E38IB016EN C Application Guide Acid Digestion For Multiwave 5000

Application Guide Acid Digestion
for
Multiwave 5000
Version: May 2022

Document is subject to change.
Latest version is saved online.
Application Guide Acid Digestion
for
Multiwave 5000
Version: May 2022

Document is subject to change.
Latest version is saved online.
Disclaimer
This document may contain errors and omissions. If you discover any such errors, or if you would
like to see more information in this document, please contact us at our address below. Anton Paar
assumes no liability for any errors or omissions in this document. This document does not alter your
contractual relationship with Anton Paar and you must not act or omit to act in reliance upon the
information contained in this document. Anton Paar assumes no liability for any losses or damages
in this regard.
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Further information
Published and printed by Anton Paar GmbH, Austria
Copyright © 2022 Anton Paar GmbH, Graz, Austria
Address of the instrument producer:

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Web: www.anton-paar.com
Date: May 2022

Document number: E38IB016EN-C
Contents
Contents ......................................................................................................................................... 5
1. About This Application Guide ................................................................................................... 7
2. General Chapters .................................................................................................................... 8
2.1 Basics of Acid Digestion....................................................................................................... 8
2.1.1 Why Acid Digestion? .................................................................................................... 8
2.1.2 Types of Transfer into Liquid Form ............................................................................... 9
2.1.3 Effect of Increasing Temperature ................................................................................. 9
2.1.4 Estimation of Vessel Pressure.................................................................................... 11
2.1.5 Pressure Control ........................................................................................................ 12
2.1.6 Problems Related to Sample Preparation................................................................... 14
2.1.7 Common Problems from Measurement ...................................................................... 15
2.2 Reagents ........................................................................................................................... 16
2.2.1 Specific Aspects of HF ............................................................................................... 18
3. How to Start Method Development ........................................................................................ 20
3.1 Access Application Knowledge .......................................................................................... 21
3.2 Consider Standard Methods............................................................................................... 21
3.3 Work with Pre-loaded methods or Generic Applications ..................................................... 23
3.3.1 Care about sample reactivity ...................................................................................... 23
3.3.2 Reactive Samples ...................................................................................................... 24
3.3.3 Inert Samples ............................................................................................................. 27
3.4 Limitations from Vapor Pressure ........................................................................................ 28
3.4.1 Vessels with SmartVent Technology (HVT and SVT Vessels) .................................... 29
3.4.2 MF, HF, X Vessels ..................................................................................................... 29
3.5 Sample Weight vs. Pressure vs. Temperature ................................................................... 29
3.6 Power vs. Temperature Programming ................................................................................ 30
3.7 Understand the Use of Sensors ......................................................................................... 31
3.7.1 IR Temperature Sensors ............................................................................................ 32
3.7.2 Pressure Sensor ........................................................................................................ 33
3.7.3 Immersion Temperature Sensor ................................................................................. 34
3.8 Assess Digestion Results................................................................................................... 35
3.8.1 Organic Material ......................................................................................................... 35
3.8.2 Inorganic Material....................................................................................................... 36
3.9 What to Change in the Chemistry of a Method ................................................................... 36
3.9.1 Increase Oxidation of Organic Matter ......................................................................... 37
3.9.2 Decrease Reactivity of HNO3 – Add Water ................................................................. 37
3.9.3 H2O2 addition – Why and How Much .......................................................................... 38
3.9.4 Optimizing Methods ................................................................................................... 38
3.10 Why to Use Pre-reaction Steps for Rotor 24HVT ............................................................... 39
3.11 Higher Sample Amount – How to deal with it ..................................................................... 40
4. Troubleshooting ..................................................................................................................... 42
4.1 Target Temperature Not Reached...................................................................................... 42
E38IB016EN-C 5/53
4.2 Big Spread in IR Temperatures .......................................................................................... 43
4.3 Pressure Increase Rate Alarm ........................................................................................... 43
4.4 Leakage ............................................................................................................................. 44
4.5 Corrosion Signs in Closed Vessels without Venting Capability ........................................... 46
4.6 How to Check and Control Venting Activity in SmartVent Vessels...................................... 46
4.6.1 How to Quantify Venting............................................................................................. 47
4.6.2 How to Avoid Acid Venting ......................................................................................... 47
5. Rotors .................................................................................................................................... 48
5.1 Overview ............................................................................................................................ 48
5.1.1 General Limits ............................................................................................................ 48
5.2 Rotors with SmartVent Technology .................................................................................... 49
5.2.1 Rotor 24HVT50, Rotor 24HVT80, and Rotor 41HVT56 .............................................. 49
5.2.2 Rotor 20SVT50 .......................................................................................................... 50
5.3 “Classic Rotors” without SmartVent Technology ................................................................ 50
5.3.1 Rotor 8NXF100 and 8NXQ80 ..................................................................................... 50
5.3.2 Specific Hints for Quartz Vessels ............................................................................... 50
5.3.3 Rotor 16MF100, and Rotor 16HF100 ......................................................................... 50
5.3.4 Rotor 64MG5 ............................................................................................................. 51
6. Special Accessories for Rotor 8NXQ80.................................................................................. 52
6.1 Microwave Induced Combustion (MIC)............................................................................... 52
6.1.1 Application range, preparation of samples.................................................................. 52
6.1.2 Sample amount .......................................................................................................... 52
6.1.3 Absorption solution and refluxing ............................................................................... 52
7. Application Matrix .................................................................................................................. 53
6/53 E38IB016EN-
1. About This Application Guide
This Application Guide Acid Digestion for Multiwave 5000 is designed as a complementary document
in addition to the Instruction and Reference Manuals. While these provide in depth instructions and
information about safe and efficient operation of the instrument, the Application Guide offers
information about the application of the instrument and its accessories in its chemical environment.
“General Chapters” cover theoretical aspects of acid digestion independent of instrumentation. The
section about “Method Development” shows strategies for method selection and optimization for
Multiwave 5000 digestion system. “Trouble Shooting” allows a direct access to solutions for
common difficulties that may occur, with cross-references to the theoretical basis where necessary.
The section on “Rotors” summarizes important hints and recommendations for the use of your rotor
in combination with the Multiwave 5000 microwave digestion system.
The chemical information is also valid to other instruments of the Multiwave family. Some limitations
apply concerning available rotors and software-related information.
What the Application Guide can do for you

The Application Guide gives the information for an effective use of a highly sophisticated, modular
microwave-assisted heating system for sample preparation by acid digestion. It contains general
chapters covering acid digestion-related topics as well as instrument specific chapters to aid the
operator to optimize his work with specific rotors and accessories:
• Basics of acid digestion

• How to start method development
• Use the right reagents for your analytical task
• Concept of its sensors and controllers
• Specifics of individual rotor/vessel systems with respect to method programming
• Help for situations, when the outcome of a digestion is not as expected
How to use the Application Guide
After your user training during the installation of the instrument you should be familiar with the
operation of Multiwave 5000. This training is the basis for the work with this Application Guide. This
guide also refers to the information of the manuals in many places.
You are invited to read the general chapters about sample preparation by acid digestion to become
familiar with the basic concept. In addition to the chapters about Method Development there are
equipment specific chapters for reading, when question concerning a specific configuration arises.
These chapters cover the differences in behavior due to the different construction of various parts of
the Multiwave 5000 system.
What the Application Guide cannot do for you
• It does not replace the user training

• It does not repeat the safety instructions and warnings included in the manuals
• It is not a basic chemistry course that covers all the necessary knowledge to safely handle
all the laboratory equipment and reagents used for acid digestion.
The Application Guide addresses operators, who are sufficiently trained in the correct and safe use
of Multiwave 5000. Operators must be able to judge dangerous situations and take the right
measures to prevent accidents, injuries and damage.
E38IB016EN-C 1. About This Application Guide 7/53

2. General Chapters
The General Chapters give an overview of sample preparation by acid digestion.
When chemical concepts are introduced here, then in a very general manner – chemists please
apologize, many of the readers without profound chemical education will probably appreciate.
2.1 Basics of Acid Digestion
2.1.1 Why Acid Digestion?

For several decades now atomic spectroscopic techniques are those predominantly used to
determine elemental concentrations in all type of samples in minor to trace concentrations. The
analytical process in all these techniques involves highly dynamic steps like nebulization, aerosol
drying, evaporation of particles, atomization/excitation or ionization and interaction with a detector.
•forms an aerosol of solution including all dissolved substances

•droplet size is strongly influenced by the main solvents
Nebulization •for good performance a very narrow distribution of droplet size is necessary
•during its travel through the spray chamber solvents start to evaporize at their
individual rate
Aerosole •dissolved substances crystallize, gas flow transports dry particles to the atomizer
Drying
•in the atomizer (flame, graphite furnace, ICP flame) particles are heated to
evaporation as single atoms
Evaporization •molecules and complexes that reach the atomizer will be broken into atoms
Atomization
•AA: atoms absorb specific λ from light source; detector measures passing light
•AE: plasma excites all atoms to emit light at specific λ for elements and is
measured in spectrometer
Measurement •ICP-MS: analyte ions are analyzed by the mass spectrometer for their mass
Fig. 1: Dynamic processes during atomic spectroscopic measurements are strongly influenced by sample composition and properties
The gas flow rate through the ICP flame is high, so even small changes in reaction rate means that
the analyte will emit its specific light outside the observation zone. The quantification is done with a
set of calibration standards so all physical properties (like viscosity, acidity, total dissolved content)
and the chemical properties (like oxidation state, chemical binding state) must be similar for the
samples and the calibration standards.
8/53 2. General Chapters E38IB016EN-

For this reason techniques for sample preparation for atomic spectroscopy aim to prepare
such uniform, acidic solutions from the different sample types.
2.1.2 Types of Transfer into Liquid Form

During acid digestion many different things can take place depending on the sample and its
components and of the reagents used. For normal operation it is not necessary to know, what
happens in detail, but it may be helpful to distinguish at least the following steps to be able to perform
method development and optimization as well as trouble shooting.
Dissolution is the simplest transformation, where the sample compound is dispersed into the acidic
liquid as molecule or ion without further chemical reaction. Normally the molecules of the liquid cover
the dissolved molecule without significant bond to the molecule.
Sometimes, however, the electronic sphere of the dissolved molecules influences the sphere of
another type of molecules in the solution. These interactions may be weak and only involve some
shifting of positive and negative charges in the molecule. The better the molecules fit together the
stronger may be the attachment to each other. This is called complex formation and creates
chemical bonds that can be weak or even very strong.
When the interaction becomes stronger, the original molecule may be destroyed. In acid digestion
the oxidation reaction is desired to destroy the organic molecules that make up for most of the
substances. The reaction product (see Table 1) of the organic carbon is CO2, which easily removes
itself from the sample solution and no longer forms a burden for the atomizer. Another example of a
dissolution involving oxidation is the dissolution of metals. Base metals may be oxidized by any acid
forming H2 gas. Metals that are nobler than hydrogen require some stronger oxidizing agents such
as HNO3. However, especially corrosion resistant alloys may require specialized mixtures of acids,
including H2SO4, H3PO4 and sometimes HClO4 for successful digestion.
This is also true for minerals and ores, where fusion with special salts like sodium peroxide (Na2O)
and many others is still a widely used technique to transform the refractory and high-temperature
oxides into more acid soluble forms of oxides and carbonates that can easily be dissolved in dilute
mineral acids. However, all the solid reagents added before will remain in the sample and can cause
spectroscopic interferences and also introduce higher blank values.
Many of the samples are mixtures of several substances, which may require different mixtures of
acids to dissolve. Sometimes it may not be necessary to dissolve the whole sample matrix as long
as it is guaranteed that the analytes are leached from the insoluble sample matrix. This is often the
case for environmental analyses, where the interest lies in the determination of the toxicologically
relevant elements. It can be assumed that elements that are not dissolved even by aqua regia at
high temperatures are not relevant to chemical interactions with biological species.
2.1.3 Effect of Increasing Temperature

Dissolution reactions of solid particles only react on their surface and tend to be slow. In chemistry
it is common knowledge that reaction speed is increased with the temperature of the reaction. A rule
of thumb states that an increase of 10 °C will roughly double the reaction speed.
This effect is widely used in chemistry, thus also for speeding up digestion reactions. However,
heating reaction mixtures in open vessels on a heating device like water bath, sand bath or hot block
is limited by the boiling point of the reaction mixture. Higher temperatures can be achieved by
performing the digestion with high boiling acids like sulfuric acid or phosphoric acid and adding
oxidizing agents such as nitric acid to the hot solution. The low boiling nitric acid is boiled off quickly
and has to be added repeatedly causing high acid consumption and danger of contamination and
cross contamination by sputtering.
E38IB016EN-C 2. General Chapters 9/53

If the same reaction is performed inside a closed vessel the temperature of the reaction can be
increased until either the temperature or pressure limit is reached. Hence all modern microwave
heated acid digestion instruments use pressure-resistant vessels.
Discussion of vapor pressure

In thermodynamics the term “vapor pressure” means the pressure above a substance (liquid or solid)
that can be measured if the condensed phase (solid or liquid) and the vapor phase above are in
equilibrium and without material or energy exchange to the outside world (“ideal” vessel). It depends
on the temperature and increases with temperature. If the vapor pressure reaches the pressure
inside the vessel, the whole substance starts to evaporate, it “boils”.
Fig. 2 shows approximate vapor pressure curves as a function of temperature for some digestion
acids. At ambient pressure the boiling point of hydrochloric acid is between 80 – 90 °C, while HNO3
and HF are about 120 °C. There are also laws for estimating the vapor pressure of mixtures, where
the vapor pressures of the components, weighted with the molar activity (~ molar concentration),
can be added up.
Fig. 2: Vapor pressure curves of some common acids
In addition, chemical reactions take place between the components of the solution as can be seen
from the steep increase of the curve for HNO3 (red): a dissociation reaction that produces gaseous
NO and NO2, thus increasing the pressure is taking place.
In the case of aqua regia it is surprising that the vapor pressure curve (purple) lies above the curve
for pure HCl (green). The reason is the formation of NOCl, setting free Cl2. As chlorine is a strong
oxidizing reagent, the elevated pressure is beneficial for the dissolution, i.e. of precious metals, as
the concentration in solution is much higher as at ambient pressure, where the chlorine is lost for the
reaction.

Generation of reaction gases
But not only has the heating of the acid increased the internal pressure of the vessel. Many of the
reactions taking place inside a vessel generate reaction gases and hence increase the internal
pressure. The following Table 1 shows a few exemplary reactions that can serve to roughly estimate
the amount of gas generated during a reaction.
Table 1: Example of reactions with generation of reaction gases
Reaction Formula Comment

~CH2~ + 2 HNO3 → CO2↑+ 2 NO↑ + 2 General decomposition of organic compounds
1
H2O (carbon-containing compounds)
Tetrafluorosilicon as intermediary reaction product
SiO2 + 6 HF → SiF4↑ + 2 H2O + 2 HF →
2 of SiO2 dissolution generates pressure, with excess
H2SiF6 + 2 H2O
of HF a dissolved form is generated
dissolution of a carbonate mineral produces carbon
3 CaCO3 + 2 HCl → CaCl2 + H2O + CO2↑
dioxide
4 Zn + 2 HCl → ZnCl2 + H2↑ dissolution of base metals produces hydrogen
The reactions given in Table 1 are examples where gas is generated as a reaction product. In all
these cases the volume of gas is proportional to the amount of sample digested. But while in
reactions (2) – (4) one molecule of gas is generated for each molecule of sample, in reaction (1) 3
molecules of gas per carbon atom generate a much higher pressure.
2.1.4 Estimation of Vessel Pressure

But what is even more important is the fact that different molecules contain different percentages of
organic carbon. Table 2 shows a simplified estimation for a comparison of a carbohydrate and a
hydrocarbon, based on a sample size of 1 g and 0.5 g respectively.
Table 2: Pressure build-up during digestion for different sample types
Carbohydrate Hydrocarbon
plant materials like cellulose

Sample type mineral or vegetable oil
or sugar
Symbolic formula
(1) C6H12O6 =(CH2O)6 -(CH2)n-
(reduced to 1 C atom)
(2) Molecular weight (of which C) 30 g (12 g C) = 40 % 14 g (12 g C) = 86 %
mMol / 1 g sample
30 mMol (15 mMol) 70 mMol (35 mMol)
(3) (mMol / 0.5 g)
Gas volume @ standard

(4) 2.2 L (1.1) 4.8 L (2.4)
conditions
Pressure in 80 mL internal
(5) 27 bar (14 bar) 60 bar (30 bar)
volume @ room temperature

Carbohydrate Hydrocarbon
(6) Pressure @ 250 °C 50 bar (25 bar) 110 bar (55 bar)
Vapor pressure of
(7) 35 bar 35 bar
HNO3 @ 250 °C
(8) Total pressure 85 bar (60 bar) 145 bar (90 bar)
Based on the molecular formula the relative molecular content of carbon is given to show that
hydrocarbons contain more than double the amount of carbon (see lines (1) – (2)). Carbohydrate
molecules contain other elements such as oxygen and hydrogen, so the carbon content (3) is less
compared to hydrocarbons. In line (4) the resulting gas volume containing CO2 and NOx is estimated.
Advantage of pressure-controlled SmartVent vessels over old-style closed vessels

If the evolving gas is contained in a closed vessel, the resulting pressure at room temperature is
given in line (5). As the reaction is performed at higher temperature, so the gas expansion of the
reaction gases adds considerably to the pressure for the same amount of gas (6). Add the vapor
pressure for nitric acid at 250 °C (7) to finally find the resulting pressure that has to be contained
inside the completely closed digestion vessel. It pays to consider sample size before trying new
samples – but more of that later on!
A pressure-activated venting valve as offered in the SmartVent vessel system allows releasing
overpressure above a defined level. The only limitation for the digestion process is to stay below the
temperature, where the vapor pressure is sufficient to open the valve, this would boil off all acid in
the vessel. The pressure release threshold of the SVT SmartVent vessel is high enough to allow
working with HNO3 up to 240 °C without losing too much of the acid.
2.1.5 Pressure Control

From the examples given it is clear that safety measures such as pressure control by reducing
heating power or opening of overpressure relief will be necessary to prevent bursting of vessels. It
is important to understand the principal difference between systems that try to control the vessel
pressure by limiting the power input to indirectly keep the pressure on a safe level by limiting the
temperature and those systems that can release excess reaction gases (“venting”) and control the
reaction temperature instead.
Closed vessels
Traditionally, closed vessels have a safety disk that releases excess gases at a pre-defined pressure
to avoid vessel rupture. If such pressure release happens, the sample typically is lost and its
digestion has to be repeated. More advanced systems use pressure monitoring in a reference vessel
or in all vessels simultaneously, like in Rotor 8NXF100 1 and 8NXQ80 from Anton Paar. Fig. 3 and
Fig. 4 illustrate the effect of a big organic sample amount on the reaction temperature in a pressure-
limited system. Due to the pressure limitation in the 1st run the achieved temperature is about 30°C
below the desired temperature for that sample type. In a 2nd run, after adding some fresh reagents,
the small remaining amount of organic matter is digested and the high temperature achieved allows
complete digestion of also the toughest components of residual fuel oils.
1
see Table 19 on p. 49 Naming conventions for Multiwave Rotors and Vessels

Fig. 3: 1st run with 0.6 g residual fuel oil
Fig. 4: 2nd run with residual fuel oil
Closed vessels with pressure-activated venting (SmartVent)

The SmartVent technology from Anton Paar uses a mechanical pressure control system that ensures
the opening/closing to happen at a reproducible pressure level.
This release of excess pressure allows the venting of the reaction gases that account for the
pressure in Table 2, line (6). However, a venting valve cannot distinguish between reaction gases
and acid vapors. The mixture contains the reaction gases and a portion of acid vapors according to
the actual vapor pressure. This vapor pressure is strongly increasing with the temperature of the
acid mixture (see Fig. 2). It is important to avoid losses of the oxidizing reagent like HNO3, so it is

best to let most of the reaction happen at the lowest possible reaction temperature. This keeps the
portion of acid vapors the smallest possible and reduces the amount of acid loss drastically.
Fig. 5: Crude oil and marine fuel samples (NIST 1634c, DNV) in a 1-step digestion with SVT vessels
2.1.6 Problems Related to Sample Preparation
Contamination
All unwanted additions of analyte to a sample from the point of sampling to the analytical
measurement are contaminations and change the analytical result. As contamination increases the
measured amount of the analyte, it has to be avoided carefully. All tools, vessels and chemicals that
come in contact with the sample can contribute to contamination. In addition laboratory air and dust
are frequent sources of contamination.
Depending on the analytical task and the concentration level at which the analyte has to be detected
the control of contamination will include one or several of the following activities.
Table 3: Types of contamination and possible remedies
Source Type of contamination Remedy

Tools (scissors, tweezers, Elements constituting steel Change material to PTFE, quartz or any
scalpel, spatula) (Fe, Ni, Cr, Mg ….) metal that is not an analyte (W, Ti …)
Constituting elements from
Milling balls Change material
steel, WC, SiC, BN
Trace elements dissolved
Digestion vessels Change material e.g. to PTFE or quartz
from material
Adsorbed elements from
Clean vessels with similar acidic media and
previous samples
thermal program as for digestion process
(cross-contamination)
• Replace by cleaner grade acid
Liquid acids Dissolved trace elements
• Clean by sub-boiling distillation

• Reduce amount used
• Avoid solid reagents
• Replace by cleaner grade reagent
Salt and alkaline solutions Dissolved trace elements
• Recrystallize
• Replace in process or change process
• Work in dust free environment
(clean bench, clean room)
Elements constituting • Use closed vessels wherever possible
Airborne dust
aerosol or dust particles
• Cover vessels & containers
• Cover tools not used
Cross contamination • Change/clean handling tools
between sample vessels • Use closed vessel procedures
Losses of Analyte
Analyte may be lost during the analytical process at various points and due to various reasons. Not
to forget the possibility that due to improper sampling it can happen that the analyte never reaches
the analytical lab. Imagine an oil sample that may contain either water as droplets or silicon as fine
solid particles, so when taking out a sample with a pipette both of the separate phases may be
missed completely, resulting in what seems to be “losses”.
Adsorption of analyte to solid surfaces of vessel walls as well as to solid sample residues or
precipitates in the digested solution will lead to incorrect results. As a rule of thumb, elements that
are similar are more likely be lost by adsorption. Si or Al ions are lost easier on glass or quartz walls
than on surfaces like polypropylene or PTFE. Hg, in contrary will be more likely adsorbed and lost in
polymer containers. Glass or quartz walls that have been conditioned with acidic media are less
adsorptive than surfaces that were in contact with neutral or even alkaline reaction media.
Precipitation of analyte or co-precipitation of analyte traces with another ion species might occur
when digesting alloys or minerals. The concentration of dissolved substances in such samples is
much higher compared to organic material. Elements such as Pb and Ag with HCl or Ca (and other
rare earth elements) with HF are well-known combinations that lead to precipitation. Where losses
through precipitation and volatilization are concerned it also pays to consult additional sources
that list the solubility of specific salts like the one in Wikipedia 2 as additional information to
confirm information found in the tables.
Volatilization of elements and compounds, a frequently observed effect in open vessel digestion,
in dry ashing techniques and to a lesser extent even in melting procedures is, however, rarely
observed in closed vessel digestion systems. The few elements that have to be considered in this
context are mercury, arsenic and antimony. Hg, As and Sb are volatile especially as organo-
metalloids (Me3As, MeHg+) and Hg even in its elemental form. Metalloids are partly oxidized by HNO3
very readily and are significantly less volatile in their oxidized forms. In delicate cases a reasonable
suggestion for venting vessels is to try to delay the venting, i.e. by slower ramps or smaller sample
sizes. By avoiding venting in the very first minutes, oxidation processes can take place and transform
the volatile elements into more stable conditions.
2.1.7 Common Problems from Measurement

Trouble shooting with users of microwave digestion showed that many problems that have been
accounted to the digestions could actually be attributed to the subsequent measurement itself. In
2
https://en.wikipedia.org/wiki/Solubility_table

fact, a number of interferences may lead to either signal enhancement or signal reduction and hence
wrong measurement when compared to the signal of standard solutions. It is not possible to cover
these interferences here in depth as they are often instrument specific and exist with a specific
instrument only and are not observed with other brands. However, a few common effects shall be
mentioned to give an overview on what to consider on the analytical instrument’s side during method
optimization and troubleshooting.
Here is only a few of them listed to give you an idea:
• Spectral Interferences
• Sample Transport Interferences
• Chemical Interferences in ICP-MS
• Nitrous oxide reduces sensitivity in hydride generation atomic spectroscopy
2.2 Reagents
Element determination at trace and low trace levels requires very clean reagents that are produced
under very strict conditions and quality control. The more advanced the requirements for low
detection limits become, the more emphasis has to be put into additional cleaning of the reagents
and special storage provisions to maintain the low level of contaminants.
For open vessel digestions it is common to use acids like H2SO4 or H3PO4 to reach high reaction
temperatures and to add the oxidants like H2O2 or HNO3 drop wise to the hot H2SO4. However, the
high-boiling acids cannot easily be cleaned by subboiling distillation.
Table 4: Acids Used for Digestion and Their Properties
Reagent Name Properties
Nitric Acid Typical concentration: ~ 65 %, ~ 14 mol/L

HNO3 Density: ~ 1.4 g/mL
Boiling point (Bp): 121 °C
• oxidizing acid, dissolves most metals into soluble nitrates

• commonly used acid to oxidize organic material
• strong when concentrated
• stronger when used above 130°C
• above 150°C decomposes into NOx
• Au, Pt etc. cannot be oxidized
• Passivation of metals like Al, Cr, etc. can be avoided in combination with
other acids
• NOx (brown gas) dissolves readily in hot nitric acid under pressure
(blueish-green solution) but degasses quickly when diluted
Hydrochloric Acid Typical concentration: ~ 32 %,~ 10 mol/L

HCl Density: 1.16 g/mL
Bp: ~ 85 °C
• non-oxidizing, but strongly complexing acid

• highly corrosive due to its corrosive gases
• dissolves as chloro-complexes Au (II), Fe(II) or Fe(III), Sn (IV), Ti (III)
• by addition of nitric acid formation of chloro-complexes can be strongly
enhanced

• stabilizes several elements in solution (Hg, As, Sb, Se …) and can also
be added after the digestion
• destroys passivation layers
• AgCl, HgCl, TiCl are insoluble; Ag re-dissolves as AgCl-2 complex
• PbCl2 only slightly soluble, forms needles, when cooling after digestion.
Hydrogen Peroxide Typical concentration: 30 %, ~ 10 mol/L

H2O2 Density: 1.1 g/mL
Bp: 115 – 120 °C
• strong oxidant, usually combined with an acid to increase oxidizing power

• ingredient in traditional closed vessel methods when the oxidation power
of nitric acid at temperatures up to around 150 °C requires a boost. Not
necessary, if digestion temperatures above ~ 170 °C are available
• forms oxygen that regenerates HNO3.
• reacts violently with reactive organic compounds
• max. 2 mL per vessel
• not very useful in closed vessels with venting capability as most O2 is lost
with 1st venting (Rotors with HVT vessels, Rotor 20SVT50).
Hydrofluoric Acid Typical concentration: 40 %

HF Density: 1.15 g/mL
Bp: 108 °C
• non-oxidizing acid
• strong complexing activity helps dissolving many minerals, especially
silicates
• used in combination with other acids, like HNO3
• requires excess to avoid losses of volatile fluorides, like SiF4
• forms poorly soluble fluorides with earth alkaline, rare earth metals and
others
• complexing of excess fluorine requires a 2nd digestion step with saturated
(~ 5 %) boric acid to conserve glassware in ICP sample introduction
system and to re-dissolve some of the earth alkaline fluorides (like CaF2)
• solid NH4F may be used to replace liquid HF
• More info below: “Specific Aspects of HF”.
Sulfuric Acid Typical concentration: 96 %

H2SO4 Density: 1.8 g/mL
Bp: ~ 300 °C
• Destruction of organic matter by dehydration

• high boiling point and fast heating in microwave
• requires internal T-sensor to prevent overheating of Teflon at
concentrations above 50 % (Rotor 8 and Rotor 16)
• observe restrictions on use for HVT vessels
• due to the high boiling point frequently used in open vessel digestions to
achieve high reaction temperatures (in closed vessels the temperature is
not limited by the boiling point)
• forms insoluble sulfates (Ba, Sr, Pb, etc.)
• attacks and corrodes Teflon surface at high temperatures
• high viscosity may influence the nebulization efficiency.

Phosphoric Acid Typical concentration: ~ 85 %

H3PO4 Density: 1.7 g/L
Bp: ~ 160 °C
• used for digestion of minerals

• high boiling point and fast heating in microwave
• requires internal T-sensor to prevent overheating of Teflon at
concentrations above 50 % (Rotor 8 and Rotor 16)
• observe restrictions on use for HVT vessels
Perchloric Acid Typical concentration: ~ 70 %

HClO4 Density: 1.77 g/mL
Bp: ~ 200 °C
• very powerful oxidizing agent above 150 – 170 °C in high concentration

• always use other oxidizing acid (like HNO3) to remove easily oxidizable
matter at temperatures below the temperature, where perchloric acid
starts to react
• HVT vessels: Use perchloric acid only with a maximum concentration of
10 %
• danger of explosions, never apply pure HClO4 on organic matter
• very strong acid, very corrosive
Boric Acid Typical concentration: 5 % (cold saturated)
H3BO3 • used for complexation of excess free fluoride after digestion in a second
reaction step
• add 6 mL per 1 mL of remaining HF
• needs to be purified by re-crystallization
• slow washout behavior in glass or quartz spray chambers
• adds a lot of dissolved salts to the solution, which may cause spectral
interferences in analytical instrumentation
2.2.1 Specific Aspects of HF

As can be seen above, HF is a very potent but also toxic agent. As its usage requires specific
precautions, many companies avoid or ban the use of HF. This limits the ability to successfully
dissolve samples containing silicates. The risks of transportation of HF as a liquid can be avoided
by using NH4F as a solid reagent. The disadvantage is the higher contamination risk of a solid
reagent as compared to HF, which is available in high purity grades. Once the NH4F is dissolved in
another strong acid, it forms HF and has to be treated like HF (complexation, first-aids equipment
etc.)
To estimate the amount of HF necessary for dissolution, take about 0.4 – 0.5 mL of HF for each 100
mg of SiO2. If NH4F is used, take ~1 g of NH4F plus 1 mL of H2O for each mL of HF.
Sometimes the use of fluoroboric acid (HBF4) is suggested to release the fluoride required to dissolve
the silicates so no precipitation of alkaline earth fluorides will occur. Use 1.2 – 1.5 ml for each ml of
HF. However, as the purity of this substance is not certified for element analytical purposes
contamination control is required.

For complexation of free fluoride use 6 mL of boric acid for each mL of remaining HF. If considerable
amounts of Si in the sample consume free HF, try to reduce the amount of boric acid required for a
clear solution.
The amount of HF and the amount of boric acid are rough estimates. If precipitates remain after the
complexation step, the amount of both reagents (HF and boric acid) to higher and to lower values
have to be optimized. In many cases also the addition of water reduces the formation of precipitates.
In geochemical applications when the amount of HF used is high and large amounts of dissolved
solids would be necessary for the complexation the evaporation of HF is a helpful alternative.

3. How to Start Method Development
This chapter is a guideline on how to approach method development or method optimization issues.
Read how to access and use available application knowledge, understand the available sensors and
make best use of their signals to interpret your run data in the course of method optimization or
method development. Finally read about your possibilities to use the chemistry to influence the
reactivity of a digestion process.
No analytical chemist wants to change an established method in his laboratory without reason.
However, there are several causes that make changes to existing methods inevitable or desirable.
The following paragraphs intend to help finding a quick path to a new or improved method. This
section only covers the acid digestion aspect of method development, it has to be complemented by
the appropriate optimization and validation of the analytical method for which the sample preparation
is made.
New sample type
1. Define your analytical task

• elements
• instrument’s LODs (limit of determination)
• required quantification level
• expected sample concentration
• required volume of digested sample for analysis, acid concentration allowed
• required sample weight
2. check literature for relevant regulations, standards
3. look for sample type in our method collection, or the methods supplied with the instrument
4. compare with task definitions and see where changes are necessary or where optimization
is possible
Changes to the analytical task, like new elements of interest, lower/higher detection limit
requirement, new regulatory requirements
1. Re-define analytical task. Check if any of the changes may lead to

• simplifications
• reduction/increase of reagents, acids
• reduction/increase of sample weight
2. use established method as starting point for optimization
New analytical instrumentation available
1. Re-define analytical task

• compare LOD’s of old/new instrument
• recalculate weight of sample required
• determine required volume of digested sample for analysis
• limitations for acid concentration
2. changes to the calibration procedure, composition of standards
20/53 3. How to Start Method Development E38IB016EN-

3.1 Access Application Knowledge
Check Application Collection for Multiwave 5000

The application experts at Anton Paar are collecting their experiences from treatment of user
samples for more than 25 years. The result is a collection of methods for several hundred samples
that is available as a pdf file named “Application Collection for Multiwave 5000”3. The complete
application collection is pre-loaded in the method library of Multiwave 5000.
3.2 Consider Standard Methods

For many analytical tasks there exist standard methods, which have to be used by laboratories that
generate data that is used for regulatory purposes in environmental analytical chemistry. Old
standards sometimes state power programs for microwave digestion without mentioning the
temperature which is expected for digestion. Nowadays many new standard methods for sample
digestion define programs with temperature corridors.
For Multiwave 5000 an Application Report (E38IA013) was published which references a list of
important standard methods in tabular form and shows the compliance of Multiwave 5000. Please
contact your Anton Paar representative to receive the application report.
Table 5: List of common Standard Methods
Number Title Typical Samples
Aqueous samples, drinking

Microwave assisted acid digestion of aqueous water, mobility-procedure
EPA 3015A
samples and extracts extracts, wastes that contain
suspended solids
Microwave assisted acid digestion of sediments, Sediments, sludges, soils and

EPA 3051A
sludges, soils, and oils oils
Ashes, biological tissues, oils,

Microwave assisted acid digestion of siliceous and
EPA 3052 oil contaminated soils,
organically based matrices
sediments, sludges and soils
Sample Digestion Using Closed Vessel Microwave

ASTM D4309-02 Surface, saline, domestic, and
Heating Technique for the Determination of Total
(2007) industrial wastewater
Metals in Water
ASTM D5258-02 Acid-Extraction of Elements from Sediments Using

Soils and sediments
(2007) Closed Vessel Microwave Heating
Coal, coke, cement raw feed

materials, and waste-derived
ASTM D5513-99 Microwave Digestion of Industrial Furnace
fuels; also fly ash, foundry
(2009) Feedstreams and Waste for Trace Element Analysis
sand, alum process residue,
cement kiln dust, etc.
Sample Decomposition Using Microwave Heating Petroleum products and

ASTM D7876 (With or Without Prior Ashing) for Atomic lubricants, fossil fuel products,
(2013) Spectroscopic Elemental Determination in coal, fly ash, coal ash coke, oil
Petroleum Products and Lubricants shale
3
E38IA046EN Application Collection Multiwave 5000
E38IB016EN-C 3. How to Start Method Development 21/53

Number Title Typical Samples
Characterization of sludges - Determination of trace

EN 13346 (S7a) elements and phosphorus - Aqua regia extraction Sludges
methods
Characterization of waste - Microwave assisted

digestion with hydrofluoric (HF), nitric (HNO3) and
EN 13656 Various types of waste
hydrochloric (HCl) acid mixture for subsequent
determination of elements
Characterization of waste - Digestion for subsequent

EN 13657 determination of aqua regia soluble portion of Various types of waste
elements in waste
Stationary source emissions - Determination of the

EN 14385 total emission of As, Cd, Cr, Co, Cu, Mn, Ni, Pb, Sb, Filter (quartz, glass or PTFE)
Tl and V
Ambient air quality – Standard method for the

EN 14902 measurement of Pb, Cd, As, and Ni in the PM 10 Filter
fraction of suspended particulate matter
EN 15297 Solid biofuels - Determination of minor elements Solid biofuels
Solid recovered fuels - Methods for the

EN 15411 Solid recovered fuels
determination of the content of trace elements
Water quality - Digestion for the determination of

EN ISO 15587-1 selected elements in water - Part 1: Aqua regia Water
digestion
Water quality - Digestion for the determination of

EN ISO 15587-2 selected elements in water - Part 2: Nitric acid Water
digestion
CPSC-CH- Determining Total Lead (Pb) in Metal Children´s

Children´s metal products
E1001-08.2 Products (Including Children´s Metal Jewelry)
Children´s siliceous (A) and

CPSC-CH- Determining Total Lead (Pb) in Nonmetal Children's
non-siliceous (B) nonmetal
E1002-08.2 Products
products
CPSC-CH- Determining Lead (Pb) in Paint and Other Similar

Paint, painted surfaces
E1003-09 Surface Coatings
Foodstuffs - Determination of trace elements –

EN 13805 Foodstuff
Pressure digestion
Lead, Cadmium, Zinc, Copper and Iron in Foods -

Foods with a fat content
AOAC 999.10 Atomic Absorption Spectrophotometry after
< 40 %; no milk powder
Microwave digestion

Standard procedures go through a long process of discussion and validation and contain numerous
rules for its application. Be sure to use the right standard and be sure to use it correctly. Read the
standard not only the implemented method. The standards allow different grades of flexibility. As
example:
• EPA 3015a: often a sample volume of 45 mL is stated as a requirement by the

standard, but it is in fact a recommendation and only true for instruments that rely on
power calibration for the programming of the method. If temperature programming is
available the recommendation of the sample volume is no longer important as long
as the differing dilution factor is accounted for4.
• EPA 3051a vs. EPA 3052: EPA 3051a is a standard that relies on partial, but
reproducible, acid extraction of trace metals and requires a very strict temperature
corridor and allows only a very limited choice of acid mixtures. Specifically it refers
samples with too high reactivity to be treated according to EPA 3052, which is a
method that aims at a complete dissolution of all environmentally and toxicologically
relevant forms of the trace metals. It allows a much wider choice of acid mixtures and
has a much less strict temperature program than EPA 3051a.
3.3 Work with Pre-loaded methods or Generic Applications

Since the introduction of the SmartVent Technology the concept of Generic Methods has been
added. Now the user software of Multiwave 5000 makes all this knowledge available with an
integrated and sample-centered approach that allows full-text searching and finding useful methods
for all installed rotors with sample tags like “apple” or “aluminiumoxide”, but also with sample
categories like “food”, or “polymers”. These entries serve as a starting point in combination with your
own knowledge and experience.
Besides specific applications we offer so called “generic methods” for broader groups of samples.
The reactivity in combination with the digestion acid mixture being one of the most relevant
parameter for a digestion method, there are generic methods for reactive and for inert samples.
Based on these, some methods were saved with minor modifications in the power or temperature
program or in the acid mixture for specific sample categories. The following chapter gives hints on
how to work with these methods as starting points and what to consider, when modifying these
generic methods.
3.3.1 Care about sample reactivity

For closed vessel digestion a high reactivity generally means that the reaction generates either
pressure by reaction gases or temperature (reaction energy) which further boosts the reaction. In
addition to the sample type also the amount of sample, its reactive surface (particle size or mixing)
the heating rate and the reagent mixture will affect the behavior of the digestion reaction.
For most rotors limits or recommendations of maximum sample weight for different sample
categories are given in the respective manual. In some cases there exist recommended and
maximum values. Be sure to understand, that the lower, recommended values will result in a trouble-
free operation most of the times, while the maximum only can be reached in favorable cases and it
is recommended to try to reach these sample sizes only step wise.
See the following chapters on sensors to understand their function and how to use their
signals to get information about the reactivity of your specific samples, and how to use
4
EPA Method 3015 a (Feb. 2002), §4.2: “When warranted by the potential reactivity of the sample, a smaller sample size
may be used, and the concentration for final calculations adjusted, but a final water volume prior to addition of acid(s) of
45 mL is recommended. A volume of 45 mL is recommended in order to retain the heat characteristics of the calibration
procedure (if used).“

chemistry to reduce the reactivity, if necessary and also to increase, if the specifc sample is
less reactive than expected or desired.
Table 6: Examples of potentially highly reactive samples
Sample type Examples
petroleum fuels, raw oil, marine fuels
fat oil, fat, grease
polymers
carbohydrates sugars, starch, cellulose
organic solvents alkanes, alcohols, ethers …
alcoholic beverages wine, spirits
Special care for sample types shown in Table 6 is necessary because of the known high reactivity .
This list contains a few examples to give you an idea; however, it is not complete and does not
include any effects in mixtures.
• Unknown samples have to be treated as very reactive for the first experiments until
their reactivity is tested and known.
• In mixtures the amount of the reactive components is important for the overall
reactivity. Interactions between components are also possible.
• Check the rotor’s manual for any limitations about sample weight for sample
categories.
• When using a power program, for partially loaded rotors the power setting should be
decreased according to the number of vessels. For this reason several versions of
methods for different vessel numbers are offered for power programs.
• During method development in Rotor 16 it is necessary to use p/T- Sensors for
pressure and temperature monitoring.
3.3.2 Reactive Samples

Rotors with HVT vessels
For Rotors 24HVT50, 24HVT80, and 41HVT56 the generic methods are temperature programs. For
these rotors Multiwave 5000 can use the IR sensor or the optional SmartTemp sensor for internal
temperature control. The SmartVent technology allows safe overpressure release of reaction gases
during a digestion. Higher temperatures for larger sample sizes can be reached than possible with
closed vessels without SmartVent technology having the same pressure limit or even higher
pressure limits. The venting should be moderate and should happen at the lowest possible
temperatures to avoid losses of digestion acid required for further reaction.
It is recommended to start with generic method Organic A, which uses a moderate ramp to 180 °C
and a hold step. Start with a sample weight of 300 mg that will eventually start the venting action
during the ramp and show some exothermic reaction. In the following and Table 8 only the method
for Rotor 24HVT50 is shown, however, the generic methods for the other rotors with HVT vessels
are the same.

Table 7: Method ".Generic-Reactive 24HVT50".
Step Ramp [min] Setpoint (T) Hold [min] Fan Stirrer
1 20 180 °C 10 1 Off / Low / High

2 70 °C 3 Off / Low / High
If, at higher sample weight, the venting action becomes too strong, switch to method Organic B,
which is a method with a hold step at lower temperature. Check the run data for the Organic A run
to determine the temperature at which the exothermic reaction starts. Use this temperature as set
point for the first ramp/hold step. When the temperature is increased from the default value of 100 °C,
also shift some ramp time from the 2nd ramp to the 1st ramp to maintain the slope of the ramps.
Table 8: Method ".Generic-Organic B 24HVT50", the parameters for the 1st setpoint have to be adapted according to the reaction
characteristics.
1 10 100 °C 10 1 Off / Low / High

2 10 180 °C 10 1 Off / Low / High
• Also the length of the pre-reaction step should be adapted to the progress of the reaction.
o A slow increase in the power curve indicates that the exothermic pre-reaction is
completed.
o If this does not happen during the hold phase of the pre-reaction step, make it longer.
• Reduce the sample amount if the acid losses during digestion are inacceptable high.
o Limit of tolerance can be objectively defined by finding the point where a decrease of
recovery of elements of interest becomes too big.
o Most users would not accept losses above 3 – 5 ml from a starting volume of
10 – 15 ml acid mixture.
• If the reaction only occurs at 150 °C or above, the pre-reaction steps loses its effect, as
significant amounts of acid vapors will be lost during venting.
• Observe pre-reactions and let them cool-down before closing the vessel and starting the
reaction. This delays the time of first venting.
Rotor 20SVT50
For reactive samples a similar method as for the HVT rotors is pre-loaded, with only a slightly higher
target temperature of 200 °C. This can readily be used for easier to digest organic samples like food,
feed, plants, but also for polyolefines and similar polymers and petroleum products that do not
require high digestion temperatures.
As the prime targets of 20SVT50 are difficult to digest samples that require a high final digestion
temperature, the strategy is somewhat different for samples like mineral oils of all types, especially
those that contain higher amounts of condensed aromatic structures or resins and polymers with
content of aromatic structures. In a slow ramp to 220 °C the larger part of reactive compounds in the
sample should be attacked and digested. This main reaction will be completed during a hold step at
220 °C, during this time most of the generation (and venting) of reaction gases happens at
temperatures that avoid losing too much acid. This saves a reasonable amount of oxidant for the
final high-temperature step that helps to destroy even the most resistant organic compounds.

Table 9: Method “Polymer hi” for high temperature digestion of organic compounds
1 5 90 °C - 1 Off / Low / High

2 25 220 °C 10 1 Off / Low / High
3 5 240 °C 15 1 Off / Low / High
4 - 70 °C - 3
Rotor 8
Rotor 8 is the ideal tool for method development with unknown samples. The availability of a fast
sensor system to measure the maximum pressure and the pressure increase rate of all vessels
continuously at the same time offers utmost safety and insight into the reaction progress inside the
reactor.
Fig. 6: Generic Power Program for Rotor 8. Example run data to the right: green curve is pressure, blue curve is microwave power
In Fig. 6, in the right graph one can observe that the reaction of the hydrocarbon sample starts after
about 10 minutes (green pressure curve), continues at a relatively constant rate until the power ramp
drives the temperature up. Shortly before the pressure limit of 60 bar is reached the power is
automatically reduced to not exceed the pressure limit. Depending on the properties of the sample
the conditions may have to be optimized to achieve the best possible results, the following
considerations may help:
• For reactive samples start with a small sample amount of up to 100 mg.
• Power-hold-step instead of ramp for pre-reaction step establishes a moderate heating
that allows the pre-reaction of the bulk of organic matter to run smoothly and build up
the reaction gas pressure in a linear way.
• If you need to know the internal temperature, use the T-Probe as a T-monitor also for
a power program. In this way you get information about inner temperatures (see
3.7.1).
• Carefully study the pressure curve to see any pressure spikes/steps (i.e. Fig 1, right
at about 10 min) during the reaction (see 3.7.1). If no spikes occur or if the pressure
increase is low or moderate and only starts at higher temperatures, the power level
for the pre-reaction step needs to be increased, to let the main reaction start already
at moderate temperature.
• If the pressure increase rate alarm occurs during the pre-reaction step reduce the
power setting of step 1.
• When, during the pre-reaction step, the slope of the pressure increase curve levels
off, the main reaction at this temperature is complete.

• If the curve doesn’t level off and/or there is a pressure increase rate warning/alarm in
the next ramp step, increase the hold time of the pre-reaction step.
• Find required temperature to define IR limit (see 3.7.1).
• For sample weight optimization see 0.
Rotor 16
The generic methods for reactive samples do not require using a p/T sensor. But in order to have
pressure control during the digestion process at least a p-Sensor is recommended. However,
method optimization is not possible without at least a p-sensor, even better use a p/T-sensor. The
generic methods for Rotor 16MF100 and 16HF100 follow the same scheme as shown in Fig. 7.
Fig. 7: Typical generic program for reactive samples in Rotor 16 (16HF100, 12-16 vessels)
• Make sure that the reference vessel with the p- (or p/T) Sensor Accessory is the one
where the strongest reaction and the highest pressure can be expected. This can be
achieved by reducing the sample weight in the other vessels.
• Start with the generic method and with the minimum sample weight specified in the
sample weight recommendation of the method, which is 100 mg for Rotor 16MF100
and Rotor 16HF100.
• Optimize/increase power levels and/or sample amount in small steps.
• If a pressure increase rate warning/alarm occurs during the ramp, reduce the target
power and/or increase the ramp time. Limit the maximum IR temperature limit to
improve the control of the reaction in all vessels for routine operation.
3.3.3 Inert Samples

For inert samples the overall aim is to heat the sample quickly to a high temperature to allow the
reactions to proceed more quickly.
Inert samples are minerals, ceramics, ores but also the more corrosion resistant metals and alloys.
Many of these samples require high temperatures without producing too high pressures and are best
digested in Rotor 8NXF100 or Rotor 20SVT50, especially when HF is required in the acid mixture.
Apart from the higher temperatures they often require specific acid mixtures for complete reaction.
If the reaction with the generic method is not complete, check the methods for similar samples in the
Classified List of Applications. If sulfuric or phosphoric acid are used at concentrations above 50 %
the use of a p/T sensor is highly recommended to avoid overheating of liner material.
A second big group of inert samples are soil and sludge samples for environmental analysis. These
samples normally don’t need complete digestion, but rather a complete, or even only a partly, but
reproducible, extraction of analyte metals from the sample matrix. The matrix often contains silicates,
which are hardly soluble without HF. For these samples standard methods exist that only require
moderate leaching or digestion temperatures.

For all digestions the reaction rate increases with increasing surface area, which means that smaller
particle size will improve the quality of the process.
Rotor 24HVT
HVT vessels are well suited for routine environmental samples, venting is not necessary and not
desired in this case. Most reactions with inert materials do not produce gases, so it is mainly the
vapor pressure from the acid mixture that defines the pressure inside a vessel.
Table 10: Method ".Generic-Inorganic 24HVT50" is similar to common leaching methods from standard procedures.
1 10 165 °C 10 1 Off / Low / High

In many cases the use of the provided standard methods (see 3.2, p. 21) is preferred.
Rotor 8NXF100, 8NXQ80
The applied power of a power program will remain at the programmed level until one of the limits for
the pressure, the pressure increase rate or the IR temperature is reached and reduces the power
input. This guarantees the highest possible temperature to be reached safely.
Table 11: Method ".Generic-Inert 8NXF100" for 4/8 vessels respectively. Apart from the predefined rotor limits the method for
Rotor 8NXQ80 is identical.
Step Ramp [min] Setpoint (P / T) Hold [min] Fan Stirrer
1 5 900/1200 W 35 1 Off / Low / High

Rotor 16MF100, 16HF100

Table 12: Method ".Generic-Inert 16HF100" for 4/8/16 vessels respectively. To achieve the desired heating rate the methods are kept at
higher power settings for a longer time.
Step Ramp [min] Setpoint (P / T) Hold [min] Fan Stirrer
1 5 1100/1500/1500 W 0/5/10 1 Off / Low / High

2 0 300/400/450 W 25/20/15 1 Off / Low / High
3.4 Limitations from Vapor Pressure

Vapor pressure is a physical property of a substance that increases with increasing temperature.
When the vapor pressure is equal or bigger than the surrounding pressure, the liquid boils and
evaporates. Low boiling liquids add more to the pressure than high boiling liquids. Vapor pressure
is not dependent on the amount of liquid present in the vessel. So, the only possibility to influence
and reduce the contribution of vapor pressure is to select acids with reduced vapor pressure.

To reduce vapor pressure in closed vessels like XF or HF, high boiling acids like H2SO4 and H3PO4
can be added to the acid mixture. The reduction of vapor pressure will allow a higher final
temperature. However, these acids may cause interferences during measurement and also
precipitations with matrix components of inorganic samples. It is often better to select a vessel
system with higher pressure rating and avoid the addition of interfering acids.
3.4.1 Vessels with SmartVent Technology (HVT and SVT Vessels)

For SmartVent vessels adding high-boiling acids has less effect. The concentration of the low-boiling
acid will be higher in the vapor and with every venting the low-boiling acid will disappear. Both acid
vapors and reaction gas add up to the internal vessel pressure. To avoid acid venting and corrosion
observe the limits given below
Table 13: Temperature limits for rotors with HVT and SVT vessels to avoid acid venting
Internal Temperature Limit [°C] HVT SVT SVT

T-Limit 5 rec. max. Target6 T-Limit
HNO3 conc. 205 230 250

7
HNO3 with H2SO4 205 250 260-270
HNO3 with HCl or HF 185 230 250
HCl 185 230 250
When a digestion produces reaction gas, this adds to the internal pressure. During venting the
excess pressure can then be released without the need to reduce power and temperature. See also
ch. 4.6.1 on how to control acid venting.
3.4.2 MF, HF, X Vessels

In closed vessels without venting capabilities the pressure contributions from decomposition
reactions and the vapor pressure together add up to the total pressure inside the vessel, which must
remain equal or lower than the pressure limit. Reducing the pressure generated by the liquid allows
• to reach a higher final temperature when the sample amount is constant, or

• to increase the sample amount, when the target temperature is kept constant.
3.5 Sample Weight vs. Pressure vs. Temperature

For acid digestion in closed vessels without venting capabilities (i.e. all MF, HF and X vessel types)
there is a strict correlation between sample weight and pressure and as a consequence with the
temperature that can be reached.
If the pressure limit in one of the 8 vessels in Rotor 8N or in the reference vessel (Rotor 16MF100
or 16HF100) is reached, the temperature cannot be further increased as the pressure limit would be
exceeded. As result the microwave power input is reduced to keep the pressure value at or below
the limit. As a consequence of the reduced power input the temperature and pressure in the other
vessels is stable.
5
‘T-Limit’ is the parameter to be defined in the method for the highest allowed temperature for any vessel in the rotor.
6
‘Target’ is the max. recommended temperature to be used in methods with control mode AVG.
7
A vessel operating at higher than target temperature will wear out faster, a lower T-limit will prevent fast ageing.

In Table 1 on p. 11 a few reaction examples that generate gaseous products are given, out of them
the reaction of organic carbon with HNO3 is the most important and causes most of the gas
production in the digestion of organic matter in samples.
To reduce the pressure from reaction gases, the sample weight has to be reduced. If the amount of
sample is halved, the pressure contribution by reagent gases is also halved. If the digestion
temperature is not high enough to achieve a satisfying quality, the sample amount can be reduced
until the digestion quality is sufficient.
If the pressure limit is not reached and the temperature is at its highest, the sample amount can be
increased stepwise until the pressure limit is reached and the final temperature is reduced to a level
that yields in incomplete digestion.
3.6 Power vs. Temperature Programming

Temperature programs offer significant advantages compared to power programs. That is the
reason, why for the SmartVent rotors with HVT and SVT vessels, temperature-controlled programs
were introduced as norm.
If the user wants to control the digestion process with a temperature program, the use of an internal
temperature control (see 3.7, p. 31) with a p/T Sensor for Rotor 16MF100, and 16HF100 or a T-
probe for Rotors 8NXF100 and 8NXQ80 is required. An exothermic reaction occurring during the
heating ramp can be observed when the temperature increases above the preset temperature even
at reduced microwave power. This can be controlled with very short reaction time by reduction of
microwave power and if needed by increasing the vessel cooling.
If such a sensor is not available, only power programs can be used. The temperatures for all vessels
are still monitored via the IR sensor.
Advantages of temperature programs:
• direct control of the most important reaction parameter

• more responsive reaction control
• transferable from one system to another system
• independent of the number of vessels in the rotor.
Important points for power programs
• Make sure there is a valid microwave power calibration of the Multiwave 5000.
• Make sure that the power program provides an appropriate heating rate for the type
of sample to be digested. This is uncritical for inert samples, but for reactive samples
the use of a p/T Sensor is highly recommended at least during method development
phase.
• Power programs are not transferable to other systems (e.g. from different suppliers).
• Limit the maximum power according to the number of vessels
• For all rotors there are recommended values in the software for different vessel
numbers. These values can be increased, if the expected heating performance is not
reached.
• For HVT rotors it is especially important to limit the maximum temperature according
to the acids used (see Table 13).

3.7 Understand the Use of Sensors
Modern digestion systems offer a number of sensors for reaction control. This section shall help you
to understand the use of the sensors and to interpret the signals for better use of the run data in
method optimization and trouble shooting.
For improved data handling and preparation of graphs use the run data which is available for export
from the instrument as .csv, and .xls.
Basic facts and limitations
• A sensor will always be active to monitor and act on the limits set in the method. So
a T-sensor will react on the reaching of the internal temperature limit as set in the
method, even, if the method is a power controlled one.
• A reference sensor checks the vessel in which it is put in. So a p/T Sensor will monitor
and react on the reaction in the reference vessel and not on reactions in the other
vessels.
• It is important to have the most reactive sample, i.e. that will generate the highest
pressure in the reference vessel to make sure that no overloading and/or overheating
occurs in one of the other vessels.
Table 14: Differences in sensor data availability for different rotors and sensors
IR temperature
Rotor p-Sensor T-Sensor
sensor
Internal T-control 8 on Mechanical p-control9

Rotor 24HVT n/a
all vessels on all vessels
Inner IR sensor
(Standard IR or Mechanical p-control
Rotor 41HVT56 n/a
SmartTemp IR) on all vessels
required
Internal temperature
Mechanical p-control
Rotor 20SVT50 control on all vessels n/a
on all vessels
via SmartTemp
Rotor 16 MF/HF All Pos. 1 Pos. 1
Rotor 8 XF/XQ All All (max. value)10 Pos. 1
16/64
Rotor 64MG5 n/a n/a
outer vessel of 4
The availability of process data is different for the various rotors in Multiwave 5000.
SmartVent Rotors with HVT and SVT vessels: Full process control by sample temperatures of all
inserted vessels. Different T-control strategies can be used according to the user’s needs.
8
Either with standard IR sensor or with SmartTemp IR sensor (optional)
9
Overpressure relief valve in screw cap
10
Integrated in all Rotor 8NX upper plates

Rotor 16: Full process control by the p/T Sensor is available for vessel 1 as a reference vessel. It is
recommended to pool or group very similar sample types for a common digestion run. If samples of
different reaction behavior are mixed, it is important to place the sensor in the sample that will
generate the highest pressure (e.g. the sample with the highest weight).
Rotor 8NX offers
• monitoring of all vessels with the IR temperature sensor,

• a permanent monitoring of the highest of the pressure in all 8 vessels,
• a fast and sensitive internal temperature reading in the reference vessel 1.
For most purposes, especially in routine operation the IR temperature values and the pressure
control are sufficient for a safe operation with even highly reactive samples.
3.7.1 IR Temperature Sensors
Fig. 8: Scheme of IR temperature sensor viewing the bottom of vessel
The IR temperature sensor (see Fig. 8) allows adding valuable temperature information on more
than the reference vessel for reliable process control and documentation of results. There are several
differences to an immersion temperature measurement as mentioned below.
• The response time on fast temperature changes i.e. from exothermic reactions is
slower compared to an immersion temperature sensor.
• The magnitude of the temperature gap between the IR temperature and the internal
temperature is depending on the vessels’ material:
o For ceramic vessels the gap is ~ 25 °C, for MF100 vessels ~ 20 °C. The gap
can be influenced by diffusion-based input of reaction gases (NOx, HCl, HF
etc.) into the material, which will increase the self-heating of the vessel
materials (see also 4.2 on p. 43).
o Quartz vessels show a gap of ~ 50 °C.
• The IR temperature limit is monitored for all vessels that are measured by the sensor.
Approaching the temperature limit will cause the controller to reduce the applied
microwave power. If the IR temperature limit is significantly exceeded, the process is
aborted and safety cooling starts.
Internal Temperature control for SmartVent vessels

For HVT and for SVT vessels temperature control based on the internal vessel temperatures
measured with an infrared sensor is available.

The standard IR sensor described above is sensitive in the far IR and measures the surface
temperature of the vessel. The combination of the relatively thin-walled HVT vessels with the
SmartVent pressure release allows to control the internal vessel temperature.
In addition a SmartTemp sensor is available as, which uses a shorter IR wavelength for temperature
measurement. In this wavelength range PTFE offers a much higher transparency for infrared
radiation, so most of the measured radiation comes from the sample inside the vessel and allows
faster response and better process control even for very exothermic reactions.
This sensor is required for the SVT vessels and can optionally also be used for HVT vessels with
faster temperature response for reactive samples.
The software allows different temperature control strategies that can be based on:
• AVG: Average, running average of one revolution of the present vessels. The
microwave power will be regulated by the average temperature of all samples. This
is the recommended mode for similar and for variable samples containing organic
matter. Also for EPA methods that require reaching a temperature corridor this
strategy is recommended. Using this control strategy the sample temperatures will be
above, below or equal to the target temperature.
• MAX: Maximum, highest temperature value of all positions. The microwave power will
be regulated by the maximum temperature of all samples. This control strategy is
recommended when a certain temperature must not be exceeded, for example, when
venting of HF has to be avoided completely. Using this control strategy all sample
temperatures are equal or lower than the target temperature. If there is a “dominant”
sample, the power introduction will be limited by this sample and the other samples
will be cooler than the target temperature.
• MIN: Minimum, lowest temperature value of one revolution. The power introduction
will be regulated by the minimum temperature of all samples. This control strategy
may be used to avoid that any sample falls below a specific temperature. Using this
control strategy all sample temperatures will be equal or higher than the target
temperature.
Especially for the AVG and MIN temperature control strategies the Internal Temperature Limit should
be set to the recommended values (see Table 13 on p. 29) to avoid unwanted strong venting of
digestion acid. When a vessel reaches the temperature limit, the controller behaves as MAX
controller (all sample temperatures will be equal or lower than the temperature limit).
3.7.2 Pressure Sensor

For Multiwave 5000 a pressure sensor is available …
• as p-sensor and as p/T Sensor (Fig. 9) measuring in one reference vessel for Rotor
16,
• as p-sensor, which is built-in into the top plate of each Rotor 8NX (Fig. 10), measuring
the pressure in the vessel with the highest pressure.
• For SmartVent vessels there is no pressure sensor, the vessels are equipped with an
autonomous mechanical pressure limiting overpressure-release valve, so there is no
further need for pressure measurement and software operated pressure control.
The pressure sensor in Multiwave 5000 is an active safety device by limiting the vessel pressure to
the maximum operating pressure. In addition it is possible to avoid too high reaction rates by
measuring the pressure at a rate of 50 measurements per second and reacting within fractions of a
second by reducing the power and if necessary by maximizing the cooling.

Fig. 9: Scheme of p/T Sensor for Rotor 16. Fig. 10: Scheme for pressure sensor system in Rotor 8.
Via the hydraulic transfer line the vessel pressure is transferred to The pressure sensor is connected to all 8 vessels and detects the
the sensor and transferred to the Multiwave electronics with an IR highest pressure of all vessels.
link. For a p-Sensor the immersion thermometer and the PEEK
transfer tube is not present.
For reaction control two controllers are implemented. A pressure limit controller and a pressure
increase rate controller. For both, limits can be defined in the method.
• A user defined “Max. Pressure increase rate” between 0.3 and 0.8 bar/s can be used
to reduce the microwave power quickly to avoid a runaway of the reaction.
• At a pressure increase rate of more than 0.8 bar/s the “Pressure rate alarm” takes
away the microwave energy immediately and switches on cooling temporarily aiming
to quench the reaction and to regain control in order to continue the digestion process.
• The activated “Pressure rate alarm” is showing a pop-up message during the run and
is also showing a warning message in run details on screen and in the report.
• In the list of “Controllers active during process” the “Pressure rate controller” activity
denotes as “r”, the “Pressure rate alarm” as “R”.
The activity of the Pressure increase rate monitor can be displayed:
• During a run in the field “Controller Status” on the far right side of the screen, if you
slide the graph to the left. Whenever “r” is displayed by the widget, the pressure
increase rate is so high that this controller is currently limiting the microwave power.
When the “R” character displays, the pressure increase rate is currently above
0.8 bar/s and temporarily the safety cooling is switched on and the magnetron power
is switched off until the pressure increase levels off again.
• In the run data file there is also a column for pressure and the pressure increase rate,
which allows tracking the temporal evolution of the pressure curve.
3.7.3 Immersion Temperature Sensor

The immersion temperature sensors for Rotor 16 and for Rotor 8NX offer a very responsive and
direct temperature control in a reference vessel that allows a very good process control. It should be
kept in mind that
• the immersion thermometer reacts quickly and shows even fast changes in the
reference vessel,
• in vessels without immersion sensors the temperature is monitored via the IR sensor,
• if H2SO4, H3PO4 are the main acids (more than 50 %) in the reaction mixture an
immersion temperature sensor is necessary (p/T Sensor or a T-probe).

3.8 Assess Digestion Results
The best way to interpret digestion results is to verify the results with the analytical instrument in use
by digesting and measuring Standard Reference Materials (SRMs).
Be sure to use all available information about the sample composition when you try to assess any
residues or fresh precipitates of a digestion.
3.8.1 Organic Material

A digestion is successful and good, if the measuring instrument in use can do the analysis and the
results are good (check with SRMs). So the quality assessment depends on the analytical setup. It
is well known that techniques like inverse voltammetry are very sensitive to residual carbon content,
while flame or especially graphite furnace atomic absorption are not. It is also known that ICP-MS is
not as tolerant to high matrix loadings as is ICP-OES. But even between two brands of the same
technique there may be significant differences.
A bluish-green color is a sign of dissolved NOx in nitric acid. It can be very intense after a high
pressure digestion with Rotor 8, but it will be less intense in lower pressure vessels. After dilution
with water and with time the nitrous oxide escapes and the color vanishes. As long as the digestates
are watery liquids, i.e. without foaming or oily residues, the color may vary from colorless to orange
without having a bad influence on the measurement.
Table 15: Digestion results and their interpretation
Observation Comment
May be heavy organic residues from incomplete digestion. When diluted

with water, typically white clouds occur.
• If all replicates of same sample look similar, the oxidation was

Yellow-brownish, oil insufficient.
swims on acid • If only one of the replicates is affected and others are ok then
check vessel for tightness. A pressure loss may prevent the vessel
from reaching the same temperature as the other vessels. This
can be seen in the temperature traces of the report or in the run
data file.
• Can happen when too much HCl is in the acid mix, like aqua regia
in organics-rich soil. Change to inverse aqua regia for better
digestion of organic matter.
Black oily residue • Swimming sample may have caught fire inside the vessel. If so,
traces of black soot can be seen in the liner above the liquid level.
The PTFE wall may also be attacked having melting signs. Check
with flash light for damaged patches. Replace liner and in case of
a HVT vessel, check also the seal surfaces for damages.
May result from graphite content of the sample. Either a digestion rotor
with can achieve higher digestion temperatures may solve this problem
Dark grey or black
or, if this happened in a Rotor 8, a second digestion run with addition of a
fine sediment
small amount of HClO4 (up to max. 10 % of the total liquid volume) can
be performed.
Fine white Silicate content of plants and other organic materials. Can be dissolved
sediment, white gel- by, or be invisible as a sol in concentrated acid, but silicate can precipitate
like sediment after dilution and with time. A sol or gel may adsorb ions from the solution
and reduce recoveries. Add HF or NH4F to dissolve silicate, if necessary.

Observation Comment
Depending on the analytical task it sometimes is sufficient to filter off

crystalline sediments as they most likely will not contain any analyte after
acid digestion.
3.8.2 Inorganic Material

For organic matrices the aim is to convert as much of the matrix carbon as possible into CO2, which
finally disappears from the sample. For inorganic samples this is not possible, most of the dissolved
substances from the sample remain in solution together with the reagents and there are many
chances for interactions between all these components. In case of residues or precipitation, it is very
important to know and consider all the major and minor components of the sample. Due to the
multitude of possible combinations, a generalized guideline of action is impossible. The main
suggestions for interpretation of digestion results are:
• Residues from the original sample will have a more crystalline structure than fresh
precipitates from the digestion or dilution.
• Undissolved silicates will preserve their structure, but may lose their yellow or brown
color due to the leaching of the colorant ions (like Fe3+, Cr, Cu, …).
• Freshly formed precipitates with very low solubility will be very fine or cloudy.
Sometimes they form during the dilution with water.
• Some precipitates form during cooling or even afterwards. Salts with a slightly higher
solubility, like PbCl2, will even form needles when standing over night. Others like
solubilized SiO2 may only show as a hazy fog, which settles as a gel-like mass, which
converts to a white sediment after a while.
• In metal digestions sometime very fine grey particles of different shades sediment
first, followed by fine, cloudy white precipitate. The grey particles are metal residues,
while the white clouds are the fresh precipitates of transition metals that form
amphoteric acids and poly-acids, like Si, Sn, Mo, As and others.
• In steel samples fine black sediments occur from the carbon present in the sample.
Example:
Mineral samples often contain not only silicate (SiO2) but also larger amounts of Ca. When dissolving
the silicate with an excess of HF, enough F- remains in solution to also precipitate the CaF2 and
other badly soluble fluorides (like Mg, rare earth elements). In this case the complexation (see p. 18)
with sufficient amount of H3BO3, which forms a complex with F-, reduces the concentration of free F-
so much that it even can re-dissolve some of the insoluble metal fluorides.
If you have no success with your experiments, call your Anton Paar representative for application
support. He will try to help either directly or by forwarding the request to the product support experts
in Anton Paar. Be sure to add as much information as possible about the sample composition and
the experiments and results you already tried out.
3.9 What to Change in the Chemistry of a Method

Method development and method optimization can help to improve the effectiveness and the
productivity of your acid digestion system. Depending on the employed configuration different
sensors should be used for method development to always work within the limits of the
specifications. (see 3.7.)

3.9.1 Increase Oxidation of Organic Matter
Organic molecules need different conditions to decompose. Some of them like carbohydrates (sugar,
starch, cellulose), alcohols (methanol, ethanol, glycerol), and unsaturated aliphatic compounds
decompose very easily (we call them: reactive) and release a lot of thermal energy, others need very
harsh conditions to be decomposed completely. Sometimes molecules can be both reactive and
difficult to digest. The first steps of the decomposition process can be very spontaneous with
generation of a lot of energy and temperature, while the remaining intermediate decomposition
products may be stable and require high digestion temperatures. Aromatic and poly-aromatic
molecules (with benzyl-, phenyl-, styrene- in the substance names) or some amino acids
(phenylalanine, glycine, alanine) are known to be stable and require higher temperatures to digest.
Incomplete oxidation as cause for insufficient digestion quality is mainly related to the reaction
temperature. The available maximum operating temperature of the digestion system may be too low
or the desired target temperature may not be achieved due to reaching the pressure limit of the
vessel first.
• Try to increase the effective digestion temperature:

If the pressure limit is the cause a reduction of sample amount will allow reaching
higher temperatures. Releasing reaction gases by SmartVent technology (HVT or
SVT vessels) or by manually venting and performing a 2nd run will allow higher
temperatures with higher sample weights.
• It is also possible to add fresh oxidant prior to the second digestion.
• Increase the volume of HNO3. As a rough estimation, 1 mL HNO3 for each 100 mg of
organic sample provides a sufficient excess for closed vessels. For venting vessels
add at least 2ml to compensate for venting losses of acid vapors.
• Addition of small amounts of H2O2 (see 3.9.3.)
• Addition of HClO4 (not more than 10 % of the total acid volume). Perchloric acid shows
its full oxidation potential at elevated temperatures of above 170 °C (see additional
details and restrictions in Table 4) In combination with HNO3, which already oxidizes
at lower temperatures and a pre-digestion at or below 150 °C most of the reactive
organic components can be destroyed before the strong oxidation of HClO4 is
activated by heating the mixture to higher temperatures.
3.9.2 Decrease Reactivity of HNO3 – Add Water

If the sample is too reactive, i.e. already reacts at room temperature with concentrated acids (e.g.
samples including organic solvents), or if strong exothermic reaction and venting is observed in early
phases of the process, water can be added to decrease the reactivity of the acid.
Another indication of too high reactivity is, when the pressure rate alarm is triggered by pressure
increase rates of more than 0.8 bar/s (see 3.7.1 on p. 32). This is a situation, where the reactivity of
the sample/acid mixture must be reduced to avoid bursting of safety disks.
• Reduce sample amount

• In a temperature program increase the ramp time
• In a power program introduce a pre-reaction step with moderate power to allow the
reaction to proceed at lower temperatures
• If applicable, remove H2O2 from the reaction mixture
• Add 1 – 3 mL water to the reaction mixture

3.9.3 H2O2 addition – Why and How Much
HNO3 is consumed during the oxidation process of organic carbon, but it also decomposes at higher
temperatures. Both reactions generate NO gas, which can be re-oxidized by oxygen in the gas phase
to NO2. This NO2 will re-dissolve as HNO3 into the liquid phase. As a consequence, regenerated
HNO3 is made available and the pressure of the system is reduced. The required oxygen can be
generated by the addition of H2O2 to the solution prior to the digestion.
This effect produces a pressure increase in the beginning of the reaction when the O2 is produced
and escapes into the headspace. When later in the course of the main oxidation the NOx is produced,
the O2 reacts with the NOx and regenerates the HNO3. This slows the further increase of the pressure
and recirculates the nitrate as oxidation medium.
The regeneration will be most effective in closed vessels that do not vent. During venting, most of
the enriched oxygen atmosphere will be lost and therefore will not have any beneficial effect. So
addition of H2O2 is not recommended in SmartVent vessels.
Adding H2O2 must be made cautiously and step-wise, as H2O2 may increase the reactivity drastically.
Always start with nitric acid alone and add H2O2 only, if the digestion result requires so. If necessary,
add only 0.5 mL of H2O2 at a time (maximum amount of 2 mL) and inspect the run data. Apart from
the final digestion result the pressure increase rate must be kept under control (see 3.7.1). If the
preset maximum pressure increase rate is reached the amount of H2O2 should be reduced.
3.9.4 Optimizing Methods

Generic methods and methods from the classified list of applications and the application library on
the instrument are starting methods, the following parameters can be optimized:
Table 16: Optimization of parameters of temperature programs
Parameter
In generic method Organic A for HVT vessels the ramp duration of 20 minutes
is cautious and long enough for up to 0.8 g of reactive samples. It provides
sufficient time for exothermic reactions to happen at low reaction
temperatures.
If no exothermic reaction is observed (no strong venting heard, no reduction

of microwave power during increase of vessels temperature above pre-set
ramp) then the ramp time can be reduced in steps of 2 minutes to shorter
ramp duration
ramps.
If venting seems too strong and does not decrease till the end of the ramp,
then ramp time can be increased to allow more time for reaction at lower
temperatures.
Check venting losses and assess the quality of digestion (like yellow color or
organic residues) during optimization.
In Rotor 8NX generic methods for reactive samples there is a pre-reaction

step at reduced power to achieve a more linear pressure increase and a
step length, continuous reaction of the majority of the reactive material.
power for pre-
reaction step To reduce/increase the steepness of the pressure curve, reduce/increase
the power of the pre-reaction step. If the pressure increase rate control is
significantly reducing power, reduce the power of the pre-reaction step.

For the typical sample amount the step length of 10 minutes is a good
measure. If the method is to be adapted for larger samples amounts it can
happen that the power ramp after the pre-reaction step activates the pressure
increase rate control/alarm. In such a case make the pre-reaction step longer.
If the pressure increase is leveling off during the pre-reaction step, its length
can be reduced accordingly.
pressure For reactive samples the pressure increase rate limit in the generic methods
increase rate is set to 0.3 bar/s. However, if the power controller reacts too “nervous”, i.e.
limit with numerous spikes, increase the limit to 0.4 or 0.5 bar/s.
For each of the modifications the user must consider his knowledge about sample behavior and
variability in relevant parameters, especially with respect to reactivity. As a guideline it can be said
that the use of sensors allows better process control and thus reduces risk when operating the
instrument as close as possible to its specified operating limits.
For method development or optimization, it is recommended to test the behavior of different samples
in separate runs. By comparing the data of the different runs, it can be decided which of the samples
is most reactive. Find out the run that has the steepest increase in pressure and check if the vessel
1 IR temperature is the highest one in the run. If another sample has a higher IR- temperature, it
seems to be more reactive and should be placed in the reference vessel for the next digestion run.
3.10 Why to Use Pre-reaction Steps for Rotor 24HVT

For Rotors 24HVT generic methods for reactive organic samples are included in the library of
Multiwave 5000. During the heating phase, organic samples may show an exothermal reaction (self-
heating) that can be recognized by an increase of temperature, while the microwave power is
reduced or even shut off. The onset (trigger) temperature may be below 100 °C for certain samples
(i.e. sugars, starch, edible oil) or above (i.e. plant material, proteins, oils). At that point significant
amounts of reaction gases are generated by the decomposition of organic samples.
• In the case of multistep methods like “Organic B”, the first target temperature shall be
adjusted.
• To determine the temperature zone where exothermic reactions will be triggered, use
generic method “Organic A”. That temperature zone can be recognized due to the
obvious decrease of power besides constant or even increasing temperatures.
• Let a moderate amount (0.3 – 0.5 g) of organic sample digest with a slow ramp
(~ 20 min) to 180 °C (generic method Organic A) and check, at which ramp
temperature the internal temperature starts to off-set (exothermal reaction) with
reduced or zero power. Use this temperature to define the hold step in generic method
Organic B, especially, if sample amounts (> 0.5 – 0.8 g) have to be digested and if
heavy venting due to large sample amount has to be reduced.
Fig. 11 shows pre-reaction optimization for a digestion of several different food-type samples. In the
upper graph the original method of Organic B can start the exothermic reaction for carbohydrate-rich
samples at the beginning of the pre-reaction step at 100°C, however it cannot start the reaction in
some other samples containing more fat and proteins, like fat, corn and grass, so these components
only become exothermic at a later stage at a higher vessel temperature.
The lower graph shows an optimized program, with replacement of the hold step at 100 °C by a
ramp to 120 °C of equal length that allows the other samples to heat up for their pre-reaction, which

allows the venting at lower temperature with smaller losses of acid vapors. In addition the final target
temperature was increased to 200 °C to allow more complete digestion of fatty components.
Because of the improved pre-reaction this higher temperature didn’t cause too much venting.
Methods can be optimized for higher sample weight (increase of the ramp and hold time), as long
as the “Restrictions on Use” 11 for samples, acids and methods are taken into account.
Fig. 11: yellow … Vegetable Fat, green … Complementary Horse Feed (corn, grass), blue … Soybean Hulls, black … fish
meal, light blue … applied power.
3.11 Higher Sample Amount – How to deal with it
Check first if bigger sample amount is necessary

Users often feel the need to digest much larger amounts of sample than the “Typical Sample Weight”
range listed in Ch. 5.2 and Ch. 5.3 as feasible for modern closed vessel acid digestion systems.
However, before trying to simply increase the sample size, it is worthwhile reflecting on the reasons.
11
Appendix D in Instruction Manual (D18IB002) or Reference Manual (D18IB001)

Reason Comments and Actions
• Check, how much of the diluted sample is really needed for the analysis
Limit of (incl. rinsing and replicates).
Detection (LoD) • A reduction of sample volume from 100 ml to 20 ml has the same effect
as increasing the sample amount from 0.5 to 2.5 g!
• New sample preparation step has to be embedded in a long-established

laboratory method that traditionally uses large sample amounts.
• This happens, when long established methods are changed in parts of the
Prolongation method, i.e. old photometric method is replaced by atomic spectroscopy
of current (AAS, ICP-OES), later the old open vessel digestion is replaced by
laboratory microwave digestion.
method • Reconsider sample volume requirements and improvements of LOD of
new instrumentation.
• Exploit advantages by considering direct transfer into graduated polymer
autosampler vial and filling up to volume there, without using volumetric
glass flasks in between.
• Bad homogeneity, grain size of sample is too big

Representative • Grind sample to a finer mesh particle size.
Sample • With particle size smaller than 100 – 200 µm, sample amounts of 0.5 g or
lower may well be representative, even for heterogeneous samples
How to increase sample amount

The sample amount given in technical data normally can be digested for typical samples of the
respective category. However, depending on reactivity, particle size and other properties it may be
possible to digest larger samples without problems, or it also may be possible that smaller samples
will cause problems.
• Check recommendations in Ch. 3.3.2 about reactive samples for the specific vessel.
• Before starting experiments to check the feasibility of a scale up of the sample weight,
check the specific limits in technical data in the manuals, (see also in Ch. 5.2 and Ch.
5.3). Start with the lower limit of the typical sample range and stepwise increase the
sample amount observing the behavior of the digestion not only during the run, but
also during vessel preparation and analysis.
• If a pre-reaction by floating dry powders occurs, foaming and even charring is
possible, that may lead to damage of vessels, liners and seals
o Soaking of dry powders (i.e. plant material) with a small amount of water prior
to addition of nitric acid leads to better mixing with the acid.
o Close vessels and start reaction quickly may prevent over-foaming.
• Floating oil or polymer samples show an increased tendency to charring and burning
inside the vessel at sample weight above 500 – 600 mg.
• Optimizations for a specific sample will have to be re-checked, if the sample
properties change!
Recommendations for SmartVent vessels:
• Scaling-up means optimization for a specific sample type.

• Flexibility of grouping together different sample types becomes smaller or is lost
• If over-foaming of sample during early venting leads to losses, reduce sample
amount.

4. Troubleshooting
This section only covers application related troubles. For comprehensive troubleshooting and
especially for a list of error messages please refer to the manual 12.
4.1 Target Temperature Not Reached

For temperature programs the controller seeks to reach the target temperature at any time. It will
increase/decrease the power input to the vessels accordingly within the limits that are set by the
methods parameters (for example: “Max. Microwave Power”).
In power programs without using an immersion temperature sensor, the temperature is monitored
by the IR sensor. The digestion method can be optimized to reach the highest possible temperatures,
which is the IR temperature limit set in the method file.
If the target temperature is not reached the following reasons are possible:
Table 17: Possible Findings and Remedies (see also “Leakage” in ch. 4.4)
Observation Possible Reasons and Comments
• Check method parameters, especially “Max. Microwave Power”,

“Max. Pressure” or “IR Temperature Limit”, if the value is
limiting the required heating power.
• Inspect venting screw for correct closure and lip type seals for
All vessels too correct expansion and for scratches and creases.
cool • Inspect, if the HVT vessels are correctly closed and the sealing
surfaces of the vessels are not damaged.
• If the sample heats slower than programmed and the power input
is at 100 %, the sample load may be too big. Reduce number of
vessels or allow for longer heating time.
• One of the vessels is hot and reaches the temperature limit – all
other vessels remain cooler.
Several vessels • One of the vessels (Rotor 8) or the reference vessel reach the
too cool pressure limit and the other vessels remain cooler
Sample in hot vessel may be too reactive, sample weight might
be too high
• Vessel contains blank solution and generates no reaction heat.

• Vessel is leaking and temperature cannot exceed the boiling
temperature at the pressure reached inside. Inspect venting
Single vessel too screw for correct closure and lip type seals for correct
cool expansion and for scratches and creases.
• For SmartVent vessels, if temperature rises initially, but decreases
later in the process, vessel may have run dry due to excessive acid
venting. Check method parameters and IR calibration, but also
sealing surfaces of vessel.
12
Appendix A in Instruction Manual (E38IB013) or Reference Manual (E38IB001)
42/53 4. Troubleshooting E38IB016EN-

Fig. 12: Graph of a Rotor 24HVT50 run with 24 samples.
The control temperature didn’t reach the programmed curve. It can be seen that the power output was limited to 1000 W, which is not
sufficient for this rotor loading.
4.2 Big Spread in IR Temperatures

There are various reasons for spreading IR temperatures.
• Differences in sample reactivity.

• Differences in humidity or grain size of similar samples
• Blank samples. For reactive samples blanks will normally behave cooler, for inert
samples the blanks will often be hotter than the samples.
• Differences in self-heating of vessel jackets and liners. They are caused by loading
of the PTFE-TFM material with acid vapors. These vapors from HNO3, NOx; HCl, and
HF diffuse under high temperature and pressure into the polymer material. Perform
the intensive cleaning procedure as described in the Reference Manual13.
• Loading of the rotor. Use the recommended loading patterns.
4.3 Pressure Increase Rate Alarm

Fig. 13 displays a digestion run of petroleum products in a Rotor 8NXQ80 that showed Pressure
Rate Alarms at two times during the process.
13
Instruction Manual and Safety Information of the respective rotor, chapter on ”Performing an Intensive Cleaning”
E38IB016EN-C 4. Troubleshooting 43/53

1st and 2nd pressure spike
Fig. 13: Graph from Rotor 8 NXQ80 digestion of petroleum products with two pressure rate alarms.
• The run as shown in Fig. 13 shows a normal start and a normal end of the run.
However, there are two pressure spikes in the pressure signal. The pressure increase
rate alarm is temporarily switching off the microwave power and maximizing the
cooling fan, until the pressure begins to decrease again. Then the power is reapplied
and the process continues.
• After the 2nd spike the pressure increase is still steep and causes the power input to
be limited, but the rate limit can be kept under control without switching off the power
and initializing the safety cooling.
It should be noted that the steep pressure spikes like in Fig. 13 are signs for starting spontaneous
reactions that tend to run away quickly. In case of a Pressure Increase Rate Alarm (explanation see
3.7.1 on p. 32) take measures to reduce the reactivity (see 3.9.2) of the samples to avoid safety disk
breakages and other equipment damages:
• Reduce sample weight.

• Reduce HNO3 and add water instead to moderate the oxidative reactivity.
• Reduce the steepness of the power ramp, or better,
• Use the “.generic-reactive” method with a pre-reaction step. If Pressure Rate Alarms
(“R”) are reported during the pre-reaction step in the run data, reduce the power level
of the pre-reaction step.
• Make the pre-reaction step longer, if “R” occurs during the ramp to the final
temperature.
4.4 Leakage
Leakage of vessels can cause corrosion of the outer vessel components and compromises their
durability and functionality. As shown in Fig. 14, it also prevents vessels to reach the desired
digestion temperature and leads to failed digestions. It shows that a vessel lags behind and
according to the list of the Max. Vessel Temperatures in the corresponding Report vessel 16 only
reaches 150 °C in the end. This is an indication of some sort of leakage of this vessel. In case of an
HVT vessel incorrect vessel closure or a leaking seal will be the most likely cause. If leakage is
suspected, find it and fight it.

Fig. 14: “All Graph” of a Rotor 24HVT50 run.
If the temperature difference is not so obvious, it may be harder to identify a leaking vessel. Make a
cleaning run, measure the acid volume after the run with a graduated vessel (i.e. 15 mL centrifuge
vial) and compare the volume with the initial acid volume.
Table 18: Reasons and remedies for vessel leakage
Reason Comment Remedy

The venting screw tap set can be used to clean
Insufficiently closed May be due to rough running
the thread in the screw cap/seal holder and on
venting screw venting screws.
the venting screw to allow smooth operation 14.
Expand the lip type seal correctly and start the
Insufficient No pressure build-up is
run in the next 15 minutes.
expansion of lip-type possible.
seal Use seal forming device for proper storage and
Reagents will be lost.
preparation of the seals.
Especially when hard, mineral When weighing in the samples take care not to
Scratches at the seal
samples are digested it may leave sample particles in the sealing area of the
or the
happen that sample particles liner. Use of an antistatic gun can help.
corresponding
adhere to the sealing areas
sealing surface of Check for scratches by staining the seals (see
and will scratch both sides of
the liner/vessel Fig. 15 a, b)
the sealing surface
Do not close with the venting screw opener.
If venting screws are closed Keep the venting screws as pair with the
Leaking at venting stronger than finger-tight, corresponding seal. Do not mix them.
screw there will be an indenting of Venting screw can be replaced alone.
the seal. When replacing a seal, also replace the venting
screw.
Incorrect closure of Reduced opening pressure of Close the screwcap until a flat surface is
HVT vessel the vessels. obtained.
Apart from scratches by hard
sample particles in rare cases, Venting flame gases will melt sealing surfaces
HVT vessel is
swimming oil or polymer both on vessel body and seal plug exchange
leaking
samples may catch fire and both parts.
the venting flame gases melt
14
see Reference Manual D19IB002, Contact your Anton Paar representative for advice.

Reason Comment Remedy
and destroy the sealing
surface before quickly
extinguishing again.
a b
Fig. 15 a, b: Staining with permanent ink makes scratches visible.
4.5 Corrosion Signs in Closed Vessels without Venting Capability

The PTFE-TFM and PFA of the inner components (liner and seal) withstand the corrosion attack of
the digestion acids. The polymers providing structural support for the liners and seals are stable
against concentrated acids in the cold only. If droplets from leakage and spills from vessel opening
remain on the components during the subsequent run, the droplets will heat up and corrosion of the
surface will occur. Corrosion of the seal holder/screw cap and PEEK/ceramic vessel jacket or even
on the PEEK protective casing and protective cover will lead to weakening of the mechanical strength
and to subsequent failure even below the specified limits of operation.
The inspection and cleaning after each run is vital to maintain the performance quality of the
components.
• Watch out for drops between seal and seal holder, some more of them may have
slipped into the gap between them. If liquid is observed between the white material of
the seal and the black material of the seal holder / screw cap, disassemble and clean
the seal according to the manual 15 . Make sure that the parts are dry before
reassembling.
• Crusts or decoloration of screw cap/seal holder: black components become brown, if
exposed to oxidative substances. These may be NOx fumes or HNO3 itself. While the
fumes of NOx only affect the color and leave the surface smooth and intact, the acid
itself also destroys the polymer material and makes the surface look crusty and rough.
This is a sign that also the mechanical properties of the material are weakened.
4.6 How to Check and Control Venting Activity in SmartVent Vessels

HVT and SVT vessels with SmartVent technology are designed for a controlled release of reaction
gases. However, due to the physical properties of gases and liquids, a few points have to be
considered. The pressure in a vessel is the sum of the pressure by the reaction gases (see ch. 2.1.4)
15
See D19IB002 Reference Manual

and the vapor pressure of the acid mixture (see ch. 3.4). Venting occurs, when the sum of the
pressure contributions exceeds the opening pressure of the seal cap.
4.6.1 How to Quantify Venting

• HVT-vessels: Observe the reaction through the door. In the initial phase the venting
can be heard by slight “pops” and “hisses” and can be seen by brown clouds above
the venting hole of the screw cap. Moderate venting will just immediately disappear
inside the cooling tube of the rotor. In more intense cases vertical jets of mist can be
seen and the cavity may be temporarily filled with brown fog that disappears after a
short while by the action of the exhaust system.
• SVT vessels: the larger cross-section of the venting channels in the screw cap makes
the venting of gases less obvious and normally very calm. Popping and hissing is
rarely heard, however, the brown clouds of escaping NOx gases can be seen.
• To determine the weight loss, weigh the closed vessel before and after the digestion.
• To estimate the volume loss, transfer the digestate into a graduated centrifuge tube
(15 mL) and read the volume of the solution after the digestion.
The reaction gases may cause a weight loss as high as 3 – 4 g per g of organic matter digested due
to the escaping CO2 and NOx gases. The loss in volume should be less than 2 – 3 mL in such cases.
For SVT vessels higher volume losses can be accepted, if the acid mixture is based on a mix of high
boiling acids like H2SO4 or H3PO4. In such a case maximum temperature of 250°C is the target and
under this condition larger parts of the low boiling acid components will escape during any venting
that occurs during maximum temperature steps. However, it is unlikely that analyte ions will be lost.
4.6.2 How to Avoid Acid Venting

If the volume loss is higher than 2 – 3 mL, take measures to avoid the venting of acids as this reduces
the amount of oxidant present to digest your sample and increases corrosion of the system.
• Check, if the IR Sensor is clean and its calibration is correct. A dirty sensor may show
too low values that lead to higher power input and higher internal temperature.
• Make sure that the pressure vessels are correctly closed, with the central tube of the
screw cap forming a flat surface with the top of the screw cap itself. Screw caps that
are not completely closed will open earlier, so the venting will be stronger and occur
at lower temperatures than expected.
• Check that the target temperature and the maximum allowed temperature are set as
recommended in Table 13, especially when using AVG or MIN temperature control
modes.
• Let the main gas-releasing reaction happen at the lowest possible temperature. For
example, insert a pre-reaction step (see 3.10 on p. 39).

5. Rotors
This section summarizes specifications of the available rotors for acid digestion in Multiwave 5000.
In addition, it summarizes application-relevant information that helps to use the equipment at its best
without over-stressing its limits.
5.1 Overview
Rotors with closed vessels without venting capability have operation limits that allow a rough
differentiation with respect to the application area or sample types as given in ch. 7. For samples
with organic matter that produce reaction gases the classification is determined by a typical sample
weight and the pressure rating of the vessel type, while for samples without significant gas evolution
the minimum temperature to digest the sample in reasonable time is the discriminating parameter.
This is only a rough orientation, as many samples are mixtures and depending on their specific
composition may fall in the next higher or lower class. As an example, oil and grease are stated as
samples for Rotor 8NXF100, mainly for reasons of necessary sample size of 500 – 700 mg. Most
likely, the oil could also have been digested with the maximum temperature of a Rotor 16HF100, if
the sample amount was small enough (100 – 200 mg) to even reach the maximum temperature
range. Samples of up to 300 mg can sometimes even be digested in a Rotor 24HVT50.
However, if aromatic compounds are present in the sample, the higher digestion temperature
achievable in Rotor 8NXQ80 will also be necessary to digest the aromatic compounds completely.
5.1.1 General Limits

Observe the Appendices on “Restrictions on Use”, Operation Parameters”, and “Technical Data” as
mentioned in the manuals 16 . For recommended numbers of vessels and loading patterns see
“Loading the Rotor” in the Instruction Manual and Safety Instructions of the respective rotor.
The maximum filling volume of closed vessels without venting is half of the total volume.
Table 19 helps to understand the Rotor and vessel names used for Anton Paar Multiwave
instruments.
16
E38IB001 Reference Manual and E38IB013 Instruction Manual and Safety Instructions | Instrument Instructions
48/53 5. Rotors E38IB016EN-

Table 19: Naming conventions for Multiwave Rotors and Vessels
Rotor Vessel
<n> <P> V <M> <Vol>
16 M F 100
<Vol> Vessel volume
<M>aterial F..luoropolymer, Q..uartz,

T..FM-PTFE, G..las
V..enting
<P>erformance M..edium, H..igh,

S … Superior, X..treme
<n> Number of vessels
5.2 Rotors with SmartVent Technology

Typical sample weight is the range from a typical lower limit up to a recommended Maximum Sample
weight as upper limit for typical samples of that category. It does not mean that all samples can be
digested up to that volume without trouble. It does not mean that a solution of such a large sample
amount is analytically useful.
5.2.1 Rotor 24HVT50, Rotor 24HVT80, and Rotor 41HVT56

• Minimum Volume is 3 mL, for small numbers of vessels use a volume of more than 5
mL to provide sufficient microwave load. Typical volume is 7 – 12 mL.
• Maximum volume is 25 mL for HVT50 or HVT56 vessels, and 55 mL for HVT80
vessels
• Typical sample weight for reactive samples is 0.3 – 0.5 g.
• Typical sample weight for organic samples is 0.3 – 1.5 g.
• Typical sample weight for inert samples is 0.1 – 3 g.
• To use these rotors successfully, be sure to check the Restrictions on Use 17, 3.4.1 on
p. 28 and Table 13 of this document.
• Temperature programs are possible with 3 different temperature control modes based
on the running average of all vessel temperatures or based on the maximum or
minimum vessel temperature. See p. 32 for a detailed explanation.
• Power programs are not recommended, however, if a power program has to be used,
see Table 13.
17
Appendix D: Restrictions on Use in E38IB001 Reference Manual and Instruction Manual
E38IB016EN-C 5. Rotors 49/53

5.2.2 Rotor 20SVT50
• Minimum volume is 3 mL, for small numbers of vessels use a volume of more than 5
mL to provide sufficient microwave load. Typical volume is 7 – 15 mL.
• Maximum volume is 25 – 30 mL
• Typical sample weight for reactive samples is 0.3 – 0.7 g.
• Typical sample weight for organic samples is 0.3 – 1.5 g.
• Typical sample weight for inert samples is 0.1 – 3 g.
• SmartTemp Sensor is obligatory for operation of this rotor
5.3 “Classic Rotors” without SmartVent Technology
5.3.1 Rotor 8NXF100 and 8NXQ80
• Typical sample weight for reactive samples is 100 – 600 mg 18

• Typical sample weight for inert samples is 300 – 800 mg18
• Min. Volume: 6 mL 19, typical Volume: 6 – 10 mL
• Rotor 8N has to be used with 4 vessels (mounted in positions 1, 3, 5, 7) or 8 vessels.
5.3.2 Specific Hints for Quartz Vessels

• Do not use HF. It will etch the quartz surface and dissolve significant amounts of
quartz (SiO2)
• Do not use solutions with high concentrations of alkaline ions, i.e. no NaOH or NaCl.
Alkaline ions will initiate devitrification that reduces the mechanical stability quickly
and drastically.
• Do not use stirrer, especially not with hard sample particles. It will scratch the quartz
surface which may lead to devitrification.
5.3.3 Rotor 16MF100, and Rotor 16HF100

• Typical Sample Weight (Reactive) is 100 – 200 mg for MF100 vessels, and up to 400
mg in HF100 vessels.
• Typical Sample Weight (Inert) is 200 – 500 mg for MF100 vessels, and up to
600 mg in HF100 vessels.
• Typical filling volume is 6 – 10 mL.
• Minimum number of vessels is 4, place them evenly distributed around the circle of
the rotor.
• If a p/T Sensor or a p-sensor is used, make sure that the reference vessel is the
“hottest” vessel. Select the most reactive sample or reduce the sample amount in the
other vessels.
• If only a p-sensor is available, method development can only be based on IR
temperature and the pressure value. Due to the slow response and relatively large
gap between IR temperature and inner temperature the power ramping has to be slow
and cautious.
18
Considered as dry weight
19
Minimum volume 12 mL when using T-probe S
50/53 5. Rotors E38IB016EN-

5.3.4 Rotor 64MG5
• Typical sample weight is 1 to 20 mg.
• Typical volume is 0.3 – 0.6 mL.
• Seals of Rotor 64MG5 are disposable (one-time usage). Check the quality of the lip
before using, do not use seals with bent lips.
• Vessels are single-use, because the mechanical stability of the borosilicate glass
deteriorates rather quickly when used at higher temperatures.
• If necessary, vessels and seals can be pre-cleaned by rinsing with dilute clean acid
and drying in a dust-free zone (ideally: laminar flow box)
E38IB016EN-C 5. Rotors 51/53

6. Special Accessories for Rotor 8NXQ80
6.1 Microwave Induced Combustion (MIC)

Combustion of flammable samples in an oxygen atmosphere (e.g. oxygen bombs or Schöniger
flasks) is widely used as sample preparation for determination of non-metals by e.g. ion
chromatography (IC) or ion-selective electrodes. Several EPA and ASTM methods are available for
the analysis of combustible solids and liquids. Multiwave 5000 with Rotor 8NXQ80 can be easily
upgraded with quartz sample holders and gas loading check valves to perform oxygen combustion.
The Oxygen combustion for microwave digestion system was developed by G. Knapp and E.
Flores20. Please refer to product description 21 and instruction sheet22 available from your Anton Paar
representative for a more detailed description of the accessory and its operation.
6.1.1 Application range, preparation of samples

• MIC is for solid, combustible samples.
• NO organic solvents with boiling point below ca. 100 °C. Their dispensing and
handling will be very irreproducible due to evaporation.
• NO reagents that are oxygen sensitive
• Pieces and coarse grains work well,
• Fine powders have to be compacted by pressing into a pill.
• Materials that are difficult to ignite can be mixed with small amounts of burning aid
like cellulose, dextran or benzoic acid.
• Pellets must not be pressed too tight
• Pastes and viscous liquids can be soaked onto filter paper disks. In such a case the
impregnation with NH4 NO3 solution has to be applied to the upper layer
6.1.2 Sample amount

The amount of organic matter that can be burnt is typically between 100 mg and around 500 mg.
The weight of burning aids has to be taken into account and will reduce the allowable sample weight.
6.1.3 Absorption solution and refluxing

The vessel is filled with 6 –10 ml of an absorption solution.
• For the absorption of anions it use 50 – 200 mM (NH4)2 CO3 solution to provide
favorable pH for the absorption of HCl, HF etc. To bring all P into the phosphate form
and all Br into the bromide form add a small amount of H2O2.
• For the absorption of cations use dilute acid.
The burning of the sample is finished after 1 – 1.5 minutes. The remaining time of the generic method
for MIC is for refluxing the absorption solution to wash down all of the analyte from the gas phase
and the vessel walls.
20
Flores et al, Determination of Halogens in Coal after Digestion Using the Microwave-Induced Combustion Technique,
Anal. Chem.2008, 80, 1865 - 1870
21
Microwave-Induced Oxygen Combustion (MIC) – Product Information (E38IE004)
22
Microwave-Induced Oxygen Combustion (MIC) – Instruction Sheet (E38IB012)
52/53 6. Special Accessories for Rotor 8NXQ80 E38IB016EN-

7. Application Matrix
SmartVent Vessels without SmartVent
HVT
SVT50 MF100 HF100 XF100 XQ80
50/56/80
Ceramics, Oxides of Al, Cr, Ta, Ti, W ○ ◐ ○ ◐ ● ○
Oxides Porcelain, Zirconia ○ ◐ ○ ◐ ● ○
Carbon Activated carbon ○ ● ○ ◐ ● ◐
Carbon fibers, - nanotubes ○ ● ○ ◐ ● ◐
Coal, coke, Graphite ○ ● ○ ◐ ● ◐
Environment EPA-procedures ● ◐ ● ◐ ◐ ◐
(Membrane) filters ● ● ● ● ● ◐
Plants, sewage sludge ● ● ● ● ● ◐
Slags, fly ash ◐ ● ◐ ● ● ◐
Soil, sediment (digestion) ● ● ◐ ● ● ◐
Soil, sediment (leaching) ● ● ● ● ◐ ◐
Water, effluents ◐ ◐ ● ● ● ◐
Food, Animal feed, minerals ● ● ◐ ● ● ●
Feed Meat, fish, milkpowder ● ● ◐ ● ● ●
Oils, sugar, vegetables ● ● ◐ ● ● ●
Ores, Bauxite (alkaline leaching) ○ ○ ◐ ◐ ● ○
Minerals Ores ◐ ● ◐ ● ● ○
Rocks, minerals, sand ◐ ● ◐ ● ● ○
Materials Carbides (B, Si, ...) ○ ○ ○ ○ ● ○
Cement ○ ◐ ○ ● ● ○
Glass, quartz ◐ ● ◐ ● ● ○
Leather ◐ ● ○ ● ● ○
Paper, cardboard ◐ ● ◐ ● ● ◐
Zeolites ○ ◐ ○ ● ● ○
Metals Alloys (from Al to Zr) ◐ ● ◐ ● ● ◐
Alloys Platinum Group Metals +
○ ○ ○ ○ ○ ◐
+
( ...HPA-S) Pure metals (Al - Zr), steel ◐ ● ◐ ● ● ◐
Petro- Crude oils, tar, pitch ○ ● ○ ○ ● ●
chemistry Fuel oils ◐ ● ○ ○ ● ●
Lubricants, wax ◐ ● ○ ◐ ● ●
Pharma- API ◐ ● ○ ◐ ● ●
ceuticals Excipients, inorganic ◐ ● ○ ● ● ◐
Excipients, organic ● ● ○ ◐ ● ●
Finished drug products ◐ ● ○ ◐ ● ●
Forensic Blood, bone ● ● ○ ● ● ●
Hair, urine ● ● ◐ ● ● ●
Polymers Polymers, filled ◐ ● ○ ◐ ● ◐
Polymers, unfilled ◐ ● ○ ◐ ● ●
○ … not applicable, ◐ … partially applicable, ● … applicable
E38IB016EN-C 7. Application Matrix 53/53

E38IB016EN C Application Guide Acid Digestion For Multiwave 5000

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E38IB016EN C Application Guide Acid Digestion For Multiwave 5000

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Application Guide Acid Digestion

Version: May 2022

Version: May 2022

Changes, copyright, trademarks etc.

Address of the instrument producer:

Tel: +43 (0) 316 257-0

Date: May 2022

What the Application Guide can do for you

• Basics of acid digestion

How to use the Application Guide

What the Application Guide cannot do for you

• It does not replace the user training

E38IB016EN-C 1. About This Application Guide 7/53

2.1 Basics of Acid Digestion

2.1.1 Why Acid Digestion?

•forms an aerosol of solution including all dissolved substances

8/53 2. General Chapters E38IB016EN-

2.1.2 Types of Transfer into Liquid Form

2.1.3 Effect of Increasing Temperature

E38IB016EN-C 2. General Chapters 9/53

Discussion of vapor pressure

Fig. 2: Vapor pressure curves of some common acids

10/53 2. General Chapters E38IB016EN-

Reaction Formula Comment

2.1.4 Estimation of Vessel Pressure

plant materials like cellulose

(2) Molecular weight (of which C) 30 g (12 g C) = 40 % 14 g (12 g C) = 86 %

Gas volume @ standard

E38IB016EN-C 2. General Chapters 11/53

Advantage of pressure-controlled SmartVent vessels over old-style closed vessels

2.1.5 Pressure Control

12/53 2. General Chapters E38IB016EN-

Fig. 4: 2nd run with residual fuel oil

Closed vessels with pressure-activated venting (SmartVent)

E38IB016EN-C 2. General Chapters 13/53

2.1.6 Problems Related to Sample Preparation

Source Type of contamination Remedy

14/53 2. General Chapters E38IB016EN-

2.1.7 Common Problems from Measurement

E38IB016EN-C 2. General Chapters 15/53

Here is only a few of them listed to give you an idea:

Reagent Name Properties

Nitric Acid Typical concentration: ~ 65 %, ~ 14 mol/L

• oxidizing acid, dissolves most metals into soluble nitrates

Hydrochloric Acid Typical concentration: ~ 32 %,~ 10 mol/L

• non-oxidizing, but strongly complexing acid

16/53 2. General Chapters E38IB016EN-

Hydrogen Peroxide Typical concentration: 30 %, ~ 10 mol/L

• strong oxidant, usually combined with an acid to increase oxidizing power

Hydrofluoric Acid Typical concentration: 40 %

Sulfuric Acid Typical concentration: 96 %

• Destruction of organic matter by dehydration

E38IB016EN-C 2. General Chapters 17/53

Phosphoric Acid Typical concentration: ~ 85 %

• used for digestion of minerals

Perchloric Acid Typical concentration: ~ 70 %

• very powerful oxidizing agent above 150 – 170 °C in high concentration

Boric Acid Typical concentration: 5 % (cold saturated)

2.2.1 Specific Aspects of HF

18/53 2. General Chapters E38IB016EN-

E38IB016EN-C 2. General Chapters 19/53

New sample type

1. Define your analytical task