Introductory text to sonochemistry
Sonochemistry is a multi-disciplinary and an emerging research field that has potential applications in many areas that include chemistry, physics, biology, materials, food science, engineering, and medicine. The primary focus of this article is to provide a basic, textbook-type introduction highlighting the fundamental aspects and selected applications of sonochemistry. The purpose of this article is not to provide a full literature review, but to give the readers a birds’ eye view of the basics of acoustic cavitation and selected examples of applied sonochemistry. Extensive review articles and book chapters are available that provide in-depth analysis of the current literature in various topics.
KeywordsSonochemistry Acoustic cavitation Ultrasound
Humans and animals use sound waves for communication. Sound passes through various media as sine waves of positive (compression) and negative (rarefaction) pressure cycles (Fig. 1). The speed of sound is dependent on the nature of the medium through which it propagates. For example, the speed of sound is about 342 m/s and 1440 m/s in air and water, respectively.
Sound waves of > 20 kHz [20,000 Hz (cycles/s) frequency are referred to as ultrasound since they are beyond human hearing range. In recent times, ultrasound has been found useful in a variety of applications [1, 2, 3]. In Fig. 2, some key applications are highlighted. Numerous studies have investigated the use of ultrasound for synthesising organic, inorganic and biomaterials with unique properties. Ultrasonic processing has resulted in the modification of physical and functional properties of proteins, carbohydrates and other constituents of food and dairy systems. Other applications include wastewater treatment, sonocrystallisation, emulsification, extraction, de-emulsification, etc.
Most of the applications arise due to a phenomenon called acoustic cavitation . When sound waves pass through a medium, part of the acoustic energy is absorbed by the medium that results in heating of the medium. If the medium is a liquid, such as water, acoustic cavitation could occur depending upon the “strength” of sound waves and properties of the liquid.
However, such high energy is not required to achieve cavitation under normal circumstances due to the existence of bubble nuclei in liquids. All liquids used in experiments under normal laboratory conditions would contain dissolved gas molecules that are also responsible for the existence of small gas pockets on the surface of the containers, in particular when there are some defects such as crevices. When such bubble nuclei exist, not much energy is required to create them.
As mentioned earlier, the literal meaning of cavitation is creation of a cavity. However, acoustic cavitation refers to the growth of existing bubble nuclei (or small gas pockets trapped in impurity particles or on the surface of containers, etc.) under the influence of acoustic force followed by their inertial collapse. The growth of bubble nuclei in an acoustic field occurs due to “Rectified Diffusion” process . When bubble nuclei experience negative pressure of the sound waves, they are forced to expand during which dissolved gas and solvent molecules diffuse into the bubble. During the compression phase of the acoustic cycle, due to an increase in pressure inside the bubbles, gas molecules would diffuse out. Due to difference in surface areas of expanded and compressed states of the bubble, and changes in concentration of gases in the liquid shell around the bubble ( provides detailed description of the area and shell effects), the amount of gas/vapour that diffuses into the bubble dominates over that diffuses out, resulting in a net growth of the bubble over many acoustic cycle.
Tmax maximum temperature, To liquid temperature, Pm liquid pressure, Pi pressure inside the bubble, normally considered to be vapour pressure of the liquid (Pv); Pmax maximum pressure; γ heat capacity ratio of the contents inside the bubble.
While theoretical estimates under specific conditions predict the temperatures and pressures to be of the order of more than 10,000 K and 100’s of atmosphere, respectively, experimentally determined temperatures are in the range 1000–5000 K [8, 9]. Irrespective of these differences, such localised high temperatures, referred to as ‘hot spots’, are responsible for initiating a variety of redox reactions. In addition, bubble oscillations and collapse also generate a number of physical effects  that could be used to enhance rates of chemical processes and reactions due to enhanced mass transfer effects, as discussed in the following section.
Sonochemistry has a very broad meaning and could be described in many ways. In general, the term refers to sound-driven chemical reactions. Chemical reactions could be initiated by the acoustic cavitation process or may simply refer to increased reaction rates/efficiencies of reactions that would otherwise occur at a slower rate or lower efficiency.
(bold letters indicate radicals; “)))” refers to ultrasound).
For quantification, sophisticated techniques such as ESR were used. For example, Reisz and coworkers  used spin-traps to identify and quantify H and OH, commonly referred to as primary radicals. Luminescence-based techniques have also been used to quantify OH radicals. For example, reaction between terephthalic acid and OH radicals leads to the formation of hydroxyterephthalic acid, which has luminescent properties . The reaction between OH radicals and luminol results in chemiluminescence (Fig. 3) that could also be used for OH radical quantification .
Molecular iodine forms triiodide complex in aqueous solutions containing excess iodide that could be quantified spectrophotmetrically.
What is interesting is that the primary radicals generated, namely, H and OH, could be used for a variety of redox reactions. H atoms and OH radicals are strong reducing and oxidizing agents, respectively. From this view point, each of the acoustic cavitation bubble can be considered as an undivided electrochemical cell, where at the anode an oxidizing agent, and at the cathode a reductant is generated, and both species can react with constituents of the solution.
Au(0) agglomerates to generate Au nanoparticles.
It should also be considered that one may want to carry out only reduction or oxidation reactions. The question here is what do we do with other radicals? For example, if only reduction reaction is required, what do we do with OH radicals and if oxidation reaction is the main focus, how can we utilise H atoms? Here, the strategy generally is to follow what radiation chemists do, namely, convert the oxidizing radicals to reducing radicals for reduction-focused reactions and vice versa.
The alcohol radicals (RCHOH) are referred to as secondary radicals. Reaction (11) may occur within cavitation bubbles (since alcohol molecules are volatile and can diffuse into the bubble along with water molecules), at the bubble wall/solution interface (since alcohol molecules are surface active) and in the bulk solution (H/OH could diffuse out of the bubble into the bulk solution). It is also possible that evaporated alcohol molecules undergo pyrolysis under the extreme heat generated on bubble collapse and generate a variety of alkyl (R) radicals which are also strong reducing agents.
Likewise, for an oxidation-focused reaction, H atoms could be converted into an oxidizing radical (HO2) by reaction 6 in oxygen-/air-saturated solutions. A number of examples where the redox radicals generated have been used will be discussed in the following sections.
Acoustic cavitation could also be achieved in organic liquids. A variety of radical species were identified in chloroform and other organic solvents. For example, the sonication of chloroform generates a variety of radicals as shown in reaction (13) .
One other example that could be highlighted is the generation of amorphous nanomaterials in organic liquids . When volatile metal complexes were dissolved in an organic solvent and sonicated, amorphous metal nanoparticles were formed. The reactions below show the formation of amorphous iron nanoparticles when octanol-containing dissolved Fe(CO)5 was sonicated. The reason for the formation of amorphous metal nanoparticles is the fast cooling rates achieved during cavitation process. As discussed above, temperatures of a few thousand degrees are generated due to near-adiabatic nature of bubble collapse. Volatile metal complexes diffuse into the cavitation bubbles during the expansion phase of acoustic cycle and decompose under the extreme heat conditions reached on bubble collapse. Since the hot spots are dispersed within the liquid that is at room temperature, the heat is quickly quenched by the surround liquid leading to cooling rates of 109 K/s. Such fast cooling of the nanoparticles results in the formation of amorphous materials that show much higher catalytic activities compared those prepared conventionally .
The above-mentioned examples highlight the chemical reactions induced by acoustic cavitation, that otherwise, would not occur or occur at much slower rates under normal conditions. The mass transfer effects generated due to acoustic cavitation could also be used to simply enhance the rates of chemical reactions or chemical processes such as emulsification (referred to as sonoprocessing). In particular, the mass transfer effects have been heavily used in heterogeneous systems [1, 2, 3].
Having introduced the basics of sonochemistry, the rest of the article will focus on applied sonochemistry with selected examples.
The physical and chemical effects generated during acoustic cavitation have been used for a number of applications [1, 2, 3]. Processes such as emulsification, de-emulsification, extraction and cleaning are not covered here since they are classified under sonoprocessing. They do not refer to chemical reactions. However, in some sonochemical reactions such as emulsion polymerisation process, both the physical and chemical effects are required, which will be discussed below under polymers and biomedical applications. Another area where the physical effects of acoustic cavitation are increasingly being used is food/dairy processing. The physical and functional properties of dairy proteins, biopolymers, dairy fat, etc., have been modified by sonication process and extensive literature is available for the readers who may be interested in this area. Various chemical applications have been developed using the physical and chemical effects of acoustic cavitation, out of which three major areas are discussed below, namely, materials synthesis, environmental and biomedical applications.
Nanomaterials including polymers
Synthesis of metal nanoparticles has been briefly discussed in Sect. 3 using gold as an example. Using a similar strategy, a variety of metal nanoparticles that include Ag, Cu, Pt, Rh, etc., have been sonochemically synthesised [19, 20, 21, 22, 23, 24, 25]. The choice of experimental conditions seems to affect the shape and size of nanoparticles generated. In general, smaller particles are generated when a higher amount of radicals are formed, which happened to be around 200 kHz – 600 kHz . A higher amount of radical production enhances the rate of nucleation resulting in smaller particles. In fact, the size of Au nanoparticles generated was shown to be controlled by the rate of radical production (see Fig. 4). High Intensity Focused Ultrasound (HIFU) was used  for the synthesis gold particles of different shapes as shown in Fig. 4.
Such metal particles have been found useful in many applications. For example, Au nanoparticles have been used in biomedical applications . Metal particles deposited on other matrices such as graphene oxide layers have been used in catalytic and electrocatalytic applications [1, 2, 3].
Sonochemical synthesis of polymer latex particles [26, 27, 28] is another interesting application. A typical system involves an organic monomer and an aqueous system containing a stabiliser. Let us consider a specific example of synthesising polymethyl methacrylate (PMMA) latex particles. Methyl methacrylate monomer could be emulsified into an aqueous solution containing sodium dodecyl sulphate (SDS) as a stabiliser. The emulsification can be achieved by the shear forces generated at (20 kHz) low-frequency ultrasound. Such sono-emulsification process is very effective in generating small (about 50–200 nm in diameter) monomer droplets with a relatively narrow size distribution. The overall sono-emulsification and sono-polymerisation processes are depicted schematically in Fig. 5.
Ultrasonic emulsion polymerisation has been used for synthesising magnetised polymer particles  that may have applications in biomedical imaging. In the synthetic process involved, magnetically active iron oxide nanoparticles were first dispersed in the monomer phase followed by emulsion polymerisation that resulted in the incorporation of iron oxide in the polymer latex matrix making the polymer particles magnetically responsive. In recent times, ultrasonic polymerisation is incorporated into RAFT  and ATRP  processes that resulted in polymers possessing “controlled” properties.
The oxidative radicals generated during acoustic cavitation could be used to oxidize organic pollutants in an aqueous environment [31, 32, 33, 34]. Taking benzoic acid as a simple organic pollutant, its sonochemical degradation is shown in Fig. 6. Benzoic acid, being a weak acid exists in neutral or ionised form depending up on the solution pH. The degradation rate vs concentration plots shown in Fig. 6 suggests that the degradation efficiency is strongly dependent on the nature of the molecule. In its neutral form, benzoic acid is surface active and can adsorb at the bubble–solution interface. Due to the close proximity between the adsorbed molecules and OH radicals, generated within the bubbles, the rate of oxidation is higher leading to an efficient degradation. In its ionised form, benzoic acid is more hydrophilic and hence, less prone to OH radical attack leading to a lower degradation rate. This is an important observation that suggests that the sonochemical degradation of organic pollutants strongly depends up on the surface activity of the pollutant molecules (further discussion is provided in Sect. 5). The mechanism of sonochemical degradation of organic pollutants involves the OH radical attack followed by completed mineralisation as shown in Fig. 6.
Ultrasound is heavily used in imaging applications in diagnostic medicine . In the past decade, ultrasonic synthesis of core–shell biomaterials has become an active research area [36, 37, 38, 39, 40]. Such materials could be used as ultrasound contrast agents or drug delivery vehicles. A variety of biopolymers are used to make core–shell biofunctional materials; however, those biopolymers containing sulfhydryl functional groups are found to be stable. The formation of a core–shell structure involves the manipulation of the physical and functional properties of the biopolymer as well as the physical and chemical effects of cavitation. A strong physical shear is necessary to make an emulsion of air bubbles (for air-filled microspheres) or oil droplets (for drug-filled microspheres) in the solution. The biopolymer needs to be surface active to stabilise the microbubbles or microdroplets. The oxidative radicals are used for cross-linking the adsorbed polymer molecules to generate a shell encapsulating air or oil/liquid drug.
Take a typical case of lysozyme-shelled air-filled microspheres . Lysozyme is a globular protein and the structure is held together by intra-molecular disulfide bonds. In the synthetic process, lysozyme is dissolved in water, partially denatured using a reducing agent to open up the structure to make the molecules surface active. The breaking of intra-molecular disulfide bonds also generates free –SH groups. During the ultrasonic emulsification process, air bubbles are generated in the solution and lysozyme adsorbs at the surface of these air bubbles. During the cavitation bubble collapse, HO2 radicals are generated which oxidize –SH groups to form inter-molecular disulfide bonds creating a network of crosslinked proteins on the surface of the bubble leading to the formation of lysozyme-shelled microspheres (Fig. 7). A similar procedure is followed to synthesise oil-filled microspheres. Both the core and shell could be functionalised for targeted drug delivery.
One of the problems for the introduction of ultrasonics technology for large-scale applications is the overall efficiency of the process vs cost of this technology. For some applications such as emulsification, extraction, etc., ultrasonic processing is found to be effective due to the very short sonication times required reducing the overall processing cost. However, for applications where the radicals are used, for example, in wastewater treatment, the overall efficiency is low due to the large amount of energy required to generate required amount of oxidizing radicals for the mineralisation of organic pollutants. In the past 10 years or so, researchers have looked at combining two or more techniques to achieve synergistic advantages. One example of a hybrid technique is sonophotocatalytic process [41, 42], a combination of sonolysis and photocatalysis, which is discussed in detail below. Other such hybrid techniques such as sonoelectrochemistry [43, 44], sono-Fenton , etc., have also been developed.
Sonochemical degradation of organic pollutants has selective advantages and disadvantages. This is demonstrated using benzoic acid as a model pollutant. Figure 6 shows the sonochemical degradation of benzoic acid as a function of solution pH. Benzoic acid is a weak acid with a pKa of about 4.2. Below pKa, benzoic acid exists in the neutral form and above pKa in its ionised form. In its neutral form, benzoic acid is relatively more hydrophobic and surface active whereas in the ionised form, it is less surface active due to hydrophilic characteristics.
Being surface active, the neutral form of benzoic acid adsorbs to the cavitation bubble–solution interface and is prone to efficient OH radical (generated on bubble collapse) attack. Whereas the ionised form exists in the bulk solution, where OH radicals need to diffuse out of the bubble to react with benzoic acid, which is a relatively less efficient process due to very short lifetime of OH radicals. This is the reason for the observed difference in the degradation rates of benzoic acid at low- and high-pH conditions, observed in Fig. 6.
What the above discussion suggests is that sonolysis is an efficient process for the degradation/oxidation of hydrophobic organic pollutants. Now, let us consider the mineralisation (complete degradation/oxidation of an organic compound to H2O and CO2) process under sonolytic conditions. TOC (total organic carbon/content) results for the sonochemical degradation of benzoic acid takes more than 24 h for complete mineralisation of the parent compound and hence, the process becomes energy intensive or less cost-effective. The reason for such a long mineralisation process is the generation of hydrophilic intermediates due to the oxidation of parent compounds. See, for example, the nature of the products identified during the sonochemical degradation of benzoic acid shown in Fig. 6.
Photocatalysis  is a technique where light energy is used to generate redox species in semiconductors. In heterogeneous photocatalysis, UV/visible light could be used to excite semiconductor particles to generate electrons and holes in conduction and valence bands, respectively. Most photocatalysts that have been extensively studied, for example, TiO2, CdS, etc., have charges on the surface and hence, efficiently degrade charged pollutants that are adsorbed on the surface of the photocatalytic particles. Hence, photocatalysis is an efficient process for the degradation of hydrophilic compounds. It can now be appreciated the reason for the hybridisation of the two oxidation techniques, sonolysis and photocatalysis–sonophotocatalysis. A few studies have shown synergistic enhancement  in the degradation and mineralisation rates of organic compounds in aqueous solutions.
Instrumentation to generate acoustic cavitation
In general, an ultrasonic reactor includes a wave generator, an amplifier and a transducer. Most commercial units put these components together in a single “cage”. For lab-scale experiments, ultrasonic baths (ultrasonic cleaning baths are commonly available in the market) or transducers in the form of a horn (usually operates at 20 kHz) or a plate (usually operates above 100 kHz) are used. Ultrasonic baths operate at very low-power density (since the volume of water used is significantly high) and hence, generate very low amount of cavitation. 20 kHz horn units operate at much high-power densities since the energy is focussed at the tip of the horn. Plate-type transducers operate at moderate power densities. Further details on ultrasonic equipment are available in Ref  and Ref .
The interaction between bubbles in a liquid and ultrasound leads to acoustic cavitation under specific experimental conditions. Extreme conditions are generated in hotspots in solutions that are kept at room temperature. As a consequence of acoustic cavitation, highly reactive radicals and physical forces are generated that could be used in many chemical reactions and processes. A few examples of applied sonochemistry discussed in this article provide an indication of how ultrasound and sonochemistry could be used in multi-disciplinary areas. Hybrid techniques utilising the advantages of acoustic cavitation have been developed. In recent years, dairy and food industries are investigating the benefits of ultrasonic processing as a non-thermal technology along with high pressure processing (HPP). Pharmaceutical industries on the other hand focus on the use of ultrasonics encapsulation technology for targeted drug delivery applications. In some countries like China, ultrasonic synthesis of graphene and other nanomaterials is tracking some attention. The basic and applied aspects discussed in this article may provide a good introduction to those interested in harvesting the benefits of ultrasonics and sonochemistry technology to develop various applications.
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