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Decomposition Procedures in Inorganic

Analysis
Zdeněk Šulcek , Pavel Povondra , Jan Doležal & F. J. Langmyhr
a
Central Geological Institute Prague , Czechoslovakia
b
Faculty of Natural Sciences Charles University Prague , Czechoslovakia
c
Faculty of Natural Sciences Charles University Prague , Czechoslovakia
d
Department of Chemistry , University of Oslo , Oslo, Norway
Published online: 18 Feb 2008.

To cite this article: Zdeněk Šulcek , Pavel Povondra , Jan Doležal & F. J. Langmyhr (1977) Decomposition
Procedures in Inorganic Analysis, C R C Critical Reviews in Analytical Chemistry, 6:3, 255-323, DOI:
10.1080/10408347708542694

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 DECOMPOSITION PROCEDURES IN INORGANIC ANALYSIS

Authors: Zdenek Sulcek

Central Geological Institute
Prague, Czechoslovakia

Pavel Povondra
Jan DoleZal
Faculty of Natural Sciences
Charles University
Prague, Czechoslovakia
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Referee: F. J. Langmyhr
Department of Chemistry
University of Oslo
Oslo, Norway

TABLE OF CONTENTS

I. Introduction

II. Decomposition under Pressure in Closed System

A. Substance Dissolution in Sealed Glass Tubes
B. Decompositions in Autoclaves

III. Decomposition in Open System

A. Decompositions by HF
B. Decompositions by Other Volatile Inorganic Acids
1. Decomposition by HC1
2. Decomposition by HBr
3. Decomposition by HI
4. Decomposition by HNO3
5. Decomposition by Aqua Regia
C. Decomposition by Less Volatile Inorganic Acids
1. Decomposition by HC104
2. Decomposition by H 2 SO 4
3. Decomposition by H3 PO4
D. Decomposition by Ion Exchangers

IV. Decomposition by Fusion

A. Alkaline Fusion
B. Acidic Fusion
1. Decomposition by Fusion with Hydrogen Sulfate and Disulfate
2. Decomposition by Fusion with Acidic Fluorides and Fluoborates

June 1977 255

 C. Fusion with Borates and Boric Oxide
D. Reductive Fusion
E. Alkaline Fusion in the Presence of Sulfur

V. Sample Decomposition by Sintering

A. Sintering with Sodium Carbonate
B. Sintering with Sodium Peroxide
C. Sintering with a Mixture of an Alkali Carbonate and a Metal Oxide
D. Decomposition by the Method of J. L. Smith and Sintering with Metal Oxides

VI. Special Decomposition Procedures

A. Thermal Decompositions
B. Decompositions of Minerals by Heating with Ammonium Halides
C. Decompositions in Gas Streams

D. Pyrohydrolysis
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VII. Conclusion

References

I. INTRODUCTION solid phase (mostly oxidation or reduction); the

products formed are also more readily decompos-
Decomposition of solids involves a series of able with acids than is the original substance.
reactions, which transform the original substance Sometimes, a gaseous or volatile compound is a
and produce quantitatively new phases. The de- product of the reaction and can be easily separated
composition usually results in the formation of from the system.
solutions or melts; sometimes new solid phases are In the present study, various procedures for the
formed. The reactions are generally accompanied decomposition of inorganic materials are critically
by the formation of gaseous phases. The conver- evaluated. Generally, natural mineral materials
sion of the original component is either complete have been selected for this purpose because of
(usually in fusion decompositions) or an undecom- their considerable variability and behavior differ-
posed fraction with the original or a changed phase ent from that of their synthetic equivalents.
composition remains (in acid decompositions). Compounds prepared in the laboratory are usually
During fusion, new solid phases with structure available in a better defined form in both chemical
similar to glasses are formed, the composition of composition and structural state. On the other
which is quite different from that of the original hand, mineral substances represent much more
substance. As the cooling period of the melts is complex materials because of isomorphous ele-
very short, the melts turn into glasses and the ment displacement, the presence of inclusion
"true" crystalline phase is not commonly found in segregated phases, and growth irregularities. The
the solidified melts. These new formed glasses are problems of decomposition can better be demon-
readily soluble in water or in aqueous solutions of strated on such complicated systems, especially
acids. the selection of the technique with consideration
Another type of decomposition reaction in- of the intended analytical procedure.
volves substances in a heterogeneous solid-gas One reason this field of analytical chemistry has
system. During the reaction, changes occur in the been selected as the main topic of study is our

256 CRC Critical Reviews in Analytical Chemistry

 long years of experience in this area. Without an compensating pressure. This pressure is attained by
experimental background, it is difficult to evaluate placing certain substances in the steel cylinder
various decomposition techniques to assess their which are turned into gases on heating and give
efficiency, and to propose an optimum decomposi- rise to approximately the same pressure as that
tion procedure for various materials being ana- formed by the reaction mixture inside the glass
lyzed. tube. Compared with substance dissolution in
autoclaves (with Teflon inserts), this system has a
II. DECOMPOSITIONS UNDER number of advantages:
PRESSURE IN CLOSED SYSTEMS
1. Relatively easy attainment and mainten-
Transfer of substances into solution is a basic ance of a high working temperature (usually up to
operation whiph, together with the analytical 300°C) under a pressure above 100 atm.
method used, determines the precision and ac- 2. Decomposition procedure is simple and
curacy of the results obtained. Decompositions of does not require complex apparatus.
natural and industrial inorganic materials represent 3. The possibility of handling large series of
such an important stage in the analysis that special samples.
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monographs have recently been devoted to this 4. Practically unlimited stability of solutions
subject.1 ' 2 At present, a new decomposition tech- in the hermetically sealed system in an inert
nique in a closed system at an elevated tempera- atmosphere and maintenance of the individual ions
ture and pressure is becoming increasingly import- in a defined valence state (e.g., Fe 2+ ).
ant in analytical practice. The pressure decomposi- 5. Minimal extent of redox reactions be-
tion of substances is based on heating the sample tween the ampule walls and the ions in the
and the solvent in a closed vessel, in which the solution.
pressure increases due to increasing temperature.
At higher temperatures and pressures the activity The main disadvantage of this pressure decom-
of mineral acids increases, resistant solid phases are position technique is partial leaching of the alkali
dissolved, and the whole dissolution process is metal ions, silicic and boric acids, and possibly
accelerated. Operations under increased pressure, other components dependent on the glass compo-
common in the synthesis of inorganic and organic sition. Therefore, this technique of substance
substances, were first applied to geological mate- dissolution is unsuitable for determination of
rials by Jannasch3"s at the end of the 19 th certain components. Dilute HF solutions and alkali
century. He decomposed a rock sample in a hydroxides also cannot be used for dissolution in
platinum vessel inserted in a sealed glass tube. This glass tubes. For series work, the analyzed samples
method of dissolution of inorganic substances did are sealed in hard glass, the surface of which must
not give good results, due to poor efficiency and • not be damaged; otherwise, an explosion may
considerable corrosion of the platinum vessel and occur during heating. Heated tubes without a
the glass used. Modern techniques of pressure metallic mantle are used for pressures up to ca. 2
decompositions chiefly involve heating of sealed MPa. Because these pressures are easily obtained
hard glass ampules and sample dissolution in a even at relatively low temperatures (especially
vessel tightly closed in a metallic autoclave. The when gaseous reaction products are formed), the
reaction vessels themselves are mostly made of tubes are placed in metallic cylinders with a tight
polytetrafluoroethylene (Teflon® PTFE), or plati- screw closing for safety. A volatile liquid (e.g., an
num and its alloys, or gold. With only slightly in- organic solvent or water) or solid carbon dioxide
creased pressure and temperature, the decomposi- which exhibits a practically linear pressure increase
tion can be carried out in tightly closed polypro- over the whole experimental temperature range is
pylene, polycarbonate, or Teflon vessels without added to the cylinder.6 Manipulations with glass
the outer metallic mantle. ampules and methods for their filling as well as
application possibilities have been reviewed and
A. Substance Dissolution in Sealed Glass Tubes are discussed in basic monographs.6"8
The pressure decomposition involves heating of Since the original but not very successful
substances with solvents sealed in hard-glass tubes experiments of Jannasch,3"5 only the study of
placed in open or closed steel cylinders, using a Wichers et al.9 has brought attention to the

June 1977 257

 practical applicability of pressure decompositions. similar structures, e.g., chrommagnesites, are read-
The prolonged effect of HC1 on a number of ily dissolved24 by heating with diluted H2SO4
resistant natural and synthetic oxides and silicates (1 + 3). Complicated oxides and some other uran-
was systematically studied (250°C for 16 to 48 ium components contained in uranium ores are
hr). Under these reaction conditions, cassiterite, readily dissolved after being heated for 2 hr with
spinel, and chromite, as well as some silicates (e.g., HC1 at 200°C; the procedure was tested for rapid
cordierite, sillimanite, amfibol, muscovite, etc.), extraction of uranium from sandstones.25
were completely dissolved. Among plagioclases, Pressure decompositions were successfully used
the basic members of the series are more easily in the preparation of solutions of certain metals of
decomposed, while albite and oligoclase remain the platinum group, especially Rh and Ir and their
virtually undissolved. Rocks were generally only alloys containing Pt, which cannot be dissolved
partially decomposed. These experiments were even by prolonged action of aqua regia at
supplemented by Brazilian authors1 ° who studied atmospheric pressure. Dissolution of these metals
the solubility of certain industrially important raw by chlorination in open systems or by fusion is
materials. Even oxides previously ignited at a high much more difficult and often leads to contami-
temperature (e.g., A12O3, BeO, SnO 2 , and HfO2) nation of the prepared solutions. The principal
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are dissolved following prolonged treatment with works in this field9'26 were published from 1940
HC1 at 230 to aStfC. 7 ' 1 1 Analogously, single to 1944. Chlorine, bromine, fuming nitric acid,
crystals of corundum and hematite, which need and hydrochloric acid (possibly in combination
not even be finely pulverized,7 can be dissolved. with chlorate) were used for oxidative dissolution.
Even prolonged action of HC1 or H2 SO4 did not Since the gaseous reaction products substantially
lead to dissolution of BaTiO3. Rutil single crys- increase the pressure in the tubes, protective
tals 12 resist the 24-hr action of concentrated HC1; metallic mantles with a compensation pressure are
only about one half of a 50-mg sample is dissolved. employed. During filling with oxidizing solutions
Decomposition of complicated oxidic sub- or liquid Cl2 and during opening, the ampules are
stances under pressure has often been used in the strongly cooled with ice.
study of ferrites. Generally, lower temperatures A special technique 27 ' 28 for rich ores and
were employed and the decompositions were chemical dressing products has been developed at
carried out in sealed tubes without an external the National Institute for Metallurgy in
pressure. The procedure proposed by van Ooster- Johannesburg. The ores and the matte are
haut and Wisser13 was utilized by Goerter14 to decomposed by aqua regia after preconcentration
determine the reducing effects of ferrites. of the Pt metals by reductive fusion to a Pb
Basically, the studies are related to the procedure button. Simple decomposition of the button with
originally developed in 1860 by Mitscherlich,15 high silver content by aqua regia in a beaker is very
who decomposed silicates in a sealed tube with difficult; buttons obtained by fusion of chromites
diluted H 2 SO 4 , in order to determine Fe(II). The are also difficult to dissolve. The Pb button is
accuracy of the results obtained was verified by decomposed in a mixture of HC1 and fuming
reference analyses16 after the decomposition of HN0 3 for 3 hr at 200°C. A reducing fire-assay
the substances with HF. The procedure was technique is also employed for treatment of
modified by Hillebrand17 and Hillebrand and residues of solutions with high contents of Cu, Ni,
Stokes. 18 ' 19 Kleinert successfully applied the and Fe and low concentrations of the Pt metals.
Mitscherlich method to analyses of Ni ferrites.20 Rich platinum ores are directly attacked by a
This kind of cubic ferrites is very difficult to mixture of HC1, fuming HN0 3 , and bromine, as
decompose using HC1 under atmospheric condi- are the residues after the extraction of mattes. The
tions; thus, the substance must be dissolved in a simultaneous presence of bromine and fuming
sealed ampule.21 >22 The solution obtained is used HNO3 facilitates the complete oxidation of
for the determination of active oxygen; the mate- sulfides without formation of elemental sulfur,
rial need not be finely pulverized, so there is no whose presence makes complete sample dis-
danger of contamination. This kind of decomposi- solution in aqua regia more difficult. Decompo-
tion is applicable to various ferrite types; phos- sition by HC1 and Cl2 is chiefly used for the
phoric acid2 3 was successfully used as the solvent preparation of defined standard solutions; atomic
for the determination of Fe. Substances with absorption spectometry (AAS) is almost

258 CRC Critical Reviews in Analytical Chemistry

i
 exclusively employed as the analytical method for of the present century. Its subsequent rapid
the final determination. Decomposition in a sealed development was the result of:
tube with HC1 and NaCl3 was recently employed
for the determination of Ir and Ru in rhodium 1. Mastering of the production technology
sponge.29 The complete decomposition takes 6 hr of organic polymers39 which are exceptionally
at 250°C. The dissolution of finely ground buttons resistant to mineral acids even at high tempera-
was described by Zachariasen,3 ° and the tures and pressures (i.e., polytetrafluoroethylene,
decompositions of the Pt metals in sealed ampules fluorinated ethylenpropylene (Teflon FEP), poly-
has been generally evaluated in Beamish's excellent propylene, etc.).
monograph.3' 2. Rapid development and the requirements
Pressure decompositions were successfully of new instrumental analytical techniques (e.g.,
applied to resistant high melting components, e.g., AAS, mass spectrometry, etc.) in which high
boron carbides. 32 ' 33 Aluminium nitride34 is contents of salts in the solution make the
decomposed within 6 to 24 hr by diluted sulfuric measurement difficult.
or hydrochloric acid in an ampule at 230°C. 3. Increased demands for the determination
A special decomposition technique is used for of submicrogram amounts of elements; fusion
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barytes, because heating of- the mineral with decompositions cannot be employed because of
concentrated HI at 300°C for 48 hr leads to high concentrations of impurities in the fusion
complete sulfate reduction to soluble sulfide.35 agent and undesirable reactions of the melt with
However, alkaline feldspars and acidic plagioclases the crucible walls.
are attacked to a lesser degree than they are by 4. Efforts to work out a universal process
HC1 under identical conditions. On the other hand, for complete dissolution of mixtures of minerals,
anorthite and sillimanite are completely de- which would make it unnecessary to consider the
composed. Selenium dioxide, which melts at phase composition of the analyzed substances; the
300°C under a pressure of 9 X 10 s Pa, was tested solution obtained could be used for the
as an effective fusion agent.36 Niobium and determination of both major and minor elements.
tantalum(V) oxides are dissolved in the melt at 5. New procedures for the preparation of
this temperature. A12O3 and Cr 2 O 3 form ultrapure acids for decompositions.
pyroselenates, which can be dissolved in an alka- 6. The difficult technology of the
line solution or in HC1. SiO2 does not react even production of very pure fusion agents and resistant
after 16 hr of heating to 420°C; SnO2 forms materials for fusion crucibles.
pyroselenate which is insoluble in the melt.
Some components can be released from the The pressure decomposition technique was used
analyzed substance by pressure decomposition widely only after introduction of polytetra-
with H 2 O. Fluoride present in a corundum single- fluoroethylene (PTFE, Teflon) as a material for
crystal plate (1 cm 2 , thickness 0.5 mm) is the reaction vessel. This method of dissolution was
quantitatively released by heating with 5 ml H2 0 employed as early as 1958 by Riley40 for the
at 240°C for 24 hr. This reaction is caused by ion determination of the alkali metals in rocks
exchange of fluoride for hydroxyl; the crystal containing resistant minerals. After common
surface is preserved for other physical tests.3 7 A dissolution in a mixture of hydrofluoric and
similar exchange reaction was. also observed with perchloric acids, the isolated undecomposed
barium titanate.3 8 fraction containing tourmaline, staurolite, rutil,
corundum, etc. was decomposed by HF in an
B. Decompositions in Autoclaves autoclave for 3 to 4 hr at a temperature of 150°C.
New models of pressure vessels with a plastic Ito 4 ' > 4 2 proposed a construction consisting of
reaction vessel closed in an autoclave metallic a steel autoclave with a PTFE crucible insert; and
mantle have been proposed, since the solutions he decomposed many minerals using a mixture of
obtained by substance dissolution in glass ampules HF and H2 S0 4 . The decomposition is remarkably
cannot be used for the determination of the main efficient: tourmaline, axinite, and cornerupine are
components (especially in silicate analysis). This dissolved within 2 to 3 hr at 240°C. A reaction
new technique, still in development, found wide time of 4 to 8 hr is sufficient for complete
use in analytical practice as late as the second half destruction of the crystal lattices of ilmenite,

June 1977 259

 chromite, magnetite, columbite, and tantalite. resistant mineral must be effected using acids
Dissolution of rutil and baddeleyite takes a long without introducing impurities from fusion agents
time (12 to 16 hr). The sample decomposition is into the reaction mixture. According to the
complete after 10 hr if only HF is present. Heating method developed in the Carnegie Institute,
to 250°C in a mixture of HF and HC1O4 leads43 50 mg of zircon are dissolved after 1 week sl
to complete dissolution of beryl, cyanite, stauro- when heated at 220°C in 2 to 3 ml of 48% HF.
lite, pyrite, chalcopyrite, and pyrrhotite within 1 Quite clear solutions are obtained. The de-
hr; only 35% of topaz is decomposed. The composition is employed routinely in many
behavior of many minerals and inorganic materials important geochronological laboratories of
(muliite, andalusite, beryl, lepidolith, zircon, Geological Surveys (e.g., in Finland or the German
corundum, quartz, cassiterite, chromite, spinel, Federal Republic). Using very pure hydrofluoric
ZrO 2 , and BaTiO3) during dissolution in a closed acid, the blank amounted to 0.5 to 5 X 10~9 g
system at 240°C, using mixtures of HF, HC1, Pb2+, while it increased to 0.2 X 10" 6 g Pb2+ with
H2 SO 4 , HC1O4 and H 3 P0 4 , has been reviewed in fusion with sodium tetraborate. The UO 2 2+ , Th4+,
the above study. 44 The reaction rate is strongly and Pb2+ ions are separated on ion exchangers
affected by continuous stirring of the mixture. after the dissolution, and their concentration is
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The decomposition is especially suitable for determined by mass spectrometry using the
complete analysis of glass-making sand. The isotope dilution method. After a short dissolution
sample need not be pulverized; a grain size below 1 period in an autoclave (3 hr) even at temperatures
mm is sufficient, so the danger of contamination of 280°C, zircon was detected microscopically in
during grinding is avoided. Simultaneously with the undecomposed residue. This mineral is not
the decomposition of quartz, resistant materials completely dissolved even in fuming 71 to 75% HF
which usually carry impurities in glass-making after 20 hr at 280°C; Borchert and Donderer52
sands (e.g., chromite and tourmaline) are had to employ a temperature of 400°C in a
completely dissolved. gold-plated autoclave.
For the determination of the isotopic
An autoclave with an aluminium mantle was
composition of U, Th, and Pb in geological
used by Wahler.4 5 He studied the decomposition
materials and chondrites, Arden and Gale 53 ' 54
process rate with HF and HC1O4 at 200°C under
recommend a HF pressure decomposition, possibly
stationary decomposition conditions. Corundum,
with the addition of HN0 3 . The dissolution takes
rutil, spinel, zircon, tourmaline, topaz, and some
from several hours to up to 2 days at a tempera-
garnets are dissolved slowly or incompletely even
ture of 110 to 200°C. Even pieces of meteorites
if the reaction time is prolonged and the grain
(~1 g) are decomposed. The reaction mixture is
size decreased. 46 ' 47 According to Wahler,4s the
evaporated in a stream of purified air or nitrogen.
Finnish Geological Survey48 uses decomposition
After dissolution of the residue in 6 M HC1, the
of spinel, beryl, and tourmaline in an Al auto-
pressure decomposition is usually repeated at 120
clave with a mixture of HF and HC1O4 to
to 180°C. In order to suppress contamination, the
determine Be by AAS. The decomposition of 5- to
Teflon vessel is first leached with 6 N HC1 at a
15-mg rock samples for the determination of trace
temperature of 120 to 180°C. Provided that zircon
elements49 by flameless AAS was successfully
does not contain an economically significant
carried out in the same type of pressure vessel.
amount of uranium, a temperature of 130 to
Dissolution of resistant rock-forming minerals,
170°C is sufficient for complete dissolution of the
such as tourmaline (schorl), sapphirine, or
uranium ore in HF and aqua regia; the time
staurolite, was studied by Popov50 in a pressure
required is 50 to 100 min, depending on the
vessel of his own construction.
analyzed material grain size. 55 Recently, various
One of the most difficult problems of pressure decomposition methods for uranium ores with
decompositions is complete dissolution of zircon; variable uranium contents bound in resistant
Dolezal et al. 44 did not succeed in decomposing minerals have been statistically evaluated.56 The
this mineral under the conditions specified by efficiency of pressure decomposition (with HC1 +
Ito. 4 ' As the data concerning the trace H 2 O 2 and H 2 SO 4 + KMnO4) was compared with
concentrations and isotopic composition of Th, U, the generally used procedure for the destruction of
and Pb in zircons are employed for geochrono- mineral materials by solutions of HF, H 2 SO 4 , and
logical purposes, the decomposition of this HNO3 at atmospheric pressure. These results show
260 CRC Critical Reviews in Analytical Chemistry
 that decomposition with HF and the two in a Teflon vessel tightly closed in an Al-block and
experimentally checked pressure decomposition heated to temperatures in the range of 150 to
procedures have an almost equivalent effect. 250°C, with continuous stirring with a Teflon-
Bernas57 managed to suppress interferences in coated magnetic stirring bar. The decomposition
the subsequent AAS determination of main rock was effected with 38% HF alone or in a mixture
components by judicious combination of reagents with HC1, HC1O4, or HNO3 (Method 2). The
and the decomposition technique. A 0.05- to excess HF is bound by adding H3BO3 or an
0.30-g sample was dampened with 0.5 ml of aqua aluminium salt. The main components and SiO2
regia and dissolved in 3 ml of 48% HF at a are determined simultaneously. The procedure
temperature of 110°C for 30 to 40 min in a developed was employed for the quality control of
pressure vessel of his own construction. The glass-making sands 78 (Method 1) and the major
solution was transferred into a plastic beaker using and minor components of bauxites 79 (Method 2).
a Teflon mouth, and the fluoride precipitate The newly proposed procedures have found use
formed was dissolved by adding 2.8 g H3 BO3. The in the analysis of ferrosilicon80 (Method 2),
solution was diluted to 100 ml and stored for 2 hr alkaline feldspars81 (Method 1), iron ores and
in a glass volumetric flask. After this time, gradual slags82 (Method 2), and sulfidic minerals83
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hydrolysis of HBF4 occurred with liberation of (Method 2) and rocks.84 No loss in SiO2 occurs
HF, causing corrosion of the glass. The universal when using the two decomposition techniques.
character of the decomposition and a favorable Decompositions of various mineral phases have
effect of HBF4 in the final AAS determination been reviewed in Langmyhr's work. 8s
were verified by other authors. The tech- A number of authors have dealt with the AAS
nique 5 7 ' 5 8 was employed for decompositions and determination of major, minor, and trace elements
analyses of tectites, lunar soils,59 clays,60 marls, in soils and rocks after an autoclave decompo-
raw powder and other cement raw materials6' and sition. 86 " 93 Grobenski94 employed a Perkin-
ceramic materials,62 oxides,63 various minerals, Elmer pressure vessel for this purpose and deter-
ores, and slags;64"67 for the determination of mined traces of Co, Cr, Cu, Ni, Pb, and V in addi-
cationic components and phosphates in natural tion to the major components in international geo-
phosphates 68 " 70 (especially when the phosphorus chemical reference materials. With ultrabasic rock
is bound to organic matter); 71 for decompositions peridotite PCC-1 and dunite DTS-1, the sample
of isolated magnetic and nonmagnetic meteorite weight had to be decreased to 0.05 to 0.1 g and
fractions;72 and for the determination of nitrogen the reaction time and the temperature increased to
in metals and nitrides. 73 ' 74 A material 30 min and 150°C, respectively. Granite, andesite,
decomposition by a mixture of HF, HC1O4, and and granodiorite are decomposed more easily; a
HC1 in a special pressure vessel was used for the 0.2-g sample is completely decomposed within 10
determination of microgram amounts of this to 30 min at 110 to 150°C. The precipitate
element in very pure Ta, Nb, Zr, and Cu. formed is dissolved in a H 3 BO 3 or an aluminium
Ammonia formed in the reaction is determined by salt solution. If a volatile component is to be
coulometric titration. 75 determined, the reaction mixture is diluted with a
F. J. Langmyhr and co-workers have recently saturated H 3 BO 3 solution immediately after
dealt systematically with the combination of opening of the reaction vessel. When destruction
pressure decomposition methods with AAS. In a of the crystal lattice of clay minerals (halloyisite,
specially constructed reaction vessel, they studied caolinite) and talc occurs as a result of mineral
the dissolution of ores, rocks, minerals, and acids attack (HC1, H 2 SO 4 , H 3 PO 4 ) at 240°C in a
inorganic products. 76 ' 77 The vessel type was Thermobox® autoclave, a gel-like silicic acid with
selected according to the decomposition tempera- a minimum content of impurities95 is precipitated
ture used. At temperatures below the boiling point in the absence of HF. Decomposition in the
of azeotropic hydrofluoric acid (112°C for 38.26% Parr-bomb was proposed for the subsequent
HF) a polypropylene or polycarbonate Erlenmeyer isolation of Rb and Sr from lunar rocks 96 from
flask should be used; this method (1) permits an the area of the Sea of Tranquility. A 0.15-g rock
increase of the temperature up to 130° C and sample spiked with 8 7 Rb isotope is dissolved in
dissolution of the many siliceus materials within 5 HF, HC1, and HC1O4 in an autoclave with a Teflon
to 30 min. Resistant material must be decomposed insert at 120 to 140°C. In order to decrease the

June 1977 261

 possibility of contamination, the analyzed material reliable results, the mineral is usually decomposed
was only very roughly pulverized in a boron by HF or H 2 SO 4 in the presence of an oxidant,
carbide mortar. whose excess is back-titrated with an Fe2+ salt.
Pressure decomposition was successfully These reagents are unstable at high temperatures
applied to analyses of other inorganic materials, and pressures and often react with the vessel walls
such as glass,97 slag,98 iron ore 99 and steel, 100 or with some rock components. The HF-H2SO4-
chiefly for the microanalysis of isolated inclusions KMnO4 system originally proposed by Ito 4 1 has
and the determination of zirconium101 and not been successful in analytical practice. Success-
aluminium.102 A similar procedure is also ef- ful methods of determining FeO in resistant min-
fective in analyses of ores and concentrates of the erals (chromite and staurolite) were obtained by
platinum metals and in the preparation of the dissolving the mineral in HF and H 2 SO 4 in the
corresponding standard solutions. It is recom- presence of excess ammonium vanadate: 110 0.25
mended for decompositions of ores and products g of the mineral is weighed into a Teflon crucible
containing iridium and osmium: 103 The material and 1 to 2 ml H 2 O, 10 ml 0.1 M ammonium
is heated in a mixture of HF and HC1 (1 + 10) at vanadate in H 2 SO 4 (1 + 1), and 5 ml 40% HF are
250°C for 3 hi, and the insoluble residue is further added. The crucible is placed in the autoclave and
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decomposed by fusion. Some platinum metals, is heated for 6 hr at 200°C. The reaction solution
which are difficult to dissolve under normal is transferred into a vessel containing 2 to 3 g
conditions, are easily transferred into solution H3 BO3, and excess vanadate is back-titrated with
using HC1 and HN0 3 in an autoclave. When heated an Fe2+ salt. The vanadate stability is checked by
at 180°C, as much as 0.5 g Rh and 0.25 g Ir are simultaneous blank determination. Although the
dissolved, as well as a Pt-Rh-Ir ternary alloy. The results obtained by this method are not
procedure is also successful in solution preparation comparable with values obtained by other
in the analysis of reforming catalysts. 104 " 106 chemical methods (they agree well with Mossbauer
Pressure decompositions are rarely used for spectroscopy), they yield the maximum FeO
differentiation among the individual valence forms contents for schorl, which are apparently most
of polyvalent elements (most frequently for the probable.
determination of FeO) in rock-forming minerals. Experience with decompositions of other
The reaction mixture containing HF is heated in a minerals has shown that vanadic acid also acts as a
tightly closed Teflon vessel in a boiling water bath decomposing agent, and its oxidizing properties
or in a metallic autoclave with a Teflon insert. The cause valence changes at the mineral-liquid
procedure developed by Riley and Williams107 for interface, thus accelerating the crystal lattice
the determination of FeO in milligram amounts of destruction. For example, the decomposition of
isolated minerals has been successfully used for the ferrilmenite (iserine) by a mixture of HF and
determination of FeO in amphibole, biotite, H 2 SO 4 was incomplete in the absence and
chamosite, and some rocks. Complete decompo- complete in the presence of vanadic acid under
sition is attained in a closed Teflon tube after 40 otherwise identical conditions; chromite behaves
min dissolution in a mixture of HF and H2 SO4 in similarly. The strong effect of this mixture
a boiling water bath. Kiss 108 employed a Teflon suggested the possibility of using this decompo-
vessel of his own construction for the same sition procedure for unpulverized materials. The
purpose. The decomposition of amphibole, solubility of isometric grains of certain garnets
magnesite, eclogite, basalt, and diabase is complete (almandine), amphiboles (kersutite and actinolite),
after 60 min in a boiling water bath. A minor and pyroxene was studied. It was found that
technical alteration can modify the reaction vessel decomposition is complete under the given
for pressure decompositions at 200°C. The same conditions and the residue does not contain an
author determined the FeO concentration in undecomposed original phase. However, the results
resistant minerals and rocks after dissolution in a of the determination fluctuated depending on the
pressure microvessel109 at a temperature of 100 degree of homogeneity of the mineral. While
to 200°C. garnets (four different samples) exhibited
relatively identical results, a greater variation was
The direct determination of FeO in solutions
observed with zonal amphiboles (four types). In
after pressure decomposition (at a temperature
any case, this procedure is advantageous for the
higher than 130°C) is not reliable. To obtain

262 CRC Critical R eviews in A nalytical Chemistry

 determination of FeO, as the gross errors con- When the concentration of the component to be
nected with the preparation and homogenization determined is low, it is preconcentrated by sorp-
of analytical samples are eliminated. The tion on an ion exchanger (together with Se, Bi, Sb,
experimental results showed that pulverization of and As). The ion exchanger is decomposed prior to
certain garnets (i.e., almandine) leads to almost the final determination by fuming nitric acid in a
complete FeO oxidation. pressure vessel116 (150°C for 4 hr). Losses in Ge
Experiments with glass ampules with pieces of as the volatile chloride or fluoride are prevented if
Teflon immersed in solutions of ferric and stannic the sulfidic material is dissolved in a Teflon
salts 1 ' ! have indicated that the Teflon vessel itself crucible closed in a pressure vessel.117 The use of
exhibits considerable reducing effects. Therefore, an autoclave prevents losses in As in the analysis of
the solution obtained by the decomposition of anorthite, petalite, muscovite, beryl, and some
cassiterite in hydrochloric acid contained pre- rocks. These materials are decomposed by an HF +
dominantly stannous ions. 44 H 2 SO 4 (HCIO4) mixture for 1 hr at 150°C, and
Reactions often occur during dissolution of sulfides are preoxidized by HC104. To determine
inorganic substances, leading to the formation of As in TiO2 using destructive activation analysis,
volatile compounds of the analyzed components the analyzed oxide is dissolved in HF (125°C for 3
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(Ge, As, B, Si, etc.). The results can then be to 4 hr) in a Parr pressure vessel complemented by
scattered even under rigidly controlled reaction a special aluminium heating block. The tightness
conditions. Sometimes these volatile elements are of the pressure vessel was tested using the 76 As
built into the crystal lattices of resistant minerals. isotope, in view of the formation of volatile AsF 3 .
Therefore, the reaction mixture temperature can- More than 88% of the As present passes into the
not be substantially increased in common decom- solution and a small part remains deposited on the
position procedures for these substances, because Teflon vessel.119
the ion or molecule formed immediately reacts There is no danger of volatilization of Hg in the
with the decomposing agents, giving rise to volatile dissolution of geological samples in a closed
compounds. Part of the element being analyzed is pressure vessel; the method was successful in the
then lost or part of the sample remains undecom- determination of nanogram amounts 120 in diabase,
posed; the results obtained are subject to a negative andesite, pyrite, and other sulfides. The decompo-
systematic error. Dissolution in a closed system sition of Hg is complete following 5 to 10 min
under pressure eliminates these disadvantages. This treatment with HF in mixture with HC1 and HNO3
procedure is chiefly employed in the determina- at 120°C. The fluoride precipitate is dissolved in a
t i o n 5 8 ' 7 7 ' 7 9 " 8 3 ' 1 1 2 of silicon in minerals, rocks, saturated H3 BO3 solution, and the Hg content is
and sulfidic ores; the SiO2 content (present as determined by flameless AAS. Although mercuric
soluble H 2 SiF 6 after decomposition with HF) is salts volatilize easily, the autoclave is closed very
then determined by AAS or spectrophotometry. A tightly and there are no losses, even with sub-
satisfactory closed vessel can also be made of microgram amounts of mercury. Copper ores,
polyethylene 113 and the decomposition can be concentrates, and tailings 121 are decomposed by
carried out at 65°C. H 2 SO 4 and KMnO4 (possibly with HF) at 150°C
Material dissolution in an autoclave has also for 1 hr. The process of quartz and glass 122
been used as a control procedure for detecting the dissolution in 40% HF solutions (in the presence
extent to which the component to be determined of HCIO4 ) was controlled by 7 Be, 7 s S e , 1 3 ' I, and
203
is lost during fusion or acid decomposition in an Hg isotopes. The losses observed were mostly
open system. Pressure decomposition generally below 1%; they amounted to as much as 4% only
yields the highest results which are very close to with iodine. Iodine diffuses into the Teflon vessel
the true value. The above procedure has been used walls and can be removed again by boiling with
for the evaluation of methods for the determina- HNO3. Nitrogen gases also diffuse into Teflon
tion of trace amounts of Re in molybdenite ores during prolonged use. In the "cold vapor" tech-
and concentrates 114 (Re 2 O 7 volatilizes at 227°C). nique (for the AAS determination of Hg), decom-
The results obtained by AAS after decomposition position in a pressure vessel (Parr) with HF and
with HNO3 with added NaC103 were compared in aqua regia yielded higher results 123 than parallel
an open and a closed system and after alkaline- dissolution in a H2SO4+HNO3 or HNO3+HC1
oxidative fusion. The dissolution of rocks in the mixture in the presence of KMnO4. On the basis
determination of Te was studied analogously.11S of the results of analyses of sediments with high

June 1977 263

l
 SiO2 contents (clays and soils), hornfels, and
andesite, it can be assumed that part of the
mercury is associated with silicates and can be
IT
ously, and defined standard SiO2 solutions can
readily be prepared. The quartz grains need not be
»d tint K<,
crushed; the dissolution is complete and suffi.
1

released only by destruction of the crystal lattice. ciently rapid with 1- to 2-mm grains. Complete
Mercury and its compounds deposited on mem- decomposition of halloyisite was achieved using
brane filters in the control of atmospheric pollu- 30% NaOH under identical conditions.95
tion are also released by oxidation with HNO3 in a Prolonged (1 week) extraction of pieces of
pressure vessel.124 Closed polypropylene bottles alkaline granite and granodiorite with dilute solu-
suffice for prevention of Sn volatilization in tions of NaOH and NaCl and with tap or distilled
decompositions of deep sea sediments, manganese water at 150°C was utilized by Ronge and
concretions, and red clays 12S by HF and HC1. The Bernhardsson136 in determining the resistivity of
organic matter is oxidized by H 2 O 2 ) which facili- rock walls of underground containers of industrial
tates liberation of Sn from sediments. One gram of hot waters. The authors determined the major
the rock sample is dissolved in 20 ml of 11 M HC1 rock components in the extracts by AAS; tap
and 5 ml HF by heating in a boiling water bath. water was most corrosive.
The use of pressure decomposition for the AAS In Teflon-covered autoclaves, pressure decom-
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determination of trace elements in coal is note- positions can be carried out at temperatures up to
worthy. 126 Organic substances (50 mg) are oxi- 250°C (the work 52 gives 280°C; Nalge manu-
dized by fuming HNO3 at 150°C for 2.5 hr; the facturer's literature 39 quotes 205°C), which some-
destruction of the inorganic fraction is completed times prevents complete sample decomposition
by adding HF after 15 min (at the same tempera- even if the reaction time is considerably pro-
ture). The Cd content 127 in coal and the SiO2 longed. Further increasing of the temperature
content in animal charcoal were determined under causes substantial deterioration of the physical
analogous conditions. 128 Procedures developed by properties; above 300°C, the formation of toxic
Kaiser et al., 1 2 9 Paus, 130 Holak et al., 1 3 1 and gaseous decomposition products may occur.
Krinitz and Holak 132 were successful in deter- Therefore, autoclaves covered with goldS2 or
mining volatile components in biological materials. platinum were constructed. 137 ' 138 The first
In analyzing ultrapure substances, the dissolu- attempts date from the end of the last century;
tion process is the principal source of contamina- however, the Jannasch device3"5 was not success-
tion and consequent error. These substances can ful because of serious technical shortcomings. In
be dissolved without contamination in special 1965 May and co-workers 137 ' 138 proposed a
pressure vessels using Teflon. Decomposition in a construction for a pressure vessel (made of the
closed system considerably decreases contamina- nichrom alloy) covered with a Pt foil or an alloy of
tion, and enables separation of the volatile reac- 80% Pt and 20% Ir, which is more resistant than Pt
tion product directly from the reaction vessel in an alone. The temperature in the 3.5-ml reaction
inert gas stream. 133 >•34 space can be increased up to 425°C. After 18
Hydroiodic acid was also employed for auto- to 20 hr, 1 to 1.5 ml of 40% HF (possibly with
clave decompositions. Its reducing effect (210°C the addition of H 2 SO 4 ) dissolves 25 mg of zircon
for 3 hr) causes conversion of baryte to soluble or 100 mg of phenakite, staurolite, and beryl. The
barium sulfide. Natural lead(II) sulfate (anglesite) crystal lattices of garnet, chrysoberyl, cyanite, and
is decomposed analogously. Thus, alkaline fusion sapphirine are completely destroyed; G-l andW-1
can be avoided; both minerals are decomposed standard rocks are also readily dissolved.
only negligibly by mineral acids under normal Chromite, corundum, and hematite are dissolved
pressure. 135 in HC1 in approximately the same time.
Reagents other than strong inorganic acids were The decomposition of zircon is not complete
employed only occasionally in pressure decompo- even at 280°C, according to Borchert and
sitions: 30% potassium hydroxide readily dissolves Donderer;52 therefore, they proposed the use of a
corundum at 240°C. In the solution obtained, the gold-covered autoclave. During the. action of
silicate is present as the monomer, which can be fuming 71 to 75% HF, the reaction temperature
advantageously utilized in the spectrophotometric must not decrease below 400°C for 30 min, in
determination of SiO2 as a silicomolybdenum order to decompose 99% of the mineral. In an
complex. Pure quartzes can be dissolved analog- 85-ml autoclave it is possible to decompose as

264 CRC Critical Reviews in Analytical Chemistry

J
 much as 10 g of zircon; the gold layer is more vessels is the Uniseal Company, 145 whose con-
resistant to corrosion caused by fuming HF than is structions are based on Bernas' works. S 7 ' S 8 )
platinum. 14 6-148 T h e wooing temperature is 110 to
The development and wide application of 180°C, and the maximum permissible pressure
certain instrumental methods (especially AAS) 8 MPa; the volume of the internal vessel is as much
have been manifested in an increased effort to as 75 ml. Teflon-covered autoclaves are also
construct and experimentally test new autoclave supplied by the Parr Company;149 the device was
types. Although they were originally only proto- used for the decomposition of lunar rocks 96 and
types, some pressure vessel types have been so coal. 126 The pressure can also be measured during
successful in practice that they are manufactured dissolution by an inbuilt manometer; this device
commercially. The reactions inside the autoclave from the Spex Company 150 can be used at
proceed either under stationary conditions or are temperatures of up to 180°C. The Juniper
hastened by rotation of the vessel, by rocking, or Company 151 recommends their autoclave for dis-
by stirring with a magnetic stirring bar encased in solution of cassiterite, columbite, asbestos,
Teflon; the vessel is then heated directly on the cyanite, and other materials. The Berghof
magnetic stirrer plate. A new modified autoclave Research Institute manufactures autoclaves152
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type was proposed by Langmyhrand Paus. 139 The (according to Tolg)34 with electronically con-
metallic mantle is made of a resistant Al alloy; the trolled decomposition temperatures. Steel pressure
temperature can be increased up to 200°C and vessels lined with Teflon are heated in an
regulated to ±0.5°C. Wahler 4S)46 employed pure aluminium block to 250°C for long periods and to
Al for the autoclave construction. Mineral 300°C for short periods; however, the Teflon
materials can be decomposed at a temperature of vessels become distorted at temperatures higher
200°C and a pressure of 2 MPa in the Teflon than 280°C. A device for simultaneous decom-
crucible insert. An apparatus for simultaneous position of ten samples is supplied commercially;
decomposition of 20 samples was described by more detailed information can be found in the
Tereshchenko. 1 ' 7 The dissolution (180°C) is appropriate journals.15 3 >' s 4
hastened by rocking of the pressure vessel. The Rantala and Loring 155 proposed a Teflon
effectiveness of this decomposition technique was pressure vessel without an outer mantle because
verified for the determination of Li, Cs, and Pb in the autoclave price is relatively high. The decom-
rocks. An interesting dissolution procedure has position of a 1 g sample (standard reference rocks
been described by Knoop. 40 Ten Teflon test tubes of the U.S. Geological Survey and sea sediments) is
each containing a 50 mg- sample and 0.5 ml 40% complete within 1 hr at a boiling water bath tem-
HF were inserted into the pressure vessel. Dolezal perature. Organic materials remain undecom-
et al. 44 proposed a thermostatted unit in which posed, 156 the residue being less than 3%. The de-
six samples are simultaneously decomposed vice is available commercially from the Morrison
and the dissolution process is accelerated by ro- Company.15 7 Decompositions under mildly in-
tating the pressure vessel; the device is com- creased pressure in a Teflon crucible with a
mercially available from Geotest under the screw lid are employed in the laboratories of the
name Thermobox®. 14 ' The construction of pres- French Geological Survey.15 8
sure vessels based on this principle was variously
The decomposition technique under slightly
modified. 39 ' 142 A cooling system 143 can also be
increased pressure has been used in analytical
built into the aluminum autoclave mantle, thus
laboratories because of its simplicity and the
accelerating the manipulation after decomposition.
availability of the instruments. Its introduction has
The device is commercially available from Perkin-
been made possible by progress in organic polymer
Elmer. The same company 144 manufactures Auto-
technology. Polycarbonate and polypropylene in
claves 2 and 3. The decomposition is carried out
particular have found successful use among new
on a metallic plate by stirring. The maximum
plastics; screw lids ensure sufficient tightness of
operation temperature is 160°C and the pressure is
the vessels, 39 ' 158 so that volatile compounds in
5 MPa; the device has a safety valve. Although
the analyzed components are not lost during
pressure decomposition with HCIO4 is often used
heating. This decomposition technique (in poly-
for rocks, the prospectus points out the danger of
ethylene vessels) was successfully employed to
explosion.
determine SiO2 content in fluorite raw materials.
One of the principal manufacturers of pressure Most common dissolution procedures lead to
June 1977 265
 losses of SiF4 formed by the reaction of CaF2 Future development should concentrate on the
with the silicates and quartz present.1 s 9 Trans- following fields:
parent polypropylene bottles were recommended
for the decomposition of silicate rocks. 160 The 1. Introduction of new organic polymers
finely powdered rock (0.1 g;-300 mesh) is dis- which are resistive and have favorable properties at
solved in aqua regia and HF on a boiling water temperatures above 400°C. Although some such
bath. Dissolution of four rock types was studied in materials have found use in cosmic research and
dependence on time; the individual phases in the military technology, they have not yet been tested
undissolved residue were identified by infrared in analytical work. The use of noble metals
spectrometry. The greatest difficulties were asso- apparently is not feasible, in view of their high
ciated with the dissolution of garnet, tourmaline, cost and easy corrosion.
andalusite, sillimanite, cyanite, staurolite, and 2. To date, changes in the redox conditions
hyperstene. Garnet and hyperstene are completely have been used minimally in pressure decom-
destroyed in 1 hr; the amount of other insoluble positions. Due to volume changes of polyvalent
minerals decreases linearly with the logarithm of ions, the complete destruction of the crystal
the reaction time. Andalusite can be dissolved lattice of the mineral to be analyzed and its
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after 5 hr, as can sillimanite and tourmaline; consequent dissolution may be attained more
cyanite and staurolite remain undecomposed. Con- readily. The necessary reaction duration may be
centrated HN0 3 or H 2 SO 4 accelerates the dis- substantially decreased and complete mineral dis-
solution process, but polypropylene is damaged. solution attained at a lower temperature. Struc-
Its decreased resistance to hydrogen peroxide in tural factors (e.g., the location of the polyvalent
HF and H 2 SO 4 solutions was described by ion in the crystal lattice, the formation and
Smith. 125 Polypropylene volumetric flasks are presence of vacancies, the structure of the product
very suitable for storage of solutions containing formed, and its behavior in the reaction mixture)
HF (after sample decomposition). can play a decisive role in this type of decompo-
Polycarbonate Erlenmeyer flasks are quite sition. The influence on the redox potential of
transparent, permitting observation of the whole some systems can help explain the dissolving
decomposition process and thus decreasing the effects of a H3PO4 + H 2 SO 4 mixture on tourma-
reaction time to a minimum. 7 7 ' 8 1 ' 8 4 ' 1 6 1 The line; a lack of polyvalent cations may be one of
maximum permissible temperature is 130°C, but the causes of the extreme resistivity of topaz and
heating of the flask in a boiling water bath usually cyanite.
causes a complete decomposition. 3. Thus far, the possibilities offered by
As some Nb and Ta minerals are weakly closed system pressure decompositions for the
attacked by HF (or HN0 3 ), Kallmann162 recom- determination of volatile components have not
mends the use of a HF+HC1 mixture under a been fully utilized. This dissolution type is still
slightly elevated pressure in a beaker covered with almost exclusively employed for the determination
a tightly fitting polyethylene foil. Tantalite, of SiO2, Hg, As, and occasionally for other
columbite, pyrochlor, microlite, euxenite, and components (e.g., B).
samarskite are dissolved, while zircon, cassiterite, 4. The treatment of the reaction solutions
and simpsonite remain undecomposed. from the autoclave has not yet been reliably
As documented by an increasing number of solved. When SiO 2 , together with excess HF, must
published works (especially since 1965), the be removed from the solution prepared from
problem of the development of a rapid and higher sample weights (> 2 g alumosilicates and
universal decomposition, enabling complete dis- rocks), surface active products, decomposable with
solution of mineral materials without respect to its difficulty, are often formed. This probably pre-
phase composition, still exists. A number of vents wider application of pressure decompo-
reviews have been published6 7 ' 8 S ' 1 4 5 ' 1 6 3 " 1 6 5 sitions in trace element determinations.
recently on this topic and a seminar was orga-
nized. 166 In order to achieve wider application of III. DECOMPOSITION IN
pressure decompositions in analytical practice, the OPEN SYSTEM
present devices must be modified for series work,
and PTFE distortion and metal autoclave corro- A. Decompositions by HF
sion during prolonged use must be decreased. Hydrofluoric acid occupies a special position

266 CRC Critical Reviews in Analytical Chemistry

 among decomposition agents. It is a weak acid (pK solutions of strong oxidants. The fluorides formed
= 2.9 in 0.5 M NaC104), and its effect as a solvent can be decomposed by evaporation with perchloric
depends primarily on its complexing properties; it or sulfuric acid directly in the Teflon dish., The
is the most pronounced of all hydrogen halide reaction time is longer in plastic vessels, as these
acids. 167 Fluoride has the smallest ionic radius polymers have poor thermal conductivity. There-
(1.33A) in comparison with other halides. It forms fore, devices for hastening the evaporation process
many series of very stable consecutive complexes, have been proposed. 168
especially with polyvalent cations with a high In analytical laboratories, 38 to 40% HF is
electric charge density (e.g., Zr4+, Ti4+, Al3+, Fe3+, generally used; its composition is similar to that of
etc.), where, due to the favorable steric conditions, the constantly boiling azeotropic mixture (38.26%
the number of ligands easily reaches the maximum HF, bp 112°C, p = 101-33 kPa). More con-
coordination number. centrated acid, 48% HF, is also commercially
Hydrofluoric acid is the only acid that reacts available; it is prepared by introduction of gaseous
with silicon, silicon dioxide, and silicates, forming HF into the azeotropic mixture. Very pure HF can
soluble H 2 SiF 6 and leading to liberation of now be prepared, utilizing new organic polymers
cationic components bound to the silicate lattice. in the construction of distillation apparatus and
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When heated, H 2 SiF 6 decomposes to gaseous reaction vessels. The costly Pt devices originally
SiF4> and the solutions formed are free of silicon. used have been replaced by distillation instruments
The formation of fluoride and oxyfluoride made of polyethylene, 169 > 270 polypropylene,46
complex anions facilitates dissolution of niobium, and Teflon. As the procedure employed often led
tantalum, and tungsten compounds and prevents to contamination of the distillate, ultrapure HF
precipitation of surface-active hydrolytic products was successfully prepared by saturation of water
in acidic solutions. However, reactions of some with gaseous HF from a pressure cylinder.171 'l 7 2
cations with fluorides yield sparingly soluble The gaseous HF was purified by passage through a
precipitates; this effect is utilized in separations of Teflon filter173 and by freezing-out in a tank
analyzed components. Procedures have been made from the Kel-F material. Isothermal and
developed for separations of rare earth cations subboiling distillation 174 " 176 in which 48%HFis
Th4+ and U4* from other ions that form soluble heated by a submersion element in a Teflon
complexes under identical conditions (e.g., Ta, Nb, container and HF distills without boiling has also
and Ti). The fluorides formed at low con- been used. This procedure enables the preparation
centrations are coprecipitated on separated in- of more concentrated HF (55 to 60%), which
soluble calcium or lanthanum fluorides. substantially shortens the reaction time required
Although hydrofluoric acid does not cause for dissolution of rock samples. Using 55 to 60%
valence changes during sample dissolution, it HF, rock pieces are completely dissolved in 1 day;
strongly affects the redox potential of the system the reaction time is 1 week using 48% HF. The
by forming various stable complexes with the efficiency of the separation of impurities was
individual ions of the redox couple. The oxidized checked by adding 2 0 8 P b ; in optimum cases it is
component usually forms more stable complexes. possible to obtain the acid with a lead content of
The reduced form of the given redox system is less than 0.001 ng Pb2+ per gram HF. The ef-
then readily oxidized by atmospheric oxygen, ficiency of various techniques has been critically
which causes negative errors (e.g., in the deter- evaluated in a study by Arden and Gale. s4
mination of Fe2+ in silicates after rock decom- Dissolution of glass and quartz in HF solutions
position by HF). was first described by Scheele 177 in 1771 and by
Substances are usually dissolved in Pt crucibles Bergman178 at approximately the same time. This
or in plastic vessels. Common polyethylene vessels decomposition was introduced into the field of
are used up to 70°C, linear polyethylene up to rock analysis by Berzelius.179 The reaction
120°C, and polypropylene or polycarbonate up to proceeds at various rates, depending on the crystal
130°C. A disadvantage of these plastic vessels is lattice type of the given SiO2-modification and on
the poor stability of the polymers toward strong the grain size of the mineral analyzed. Both a- and
oxidants (hydrogen peroxide, aqua regia, etc.). 0-quartz are dissolved rapidly enough even with a
Teflon is an ideal material as it can be used up to a relatively large grain size (glass-making sands and
temperature of 240°C and is stable even in fractions of very pure quartzes). The high-

June 1977 267

 temperature modification crystoballite (obtained Feldspars and most micas, amphiboles, and
by ignition of silicic acid gel) reacts violently, pyroxenes are readily decomposed. In order to
especially with fine grain dispersion. Coesite and dissolve accompanying sulfides (especially pyrite),
stishovite, polymorphous SiO2 forms (formed by an effective oxidant must be added (e.g., HN0 3 or
so-called shock metamorphism), do not dissolve in aqua regia). Chromite, occurring frequently in
HF solutions; on the other hand, prolonged basic rocks, remains undecomposed, as does
extraction of rocks in dilute HF and H2SO4 cassiterite in granite rocks. The resistivity of
solutions is used for the separation of these rare cassiterite toward HF was useful in studying
minerals from quartz and other common rock- differences between tin bound to this mineral and
forming minerals. 180>18 ' Hydrofluoric acid alone tin bound to silicates. 1 8 5 Analogously,
is sometimes used for dissolution, but de- chromite, 186 common spinel, chrysoberyl, rutil,
compositions are carried out in mixture with corundum, and graphite or diamond can be
strong acids (especially H 2 SO 4 , HC104, HC1, isolated. These accessory minerals are con-
HNO3, and aqua regia), which simultaneously centrated in the undissolved rock fraction and can
destroy the crystal lattices of other accompanying readily be identified microscopically or by X-ray
nonsilicate rock minerals (pyrite, magnetite, and spectral analysis;187 however, the original
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calcite, etc). When the solution evaporates, a undissolved mineral phase must be differentiated
ternary azeotropic mixture of H2O (54%) HF from newly formed precipitates. 188 Dissolution of
(10%) and H 2 SiF 6 (36%) is formed. This mixture sediments in HC1 and HF is utilized for the
boils without changing composition, and the final isolation of organic matter and micro fossils;189
solution is free of silicon. Because of the HF however, about 30% of the organic component
character (weak acid) and the formation of passes into solution.
complex fluorosilicate as the reaction product, the Owing to the complexing properties of HF, the
reaction is slowed down by addition of a strong selection of analytical methods for the determi-
mineral acid. 4 3 ' 1 8 2 The dissolution kinetics was nation of the individual components is rather
followed in detail with quartz, staurolite, and limited. For example, fluoride prevents quanti-
epidote 43 in HF solutions and after addition of tative separation of aluminium hydroxide, and
HC1, HCIO4, or H 2 SO 4 . The dissolution rate is its complex formation interferes with the spec-
most significantly decreased with quartz and trophotometric determination of many metal
epidote; there is no effect with staurolite. Alkali ions (e.g., Zr4+, Ti4+, Fe 3+ , Al3*, Be2+, etc.).
metal, alkaline earth, and heavy metal silicates, as Fluoride is thus displaced from the reaction
well as minerals of the zeolite group, are very mixture by heating with another mineral acid,
easily dissolved when treated with HF. Silicates generally H 2 SO 4 , HC104, or H 3 PO 4 . So far it has
with high aluminium contents (especially topaz been assumed8 that addition of a strong acid
and modifications of the Al2SiOs compound) and prevents the formation of volatile fluorides
with a lack of polyvalent cations are decomposed (especially Ti4+ and Zr4+) during evaporation.
with difficulty. However, it is more probable that an apparent loss
To date, no relationship between the silicate in these elements is caused by the masking effect
structure and its solubility in HF has been found. of fluoride in the final determination method,
Andalusite, sillimanite, disthene, zircon, staurolite, rather than by the formation of volatile
axinite, and tourmaline are very poorly soluble. compounds. Removal of fluoride from the
The solubility of some minerals (especially garnets, reaction mixture by repeated evaporation with a
some kinds of tourmaline, beryl, and lepi- strong, poorly volatile mineral acid is tedious.
dolith) 183 depends on changes in the isomorphous Moreover, the data published in older works are
composition. This procedure has been employed not quite reliable, because sensitive methods for
for purification of monomineral zircon the determination of small fluoride amounts,
fractions184 because zircon is resistant to HF + especially in rock polycomponent materials, have
H 2 SO 4 mixture, even at an elevated temperature been developed only recently. Fluoride displace-
of 240°C. The dissolved Zr4+ ion (3 to 5%) ment by H 2 S0 4 is more efficient than by HC104,
probably comes from the more easily decom- as a substantially higher reaction mixture
posable ZrO2 (baddeleyite) or, more likely, temperature is attained during evaporation (200 to
from a metamict conversion in the mineral surface. 250°C). After repeated evaporation, the fluoride is

268 CRC Critical Reviews in Analytical Chemistry

 . practically completely removed. 7 6 ' 1 9 0 ' 1 9 1 If the analysis yielded fluoride contents of up to 48%
solution contains a larger amount of calcium salts and aluminum contents of up to 20%; other major
(when H2SO4 is used), the fluoride displacement components included Fe, Mg, Na, and K. In order
is not complete even after two evaporations; the to dissolve these precipitates, concentrated
fluoride remains adsorbed in the precipitated solutions of beryllium and aluminum salts are
CaS0 4 . The removal of fluoride is especially employed, 76 ' 198 as they react with the precipi-
strongly hindered by the presence of excess Al3+ tate to give simpler soluble fluoride complexes.
(Ti4+, Zr4+) in the use of both H 2 SO 4 and HC104. The most frequently used, but less effective,
It is sometimes recommended that H3PO4 be used reagent is boric acid. One disadvantage of these
for this purpose, but the most reliable procedure is dissolution procedures is the introduction of
fusion of the evaporation residue (after the another compound into the solution, which makes
decomposition of the rock material with HF) with some determinations more difficult or prevents
K 2 S 2 O 7 . Fluorides must be carefully removed in them (e.g., Al). Difficulties are also encountered in
the determination of zirconium. 192 ' 193 Oxalic the AAS determination of low concentrations of
acid has also been used for removal of fluoride; an alkaline earths in the presence of extreme excesses
excess can readily be decomposed by heating to of Al. Here the addition of H3BO3 is more
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200 to 250°C, which produces carbonates which advantageous. Beryllium aerosols are very toxic.
can easily be dissolved in acids. 194 However, precipitates formed during the
Evaporation of solutions with dissolved decomposition or during solution evaporation to a
alumosilicates leads, especially with higher sample small volume or to dryness (sometimes after
weights (> 1 g), to the formation of sparingly evaporation of the residue with HC1O4 and
soluble reaction products with high contents of dissolution in dilute HC1) could not be completely
aluminum and fluoride. These compounds are not dissolved by this procedure. Insoluble reaction
completely decomposed even after multiple products are also formed even with small sample
evaporation with HC1O4, H 2 SO 4 , or HC1. For weights and are usually imperceptible in solutions
example, in a German rock standard, slate TB, the due to the very fine precipitate dispersion. With
insoluble fraction (after decomposition with HF, higher sample weights (>1 g), variable amounts of
evaporation with HC104, and dissolution of the reaction products are often formed; this fraction
residue in HC1) consists mainly of a precipitated varies irreproducibly between 0.5 and 7% with the
complex fluoride, while the fraction of resistant above standard slate. 195 When a larger amount of
minerals actually present in the rock is small. 19S rock is employed for the analysis, the con-
Langmyhr and Kringstad196 chiefly identified centrations of the reactants are markedly increased
compounds of the type Fe11 (All F e i n ) F S ' toward the end of the decomposition, thus,
xH 2 O, NaAlF4-xH2O and MgAlF5-xH2O in compounds unusual in both type and structure are
the isolated fraction; these substances were precipitated. Their identification is difficult, as the
mostly obtained by dissolving pure oxides or appropriate X-ray structural data are lacking.
carbonates in HF. Precipitates obtained in Some data on the solubility of certain simple
common dissolution procedures with rocks have compounds were given by Langmyhr et a l . ; 1 " the
more complicated compositions, determined by MgAlFs compound, obtained by precipitation in
the initial composition of the analyzed rock and solutions containing Al3+ and Mg2+, is least soluble
by the decomposition conditions.19 5 " 19 7 (Table 1).
In the decomposition of the mentioned The formation of insoluble compounds during
standard slate TB with a defined phase compo- the decomposition complicates the determination.
sition, a substance structurally close to rare of Ca in kaoline; the complex fluoride separated,
mineral ralstonite, Na(Mg, Al)6 [F, OH] 1 8 -3H2O, containing adsorbed Ca2+ ions, is not completely
was isolated from the residue after evaporation dissolved even by prolonged evaporation with
with HF and HC1O4. The distribution of the HC104. The determination of traces of Ba2+ is
individual elements, particularly F, Al, Fe, Mg, Ti, subject to similar difficulties;200 among 14
and Na, was studied in this precipitate using an analyzed rocks, the insoluble residue contained
X-ray microanalyzer;195 only negligible amounts more than 20% of the Ba present in seven cases,
of the original undecomposed phases were present even if the rocks analyzed did not contain resistant
(virtually only rutil and tourmaline). Chemical baryte. This problem can be partially solved by

June 1977 269

 TABLE 1 SrCl2 is separated from excess aluminum 203 by
treatment with very dilute HC1.
The Solution Composition in the Iron and aluminum sulfates formed during the
Analysis of Slate Tonschieffer TB
decomposition are thermally decomposed, forming
Concentration oxides, from which alkali metal sulfates can be
Ion (mol/l) extracted with water. 2 0 4 " 2 0 6 However, alkaline
earth sulfates are thermally stable under these
Na+ 1.7 conditions. The extraction of K+ and Li+ is not
K* 3.3
Ca" 0.2 complete, 207 " 209 as they are absorbed by ignited
MgJ* 1.9 A12O3. These procedures have been superseded by
Mn" 0.03 flame spectrometric methods for direct
Al3* 16.1 determination of the alkali metals without
Fe3* 3.5 separation.
PO 4 3 0.05
Polyvalent elements are present in various
valence states in crystal lattices of solid substances.
Note: Standard rock from ZGI Berlin;
the concentrations given above On dissolution they can be reduced or oxidized;
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are obtained after dissolution of 2 sometimes they react with the solvent, are
g of the rock and solution evap- oxidized by atmospheric oxygen, or the ions
oration to 0.5 ml. formed react together. In inorganic analysis these
problems are encountered particularly in analyses
AAS determination using a low-weight sample in of ferrites and in the determination of Fe2+ in
an HF solution without preliminary removal of various materials (e.g., glass and rocks). 210 In
SiO 2 ; a small amount of a precipitate can be lunar rocks, lower valence states of other elements
dissolved by adding H 3 BO 3 . The fluoroborates must also be determined, e.g., Ti3+ and Cr2+. Thus,
formed decrease mutual interferences in the a successful'determination depends not only on
determination of major rock components by complete dissolution of the analyzed substance,
AAS.5 7 Another reliable procedure is isolation of but also on the maintenance of the given ion in the
the precipitate by filtration and its transfer into original valence state. Errors may have been
solution by fusion (with lithium borate, B 2 O 3 , committed in the initial stage of sample prepara-
Cs2CO3 or CS2S2O7) and dissolution of the melt tion. Fine powdering of a mineral in the presence
in a strong acid. For decomposition of these of air causes rapid oxidation of the FeO present,
sparingly soluble fluorides, treatment with 6 N which is the most important cause of errors in
HC1 at 120 to 180°C in a closed system under determinations, especially with hard minerals
pressure has been recommended.54 Difficulties are requiring prolonged powdering for preparation of
encountered, especially in the determination of the analytical sample. Certain garnets (especially
high concentrations of potassium. The precipitate almandine), pyroxenes, and amphiboles are
formed, containing complex fluorides,201 retains oxidized very rapidly. Therefore, it is recom-
substantial amounts of potassium and is usually mended that the final fine analytical sample be
enriched in potassium compared to the originally prepared by pulverizing small pieces under acetone
analyzed mineral. The precipitate slowly dissolves or ethanol or in an inert gas atmosphere.
in 1 M HC1 and the final AAS determination of The results obtained were improved by using
potassium is carried out after standing in a diluted Teflon vessels for the decomposition; an inert
solution for 24 to 72 hr. After ignition of the atmosphere can also be maintained perfectly.
residue obtained by evaporation of the sample with Transparent polypropylene bottles with screw
HF and HC104, thermal decomposition of caps 211 or polycarbonate flasks39'77 in which the
perchlorates occurs, alkali metal salts are whole dissolution process can be watched are also
converted into the chlorides, and alkaline earth suitable. The dissolution is best carried out in a
salts are decomposed to a mixture of chlorides and boiling water bath.
oxides. At 500 to 550°C ferric and aluminum Undesirable chemical reactions frequently
perchlorates are converted into the corresponding occur in the solutions obtained, leading to
oxides. Alkali metal chlorides 202 are isolated by oxidation of Fe2+ or reduction of Fe 3+ . Higher
extraction of the ignited residue with water, and oxides of manganese exhibit oxidizing effects.

270 CRC Critical Reviews in Analytical Chemistry

 Organic matter and certain other as yet sample weights (0.2 to 0.5 g), 10 ml HF and 0.1 g
unidentified rock components always present in vanadate (as a solution acidified with H 2 SO 4 ) are
rocks of sedimentary origin have reducing added. The reaction is allowed to proceed in a
properties. 212 ', 213 Graphite does not react with Teflon dish, preferably overnight without heating.
the Fe 3+ present. The reducing properties of some Excess oxidant is back-titrated with a ferrous salt
components (sulfides including pyrite and organic using diphenylamine indicator. Sulfides (including
materials) are especially pronounced if the pyrite) and organic materials interfere. This
decomposition proceeds in the presence of excess method was successfully applied to the
oxidant. Metallic iron 2 1 4 also has strong reducing determination of FeO in rocks, 2 2 0 " 2 2 3 ashes, 224
properties (from abrasion of homogenization and mineral allanite. 225 Heating of silicates in
devices). solutions containing HF, H 2 SO 4 , andK 2 Cr 2 0 7 in
The FeO concentration is usually determined order to determine FeO was proposed by
by oxidimetric titration or the excess oxidant is Hackl 226 as early as 1925. When small amounts of
back-titrated with a reductant (the Mohr salt). Fe 3+ are present in the analyzed solution,
Usually, only easily decomposable minerals are dichromate is spontaneously reduced; the cause of
dissolved directly in HF and H 2 SO 4 . If a mineral this reduction in HF solutions has not yet been
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decomposes very slowly, it is dissolved in the unambiguously clarified.227 This undesirable

presence of excess vanadate, bichromate, or reaction is strongly suppressed by addition of a
permanganate. It is then unnecessary to maintain ferric salt, 2 2 7 " 2 2 9 so that the FeO can then be
an inert atmosphere during dissolution, as Fe2+ determined in some garnets, augite, epidote,
ions liberated are immediately oxidized to Fe3+; glaucophane, and other minerals. The two
complete decomposition by HF and an oxidant is procedures were critically evaluated 230 and the
sometimes achieved at laboratory temperature. As vanadate procedure was found to be better.
the fluoride complexes of tervalent iron are much Permanganate, which is also used occasionally is
more stable than those of divalent iron, the formal poorly stable in HF solutions.2 3 1
redox potential of the Fe3*/Fe2+ system con- Divalent iron can also be determined after
siderably decreases. Therefore, Fe 2+ ions are very oxidation with IC1 in a medium of HF and
easily oxidized in HF solutions and an inert HC1; 232 the iodine liberated according to the
atmosphere must be very carefully maintained reaction
during dissolution. Before titration, the fluoride is
bound by adding boric acid, which dissolves 2IC1 + 2 F e " - 1 , + 2C1" + 2Fe 3 *
complex fluoride precipitates which can contain
Fe 2+ . In spectrophotometric determination of is determined by titration with iodate (in the
FeO, a reagent that reacts only with Fe2+ is used; presence of CC14) or with thiosulfate. Obsidian
the sample is dissolved most frequently in the and plagioclase are dissolved within 1 to 2 min in
presence of phenanthroline or a triazine deriva- solutions of HF, HC1, and IC1 in a Pt dish 2 3 3
tive. 1 0 9 - 2 1 6 while pyrite is not attacked to a greater extent.
This direct method of determining FeO is not Nichols 234 modified this procedure for sedi-
suitable for resistant materials. The behavior of mentary rocks with organic components. The rock
garnets and glaucophanes2 l l in HF solutions decomposition can be visually followed in a
depends on their chemical composition. Among centrifugation test tube 2 3 s made of an ethylene-
micas, flogopite is dissolved most slowly; alkaline tetrafluoroethylene polymer (Tefzel® from the
amphiboles and pyroxenes require prolonged Nalge Company 39 ). Oxidation with IC1 was also
treatment with HF and H 2 SO 4 for complete employed in the determination of Fe2+, Cu+,
decomposition. Siderite 2:8 is slowly dissolved in metallic copper, and arsenite in glasses. 236 " 239
this medium, which is uncommon among Iodate is reduced to iodine by Fe2+ in a HF and
carbonates. Rutil, corundum, cassiterite, spinel, H 2 SO 4 medium; the iodine is removed by boiling
and chromite remain completely undecomposed. the reaction mixture:
Vanadate is most suitable for decompositions in
the presence of excess oxidant; dichromate is also 10FeJt + 2IO3 " + 12H* - 10Fe3f + I, + 6H,0
used often, while permanganate 2 ' 9 is only
occasionally used. When employing common Excess iodate is titrated with thiosulfate. This

June 1977 271

 method was employed for the determination of the isolated resistant fraction fused with KHSO4
FeO in standard G-l and W-l rocks. 240 or Na2 O 2 .
The decrease in the redox potential of the Decomposition with HF is also one of the few
Fe3+/Fe2+ system due to the presence of fluoride reliable procedures for obtaining a stable solution
enables selective oxidation of FeF 6 4 " ions by a after dissolution of Nb and Ta minerals; it is used
silver salt: 241 with both poor ores and concentrates. The disso-
lution is facilitated by the formation of complex
anions, (TaF 7 ) 2 " or (NbF 7 ) 2 ". A decrease in the
HF concentration is accompanied by conversion of
Excess Ag+ is titrated with bromide. This proce- the niobium complex 251 into an oxyfluoride
dure has been successful in practice especially in complex (NbOF s ) 2 ~; this effect was analytically
the determination of FeO in the presence of utilized (e.g., in the extraction separation of the
organic substances and small amounts of sulfides. two similar elements). The decomposition of Nb
The precision of the FeO determination (Ta) minerals by HF was introduced into ana-
depends not only on the presence of interferants, lytical practice as early as 1883 by Smith2 S 2 in
but also on the Fe(IH)/Fe(II) ratio in the analyzed the analysis of samarskite. Minerals with niobium
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material. Therefore, Fe2O3 is sometimes deter- predominating are decomposed more easily; the
mined directly (e.g., by titration with a mercurous decomposition is usually terminated by fusion
salt, 242 ferrocene,243 EDTA, 244 or coulometri- with KHSO4. In analyses of polycomponent ores
cally 2 ' 3 by generated Ti 3+ ). (e.g., containing cassiterite and zircon), dissolution
Hydrofluoric acid is a very important solvent in HF is sometimes combined with acidic
for titanium ores. It decomposes the silicates pres- (KHSO4) and alkaline (Na2CO3-sodium tetra-
ent and hastens the dissolution process by forma- borate or Na 2 O 2 ) fusion of the undissolved frac-
tion of stable fluoride complexes. The solutions tion. 253 Microlite is almost completely dissolved
thus obtained do nothydrolyze; consequently, this in dilute HF at laboratory temperature, 254 but
procedure has found use in analyses of niobates columbite reacts more slowly. Pyrochlor is also
and tantalates with high titanium contents. The dissolved;255 when a high concentration of iron is
material is usually dissolved in HF in the presence present, the ore is first extracted with diluted HC1,
of another acid, especially sulfuric or perchloric. in which this mineral is virtually insoluble.
In order to ensure complete material dissolution, Brazilian ores containing barium niobate (pan-
the decomposition is terminated by fusion with daite) are extracted with a mixture of HF and
KHSO4. Among titanium oxides, rutil does not HC1, which yields more reliable results than direct
dissolve in HF even under elevated pressure; on the fusion with KHSO4 and dissolution of the melt in
other hand, anatase is readily dissolved in the above tartaric acid. 256 " 257 During dissolution of Nb
acid mixture. Ilmenite and loparite are decom- (Ta) minerals in HF, a precipitate of thorium(IV)
posed analogously, as is titanite. 245 " 248 and uranium(IV) fluorides is formed; it has been
Generally, in combination with HF, HC104 is less experimentally verified that the precipitate also
effective as a dissolution agent than H 2 SO 4 , with contains hexavalent uranium. 258 If the com-
which the reaction mixture temperature can position of the analyzed ore is not known exactly,
further be increased by adding an alkali sulfate the whole sample must be dissolved prior to
that also serves as a fusion agent in the terminal analysis by combining various decomposition pro-
stage of the decomposition. Perovskite structure cedures. The specialized literature often contains
minerals are dissolved with difficulty, and the contradictory data concerning the decom-
entire process must be repeated many times. 249 posability of various Nb-Ta minerals, which can be
Dissolution of large samples (up to 30 g) of Ti ores explained by changes in solubility due to mutual
is a very difficult analytical task; in spite of this isomorphous displacement between Nb and Ta, as
fact, many very effective procedures have been well as by variability of the concentrations of
developed (e.g., for the determination of traces of other mutually exchanging components.
platinum metals in titanomagnetites or kimber- Decomposition with HF combined with HN0 3 >
lites). 2s0 Samples with excess Ca2+ are dissolved H 2 SO4, or HCIO4 belongs among standard
in a HF and HC1 mixture. The individual decom- procedures employed in analytical evaluation of
position stages must be repeated several times and uranium and thorium ores. These procedures are

272 CRC Critical Reviews in Analytical Chemistry

 particularly useful when the ore-bearing mineral is H 2 SiF 6 concentration is much lower than in the li-
finely included in silicate rocks. The chief indus- quid. 7 6 ' 2 6 6 When solutions containing H 2 SiF 6
trially important uranium ore minerals (e.g., are evaporated at laboratory temperature or heated
pitchblende, uranium micas, uranium blacks) are to 60°C and the liquid volume is not decreased sub-
readily dissolved in this way; tetravalent uranium stantially, losses in SiO2 are negligible. Even at a
is oxidized to hexavalency during the dissolution. temperature of 100°C there is no perceptible vola-
Thorium minerals (e.g., monazite), are more tilization of H 2 SiF 6 in the initial stages of evapora-
difficult to decompose. However, for geochemical tion. 2 6 7 After evaporating to a small volume, the
purposes, it is often necessary to determine even composition of the liquid phase becomes identical
trace contents of the two elements (of the order of to that of the constant-boiling ternary mixture of
units or tenths of parts per million); the whole HF-H2SiF6-H2O; H 2 SiF 6 quickly escapes from
analyzed rock sample is then dissolved, usually the solution. This provides the necessary
combining several very effective decomposition theoretical conditions for the determination of
techniques in order to decompose resistant SiO2 after dissolution in HF (e.g., in iron
minerals containing U and Th, such as zircon. ores 2 6 8 ' 2 6 9 andfluorites 159 ).
After decomposition with HF, the residue is Fluorides of a number of other elements are
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isolated and fused with sodium carbonate and also volatile; the melting and boiling points for
tetraborate or with B 2 O 3 or it is sintered with some compounds are given in Table 2. These
N a 2 O 2 . 2 5 9 ' 2 6 0 With basic rocks and sediments values 270 often are not in accordance with
with a high concentration of CaCO3, formation of knowledge gained during long analytical studies. In
CaSO4 during the decomposition should be reactions of HF with solid phases, volatile fluo-
avoided, as it may retain thorium. rides of the above-given composition are not
The low solubility of uranium(IV), thorium, formed under the decomposition conditions. The
and rare earth fluorides is often utilized in overall reaction is further complicated by side
analytical practice for group separation of these reactions, giving rise to nonvolatile complex
components. As the precipitates formed are fre- fluoride anions (with the maximum coordination
quently colloidal and present difficulties in filtra- number in the presence of excess HF) and to the
tion, a calcium salt is added. The CaF2 precipi- formation of oxyfluorides and other hydrolytic
tated forms isomorphous compounds with UF4 products. Substantially larger losses in the form of
and serves as a collector. 261 " 263 However, the volatile fluorides have been observed with As(III)
precipitate is often contaminated with Fe, Al, Zr, than with As(V); Se(IV) and Te(IV) behave
and Ti salts, which form binary fluorides with analogously in comparison with Se(VI) and
Ca2+. Te(VI). According to Table 2, fluorides of higher
Combinations of decomposition agents (HF, valence states are much more volatile; however,
HNO3, HC1) have proven effective in treatments of they are probably not formed in the reaction
large soil samples for determinations of certain
transuranium elements. 264 Plutonium is isolated TABLE 2
from the final nitrate solution by anion exchange.
The Melting and Boiling Points of Some Fluorides
The efficiency of the procedure equals 53 to 60%
of the overall Pu content, compared with the Melting Boiling
results obtained after sample decomposition by Compound point (°C) point (°C)
fusion with Na 2 CO 3 . Of tungsten minerals,
scheelite, wolframite, and tungstite dissolve in HF BF3 -128 -100
GeF4 — -37 a
solutions; tungstate is extracted using potassium
SiF4 — -95 a
hydroxide from the evaporation residue.2 6 s SnF4 450 705
Under strictly defined reaction conditions the TiF4 - 284
solution obtained after dissolution of SiO2 by HF ZrF4 — 900
AsF3 -8.5 63
can be heated in a water bath without volatiliza-
AsF5 -79.8 -52.8
tion of SiF 4 . This can be explained on the basis of SbF3 292 376
the ternary diagram for the H 2 O, HF, and H 2 SiF 6 SbF5 7 150
system: Close to the region of azeotropic mixture NbFs 72 236
of HF and H 2 O, the liquid ternary mixture is in
a
equilibrium with a gaseous phase in which the Sublimation.
June 1977 273

L
 mixture during decompositions with HF or H 2 SO 4 , and I I 9 S n causes considerable losses in
immediately undergo hydrolytic reactions. On the Sn (up to 25%).' 2 5 In view of the high boiling
other hand, experimental results indicate that point of SnF 4 , this loss cannot be explained by
fluorides of lower valence states are formed the formation of volatile SnF 4 .
rapidly and cause great losses in some elements Because of the exceptionally high volatility of
through volatilization, e.g., As(III). Contradictory BF 3 , the materials for the determination of boron
data on the volatility of various components (quartz, silicon, silicates) must be dissolved very
frequently appear in the literature. Apparent losses cautiously, preferably at a temperature of 20°C in
may be due to the masking effect of fluoride in a plastic vessel. 283 ' 284 Nonvolatile fluoroboric
the determination of the element or to formation acid is formed by the reaction between borates
of insoluble films irreversibly adsorbed on the and HF; it then reacts with basic dyes giving rise to
vessel walls, etc. The data concerning volatilization a colored associate extractable into organic
of As from HF solutions are often very variable. solvents. Other components, e.g., the TaF 7 2 ~
Most authors 2 7 1 ' 2 7 2 agree that As(III) volatilizes anion, react analogously. In the determination of
as AsF 3 ; during evaporation of solutions to tantalum, the interfering boron is removed from
H 2 SO 4 fumes, losses of up to 45% were detected the solution by a suitable modification of the
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using the 74 As radioisotope. Heating of As com- dissolution conditions, 2 8 5 so that BF 3

pounds in an oxidizing mixture of HNO3-HCIO4- quantitatively escapes. All the boron is also lost
HF leads to complete volatilization2 7 3 ' 2 7 S of As. after evaporation of an HF solution with H G 0 4 .
However, this decomposition technique was used The formation of BF 3 is prevented by adding
for the determination of microgram amounts of As mannitol. The mannito-boric acid formed does not
in silicate rocks and minerals without observing volatilize even during evaporation of solutions to a
losses 276 of As. During cautious evaporation of smaller volume; 2 8 6 ' 2 8 7 the procedure has been
As(III) salt solutions with HNO3 and HF, used in the analysis of quartz and quartz glass. The
losses 273 in As of up to 30% have been detected effect of H3PO4, which binds boron and prevents
using 7 4 As; this is in accordance with data given its volatilization,288 is noteworthy. The solutions
by Ploum. 277 Nevertheless, this solution prepa- are evaporated after addition of H 3 PO 4 and SiF4
ration is employed in the analyses of sulfidic volatilizes completely. In the terminal stage, the
ores. 278 No losses in As have been observed279 in reaction mixture can be heated up to 150°C
the analysis of silicates after material dissolution in without formation of BF 3 . Dissolution of soils in
HF and HN0 3 and oxidation with KMnO4. This HF and H2SO4 was recommended in geochemical
oxidizing mixture has been recommended for the prospection for colemanite. 289 However, standard
decomposition of glasses280 (the determination of G-l and W-l rocks do not release boron com-
total arsenic); AsF3 volatilizes after treatment pletely when treated with HF at laboratory
with HF, and As(V) remaining in solution can be temperature.
determined. The content of the individual valence
The accuracy of the determination of traces of
states of arsenic can be found from the difference
Ge in rocks depends strongly on the method of
between the two determinations. As the data given
preparation and dissolution of the, analyzed
for the As volatility are quite contradictory for
material. The use of HF cannot be avoided, as
certain decomposition procedures, it is necessary
Ge(IV) is isomorphous with Si(IV) and is built
to assume further interaction with the components
into the crystal lattices of silicate materials.
of the dissolved material. In contrast to arsenic,
Sulfides may also contain Ge(II); thus, the
antimony compounds do not volatilize when
decomposition must be oxidative. In the analysis
treated with HF and H 2 SO 4 mixture even if the
of coal ashes, considerable losses in Ge occur
solutions are evaporated to the appearance of
during the combustion process. A mixture of HF
dense SO3 fumes. No losses have been observed,
with HN0 3 and H 2 SO 4 is usually employed for
even with trace concentrations 281 or in the
silicate dissolution, but more reliable results are
analysis of raw Sb 2 O 3 . 2 8 2 During evaporation of
obtained using H 3 PO 4 as an acid of low
solutions with a HF and HC104 mixture, the losses
volatility, 290 ' 294 instead of H 2 SO 4 . Adding
amounted to 10%. Addition of HN0 3 causes a
potassium phosphate is also very . effective.
decrease in these losses similar to that caused by
Reactions taking place between germanic (boric)
2 73,2 75
A s
and phosphoric acids are not sufficiently
Evaporation of solutions containing HF, understood; in view of the similarity between
274 CRC Critical Reviews in Analytical Chemistry
 germanic and boric acids, their reactions will be of in HF and solution evaporation with HC104.
the same type. With boric acid, BPO4 is probably Thallium compounds do not volatilize when
formed. 295 solutions containing HF, HN0 3 , and H 3 PO 4 are
Substantial amounts of Se(IV) volatilize during evaporated to a syrupy consistency.3 * 2
evaporation,296 even if the temperature is not Radioisotopes were employed to monitor losses
high. The losses increase when the temperature of in Rb and Cs during silicate destruction 313 by HF
the reaction mixture is increased during and HC1O4; the losses amounted to 0.2 to 0.3% in
evaporation with HF, HNO 3) and HC1O4; closed vessels and to 1.3 to 1.4% in open crucibles.
microgram amounts of Se can escape The product of the reaction between H3BO3
completely. 274 ' 275 In the decomposition of deep and HF is fluoroboric acid, which is also
sea sediments labeled with 7S Se, Se(IV) fluoride sometimes employed for dissolving inorganic
does not volatilize 297 in solutions of HF and materials. HBF4 formation is catalyzed by H+ ions;
HNO 3 . Therefore, included selenide impregnations acids of the HBF4_,, (OH)n type are formed as
in sulfidic ores can be oxidized and converted into intermediates. 283 ' 284 The hydrolytic process
selenites in this manner. Using the same isotope,
the decomposition technique was later verified2 9 8 HBF4 +nH,O^HBF 4 . n (OH) n + nHF
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for the determination of trace amounts of Se. The

experimental procedures proposed mainly employ proceeds in the opposite direction.
this decomposition; 2 9 9 ' 3 0 0 sometimes the HBF4 is a selective solvent for silicates;314
solution formed is heated until the appearance of while quartz remains unattacked (the
HCIO4 fumes, without observing losses in determination of free SiO2). Among silicates3 l s
Se. 301 > 3 0 2 Chromium seriously volatilizes in this with isolated tetrahedrons, hessonite and
solution, probably as the oxyfluoride CrO 2 F 2 ; almandine are partly attacked, while cordierite is
microgram amounts can be lost completely. dissolved smoothly. Micas, some amphiboles, and
However, analyses of standard rocks have shown (among clay materials) kaolinite and illite are
that the loss in Cr is negligible with small amounts decomposed. The solubility of plagioclases
of HC10 4 at the minimum evaporation decreases with increasing basicity. Magnetite reacts
temperature. 303 very rapidly, while pyrite is damaged very little.
The loss of tellurium compounds is small HBF 4 dissolves zeolites 316 at laboratory
compared to that of selenium. Bock 304 studied temperature; the solution obtained was used for
the behavior of Te during decompositions in X-ray spectral analysis. Lead alloys 317 are
detail; he reports a maximum loss of 5.4 and 7.3% dissolved within 30 sec in this acid. Objective
(when glass is dissolved in HF and H 2 SO 4 , evaluation of the decomposition effects of HBF4
respectively). When H2SO4 is replaced by aqua is complicated by the complex decomposition
regia, no loss of Te occurs.1 ] s kinetics and by the effect of hydrolytically
When the reaction mixture temperature is liberated HF.
increased during removal of fluoride (by adding The decomposition technique using HF vapors
HC104 or H 2 SO 4 ), a loss in Re 3 0 5 is encountered. (rarely used) meets even exceptionally high
No loss in Re (1 jig) was observed when a solution demands on the blank value. 318 The gaseous
of HF alone was evaporated. Losses of 4.7 to 7.6% phase formed by vaporization of specially pure
have been reported for 50- to 100-mg samples; the acids contains a minimum amount of impurities.
amount of Re volatilized decreases to 1% This decomposition technique has been especially
following the addition of H 3 PO 4 . 3 0 6 used in the analysis of quartzes, quartz glass, and
It is difficult to dissolve a sample without losing silicon. 3 1 9 ' 3 2 0 Even large grain materials can be
part of the markedly volatile Tl compounds. dissolved in a special Teflon apparatus. 321
Radiochemical testing with 2 0 4 T l has indicated Decompositions with dry HF have been reviewed
that up to 40% of the total amount of Tl can be in the above-cited study. 270
lost during prolonged evaporation with HF and
HCIO4 or H 2 SO 4 . Reproducible results were B. Decompositions by Other Volatile Inorganic
achieved 307 " 309 after rock material dissolution in Acids
HF and HN0 3 and removal of the fluoride by 1. Decomposition by HCl
evaporation with the latter acid.3 ° 7>3 • ° No loss in Hydrochloric acid is the most frequently used
Tl has been observed311 after cautious dissolution reagent in decompositions of inorganic materials.
June 1977 275
 It is employed both for direct dissolution of the pitchblende (U 3 O 8 ) decreases with increasing
analyzed solid phase and for conversion of melts contents of U(IV). Hydration products of A12O3
into soluble salts. Its effect as a strong acid is behave analogously, but their solubility in HC1 is
hastened by its pronounced complex-forming substantially lower (A1C13, poorly soluble in HQ,
ability (especially with the transition elements) is probably formed at the liquid-mineral interface).
with stepwise formation of chloride complexes Anhydrous a-Al2O3 (corundum) is virtually
which are often intensely colored (e.g., those with insoluble in this acid. Quartz and cassiterite are
Fe3+ and Co2+). These reactions are utilized in insoluble and only some colloidal forms of natural
a n a l y t i c a l chemistry in ion-exchange Sn(IV) oxides are soluble. Rutil behaves similarly,
chromatography and in extraction separations of while another TiO2 modification, anatase, is quite
complex mixtures, especially with oxonium soluble. Natural and synthetic MnO2 is
solvents and long-chain amines. decomposed, producing Cl 2 ; the dissolution
process is hastened by H 2 O 2 , which acts as a
Hydrochloric acid exhibits slight reducing
reductant.
properties as a solvent, manifested by reduction of
Synthetic substances are generally more readily
higher oxides of manganese. However,
soluble in HC1 than minerals of the same chemical
hydrochloric acid is mostly used in mixtures with
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composition. Freshly precipitated PbS0 4

other inorganic acids, especially HNO 3 ; highly
smoothly dissolves in 6 N HC1 with formation of
efficient oxidizing mixtures (aqua regia and the
chloride complexes, while mineral anglesite of the
Lefort modification of aqua regia) result from this
same composition is not dissolved completely even
combination.
in concentrated HC1 or aqua regia. After ignition,
Hydrochloric acid has enjoyed extensive use in the PbO formed dissolves in the acid; however,
the analysis of natural and synthetic carbonates. some ore minerals react with the silicates present
Calcite and heavy metal carbonates react most during ignition and form resistant compounds,
rapidly and are decomposed at normal from which metallic components (Cu) can be
temperature even by very dilute HG solutions. On extracted only after total destruction of the
the other hand, siderite and magnesite react slowly silicate lattice by HF. Hydrated calcium sulfate
in hot 6 to 12 N HC1. The solubility of magnesite (gypsum) is decomposed easily by HC1, but
depends on the conditions of its formation. anhydrous anhydrite is dissolved slowly and
Magnesites of metasometic origin are decomposed incompletely. Baryte is not attacked to a
slowly, while the same minerals bound to perceptible extent, and coelestine is decomposed
serpentine bodies are dissolved approximately only to 5 to 10% in HC1 (1+1), depending on the
twice as rapidly. The different reaction rates decomposition conditions.
cannot be ascribed to different structures as X-ray Apatite reacts very rapidly,3 2 3~3 2 s as do heavy
diffraction data and IR spectra of the two metal phosphates and phosphates of the type R(II)
magnesite types are identical. 322 The solubility of (UO 2 ) 2 (PO 4 ) 2 "x H 2 O, which belong among
oxides varies according to the temperatures to uranium micas. Rare earth and thorium phosphate
which the analyzed substances were exposed and (monazite and xenotime) are dissolved in-
the rate of back-hydration. The specific surface of completely.
solid phases is decreased by high temperatures, and Tungsten ores, containing chiefly wolframite or
the crystal lattice is often reorganized. Both of scheelite, are decomposed in HC1, yielding
these processes are connected with a decrease in insoluble tungstic acids. Various modifications of
the substance reactivity with mineral acids, this decomposition procedure are used to separate
especially HC1. Hydration reactions lead to forma- tungsten from accompanying components.
tion of H2O molecules or OH-groups in the mineral However, molybdenum is not separated in this
structure, causing an increase in the mineral reac- way.
tivity. With complex iron oxides, components with
Among borates, industrially important mineral
higher concentrations of the hydrates oxides
colemanite is readily dissolved in HC1; the
or. Fe(II) react more rapidly with HC1. For
decomposition is carried out in a quartz glass
example, hydrated ferric oxide (limonite) and
vessel under reflux, because of the volatility of
ferrous—ferric oxide (magnetite) react faster than
H 3 BO 3 . Fluorite is dissolved slowly in HC1, and
two anhydrous forms of Fe 2 O 3 (hematite and
the dissolution is hastened by addition of
specularite). On the other hand, the solubility of
aluminium salts or H 3 BO 3 . 3 2 6
276 CRC Critical Reviews in Analytical Chemistry
 [Link] to a negligible degree, depending During dissolution, compounds of As(III),
on the solution composition and probably also on Sb(III), and Sn(IV) volatilize, and losses in In (up
genetic factors. 327 Galenite is dissolved within 10 to 18%) are encountered. Volatilization of InCl3 is
min in diluted HCl (1+1); Ag+, Bi3+, and Tl+ are eliminated by addition of KC1. 340 An analogous
adsorbed by PbCl 2 precipitated during effect is exhibited by ZnCl2 which is formed by
cooling. 3 2 8 ' 3 2 9 For trace amounts of silver, 3 M the dissolution of zinc ores, preventing losses in Hg
HCl suffices for dissolution of AgCl (in the form in the form of HgCl 2 . 341 Selenium(IV) forms a
of AgCl2"), but 8 M HCl is necessary for con- volatile oxychloride2 9 7 with HCl, while tel-
version of precipitated PbCl2 to soluble chloride lurium(IV) does not volatilize under identical
complexes. 330 High acidity of the analyzed conditions. 304 GeCl4 volatilizes342 even at 20°C
solution can be avoided by adding diethylene from 8 At HCl.
triamine, 3 3 1 ' 3 3 2 which forms stable complexes
with Pb2+ and Ag+ even at pH 1. Other industrially 2. Decomposition by HBr
important sulfides, antimonite, and sphalerite are HBr is used less frequently than HCl for
also dissolved. An oxidant is added to prevent dissolution of inorganic materials. The effect of
formation of volatile SbCl3; however, complex HBr is increased by addition of bromate or HN0 3 .
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anions [SbCl6 ] " tend to hydrolyze even in 6 At Free bromine is liberated from HBr solutions by
HCl. Volatilization of AsCl3 is prevented by the oxidizing effect of HN0 3 ; the mixture
oxidation of As(III) to pentavalency. energetically oxidizes the solid phase, similar to
aqua regia.
Decomposition of sulfidic ores is hastened by
HBr alone is an excellent solvent for magne-
addition of oxidants, especially HNO3, Br 2 ,
tite.2 ' 3 Sulfides are readily dissolved when HBr is
H 2 O 2 , or KCIO3. 333 A strongly oxidizing mixture
combined with the above oxidants. Pyrite, sphale-
of Cl2 and C1O2 is produced from KC1O3 depend-
rite, and tetrahedrite are rapidly dissolved, and
ing on the reaction conditions. When the analyzed
arsenides, sulfoarsenides, and selenides are also
substance is heated in an HCl solution, H 2 S is first
oxidized. This oxidizing mixture readily dissolves
displaced, and the decomposition is then completed
tellurium minerals.3 4 3 ~ 3 4 S Gold is completely
by added oxidant. In this way, the formation of
extracted from rock samples, as has been verified
sparingly soluble PbS0 4 is suppressed. KC1O3 is
using radioisotopes. 3 4 4 ' 3 4 6 ' 3 4 7 The bromide
used when the presence of HN0 3 interferes in the
complexes of Au(III) obtained are extracted into
final analytical procedure. This procedure ensures
methylisobutylketone and are determined by
complete dissolution of cinnabar, pyrite,
AAS. Platinum and palladium are extracted under
molybdenite, Ni and Co arsenides and sulfo-
the same conditions. 348
arsenides, arsenopyrite, and other sulfidic
minerals. On heating of solutions with HBr and HC104,
bromides of As(V), Sb(V), and Sn(IV) volatilize;
Heavy metal silicates and minerals of the zeolite this procedure was employed for separation of
group • release silicic acid gel when treated with these elements in the analysis of lead ores. 3 4 9 ' 3 5 1
HCl. The gel has strong adsorptive properties; A high evaporation temperature may also lead to
structurally it retains the form of the original losses in indium; however, volatilization is
mineral, 334 but the cations are replaced by H 3 O + prevented by adding KC1. Tellurium does not
ions. Heulandite, desmine, chabasite, analcime, volatilize during evaporation of HBr solutions. 304
and other zeolites react in this way. However, Elemental bromine is readily formed by oxi-
most rock-forming silicates are resistant and are dation of HBr and is an effective solvent for many
only partially damaged by HCl. minerals, especially sulfides. Liquid bromine
Graphite and organic materials are often dissolved in an organic solvent (methanol, ethanol,
separated from carbonates by dissolution in HCl. or carbon tetrachloride)3S3 is generally used.
However, because of the variable character of Bromine selectively dissolves metallic iron from a
organic substances in sedimentary rocks, this mixture of oxides;3 5 4 ~ 3 S 7 a bromine solution in
procedure may lead to gross errors in the ethyl ether is an efficient extractant for gold from
determination of organic carbon, 335 " 339 as some large samples.3 S 8
organic compounds (especially those containing
nitrogen) dissolve in HCl; the losses amount to 30 3. Decomposition by HI
to 50% of the total nitrogen. Hydroiodic acid has been used chiefly as a
June 1977 277
 strong reductant in decomposition techniques. Its sulfates is usually formed. In order for oxidation
effect is further increased by addition of to lead to a defined valence state (preferably
hypophosphorous acid or hypophosphite. Barium sulfate), the dissolution must be carried out under
sulfate is reduced to the sulfide 3 5 9 ' 3 6 0 by these rigorously maintained conditions and in the
reagents in the presence of HC1 or H 3 PO 4 , and the presence of other reagents, such as chlorate and
H 2 S liberated is absorbed in a solution of a Cd bromine. The decomposition is unsuitable for the
salt. This procedure has also been successful in the determination of lead in rich ores, as the sulfate
determination of sulfates in soils. 361 The formed reacts with Pb2+ to give PbS0 4 , which
decomposition of baryte is often incomplete; separates along with the insoluble residue.
strontium sulfate is reduced more easily.35 The Cinnabar is not dissolved even in concentrated
decomposition of baryte in solutions containing HNO3; only the fuming acid dissolves this mineral
H 2 SiF 6 , HI, and oxalic acid is complicated;362 readily. Insoluble substances, called metaacids, are
the reaction proceeds through barium fluoro- formed by reaction of Sb or Sn with HNO3.
silicate and oxalate. A mixture of HI and HC1 However, this reaction is not suitable for
releases H 2 S quantitatively from galenite and separation of the two metals from other
sphalerite. 363 The decomposition of pyrite, components, as the metaacids do not separate
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chalcopyrite, and other sulfides can be hastened completely and other cations are adsorbed on their
by adding a drop of mercury. An increase in the active surface. The formation of these compounds
HI reactivity in this system is probably caused by can be prevented by addition of organic oxyacids,
electrochemical processes.364 especially tartaric and citric, and by carrying out
the reaction at 20°C or at a slightly elevated
4. Decomposition by HNO3 temperature. 365 " 368
Nitric acid is a strong acid, used most The effect of HNO3 is increased by the
frequently for oxidative dissolution of minerals addition of other reagents (e.g., H 2 O 2 or KI)
containing polyvalent elements, especially sulfides, which also accelerate the process; these procedures
selenides, tellurides, arsenides, and sulfoarsenides. have been used 3 6 9 ' 3 7 0 in the determination of Ge
Anionic and cationic components of the mineral and Se in sulfides. A mixture of HNO3 and Br2 is
are usually oxidized during the decomposition. an excellent solvent for sulfides and arsenides.
The reaction products of HNO3 itself (mostly NO) Chlorate affects the decomposition process
are gases, which are easily expelled by boiling the analogously. This decomposition type was
solution. Natural and synthetic phosphates, successful in the determination of Re in
arsenates, and tungstates (e.g., scheelite and molybdenite concentrates. 114 Because HNO3 is
wolframite) are rapidly decomposed by this acid. an excellent reagent for sulfides, it has become the
Resistant oxide minerals are not decomposed most widely used solvent for the determination of
by HNO 3 ; rather, the acid is used (in combination Ag in galenite and sphalerite371 and in geo-
with other acids) for their isolation from complex chemical prospection- If the decomposition is
mixtures (e.g., with cassiterite, corundum, and carried out in the presence of Hg(NO3)2, AgCl is
nibium oxide minerals). 249 Mixed uranium oxides not formed from chlorides present as impurities in
(uraninite) are readily dissolved in HNO3 and the the decomposition mixture. 3 4 4 ' 3 6 6 AgCl is
U(IV) present is oxidized to uranyl ions. Iron readily adsorbed on the undecomposed fraction
oxide ores are decomposed by HNO3, but form and the vessel walls.3 7 2
insoluble products (called basic nitrates) when the A mixture of HNO3 and HC104 is employed
solutions evaporate. The acid is equally unsuitable for the oxidation of organic components in
for dissolution of oxidic antimony ores. sedimentary rocks. By increasing the temperature
Nitric acid has been used in analyses when during evaporation of HC104, the HNO3 is easily
other acids interfere in the final determination removed. This process is more complicated with
(e.g., in the determination of chlorides in apatite); H 2 SO 4 , as nitrosylsulfuric acid is formed. Only
however, very dilute HNO3 (1+19) must be repeated evaporation after solution dilution causes
employed in order to avoid oxidation of the complete displacement of HNO 3 .
chloride. The use of HNO3 combined with mannitol is
The widest use of HNO3 is in sulfide rather unusual, but in this way H3BO3 volatiliza-
decomposition; a mixture of elemental sulfur and tion during evaporation 373 is suppressed. A

278 CRC Critical Reviews in Analytical Chemistry

 similar effect is exhibited by addition of aluminum this was not observed with quartzes. 3 8 2 ' 3 8 3 The
salts; this finding has been utilized in the content of Pd and Pt can be determined3 8 4 ' 3 8 s at
determination of boron in aluminum alloys.3 7 4 the same time as Au and Ag, but sperylite 386 and
the natural platinum disulfide are not decomposed
5. Decomposition by Aqua Regia by aqua regia. The extraction procedure yields
Mixtures of HNO3 and HC1 are very powerful unsatisfactory results with chromites, in which
oxidants. Active chlorine is liberated by reaction part of Pd can be bound in the mineral lattice. The
between the two components, and nitrosylchloride extraction recoveries for the platinum metals are
is formed, which dissociates to give chlorine. A probably subject to a systematic negative
mixture containing 3 volume parts of concentrated error. 387
HC1 and 1 volume part of concentrated HNO3 is Aqua regia readily dissolves sulfides (including
called aqua regia; the reverse ratio of the two cinnabar), arsenides, selenides, and tellurides.
mentioned acids produces the Lefort (Lunge) Selenium and tellurium are oxidized to nonvolatile
mixture. As aqua regia readily dissolves metallic selenate and tellurate; 388 the oxidation process
gold and its alloys, it has been successfully was controlled by radioisotopes.304 Aqua regia
employed for the extraction of gold ores. This further dissolves natural oxides of antimony.
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technique has gained importance, particularly in Antimony and arsenic are oxidized to nonvolatile
combination with AAS, where the procedure (even pentavalency during the dissolution. The same
in a simple prospection modification) enables decomposition technique was used for the
determination of Au at levels of parts per billion. determination of Hg in sulfides and sedi-
Compared with the classical reduction fusion, the ments. 3 8 9 ' 3 9 0 If the solution formed is evapo-
dissolution in aqua regia is much simpler and the rated in a water bath, there are no losses in Hg.
results of the two procedures are in good agree- Molybdenite is readily dissolved in aqua regia, the
ment. Samples of 5 to 500 g are treated by this losses in Re being lower than 8%.3 ° 6
technique. 375 The sample is first ignited at 550 to Natural uranium oxides (uraninite) are easily
600°C to volatilize the sulfidic sulfur and oxidize decomposed in aqua regia. Industrially important
the organic matter. 3 7 6 ' 3 7 7 If the sample contains tungsten minerals (wolframite and scheelite) are
arsenopyrite, the ignition temperature is decreased also dissolved.391 Among sulfates, coelestine is
to 480°C in the first stage; otherwise, volatile attacked by aqua regia to ca. 25%, while baryte is
compounds are formed 378 by a reaction between virtually not attacked.
Au and As and losses in Au occur. It is advan- The Lefort mixture has been used most widely
tageous to add NH4NO3 for ignition, as the in the determination of sulfur in sulfides,
sample consistency is improved and the oxidation especially in pyrite concentrates. The oxidation
processes are hastened. Ifsulfidesarenot removed takes place at 20°C or even in cooled solutions;
from the sample beforehand, elemental sulfur complete conversion of sulfides to sulfates is
separates during treatment with aqua regia and ensured by addition of chlorate or bromine.
gold is coprecipitated. Organic matter has similar
effects. The completeness of the gold extraction
C. Decompositions by Less Volatile Inorganic
from the sample depends on the amount of gold
Acids
and the composition of the analyzed material. The
1. Decomposition by HCIO4
losses are usually lower than 15%, with quartz
In decompositions of inorganic materials by
losses often below 1%. Concentrations of Au were
HCIO4, specific properties of this acid as an
determined in the fraction undecomposed by aqua
oxygen donor and a dehydration agent are
regia, both by reduction fusion and by activation
employed. All perchlorates, except those of K, Rb,
analysis. 376 " 379 The radioisotope techniques
and Cs, are readily soluble in water. HC104 has
indicated that the loss in Au is caused not only by
oxidizing properties only in hot concentrated
the presence of undecomposable Au minerals, but
solutions; when diluted, its oxidizing properties
also by adsorption of Au on the vessel walls and
are lost. 392 " 39S Ferrous compounds are not
losses in the filter during filtration of the
oxidized in a 50% solution of the acid even at
undecomposed fraction. 380 The extraction
100°C; in 70% acid, the oxidation is very rapid at
process is sometimes repeated 377 and the fraction
150°C. Hot concentrated HC104 reacts explosively
of the gold liberated is further increased by the
with organic substances, but Teflon is resistant to
destruction of silicates 376 ' 381 by HF. However,
its effects even at the boiling point of the
June 1977 279
 azeotropic mixture (72.5%, 203°C). Inorganic mixture as a product of HC104 decomposition.
substances containing organic impurities or HCIO4 is frequently used for decompositions of
components with reducing properties are thus rocks in combination with HF (see Section IIIA).
[Link] a mixture of HC104 and HNO3. In geochemical prospection for molybdenum, a
HNO3 is partially dehydrated by HC104 and its HCIO4 and HNO3 mixture did not yield good
oxidizing effect strongly increases at temperatures results and Mo compounds were not completely
near 120°C. Organic substances are oxidized, but extracted from the analyzed soils; 412 this
further increasing of the temperature leads to mixture, however, very rapidly dissolves prac-
displacement of HNO3 from the solution. H2SO4 tically all sulfidic minerals. 351 Lead(II) perchlor-
causes HC104 dehydration, and an acid with a ate (formed during the decomposition of galenite)
concentration higher than 85% is formed. This is thermally unstable and decomposes at tempera-
mixture oxidizes many substances even at a low tures above 130°C, yielding sparingly soluble
temperature; for example, chromium(III) salts are compounds. 413 ' 414 These products are most
oxidized at 138°C. H3PO4 has a similar effect. rapidly dissolved in alkaline tartrate or citrate; this
Gaseous chlorine and a small amount of H 2 O 2 are method of dissolving the precipitate has been
the products of the HC104 decomposition, the employed in the determination of Ag and Bi in
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latter causing back-reduction of the oxidation lead ores. 4 1 4 ' 4 1 5

products. Its formation can be prevented by rapid Data on the behavior of selenium are contra-
cooling of the reaction mixture. Safety pre- dictory. Although volatilization of Se compounds
cautions must be observed in work with HC104; has been proven, 2 9 6 ' 4 1 6 HC104 combined with
special apparatus, including fume cupboards, have HNO3 and H2SC>4 has been used for decomposi-
been constructed for 3 9 6 " 3 9 8 series sample tions of sulfidic compounds.4 ll'4i9 During pro-
decompositions with HC104. longed evaporation, selenium is oxidized to
Perchloric acid is specifically used as a selenate. Tellurium compounds do not volatilize
dehydration agent in the separation of silicic acid under identical conditions. 304 ' 420 Losses in
(limestones, dolomites, magnesites, cement, etc.). mercury occur 421 only after an increase in the
When mixed with H 3 BO 3 , it causes rapid reaction mixture temperature above 200°C. Vola-
decomposition of fluorite; 399 " 401 while quartz tile Re 2 O 7 can be separated from molybdenite
remains unattacked. However, this process of concentrates4 2 2 by distillation from a HCIO4 and
silicic acid precipitation has not been successful in H2SO4 solution. RuO4 and 0s0 4 distill when
silicate analysis; the results have also been boiled with HCIO4; this decomposition procedure
considerably scattered with spinels. has been employed for isolation of these com-
The decomposition of monazite in HC104 pounds from native Ag, 423 Pt-rich chromites, 424
solutions is very rapid 4 0 2 " 4 0 4 and the reaction stone meteorites,4 2 S and dressing products of Pt
mixture is turned orange by the Ce(IV) ores. 426 Losses in iridium also occur under the
compounds formed. Apatite is also readily same conditions. 427
dissolved.405 Extraction of phosphates from soils Perchloric acid has an important application in
using HCIO4 is usually slow and often in- the so-called wet combustion of coal. Its combina-
complete; 406 this may be caused by inclusions of tion with periodic acid is especially effective,428
phosphates in crystalline Al and Fe oxides, which as periodic acid attacks the bonds in organic
are decomposed with difficulty. compounds and converts these compounds into
Perchloric acid alone or in mixture with H2SC>4 smaller molecules readily oxidizable by HCIO4.
or H3PO4 oxidizes resistant minerals such as The oxidation course is complicated. During the
chromspinelides (including the industrially oxidation of organic matter, periodic acid is
important mineral chromite). 407 " 41 ' The dis- reduced to iodic acid and finally to iodine (I)
solution takes several hours even when the sample perchlorate.
is very finely powdered. However, this
decomposition is no longer used in the determi- 2. Decomposition by H2SO4
nation of the major component (chromium) as Hot concentrated H2 SO4, often employed for
losses have been encountered, probably due to the decompositions of inorganic substances, acts as a
formation of volatile CrO 2 Cl 2 ; small amounts of mild oxidant. Its effect is much weaker than that
chlorides are always present in the reaction of HCIO4. Stannous compounds are oxidized to

280 CRC Critical Reviews in Analytical Chemistry

 stannic (e.g., in dissolution of sulfides) and ferrous H 2 SO 4 or in a mixture of H 2 SO 4 and HC1.
to ferric. The acid is reduced to H2 S (especially in Fluorite is readily decomposed when evaporated
the dissolution of some alloys), elemental sulfur, with H 2 SO 4 ; insoluble calcium sulfate precipitates
or SO 2 . Sulfur dioxide is commonly formed and is dissolved by heating with HC1.
during decompositions of mineral materials and Sulfuric acid is most frequently employed for
can be readily expelled by boiling the diluted the decomposition of arsenides and sulfidic arsenic
reaction mixture. The dehydrating properties of and antimony ores. 433 However, oxidic antimony
H2SO4 are most pronounced and are analytically ores (valentinite, senarmontite, etc.) are quite
utilized in the precipitation of silicic acid. Simul- resistant to the effect of H 2 SO 4 ; the insoluble
taneously, the alkaline earth and lead sulfates are residue is further dissolved in tartaric acid or aqua
precipitated, as are the anhydrous sulfates of regia or is decomposed by fusion. Sb(V) oxides are
transition metals, which are difficult to rehydrate reduced during the decomposition. The reaction is
and dissolve (especially nickel, cobalt, and ferric generally complicated by the presence of the
sulfates). The insoluble sulfates adsorb many sulfide component of the ore, which is oxidized by
cations. Although hot concentrated H2 SO4 acts as H2SO4 to elemental sulfur; this mixture has
an oxidant, it is combined with other acids and reducing properties. No reduction of pure Sb2Os
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oxidants (e.g., HNO3, HC104, H2 O 2 , MnO2, and has been observed434 when it is evaporated with
KMnO4) to accelerate the decomposition. The H 2 SO 4 . Decomposition with H 2 SO 4 and S is
oxidizing effect of these substances is further utilized analytically in solution preparation for the
increased by the dehydrating effect of H2SO4 determination of As in ores. 4 3 5 ' 4 3 6 Cinnabar is
under suitably selected conditions. dissolved by heating in a mixture of H2SO4 and
Sulfuric acid is rarely employed for disso- KMnO4. If the material analyzed contains organic
lution of oxides, as the reaction is slow matter, nitric acid is added to the mixture. The
and mostly incomplete. Corundum and cassiterite procedures developed have been applied to the
are not decomposed, and rutil is only partially determination of Hg in sulfidic ores, 4 3 7 " 4 3 9
decomposed, even if the reaction mixture tempera- rocks, 4 4 0 ' 4 4 1 separated heavy minerals, 442 and
ture is increased by addition of an alkali sulfate. coal. 4 4 3 ' 4 4 4 Gold inclusions in rocks are not
Anatase, however, is dissolved. The degree of dissolved in H2 S0 4 , but tellurides and selenides of
decomposition of pitchblende increases with in- gold are decomposed. The SO2 dissolved in
creasing UO2 content; oxide uranium ores are H2SO4 reduces Au+ from the minerals decom-
rapidly and quantitatively decomposed by a mix- posed, and the gold is adsorbed on the undecom-
ture of H 2 SO 4 , HNO3, and HF. Composite oxides posed fraction. This procedure is employed for
of the spinel type are not decomposed by H 2 SO 4 . preliminary separation of Au from other compo-
Certain titanates, especially loparite, ilmenite, nents.
titanomagnetite, titanite, and perovskite, are During solution evaporation to SO3 fumes,
better dissolved. Depending on the reaction condi- most of the Se volatilizes, but the loss is decreased
tions, TiOSO4 or Ti (SO4 ) 2 may be formed.4 2 9 considerably by adding HNO3. 2 9 7 ' 4 4 5 However,
Among phosphates, monazite 4 3 0 ' 4 3 1 dissolves tellurium compounds do not volatilize.304 Even
in H 2 SO 4 ; dissolution in H 2 SO 4 was also em- graphite is oxidized in a 9 + 1 mixture of H2 SO4
ployed technologically for obtaining Th, U, and and the Caro acid at 150°C. 446
the rare earths from monazite concentrates. Am-
blygonite, tourquoise, and other phosphates 432 3. Decomposition by H3PO4
are also decomposed. Wolframite and scheelite are Phosphoric acid is especially suitable for dis-
dissolved in H 2 SO 4 , but this decomposition proce- solution of oxide compounds. Its very low vola-
dure is not very advantageous because of the tility and pronounced complexing properties are
strong adsorbing properties of the tungstic acid utilized. Phosphoric acid readily displaces volatile
precipitated. Some silicates of the zeolite group inorganic acids from their salts and reinforces the
are smoothly dissolved in H 2 SO 4 and silicic acid oxidizing properties of sulfuric acid due to its
precipitates. This procedure can be employed strong dehydrating effect. Condensation reactions
analytically in the determination of the major take place when H3PO4 is heated with forming
components of biotite: the finely powdered miner- polyphosphoric acids which substantially acceler-
al is decomposed after it is boiled for 30 min in ate the dissolution of the analyzed material be-

June 1977 281

 cause of their complexing properties. Phosphate demanding. The decomposition is carried out
complexes of some transition metals are stable under a perfectly inert atmosphere or in the
even in strongly acidic media. Although H3PO4 presence of a defined excess of an oxidant at
has no oxidizing properties, even at temperatures temperatures varying from 270 to 360°C. Both
near 300°C, it strongly affects redox equilibria by procedures have certain drawbacks. FeO is oxi-
formation of variously stable complexes with the dized very easily in solutions of H3PO4 and
individual members of redox couples (e.g., H2SO4 at the given temperatures and the oxidants
Fe(III)/Fe(II), U(VI)/U(IV). Concentrated H3PO4 added are not very stable under these conditions.
(density = 1.92) is much more effective than the SO2 is liberated in the reaction mixture by the
dilute acid. The oxidation of Fe2+ by atmospheric reducing effect of FeO and is absorbed 460 in
oxygen is very rapid in these concentrated solu- K 2 Cr 2 0 7 . If the decomposition takes place in a
tions, while U(IV) compounds are stable in con- CO2 stream, the CO2 is reduced to CO and the
centrated H3PO4. Considerable disadvantages of latter is oxidized in the absorption vessel con-
these decomposition techniques are that analytical taining dichromate. 407 Dissolution of chromite in
procedures (especially methods of group separa- a mixture of H3PO4 and H2SO4 with excess
tion and spectrophotometric methods) are compli- oxidant must be performed rapidly; otherwise, the
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cated by the presence of excess H3PO4 and eerie salt 4 6 1 " 4 6 4 or vanadic a c i d 2 2 0 ' 4 6 5 ' 4 6 6
phosphates insoluble even in dilute acids are added is spontaneously reduced. On the basis of
formed with many elements (e.g., Ti, Zr, Th, critical evaluation of these procedures, the de-
U(IV), Bi, rare earths). composition in the presence of excess eerie salt is
A mixture of H 3 PO 4 and H2SO4 or HC104 is preferred,461 as vanadic acid is less stable and is
an excellent solvent for oxide iron ores. 447 The 16 to 20% reduced. Manganese(III) compounds
decomposition is complete 5 to 10 min after H2O have also been successfully applied; 4 6 7 ' 4 6 8 they
is expelled from the reaction mixture by boiling. are prepared by Mn2+ oxidation with perman-
Fused A12O3 can be decomposed by the same ganate in a H3PO4 medium.
mixture. 448 Composite polyvalent uranium oxides Natural carbonates readily release carbon
(U3 O8 ) are also dissolved in H3 PO 4 ; the stability dioxide when treated with H 3 PO 4 ; the reaction is
of U(IV) compounds in this medium has been slowest with siderite and magnesite,4 6 9 for which
utilized in the determination of U(IV). 4 4 9 ' 4 5 0 85% H3PO4 must be employed. The CO2 liberated
The decompositions are usually carried out in Pt, is at present mostly determined gas
quartz, glass, or Teflon vessels. chromatographically 470 ' 471 or by coulometric
Oxidic Mn ores are readily dissolved in solutions titration. 469 The procedure can also be applied to
containing H3PO4 and H 2 O 2 ; at higher tempera- sedimentary rocks with a high content of organic
tures, Mn2+ ions are oxidized by atmospheric substances; they are not substantially attacked
oxygen in anhydrous H3PO4 to purple complex even by hot concentrated H 3 P0 4 , but the organic
compounds of tervalent manganese. The oxidation substances are oxidized when CrO3 is added. A
can be accelerated by the addition ofHC10 4 .The mixture of H3PO4 and CrO3 (the so-called Dixon
proposed dissolution processes have been success- m i x t u r e ) 4 7 2 has found wide application,
ful in the determination of FeO and active oxygen especially in the determination of organic carbon
in Mn ores and other minerals. 451 " 456 If higher in rocks and soils. 4 7 3 ; 4 7 4
Mn oxides are present in the analyzed substance, Even resistant silicates (e.g., tourmaline, biotite,
they are selectively reduced by oxalic acid, and and garnet) are dissolved in H 3 PO 4 with H 2 SO 4 (2
FeO is determined by oxidimetric titra- + 1) added. Quartz remains unattacked, 475 so this
tion. 4 5 6 ' 4 5 7 dissolution procedure can be used for the
Phosphoric acid has found widest use in decom- determination of quartz in the presence of
positions of chromites. The decomposition effi- silicates. If a silicate contains FeO, an equivalent
ciency is increased by the formation of phosphate amount of SO2 is formed (by reduction of
complexes with the major mineral components. H 2 SO 4 ) which is determined by automated
The solutions obtained were used for the deter- iodometric titration. 476 FeO can be determined in
mination of principal elements in minerals 458 by tourmalines after mineral dissolution in H3PO4
AAS. 4S9 The conditions for the determination of containing NH 4 F and KHF 2 . The optimum de-
FeO in chromite and Cr ores are much more composition temperature 477 is 210 to 220°C; at

282 CRC Critical Reviews in Analytical Chemistry

 higher temperatures, uncontrollable oxidation of solubility product, the selectivity coefficient, and
FeO occurs. The combination of H 3 PO 4 and the dissociation constants of the acids formed. 880
HNO3 makes an excellent solvent for ashes; the Phosphates and fluorophosphates can be
silicate lattice is destroyed and the Ge present is decomposed using ion exchangers; alkaline earth
released 478 ' 479 without adding HF. Sulfides480 carbonates; and natural sulfates of calcium,
are decomposed equally smoothly; a mixture of barium, lead, and iron. The complexing ion
HCIO4 and H3PO4 is generally used in order to exchanger Dowex Al, with iminodiacetic
accelerate the dissolution process. functional groups, 881 has also been employed for
A SnCl2 solution in H 3 PO 4 is a strong the decomposition of calcium carbonate. Natural
reductant and readily liberates H 2 S from pyrite phosphorites are decomposed in aqueous sus-
and other sulfides.4 8 1 " 4 8 S A mixture containing pension by a combination of cation and anion
H3PO4, red phosphorus, Nal, and propionic exchangers: the two ion exchanger kinds can then
acid 486 exhibits similar effects. The extent of be separated mechanically on screens. The
decomposition for the determination of small insoluble residue remaining after the decompo-
amounts of S was verified by analyzing standard sition did not contain a detectable amount of
rocks. The H3PO4 condensation products phosphate. 882 Decomposition of an aqueous
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combined with SnCl2 reduce natural sulfates to suspension of the rock by a cation exchanger for
H 2 S. Selenium compounds are reduced to H2Se. the determination of fluoride has been
This condensation product decomposes glasses and described. 883
other natural silicates487 at an elevated tempera- In addition to decompositions of simple natural
ture. compounds, dissolution of melts by a strongly
acidic cation exchanger has been de-
D. Decompositions by Ion Exchangers
scribed. 6 1 4 ' 6 1 5 A rock is decomposed by fusion
Ion exchangers are solid acids or bases and,
with an alkali metab orate, and the mechanically
therefore, can be employed as solvents for solid
crushed melt is agitated with the exchanger. The
phases. This decomposition technique has not
sorbed cations are either eluted by an acid from
been used very widely, even though some ad-
the separated exchanger and determined by AAS
vantages are evident. No impurities or large
in the eluate or the dried resin is directly analyzed
amounts of salts are introduced into the solution
spectrochemically. The purpose of the decompo-
analyzed; moreover, cations are separated from
sition is rapid separation of cations from excess
anions during the decomposition.
anions coming from the fusion agent and from
The solubility of a solid in water at a given silicic acid, as both of these components adversely
temperature is expressed by the solubility product. affect the subsequent spectrochemical determi-
If some kind of ion is removed from a saturated nations.
solution of a sparingly soluble substance by ion
exchange, the equilibrium between the solid phase
and the solution is disturbed and the solid begins IV. DECOMPOSITION BY FUSION
to dissolve. The decomposing effect of an ion
exchanger depends on the ion distribution coef- Fusion belongs among energetic decomposition
ficient between the ion exchanger and the procedures; it is employed with analyzed materials
solution. Optimum conditions are created when insoluble in acids and often also serves for partial
the hydrogen ions liberated from the strongly separation in the analyzed mixture. During fusion,
acidic cation exchanger in the H+ cycle react with compounds soluble in water or in acids are formed
the anion of the compound being decomposed and from insoluble substances. An important factor in
are thus removed from the system. This occurs fusion is a high temperature causing rapid
during decompositions of carbonates, sulfides, or heterogeneous reactions between solids and the
phosphates. When an anion exchanger in the OH" melt. A general drawback of fusion procedures is
cycle is simultaneously employed, the the necessity of using considerable excesses of
decomposition will be hastened by simultaneous fusion agents (more than the sample weight),
sorption of the anions and by the neutraliza- leading (together with corrosion of the vessels
tion of the solution by the OH" ions liberated. used, crucibles, and dishes) to serious contami-
Very small amounts of ion exchangers are required nation of the solutions to be analyzed. Excess
and can be calculated from the values of the neutral salts complicate many analytical reactions.

June 1977 283

 Impurities introduced into the solution prevent present in the melt. The platinum-iron alloy formed
the determination of minor and trace elements. during fusion causes a loss of iron in the material
Fusion procedures can be classified according analyzed. It could be removed either by repeated
to the heterogeneous reactions taking place in the extraction with hot concentrated hydrochloric
fusion agent substance system as follows: acid or by fusion with pyrosulfate. In decomposi-
tions of iron(II)-rich silicates, the amount of
1. Alkaline fusion — fusion with carbonates, platinum in the melt may amount to 10 mg.
hydroxides, peroxides, and borates Corrosion of platinum crucibles and platinum
2. Acidic fusion - fusion with pyrosulfates, distribution during the classical silicate analysis
hydrofluorides, fluorobarates, and boric oxide was studied. 489
3. Oxidizing-reducing fusion — alkaline Certain metals volatilize during carbonate
fusion agents mixed with oxidants or reductants fusion: arsenic and selenium partially and thallium
are usually employed, including alkaline fusion in and mercury completely. 490 The behavior of a
the presence of elemental sulfur. number of cations was studied during melt extrac-
tion with water. Most carbonates may form
A. Alkaline Fusion colloidal solutions during the extraction of the
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Basic properties of the above alkaline fusion melt with water and thus may pass into the
agents are discussed in this section. Fusion with extract. 491
borates has gained considerable importance in Sodium carbonate is one of the oldest fusion
combination with atomic absorption spectrometry agents. Most inorganic substances can be decom-
(see Section IV.C). posed by it, but its widest application is in silicate
Sodium and potassium carbonates or their analysis. An alkaline mono- or disilicate is formed
equimolar mixture are the alkaline fusion agents in the reaction with silicon dioxide and can readily
employed most frequently. The melting points are be dissolved in mineral acids. Aluminum from
850, 980, and ca. 500°C for the sodium, potas- alumosilicates is partially converted into aluminate
sium, and sodium-potassium salts, respectively. and partially forms basic and composite carbon-
Because commercial substances, especially sodium ates with other cations. Most silicate minerals can
carbonate, contain rather high concentrations of be decomposed by this fusion agent; completeness
silicon and calcium oxides, hydrogen carbonate is of the decomposition depends on the grain size of
recommended as the fusion agent. This can readily the material to be decomposed, the duration of
be prepared very pure and converted into carbon- the fusion, and the temperature used. Silicates rich
ate by heating at 300°C. Alkali carbonate melts in aluminum, as well as beryl, zircon, and titanite
partly dissociate forming the appropriate oxides, are decomposed pooriy.
which seriously corrode the fusion crucible. This Carbonate fusion is oxidative, especially when
process is especially marked with lithium carbon- the air is in contact with the melt, or the fusion is
ate, which is quantitatively converted into the performed in an oxygen atmosphere. The oxi-
oxide at ca. 710°C. However, the carbonate dizing effect can be increased by adding additional
decomposition is suppressed to a minimum by reagents, such as nitrates and chlorates; however,
fusing under a carbon dioxide atmosphere. Cesium corrosion of the platinum vessels increases propor-
carbonate has been employed in special silicate tionate to the concentration of oxidating agents.
decompositions. After precipitation of silicic acid, The procedure can be made more universal by
the solution is used for the flame photometric adding sodium tetraborate, an alkali hydroxide,
determination of alkali metals. 488 peroxide, metal oxides, etc. These mixtures are
Platinum or platinum alloy crucible is most then efficient fusion agents for many resistant
frequently used for carbonate fusion. Alloying minerals. In analytical practice, aqueous extracts
with indium or rhodium improves the mechanical of carbonate melts are frequently employed; they
strength of platinum, while the addition of gold have been used in the separation of anionic
(5%) or zirconium (0.1%) increases its chemical components or in the isolation of sparingly soluble
resistivity. Platinum is corroded not only by carbonates and hydroxides. Classical carbonate
sodium oxide produced by the thermal dis- fusion will long remain the basic decomposition
sociation of sodium carbonate during fusion but technique for inorganic materials. Its complete
chiefly by reaction with ferrous compounds replacement by acid decompositions at elevated

284 CRC Critical Reviews in Analytical Chemistry

 temperatures depends on whether sufficiently Re) occur during the fusion. There are consider-
resistant inlays for pressure vessels will be dis- able losses in tellurium when the fusion is
covered, permitting the use of temperatures near performed in iron or nickel crucibles; when using
500°C. sintered corundum crucibles there is no loss. 304
Alkali hydroxides are other efficient alkaline Fusion with alkali hydroxides in silver crucibles
fusion agents, permitting decomposition of most is an ideal decomposition technique for the deter-
oxygen-containing and silicate minerals. The mination of iron in silicate analysis. Iron is not
melting points of these substances (NaOH, 328°C; reduced in this medium and does not form alloys
KOH, 360°C) are somewhat lowered by the with silver. Fusion decomposition with hydroxides
presence of water and carbonates. They are quite in a platinum vessel under a pure nitrogen atmos-
volatile when fused; the cooled melt is strongly phere 490 is an effective technique for the deter-
hygroscopic. As hydroxides release water during mination of trace elements. Among mixed fusion
fusion and melt splashing occurs, the fusion agent agents, mixtures with alkali peroxides and
is usually first dehydrated at the melting point and especially alkali cyanides are effective fusion
the sample is then placed on the solidified agents for cassiterite. Hydroxide fusion is advan-
melt. 2 4 9 ' 4 9 2 Dehydration of fused hydroxides is tageously employed as a procedure for the sepa-
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not complete 493 and the equilibrium, 2OH~ = ration of acidic and amphoteric elements of the V
H2O + O 2 ' , is established. and VI groups from ions forming sparingly soluble
Fused hydroxides seriously corrode the fusion hydroxides.
vessel material. Zirconium is most resistant to their Sodium peroxide is undoubtedly the most
effect, along with gold, 494 silver, and nickel. effective alkaline fusion agent. In addition to
Teflon is not corroded by a fused mixture of having an energetic decomposing effect, the fused
sodium and potassium hydroxides at 280°C. For peroxide is also a strong oxidant. Most cations are
some decompositions, iron, corundum, and similar oxidized to their highest valencies during fusion.
crucibles can also be used. Platinum is dissolved by Two crystalline modifications of this compound
fused hydroxides only in the presence of atmos- are known; 498 the behavior of the substance has
pheric oxygen. The extent of corrosion was often been studied using thermogravimetric
studied experimentally;495 it has been found that analysis.499 It has been found that composite
the metal is decomposed relatively far under the sodium and hydrogen peroxides are formed when
surface. Following repeated leaching of the dried in vacuo. Similar compounds are also formed
crucible which contained 6MHC1, 6 X 10"5 g of on drying in the air. The peroxide melts at 495°C
the metal was still found in the fifth extract. When without danger of explosion. The vapor pressure
the fusion is carried out in a platinum crucible above its melt is relatively high; at a higher
under a rigorously inert atmosphere, its losses are temperature, the substance decomposes to sodium
somewhat lower than in fusion with sodium oxide and oxygen. The danger of explosion
carbonate. 496 increases if easily oxidizable substances (e.g.,
For the decomposition of most mineral organic compounds, graphite, sulfides, or
materials, approximately a tenfold excess (over the powdered metals) are present in the mixture being
sample) of the fusion agent is sufficient. The decomposed. Although the peroxide decomposes
decomposition generally takes about 5 to 15 min; practically all minerals, its use in chemical analysis
some resistant minerals must be decomposed is limited to certain determinations; it is
longer. Aqueous or alcoholic solutions of hy- rather rare in complete analyses because the
droxides can also be used for the decomposition. commercial substance is usually insufficiently pure
After sufficient dampening of the material, the and the analyzed sample is seriously contaminated
mixture is evaporated to dryness. Heating of the by the crucible material during fusion. Metallic
upper part of the crucible must be prevented zirconium, gold, and silver (in that order) resist
during fusion or undesirable creeping of the melt fused peroxides. However, nickel, iron, or sintered
up the walls occurs. The cooled melt is easily corundum crucibles frequently suffice. Platinum
leached with hot water and falls apart very rapidly. can be protected against the peroxide effect by a
Melt leaching with hydrochloric acid vapors in an layer of sodium carbonate melt formed prior to
evacuated space has also been described.497 the decomposition. Analogously, nickel crucibles
are protected by a solidified melt of an alkali
Losses in some elements (e.g., Hg, Se, Tl, and

June 1977 285

 hydroxide. The loss in zirconium crucible material converted into pyrosulfates. As this reaction jj
is about 5 mg/gram of the fusion agent during rapid and the melt fumes and splashes, it is more
normal fusion time (5 to 10 min); this is not a advantageous to fuse directly with pyrpsulfate ot
small amount, but is negligible compared with the to dehydrate hydrosulfate before sample intro-
loss of silver or nickel (100 to 200 mg). Older, duction. Sulfur trioxide, dissociated from pyro.
recrystallized zirconium is lost to a much greater sulfate at a higher temperature, is the active
degree than the new material. A comparative study component of the fusion mixture. Pyrosulfate is
was conducted 5 0 0 ' 5 0 1 on the corrosion of various converted into inactive alkali sulfate. Therefore, it
fusion crucible materials during peroxide fusion. is necessary to add a little sulfuric acid to the
In addition to the classical fusion procedure, an solidified and cold melt (especially after prolonged
explosive decomposition is also employed; the fusion) in order to form new hydrosulfate, so that
sample is mixed with peroxide and carbon, and the the fusion can be carried out for the required time.
mixture is ignited. The decomposition reaction The sodium salts are, in many respects, more
temperature is high (1450°C), but the crucible is suitable than the potassium salts, as they form
not damaged.502 Explosive decompositions can more soluble binary sulfates with aluminium,
also be carried out in closed pressure vessels, such zirconium, and other metals. However, their
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as the Parr autoclave, etc. Other substances sup- melting point is somewhat lower than that of the
porting the reduction must also be present in potassium salts which may cause incomplete
addition to the peroxide. decomposition. The lower thermal stability of
Mixtures of sodium peroxide and carbonate, sodium pyrosulfate is also disadvantageous. It is
hydroxide, or metal oxides are also frequently difficult to prepare anhydrous sodium pyrosulfate.
used for decompositions. Most of these additives Dehydration in the air leads to a substance with
retard rapid or even explosive decomposition about 70% content of the active component, since
reactions in the decomposition of sulfides, etc. pyrosulfate begins to decompose in the melt
Barium peroxide, which has similar decomposing before all the water has escaped. A product
effects, is employed less frequently. suitable for analysis is obtained by heating the
The peroxide fusion decomposition is advan- hydrosulfate for 24 hr at 170°C in vacuo. The
tageous for those elements which form readily water liberated by the reaction is freezed out of
soluble anions of the acid of the highest valence the system. 507
state in alkaline media. By leaching the melt with Considerable excesses of the fusion agent must
water, amphoteric elements can be readily be used in fusion of most materials. However, too
separated from weakly basic elements. The much neutral salt is introduced into the analyzed
peroxide is also an outstanding fusion agent for solution which may unfavorably affect further
very resistant minerals, especially composite analysis. Commercial substances are not always
oxides of the spinel type (viz., chromites, cas- sufficiently pure and contain various cations which
siterite, oxygen-containing and silicate compounds prevent the determination of traces of elements.
of zirconium, niobium, tantalum, and platinum These disadvantages of alkaline fusion agents can
metal minerals, etc.).4 ° 8 ' 4 ' l > s ° 3"5 ° 5 Peroxide has be eliminated by using ammonium pyrosulfate.
been used in rapid analyses of silicates when the The reagent itself is somewhat less effective than
analyzed material must be quantitatively dis- the potassium salt, but can be readily decomposed
solved.506 and removed after completion of the decom-
position by evaporation at an increased tempera-
B. Acidic Fusion ture. The fusion can be carried out under a tightly
1. Decomposition by Fusion with Hydrogen closed lid at temperatures as high as 475°C. At
Sulfate and Disulfate higher temperatures, the melt boils quietly, with-
This is a weakly oxidizing acidic fusion, out forming froth. Ammonium pyrosulfate is
employed chiefly for decompositions of oxygen- supplied pure enough for analysis.508 Ammonium
containing compounds. A number of sulfides and hydrosulfate was used for decompositions of
phosphates can also be decomposed using this sulfides of Fe, Cu, Pb, and Zn. 509 Cesium
procedure, but it has been used only rarely for pyrosulfate is a special fusion agent, used because
these purposes. Alkali metal hydrosulfates dis- of the subsequent flame photometric deter-
sociate water in the initial stage of heating and are mination of the alkali metals; cesium ions regulate

286 CRC Critical Reviews in Analytical Chemistry

 the ionization processes in the flame. Persulfate is Alkali metal pyrosulfates are excellent fusion
used only rarely as a fusion agent for some rare agents for all titanium dioxide modifications (rutil,
earth oxides and phosphates. Pyrosulfate fusion is anatas, and brookite). Iron-, tin-, niobium-, and
frequently combined with preliminary acid decom- tantalum-containing rutil varieties are readily
position. Silicate crystal lattices are destroyed by decomposed. The melt extract in H 2 SO 4
sulfuric and hydrofluoric acids, and the salts was employed for direct determination of
formed are decomposed by fusion with pyro- titanium, iron, niobium, phosphorus, and
sulfate. Combined fusion with an alkali fluoride zirconium. s ' °~ s ' 2 Natural titanates, ilmenite,
and pyrosulfate is also effective; this decom- perovskite, and pyrofanite are decomposed well by
position technique is universal and is advantageous pyrosulfates. Fusion was used for subsequent
because the acidic character of the melt prevents determination of iron and titanium, sl3 chro-
the formation of insoluble bases and increases the mium,5 ' 4 ' 5 ' 5 and vanadium. 5 ' 6
effect of fluoride ions. Moreover, the fluoride, Pyrosulfates can be used for analysis of many
which interferes in the subsequent analysis, is binary oxides of di- and tervalent cations, called
quantitatively removed during the fusion. A spinels. Chromium-containing compounds require
number of oxygen- and sulfur-containing ores can a prolonged fusion time; the decomposition is com-
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be decomposed by fusion with a mixture of plicated particularly by the presence of larger

ammonium hydrosulfate and chloride or nitrate. amounts of silicon dioxide (e.g., in chromium ores
The fusion takes place at low temperatures and and fireproof chromite ceramics). 408 For these
can be carried out in a glass apparatus. 509 materials, a mixed fusion agent (sodium fluoride
For pyrosulfate fusion, fused quartz or pre- and hydrosulfate) is more suitable.4 ' ' Pyrosulfate
dominantly quartz glasses, such as Vycor®, are the fusion has been used to determine titanium in
most suitable materials. Test tubes of borosilicate chromium ores and chromites. 5 ' 7
glass are suitable for routine analysis. Corrosion of Milner 5 ' 8 studied the behavior of many ignited
this material is negligible during fusion, and the oxides during fusion with ammonium hydro-
melt virtually does not form froth on contact with sulfate. Uranium, vanadium, and zirconium oxides
a nonmetallic material. Pyrosulfate does not are decomposed completely after 3 hr of fusion at
damage gold and iridium at temperatures as high as 400°C. Titanomagnetite isolated from kimberlites
600°C and Teflon up to 280°C. On the other is decomposed after 45 min at 150°C; ammonium
hand, fused pyrosulfate causes considerable cor- hydrosulfate is first dehydrated slowly. A mixture
rosion of platinum ware; the loss in the metal is of the fusion agent and ammonium hydrofluoride
several milligrams in a single operation and is more suitable for silicate materials. This decom-
increases with increasing fusion duration. Am- position procedure was used to determine
monium pyrosulfate is a less corrosive reagent for platinum metals. 250
platinum than are the alkali metal salts, but the Pure tin dioxide (cassiterite) is only negligibly
fusion is slower and must be performed in a quartz decomposed by fusion with a pyrosulfate. How-
crucible. Sintered corundum is also not a very ever, if the mineral contains larger amounts of
suitable material for pyrosulfate fusion crucibles, niobium and tantalum, these elements can be
as colloidal aluminum oxide is formed during the dissolved during fusion. A mixture of sodium
fusion and passes into the melt extract. fluoride and pyrosulfate is an effective fusion
Pyrosulfates belong among the few fusion agent for cassiterite. 5 ' 9 Natural thorium oxides,
agents that reliably decompose the natural alu- broggerite, and thorianite often containing
minum oxides, corundum, sapphire and ruby, and uranium and rare earths are readily soluble in the
their synthetic equivalents. Hydrated aluminum pyrosulfate melt. The melt is advantageously
oxides (such as diaspor, gibbsite, and bohmite), dissolved in complex-forming electrolytes, such as
which are major components of bauxites, are also tartaric and oxalic acids. Most oxygen-containing
readily decomposed, as are oxygen-containing iron minerals of niobium and tantalum, especially
ores. As the latter can readily be decomposed by columbite, tantalite, loparite, and others, are
mineral acids, pyrosulfates are used for subsequent completely decomposed by fusion with pyro-
fusion of insoluble residues in which aluminium, sulfates. A scheme has been developed for com-
chromium, titanium, and other oxides are con- plete analysis of these compounds after the above
centrated. decomposition procedure. 520 If tantalum pre-

June1977 287
 dominates over niobium in the sample, a sodium volatilizes; it can be quantitatively removed from
salt is used as the fusion agent, since potassium the system and the melt solution can be used to
ions lead to the formation of sparingly soluble determine the individual components. 167 The
binary rare earth sulfates or fluorotantalate. The fusion is performed in platinum crucibles; to
melts must be extracted by complex-forming remove fluoride, the melt is heated with sulfuric
electrolytes. A photometric determination of acid or is further fused with the hydrosulfate
niobium 521 and tantalum 522 in poor ores using formed. When using 2 g of potassium hydrofluo-
this decomposition procedure was described. ride, a loss of 0.15 mg of platinum was ob-
Tungstates, such as scheelite and wolframite, can served.539 In addition to silicon, molybdenum,
be readily decomposed by pyrosulfates. This de- niobium, and tantalum also partly volatilize.s 3 8
composition procedure was employed in the gravi- The decomposition itself proceeds in two steps:
metric determination of tungsten in minerals 523 first, the fusion agent, potassium hydrofluoride
and in the photometric determination of small dissociates at a low temperature to yield free
amounts and traces of tungsten in ores, S24 hydrofluoric acid, which effectively destroys the
soils, 525 and rocks. 5 2 5 ' 5 2 6 It is suitable for the crystal lattices of the mineral phases present. This
determination of silicon dioxide in wolframite fusion stage must proceed at a low temperature
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concentrates 527 and niobium in separated tung- and should last as long as possible. The end of the
sten minerals. 528 thermal decomposition is indicated by solidi-
Although pyrosulfate fusion has a limited fication of the melt. During the second phase of
importance in silicate analysis, it is often decomposition, the temperature is slowly in-
employed in geochemical prospecting to study creased up to 700 to 800°C and is maintained
rocks, soils, stream sediments, and plants. The until a transparent melt is formed. Ammonium
decomposition is effectively performed in glass fluoride acts similarly: ammonia is dissociated at
test tubes, and the melt extract is used for direct 145°C and free hydrogen fluoride is formed. An
photometric or AAS determination of the ele- advantage of ammonium fluoride is that an excess
ment. Organic substances are completely de- can be readily destroyed. However, it is not as
stroyed by the fusion. The determinations of zinc universal a reagent as potassium hydrofluoride, as
in ores, 529 traces of molybdenum in sedi- it does not decompose minerals of the Al 2 Si0 5
ments 530 and soils, 531 vanadium, 532 and anti- group (i.e., sillimanite and cyanite, as well as
mony 5 3 3 have been described. The fusion decom- zircon, rutil, and others. 540 Decomposition effec-
position for geochemical purposes is equally tiveness is increased by the formation of stable
effective as dissolution in mineral acids. 534 Tel- fluoride complexes (of berylium, niobium, tan-
lurium volatilization during the fusion is talum, zirconium, etc.) in the melt. The fusion is
negligible.304 also advantageous for decompositions of rare earth
In order to decompose silicates completely, it is minerals, as these are removed from the analyzed
best to first treat the sample with mineral acids mixture as sparingly soluble fluorides formed
(H 2 SO 4 and HF) and to fuse the residue with during the decomposition. Potassium hydrofluo-
pyrosulfate. The solution obtained is used for an ride is one of the few agents that reliably
AAS determination 535 of major rock com- decompose the silicates beryl and zircon. The
ponents, for example for the determination of natural zirconium oxides cyrtolite and bad-
aluminum in an NBS standard feldspar536 and tin deleyite 541 are readily decomposed during fusion,
in standard rocks. 537 as are the niobotantalates columbite and tanta-
l i t e 5 4 2 ' 5 4 3 and a mixture of complex oxides of
the so-called heavy minerals. 442 The potassium
2. Decomposition by Fusion with Acidic Fluorides
hydrofluoride fusion is suitable for the decom-
and Fluoroborates
position of rare earth phosphates, monazite, and
Potassium hydrofluoride and ammonium fluo- xenotime. Most procedures utilize the insolubility
ride are used for decompositions of oxides, of the rare earth fluorides formed during the
niobates, tantalates, and silicates which are other- decomposition for their isolation, followed by the
wise decomposed with difficulty. As certain determination of individual elements, especially
elements volatilize as fluorides during fusion, this uranium and thorium. 544 " 546 Rutil is rapidly
decomposition procedure cannot be used for decomposed during fusion with potassium hydro-
complete analysis. A large proportion of silicon

288 CRC Critical Reviews in Analytical Chemistry

 fluoride; 50 mg of the mineral is dissolved in a salts. The metafluoroborate fusion is suitable for
tenfold excess of the fusion agent within 30 rapid decomposition of most rock-forming
min. 12 The use of sodium fluoride as a suitable minerals. At a temperature of about 850°C, silicon
fusion agent for the decomposition of beryl 547 is removed during the fusion by the fluoride
and for the spectrochemical determination of present. Fluoride and borate are readily separated
beryllium in some of its minerals has been de- from the melt by evaporation with sulfuric acid;
scribed. 548 Fusion with ammonium hydrofluoride the insoluble residue consists of barium sulfate,
was employed for isolation of the platinum tungstic, niobic acid, etc. Carbon and sulfide sulfur
metals and oxygen-containing minerals from present in the sample are readily oxidized by the
kimberlites. The rock (50 g) is decomposed in a frequent introduction of air into the crucible. 558
nickel dish containing 500 g of the fusion agent at Crucible corrosion is considerable and amounts to
a controlled temperature of 150 to 170°C, the as much as 6.5 mg of platinum when 4 g of the
fusion is terminated at 600°C and is repeated after fusion mixture is used. S39 The fusion is often
the addition of hydrofluoric acid. Isolated oxygen- carried out using a mixture of an appropriate
containing minerals, especially titanomagnetite, fluoride and boric acid at various ratios. The
are decomposed by fusion with hydrosulfates.250 decomposabihty of rocks 5 5 9 ' 5 6 0 and the effect of
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An analogous procedure has also been described added lithium on the subsequent determination of
for isolation of ruthenium and osmium from some cations by atomic absorption spectrometry
enriched ores, with subsequent neutron activa- were studied. The sodium or potassium salt of the
tion. 549 fusion agent was employed for decomposing
Fluoride fusion is frequently used to determine silicates in the determination of gallium,561
certain components of silicate rocks, soils, glass- beryllium in beryl, 562 free silicic acid, 563 and
making sand, and ceramic products. It has been barium.5 7 0 The mixture of fluoride and boric acid
used to isolate radionuclides, 550 ' 551 alkali is an ideal fusion agent for uranium and thorium
metals, 552 rare earth metals, 553 and thorium. 554 minerals; it readily decomposes torbernite,
This decomposition procedure is often combined carnotite, and uraninite. 564>56S As it also
with subsequent fusion of the undecomposed decomposes zircon, it has been used for rocks
phases with hydrosulphates; it has been used in the containing this resistant mineral; after the fusion,
determination of traces of tin in rocks 555 and of zirconium and hafnium were determined by
niobium and tantalum in ores, 556 and in other isotopic dilution analysis for geochronological
procedures. purposes. 566 Cassiterite is easily decomposed by
Sodium and lithium fluoroborates have proven this mixture; otherwise, it must be decomposed by
useful as fusion agents for especially resistant alkaline-oxidation fusion with sodium peroxide.
silicates. Sodium fluoroborate melts at 400 to After preliminary silicate decomposition by hydro-
450°C; its decomposition occurs at a substantially fluoric acid, the mineral decomposition takes
higher temperature. Metafluoroborates have a about 15 min; the melt is minimally contaminated
similar effect. This fusion agent is prepared by by the crucible material. 567 " 569
mixing and fusing equivalent amounts of sodium As has been mentioned, 557 this fusion agent is
fluoride and boric acid at 750 to 1000°C, forming suitable for the determination of FeO in silicates
a transparent melt. The composition of the that are not readily decomposed by hydrofluoric
products roughly corresponds to the formula acid. The fusion is performed in a closed tube; the
Na2B 2 O 3 F 2 . This fusion was introduced into cooled melt is dissolved in sulfuric acid, and the
analytical chemistry by Rowledge,557 who divalent iron is determined oxidimetrically. The
employed it for the determination of FeO in determination was modified for an open system
resistant minerals. Metafluoroborates effectively and is carried out in an inert gas stream. As the
decompose silicates with high contents of solidified melt is dissolved with difficulty in
aluminum (for example, cyanite, sillimanite, mineral acids, some authors crush the glassy
andalusite, and topaz); staurolite, tourmaline, and material and dissolve it in a known excess of an
zircon can also be readily decomposed. Among the oxidant. 571 Traces of oxygen which may be
oxides, corundum, spinels, cassiterite, and rutil are present in the inert gas cause partial oxidation of
decomposed. The sodium salts as the fusion agent the divalent iron. Carbon dioxide is not suitable as
are substantially more effective than the lithium the inert gas, as it dissociates to oxygen and

June 1977 289

 578
"II
carbon monoxide at the fusion temperature, sapphire ) can be decomposed, as can their
changing the ratio of the two iron redox forms. synthetic equivalents. Among titanium minerals,
This procedure was used to determine FeO in all three natural oxides and the titanates ilmenite
gabbro, olivine, glauconite,S72 garnets, ilmenite, and perowskite can be decomposed. The fusion
tourmaline, and other resistant minerals. 573 ' 574 agent also decomposes cassiteriteS79 and is
The amount of divalent iron found depends on the suitable for iron ores containing iron oxides and
fusion time, indicating that ferric iron is reduced silicates. 5 8 0 Tetraborates have been very
to ferrous during the fusion. 573 ' 575 The reduc- successfully employed as fusion agents for natural
tion is probably catalyzed by platinum, which is compounds of zirconium, mineral zircon,
transferred into the melt during fusion.576 This baddeleyite, 5 8 1 ' 5 8 2 etc. They are equally
method was used on a semimicroscale for the effective for oxygen-containing compounds of
determination of FeO in many minerals; after niobium and tantalum, chromium, and some
completion of the decomposition, the melt is resistant silicates, such as micas and tourma-
dissolved in a known amount of potassium lines. 492 In this fusion procedure, fluorine is not
dichromate, and the excess is determined reducto- lost during decomposition, so that the aqueous
metrically. 228 An interesting modification of the extract of the melt is suitable for the determi-
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Rovvledge procedure is fusion with fluoroborate in nation of fluorides after preliminary distil-
the presence of a known amount of vanadate in a lation. 583 An aqueous solution of the melt of
nitrogen stream. The unreacted vanadate is again silicon dioxide with tetraborate is stable for several
determined reductometrically.577 The proposed months and, thus is suitable for preparation of
procedure was applied in the determination of silicic acid standard solutions.5 8 4
FeOinchromites. 462 Alkali metal tetraborates are often employed
for sample preparation for emission spectrography,
C. Fusion with Borates and Boric Oxide X-ray fluorescence spectrometry (XRF), flame
Alkali metal meta- and tetraborates are efficient spectrometry, etc. The sample fusion essentially
nonoxidizing fusion agents and are commonly reduces the matrix effect if rocks of varying
employed for decompositions of resistant composition are to be analyzed; it also enables
minerals. They are usually used as anhydrous salts, preparation of a homogeneous material and the
after dehydration at 700 to 800°C. Platinum homogenization of heavy metals added as internal
crucibles are generally employed, but graphite standards. When melts are prepared in graphite
ones are also commonly used. A particularly crucibles, losses in cobalt and iron are encountered
suitable material is a 95:5 alloy of platinum and due to the process of reduction to metals.5 8 S
gold. This alloy is not wetted by the tetraborate Similarly, losses in copper were observed in
melt and, therefore, is easily quantitatively poured decompositions of cupric zeolites by fusion in
out of the crucible. After the sample decomposes, platinum. 3 ' 6 Procedures have been described for
it is sometimes necessary to separate the boron sample preparation for spectral analysis and 5:95
added (either as boric acid methylester or as BF 3 ) gold-platinum alloy casting molds which ensure a
before further analytical treatment. constant cast geometry. 5 8 6 ' 5 8 8 The Claisse
Tetraborates are efficient fusing agents for Fluxer® automatic device, 589 enabling simul-
oxygen-containing minerals of aluminum, iron, taneous preparation of six glasses in suitable
titanium, tin, niobium, and tantalum. The fusion is gold-platinum alloy crucibles, is advantageous for
first carried out at a low temperature, then the preparation of beads and plates for X-ray
temperature is increased to 1000°C and the fusion fluorescence analysis. The fusion is carried
is continued until a transparent melt is obtained. out with sodium tetraborate, which is suitable for
Titanium minerals are decomposed after about 1 elements at higher concentrations, or with lithium
hr; niobium and tantalum minerals must be salt suitable for the determination of light
decomposed for substantially longer times. The elements and trace concentrations of heavy
melt formed is generally extracted with mineral elements. Barium peroxide or lanthanum(IH)
acids; any insoluble residue which is present is oxide is used as an additive in order to decrease
separated and ignited; then the fusion is the differences in the absorption of X-rays by
repeated. In this way, natural aluminum(HI) oxide various rock types. A fusion agent-sample ratio of
(corundum and its colored varieties, ruby, and 100:1 is sufficient for many elements at

290 CRC Critical Reviews in Analytical Chemistry

 concentrations above 1%. This dilution removes be 15 min; otherwise, losses of the alkalies occur.
jnterelemental effects and the X-ray intensities are When the mixture is insufficiently homogeneous,
proportional to the element concentrations. microcrystalline silicon dioxide (insoluble in
This method has been used for the determi- mineral acids and consequently undetected in the
nation of principal and trace element concen- subsequent determination) is formed. The
trations in rocks, 59 °" S93 in analyses of lunar disadvantage of this fusion agent is that it is
samples,S94 and in the determination of thorium sometimes not available in sufficiently pure form
in ore concentrates59 s and silicon and aluminium and must be purified by recrystallization.
in bauxites. 596 Borate melts are also suitable for For the determination of elements by XRF,
direct reading spectrometers 597 and for the pellets or a button can be prepared from the
analysis of rocks by an electron microprobe crushed melt. Methylcellulose 605 ' 606 is suitable
analyzer 598 and mass spectrometry. 599 A melt as a binder for pellet pressing. In the preparation
solution in nitric acid was employed for the of buttons for XRF, metaborate is usually
determination of lithium in silicates600 and the obtained by mixing equivalent amounts of lithium
alkaline earth and other elements in geochemical tetraborate and carbonate.6 ° 7 >6 ° 8
reference materials by AAS. 90 Fusion with lithium metaborate is used in the
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Lithium metaborate is a substantially more preparation of a stock solution used in rapid

efficient fusion agent than sodium tetraborate; it silicate analysis. 609 It is also advantageous for the
rapidly decomposes even resistant oxygen- determination of some trace elements in rocks: a
containing compounds other than silicates (e.g., number of cations can be extracted with a liquid
spinels, chromites, ilmenite, and others). In ion exchanger 610 after dissolving the melt in
addition to solution analyses, the fusion agent is EDTA. Fusion with boron(III) oxide and lithium
also frequently employed for sample preparation carbonate was employed in the determination of
for X-ray fluorescence and emission spectroscopy. SiO2 in the presence of large amounts of phos-
Keith 60 * employed the fusion agent in the former phorus, zirconium, and titanium. 61 ' ' 6 ' 2 The melt
method; it was introduced into analytical practice is dissolved in EDTA and the interfering ions are
by Ingamells; 602 ' 603 he has reviewed604 the separated by ion exchange.
application of this substance in decompositions. Sample fusion with lithium metaborate can also
The borate glasses obtained are mechanically be used directly for the spectrochemical
resistant, not very hygroscopic, and soluble in determination of the individual components. The
dilute acids. The fusion is performed in platinum, pulverized melt is introduced between the elec-
gold, gold-plated platinum, gold-platinum alloy, trodes using a tape machine. 6 ' 3 The melt can also
graphite, or boron carbide crucibles. A strongly be dissolved in dilute nitric acid, and the rotating
oxidizing atmosphere is required; otherwise, iron, disk method is used for the analysis.603 Both
copper, lead, cobalt, and other metals are reduced techniques employ spark excitation and a direct
and alloys are formed with platinum. Alloy reading spectrograph. The melt can be dissolved
formation may lead to losses during the analysis using a suspension of a strongly acidic cation
and creates the danger of melt contamination in exchanger. After separation, the resin contains
subsequent fusions. The platinum contents in the most of the cations from the solution; it is dried
melt solutions indicate that corrosion of platinum and analyzed spectrographically.6'4 A new
crucibles by the fusion agent is negligible.539 Gold scheme of silicate analysis for 16 principal and
and gold-platinum (5:95) crucibles are most minor elements has been developed utilizing this
suitable. Specially made glassy carbon crucibles are principle. 6 ' 5
very advantageous for routine work. If a carbon
A solution prepared from silicate and lithium
crucible is preignited and its internal surface is not
metaborate melt is an ideal medium for direct
mechanically damaged, it is not wetted by the
determination of a number of cations by AAS.
melt and the melt can easily be poured out
The fusion is usually carried out in a graphite
without losses. The fusion proceeds smoothly at a
crucible, and the glass is dissolved in dilute nitric
suitable fusion agent-sample ratio, provided that
acid while still hot. According to Medlin et al., 6 ' 6
both substances have been thoroughly pulverized
silicic acid can not be determined in this way
and mixed together. The fusion temperature
because of strong polymerization of the solution.
should not exceed 900°C and its duration should
On the other hand, this acid may be determined in

June 1977 291

 T the scheme67 in a hot flame without solution
pretreatment. This method of SiO2 determination
is also recommended by other authors. 6 1 5 ' 6 1 8
rocks up to 1:20 for strongly basic substances. A
melt solution can be used to determine elements
using AAS; strontium ions act as a releasing ele-
There are numerous applications of the procedure ment. 639 Barium tetraborate is an energetic fusion
in silicate analysis. 9 0 ' 6 1 9 " 6 2 2 The fusion agent agent for resistant minerals (e.g., corundum, zircon,
was also employed in the decomposition of etc.). The fusion agent is mixed with the sample in
fluorites and ceramic silicates.623 With the latter, a 10:1 ratio and the melt is dissolved in dilute
a preliminary decomposition with hydrofluoric mineral acids. The solution can readily be
acid, followed by fusion of the residue, has been employed for the photometric determination of
recommended. In analyses of coal ashes containing the alkali metals and calcium. 640
larger amounts of magnetite, ammonium vanadate Boron (III) oxide, nonoxidizing fusion agent as
is added to the fusion mixture to ensure complete effective as borates, is employed for the decom-
oxidation of iron. 624 Some analytical procedures position of resistant silicates and substances con-
are combinations of AAS and other photometric taining larger amounts of fluorine. This fusion
methods. 625 Materials other than rocks can also agent is prepared from very pure boric acid by
be analyzed using this procedure. This dehydration at 1000°C. The substance formed is
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decomposition technique has been recommended strongly hygroscopic and must be stored in a
for rapid analysis of copper slags6 7 and for the tightly closed vessel. The oxide volatilizes during
determination of tungsten in poor ores, 626 the fusion, especially at temperatures around
neodymium in yttrium garnet single crystals, 627 1550°C. The fusion is carried out in a platinum
and beryllium and vanadium in rocks. 628 crucible with negligible corrosion. For the decom-
Titanium-rich minerals, such as titanomagnetite, position of resistant silicates (e.g., distene, stauro-
rutil, etc., can be decomposed by this fusion agent lite, tourmalines, etc.), a five- to sixfold excess of
when a sufficient amount of silicon dioxide is the fusion agent over the sample is sufficient.
added. 629 The melt solution is also suitable for When fusion is completed, the melt must be
the flame photometric determination of the alkali mechanically cracked (e.g., by repeated heating
metals. The melt can be dissolved in dilute mineral and rapid cooling) and then dissolved in dilute
acids 6 3 0 " 6 3 2 or in complexing agents, e.g., citric hydrochloric acid. In most cases, the boric acid
acid. 6 3 3 ' 6 3 4 Lithium metaborate fused in vacuo formed must be separated as methylester. In view
can also be used for mineral fusion in vacuo for of the relatively high melting point, this decom-
K-Ar dating. During the fusion, no gaseous position technique is used for special purposes,
products which would interfere in the subsequent such as the determination of silicon dioxide in the
isolation of argon and its mass spectrometric presence of fluoride. In order to completely
measurement are formed. 635 remove boron trifluoride from the melt, the
strongly viscous melt must be heated to 1200°C,
Sodium metaborate is also an efficient
stirring with a platinum wire.
decomposing agent. The fusion agent is usually
prepared by mixing equivalent amounts of sodium This decomposition procedure has been used to
tetraborate and carbonate and is used chiefly for determine uranium in rocks, where it is carried by
the decomposition of resistant minerals. It has zircon or another resistant mineral. The rock is
been used in analyses of zircons, 636 spinels, 637 first decomposed by hydrofluoric acid and the
and iron ores, 638 as well as for reliable de- residue is fused with boron(III) oxide. The melt is
compositions of chromium ores and chromium- dissolved in hydrofluoric acid and then evaporated
containing ceramics. 408 After the preparation of with perchloric acid, thus removing fluoride and
the sample solution, chromium is separated using a borate. 2 6 0 ' 6 4 1 A fusion agent containing 10%
liquid ion exchanger, and most remaining cations lithium carbonate was proposed for the decom-
are determined titrimetrically or photometrically. position of silicates; the melt is dissolved in 0.1 A^
Strontium metaborate is also an effective fusion hydrochloric acid containing peroxide. The
agent for natural silicates. Its melting point is solution is used for the atomic absorption spectro-
1150°C, but the presence of other phases de- metric determination of potassium. 642 Boric acid
creases this value by about 100°C. The fusion can be used for fusion instead of the oxide. The
agent-to-sample ratio depends on the sample's decomposition was applied to a rapid deter-
basicity and increases from 1:5 for strongly acidic mination of silicon dioxide present at a level of

292 CRC Critical Reviews in Analytical Chemistry

 over 90%. When evaporated with hydrofluoric increased by adding quartz or glass. Of course, the
acid, both silicon and boron oxides volatilize; the calculation must also include the amount of the
difference between the sample and residue weights effective components contained in the ore
yields the SiO2 content. 643 sample. 657 Sodium tetraborate or calcium fluo-
ride is used to achieve a suitable slag viscosity.
D. Reductive Fusion Knowledge of the redox character of the ore
Reductive fusion is a special procedure for material is also important, as the amount of the
decomposition of some mineral raw materials. reduced metal depends on it. Sulfides, especially
During this procedure, the valence of the cations is pyrite, have a reducing effect; if a sulfide is present
decreased due to the effect of the reducing in a great amount, an oxidant must be added to
component of the fusion agent; some can even be modify the redox character of the ore material or
reduced to the metals, which can then be mechan- sulfur (arsenic, selenium, etc.) must be removed by
ically separated from the slag obtained. The preliminary ignition. Large amounts of nonferrous
reduction product is usually more readily decom- metals, especially copper and nickel, make
posable than the initial substance (e.g., very reducing fusion difficult; thus, it is advantageous
stable cassiterite can be reduced to metallic to separate them beforehand by ore decom-
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tin during the fusion and is then easily soluble in position in nitric or sulfuric acid.
mineral acids). The pretreated sample is mixed with the fusion
Heavy metal oxides are readily reduced in mixture, containing, in addition to the above-
alkaline melts, especially those of lead, copper, mentioned reagents, a collector (usually lead[II]
antimony, and bismuth. If noble metals (gold, oxide) and a reductant, most frequently carbon or
silver, platinoids) are present in the system, various flour. The mixture is heated to a suitable tempera-
binary and ternary alloys are formed by their ture at which it melts, and lead(II) oxide is
reactions with the fused metals. As the reduced simultaneously reduced to metallic lead. The small
metals have considerably higher specific weights beads of the reduced lead move in the melt and
than silicate melts, they are collected on the come into contact with the noble metals, forming
bottom of the fusion vessels in the form of a an alloy. The initial stage of the fusion is turbulent
button, containing the entire amount of the noble and is accompanied by intense gas evolution,
metals originally present in the substance. Some which stirs melt. Upon completion of the decom-
platinoids are also carried mechanically into the position and reduction reactions, the melt
button. This principle underlies an ancient ana- becomes quiescent and the metal beads drop to
lytical procedure called the fire-assay method, the crucible bottom, where they are collected as a
which was known as early as the second millenium button. The crucible content is poured into an
B.C. and is still employed in the laboratory. A iron mold, is allowed to cool, and the button is
number of monographs 3 1 ' 6 4 4 " 6 5 0 and re- removed and thoroughly cleaned. The third stage
views 651 " 656 have treated the subject. Large involves scorification, The button is covered with
sample weights treatable by this procedure ensure fused sodium tetraborate on a scorification dish
the homogeneity of ore samples containing noble and is heated to 950°C. All the metals, except for
metals in the form of random inclusions; there- the noble metals, are transferred into the tetra-
fore, the method is employed as the standard borate melt where they form appropriately
procedure for determination of silver, gold, and colored metaborates. Scorification can also be
the platinum metals. carried out without tetraborate; the lead(II) oxide
The procedure consists of four steps. First, the formed serves as the fusion agent. In the final stage
ratio of acidic and basic components in the of the determination, the substantially diminished
material analyzed must be determined in order to button is freed of lead by cupellation on a small
select a suitable composition of the fusion mix- cupel made of calcium and magnesium phosphates.
ture, the main constituents of which are sodium The lead is partially evaporated as the oxide and
carbonate and fused sodium tetraborate. The ratio partly percolates into the cupel. After cupellation,
of the substances is selected so that silicic acid in the noble metals remain as a grain at the bottom
the melt is converted into an alkaline mono- or of the cupel. The grain is then analyzed for
disilicate. If the material contains too much basic individual components. In the final stage of
component, the acidity of the mixture must be cupellation, it is essential that the cupel be

June 1977 293

 removed when the metal bead rotating on the separation was verified. Both of the variable
cupel bottom stops and lightens and then darkens components cause a constant loss of less than 1%
(Silberblick); otherwise, part of the silver is lost. of the gold originally present. Volatilization of the
The loss of silver during the whole fusion alloy during cupellation and the process of dissolu.
process was monitored using the 1 1 0 Ag isotope; tion of the gold and silver grains at various tempera-
losses depend on the total button weight and the tures and nitric acid concentrations (parting
magnitude of the silver distribution coefficient process) were further studied; it was found that
between the alloy and the melt. During cupellation losses due to volatilization are negligible, but part
a small amount of silver is lost by percolation into of the lead from the cupel diffuses into the grain
the cupel 658 with lead(II) oxide. A number of during prolonged cupellation. More serious losses
works have been devoted to the behavior of gold were observed during the fusion process; during
during fire assay. For the determination of its mixing of the ore with the fusion agent on foil, as
distribution during the fusion processes, radioiso- much as 1.5% of the gold was carried away in the
topic monitoring or neutron-activation were dust. The effect of the fusion temperature can also
employed. The transport of gold was monitored in be observed: lower temperatures lead to melts
all components of the system and in the devices with higher viscosities; at high temperatures the
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used. It was generally found that gold deposits on melt splashed. The overall gold distribution is as
the melt contact with the crucible and on the follows: the grain contains 99.5%, the fusion
cupel underneath the metal bead. 659 Shima 659 crucible 0.7%, and the cupel 0.03%, while the slag
points out the danger of incomplete Au collection and the solutions used for parting were free of
caused by large contents of copper, iron, and gold.**5
sulfur. The accuracy of the results depends on the The behavior of the platinum metals during fire
button size, the weight of which should be assay was studied analogously.3' Statistical evalu-
between 25 and 35 g. Copper (3 g) and nickel ation of the scatter of the results in the deter-
(0.025 g) in the button render cupellation mination of the platinum metals by emission
impossible. Losses in cupellation are also caused spectral analysis after fire-assay isolation of the
by selenium, tellurium, and small amounts of metals, carried out in six Canadian laboratories,
bismuth.* * 0 '* 6 1 The results of parallel analyses of showed that the separation is complete. Scattering
synthetic gold-bearing ores obtained by activation is caused by further analytical treatment. 666
analysis, by wet chemical procedures, and by fire Losses of iridium and other platinoids were
assay indicated that the last method is most studied by means of radioisotopes and neutron
reliable. However, generally this is only true when activation. It was found that losses during reduc-
noble metals are present in the ore in a form tion fusion are minimal; repeated fusion of the slag
amenable for collection. 382 Greater loss of silver leads to complete separation of iridium into the
during cupellation was observed; AAS is recom- button. Considerable loss, 25-50%, occurs during
mended for its determination.662 In an attempt to cupellation; iridium was detected in • the cupel
standardize methods and materials, lead has been material, as well as in the walls of the cupellation
recommended as a suitable collector for all noble furnace. 6 6 7 ' 6 6 8 The distribution of the platinum
metals. Losses in ruthenium and osmium can be metals in the lead button was monitored using
compensated for by "spiking" the ore with a known radioisotopes; it was confirmed 669 ' 670 that
amount of radioisotopes.387 The effect of a iridium and rhodium cannot be concentrated in a
critical amount of lead on the quantitative depo- silver grain. If lead is present, both the noble
sition of gold was verified663 during the study of metals are protected against oxidation and volatili-
metal loss in dependence on its absolute amount zation; therefore, it is recommended to cupellate
and of the efficiency of various reductants. Too the button to a weight of 0.5-0.7 g and then to
large a button requires prolonged cupellation time, subject it to neutron activation analysis. The loss
leading to a greater loss of gold. Wall and of the noble metals does not exceed 8%.
Chow 664 dealt in detail with the question of
losses of noble metals during the whole process Collection of the platinum metals in lead is
under standard conditions and at controlled rather complicated. Added silver powder usually
temperatures. The effect of the lead weight and of acts as the collector; larger amounts of nickel
the Au/Ag ratio on the completeness of the strongly inhibit the process. The latter must be
removed by extraction with acids after thermal

294 CRC Critical Reviews in Analytical Chemistry

 pretreatment of the sample. Metal sorption on the Another method for the final determination of
walls of the fusion crucible is a source of error in the preconcentrated noble metals is by A AS.
the reduction of platinum; repeated fusion of the Gold and platinoids can be accumulated in a silver
slag is necessary. grain after removal of lead; the grain is dissolved in
Rhodium readily dissolves in lead, but the aqua regia and determination is carried
completeness of its separation depends on the size Q u t 66 77 77, 667 88

of the button formed. Iridium does not form collectors of Pt-metals; the amount added
alloys with lead or silver and is deposited in the should be three orders of magnitude higher than
button in the form of a suspension. The fusion the amounts to be determined. 679 In analyses of
mixture must be neutral or acidic, as it readily chromite concentrates 680 it has been found that
reacts with basic slags. Ruthenium and osmium are no basic or acidic fusion agent is sufficiently
easily lost during cupellation, as they are readily efficient for the decomposition of these minerals;
oxidized to volatile oxides. with small sample weights (3 g), the efficiency of
Thus, it is evident that the platinum metals are the reduction decomposition is 90% and it rapidly
separated into the lead button almost quantitatively decreases with increasing sample weight. An
following repeated slag fusion. Substantial losses addition of 50 mg of gold must be used when
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occur only during cupellation. However, the iridium is to be determined in basic rocks; the
button can be used as a collector, which is then detection limit is 2.5 ppm. 6 8 1 Gold, silver,
analyzed for the platinum metals by solution palladium, and platinum can be determined by
chemistry or by one of the radiochemical AAS after standard separation into a lead button
methods. Agrawal and Beamish671 examined the and cupellation. The grain obtained is dissolved in
distribution of the platinum metals between the aqua regia and the final solution contains KCN and
button and slag during repeated basic fusion and EDTA. 6 8 2 ' 6 8 3
the behavior of the platinum metals during parting Neutron activation often finds application in
with nitric acid. It was found that platinum and determination of noble metals. It is possible to
iridium remain almost quantitatively in the residue activate the initial material and measure the
after acid extraction and 20% of the rhodium is 7-spectrum of the grain after cupellation or to
dissolved, while palladium is dissolved almost activate the button or grain after collector
quantitatively. Solubility of platinum and removal. The former procedure was used 684 fora
especially iridium in an acid increases with in- highly sensitive determination of gold in rocks and
creasing copper content in the button. for the determination of iridium in meteorites
Fire-assay preconcentration of traces of after preconcentration of the metal in 50 mg of a
platinum metals in a lead button is often platinum-rhodium alloy by fire assay. 690 Traces
employed in determination of these elements in of platinoids in rocks could be collected by gold
geological materials by emission spectrography. and the grain was activated after cupellation.6 8 S
Haffty and Riley 672 determined the content of Neutron activation analysis of the lead button was
the platinum, palladium, and rhodium in standard employed 686 " 689 in the determination of gold
rocks of the U.S. Geological Survey. They assayed and the platinum metals in ores and products of
the samples after adding gold as the collector. The affination treatment. In measurements of charac-
grain obtained after cupellation was dissolved in teristic 7-spectra, high-resolution spectrometers
aqua regia and the determination was carried out with Ge(Li) detectors have been used.
in solution. Gold and the platinum metals were Errors connected with collection of the
determined in a similar material after reduction platinum metals in a lead button during fire assay
fusion without a collector. 673 ' 674 According to stimulated the search for more suitable collectors.
Lupan et al., 67S concentrations as low as 5 ppb of Faye 656 proposed fused tin as an effective col-
the metals can be determined in this way with an lector, as it readily forms intermetallic compounds
error of 20 to 40% depending on the amounts of with silver, gold, and the platinum metals. Copper,
noble metals and impurities. Iridium, ruthenium, nickel, and iron dissolve simultaneously. Ore
and osmium can be separated from ores using concentrates containing larger amounts of sulfur
weakly acidic fusion agents and platinum as the and arsenic in addition to the above elements must
collector; the procedure was verified using first be ignited and extracted with mineral acids to
tracers.
676 prevent the formation of undesirable matte and

June 1977 295

 T arsenides. The platinum metals transferred into the
solution are reduced and joined with the insoluble
residue after acid extraction. The fusion mixture
platinum and 5% of the total amount of pal-
ladium; however, its formation can be prevented
by preliminary combustion of the sulfur. The
consists of sodium carbonate, sodium tetraborate, fusion is important chiefly for isolation of the
quartz, tin(IV) dioxide, and coke; the fusion platinum metals which are often bound to
proceeds at a higher temperature (1200°C). After ferrous-nickel(II) sulfide. The presence of nickel
solidification the alloy formed is refused at 600 to leads to considerable losses of the platinum metals
700°C in a nitrogen atmosphere and then rapidly in classical fire assay using lead. On the contrary,
cooled in water; the button cracks and can be collection on an alloy has proved successful in the
crushed mechanically. The reduced metal is determination of platinum, palladium, and
dissolved in hydrochloric acid with hydrogen rhodium in sulfide concentrates and in the
peroxide and the solution is analyzed chemically. determination of osmium and ruthenium.
Osmium can be distilled off as the chloride and Although the solubility of iridium in the alloy is
excess tin can be removed as the volatile bromide. somewhat limited, the alloy still contains up to
Ion-exchange chromatography426 is suitable for 95% of the metal present. The fusion is suitable
the separation of the other platinoids. even for the decomposition of resistant materials,
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The effect of the composition of the analyzed such as natural alloy osmiridium.
material on the fusion process was studied Alloys of iron, nickel, and copper are also
systematically. Some products, such as ore collectors of the platinum metals. 694 They are
concentrates, Cu-Ni-matte, and meteorite metal suitable for isolation of all platinum metals,
phases, must first be extracted in HC1-NH4C1 including osmium. 69S The processs of collection
mixtures. The efficacy of reductive decomposition of noble metals was verified by evaluation of a
of magnetite, ilmenite, and Cu-Ni concentrates noble metal-bearing ore standard. 387 A copper
containing platinoids as arsenides or as solid button 6 9 6 was proposed for separating rhodium in
solutions in sulfides was also verified. The the presence of larger amounts of copper. Copper
chemically resistant natural alloy osmiridium can forms several defined compounds and a number of
readily be decomposed. Chromite is not de- solid solutions with rhodium. The fusion proceeds
composed by reduction fusion and must first be at 1200°C and is very efficient for traces of
sintered with sodium peroxide. 691 Tin button is a rhodium. Losses of the metal into the slag and the
suitable collector for silver; analyses of the slags crucible walls are usually less than 4%.
after fire assay with a tin button indicated a Nickel(II) sulfide is also suitable as a collector
residue of 0.015% of the silver originally present. of the platinum metals. Fusion yielding this
After dissolution of tin button in hydrochloric button is very universal and is virtually unaffected
acid, the dissolved silver is reduced with metallic by the sample composition. The fusion mixture
tin. the separated precipitate is dissolved in a HC1 + consists of sodium carbonate and tetraborate,
H 2 O 2 mixture, and the silver is determined by nickel(II) carbonate or oxide, and an equivalent
atomic absorption. 692 According to Jones et amount of sulfur. If the materials analyzed are
al. 6 9 3 distillation separation of osmium from the very basic, quartz is added. The fusion tempera-
dissolved button is unsuccessful; therefore, ture lies between 800 and 1000°C. The slag
reduction fusion using NiS matte is recommended. formed .is not very viscous and contains no NiS.
Other efficient collectors for noble metals The fusion mixture is used in a threefold excess
during reductive fusion include iron and nickel over the sample and the slag must be repeatedly
alloys. Both metals are present in sulfide con- fused. The main parameters of the fusion, 6 9 7 ' 6 9 8
centrates in substantial amounts; the fusion the temperature and its duration, the effect of the
mixture contains sodium carbonate and sodium matrix, and the effect of the button size and
tetraborate, and a graphite crucible or added excess sulfur on the platinoid recovery were
graphite acts as the reductant. The reduction verified. During fusion, noble metal sulfides and
occurs at 1350°C. A maximum amount of the transition metal sulfides form the button.
alloy is formed within 15 min after attaining this Sulfides are very suitable collectors for the
temperature. The quiescent melt consists of three platinum metals, but the results for gold are
phases: the alloy, a sulfidic matte, and slag. The markedly scattered. Advantages of the procedure
matte formed contains only trace amounts of include the low fusion temperature and the fact

296 CRC Critical Reviews in Analytical Chemistry

 that thermal and chemical sample pretreatment is containing sodium carbonate and potassium
generally not necessary. The matte is sufficiently oxalate (5 + 1). When heated, carbon monoxide is
heavy and is easily pulverized mechanically. The formed by oxalate decomposition and reduces part
subsequent extraction with acids is very easy. of the trivalent iron to divalent, thus facilitating
Difficulties are encountered in the fusion if the rapid decomposition of silicates by the alkaline
material contains too much iron and copper. If fusion agent.
iron and copper sulfides comprise more than 10%
of the sulfide present, another sulfide phase is E. Alkaline Fusion is the Presence of Sulfur
formed, causing losses of noble metals in the This type of fusion, also called Freiberg
slag. 703 The decomposition efficiency was decomposition, is suitable for decompositions of
checked using radioisotopes, 6 6 7 ' 6 6 8 ' 6 9 9 and a sulfidic raw materials containing arsenic, anti-
comparison was made with other fire-assay mony, tin, and molybdenum. During heating, an
procedures. 387 ' 700 The procedure was employed, alkali polysulfide is formed from a mixture of
among other applications, for the decomposition sodium or potassium carbonate and sulfur, which
of osmiridium701 and for other platinum-bearing reacts with a number of elements yielding sulfides
raw materials. 693 ' 702 and sulfosalts. Undissolved sulfides can then be
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Reductive fusion is only rarely used for the separated from soluble sulfosalts by extracting the
determination of metals other than the platinoids. melt with water. The ratio of the fusion agents is
One example is reductive fusion with potassium selected so that all sulfur is bound by the alkali
cyanide, employed for the decomposition of metal present. Porcelain crucibles are used for the
tin(IV) dioxide (cassiterite). Similar effects are fusion. The analyzed sample must be very finely
achieved by fusion with sodium carbonate and powdered and thoroughly mixed with an 8- to
finely dispersed carbon. If the melt does not come 15-fold excess of the fusion agent. An alkali
in contact with air, the reduced tin separates on sulphide is formed during first stage of the fusion,
the crucible bottom. The reduced tin can be which takes place at a low temperature. At a
converted into an alloy with copper, which is higher temperature, the decomposition itself and
added to the fusion mixture as the oxide. the formation of a polysulfide occur; the tempera-
Other examples of systems suitable for ture must then be decreased slowly. Ferrous,
reductive fusion include mixtures of alkali nickel (II), and cobalt (II) sulfides tend to form
hydroxides with metallic sodium or zinc or a colloidal solutions; the melt extract must then be
mixture of sodium hydrocarbonate with aluminum heated in a water bath, adding potassium or
and carbon. 704 The former was employed for the ammonium chloride. Copper and mercury form
decomposition of cassiterite; the latter can soluble sulfosalts in the presence of excess sodium
quantitatively reduce sulfate to sulfide. For ions and appear in both phases; the formation of
determination of sulfur in coal by reductive these compounds can be prevented by using
fusion, reduction of sulfur compounds to sulfide potassium salts. With rich mercury ores, the sulfide
with fused alkali metals or metallic magnesium was recovery is not quantitative due to metal volatili-
proposed. 705 zation during the fusion.
Silicates which are fused with difficulty (e.g., Freiberg decomposition has been used in the
tourmalines) can readily be decomposed by fusion analysis of separated minerals, rich ores, and
with a mixture of sodium hydroxide and concentrates. The simple separation of sulfosalts
aluminum powder. Following mild heating, an from sulfides considerably simplifies the analysis.
exothermic reaction starts and the mineral The decomposition has been applied to lead
decomposes within several minutes. 706 Mag- sulfoantimonates, bournonite, boulangerite,
nesium powder was employed for decompo- jamesonite, and other minerals of this group.
sition of a silicate mixture in the determination of Noble silver ores, miargyrite, pyrargyrite,
the sum of alkali metals. The reaction mixture is proustite, and sulfostannate stannin can also be
extracted with 50% ethanol and the alkali hy- decomposed, as can germanium minerals. The
droxide liberated is determined by alkalimetric procedure is advantageous for the separation of
titration. 707 antimony 7 ' ° > 7 ' ' from polymetallic ores, bismuth
To determine total iron in silicate ores (which from excess arsenic, and molybdenum in the
are difficult to decompose in acids), analysis of bismuth ores. The fusion has also been
Quadrat 7 0 8 ' 7 0 9 recommended a fusion mixture used in decompositions of cobalt and nickel

June 1977 297

 arsenides from the safflorite-skutterudite group. are usually determined empirically for each
During the decomposition of a copper concentrate analyzed material.
by a mixture of potassium carbonate and sulfur, Sintering involves solid state reactions; i.e., the
copper can be quantitatively separated as the reactants and the products are solids. The reaction
sulfide and antimony can be determined in the mechanism is assumed to involve the formation of
extract polarographically, photometrically, or by a monomolecular layer of the reaction product at
atomic absorption. 712 ' 713 The loss of antimony the interface of two crystalline solids. Particles
has been observed in materials containing large constituting the crystal lattice oscillate with a
concentrations of silicon dioxide; this is probably higher energy with increasing temperature. There-
caused by sorption of antimony on the silica gel fore, when.a mixture of crystalline powders is
formed. 282 heated, ions or molecules can overcome the lattice
Tetrahedrites are important members of the forces due to their increased oscillation amplitude
sulfosalts mineral group. They are economically and can exchange their positions. The exchange
important sources of copper, silver, and mercury. probability is, of course, very low for particles in
Their complete analysis can also be effectively solids with ideal crystal lattices. The temperature
carried out using the Freiberg decomposi- at which this initial exchange starts marks the
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tion. 7 1 4 ' 7 1 5 A rapid determination of anti- beginning of internal diffusion, which then con-
mony in a flotation tetrahedrite concentrate tinues at a measurable rate. It has been found that
and in thermal treatment products has been the absolute initial temperature of internal dif-
described. 713 ' 715 fusion is 57% of the absolute fusion temperature
Small amounts of cassiterite can also be for some salts. The reaction products are
decomposed by fusion: the decomposability of transported by diffusion from the interface and
this mineral probably depends on the amount of the reactants again come into contact and react.
heterogeneous inclusions. Alkaline fusion in the This diffusion corresponds to very slow stirring of
presence of sulfur was proposed for the deter- the solid reaction mixture. Reactions among solids
mination of tin in rocks and poor ores. 716 thus proceed very slowly and usually are not
However, determinations of this element in completed during the experiment. The substance
galenite and other sulfides have indicated that the activity may simultaneously depend on the pre-
separation of the sulfostannate from separated paration procedure, the presence of a gaseous or
sulfides is not quantitative, 717 as losses in tin liquid phase, distortions of the crystal lattice, the
amounted to as much as 50%. presence of other compounds, and ion polari-
zation. For example, the recovery of magnesium
chromite formed by reaction of ferrous chromite
V. SAMPLE DECOMPOSITION
with magnesium oxide is lower at the same
BY SINTERING temperature than with a mixture of chromite and
As fusion decompositions always lead to sub- carbonate. When using carbonate thermal decom-
stantial contamination of the analyzed material by position, a much more active oxide is formed than
introduction of salts and trace elements and/or by with an oxide whose lattice is ordered by ignition.
crucible corrosion, attention has been centered on An increase in reactivity due to distortion of crys-
decompositions in which the amount of the fusion tal lattices has the same basis. Active oxides, pre-
agent is limited to the necessary minimum. Such pared by dehydration of hydroxides, react more
procedures are called sintering; during the effectively than oxides prepared by prolonged
decomposition, the mixture is not fused by ignition, as the crystal lattices of the former are
sintered and the reaction of the mixture with the expanded or distorted.
vessel material is minimal, because of the low The reactivity of solids can be affected by the
temperature used. The residue formed can usually presence of some gasses, although there is no
be readily removed from the crucible and is reaction between the gas and the solid. The gas
generally easily soluble in mineral acids. The may penetrate into the crystal lattice and dissolve
completeness of the decomposition depends on in the substance, changing its reactivity. For
the reaction conditions, i.e., the decomposition example, sulfur trioxide decreases the quartz
mixture composition and its amount, the heating activity, while sulfur dioxide and oxygen increase
gradient, and the heating time. These conditions it. A change in the activity has been observed in

298 CRC Critical Reviews in Analytical Chemistry

 syntheses of calcium silicate from the oxides. determinations) and hinders the separation of
Other contaminants capable of forming solid silicic acid. However, the amount of salts can be
solutions or intermediates with the reactants have decreased by using sintering. This decomposition,
similar effects. proposed by Finn 7 1 8 and developed by
Reactions in the solid phase occur much faster Hoffman,7*9 has recently been verified for series
in the presence of a liquid phase, not only due to application. The sintering is carried out in a
hastening of diffusion processes, but also due to platinum crucible with a 1.5 to 2-fold excess of
the considerable increase in the interface area, as sodium carbonate containing 10% sodium nitrate.
the reaction surface then equals the total surface The sintering temperature should not exceed
of the solid particles. The reaction surface is often 780°C; its duration (30 to 180 min) depends on
liquid; then, a liquid product layer is formed at the the chemical nature of the compounds subjected
interface of the crystal lattices, and its thickness to decomposition. The aggregate formed is readily
increases in time. The course and rate of the soluble in hydrochloric acid. The study of
reaction are then determined by the mode and decomposability of monomineral fractions has
velocity of the reactant particles through this layer shown that the decomposition is as universal as
and by the reaction rate at the interfaces where fusion; most rock-forming minerals, quartz,
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the reactant crystal lattices are destroyed. During feldspars, micas, pyroxenes, and amphiboles are
sintering, the reaction rate is increased by even smoothly decomposed. Accessoric components,
minute amounts of a liquid phase: the layer of the such as tourmaline, garnets, axinite, zeolites, and
powdered mixture is not fused, but is sintered into foids, can also be readily decomposed. Zircon and
a solid agglomerate. aluminum silicates (e.g., cyanite etc.) remain
The rate of reaction between solids can be unattacked. X-ray patterns of the sintering
increased by adding substances which cause the products indicate that a new product was formed
formation of eutectic melts. The reaction heat during the decomposition; the determination of
liberated usually suffices for heating the mixture the CO2 released corresponds to 99.0 to 99.9%
to the temperature required for fusion of the completion of the decomposition reaction. 721
reactants or for heating their eutectic mixtures The undecomposed residue contains mainly
with the newly formed compounds. The solid state aluminium oxide. The decomposition has been
process is only the initial reaction stage; it is slow, verified many times using standard rocks 720 and
but is hastened during formation of a liquid phase. has been introduced in the laboratories of some
geological surveys. Acidic rocks (e.g., granite,
If solid solutions are not formed among the
gneiss, or greisen) are decomposed after as little as
reactants and the products during the reactions of
20 min heating, while basic rocks (such as basalts,
solids, the activity of all components remains
serpentinites, and gabbros) require longer
constant throughout the reaction. Hence, these
decomposition times (up to 3 hr). Even beryl can
reactions cannot attain equilibrium. The reaction
be decomposed by sintering at 1000°C. For
is terminated when the reactants are consumed.
successful decomposition, the material must be
Reactions in the solid phase proceed in the
finely powdered and thoroughly mixed with the
direction of decreasing free energy of the system.
reagent, as by pulverizing the mixture on an agate
If only solids participate in the reaction, the
mortar. Crucibles made of any material which is
entropic change is small and can be neglected in
not fused at the given temperature can be used in
practice. Therefore, the direction of these
addition to platinum crucibles.
reactions is determined by diminishing the
enthalpy; solid state reactions are always exo- If enough air comes into contact with the
thermic. sintered mass, sulfide sulfur is quantitatively
oxidized to sulfate, and tellurides and selenides
A. Sintering with Sodium Carbonate yield soluble compounds of the tetra- and
The decomposition of silicates by fusion with hexavalent elements. The sulfide of tetravalent
excess sodium carbonate causes an enormous molybdenum (molybdenite) can be completely
increase in the sodium ion concentration and thus oxidized with formation of sodium molybdate and
creates unfavorable conditions for subsequent sulfate. 722 This decomposition procedure has
determination of the individual elements (e.g., for been recommended for the determination of
chelatometry and most flame photometric phosphate in a molybdenite concentrate. 723

June 1977 299

 Certain chromites 724 and iron and aluminium 721,728,729 J J ^ m a t e r i a i should be finely
oxides (bauxites) 723 can also be decomposed. powdered and thoroughly mixed with dry
This procedure is also effective for rapid analysis peroxide; this process is similar to sintering with
of oxidic iron ores; the decomposition is carried sodium carbonate. Small sample weights (20 to
out at a higher temperature (1000 to 1100°C) for 100 mg) and a longer heating time have been
1 min. It has been prescribed as a standard method recommended728 for silicate decomposition.
because of its universal character. 725 Boron Under the given conditions, decompositions with a
bound in coal ashes can be converted into an alkali mixture of sodium peroxide and hydroxide (3 + 2)
borate by sintering at 950°C for 15 min. The coal can be performed in a platinum crucible. The
is combusted with sodium carbonate at 500°C for mixture is effective particularly for the de-
24 hr prior to the sintering.726 composition of resistant minerals and silicates with
high contents of ferrous oxide. The balance of the
B. Sintering with Sodium Peroxide iron and platinum distribution between the
Application of the strong decomposing effect sintered aggregate and the crucible walls is more
of sodium peroxide is limited by its strong favorable than in fusion with sodium carbonate.
corrosive effect on the crucible material. However, Sintering has been successful in decompositions of
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thermal study of decomposition reactions with thorium-bearing, rock-forming, resistant minerals

this substance has shown that numerous resistant (e.g., zircon, thorite, euxenite, and black sands).
minerals can be decomposed by peroxide at low This decomposition procedure is frequently
temperatures. Most mineral phases can be sintered employed for these purposes. 730 " 732 However, it
with peroxide in a platinum crucible; the corrosion has been observed that acid-insoluble thorium
of platinum is negligible,727 provided that the compounds 733 are formed during leaching of the
material does not contain sulfides and the residue with water. It has been recommended554
temperature does not exceed 500°C. A fourfold that the extract be filtered off and the residue
peroxide excess suffices for the decomposition of decomposed by fusion with fluoride.
most minerals and rocks. The crucible with the Zircon or rutil alone can be decomposed by
analyzed mixture is placed in an oven at a sintering with peroxide in a platinum 734 or glassy
controlled temperature and is heated for 7 to 8 carbon crucible. 636 As traces of platinum in the
min; it is then removed and cooled. In this solution may interfere in the determination of
manner, numerous minerals and ores, including thorium, iron crucibles were also recommended
magnetite, gypsum, celestine, wolframite, for zircon decomposition.
scheelite, titanite, quartz, feldspars, micas, clay Sintering with peroxide can also be successfully
minerals, etc., can be reliably decomposed. Even employed to isolate gold and platinum metals. It
resistant minerals, such as zircon, rutil, ilmenite, has been used in analyses of rocks from
cassiterite, and chromite, are decomposed. For W i t w a t e r s r a n d , 7 3 5 ore concentrates,
rocks, the decomposition of basalts, trachytes, chromites, 691 and residues after extraction of
andesite, and granites was verified. A detailed mattes 504 containing platinum metals. Alimarin et
thermal study showed that a majority of rock- al. 7 3 6 studied the decomposition of natural
forming minerals are decomposed at temperatures materials by sintering with peroxide to determine
from 250 to 300°C; the decomposition involves an ruthenium and osmium content. Both metals pass
exothermic reaction. With resistant minerals, an into an alkaline extract of the aggregate. Using
endothermic reaction is first encountered, which is radioisotopes, it has been found that as much as
an approximate criterion of the mineral stability. 25% of the two metals is lost through adsorption
Rafter 727 quantitatively recorded the amount of on the walls of nickel and iron crucibles during the
oxygen released during decomposition and, from decomposition of silicate materials by sintering
this information, derived the reactions taking place with peroxide at 500°C for 100 min; no loss has
in various phases. Resistant minerals (e.g., beryl, been observed with sintered corundum crucibles.
ilmenite, and rutil) must be sintered with a larger
Sintering with peroxide is a reliable de-
reagent excess and the duration of heating must be
composition method for resistant chromites, as is
extended to 15 to 30 min.
fusion; it has been used for complete analysis of
The decomposition of mineral silicate materials separated mineral fractions, 411 as well as
by sintering with peroxide was evaluated. 534 ' chromium ores and ceramics. 408 According to

300 CRC Critical Reviews in Analytical Chemistry

 Bouberlova,737 the decomposition of cassiterite carbonate and MgO (4 + 1) at 900°C, chromium,
by sintering with peroxide is complete, but some- molybdenum, and vanadium pass quantitatively
times only 90% recovery or less has been attained; into the aqueous extract of the aggregate and can
this is in accordance with our previous experience. be determined photometrically; 741 " 743 halides
It seems that mineral reactivity is closely con- are also extracted and can be determined. 744 ' 745
nected with the amount of isomineral elements in For the determination of iodine, it is necessary to
the lattice and heterogeneous contaminants. A decompose in a nickel crucible. The Eschka
spectrophotometric determination of tin in rocks mixture containing metallic zinc can also be
after this decomposition procedure has been employed for an indirect iodometric determi-
described.738 In technological practice, sintering nation of sulfur in sulfides and their con-
with peroxide is also employed for the centrates. 746
decomposition of phosphate raw materials, iron In some sintering procedures, magnesium oxide
and manganese ores, slags, and foundry sands. is replaced by calcium oxide or caustic lime. The
Decompositions of sulfides are rarer, as the increased basicity of the mixture is particularly
platinum crucible must be protected against useful in decompositions of chromites. During
corrosion by a layer of fused sodium carbonate or heating, iron and chromium are oxidized to higher
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sulfate. valence states. Spinels of the type,Ca(Fe,Cr)264

are formed as intermediates and finally lead to the
C. Sintering with a Mixture of an Alkali Carbonate formation of chromates; fireproflf silicates (e.g.,
and a Metal Oxide sillimanite and mullite) can be decomposed :
For sintering decomposition of sulfides, oxides, equally well.
silicates, and solid caustobiolites, a mixture of an A mixture of sodium carbonate and zinc oxide1'
alkali carbonate and a divalent metal oxide has been used widely in sintering decompositions.
(magnesium, calcium, and zinc) is often employed. Zinc silicate formed during decomposition of
The composition of these mixtures is mostly minerals has low adsorptive activity, and is a
empirical, depending on the character of the suitable substance for the separation of silicic acid
analyzed material. Metal oxides react pre- from many elements.
dominantly with silicic acid and some volatile The mixture is very frequently employed for
oxides to form sparingly soluble salts; they also act the determination of sulfur in sulfides, carbonates,
as a lightening agent. Sodium carbonate forms a and silicates; this decomposition procedure is
weakly alkaline medium and contributes to the recommended as standard. Sulfides are oxidized to
formation of aluminates and carbonates. Sintering sulfates and baryte is partially decomposed, while
can be carried out in a platinum or corundum less stable natural calcium and iron sulfates are
crucible; porcelain crucibles often suffice, as well. decomposed completely. Selenium, contained in
A mixture of sodium-potassium carbonate and the analyzed sulfide minerals, can also be oxidized
magnesium oxide is the Steady alkaline fusion in the same way and passed into an aqueous
agent; a similar mixture with MgO predominating extract of the aggregate.740 Minerals of arsenic
is the Eschka mixture. The former is suitable for and antimony, sulfides, oxides, or arsenides are
decompositions of fireproof steel mill ceramic readily decomposed by sintering with this mixture.
materials and chromites. Chromium is oxidized to Arsenic passes into the extract in the form of
chromate during the decomposition and can be arsenate ion.
separated from the other elements by extraction The decomposition mixture is an ideal reagent
with water. The Eschka mixture is frequently for decomposition of a great majority of rock-
employed for the decomposition of sulfides, forming silicates and is applicable chiefly to rapid
polysulfides, and sulfosalts. Sulfur is oxidized to isolation of halides and boric acid; the decompo-
sulfate during heating; selenium also yields soluble sition is very rapid and complete. The distribution
selenite, while the analogous tellurium compound of certain elements between the aggregate and the
remains quantitatively in the insoluble water extract was studied; 747 for subsequent
fraction. 739 The Eschka mixture with an oxidant boron determination the dissolved alkali
added is suitable for the determination of sulfur, carbonates and aluminates can be decomposed by
arsenic, and germanium in bitumens and coal. 740 a solid cation exchanger. In the extract, boron and
After sintering of rocks with a mixture of sodium halogenides are determined titrimetrically,

June 1977 301

 photometrically, or by ion-selective elec- determination of alkalies is based 764 on sintering
trodes. 748 " 754 The method of silicate decompo- with calcium carbonate and ammonium chloride.
sition and subsequent determination of halides has Calcium oxide, which is formed during the
been verified many times using standard rocks, decomposition, is highly reactive and gives rise to
lunar materials, meteorites, etc. The results of the insoluble silicates, borates, phosphates, and
determination are in excellent agreement with sulfates. On thermal dissociation of added
those obtained after distillation or pyrolytic ammonium chloride, hydrogen chloride formed
separation. reacts with the alkali metals. An advantage of the
This decomposition procedure has also been decomposition, compared with solution pro-
employed for the determination of silicon dioxide cedures, is perfect separation of magnesium. A
in silicates with a high fluorine content. 755 very finely pulverized sample thoroughly
Among other anions which can be separated by homogenized with the sintering agent is necessary
passage into the extract, molybdenum and for complete decomposition. The method of J. L.
vanadium should be mentioned. The procedure has Smith is generally employed for decomposition of
been recommended for the determination of rocks; acidic rocks are decomposed rapidly, while
molybdenum in copper concentrates. 756 Phos- basic ones require several hours of treatment.
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phate ions do not completely pass into the ex- Aluminium silicates, andalusite, cyanite, and topaz
tract; some of it is retained in the precipitate, are among the poorly decomposable minerals.
probably as basic ferric phosphate. Magnesium micas, staurolite, beryl, chlorites, and
The sintering mixture can be modified by some garnets are also decomposed with difficulty.
adding further reagents. After adding magnesium On the other hand, alumosilicates, especially
carbonate, it can be used for the determination of feldspars, and minerals with higher contents of
total sulfur in rocks 721 and fluorine in silicates.757 ferrous iron are readily decomposed. Crystal
The addition of sodium tetraborate improves the lattice contraction during iron oxidation contri-
decomposition of chromite. 758 Sintering with a butes to more rapid destruction of the mineral.
mixture of sodium carbonate and calcium oxide or It is advantageous to release sodium and
barium, carbonate and calcium oxide has yielded potassium from the silicate lattice by the above-
good results in the decomposition of titanium, described decomposition technique; this procedure
zirconium, niobium, tantalum, and other is unsuitable for isolation of the other alkali
borides. 759 metals. The decomposition method now has only
A mixture of sodium carbonate, nitrate, and historical value and it has been replaced by
chloride was used for the decomposition of wolf- decompositions with acids. An interesting modifi-
ramites. 760 Beryl can be decomposed by heating cation is the decomposition of silicates under
with fluorosilicate; fluoroberylate can be separated pressure, using the Smith mixture. 631 The pellet
in the extract from sparingly soluble aluminum formed is directly atomized in an acetylene-air
and iron fluorides. flame in the AAS determination.
A mixture of iron powder and zinc oxide serves Ignition of silicate materials with calcium
for reductive sintering of sulfur-containing ores, carbonate or oxide is similar to the procedure of J.
especially cinnabar. Ferrous sulfide is formed by L. Smith. Calcium monosilicate is formed by
the thermal reaction, while mercury is distilled off reaction with the active oxide and is readily
quantitatively. A layer of copper filings and soluble in mineral acids. The procedure has been
magnesium oxide is used 76l for complete depo- used for decomposition of aggregates and cement
sition of arsenic and antimony. Sintering mixtures raw materials,61 silicates, and glasses765 and for
containing calcium oxide and nitrate or magne- the determination of fluorine in coal. 766 This
sium oxide and calcium hydroxide have been sintering also produces rapid and selective release
proposed for quantitative combustion of coal in of rhenium from natural materials. The
the determination of arsenic and germani- decomposition is hastened by the presence of an
762,763 oxidant, usually potassium permanganate. Tetra-
um.
valent rhenium, present mostly as the sulfide, is
D. Decomposition by the Method of J. L. Smith oxidized to heptavalency during the decompo-
and Sintering with Metal Oxides sition and forms calcium perrhenate soluble in
A classical decomposition of silicates for the water. On the other hand, molybdenum that

302 CRC Critical Reviews in Analytical Chemistry

 carries rhenium yields water-insoluble calcium metallic uranium and the resultant gaseous
molybdate; arsenic, selenium, and tellurium yield mixture is analyzed by mass spectrometry. 777
water-insoluble salts, thus enabling simple separ- Rock fusion in vacuo is used to isolate gaseous
ation of rhenium by extraction. 767 A number of inclusions and gases retained in the crystal lattice.
applications have been described for the deter- The combustion oven is usually combined with a
mination of this element in molybdenum and device for separation of the gases released from
copper minerals, and their dressing products. 768 " water; the whole system is maintained in a high
770
Magnesium oxide combined with an oxidant vacuum. High-frequency radiation 778 " 780 is
has similar effects and has been used for the same generally used for heating. The decomposition is
purposes.7 7 1 ,7 7 2 effective for isolation of radiogenic argon in
absolute dating and analysis of gaseous compo-
nents of rocks and minerals. 779 " 781 Mass spectro-
VI. SPECIAL metry is most frequently employed for the final
DECOMPOSITION PROCEDURES determination; gas chromatography is used less
frequently. Interpretation of nitrogen bonding in
rocks is difficult; it is usually present as ammonia,
A. Thermal Decompositions
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either as a component of minerals or due to a

Physicochemical processes taking place in
reaction between hydrogen and nitrogen. 2 4 9 ' 7 8 2
minerals during heating fall into two groups: (1)
Oxygen in coal is determined by vacuum py-
Release of volatile material components in the air,
rolysis. 783
in a controlled atmosphere or in vacuo. Oxidation
or reduction of some elements and thermal disso- When ignited at a defined temperature, organic
ciation of compounds may also occur. (2) Struc- substances can be destroyed and converted to
tural changes occur during heating, accompanied elemental carbon or carbon dioxide. The tempera-
by formation of new phases, incongruent fusion, or ture selected by convention for differentiation
(in the presence of decomposition agents) reac- between organic and carbonate carbon is
tions in the solid state. The phases formed are 550°C. 7 8 4 ' 7 8 s However, some sulfides catalyze
generally easier to decompose than the original the decomposition of siderite and magnesite below
material. this temperature. 786 Electronic low-temperature
Moisture and bound water are most frequently ashing 787 was developed for mineralization of
released from minerals during ignition, which is bituminous coals. Organic compounds can be
carried out in a tube through which a dried inert combusted readily in an oxygen stream with a
gas passes and transports the water vapors into an slow increase in the temperature or in the presence
absorption system. The other manner of of catalysts. 788 ' 789 Most carbonates dissociate
decomposition consists of various modifi- quantitatively at 1100°C; only barium and stron-
cations of the Penfield procedure, based tium carbonates require higher temperatures. 249
on sample ignition in a closed system with- Sulfide sulfur can be combusted to a mixture of
out a carrier gas.8 Water then condenses 773 oxides in an oxygen stream or using catalysts.
on cool places in the decomposition tube. The Vanadium(V) or tungsten(VI) oxides are suitable
decomposition can be carried out either by heating catalysts. 790 " 792 Induction heating is advan-
to a high temperature 774 or by adding suitable tageous and has been employed in the deter-
fusion agents which decrease the substance melting mination of sulfur in soils, rocks, and ores. 793 In
point; the fusion agent also binds sulfur and an induction furnace, the sample is combusted in
halogens and prevents water decomposition by an oxygen stream at 1450°C in the presence of
ferrous iron at high temperatures. Lead(II) oxide, metallic tin or iron powder; the latter yielded
calcium tungstate, and lead(II) chromate are used better results. 794 Sulfur in sperrylite, 795 rocks,
as fusion agents. 218 A mixture of oxide and and iron ores can be determined in this way. There
chromate or magnesia and lead dioxide yielded are also automatic sulfur analyzers, such as Leco®,
good results for minerals fused with difficulty.775 etc. Sulfur in coal can be oxidized with oxygen in
The water deposited can be determined gravi- the Parr autoclave to form sulfuric acid, which is
metrically or by titration with the Karl Fischer 774 then titrated. 796
reagent or conductometrically and coulometri- Traces of tellurium in rocks can be separated by
cally. 776 For the determination of deuterium heating the sample with pyrite. Tellurium
oxide, the water deposited is decomposed by condenses with sulfur on colder parts of the
June 1977 303
 I

apparatus 797 or can be deposited in graphite, sodium aluminate when heated. For differen-
which is then used for spectrochemical determi- tiation between ilmenite and titanosilicates,
nation. 798 ignition at 800°C is recommended. Ferrous iron of
A number of other compounds volatilize during ilmenite is oxidized to hematite and titanium is
thermal decomposition of materials. In analytical separated as the resistant oxide. 81S By igniting
chemistry, separation and deposition of mercury chromite first in a stream of nitrogen and then in
are at present most important, followed by deter- oxygen, the increase in the oxygen content,
mination, usually by AAS. The sample is heated proportional to the divalent iron content, can be
either alone or with a fusion agent in an air stream; determined. The method is more reliable than
the mercury vapors are deposited on a gold common fusion with vanadate and metafluoro-
foil 7 9 9 " 8 0 2 or are freezed-out.803 The isolated borate. 462 Calcium fluoride and barium sulfate
mercury is released from the amalgam by heating can be readily decomposed 816 ' 817 by heating
and its vapors are determined by AAS. This with silicon dioxide. Ignition of the latter in vacuo
principle has been utilized in a number of com- at 1400°C yields sulfur dioxide and oxygen, while
mercial mercurometers. Coal can be combusted at barium oxide reacts with quartz to form a silicate.
a lower temperature in an oxygen stream and
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mercury can be absorbed in a KMnO4 solu- B. Decompositions of Minerals by Heating with

tion. 804 Ammonium Halides
The behavior of tellurium during combustion of Ammonium salts of various acids are suitable
organic materials was studied by Bock. 304 If the fusion agents; their melting point is low and,
substance is heated with added magnesium oxide except with fluoride, the decomposition can be
and nitrate, no loss occurs. The behavior of 14 performed in glass vessels at Bunsen burner tem-
elements during a 3- to 24-hr heating period (at peratures. Their acidic character, given by the
400 to 900°C) was studied using radioisotopes.805 dissociation of an active hydrogen atom during
There are losses through adsorption on the thermal decomposition, makes ammonium salts
combustion vessel (Pb, Cu, Zn) or by volatilization suitable for reaction with basic oxides and sulfides.
(Fe, As, Sb, Au, Hg). The behavior of arsenic 806 Reactions of ammonium iodide with antimony
during sediment combustion or of gold during the and tin compounds are especially effective.
ignition of sulfidic ores 3 7 8 was further studied. Volatile iodides are formed during the decom-
Amounts as small as a nanogram of lead can be position and sublime from the reaction mixture.
separated 2 4 9 ' 8 0 7 from rocks by sublimation in This simple decomposition was first used in
vacuo or in a nitrogen stream at a high geochemical prospection for t i n 8 1 8 ' 8 1 9 in soils
temperature. Trace concentrations of thallium, and sediments. It was later modified for quanti-
bismuth, cadmium, indium, and zinc can be tative determination of tin in cassiterite ores and
preconcentrated from these materials by selective concentrates; 820 ' 821 the effect of the amount of
evaporation and determined after dissolution of fusion agent, temperature, and fusion duration
the sublimate. 49 ' 808 upon decomposition completeness was studied.
Heating is sometimes successful in destroying The procedure has been used to determine small
the crystal lattices of stable minerals containing amounts of tin in rocks 8 2 2 ' 8 2 3 and poor
bound water, thus preparing a phase more readily ores. 8 2 4 > 8 2 S Sulfur compounds of tin can readily
soluble in mineral acids. After brief ignition at be decomposed by this reagent; certain kinds of
700°C, kaoline, bauxite, silicate iron ores con- cassiterite (stream tin and wood tin) are attacked
taining ferrous chlorites, and many clay minerals by the iodide only after preliminary extraction
which are component parts of cements 8 0 9 " 8 1 ' with hydrochloric acid, which removes secondary
can be decomposed in hydrochloric acid. On the layers of iron oxides from the mineral.64 This
other hand, more intense ignition of these decomposition technique is not quantitative for
*>"?
materials leads to insoluble aluminosilicate mullite. greisens, as the tin bound in silicates is not
When heated at the above temperature, vesuvian is liberated by the iodide. A simple separation
converted into a soluble form, 8 ' 2 while all the procedure has been developed for differentiation
cesium can be extracted from pollucite 813 after of tin bonding: after rock decomposition by
heating the mineral at 200°C. Carbonate hydrofluoric and nitric acids, part of the insoluble
dawsonite 814 is converted into alkali-soluble residue is heated with ammonium iodide. All of

304 CRC Critical Reviews in Analytical Chemistry

 the tin is contained in the sublimate. The decomposable compounds. Some elements react
remaining part of the insoluble residue is treated with gases to produce volatile compounds, thus
with hydroiodic acid, which dissolves fresh tin combining separation with decomposition. The
dioxide formed from the silicates, but not cas- original sample is separated into the following
siterite. 18S Cassiterite can also be separated from parts: a residue in the boat (resistant toward the
tungsten minerals by sublimation. Generally, the gas employed), a sublimate depositing on cold
decomposition temperature is between 400 and parts of the reaction tube, and gaseous products.
500°C; finely pulverized analytical samples are Advantages of using gases for decompositions
required. Mechanical devices have been con- include that they can be obtained in a very pure
structed for series analyses, ensuring complete form and the minimal possibility of contamina-
decomposition and deposition of the subli- tion, compared to other decomposition tech-
mate. 8 2 6 ' 8 2 7 The tin in the extract of the niques. Therefore, this procedure may be useful in
decomposed matter is most frequently determined determining micro and ultramicro amounts of
byAAS.64'820'823"825 elements. 2 3 3 ' 4 9 0
An analogous decomposition and determination The reducing effect of gaseous hydrogen at an
of antimony in soils and geological materials was elevated temperature can be used in the reduction
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proposed, 828 and the efficiencies of various of some oxides, such as cassiterite, which is readily
decomposition procedures were compared. The reduced to metallic tin; 8 3 s the metal is then easily
proposed procedure was applied to the deter- dissolved in hydrochloric acid, while the original
mination of antimony in ores 829 and concen- mineral can be decomposed only by energetic
trates; 830 the optimum decomposition conditions, alkaline-oxidative fusion. The procedure was also
the reagent amount, temperature, decomposition employed in the separation of tin from wolframite
duration, and the grain size of the analyzed and columbite-tantalite concentrates. 836
material were determined. It has been pointed Bi- and trivalent iron oxides, major components
out 8 3 1 that the analyzed mixture must be of various iron ores, can be quantitatively reduced
thoroughly dried in order for the decomposition to the metallic iron by hydrogen at 600°C. The
to be incomplete. After dissolution of the varying reducibility of iron silicates has been
sublimate and the residue in mineral acids, applied to phase analysis of oxygen-containing and
antimony can be determined by AAS in silicate ores; chlorite and pseudochlorite837
extract 8 2 8 ' 8 2 9 or in an organic phase obtained by minerals can be differentiated. Ilmenite is decom-
extraction of the antimony complex with trioctyl- posed in the stream of hydrogen to TiO2 and
phosphineoxide in isobutylmethyl ketone. 83 ' metallic iron, which is soluble in diluted HC1. 838
Antimony and tin minerals can also be decom- Compounds of zinc, cadmium, and lead can also
posed by heating with ammonium chloride. The be reduced to metals; then the elements can be
chlorides formed are dissolved in hydrochloric separated from the rock matrix by distillation in a
acid, and the determination is carried o u t 8 3 2 ' 8 3 3 nitrogen stream. 839 " 841 Hydrogen was employed
in the solution. For decomposition of tin ores and for chloride separation from synthetic hematite.
concentrates, a mixture of zinc powder with Produced hydrogen chloride is carried by the gas
ammonium chloride (1 + 2) was proposed; the into a suitable absorber and is determined. 842
decomposition takes place at a higher temperature Cu-Ni-Fe sulfides, used as collectors for platinum
than with the iodide. 704 Natural carbonates can metals, can also be reduced by hydrogen; the
be converted into chlorides by the effect of platinum metals are determined coulometrically
ammonium chloride at increased temperatures; an after dissolution in acids. 3 0 ' 8 4 3
aqueous extract is then used in subsequent Gaseous halogens, especially chlorine, are the
analyses.834 The use of NH 4 F and NH4HSO4 is most effective reagents. Chlorine reacts rapidly at
mentioned in Sections IV.B.l and IV.B.2. an elevated temperature with many metals, yield-
ing corresponding chlorides, differing in their
C. Decompositions in Gas Streams melting and boiling points, on the basis of which
Decomposition of inorganic materials in a gas they can be separated. Halogenation can also be
stream is often a very effective method of treating carried out in aqueous solutions: soluble halides
the analyzed mixture. Some gases can convert the can be separated from insoluble oxides, e.g., SiO2.
substances originally present into more easily In order to prevent changes in solution acidity and

June 1977 305

 consequent changes in the solubilities of the chlorides of sulfur, arsenic, and the other volatile
substances present, anhydrous solvents, alcohols, elements mentioned earlier are readily distilled off.
and esters are employed. The procedure can be advantageously applied to \
Halogenation is carried out by means of halo- decompositions of sulfosalts and sulfides included
gens alone, by anhydrous hydrogen halides, or by in silicate matrix. Rarer germanium compounds,
interhalides. Chlorinated hydrocarbon derivatives, including complicated organo complexes of this
such as carbon tetrachloride or chloroform, can element, occurring in coal, 846 are also readily
also serve as a source of chlorine, as can certain decomposed. Chlorination has attained great
sulfur-containing compounds (e.g., sulfur chloride, importance in the phase study of meteorites.
sulfuryl chloride, etc.). The apparatus and pro- Metallic iron containing nickel, sulfides, and
cedures are very simple and universal: the sample phosphides is decomposed by hydrogen chloride-
is placed on a boat in the hot zone of the free chlorine and produced chlorides are distilled
decomposition tube and the reagent gas is passed off. However, iron oxides and silicates are not
over it at the given temperature. The tubes are attacked. The decomposition of meteorite iron is
made mainly of fused quartz or suitable ceramics; limited 8 4 7 ' 8 4 8 by the nickel content (more than
platinum is satisfactory for gaseous fluorine. 25%) in the alloy. Chlorination is effectively
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Traces of oxygen are removed from the gas by employed for the separation of rare earth element
absorption in reducing reagent solutions. The groups from iron and aluminum. 849 A procedure
purified gases must be perfectly freed of humidity for isolation and purification of rare earth,
by drying with desiccating agents, e.g., sulfuric thorium, and scandium oxides obtained from
acid, phosphorus pentoxide, or magnesium per- silicates 249 or radioactive raw materials 844 has
chlorate. Devices made of Teflon or other resistant been described. Rare earth, niobium, and tantalum
materials were constructed for decompositions in minerals, such as fergusonite, samarskite, pyro-
gas streams at low temperatures. 133 ' 321 chlor, and others, are decomposed by chlorina-
Variously volatile chlorides are formed at a tion.8 4 4 > 8 S 0 Niobium compounds yield a volatile
slightly increased temperature by the effect of dry oxychloride, which is difficult to condense; there-
chlorine or hydrogen chloride. The chlorides of fore, it must be reduced to the chloride during the
copper, silver, nickel, cobalt, lead, and some other decomposition by adding active charcoal. 851 The
metals are most stable. Iron and zinc chlorides varied volatility of aluminum, iron, and zirconium
exhibit medium volatility. Chlorides of sulfur, chlorides has been utilized in the determination of
selenium, tellurium, arsenic, antimony, and tin the latter in rocks and zirconium concentrates. 852
distill very easily. Among rarer elements, the The same principles underlie technological pro-
chlorides of beryllium, zirconium, hafnium, cedures for the production of this metal with a
niobium, tantalum, vanadium, molybdenum, tung- minimum hafnium content. Transuranium ele-
sten, etc. are volatile. Some platinum metals and ments up to an atomic number of 98 have been
their alloys can be decomposed and separated by separated on the basis of various volatilities; the
chlorination. On the other hand, the alkali metals, distillation is carried out at a programmed tem-
alkaline earths, and the rare earths are very stable perature. 853 The separation of europium and
toward chlorine, so that chlorination is advan- cerium has also been described.8 s 4
tageously employed for isolation and purification . Chlorination at an elevated temperature is
of rare earth element compounds. 844 The selec- important for the dissolution of metallic gold and
tivity of the distillation separation can be im- platinum metals remaining after fire-assay separa-
proved by adding graphite or metal oxides to the tion. The platinum metal chlorides have a low
substance to be decomposed. volatility, except for osmium and ruthenium
The use of halogens for decompositions in chlorides. Chlorination is facilitated by the
inorganic analysis has been reviewed.270 The presence of sodium chloride; while iridium and
applications are usually based on the different rhodium yield insoluble compounds in direct
behavior of chlorides during heating; molybdenum chlorination, chlorocomplexes readily soluble in
and vanadium chlorides can thus be separated hydrochloric acid are formed in the presence of
from tungsten chlorides. 845 Tungsten minerals are sodium chloride. This salt also decreases the
decomposed only at high temperatures. Sulfides volatility of platinum and rhodium chlorides. 855
can readily be decomposed by chlorination; The effect of temperature, the amount of sodium

306 CRC Critical Reviews in Analytical Chemistry

 chloride, and chlorination duration on the solu- oxide, alumina, 8 s 9 ' 8 6 4 silica, 8 6 8 ' 8 6 9 vanadium
bility of the compounds formed was studied. 386 p e n t o x i d e , 8 7 0 ' 8 7 1 and tungsten triox-
Metal recoveries after chlorination were generally i d e . 8 6 3 ' 8 6 7 ' 8 6 8 Overheated water va-
higher than after fire assay and extraction with por
8S 7-862,864-866
aqua regia and amounted to 96 to 98% of the air 867-869,87i-873 are used for decomposition at
initial metal content. Chlorination in a closed temperatures between 800 and 1200°C.
system has also been described.28 Chlorine is also Numerous applications of this method 8 7 5 " 8 7 7
suitable for the decomposition of osmiridium, have been devoted to the determination of
sperylite, and platinum disulfide.795 Volatile fluorine in rocks and other natural silicates. It has
osmium chloride is absorbed in traps with 6 N HC1 been found that micas with high concentrations of
saturated with a sulfite. Chlorination was also alkali metals are poorly decomposed by the above
successful in the dissolution of gold grain after fusion agents; a [Link] mixture of bismuth(III)
cupellation, gold being used as a collector for oxide, sodium tungstate, and vanadium(V) oxide
rhodium. 696 Ore concentrates were analyzed for has proven effective and has been applied to the
gold after preliminary reduction with hydrogen, determination of fluorine in standard rocks. 872 A
followed by several hours of chlorination at 1:10 mixture of lithium metaphosphate and U 3 O 8
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700°C. Gold was coprecipitated on tellurium 382 has been recommended for the same purpose. 873
from dissolved metal chlorides. In the analysis of The metaphosphate acts as an efficient acidic
native gold, chlorination was employed for the fusion agent and excess uranium suppresses the
destruction of the residue, after dissolution of the volatility of phosphorus oxides. Sodium or lithium
metal in aqua regia. The residue is first extracted pyrotungstate, 874 acting as a catalyst and a fusion
by dilute nitric acid, then mixed with sodium agent, gave good results in the rapid quantitative
chloride and chlorinated. 856 separation of fluorine from glasses and fluorite.
The other halides 875 " 879 can be separated
D. Pyrohydrolysis under conditions identical to those used for
Pyrohydrolysis is a special decomposition tech- fluorides. The method has been used in the
nique in a gas stream. Materials are decomposed at determination of trace amounts of these elements
a high temperature by a stream of water vapors or in mineral materials and is especially well suited
damp gas in a suitable reaction tube. Volatile for geochemical purposes. Final determination of
acids, especially hydrogen halides and sulfuric, halides can be carried out photometrically or
fluorosilicic, and boric acids, are released and can preferably using ion-selective electrodes. Pyro-
thus be separated from the matrix and determined hydrolytic determination of boron has not
in the condensate. The decomposition technique enjoyed very extensive application because of
was proposed by Warf85 7 and has been applied by demanding conditions for the decomposition and
many authors,8 5 8~8 7 7 chiefly for the determina- incomplete separation of the substance to be
tion of fluorine. The apparatus and the procedure determined.
are practically universal; only the reaction condi-
tions, the temperature, the steam flow rate, the
amount of a liquid passed, and the kind of VII. CONCLUSION
accelerator vary, depending on the composition of
the material to be decomposed. Decompositions The chief methods for the decomposition of
are carried out in platinum, 8 5 7 ' 8 5 9 " 8 6 2 nick- natural inorganic compounds have been evaluated.
el8S8,864,86S quartz>8 6 6 ,86 7 , 869-8 7 3 glass> a n d Attention has been centered on a modern, very
868
ceramic devices. Some substances, such as effective, and promising decomposition technique,
fluorides of weakly basic elements, are decom- namely, decomposition at an elevated temperature
posed very rapidly pyrohydrolytically. On the and pressure. Further, the decomposing properties
contrary, alkali metal and alkaline earth fluorides of hydrofluoric acid and effective fusion with
decompose poorly, as the hydrofluoric acid alkali meta- or tetraborates were dealt with in
formed reacts again with the strong alkali liber- detail. The latter technique has gained importance
ated. These cations must be bound by so-called with the progress in AAS and other physico-
accelerators, which are thermally stable weakly chemical methods for the final determination of
acidic substances, mostly amphoteric metal oxides, elements. The introduction of these methods in
such as uranium(IV)-uranium(VI)8",862,863,86s analytical practice required simple preparation of
June 1977 307
L
 analytical solutions with a constant background classical fusion procedures have been evaluated
for very heterogeneous materials; therefore, fusion very briefly. Their application is quite general, and
with metaborates has proven most advantageous. no substantial development can be expected using
Reduction fusion has been broadly discussed in them. In discussing the individual decomposition
view of the economical importance of the techniques, their applicability, possibilities of
analyzed materials. Other commonly used losses in the material, and contamination of the
decomposition techniques employing acids and analyzed substances have been stressed.

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144. Perkin-Elmer, Ueberlingen, West Germany, Catalogue, 1975.
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310 CRC Critical Reviews in Analytical Chemistry

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176. Kuehner,C.C., Alvarez, R., Paulsen, P. J.,and Murphy,T.3.,Anal Chem., 44,2050(1972).

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340. Kv3iek,M., diem. Listy, 58,305(1964).
341. Dreyer, H. and Lessmann, O., Z Erzbergbau MetallhUettenwes., 8, 263 (1955).
342. Gi\fc\nn2i,G.\.,[Link]., 34,1194(1968).
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344. Ward, F. N., Nakagawa, H. M., Harms, T. F., and Van Sickle, G. H., U.S. Geol. Surv. Bull, 1289,38 (1969).
345. Hubert, A. F., U.S. Geol. Surv. Prof. Pap., 750B, B188 (1971).
346. Weiss, D., RubeSka, I., and KoieEkova", J., Chem. Listy, in press.
347. Thompson, C. E., Nakagawa, H. M., and van Sickle, G. H., U.S. Geol. Surv. Prof. Pap., 600B, B130 (1968).
348. Thompson, C. E., U.S. Geol. Surv. Prof. Pap., 575D, D236 (1967).
349. Hoffman, J. I. and Lundell, G. E. F.,J. Res. Natl Bur. Stand., 22,465 (1939).
350. Nonvitz, G. and Norwitz, I.,Metallurgia, 46, 318 (1952).
351. Goetz,[Link],F.J.,/lnfl/. Chem., 27, 1972(1955).
352. Kva&k, M. and Kilhn, P., Chem. Listy, 58,584(1964).
353. Karapetyan, E. T., Zavod. Lab., 34, 939 (1968).
354. Jon, M. and Rouby, M., Chim. Anal., 49, 73 (1967).
355. Krath, E.,Arch. Eisenhuttenwes., 39,49 (1968).
356. Leblond, A. M., Wehdling, R., and Bourdieu, J. M., Chim. Anal, 50, 431 (1968).
357. Sen Gupta, N. R., Z Anal. Chem., 268, 32 (1974).
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358. Van Sickle, G. H. and Lakin, H. W., U.S. Geol. Surv. Circ, No. 561, 1 (1968).
359. Vandael, C, Chim. Anal, 44, 295 (1962).
360. Thode, H. G., Monster, J., and Dunford, H.B., Geochim. Cosmochim. Ada, 25, 159 (1961).
361. Keattch, C. J.,J. Appl Chem., 14, 218 (1964).
362. Pungor, E. and Zapp, E. E.,Mikrochim. Ada, p. 150 (1957).
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365. Hampe, W., Chem. Ztg., 15, 443 (1891).
366. Rubeska, I., Sulcek, Z., and Moldan, B.,Anal Chim. Ada, 37, 27 (1967).
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371. Chao, T. T., Ball, J. W., and Nakagawa, H. U.,Anal. Chim. Ada, 54, 77 (1971).
372. West, F. K., West, P. W., and Ramakrishna, T. V., Environ. Sci. Technol, 1,717 (1967).
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374. Zakhariya, N. F., Anbinder, I. S., Pashkova, L. I., and Vustyanuk, E. V., Zh. Anal. Khim.,26, 1163 (1971).
375. Law, S. L. and Green, T.E.,Anal. Chem., 41,1008 (1969).
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379. Mirova, L. F., Tolkacheva, L. F., Malkov, E. M., and Talipov, Sh. T., Zavod. Lab., 38, 645 (1972).
380. Blyum, I. A., Pavlova, N. I., and Kalupina, F. P., Zh. Anal. Khim, 26, 55 (1971).
381. Carlson, G. G. and Van Loon, J. C.,At. Absorpt. Newsl, 9, 90 (1970).
382. Chow, A. and Beamish, F. E., Talanta, 14, 219 (1967).
383. Hildon, M. A. and Sully, G. R.,Anal Chim. Ada, 54, 245 (1971).
384. Grimaldi, F. S. and Schnepfe, M. M., U.S. Geol. Surv. Prof. Pap., 600B, B99 (1968).
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386. Palmer, I., Palmer, R., and Steele, T. W., /. S. Afr. Oiem. Inst., 25, 190 (1972).
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314 CRC Critical Reviews in Analytical Chemistry

 400. Galkina, L. L. and Strelcova, S. A., Zh. Anal. Khim., 26,1764 (1971).
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407. Bilgrami, S. A. and Ingamells, C. O.,Am. Mineral., 45, 576 (1960).
408. Bennett, H. and Reed, K. X., Analyst, 97,794(1972).
409. Malhotra. P. D. and Prasada Rao, G., flee. Geol. Surv. India, 93,215(1966).
410. Khalifa, M.,Ghonaim, A. K., and Ismail, A., Z. Anal. Chem., 272,367(1974).
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418. Newberry, C. L. and Christian, G. D., J. Assoc. Off. Agric. Chem., 48, 322 (1965).
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439. Bogatyreva, L. P. and Afanaseva, G. V., Zavod. Lab., 36, 663 (1970).
440. Head, P. C. and Nicholson, R. A.,Analyst, 98,53 (1973).
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444. Schlesinger, M. D. and Schultz, H., US Bureau of Mines, Report of Investigations No 7609, Washington, D.C., 1972.
445. Murashova, V. I., Sushkova, S. G., and Bakunina, L. I., Zavod. Lab., 33, 280 (1967).
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June 1977 315

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467. Songina, O. A., Kemeleva, N. G., Egorova, L. G., and Lebedyanceva, A. I., Zavod. Lab., 34, 794 (1968).
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469. Sixta, V., private communication.
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472. Dixon, E. K., Analyst. 59, 739 (1934).
473. Allison, L. E., Bollen, W. B., and Moodie, C. D., Agronomy, 9, 1346 (1965).
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479. Sendulskaya, T. I., Shpirt, [Link]., and Yurovskii, A. Z., Zh. Anal. Khim., 22,445 (1967).
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488. Huka, M., private communication.
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511. Meyrowitz, R., U.S. Geol. Surv. J. Res., 1, 549 (1973).
512. Stanton, N. B.,Anatyst, 93, 802 (1968).
513. Lunina, G. E. and Romanenko, E. G., Zavod. Lab., 34, 538 (1968).
514. Pilkington, E. S. and Smith, P. R., Anal. Chim. Acta, 39, 321 (1967).
515. O'Shaughnessy, P. T.,Anal. Chem., 45, 1946 (1973).
516. Pilkington, E. S. and Wilson, W., Anal. Cliim. Acta, 47,461 (1969).
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520. Dams, R. and Hoste, J., Talanta, 11, 1605 (1964).
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316 CRC Critical R eviews in A nalytical Chemistry
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531. Quin, B. F. and Brooks, R. R.,Anal. Oiim. Acta, 74, 75 (1975).
532. Roberts, J. L., Talanta, 18, 1070 (1971).
533. Schnepfe, M. M.,Ta!anta, 20, 175 (1973).
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536. Everson, W. L.,Anal. Chem., 41, 201 (1971).
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540. Biskupsky, V. S., Anal. Cliim. Acta, 33,333 (1965).

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