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Principles
Microwaves are high-frequency electromagnetic waves in the same frequency band as radar waves. Only 4
microwave frequencies are permitted for industrial and scientific use. Of these, 2.45 GHz is the most
frequently used.
Electromagnetic waves are interconnected electric and magnetic fields which change over time and
propagate at the speed of light through space. The electromagnetic field produced is described by the field
strength vectors E and B.
E
=c
B
E...electric field
B...magnetic field
c...speed of propagation
λ...wavelength
All electromagnetic waves are sky waves which propagate at the speed of light and transport energy (without
loss in a vacuum; with loss in dielectric material).
They show the same effects as light:
• Interference
• Diffraction
• Refraction
• Reflection
• Polarizability
Which of these effects occurs depends on the wavelength and the molecular structure.
Microwaves
• are reflected by non-polar metals
• pass through ceramic, glass and porcelain
• are absorbed by food, human tissue and polar materials
Microwave radiation is not an ionizing radiation and is therefore not hazardous for human tissue.
Producing microwaves
Low microwave frequencies can be produced using electron tubes or transistors. High and very high
frequencies (>100 MHz) are produced by klystrons, magnetrons or traveling wave tubes
In decomposition instruments, microwaves are produced using magnetrons.
Resonators Anode
Cathode
Heating
Uncoupling Loop
The lower the loss factor, the lower the absorption capacity of the substance. Materials with a low absorption
capacity can be used as neutral components, e.g. as vessel material.
Some substances, e.g. water, have a relatively high loss factor at room temperature but this decreases once
a certain temperature has been reached.
The dielectric loss factor is dependent on:
• the substance
• the frequency
• the temperature
Microwave absorption
To heat a substance, the material must couple to the microwaves. In other words, the substance must
absorb electromagnetic energy.
Generally speaking, two mechanisms are available:
Dipole rotation
This is the case with materials which have a pronounced dipole (water, acids, solvents). In the rapidly
changing electric field, the molecules try to orient themselves in the direction of the field lines. This sets them
in rotation-vibration. The energy absorption from the microwave field is more intensive the closer the
resonance frequency of the molecule is to the frequency of the microwave.
δ− δ− δ−
δ+ δ+ δ+
Dipole moments
[Debye]
HF 1.82
HNO3 2.17
HCl 1.03
H20 1.844
C3H8O 1.66
NH3 1.46
CCl4 0
CH3Cl 1.87
Both mechanisms, dipole rotation and ionic conductance, are influenced by various factors:
• Wavelength
• Energy minimization
• No inertia. When the microwave radiation is switched off, the source of heat is immediately removed
from the object
Example: Heating a vessel in an oil bath (A) and using microwaves (B)
Heating from outside in – heating from inside out
(A) (B)
Microwave decomposition
Decomposition is the conversion of a solid sample into a liquid, homogeneous state.
This makes the sample easier to aliquot and has all the prerequisites for an interference-free qualitative and
quantitative determination of the elements or compounds of interest. After mechanical sample preparation,
decomposition is the most time-consuming step in wet-chemical procedures. It is therefore very useful to
optimize this step and reduce the required time while retaining or increasing the quality of the analysis.
Contamination by the decomposition agent can be prevented either by using purchased super-pure acids or
subboiling analytical reagent quality acids to purify them.
Adsorption on the vessel walls is prevented by using highly pure materials which are chemically and
thermally resistant, e.g. PFA, PTFE and quartz glass.
PFA Perfluoralkoxy
—[(CF2)4- CF(-O-CF2-CF2-
CF3) — (CF2)5]n—. High melting point (310°C)
High thermal stability
Chemically inert
Low water absorption/adsorption
Insoluble
Quartz
Pure
Chemically resistant
Thermal-shock resistant
Temperature resistant
Pervious to UV and IR
Electrically insulating properties
Open decomposition
Samples and reagents are heated on a hotplate, in a sand bath or in a microwave-heated system. The
sample and reagents are in open vessels made of glass, quartz, glassy carbon or PTFE. The gas vapors
which are produced are either extracted or caught by a reflux condenser and returned to the reaction
mixture.
The maximum reaction temperature is dictated by the boiling point of the acid mixture at ambient pressure.
Decomposition duration 2 to 10 h
Use:
• Inhomogeneous samples
• Easy to dissolve samples
• High analyte concentration
• In combination with flame AAS
Benefits:
• Simple and reasonably priced equipment
• Easy to use
• High sample throughput, very good for inhomogeneous samples
• Any reaction gases can evaporate unhindered (no buildup of pressure)
• Maximum temperature is limited to the boiling point of the reagent mixture; poor decomposition
quality
• Long decomposition time
• Use of H2SO4 to increase the temperature of the mixture
Disadvantages of sulfuric acid:
Difficult to produce pure sulfuric acid
Interferes with many subsequent analysis methods due to its high viscosity and
forms sulfates with low solubility when mixed with many metals (e.g. Cd, Pb, etc.),
which leads to values which are lower than the actual values
• High consumption of reagents, high numbers of blank readings
• Evaporated reagents must be refilled during the decomposition
• Possible contamination from reagents and the environment
• Produces corrosive air in the laboratory, despite using an fume hood
• Loss of volatile elements
Hg (elemental)
As, B, Cr, Ge, Pb, Sn, Te, Ti, Zn, Zr (as halogen compounds)
Os, Rh, Ru (under oxidative conditions)
Se, Te (under reductive conditions)
• Large vessels (i.e. 250ml) with large surfaces, adsorption effects and loss of analytes
• Time-consuming cleaning required after decomposition
Closed decomposition
Sample and reagents are heated in closed pressure vessels made of fluoroplastics (PFA, PTFE, PTFE-TFM)
or quartz. The pressure vessels can be heated conventionally (autoclave, heating block) or using microwave
technology. The reaction is controlled via temperature and pressure sensors.
The maximum reaction temperature depends on the thermal stability and pressure stability of the vessel
material used.
Reagent consumption 2 to 10 mL
Use:
• All materials
• Matrices which are difficult to dissolve
• For all measuring methods (spectrometry, voltammetry)
Benefits:
• High temperatures (up to 320°C depending on the instrument and vessel type)
• High pressures (up to 80 bar depending on the instrument and vessel type)
• Complete decomposition results due to the high temperatures and pressures
• Simple acid mixtures; HNO3 is sufficient for organic samples
• H2SO4 or HClO4 are not required
• Low reagent volumes, reduction of blank readings and reagent costs
• Short reaction times
• No loss of volatile elements
• Does not lead to corrosive air in the laboratory
• Small vessels and inert materials, extremely low adsorption effects and no loss of analytes
Disadvantages:
Microwave-assisted extraction
If solvents are used for microwave-assisted extractions, there must be sufficient polar solvents in the mixture.
The polar solvent volume must be at least 3 mL.
For more information on our microwave decomposition instruments, take a look at our
website:
http://www.anton-paar.com/sample-preparation/microwave_CXSN-5QTJQ5.en.0.jsp