed in presence of air, oxygen, nitrogen and carbon dioxide respectively which has been shown in the figure 4.27. In same reactor sonication was also done on 100 ppm salicylic acid using all above mentioned gases. It was noticed that effect of gases showed the same trend as that in the case of sonication of potassium iodide. Carbon dioxide resulted in maximum benefits and gave the largest increase in the percent degradation. Extent of effect of carbon dioxide was followed by oxygen, air and nitrogen respectively. In absence of any gases, sonication of salicylic acid gave 23.5% degradation. Carbon dioxide increased this degradation by 52 %. Similarly due to the presence of oxygen, air and nitrogen degradation increased by 41 %, 28.5% and 9 % respectively. Results has been given in the figure 4.28.
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90 80 Iodine liberated (ppm) 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 Time (min) Without any gases Using Air Using Oxygen Using Nitrogen Using CO2
Figure 4.25: Effect of gaseous additives on KI (100 ppm) oxidation (25 KHz reactor)
250
200 150 100 50 0 0 20 40 Time (min) 60 80 Without any gases Using Air Using Oxygen Using Nitrogen Using CO2
Figure 4.26: Effect of gaseous additives on KI (300 ppm) oxidation (25 KHz reactor)
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300
250 iodine liberated (ppm)
200 Using CO2 150 Using Nitrogen Using Oxygen 100 Using Air Without any gases 50
0 0 10 20 30 40 50 60 70 Time (min)
Figure 4.27: Effect of gaseous additives on KI (500 ppm) oxidation (25 KHzreactor)
45.00 40.00 35.00 30.00 % change 25.00 20.00 15.00 10.00 5.00 0.00 -5.00 0 10 20 30 40 Time (min) 50 60 70 Without any gases Using Air Using Oxygen Using Nitrogen Using Carbon Dioxide
Figure 4.28: Effect of gaseous additives on S.A. (100 ppm) oxidation (25 KHz reactor)
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Effect of gases was also investigated in the 36 kHz reactor. Similar trends as in earlier two reactors were observed. Only quantitatively, it was different as the reactors parameters were different than the previous ones. The reasons for that already discussed in previous sections. Same set of reaction solutions (100 ppm KI, 300 ppm KI, 500 ppm KI and 100 ppm salicylic acid) were used. Studies were carried out using same gases (Air, O 2, N2 and CO2). Flow rate of each gas was maintained at 20 lph. All the results of this set are shown in the table 4.9. All values in the table indicate the percent increase in cavitational yield. Table 4.9: Effect of gaseous additives on sonochemical reactions ( using 36 kHz reactor).
System\gases
Air
Oxygen
Nitrogen
Carbon dioxide
100 ppm KI 300 ppm KI 500 ppm KI 100 ppm Salicylic acid
30 28.5 26 34
41.5 36.5 30 42
12.5 8 10 11.5
51 50 49.5 55.5
This observed increase in cavitational yield is attributed to the fact that, presence of gases increases the heterogeneity of the medium. Due to this increased heterogeneity, additional nuclei are supplied for the cavitation events. So with an increase in nuclei, cavitational events get increased (Chakinala A. G. et al., (2007), Katekhaye and Gogate (2011), Pang Y. L. et al., (2011)). As every cavity works as a micro-reactor, additional available nuclei increase the number of microreactors. Each microreactor produces a thousand fold temperature and pressure at a local point resulting in the reactive radical formation. Hence with an increase in number of microreactors, amount of radical formation
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automatically get increased. This additional radical helps in increasing the cavitational yield to further level. Another possible reason for the increased cavitational yield is that, presence of gases changes the physical properties of the medium like density, Cp/Cv value (polytropic constant), viscosity etc. The gases decrease the overall viscosity of the solution. Gogate and Pandit (2004) in their study of scale up of sonochemical reactor mentioned that at low viscosity cavitational yield would be greater. Also Gogate and Pandit (2004) and Entezari and Kruus (1996) mentioned that final temperature and pressure at the cavity collapse is depends on the polytropic index of the gases. Both temperature and pressure at cavity collapse are directly proportional to the polytropic index of the present gases. Diatomic species like oxygen nad nitrogen has more polytropic index (~1.4) than the carbon dioxide (~1.2). As polytropic index of water is lower than all the gases used. Hence when gases passed through the reaction solution it increases the overall polytropic index of the medium. Hence the temperature and pressure of cavity collapse ia increased as more violent cavity collapse takes place. This more violent cavitation yields in increased number of reaction radicals in the medium. These reactive radicals further increase the cavitational yield of the reaction. Another possible means of raising the cavitational yield is to scavenge the radicals in the bulk medium as well as inside the bubble. It means reacting the radicals with other species (present in relatively large quantities in the bubble or in the liquid medium) to generate new species. This species might or might not take a direct part in the reactions but this prevents radical recombination. Hence the loss of oxidation potential of cavitation events gets prevented. Scavenging of radicals inside the bubble by other species present in the bubble (such as oxygen molecules) could result in greater release of radical species in the bulk medium. Moreover, scavenging of the radicals in the bulk medium results in penetration (or diffusion due to concentration gradient) of the radicals in the bulk medium to greater distances from the location of the collapse of cavitation bubble. This helps in minimizing the dead zones in the reactor as due to diffusion a raction molecule in dead zone also get a chance to react with the oxidative radical and hence resulting cavitational yield increases (Sivasankar and Moholkar (2009).
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Also one more probable reason for the increased cavitational yield is that due to continuous sparging of the gases gives an additional mixing effect. Due to this agitation, more and more reaction solution gets exposed to the active cavitational zone. Hence the dead zone effect of the sonochemical reactor decreases, leading to better cavitational yield. Also Entezari and Kruus (1996) had mentioned that the effect of each gas is depends on the nature of the gases and the involvement of the gas in sonochemical reaction. Nature and involvement of gas molecule of each gas has been discussed below (Sivasankar and Moholkar (2009). Nitogen: The presence of nitrogen increases the cavitational yield. It is attributed to the fact that it gives the extra nuclei for cavitation by virtue of heterogeneity and also lowers the vapor pressure to improve the cavitation effect. Also it increases the polytropic index of the medium, which results in the more violent cavitational activity. Oxygen: Similar to nitrogen, oxygen also supply nuclei for the cavitation effect. Also the polytropic index of medium gets increased due to presence of oxygen which helps in more efficient cavitation. With lowering the vapor pressure it also acts as a scavenging agent which further improves the cavitational activity. In addition, oxygen can also participate in the reaction by forming 2 OH. radicals per molecule of oxygen. Formation of hydroxyl radical from oxygen takes place by following reaction. O2 O + H2O 2O 2OH
This hydroxyl radical helps in further increase in the cavitation yield. Also some oxidative species like peroxide and ozone are formed from the recombination of oxygen radical with water molecule or HO2 radical and oxygen radical with oxygen molecule respectively. These oxidative species further helps in improvement of both the reaction species under study.
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Air: The major part of air is nitrogen and air (nearly 99.9%). Thus it gives the effect of both the species in the sonochemical reaction. Due to presence of oxygen gas, air gives more cavitational yield than nitrogen. But at the same time 70 percent of nitrogen pull down the overall cavitational yield lesser than that of pure oxygen. In air, nitrogen as a scavenging agent produces the species likes NO, N 2O, NO2, HNO and HNO2. These species recombine with the oxygen molecule and produce the reactive radicals likes OH followed by O, HO2 and H (Sivasankar and Moholkar (2009)). Carbon Dixide: Polytropic index of the carbon dioxide is less than that of oxygen and nitrogen. (Cp/ Cv for CO2 is 1.29 and that for O2 and N2 is nearly 1.4). Also Rooze J. et al. (2011) mentioned that there is no significant radical production in the presence of this gas. But still the presence of the carbon dioxide during sonication yields largest efficiency. This might be because of bubble size is comparatively large in the presence of carbon dioxide because of its higher solubility in the water. This makes more nuclei available for cavitation, and it makes bubble growth easier. This helps in increase in cavitations rate of the system. Also carbon dioxide may form some carbanium ions by interacting with radicals present in the system. This ions lowers the pH of the system. Chakinala A. G. et al. (2007) mentioned that lower pH, i.e. acidic conditions helps to increase the concentration of the hydrophobic species at the bubble interface leading to exposure of a higher quantum of the reaction molecule to the cavitating conditions. Thus, higher rates of reactions can be achieved. In addition to that it might possible that carbon dioxide also some scavenging effect like nitrogen and oxygen. Also it might take the direct part in sonochemical reactions by producing some oxidative species or hydroxyl radicals. 4.7 Effect of air flow rate on sonochemical reactions: Effect of air flow rate was studied on sonolysis of KI and degradation of salicylic acid using ultrasound reactors of frequencies 20, 25 and 36 kHz. It was observed that the amount of iodine liberated after sonolysis of KI increases when air is passed through the
solution. The amount of iodine liberated increases with an increase in air flow rate; goes through a maxima and then reduces again, as shown in Fig. 4.29- 4.31. Similar trend is observed for degradation of salicylic acid as well, as shown in fig. 4.32-4.34. In the case of the 20 kHz reactor (reactor volume = 300 mL), iodine liberation from sonolysis of KI was maximum for air flow rate of 6 lph. The amount of iodine liberated at this flow rate was 81.25 ppm. Similarly, maximum degradation of salicylic acid using this reactor was observed for air flow rate of 6 lph, and the percent degradation observed at this flow rate was about 39 %. The effect of air flow rate in case of 20 kHz reactor is as shown in fig. 4.32. For the 25 kHz reactor, the reaction volume used was 7.5 liters. Similar to the 20 kHz reactor, degradation studies were carried out for various air flow rates for degradation of KI and Salicylic Acid. It was observed that maximum amount of iodine is liberated from KI when air is passed through the reactor at a flow rate of 30 lph. The amount of iodine liberated at this air flow rate was approximately 80 ppm. Similarly maximum degradation of Salicylic acid was observed for an air flow rate of 40 lph, and the percent degradation of salicylic acid at this flow rate was observed to be about 30%. Similar study was carried out using 36 kHz reactor with reaction volume of 9.5 liters. In this case maximum amount of iodine was liberated for air flow rate of 60 lph, and it was observed to be 30 ppm. In case of degradation of salicylic acid as well, the maximum degradation was obtained at 60 lph air flow rate and the degradation at this flow rate was about 30% This enhancement in the yield can be attributed to reason that the presence of air bubbles in the system provides additional nuclei by virtue of heterogeneity, resulting in an increase in the intensity of cavitation by increasing the number of cavitation events as compared to the absence of bubbling. This was also visually observed during the experimentation. The increase in intensity of cavitation should in turn lead to an increase in the amount of hydroxyl radicals generated in the reactor. (Chakinala A. G. et al., 2007)
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Another factor that contributes to enhancement in the yield is that air contains approximately 30 % of oxygen, which can take part in sonochemical reactions. Oxygen promotes the generation of additional oxidizing species in the system, which would increase the extent of degradation. It can be observed that as the air flow rate increases, iodine liberation and salicylic acid degradation increases only up to certain point. After that it decreased with a further increase in air flow rate. This may be because of the presence of excess of gaseous species in the liquid, which reduces the intensity of cavitation at collapse. Air penetrates into the cavity to a greater extent and reduces the intensity of the shockwave produced upon the collapse. Also, presence of air in large quantum might interfere with the passage of ultrasound into the system thereby decreasing the available energy for the cavitation events. (Sivshakanr T. et al., 2009). Furthermore presence of more amount of gas produces cushioning effect, i.e. using higher flow rates of air possibly also could result in the formation of a blanket of bubbles in the immediate vicinity of the transducer surface, thereby minimizing the transfer of energy into the system, and hence results in decrease in the cavitational yield. It was also observed that the optimum value of air flow rate was different for all three reactors. This is probably due to the fact that as the reaction volume increases, the amount of air required to achieve the desire heterogeneity in the reaction medium also increases. As already discussed due to heterogeneity additional nuclei are get provided for the cavitational events. Hence for a reactor having lower volume capacity like 20 kHz reactor (300 ml), a less amount of air is required to achieve the heterogeneity compare to the 25 kHz (7.5 liters) and 36 kHz (9.5 liter) reactors. Hence to achieve a desired heterogeneity and so the desire amount of nuclei per unit volume in large volume reactors, amount of air required is also larger. Also if the reaction solution is saturated with the air, then sufficient gas is get entrapped in each cavity. So at the collapse more radicals can be formed. With increase in the reaction volume, amount of air required to saturate the reaction mixture is also increases. Hence a low air flow rate is sufficient only for low volume reactors like 20 kHz reactors
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but not in 25 kHz and 36 kHz reactors. Hence larger reactors require higher air flow rates to achieve similar enhancements in the yield.
100 90 80 70 60 50 40 0 2 4 6 8 10 12
iodine liberated (ppm)
Air flow rate (lph)
Figure 4.29: Effect of air flow rate on iodine liberation of 300 ppm KI (20 KHz horn)
35 30 Iodine liberated (ppm) 25 20 15 10
5
0 0 20 40 60 80 100 Flow rate (lph)
Figure 4.30: Effect of air flow rate on iodine liberation of 300 ppm KI (36 KHz longitudnal horn)
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90 80 Iodine liberated (ppm) 70 60 50 40 30 0 10 20 30 40 50 60 70 Air Flow rate (lph)
Figure 4.31: Effect of air flow rate on iodine liberation of 300 ppm KI (25 KHz reactor)
41
39 37
% change
35 33 31 29 27 25 0 2 4 6 8 10 12
Air flow rate (lph)

Figure 4.32: Effect of air flow rate on iodine liberation of 100 ppm S.A. (20 KHz horn)
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35
% change in SA concentration
30
25
20
15
10 0 10 20 30 40 50 60 70 80 Air flow rate (lph)
Figure 4.33: Effect of air flow rate on iodine liberation of 100 ppm S.A. (36 KHz longitudnal horn)
31 29 27 % degradation 25 23 21 19 17 15 0 10 20 30 40 50 60 70 80 Air Flow rate (lph)
Figure 4.34: Effect of air flow rate on iodine liberation of 100 ppm S.A. (25 KHz longitudnal horn).
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5. Conclusion: The present work has shown that both the standard sonochemical reactions, oxidation of potassium iodide and salicylic acid dosimetry were strongly influenced by operating parameters. Optimization studies with different operating parameters indicated that lower temperature, optimized power supply and duty cycle result in maximum extent of degradation. Study on effect of initial concentration on cavitation yield has shown that cavitational activity shows the direct relation with the initial concentration. As initial concentration of potassium iodide increases, iodine liberation at the end of sonication increases. Also the comparison study between three reactors shown that the cavitational activity using ultrasonic irradiation was the maximum in the case of 20 kHz followed by 25 kHz longitudinal horn and 36 kHz longitudinal horn respectively. Gaseous additives have increased the cavitational yield of the reaction. But the extent of increase in cavitational yield was vary with the gases. In the case of oxidation of potassium iodide, amount of iodine liberation at the end of sonication was increased by around 20-30 % in the presence of air in all three reactors. Increase in the iodine liberation was maximum in the presence of carbon dioxide (45 55 %) followed the sonication in presence of oxygen (30-40 %). Presence of nitrogen gave the lowest increase in iodine liberation (8-14%). Similarly extent of degradation of salicylic acid increased in the presence of gases additives in all three reactors. Percent increase in the degradation of salicylic acid was nearly same as that obtained in the case of oxidation of potassium iodide. Study of effect of air flow rate on sonochemical reaction has shown that the cavitational yield increases in the presence of air. Cavitational yield increased with the air flow rate up to a certain optimum point. After that peak, cavitational yield decreased with increase in the flow rate of air. Also the optimum value of air flow rate was different for all the three reactors.
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6. Future Scope: In the present work effect of operating parameters, comparison of different reactors, effect of gaseous additives, and effect of air flow rate on the sonochemical reaction has been studied. However there are some suggestions for future work to analyze same study in detail. Also it can help in obtaining enhanced intensification of sonochemical reaction. Use different configuration of sonochemical reactors like high frequency and low frequency bath, hexagonal sonochemical reactor to find out the suitable geometry and specifications required for the design, feasible for the large scale operations. Study the effect of noble mono-atomic gases as additives and compare those with present additives. Also study a combination of different gases to get more cavitational yield. Try different methods of sparging and different types of reactor to make it more suitable for improving the cavitational yield. This will help you to find out most suitable gas or combination of gases for the desired intensification of sonochemical reactions. Also try to conduct whole study on hydrodynamic reactor which is more suitable for the industrial scale operation. Modeling study can be performed with the help of available software like COMSOL or CFD.
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Study of intensification of sonochemical reactions using gaseous additives

Thesis submitted to for the degree of

MASTER OF CHEMICAL ENGINEERING

Department of Chemical Engineering Institute of Chemical Technology, Mumbai Maharashtra, India

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reaction using gaseous additives

MASTER OF CHEMICAL ENGINEERING

Professor (Dr.) Parag R. Gogate

Study of intensification of sonochemical reactions using gaseous additives

INSTITUTE OF CHEMICAL TECHNOLOGY, MUMBAI

Approval of the Research Supervisor and the External Examiner

, that the thesis titled Study of intensification of sonochemical

External Examiner: Affiliation:

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Dedicated to my family and friends..!!

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Signature: Research Scholar: Mr. Suraj S. Shaha

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Experimental 3.1 Reaction scheme 3.2 Materials 3.3 Analytical procedure

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Figure 1.1: Growth collapse cycle of cavitation bubbles, Suslick (1998)

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Area Physical Processes

References Gandhi K. S. et al., (1994) Martin (1993) Mason, (1990)

Cutting and drilling Machining Metal Tube Drawing

Mason, (1990) Gandhi K. S. et al., (1994)

Study of intensification of sonochemical reactions using gaseous additives

2) Shivkumar Pandit., (2001)

intracellular enzymes or enzymes

Study of intensification of sonochemical reactions using gaseous additives

3) Balasundaram Pandit, (2001)

In petroleum industry for refining 1) Patra fossil fuels, determination of (2006)

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

Study of intensification of sonochemical reactions using gaseous additives

ultrasonic that the

Results iodide Kimura T. et al., (1996)

ultrasonic power for sonochemical reaction.

parameters sonochemistry dosimetries

the An examination of the efficacy of power- Dominick J. et al.,

Study of intensification of sonochemical reactions using gaseous additives

assumptions was verified by conducting experiments with KI solutions of different concentrations

cavitational activity in different configurations