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Elemental Analysis of Organic Compounds With The Use of Automated CHNS Analyzers

New compounds and materials, which appear as a result of the development of organic chemistry, are characterized by a complex elemental composition and structure. Problems in the determination of carbon, hydrogen, and nitrogen in complex hardly degradable compounds are well known. Of significant difficulty is the analysis of polyfluorinated compounds, e.g., polyfluoroaromatic compounds, fluoroelastomers, lubricants, etc.

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0% found this document useful (0 votes)
243 views14 pages

Elemental Analysis of Organic Compounds With The Use of Automated CHNS Analyzers

New compounds and materials, which appear as a result of the development of organic chemistry, are characterized by a complex elemental composition and structure. Problems in the determination of carbon, hydrogen, and nitrogen in complex hardly degradable compounds are well known. Of significant difficulty is the analysis of polyfluorinated compounds, e.g., polyfluoroaromatic compounds, fluoroelastomers, lubricants, etc.

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vc_davv
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

ISSN 1061-9348, Journal of Analytical Chemistry, 2008, Vol. 63, No. 11, pp. 10941106. Pleiades Publishing, Ltd.

., 2008.
Original Russian Text V.P. Fadeeva, V.D. Tikhova, O.N. Nikulicheva, 2008, published in Zhurnal Analiticheskoi Khimii, 2008, Vol. 63, No. 11, pp. 11971210.

1094

New compounds and materials, which appear as a
result of the development of organic chemistry, such as
different polycyclic, nitrogen containing, heterocyclic
(imidazoles, oxazoles, triazoles, pyrroles, stable
nitroxyl radicals, nitrones, pyrimidines, quinazolines,
etc.), polyhalogen-containing aromatic including poly-
uoroaromatic, organometallic, carbonaceous, etc., are
characterized by a complex elemental composition and
structure, a variety of properties, thermal and chemical
stability, incombustibility, volatility, hygroscopicity,
instability in light, etc. A necessary condition of their
reliable identication and the verication of their purity
is still the determination of the elemental composition
of the compound performed by methods of organic ele-
mental analysis. Its problems in the determination of
carbon, hydrogen, and nitrogen in complex hardly
degradable compounds by both classical and automated
methods are well known. For example, in the determi-
nation of nitrogen in heterocyclic compounds contain-
ing nitrogen in the cycle or in groups such as azide,
nitrile, nitro, nitrone, and amine groups in concentra-
tions >30%, the incomplete conversion of different
forms of nitrogen to elemental nitrogen was observed
and, hence, underestimated results were obtained. Of
signicant difculty is the analysis of polyuorinated
compounds, e.g., polyuoroaromatic compounds, uo-
ropolymers, uoroelastomers, lubricants, uorine-con-
taining graphites, polyuorocarbons, etc. Many of
these compounds contain peripheral

>

CF

2

and


CF

3

groups along with the CF bonds constituting a rigid
uorinated framework, and different uorinated graph-
ites contain, e.g., intercalated halogen uorides ClF

3

,

ClF

5

,

and BrF

3

or alkali fluorides. The elemental analy-
sis of these uorides is complicated by the aggressive-
ness of uorine and HF formed during the course of the
decomposition, which leads to the corrosion of analyt-
ical instruments. Many uorine-containing compounds
require more stringent decomposition conditions,
because they are thermally stable, and the removal of
uorine as an interfering element from the combustion
zone.
The major elements of an organic substance,
namely, carbon, hydrogen, and nitrogen, are commonly
determined using commercially available CHN and
CHNS analyzers, in which the organic substance
undergoes oxidative decomposition and the subsequent
reduction of nitrogen and sulfur oxides with the forma-
tion of the nal products: carbon dioxide, water, ele-
mental nitrogen, and sulfur dioxide. Currently, both old
types of analyzers (Carlo Erba, models 1106 and 1108;
Hewlett-Packard, model 185; Perkin Elmer, model 240;
etc.) and new types (Euro EA 3000; Perkin Elmer 2400,
series II; CE 440; Vario EL III; etc.) are used in the
practice of organic elemental analysis. It is known that
the oxidants and catalysts developed and proposed in
classical methods of elemental CHN analysis also nd
application in automated analyzers.
Co

3

O

4

, the product of the thermal decomposition of
silver permanganate [1], Cr

2

O

3

[2, 3], NiO [4], WO

3

[5, 6],

V

2

O

5

[7],

SnO

2

[8, 9],

eO

2

[10], MgO [11], or their
mixtures are used as additives to samples including
hardly combustible substances containing, e.g., B, P, Si,
and alkali metals; oxide additives improving the com-
bustion of pyrimidines and triazoles (Co

3

O

4


V

2

O

5

)
[12], and polycyclic and organometallic compounds
(V

2

O

5

,

MnO

2

,

K

2

Cr

2

O

7

, etc.) were also proposed [13
15]. The reagents added to a portion of a sample were
calculated for a single effect and are removed before the
analysis of the next sample. These are oxygen donors,
oxidation catalysts, and absorbers of the interfering
compounds. The functions of these reagents can hardly
be separated.
Commonly, in both classical and automated meth-
ods, the sample is not completely oxidized in the pyrol-

ARTICLES

Elemental Analysis of Organic Compounds
with the Use of Automated CHNS Analyzers

V. P. Fadeeva, V. D. Tikhova, and O. N. Nikulicheva

Vorozhtsov Institute of Organic Chemistry, Siberian Division, Russian Academy of Sciences,
pr. akademika Lavrenteva 9, Novosibirsk, 630090 Russia

Received July 9, 2007; in nal form, October 31, 2007

Abstract

Results of many years worth of studies on the determination of carbon, hydrogen, and nitrogen on
automated CHNS analyzers were summarized. Catalytic oxide compositions were selected that allow for the
analysis of synthetic and natural organic compounds and materials of any elemental composition and structure:
polycyclic, condensed aromatic, heterocyclic, carbonaceous (graphites and carbons), organometallic, organo-
element, etc.

DOI:

10.1134/S1061934808110142

JOURNAL OF ANALYTICAL CHEMISTRY



Vol. 63



No. 11



2008

ELEMENTAL ANALYSIS OF ORGANIC COMPOUNDS 1095

ysis zone. Therefore, the reagents facilitating the com-
plete oxidation of the pyrolysis products are placed
downstream in the reaction tube. Among these are com-
pounds providing the long-term oxidizing effect and
acting as a catalyst or an oxygen donor. The main
reagents that were proposed in classical methods are
Cr

2

O

3

, CuO, CeO

2

,

SnO

2

,

AgVO

3

[1618],

MnO

2

+

Cr

2

O

3

+

WO

3

[19],

WO

3

[20],

WO

3

+

Ag

2

WO

4

+

AgMnO

4

[21],

Co

3

O

4

on Al

2

O

3

, with Ag on pumice, and
CeO

2

[22], Pt/asbestos + Ag

2

WO

4

+ MgO + ZrO

2

+
Pt/asbestos + Ag + Au [23], etc. All of these composi-
tions can also be used in automated analyzers. To
improve the analysis of uorine-containing compounds
in Carlo Erba automates, using CeO

2


MgO

[24],

WO

3

,
or WO

3

in a mixture with Al

2

O

3

was proposed [25, 26].
In the reaction unit of automated elemental analyz-
ers, interfering C, H, and N compounds were also
absorbed with the use of selective absorbing reagents.
Combined reagents Co

3

O

4

+ Ag [27], SnO

2

+ Ag [9],
AgVO

3

, and Ag with Al

2

O

3

[28] are efficient in the anal-
ysis of substances containing halogens and sulfur; the
mixed reagent

3

MgOAl

2

O

3

more intensely absorbs
hydrogen uoride than individual MgO. These reagents
are placed either in the additional oxidation zone or in
the reduction zone according to the optimum tempera-
ture required for their action.
Oxide additives proposed by the companies produc-
ing automated elemental analyzers to provide the com-
plete decomposition of the substance are sometimes
insufciently efcient in the analysis of complex multi-
element hardly degradable organic compounds; there-
fore, substantial improvements are required, primarily
at the step of substance decomposition.
The aim of this work was to consider the efciency
of the use of our universal catalytic oxide compositions;
the use of these compositions in elemental CHNS ana-
lyzers provides the complete decomposition of organic
compounds and the successful determination of C, H,
and N in substances of any elemental composition and
structure: polycyclic, condensed aromatic (naphthols,
anthraquinones, ceramidonines, etc.) including poly-
uoroaromatic, organometallic (containing any met-
als), graphites, humic acids, and nitrogenous hetero-
cyclic compounds like pyrimidines, pyrazolones, tria-
zoles, etc.
EXPERIMENTAL

Reagents and Instruments.



Preparation of cata-
lytic oxide compositions.

For the preparation of cata-
lysts and oxides, we used reagents of the chemically
pure or analytical grade from Reakhim.

Catalytic oxide composition for lling the oxida-
tion reactor of the CE analyzer.

The composition was
prepared by mixing Ag

2

WO

4

,

ZrO

2

, and MgO (analyti-
cal grade) in the mass ratio 2 : 8 : 1 or 2 : 7 : 2, cau-
tiously ground in a mortar with a small amount of water
to form a thick homogeneous paste, which was forced
through a sieve with a mesh diameter of 2 mm. The
obtained granules were kept for 2 h at a temperature of

120

in a drying oven, screened from dust, and, next,
baked in a mufe furnace for 2 h at

500600

. The
granules were stored in a glass-stoppered bottle. The
ratio of the ZrO

2

and MgO components in the composi-
tion can be changed depending on the composition of
the analyzed substances. To obtain Ag

2

WO

4

33

g of
Na

2

WO

4

H

2

O was dissolved in 1 L of distilled water
and heated, an equal amount of a solution containing
34 g of AgNO

3

was added with stirring, and the mixture
was boiled for 1015 min. The precipitate was washed
on the lter with hot and then cold, distilled water until
silver ions were removed and next dried at

105110

in a drying oven for at least 2 h. ZrO

2

was obtained by
the cautious decomposition of ZrO

(

NO

3

)

2



2

H

2

O or
Zr

(

NO

3

)

2

in a porcelain crucible heating it on an electric
hotplate until the evolution of nitrogen oxides stopped.
Next, it was baked in a mufe furnace at

1000

for 3 h.
Cr

2

O

3

was prepared from

(

NH

4

)

2

Cr

2

O

7

as described in
[29]. Co

3

O

4

of an analytical grade was used.

Catalytic oxide composition for addition to a por-
tion of a substance in the HP analyzer.

As the addi-
tion to a portion of a substance in combustion in the
automated analyzer Hewlett-Packard, model 185, we
used a catalytic oxide composition developed by us,
which consisted of four components (mass %): MnO

2


64%,

Cr

2

O

3
13%, PbO
2
13%, SiO
2
, 10. The proce-
dure for the preparation of the composition was
described in [29].
The oxidation zone in the reactor of the EA analyzer
was lled with tungsten anhydride (WO
3
) provided by
the producing company or prepared from powdered
WO
3
by pressing it with alumina, subsequent commi-
nution in a porcelain mortar, and screening to a particle
size of 12 mm. The lifetime of the lled vertical oxi-
dation reactors (in CE and EA analyzers) was deter-
mined by the amount of ash accumulated in the com-
bustion zone; it was 300 combustions at the average
Copper that was used in the reduction zone of ana-
lyzers was prepared by the reduction of wire copper
oxide in a hydrogen ow at a temperature of 500.
As standard (reference) compounds for the calibra-
tion of instruments, we used acetanilide, 4-nitroaniline,
benzoic acid, cyclohexanone 2,4-dinitrophenylhydra-
zone, 2,5-bis-(5-tert-butyl-2-benzoxazolyl)thiophene,
S-benzylthiuronyl chloride, sulfanilamide, and cystine
provided by Carlo Erba and enterprise standards
(Vorozhtsov Institute of Organic Chemistry): pentau-
orobenzoic acid, toluene sulfochloride, urea, and decaf-
luorophenyl disulde previously puried by recrystalli-
zation and analyzed.
Elemental analysis was performed in the following
analyzers: Hewlett-Packard, model 185 (United States)
(HP); Carlo Erba, model 1106 (Italy) (CE); and Euro
EA 3000 (Italy) (EA). Samples were weighed on a bal-
ance Mettler Toledo AT-20 (Switzerland) or Sartorius
CP2P (Germany).
1096
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
FADEEVA et al.
Analysis. Portions of samples with a mass of no
more than 1 mg were weighed in tin containers (alumi-
num boats can be also used in the HP analyzer). In the
HP analyzer, the holder with the sample was com-
pletely covered with the catalytic oxide additive
described above and introduced into the horizontal tube
in the combustion zone at 1100, where samples were
burned in the static mode for 50 s. The pyrolysis prod-
ucts were afteroxidized at the end of the tube with cop-
per oxide and blown with the carrier gas (He) into the
reduction tube lled with reduced-wire Cu (580), in
which nitrogen oxides were reduced to elemental nitro-
gen and excess oxygen was absorbed. Resulting N
2
,
CO
2
, and H
2
O were separated on a column with Pora-
pak Q and determined with a heat conductivity detector
(catarometer).
In CE and EA automated analyzers, a sample was
burned in a vertical reactor (oxidation tube) in the
dynamic mode (at 1020 in CE and at 1050 in EA)
in an He ow with the addition of O
2
(10 mL) at the
instant of sample introduction. Portions of the sample
in tin capsules were placed in the automated sampler,
from which they were transferred to the oxidation tube
at regular intervals. After the pyrolysis, the resulting
products were afteroxidized in the lower part of the
reactor lled with a catalytic oxide composition and
then passed through the reduction zone. In the EA ana-
lyzer, the mixture of sulfur oxides was quantitatively
converted to SO
2
on reduced copper. The end of the
analysis is analogous to that described above for HP.
The concentration of each element in the HP instru-
ment was calculated after the measurement of the cor-
responding peak heights in the chromatogram. In the
CE analyzer, calculations were performed using the
areas of these peaks obtained on the integrator. In the
EA analyzer, calculations were performed using the
Callidus program supplied with the analyzer.
RESULTS AND DISCUSSION
Determination of carbon, hydrogen, and nitro-
gen on the Carlo Erba analyzer. For the CE analyzers,
the company supplies reagents, llers of the oxidation
reactor: Cr
2
O
3
, Ag Co
3
O
4
, and WO
3
. We used two types
of llings of the oxidation reactor of the analyzer pre-
sented in Fig. 1. Filling a involved three components:
Co
3
O
4
, combined catalytic oxide composition Ag
2
WO
4
,
ZrO
2
+ MgO, and Cr
2
O
3
. Filling b consisted of two
components and involved no Co
3
O
4
. ZrO
2
and MgO
involved in the composition are highly active afteroxi-
dation catalysts and, in addition, excellent absorbers of
uorine-containing products [30] produced on burning
organouorine compounds. The Ag
2
WO
4
component
absorbs halogens, sulfur oxides, and other interfering
elements, which is favored, along with oxidizing prop-
erties, by Co
3
O
4
. Filling a was found to be optimum; it
forms the basis of the approved procedure, and the
results presented in Tables 1 and 2 were obtained with
the use of this three-component lling.
To obtain calibration coefcients with this lling, it
is not necessary to bring the quantitative elemental
composition of reference samples close to the analyzed
samples, as done by some researchers [24]. Figure 2
presents the dependences of the calibration coefcients
on the percentage of the determined elements. As seen
in Fig. 2, this dependence is absent for the studied con-
centration ranges (H, from 1 to 12%; C, from 30 to
90%; N, from 0 to 60%).
With the used of the proposed catalytic oxide com-
position, the analyses of synthetic organic and natural
compounds with different elemental composition and a
rather wide concentration range of the determined ele-
ments were preformed on the Carlo Erba analyzer for
many years (Table 1). For example, a specic feature of
compound 1 is the high concentration of carbon (above
80%), and the specic feature of compounds 2 and 3 is
the high concentration of nitrogen in different forms
(35 and 64%, respectively). Compounds 5 and 6 con-
tain more than 50% uorine, which is specied in the
second column of Table 1. Other compounds presented
in Table 1 contain heteroelements in different combina-
tions: sample 2, more than 64% sulfur; sample 4, iodine
and sulfur; sample 8, phosphorus; sample 9, bromine
and sulfur; sample 10, uorine and chlorine; samples 11
and 12, bromine, chlorine, and a metal atom (copper
and cobalt, respectively). Table 2 presents the results of
the analysis of samples of chalcogenide cluster com-
pounds (13) and samples of the complexes of metals
with organic ligands (46).
Measurements of the concentrations of carbon,
hydrogen, and nitrogen in samples of organic sub-
() (b)
3
2
1
1
2
Fig. 1. Filling of the oxidation tube in the Carlo Erba auto-
mated analyzer: (a) (1) Co
3
O
4
, 25 mm; (2) Ag
2
WO
4
+
ZrO
2
+ MgO, 50 mm; (3) Cr
2
O
3
, 60 mm; (b) (1) Ag
2
WO
4
+
ZrO
2
+ MgO, 65 mm; (2) Cr
2
O
3
, 70 mm.
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
ELEMENTAL ANALYSIS OF ORGANIC COMPOUNDS 1097
C
o
e
f

c
i
e
n
t
s
10 20 30 40 50 60
%N
0
0.2
0.4
(c)
2 4 6 8 10 12
%H
0
0.03
0.05 (b)
30 40 60 70 80 90
%C
0
0.04
0.12 ()
0.08
50
0.01
Fig. 2. Dependence of calibration coefcients on the per-
centage of the determined elements: (a) carbon, (b) hydro-
gen, and (c) nitrogen; average values are 0.1104, 0.0449,
and 0.3905, respectively.
stances with the use of the Carlo Erba automated ele-
mental analyzer (MVI NIOKh SO RAN No. 01-95)
were performed by the procedure approved according
to GOST R8.563 by FGUP Ural Research Institute of
Metrology.
Determination of carbon, hydrogen, and nitro-
gen on the Hewlett-Packard analyzer. With the use of
oxide additives supplied by the company for the HP
CHN analyzer, the results for carbon and nitrogen in the
case of complex substances in an elemental composi-
tion were underestimated commonly by 15% and
above. The errors are evidently related to the properties
of the analyzed compounds and the character of their
thermal decomposition. The decomposition of nitro-
gen-containing substances, depending on the speciation
of nitrogen in the substance, can yield such nitrogen-
containing pyrolysis products as ammonia, dicyan,
hydrogen cyanide, dinitrogen monoxide, nitrogen
oxide, nitrogen dioxide, and free nitrogen; however, in
the case of the complete oxidation, only nitrogen and
nitrogen oxide and/or dioxide are formed. In the com-
bustion of some compounds, there is a possibility of the
underoxidation of the resulting hydrocarbons, which
affects the results of the determination of carbon and
hydrogen, or the formation of the nitrile group, which
leads to their binding to copper cyanide (in the zone of
the formation of nitrogen oxides), and the results of the
analysis for nitrogen are underestimated. We studied
oxides and their mixtures (NiO, V
2
O
5
, MnO
2
, PbO
2
,
Cr
2
O
3
, WO
3
, etc.) as oxidizing additives to a sample and
developed a catalytic oxide composition (MnO
2
,
64 mass %; Cr
2
O
3
, 13 mass %; PbO
2
, 13 mass %; SiO
2
,
10 mass %), which is suitable for the analysis of a wide
range of compounds of different classes including
hardly combustible compounds [29]. The selection of
this composition was justied by the fact that Cr
2
O
3
is
a strong catalyst of the surface action stable up to a tem-
perature of 2000 and MnO
2
and PbO
2
are oxygen
donors, which are necessary for oxidation without oxy-
gen additions. In addition, PbO forms at a temperature
above 500; it melts at a temperature of 886 and
occurs in the molten state in the combustion zone pro-
viding favorable conditions for the rapid oxidation of
carbon in substances of a complex composition,
because PbO can form melts with oxides of heteroele-
ments interfering with the oxidation. Silica, on the one
hand, is used as a dilutant, which imparts the owabil-
ity to the composition, and, on the other hand, at 600
850 interacts with many elements to form silicates or
molecular compounds of the type (MO)
y
(SiO
2
)
x
[31].
Along with the role of an oxidant, the developed cat-
alytic oxide composition provides the retention of such
elements as halogens, sulfur, phosphorus, arsenic, anti-
mony, boron, selenium, tellurium, osmium, and alkali
and other metals, which interfere with the determina-
tion of carbon, hydrogen, and nitrogen, in the combus-
tion zone. This additive was insufciently efcient only
in the case of the combustion of graphite, which was
oxidized by only 50%, because an excess of oxygen
provided in the CE and EA analyzers is necessary for
its successful analysis.
The developed catalytic oxide composition has been
used for the analysis of different compounds for many
years. Table 3 presents examples of the results of the
analysis of some compounds, which are difcult for
analysis and, however, were successfully analyzed:
organouorine, nitrogenous heterocyclic, polycyclic,
etc.
Determination of carbon, hydrogen, nitrogen,
and sulfur on the Euro EA 3000 analyzer. The EA
analyzer is a completely automated complex for the
determination of four elements: C, H, N, and S. As
mentioned above, the principle of the method is the
same as in the CE analyzer; however, the use of a com-
mon on-line scheme, which includes a microbalance, a
high-temperature main unit, and computer control,
makes it possible to increase the speed of analysis, to
automatically take into account the mass of the intro-
1098
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
FADEEVA et al.









T
a
b
l
e

1
.


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s
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l
t
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o
f

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,

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2
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+
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F
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3
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4
.
6
%

F
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
ELEMENTAL ANALYSIS OF ORGANIC COMPOUNDS 1099
T
a
b
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e

1
.


(
C
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d
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S
1100
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
FADEEVA et al.
T
a
b
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e

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.


(
C
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n
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d
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2
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
ELEMENTAL ANALYSIS OF ORGANIC COMPOUNDS 1101






T
a
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e

2
.


R
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S
3
1102
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
FADEEVA et al.














T
a
b
l
e

3
.


R
e
s
u
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t
s

o
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C
l
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
ELEMENTAL ANALYSIS OF ORGANIC COMPOUNDS 1103
T
a
b
l
e

3
.


(
C
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5

C
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1104
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
FADEEVA et al.







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r
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
ELEMENTAL ANALYSIS OF ORGANIC COMPOUNDS 1105
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F
1106
JOURNAL OF ANALYTICAL CHEMISTRY Vol. 63 No. 11 2008
FADEEVA et al.
duced sample, and to automate the calculation of the
results of the analysis. The use of an oxide layer con-
sisting of WO
3
in the reactor and the addition of V
2
O
5
to the portion of the sample made it possible to solve
the rather complex problem of elemental analysis: the
determination of sulfur (along with carbon, hydrogen,
and nitrogen) in selenium-containing substances (Table 4).
As seen in Table 4, under the conventional conditions of
the operation of this analyzer, selenium-containing sub-
stances are completely oxidized; the presence of Se in
the range from 29 to 50% does not affect the quantita-
tive determination of carbon and hydrogen; and sele-
nium oxides are completely absorbed in the reactor, do
not arrive at the chromatographic column, and, conse-
quently, do not change the determined concentration of
sulfur in the studied substances. The EA analyzer was
also successfully used for the analysis of substances
containing different metals, phosphorus, halogens
(including uorine), sulfur, silicon, boron, etc.
Thus, based on the results of many years of work,
we can state that carbon, hydrogen, nitrogen, and sulfur
can be determined on automated element analyzers in
substances of any elemental composition and structure
with the selection and use of particular catalytic oxide
compositions and absorbers of interfering elements.
The catalytic oxide compositions that were proposed
and used by us allow the successful analysis of complex
multicomponent hardly combustible substances.
REFERENCES
1. Rezl, V. and Janak, I., J. Chromatogr., 1973, vol. 81,
no. 2, p. 233.
2. Pella, E. and Colombo, B., Mikrochim. Acta, 1983, no. 5,
p. 697.
3. Kirsten, W.J. and Hesselins, A., Microchem. J., 1983,
vol. 28, no. 4, p. 529.
4. Culmo, R.F., Mikrochim. Acta, 1969, vol. 57, no. 1,
p. 175.
5. Pella, E. and Colombo, B., Mikrochim. Acta, 1978,
nos. 34, p. 271.
6. Kissa, E. and Seepex-Yllo, M., Mikrochim. Acta, 1967,
no. 2, p. 287.
7. Gelman, N.E. and Kiparenko, L.M., ZhVKhO Im. D.I.
Mendeleeva, 1980, vol. 25, no. 6, p. 641.
8. Rezl, V. and Uhdeova. J., Mikrochim. Acta, 1979, vol. 71,
nos. 56, p. 349.
9. Rezl, V. and Buresova, A., Mikrochim. Acta, 1982,
vol. 78, nos. 12, p. 95.
10. Monar, I., Iikrochim. Acta, 1972, vol. 60, no. 6, p. 7 84.
11. Kirsten, W.J., Microchem. J., 1971, vol. 16, no. 4, p. 610.
12. Tefft, M.L. and Gustin, G.M., Microchem. J., 1966,
vol. 10, nos. 14, p. 175.
13. Larionov, V.P., Alyanov, M.I., Khlyupin, Yu.M., Borod-
kin, V.F., Yashin, Ya.I., and Smirnov, R.P., Trudy
Ivanovskogo Khim.-Tekhnol. In-Ta, 1973, no. 15, p. 71.
14. Miroshina, V.P. and Dubina, E.M., Zh. anal. khim., 1991,
vol. 46, no. 3, p. 493.
15. Kiparenko, L.M., Gelman, N.E., Maslennikova, N.D.,
and Smirnova, V.I., Zh. anal. khim., 1980, vol. 35, no. 2,
p. 328.
16. Ebeling, M. and Malter, L., Microchem. J., 1963, vol. 7,
p. 179.
17. Lebedeva, A.I., Nikolaeva, N.A., and Orestova, V.A., Izv.
Akad. Nauk SSSR, Otd. Khim. Nauk, 1961, no. 7,
p. 1350.
18. Macdonald, A.M.G.. and Turnton, G.G., Microchem. J.,
1968, vol. 13, no. 1, p. 1.
19. Celon, E. and Bresadola, S., Anal. Chem., 1968, vol. 40,
no. 8, p. 972.
20. Mizukami, S. and Jeki, T., Microchem. J., 1963, vol. 7,
no. 4, p. 485.
21. Fildes, J.E., Mierochim. Acta, 1970, vol. 58, no. 5,
p. 978.
22. Binkowski, J. and Levy, R., Bull. Soc. Franne, 1968,
no. 10, p. 4289.
23. Yeh, C.S., Microchem. J., 1963, vol. 7, no. 3, p. 303.
24. Borda, P.P., Z. Analyt. Chem., 1989, vol. 334, no. 7,
p. 715.
25. Maslennikova, N.D., Kiparenko, A.M., Buyanovskaya, A.G.,
and Terenteva, E.A, Zh. anal. khim., 1993, vol. 48, no. 3,
p. 547.
26. Baccanti, M. and Colombo, B., JOP, 1990, vol. 18, no. 1,
Ref. zh. chem., 1990, no. 15A337.
27. Kainz, G. and Horvatitsch, H., Mikrochim. Acta, 1962,
vol. 50, no. 1, p. 7.
28. Padowertz, W., Microchem. J., 1969, vol. 14, no. 1,
p. 110.
29. Fadeeva, V.P. and Moryakina, I.M., Izv. Sib. Otd. Akad.
Nauk SSSR, Ser.: Khim., 1981, vol. 6, no. 14. p 113.
30. Gelman, N.E. and Korshun, M.O., Dokl. Akad. Nauk
SSSR, 1953, vol. 38, no. 4, p. 685.
31. Gelman, N.E., Terenteva, E.A., Shanina, T.M., et al.,
Metody kolichestvennogo organicheskogo elementnogo
mikroanaliza (Quantitative Methods for Organic Ele-
mental Micronalysis), Moscow: Khimiya, 1987.

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