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Analytical uses of ultrasonic

By: Farzad Torabi

Supervisor:
Dr. Sereshti

May 2015
Properties of ultrasonic waves

Audible sound has a frequency of between 10 and 18 kHz.

“Ultrasound” refers to frequencies greater than 20kHz, the limit of

human hearing.

They have smaller wavelength and higher energy content.

They act as catalytic agents to accelerate chemical reactions.

They produce intense heating effect when passed through the

medium.

Just like ordinary sound waves, ultrasonic waves get reflected,

refracted and absorbed.

They can be transmitted over large distances with no appreciable

loss of energy.
Introduction
 Sound waves are mechanical vibrations in a solid, liquid or gas and
are intrinsically different from electromagnetic waves.

 While the latter electromagnetic waves

(radio waves; infrared, visible or
ultraviolet light; X-rays; gamma rays) can
pass through vacuum, sound waves must
travel in matter, as they involve
Rarefaction and compression cycles
traveling through a medium. Rarefaction
pulls molecules apart, whereas
compression pushes them together.
Introduction
 Ultrasound is simply sound pitched above human hearing

 Ultrasound waves are used for a growing variety

of purposes such as:

 Industry (large-scale cleaning, emulsification

of cosmetics and food)

 Medicine (nonsurgical removal of kidney

stones, treatment of cartilage injuries,
imaging fetal development during
pregnancy),

 Engineering (welding plastics, cutting

alloys),

 chemistry (synthesis of fine chemicals).

 Introduction
Scientific community engaged in

Those who use it to induce physical or chemical effects in a medium (by using high-
work on ultrasound

power, low-frequency ultrasound from 20 kHz to 2 MHz in sonochemistry).

Those who use it for measurement without altering the medium (e.g. use of high-
frequency (5 MHz to several GHz), low-power ultrasound for nondestructive testing).

Reference: http://www.online-sciences.com/the-waves/the-types-of-the-sound-waves/
Analytical applications of ultrasound

PRIOR TO THE ANALYTICAL PROCESS

SAMPLE PREPARATION

The different Uses of ultrasound energy in

analytical chemistry
ASSISTANCE TO DETECTION

ULTRASOUND-BASED DETECTION
TECHNIQUES
Uses of ultrasound before the analytical process

PRIOR TO THE ANALYTICAL PROCESS

Cleaning Degassing Atomization

 Uses of ultrasound before the analytical process

Ultrasound-assisted cleaning:

 Ultrasonic cleaning has become a major application

of power ultrasound.

 Ultrasound is widely used to facilitate the cleaning of

analytical equipment ranging from glassware to
columns to a variety of devices liable to clogging or
malfunctioning as a result of the effect of dirt.

 Applications such as cleaning and disinfection of surgical and dental

instruments, decontamination of minimally processed fruits and vegetables,
and cleaning of membranes of various materials, metal surfaces, and fine
mineral suspensions are quite commonplace.
Uses of ultrasound before the analytical process
Ultrasound-assisted degassing

Ultrasound-based degassing involves removing

gases from solutions without heating or evacuation.

 Cavitational effects, which are the basis of sonochemical action, are also the
origin of the extreme efficiency of ultrasound for degassing liquids.
 Cavitation and Implosion
In non-elastic media such as water and most liquids, there is
continuous transition as long as the amplitude or "loudness" of the
sound is relatively low.
As amplitude is increased, however, the magnitude of the negative
pressure in the areas of rarefaction eventually becomes sufficient to
cause the liquid to fracture because of the negative pressure, causing a
phenomenon known as cavitation.
Cavitation "bubbles" are created at sites of rarefaction as the liquid
fractures or tears because of the negative pressure of the sound wave
in the liquid. As the wave fronts pass, the cavitation "bubbles" oscillate
under the influence of positive pressure, eventually growing to an
unstable size.
Finally, the violent collapse of the cavitation "bubbles" results in
implosions, which cause shock waves to be radiated from the sites of
the collapse. The collapse and implosion of myriad cavitation
"bubbles" throughout an ultrasonically activated liquid result in the
effect commonly associated with ultrasonics.

Reference: Seidi, Shahram, and Yadollah Yamini. "Analytical sonochemistry;

developments, applications, and hyphenations of ultrasound in sample
preparationandanalyticaltechniques."CentralEuropeanJournalofChemistry10.4
(2012):938-976.
Uses of ultrasound before the analytical process

Ultrasound-assisted atomization

Atomization is the popular name given to the first stage of spray-drying, that
is, the fine division of a liquid, suspension, or emulsion into fine, narrow-size-
range droplets or particles which can rapidly lose their liquid phase under
appropriate physical conditions.

It is occasionally used instead of freeze-drying for sample conservation. The former

is faster and cheaper than the latter, and is also the only way of effectively removing
the liquid phase when the sample is rich in fat.
 Digestion
Solid samples Leaching

Slurry formation
Acceleration of reactions

Liquid–liquid extraction
Liquid
Uses of
samples Emulsification
ultrasound for
sample Homogenization
preparation
Filtration

Aggregation

Dissolution of solids
Heterogeneous
samples Sonocrystallization /
sonoprecipitation
Defaming

Degassing
Uses of ultrasound for sample preparation for Solid Samples
Uses of ultrasound for sample preparation for Solid Samples

Ultrasound-assisted digestion
 Ultrasound can assist digestion by mechanical and chemical effects, which, despite
they being simultaneous, have different effects.
USASD: USASTD:
Drastic conditions including high Drastic conditions including high
temperatures & highly reactive chemicals temperatures and highly reactive
e.g. pure or highly concentrated oxidants chemicals e.g. pure or highly
or reductants) in addition to concentrated oxidants or reductants) in
ultrasonication. addition to ultrasonication.
Main effect: Mechanical effects Main effect: Mechanical effects+
Chemical effects
Suitable for complex matrix that must
USASD may suffice to accelerate usually be decomposed
sample’s dissolution
Example1: determination of metals in
biological samples (particularly tissues),
for which a strongly basic medium
Example: analysis of pharmaceutical (tetramethylammonium hydroxide/water)
formulations in diverse dosage forms
(tablets, capsules, suppositories, and Example2: Seafood products have also
powder) with different solvents. been digested with ultrasonic assistance
and high concentrations of a mixture of
HNO3 , HCl and H2 O2 .
Uses of ultrasound for sample preparation for Solid Samples

Ultrasound-assisted leaching (USAL)

The advantages of ultrasound-assisted leaching over classical leaching are:

 reduces leaching times, use of hazardous reagents, and intervention of the analyst.

 USAL can be also coupled with other steps of the analytical process in continuous
systems to automate a process with dramatically reduced leachant consumption

The advantages of ultrasound-assisted leaching over other new methods

 Compared with microwave assisted leaching (MAL), USAL is normally simpler and safer,
because it does not require high pressures or temperatures.

 USAL requires much simpler equipment than supercritical-fluid leaching (SFL), more commonly
known as “supercritical fluid extraction”USAL also enables leaching of a wider variety of
compounds without the need to use a co-leachant, enables operation at ambient temperature
and pressure, which ensures the stability in thermolabileanalytes, and is usually more
expeditious than SFL
Uses of ultrasound for sample preparation for Solid Samples

Ultrasound-assisted slurry preparation:

Slurries are prepared by adding a liquid to a previously ground, sieved, and
weighed solid sample.

Low-frequency, high-energy, ultrasound power in the kHz range is used to

assist slurry formation, so mechanical and chemical effects of cavitation are
significant

Ultrasound assisted slurry formation is a simple, efficient means of

circumventing problems associated with digestion of samples with complex
matrices, because of the hazardous conditions required.;
Uses of ultrasound for sample preparation for Liquid Samples

Liquid–liquid extraction from an aqueous to an organic phase or vice versa is highly

affected by the presence of ultrasound, albeit not always favorably. Some systems
are improved, others undergo undesirable emulsification.
Systems in which a chemical reaction is coupled with liquid–liquid extraction are more
markedly improved, because the ultrasound affects both. Examples include
continuous liquid–liquid extraction without phase separation and hydrolysis of
paracetamol in suppositories.
Uses of ultrasound for sample preparation for Liquid Samples

Emulsification is greatly promoted by ultrasound. The effect of ultrasound here is

based on droplet disruption in sonicated liquid–liquid systems as a result of
cavitation. These systems are barely used in analytical chemistry, but have a wide
scope in the pharmaceutical industry.

Homogenization is also effectively assisted by use of ultrasound, without altering

the chemical characteristics of the system. This step can be required one or
several times during sample preparation to facilitate contact between solutions;
alternatively,
Uses of ultrasound for sample preparation for Heterogeneous samples

The main purpose of ultrasound as applied to heterogeneous media is in separating a

solid from a liquid phase in which it is dissolved; this favors or accelerates formation of
the solid phase. The solid phase can exist in the sample as such or be formed as a result
of, mainly, a chemical reaction (e.g. precipitation); a physical phenomenon such as
crystallization or aggregation can, however, also be the origin of the solid phase.

Filtration

Aggregation

Dissolution of solids
Heterogeneous
samples Sonocrystallization /
sonoprecipitation
Defaming

Degassing
Uses of ultrasound for sample preparation for Heterogeneous samples

Filtration is one conventional means of separation of phases that is dramatically aided

by use of ultrasound. Analytical applications of filtration include:

1) separation of a solid phase formed in a chemical step involved in sample

preparation (e.g. in an automated, on-line system for bioprocess control based on
flow injection).
2) preliminary use in sample preparation to remove undesirable particles.

Aggregation (also known as

agglomeration) is the formation of large
particles from small ones which
agglomerate rapidly and efficiently when
subjected to ultrasound; this enables easier
separation of the solid phase, if isolation of
the phases is the pursued objective. This
technique can be used before or after
sampling, and also at an intermediate stage
if finely divided solid is formed during Reference:
http://www.ultrasonic-scientific.com/products/hrus_csa.htm
sample preparation.
Uses of ultrasound for sample preparation for Heterogeneous samples

Analytically, dissolution of solids present in a heterogeneous sample is performed to

determine an analyte present in the solid phase or randomly distributed between both
phases.
Sonocrystallization is the name currently given to use of ultrasound power to control
and accelerate the course of a crystallization process. This effect had been used in the
salting-out process for years and has proved to have a favorable effect on the initial
nucleation stage of crystallization. The wide use of this form of energy in food technology
clearly testifies to the advantages of ultrasound in this discipline. Ultrasound has also
been used to assist the formation of extremely finely divided, uniform particles; this is
known as sonoprecipitation. This effect, which has been exploited in analytical chemistry,
can facilitate sample preparation in nephelometric and turbidimetric methods.

Refrence: Ruecroft, Graham, et al. "Sonocrystallization: the use of ultrasound for improved industrial crystallization." Organic
Process Research & Development9.6 (2005): 923-932.
Uses of ultrasound for sample preparation for Heterogeneous samples

Defoaming is the operation performed to remove

foam. Foam can cause problems in analytical
operations, for example chromatographic separations
and molecular spectrometric detection, among others.
Acoustic transducers operating at 10 and (or) 20 kHz
are capable of defoaming liquids if the acoustic source
is placed above the liquid surface on which the foam is
being generated.

Although the analytical uses of ultrasound-assisted degassing are almost

restricted to the step preceding sample preparation, several analytical methods
produce gas during one of the stages.
One example is the ion chromatographic determination of bromate in drinking
water, in which the decrease in the concentration of chloride and carbonate on an
on-guard Ag and H cationic column produces an eluate containing CO2 and H2
bubbles that are effectively removed by 10 min sonication in an ultrasonic bath.
Uses of ultrasound to improve detection

Ultrasound has been used in other ways to improve the performance of detection
techniques.

 The analytical sensitivity, selectivity, and resolution of atomic detectors has been markedly
improved by use of USNs.
 USNs have also been successfully implemented in the electrospray-formation devices used as
interfaces between CE or HPLC equipment and mass detectors.
 It is well-known that USN results in higher analyte transport efficiency than does pneumatic
nebulization (usually 8–15 times better); this results in improved sensitivity and lower
detection limits, which is particularly important for analysis of species at trace or ultratrace
levels.
 Sample levitation can be accomplished in different ways, one of which is the use of
ultrasonic energy. The flexibility and potential of acoustic levitation in a variety of
disciplines, especially analytical and bio analytical studies, is widely documented

 Use of ultrasound during the electroanalytical process is known as sonoelectroanalysis,

mainly focused on voltammetry for determination of inorganic species in different types of
sample in which the sensitivity of silent classical voltammetric techniques is usually reduced
by fouling of the electrode.
Ultrasound-based detection techniques

 Ultrasonic detection techniques rely on measurements of low-intensity waves or

mechanical deformations at frequencies higher than 50 kHz (mostly in the MHz
region, but also in the GHz region).

 In contrast with light waves, ultrasonic waves can propagate through most types of
material and their wavelength is fairly easy to change as they are synthesized
electronically.
 Ultrasonic detection modes differ in:
1) the manner in which ultrasound is applied (e.g. as a single frequency, as broad-
band pulses, or as a scanning frequency), after which modes are named;
2) the manner in which ultrasound impinges on the sample (normal, parallel, oblique),
after which the waves produced in the material (longitudinal, shear, oblique) are
named; and
3) the manner in which the experimental data are used (viz. as amplitude or phase
spectra) or processed (viz.in the frequency or time domain).
Ultrasound-based detection techniques

Ultrasonic spectrometry usually relies on measurements of some characteristic of ultrasonic

waves propagating through the sample that provide information on the interaction of the
ultrasonic waves with the inside of the sample, thus enabling analysis of its physical and
chemical properties. Propagation of ultrasonic waves is determined by ultrasonic velocity and
attenuation; these, with reflectance, are the primary acoustic responses. Attenuation is the
best property for characterizing dispersed phase composition and particle size; in ontrast, the
speed of the sound is better for characterizing chemical composition at the molecular level.

Ultrasound-based detection techniques can benefit from use of lasers as energy sources.
Laser-based ultrasound techniques have many attractive features, including the possibility
of making noncontact, non-destructive, remote measurements. These modes of optical
detection are, typically, one or two orders of magnitude less sensitive than their contact
transducer counterparts, where available. Thus, acoustic microscopy uses transmitted ultra
highfrequency ultrasound in the range 10 MHz to 2 GHz to produce images, mainly of
biological structures, with a resolution approaching that of light microscopy. This
technique, which is usually sensitive to the mechanical properties of the materials under
inspection and contrast,provides useful information about the physical structure of
the sample.
Refrences:
1) Priego-Capote, F., and MD Luque De Castro. "Analytical uses of ultrasound I. Sample
preparation." TrAC Trends in Analytical Chemistry 23.9 (2004): 644-653.
2) Andruch, Vasil, et al. "Application of ultrasonic irradiation and vortex agitation in solvent
microextraction." TrAC Trends in Analytical Chemistry 49 (2013): 1-19.
3) Priego-Capote, F., and MD Luque De Castro. "Analytical uses of ultrasound I. Sample
preparation." TrAC Trends in Analytical Chemistry 23.9 (2004): 644-653.
4) Capote, F. Priego, and MD Luque de Castro. Analytical applications of ultrasound. Vol. 26. Elsevier,
2007.
Thanks for your attention
Any question?